Handbook of Polymer Reaction Engineering

Handbook of Polymer
Reaction Engineering
Edited by
Th. Meyer, J. Keurentjes
Handbook of Polymer Reaction Engineering. Edited by T. Meyer, J. Keurentjes
Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
ISBN: 3-527-31014-2
Further Titles of Interest
E. S. Wilks (Ed.)
Industrial Polymers Handbook
Products, Processes, Applications
2000
ISBN 3-527-30260-3
H.-G. Elias (Ed.)
Macromolecules
Vols. 14
2005
ISBN 3-527-31172-6, 3-527-31173-4, 3-527-31174-2,
3-527-31175-0
M. F. Kemmere, Th. Meyer (Eds.)
Supercritical Carbon Dioxide
in Polymer Reaction Engineering
2005
ISBN 3-527-31092-4
M. Xanthos (Ed.)
Functional Fillers for Plastics
2005
ISBN 3-527-31054-1
R. C. Advincula, W. J. Brittain, K. C. Caster, J. Ru u he (Eds.)
Polymer Brushes
2004
ISBN 3-527-31033-9
H.-G. Elias (Ed.)
An Introduction to Plastics
Second, Completely Revised Edition
2003
ISBN 3-527-29602-6
Handbook of Polymer Reaction Engineering
Edited by
Thierry Meyer, Jos Keurentjes
Editors
Dr. Thierry Meyer
Swiss Federal Institute of Technology
Institute of Process Science
EPFL, ISP-GPM
1015 Lausanne
Switzerland
Prof. Jos T. F. Keurentjes
Process Development Group
Eindhoven University of Technology
P.O. Box 513
5600 MB Eindhoven
The Netherlands
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including this book, to be free of errors.
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statements, data, illustrations, procedural
details or other items may inadvertently be
inaccurate.
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KGaA, Weinheim
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ISBN-13 978-3-527-31014-2
ISBN-10 3-527-31014-2
Foreword
A principal dierence between science and engineering is intent. Science is used
to bring understanding and order to a specic object of study to build a body of
knowledge with truth and observable laws. Engineering is more applied and prac-
tical, focused on using and exploiting scientic understanding and scientic prin-
ciples to make products to benet mankind. A polymer reaction engineer seeks the
applied and practical as the title implies, but the path to success is most often
through polymer science. This truth is steeped in history there are many exam-
ples of polymeric products commercialized without adequate understanding of the
chemistry and physics of the underlying polymerization. Polymer reaction engi-
neers, faced with detriments in process safety, product quality or product cost, be-
come the driving force behind many polymer science developments. As such, poly-
mer reaction engineering is more a collaboration of polymer science and reaction
engineering. A collaboration where polymer reaction engineers develop a rm un-
derstanding of the many aspects of polymer chemistry and physics to successfully
apply chemical engineering principles to new product developments. Only through
the integration of science and engineering are such products realized.
This handbook is a testimony to this melding of polymer science and chemical
engineering that denes polymer reaction engineering. Thierry Meyer and Jos
Keurentjes have compiled a strong list of contributors with an even balance from
academia and industry. The text oers a comprehensive view of polymer reaction
engineering. The text starts with an overview describing the important integration
of science and engineering in polymer reaction engineering and ends with recent
and potential breakthrough developments in polymer processing. The middle
chapters are divided into three sections. The rst section is devoted to the science
and chemistry of the major types of polymerization. Included are step and chain
growth polymerizations with chapters devoted specically to several dierent chain
growth methods. The central section of the middle chapters is dedicated to poly-
mer reaction engineering tools and methods. The very important topics of safety
and process control are detailed and help frame the conditions through which suc-
cessful scale-ups are achieved. The last section of the middle chapters is focused on
the physics and physical nature of formed polymers including their physical and
mechanical structure. In these chapters, many of the processes that modify poly-
V
mers through man-made and natural change are discussed. The details of polymer
end use are also presented.
This tome represents the rst published handbook on polymer reaction engi-
neering and should be well received in academia and industry. Polymer reaction
engineering became recognized as a separate engineering discipline in the 1970s.
It is well past due that such a handbook be published. The broad scope and depth
of coverage should make it an important reference for years to come.
Michael C. Grady, ScD
Senior Engineering Associate
DuPont
Philadelphia, Pennsylvania
VI Foreword
Contents
Volume 1
Foreword V
Preface XXIX
List of Contributors XXXI
1 Polymer Reaction Engineering, an Integrated Approach 1
Th. Meyer and J. T. F. Keurentjes
1.1 Polymer Materials 1
1.2 A Short History of Polymer Reaction Engineering 4
1.3 The Position of Polymer Reaction Engineering 5
1.4 Toward Integrated Polymer Reaction Engineering 7
1.5 The Disciplines in Polymer Reaction Engineering 9
1.5.1 Polymerization Mechanisms 11
1.5.2 Fundamental and Engineering Sciences 12
1.6 The Future: Product-inspired Polymer Reaction Engineering 14
1.7 Concluding Remarks 15
References 15
2 Polymer Thermodynamics 17
Theodoor W. de Loos
2.1 Introduction 17
2.2 Thermodynamics and Phase Behavior of Polymer Solutions 18
2.2.1 Thermodynamic Principles of Phase Equilibria 18
2.2.2 Fugacity and Activity 18
2.2.3 Equilibrium Conditions 20
2.2.4 Low-pressure VaporLiquid Equilibria 21
2.2.5 FloryHuggins Theory and LiquidLiquid Equilibria 21
2.2.6 High-pressure LiquidLiquid and VaporLiquid Equilibria 25
2.3 Activity Coecient Models 29
2.3.1 FloryHuggins Theory 30
VII
2.3.2 Hansen Solubility Parameters 32
2.3.3 Correlation of Solvent Activities 34
2.3.4 Group Contribution Models 35
2.4 Equation of State Models 39
2.4.1 The SanchezLacombe Lattice Fluid Theory 40
2.4.2 Statistical Associating-uid Theory 44
2.4.2.1 SAFT and PC-SAFT Hard Chain Term 44
2.4.2.2 SAFT Dispersion Term 45
2.4.2.3 The PC-SAFT Dispersion Term 46
2.4.2.4 SAFT and PC-SAFT Applications 47
2.4.2.5 Extension to Copolymers 48
2.5 Conclusions 50
Notation 52
References 54
3 Polycondensation 57
Mario Rui P. F. N. Costa and Rolf Bachmann
3.1 Basic Concepts 57
3.1.1 A Brief History 57
3.1.2 Molecular Weight Growth and Carothers Equation 59
3.1.3 The Principle of Equal Reactivity and the Prediction of the Evolution of
Functional Group Concentrations 62
3.1.4 Eect of Reaction Media on Equilibrium and Rate Parameters 62
3.1.5 Polycondensation Reactions with Substitution Eects 64
3.1.6 Exchange Reactions 66
3.1.7 Ring-forming Reactions 67
3.1.8 Modeling of Polymerization Schemes 68
3.2 Mass Transfer Issues in Polycondensations 69
3.2.1 Removal of Volatile By-products 69
3.2.2 Solid-state Polycondensation 80
3.2.3 Interfacial Polycondensation 82
3.3 Polycondensation Processes in Detail 85
3.3.1 Polyesters 85
3.3.1.1 Structure and Production Processes 85
3.3.1.2 Acid-catalyzed Esterication and Alcoholysis 86
3.3.1.3 Catalysis by Metallic Compounds 87
3.3.1.4 Side Reactions in Aromatic Polyester Production 89
3.3.1.5 Side Reactions in the Formation of Unsaturated Polyesters 90
3.3.1.6 Modeling of Processes of Aromatic Polyester Production 91
3.3.1.7 Modeling of Processes for Unsaturated Polyester Production 92
3.3.2 Polycarbonates 93
3.3.2.1 General Introduction 93
3.3.2.2 Interfacial Polycondensation 94
3.3.2.3 Melt Transesterication 96
3.3.3 Polyamides 98
VIII Contents
3.3.3.1 Introduction 98
3.3.3.2 Kinetic Modeling 98
3.3.3.3 Nonoxidative Thermal Degradation Reactions 100
3.3.3.4 Process Modeling 101
3.3.4 Polymerizations with Formaldehyde: Amino Resins (Urea and
Melamine) and Phenolics 102
3.3.4.1 Formaldehyde Solutions in Water 102
3.3.4.2 Amino Resins 102
3.3.4.3 Phenolic Resins 107
3.3.5 Epoxy Resins 108
3.3.6 Polyurethanes and Polyureas 109
3.4 Modeling of Complex Polycondensation Reactions 113
3.4.1 Overview 113
3.4.2 Description of Reactions in Polycondensations of Several Monomers
with Substitution Eects 113
3.4.3 Equilibrium Polycondensations with Several Monomers 117
3.4.4 Kinetic Modeling of Irreversible Polycondensations 129
3.4.5 Kinetic Modeling of Linear Reversible Polycondensations 133
Notation 136
References 144
4 Free-radical Polymerization: Homogeneous 153
Robin A. Hutchinson
4.1 FRP Properties and Applications 153
4.2 Chain Initiation 154
4.3 Polymerization Mechanisms and Kinetics 156
4.3.1 Homopolymerization 157
4.3.1.1 Basic Mechanisms 157
4.3.1.2 Kinetic Coecients 161
4.3.1.3 Additional Mechanisms 169
4.3.2 Copolymerization 179
4.3.2.1 Basic Mechanisms 179
4.3.2.2 Kinetic Coecients 183
4.3.2.3 Additional Mechanisms 187
4.3.3 Diusion-controlled Reactions 190
4.4 Polymer Reaction Engineering 193
4.4.1 Types of Industrial Reactors 195
4.4.1.1 Batch Processes 195
4.4.1.2 Semi-batch Processes 196
4.4.1.3 Continuous Processes 196
4.4.2 Mathematical Modeling of FRP Kinetics 197
4.4.2.1 Method of Moments 198
4.4.2.2 Modeling of Distributions 201
4.4.3 Reactor Modeling 203
4.4.3.1 Batch Polymerization 204
Contents IX
4.4.3.2 Continuous Polymerization 204
4.4.3.3 Complex Flowsheets 205
4.4.3.4 Computational Fluid Dynamics (CFD) 205
4.4.3.5 Model-based Control 206
4.5 Summary 206
Notation 206
References 209
5 Free-radical Polymerization: Suspension 213
B. W. Brooks
5.1 Key Features of Suspension Polymerization 213
5.1.1 Basic Ideas 213
5.1.2 Essential Process Components 214
5.1.3 Polymerization Kinetics 214
5.1.4 FluidFluid Dispersions and Reactor Type 215
5.1.5 Uses of Products from Suspension Polymerization 216
5.2 Stability and Size Control of Drops 216
5.2.1 Stabilizer Types 217
5.2.2 Drop Breakage Mechanisms 218
5.2.3 Drop Coalescence 222
5.2.4 Drop Size Distributions 223
5.2.5 Drop Mixing 224
5.3 Events at High Monomer Conversion 228
5.3.1 Breakage of Highly Viscous Drops 229
5.3.2 Polymerization Kinetics in Viscous Drops 229
5.3.3 Consequences of Polymer Precipitation Inside Drops 230
5.4 Reaction Engineering for Suspension Polymerization 234
5.4.1 Dispersion Maintenance and Reactor Choice 234
5.4.2 Agitation and Heat Transfer in Suspensions 235
5.4.3 Scaleup Limitations with Suspension Polymerization 237
5.4.4 Reactor Safety with Suspension Processes 238
5.4.5 Component Addition during Polymerization 238
5.5 Inverse Suspension Polymerization 239
5.5.1 Initiator Types 239
5.5.2 Drop Mixing with Redox Initiators 240
5.6 Future Developments 240
5.6.1 Developing Startup Procedures for Batch and Semi-batch Reactors 240
5.6.2 Maintaining Turbulence Uniformity in Batch Reactors 242
5.6.3 Developing Viable Continuous-ow Processes 242
5.6.4 Quantitative Allowance for the Eects of Changes in the Properties of
the Continuous Phase 242
5.6.5 Further Study of the Role of Secondary Suspending Agents 243
5.6.6 Further Characterization of Stabilizers from Inorganic Powders 243
Notation 243
References 244
X Contents
6 Emulsion Polymerization 249
Jose C. de la Cal, Jose R. Leiza, Jose M. Asua, Alessandro Butte`, Guiseppe Storti,
and Massimo Morbidelli
6.1 Introduction 249
6.2 Features of Emulsion Polymerization 250
6.2.1 Description of the Process 250
6.2.2 Radical Compartmentalization 254
6.2.3 Advantages of Emulsion Polymerization 254
6.3 Alternative Polymerization Techniques 256
6.4 Kinetics of Emulsion Polymerization 258
6.4.1 Monomer Partitioning 259
6.4.2 Average Number of Radicals per Particle 260
6.4.3 Number of Polymer Particles 264
6.4.3.1 Heterogeneous Nucleation 264
6.4.3.2 Homogeneous Nucleation 266
6.4.3.3 Simultaneous Heterogeneous and Homogeneous Nucleation 267
6.4.3.4 Coagulative Nucleation 267
6.5 Molecular Weights 267
6.5.1 Linear Polymers 268
6.5.1.1 ZeroOne System (SmithEwart Cases 1 and 2) 268
6.5.1.2 Pseudo Bulk System (SmithEwart Case 3) 270
6.5.2 Nonlinear Polymers: Branching, Crosslinking, and Gel Formation
272
6.6 Particle Morphology 273
6.7 Living Polymerization in Emulsion 275
6.7.1 Chemistry of LRP 275
6.7.1.1 Nitroxide-mediated Polymerization (NMP) 277
6.7.1.2 Atom-transfer Radical Polymerization (ATRP) 277
6.7.1.3 Degenerative Transfer (DT) 278
6.7.1.4 Reversible AdditionFragmentation Transfer (RAFT) Polymerization
279
6.7.2 Polymerization of LRP in Homogeneous Systems 280
6.7.3 Kinetics of LRP in Heterogeneous Systems 282
6.7.4 Application of LRP in Heterogeneous Systems 284
6.7.4.1 Ab-initio Emulsion Polymerization 284
6.7.4.2 Miniemulsion Polymerization 285
6.8 Emulsion Polymerization Reactors 286
6.8.1 Reactor Types and Processes 286
6.8.1.1 Stirred-tank Reactors 286
6.8.1.2 Tubular Reactors 287
6.8.2 Reactor Equipment 288
6.8.2.1 Mixing 289
6.8.2.2 Heat Transfer 290
6.9 Reaction Engineering 290
6.9.1 Mass Balances 291
Contents XI
6.9.2 Heat Balance 292
6.9.3 Polymer Particle Population Balance (Particle Size Distribution)
294
6.9.4 Scaleup 295
6.10 On-line Monitoring in Emulsion Polymerization Reactors 296
6.10.1 On-line Sensor Selection 297
6.10.1.1 Latex Gas Chromatography 298
6.10.1.2 Head-space Gas Chromatography 298
6.10.1.3 Densimetry 298
6.10.1.4 Ultrasound 299
6.10.1.5 Spectroscopic Techniques 299
6.10.1.6 Reaction Calorimetry 302
6.11 Control of Emulsion Polymerization Reactors 305
Notation 312
References 317
7 Ionic Polymerization 323
Klaus-Dieter Hungenberg
7.2 Anionic Polymerization 325
7.2.1 Anionic Polymerization of Hydrocarbon Monomers Living
Polymerization 326
7.2.1.1 Association Behavior/Kinetics 326
7.2.1.2 Molecular Weight Distribution of Living Polymers 331
7.2.1.3 Side Reactions 336
7.2.1.4 Copolymerization 338
7.2.1.5 Tailor-made Polymers by Living Polymerization Optimization 341
7.2.1.6 Industrial Aspects Production of Living Polymers 343
7.2.2 Anionic Polymerization of Vinyl Monomers Containing Heteroatoms
344
7.2.3 Anionic Polymerization of Monomers Containing Hetero Double Bonds
346
7.2.4 Anionic Polymerization via Ring Opening 346
7.3 Cationic Polymerization 351
7.3.1 Cationic Polymerization of Vinyl Monomers 351
7.3.2 Cationic Ring-opening Polymerization 353
7.4 Conclusion 356
Notation 357
References 359
8 Coordination Polymerization 365
Joao B. P. Soares and Leonardo C. Simon
8.1 Polyolen Properties and Applications 365
8.1.1 Introduction 365
8.1.2 Types of Polyolens and Their Properties 366
XII Contents
8.1.3 The Importance of Proper Microstructural Determination and Control
in Polyolens 369
8.2 Catalysts for Olen Polymerization 372
8.2.1 ZieglerNatta, Phillips, and Vanadium Catalysts 378
8.2.2 Metallocene Catalysts 379
8.2.3 Late Transition Metal Catalysts 381
8.3 Polymerization Kinetics and Mechanism with Coordination Catalysts
383
8.3.1 Comparison between Coordination and Free-radical Polymerization
383
8.3.2 Polymerization Kinetics with Single-site Catalysts 383
8.3.2.1 Homopolymerization 383
8.3.2.2 Copolymerization 388
8.3.3 Polymerization Kinetics with Multiple-site Catalysts 392
8.3.4 Long-chain Branch Formation 395
8.4 Single Particle Models Mass- and Heat-transfer Resistances 399
8.5 Macroscopic Reactor Modeling Population Balances and the Method
of Moments 408
8.5.1 Homopolymerization 408
8.5.2 Copolymerization 413
8.6 Types of Industrial Reactors 416
8.6.1 Gas-phase Reactors 420
8.6.2 Slurry Reactors 422
8.6.3 Solution Reactors 423
8.6.4 Multizone Reactors 425
Notation 425
References 428
9 Mathematical Methods 431
P. D. Iedema and N. H. Kolhapure
9.2 Discrete Galerkin hp Finite Element Method 432
9.3 Method of Moments 435
9.3.2 Linear Polymerization 435
9.3.3 Nonlinear Polymerization 438
9.4 Comparison of Galerkin-FEM and Method of Moments 440
9.5 Classes Approach 444
9.5.2 Computing the CLD of Poly(vinyl acetate) for a Maximum of One TDB
per Chain 444
9.5.3 Multiradicals in Radical Polymerization 446
9.6 Pseudo-distribution Approach 449
9.6.2 CLD/DBD for Mixed-metallocene Polymerization of Ethylene 451
Contents XIII
9.6.2.1 Formulation of Pseudo-distribution Problem 451
9.6.2.2 Construction of the Full 2D Distribution 456
9.6.3 CLD/Number of Terminal Double Bonds (TDB) Distribution for
Poly(vinyl acetate) More than one TDB per Chain 458
9.6.3.1 General Case 458
9.6.3.2 TDB Pseudo-distribution Approach for a Maximum of one TDB per
Chain 466
9.6.3.3 TDB Pseudo-distribution Approach for More than one TDB per Chain
467
9.6.4 Radical Polymerization of Ethylene to Low-density Polyethylene (LDPE)
469
9.6.5 Radical Copolymerization 473
9.6.5.2 Balance Equations 474
9.7 Probability Generating Functions 480
9.7.2 Probability Generating Functions in a Transformation Method 480
9.7.3 Probability Generating Functions and Cascade Theory 481
9.8 Monte Carlo Simulations 485
9.8.2 Weight-fraction Sampling of Primary Polymers: Batch Reactor,
Transfer to Polymer 486
9.8.3 Example 490
9.8.4 CSTR with Transfer to Polymer 491
9.8.5 Comparison of Galerkin-FEM Classes Model and CSTR with Transfer
to Polymer 492
9.8.6 Batch Reactor, Terminal Double Bond Incorporation 493
9.8.7 CSTR, Terminal Double Bond Incorporation 497
9.8.8 Incorporation of Recombination Termination 498
9.8.9 Incorporation of Random Scission, Linear Chains, Batch Reactor 498
9.8.10 Combined Scission/Branching 501
9.8.11 Scission in a CSTR 501
9.9 Prediction of Branched Architectures by Conditional Monte Carlo
Sampling 502
9.9.2 Branched Architectures from Radical Polymerization in a CSTR 503
9.9.3 Branched Architectures from Polymerization of Olens with Single
and Mixed Branch-forming Metallocene Catalysts in a CSTR 505
9.9.3.2 Single-catalyst System 505
9.9.3.3 Synthesis of Topology 505
9.9.3.4 Mixed-catalyst System 508
9.9.4 Mathematical Methods for Characterization of Branched Architectures
510
9.9.4.1 Graph Theoretical Connectivity Matrices 510
XIV Contents
9.9.4.2 Characterization of Architectures by Radius of Gyration 511
9.9.4.3 Characterization of Architectures by Seniorities and Priorities 512
9.10 Computational Fluid Dynamics for Polymerization Reactors 517
9.10.1.1 Modeling Challenges 517
9.10.2 Development and Optimization of Modern Polymerization Reactors
518
9.10.2.1 Benets of CFD 519
9.10.2.2 Limitations of CFD 519
9.10.3 Integration of CFD with Polymerization Kinetics 520
9.10.3.1 Classication and Complexity of CFD Models 521
9.10.3.2 Treatment of Polymerization Kinetics 522
9.10.3.3 Illustration of Homogeneous Reactor Model Formulation 522
9.10.4 Target Applications 523
9.10.4.1 Illustrative Case Studies 523
9.10.5 Concluding Remarks 528
Acknowledgments 530
References 530
10 Scaleup of Polymerization Processes 533
E. Bruce Nauman
10.1 Historic and Economic Perspective 533
10.2 The Limits of Scale 533
10.3 Scaleup Goals 534
10.4 General Approaches 535
10.5 Scaleup Factors 537
10.6 Stirred-tank Reactors 537
10.7 Design Considerations for Stirred Tanks 541
10.8 Multiphase Stirred Tanks 542
10.9 Stirred Tanks in Series 542
10.10 Tubular Reactors 543
10.11 Static Mixers 545
10.12 Design Considerations for Tubular Reactors 546
10.13 Extruder and Extruder-like Reactors 549
10.14 Casting Systems 549
10.15 Concluding Remarks 550
Notation 550
References 551
Volume 2
11 Safety of Polymerization Processes 553
Francis Stoessel
11.2 Principles of Chemical Reactor Safety Applied to Polymerization 554
11.2.1 Cooling Failure Scenario 554
Contents XV
11.2.2 Criticality Classes Applied to Polymerization Reactors 557
11.2.2.1 Description of the Criticality Classes 558
11.2.3 Heat Balance of Reactors 559
11.2.3.1 Heat Production 559
11.2.3.2 Heat Exchange 560
11.2.3.3 Heat Accumulation 561
11.2.3.4 Convective Heat Transport due to Feed 561
11.2.3.5 Stirrer 561
11.2.3.6 Heat Losses 562
11.2.3.7 Simplied Expression of the Heat Balance 562
11.2.4 Dynamic Control of Reactors 562
11.2.5 Thermal Stability of Polymerization Reaction Masses 563
11.3 Specic Safety Aspects of Polymerization Reactions 564
11.3.1 Kinetic Aspects 564
11.3.2 Thermochemical Aspects 565
11.3.3 Factors Leading to Changing Heat Release Rates 568
11.4 Cooling of Polymerization Reactors 570
11.4.1 Indirect Cooling: Heat Exchange Across the Reactor Wall 570
11.4.2 Hot Cooling: Cooling by Evaporation 574
11.4.3 Importance of the Viscosity 578
11.5 Chemical Engineering for the Safety of Polymerization Processes
579
11.5.1 Batch Processes 579
11.5.2 Semi-batch Processes 580
11.5.2.1 Initiation 581
11.5.2.2 Feed 582
11.5.2.3 Final Stage 583
11.5.2.4 Practical Aspects 583
11.5.3 Continuous Processes 584
11.5.3.1 Concentration Stability 584
11.5.3.2 Particle Number Stability 584
11.5.4 Design Measures for Safety 585
11.5.4.1 Process Design 586
11.5.4.2 Reactor Design 586
11.5.4.3 Control of Feed 587
11.5.4.4 Emergency Cooling 587
11.5.4.5 Inhibition 588
11.5.4.6 Quenching 588
11.5.4.7 Dumping 588
11.5.4.8 Controlled Depressurization 588
11.5.4.9 Pressure Relief 588
11.5.4.10 Time Factor 589
11.6 Conclusion 589
References 590
Notation 591
XVI Contents
12 Measurement and Control of Polymerization Reactors 595
John R. Richards and John P. Congalidis
12.1.1 Denitions 595
12.1.2 Measurement Error 597
12.2 Measurement Techniques 598
12.2.1 Temperature 599
12.2.1.1 Resistance Thermometers 599
12.2.1.2 Thermocouples 600
12.2.1.3 Expansion Thermometers 601
12.2.1.4 Radiation Pyrometers 601
12.2.2 Pressure Measurement 602
12.2.3 Weight 604
12.2.4 Liquid Level 605
12.2.5 Flow 608
12.2.6 Densitometry, Dilatometery, and Gravimetry 617
12.2.7 Viscosity 619
12.2.8 Composition 620
12.2.9 Surface Tension 622
12.2.10 Molecular Weight Distribution (MWD) 622
12.2.11 Particle Size Distribution (PSD) 623
12.3 Sensor Signal Processing 625
12.3.1 Sensors and Transmitters 625
12.3.2 Converters 626
12.3.3 Indicators 626
12.3.4 Filtering Techniques 627
12.4 Regulatory Control Engineering 627
12.4.1 General 627
12.4.2 Process Dynamics 630
12.4.2.1 First-order System 631
12.4.2.2 Second-order System 632
12.4.2.3 High-order and Dead Time Systems 636
12.4.2.4 First-order Plus Dead Time System 636
12.4.2.5 Integrating System 638
12.4.2.6 Integrator plus Dead Time System 639
12.4.3 Controllers 639
12.4.3.1 Proportional Control 640
12.4.3.2 Integral Control 641
12.4.3.3 Derivative Control 641
12.4.3.4 PI, PD, and PID Control 642
12.4.3.5 Digital Controllers 642
12.4.3.6 Controller Tuning 644
12.4.3.7 OnO Controllers 646
12.4.3.8 Self-operated Regulators 647
12.4.4 Valve Position Controllers 650
Contents XVII
12.4.5 Single-loop Controllers 650
12.4.6 Digital Control Systems 650
12.4.7 Actuators 652
12.5 Advanced Control Engineering 656
12.5.1 Feedforward Control 659
12.5.1.1 Steady-state Model Feedforward Control 660
12.5.1.2 Ratio Control 660
12.5.2 Cascade Control 661
12.5.3 FeedforwardFeedback Control 663
12.5.4 State Estimation Techniques 666
12.5.5 Model Predictive Control 668
12.5.6 Batch and Semi-batch Control 669
12.5.6.1 Operation and Variability 669
12.5.6.2 Statistical Process Control 671
12.5.7 Future Trends 671
Notation 672
References 675
13 Polymer Properties through Structure 679
Uday Shankar Agarwal
13.1 Thermal Properties of Polymers 679
13.1.1 Crystalline and Amorphous Polymers 680
13.1.2 Inuence of Polymer Structure on Crystallizability of Polymers 682
13.1.3 The Glass Transition Temperature 683
13.1.4 Inuence of Polymer Structure on T
g
of Polymers 684
13.1.5 The Crystallization Temperature and the Melting Point 686
13.1.6 Tuning Polymer Crystallization for Properties 686
13.1.7 Morphology of Crystalline Polymers 688
13.1.8 Tailoring Polymer Properties through Modication, Additives, and
Reinforcement 690
13.1.8.1 New Morphologies through Block Copolymers 691
13.1.8.2 Polymeric Nanocomposites 692
13.2 Polymer Conformation and Related Properties 692
13.2.1 The Chain Conformation 692
13.2.2 Solubility of Polymers 694
13.2.3 Dilute Solution Zero-shear Viscosity 695
13.2.3.1 Polymers as Dumbbells 696
13.2.3.2 Polymers as Chains of Beads and Springs 697
13.2.4 Viscosity of Concentrated Solutions and Melts 698
13.2.5 Nonlinear Polymers 699
13.2.6 Rigid Rod-like Polymers 701
13.3 Polymer Rheology 702
13.3.1 The Viscous Response: Shear Thinning 702
13.3.2 Normal Stresses during Shear Flow 703
13.3.3 Extensional Thickening 705
XVIII Contents
13.3.4 The Elastic Response 706
13.3.4.1 Ideal Elastic Response 706
13.3.4.2 Rubberlike Elasticity 706
13.3.5 The Viscoelastic Response 707
13.3.5.1 Linear Viscoelasticity in Dynamic Oscillatory Flow 709
13.3.6 Inuence of Polymer Branching Architecture in Bulk Polymers 711
13.3.7 Polymers as Rheology Modiers 712
13.3.8 Rheological Control with Block Copolymers 714
13.3.9 Polymer-like Structures through Noncovalent Associations 715
13.4 Summary 715
Notation 716
References 718
14 Polymer Mechanical Properties 721
Christopher J. G. Plummer
14.1.1 Long-chain Molecules 721
14.1.2 Simple Statistical Descriptions of Long-chain Molecules 722
14.2 Elasticity 724
14.2.1 Deformation of an Elastic Solid 724
14.2.2 Thermodynamics of Rubber Elasticity 725
14.2.3 Statistical Mechanical Approach to Rubber Elasticity 727
14.3 Viscoelasticity 729
14.3.1 Linear Viscoelasticity 729
14.3.2 TimeTemperature Superposition 734
14.3.3 Molecular Models for Polymer Dynamics 736
14.3.4 Nonlinear Viscoelasticity 740
14.4 Yield and Fracture 741
14.4.1 Yield in Polymers 741
14.4.2 Models for Yield 744
14.4.3 Semicrystalline Polymers 746
14.4.4 Crazing and Fracture 748
14.5 Conclusion 752
References 755
15 Polymer Degradation and Stabilization 757
Tuan Quoc Nguyen
15.2 General Features of Polymer Degradation 759
15.2.1 Degradative Reactions 759
15.2.1.2 Propagation 760
15.2.1.3 Chain Branching 761
15.2.1.4 Termination 762
15.2.2 Some Nonradical Degradation Mechanisms 763
Contents XIX
15.2.3 Physical Factors 763
15.2.3.1 Glass Transition Temperature 764
15.2.3.2 Polymer Morphology 766
15.3 Degradation Detection Methods 767
15.3.1 Mechanical Tests 768
15.3.2 Gel Permeation Chromatography 771
15.3.3 Fourier Transform Infrared Spectroscopy 773
15.3.4 Magnetic Resonance Spectroscopy 775
15.3.4.1 Nuclear Magnetic Resonance (NMR) 775
15.3.4.2 Electron Spin Resonance (ESR) 776
15.3.5 Oxygen Uptake 776
15.3.6 Chemiluminescence 778
15.4 Thermal Degradation 778
15.4.1 Thermal Stability 779
15.4.2 Polymer Structure and Thermal Stability 779
15.4.3 Computer Simulation 780
15.4.4 Thermal Oxidative Degradation of Polypropylene 782
15.4.4.2 Propagation 784
15.4.4.3 Chain Branching 785
15.4.4.4 Termination 786
15.4.4.5 Secondary Reactions 786
15.4.4.6 Formation of Volatile Compounds 788
15.4.5 Homogeneous versus Heterogeneous Kinetics 789
15.4.6 Applications of Thermal Degradation 790
15.4.6.1 Analytical Pyrolysis 790
15.4.6.2 Introduction of New Chemical Functionalities 791
15.4.6.3 Chemical Modication of Polymer Structure 791
15.4.6.4 Metal Injection Molding (MIM) 792
15.4.6.5 Recycling 792
15.5 Photodegradation 793
15.5.1 Absorption of UV Radiation by Polymers 793
15.5.2 The Solar Spectrum 796
15.5.3 Photo-oxidation Prole 796
15.5.4 Inuence of Wavelength: the Activation and Action Spectrum 799
15.5.5 Photodegradation Mechanisms 802
15.5.5.1 Photoinitiation 802
15.5.5.2 The Norrish Photoprocesses 803
15.5.5.3 Photo-Fries Rearrangement 803
15.6 Radiolytic Degradation 805
15.6.1 Interaction of High-energy Radiation with Matter 805
15.6.2 Radiation Chemistry 807
15.6.3 Radiolysis Stabilization 810
15.6.4 Applications 811
15.6.4.1 Radiation Sterilization 812
XX Contents
15.6.4.2 Controlled Degradation and Crosslinking 812
15.7 Mechanochemical Degradation 813
15.7.1 Initiation by Mechanical Stresses 813
15.7.1.1 Eect of Tensile Stress on Chemical Reactivity 813
15.7.1.2 Breaking Strength of a Covalent Bond 814
15.7.1.3 Rate of Stress-activated Chain Scission 815
15.7.2 Extrusion Degradation 816
15.7.3 Applications 817
15.8 Control and Prevention of Aging of Plastic Materials 818
15.8.1 Antioxidants 818
15.8.1.1 Radical Antioxidants 818
15.8.1.2 Hindered Amine Stabilizers (HAS) 819
15.8.1.3 Peroxide Decomposers 821
15.8.2 Photostabilizers 822
15.8.3 PVC Heat Stabilizers 823
15.8.4 Other Classes of Stabilizers 824
15.8.4.1 Metal Deactivators 824
15.8.4.2 Antiozonants 824
15.9 Lifetime Prediction 824
15.10 Conclusions 826
Notation 827
References 830
16 Thermosets 833
Rolf A. T. M. van Benthem, Lars J. Evers, Jo Mattheij, Ad Hoand, Leendert J.
Molhoek, Ad J. de Koning, Johan F. G. A. Jansen, and Martin van Duin
16.1.1 Thermoset Materials 833
16.1.2 Networks 834
16.1.3 Advantages 835
16.1.4 Curing Resins 835
16.1.5 Functionality 835
16.1.6 Formulation 836
16.1.7 Production 837
16.1.8 General Areas of Application 837
16.2 Phenolic Resins 838
16.2.2 Chemistry 838
16.2.2.1 Resols 840
16.2.2.2 Novolacs 840
16.2.2.3 Epoxy-novolacs 841
16.2.2.4 Discoloration 841
16.2.4 Properties and Applications 842
16.3 Amino Resins 843
Contents XXI
16.3.2.1 Polymerization Chemistry 845
16.4 Epoxy Resins 849
16.4.2.1 Cure 851
16.4.3.1 Standard Liquid 853
16.4.3.2 Tay Process 854
16.4.3.3 Advancement Process 854
16.5 Alkyd Resins 855
16.5.2.1 The Alkyd Constant 858
16.5.2.2 Autoxidative Drying 858
16.5.4.1 Short Oil Alkyds 861
16.5.4.2 Long Oil Alkyds 861
16.5.4.3 Medium Oil Alkyds 861
16.5.5 Alkyd Emulsions 861
16.5.5.1 The Inversion Process 862
16.6 Saturated Polyester Resins 862
16.6.3.1 Monitoring the Reaction 865
16.6.5 Powder Coatings 866
16.6.5.1 Application 867
16.6.5.2 Crosslinking 868
16.6.5.3 Advantages 869
16.7 Unsaturated Polyester Resins and Composites 869
16.7.2.1 Crosslinking 871
16.7.2.2 Styrene Emission 871
16.7.2.3 Vinyl Ester Resins 873
16.7.4 Reinforcement 875
16.7.5 Fillers 878
XXII Contents
16.7.6 Processing 879
16.7.6.1 Hand Lay-up and Spray-up 882
16.7.6.2 Continuous Lamination 882
16.7.6.3 Filament Winding 882
16.7.6.4 Centrifugal Casting 882
16.7.6.5 Pultrusion 883
16.7.6.6 Cold-press Molding 883
16.7.6.7 Resin Infusion 883
16.7.6.8 Resin-transfer Molding 883
16.7.6.9 Hot-press Molding 883
16.7.6.10 Casting, Encapsulation, and Coating (Non-reinforced Applications)
886
16.7.7 Design Considerations: Mechanical Properties of Composites 886
16.8 Acrylate Resins and UV Curing 889
16.8.3.1 Epoxy Acrylates 891
16.8.3.2 Polyester Acrylates 891
16.8.3.3 Urethane Acrylates 892
16.8.3.4 Inside-out 893
16.8.3.5 Outside-in 894
16.8.3.6 Comparing Inside-out with Outside-in 894
16.8.3.7 Stabilization 894
16.8.3.8 Dilution 895
16.8.3.9 Safety 895
16.8.4 Properties 895
16.8.5 Introduction to UV Curing 896
16.8.5.1 General Introduction to UV-initiated Radical Polymerization 896
16.8.5.2 Photoinitiators for Radical Polymerization 897
16.8.5.3 Resin 897
16.8.5.4 Reactive Diluent 898
16.8.5.5 Curing Process 899
16.8.5.6 Cationic Curing 900
16.8.5.7 Base-mediated Curing 901
16.9 Rubber 901
16.9.1.1 Types of Rubber 902
16.9.2 Polymerization 903
16.9.3 Crosslinking 904
16.9.3.1 Sulfur Vulcanization 904
16.9.3.2 Peroxide Curing 905
16.9.3.3 Processing 906
16.9.4.1 Advantages and Disadvantages 907
Contents XXIII
16.9.4.2 Thermoplastic Vulcanizates 907
Notation 908
References 909
17 Fibers 911
J. A. Juijn
17.1.1 A Fiber World 911
17.1.2 Scope of this Chapter 912
17.2 Fiber Terminology 912
17.2.1 Denitions: Fibers, Filaments, Spinning 912
17.2.2 Synthetic Yarns 914
17.2.3 Titer: Tex and Denier 914
17.2.4 Tenacity and Modulus: g denier
C1
, N tex
C1
, or GPa 915
17.2.5 Yarn Appearance 916
17.2.6 Textile, Carpet, and Industrial Yarns 917
17.2.7 Physical Structure 918
17.3 Fiber Polymers: Choice of Spinning Process 920
17.3.1 Polymer Requirements 920
17.3.2 Selection of Spinning Process 920
17.3.3 Spinnability 922
17.4 Melt Spinning 923
17.4.1 Extrusion 923
17.4.2 Polymer Lines and Spin-box 924
17.4.3 Spinning Pumps 925
17.4.4 Spinning Assembly 926
17.4.4.1 Filtration 926
17.4.4.2 Spinning Plate 926
17.4.5 Quenching 928
17.4.6 Finish 929
17.4.7 Spinning Speed 931
17.4.8 Winding 931
17.4.9 Drawing 931
17.4.10 Relaxation and Stabilization 934
17.4.11 Process Integration 934
17.4.12 Rheology 934
17.4.12.1 Shear Viscosity 934
17.4.12.2 Elasticity 936
17.4.12.3 Elongational Viscosity 936
17.4.13 Process Calculations 936
17.4.13.1 Mass Flow 937
17.4.13.2 Volume Flow 937
17.4.13.3 Extrusion Speed and Elongation in the Spin-line 937
17.4.13.4 Pressure Drop over the Spinning Holes 938
XXIV Contents
17.4.14 Polyester (Poly(ethylene terephthalate), PET) 938
17.4.14.1 PET Polymer 938
17.4.14.2 Spinning of PET 939
17.4.14.3 PET Staple Fiber 939
17.4.14.4 PET Textile Filament Yarns 940
17.4.14.5 PET Industrial Yarns 940
17.4.15 Polyamide (PA6 and PA66) 941
17.4.15.1 PA Polymer 941
17.4.15.2 PA Spinning 941
17.4.15.3 PA Staple Fiber 942
17.4.15.4 PA Textile Filament Yarns 942
17.4.15.5 PA Industrial Yarns 942
17.4.16 Polypropylene (PP) 943
17.4.16.1 PP Polymer 943
17.4.16.2 PP Spinning 943
17.4.16.3 PP Staple Fiber 943
17.4.16.4 PP Split Fiber 943
17.4.16.5 PP Filament Yarns 944
17.5 Solution Spinning 944
17.5.1 Preparation of Spinning Dope 944
17.5.2 Dry Spinning 944
17.5.2.1 Cellulose Acetate 945
17.5.2.2 Acrylics 946
17.5.2.3 Poly(vinyl alcohol) 946
17.5.3 Wet Spinning 946
17.5.3.1 Viscose Rayon 948
17.5.3.2 Acrylics 951
17.5.3.3 Poly(vinyl alcohol) 952
17.6 Comparison of Melt and Solution Spinning 953
17.7 High-modulus, High-strength Fibers 956
17.7.1 Air-gap Spinning 956
17.7.1.1 Aramids 956
17.7.1.2 Other Liquid-crystalline Polymers 960
17.7.2 Gel Spinning 961
17.7.2.1 Theory 961
17.7.2.2 Gel Spinning of Polyethylene 962
17.7.2.3 Other Gel-spun or Superdrawn Fibers 964
17.7.3 Carbon Fiber 965
17.7.3.1 Carbon Fiber from PAN 965
17.7.3.2 Carbon Fiber from Pitch 966
17.7.3.3 Applications of Carbon Fibers 966
17.7.4 Other Advanced Fibers 966
Notation 967
Acknowledgments 969
References 969
Contents XXV
18 Removal of Monomers and VOCs from Polymers 971
Mar a J. Barandiaran and Jose M. Asua
18.2 Polymer Melts and Solutions 972
18.2.1 Devolatilization 973
18.2.1.1 Fundamentals 973
18.2.1.2 Implementation of Devolatilization 975
18.2.1.3 Equipment 975
18.3 Polyolens 979
18.4 Waterborne Dispersions 979
18.4.1 Post-polymerization 980
18.4.1.1 Modeling Post-polymerization 981
18.4.2 Devolatilization 981
18.4.2.1 Modeling 982
18.4.2.2 Rate-limiting Steps 985
18.4.2.3 Devolatilization under Equilibrium Conditions 986
18.4.2.4 Equipment 986
18.4.3 Combined Processes 988
18.4.4 Alternative Processes 989
18.5 Summary 989
Notation 990
References 991
19 Nano- and Microstructuring of Polymers 995
Christiane de Witz, Carlos Sanchez, Cees Bastiaansen, and Dirk J. Broer
19.1.1 Patterning Techniques 996
19.1.2 Photoembossing 998
19.2 Materials and their Photoresponsive Behavior 999
19.3 Single-exposure Photoembossing 1001
19.4 Dual-exposure Photoembossing 1007
19.5 Complex Surface Structures from Interfering UV Laser Beams 1007
19.6 Surface Structure Development under Fluids 1010
19.7 Conclusion 1012
Acknowledgments 1012
Notation 1013
References 1013
20 Chemical Analysis for Polymer Engineers 1015
Peter Schoenmakers and Petra Aarnoutse
20.2 Process Analysis 1017
20.2.1 Near-infrared Spectroscopy 1017
20.2.2 In-situ Raman Spectroscopy 1018
20.2.3 At-line Conversion Measurements 1020
XXVI Contents
20.3 Polymer Analysis 1022
20.3.1 Basic Laboratory Measurements 1022
20.3.1.1 Conversion 1022
20.3.2 Detailed Molecular Analysis 1023
20.3.2.1 FTIR Spectroscopy 1023
20.3.2.2 NMR Spectroscopy 1024
20.3.2.3 Mass Spectrometry 1025
20.3.3 Polymer Distributions 1030
20.3.3.1 Molecular Weight Distributions 1030
20.3.3.2 Functionality-type Distributions 1034
20.3.3.3 Chemical Composition Distributions (CCDs) 1037
20.3.3.4 Degree of Branching Distributions 1040
20.3.3.5 Complex Polymers (Multiple Distributions) 1041
Notation 1044
References 1045
21 Recent Developments in Polymer Processes 1047
Maartje Kemmere
21.2 Polymer Processes in Supercritical Carbon Dioxide 1048
21.2.1 Interactions of Carbon Dioxide with Polymers and Monomers 1050
21.2.1.1 Solubility in Carbon Dioxide 1051
21.2.1.2 Sorption and Swelling of Polymers 1052
21.2.1.3 Phase Behavior of MonomerPolymerCarbon Dioxide Systems 1054
21.2.2 Polymerization Processes in Supercritical Carbon Dioxide 1055
21.2.3 Polymer Processing in Supercritical Carbon Dioxide 1058
21.2.3.1 Extraction 1060
21.2.3.2 Impregnation and Dyeing 1061
21.3 Ultrasound-induced Radical Polymerization 1062
21.3.1 Ultrasound and Cavitation in Liquids 1063
21.3.2 Radical Formation by Cavitation 1065
21.3.3 Cavitation-induced Polymerization 1067
21.3.3.1 Bulk Polymerization 1067
21.3.3.2 Precipitation Polymerization 1069
21.3.3.3 Emulsion Polymerization 1070
21.3.4 Cavitation-induced Polymer Scission 1072
21.3.5 Synthesis of Block Copolymers 1073
21.4 Concluding Remarks and Outlook for the Future 1074
Acknowledgments 1076
Notation 1076
References 1077
Index 1083
Contents XXVII
Preface
Freshly started as chairman and secretary of the Working Party on Polymer Reac-
tion Engineering it never crossed our mind to edit a book on this subject. This
changed when Wiley-VCH asked if the working party would be able to provide a
translation of the Handbuch der Technischen Polymerchemie, written in 1993 by
Adolf Echte. We decided to do so, but not exactly. Very rapidly we were convinced
that we needed a completely new book, covering the eld of polymer reaction engi-
neering in a modern, broad and multidisciplinary approach. Many of the working
party members directly agreed to participate, others needed somewhat stronger
persuasion techniques, and for some chapters we hired authors from other in-
stitutions. In June 2003 we had completed the list of contributors, coming from
Europe, Canada and the USA. Now, roughly one year later, the new handbook is
there.
The quality an edited book like this very much depends on the quality of the in-
dividual contributions. It has been a great pleasure for us to see that all authors
have taken their writing jobs very seriously. With these contributions, we are sure
that this book represents the state of the art in polymer reaction engineering. It
is intended to attract equally readers that are new in the eld as well as readers
that may be considered expert in some of the topics but want to broaden their
knowledge. We are convinced that the multidisciplinary and synergetic approach
presented in this book may act as an eye-opener for research and development ac-
tivities going on in strongly related areas. We hope the reader will take advantage
of this approach, where the references given in the various chapters may be a start-
ing point for further reading.
Reading books, you often read the preface as well. We have seen numerous ex-
amples from which the frustration is quite obvious. Of course things may not al-
ways work out the way you plan, that has also been the case for this book. Maybe
we were just lucky, but we have greatly enjoyed doing this. Editing this book has
also been a starting point for the editors to become friends, including Swiss cheese
fondue and Dutch Friese nagelkaastaart in a friendly home setting. From that
perspective also Francine and Maartje have had their part both of the workload
but also of the fun of all this.
Finally, we would like to thank Karin Sora and Renate Doetzer from Wiley-VCH
XXIX
for their help with the editing process. They really know to nd the balance be-
tween waiting and pushing in order not to diverge too far from the schedule.
Lausanne & Eindhoven, fall 2004
Thierry Meyer & Jos Keurentjes
XXX Preface
List of Contributors
P. Aarnoutse
Polymer-Analysis Group
Department of Chemical Engineering
(ITS)
Faculty of Science, University of
Amsterdam
Nieuwe Achtergracht 166
1018 WV Amsterdam
The Netherlands
Dr. U. S. Agarwal
Polymer Technology Group
and Chemistry
P.O. Box 513
5600 MB Eindhoven
The Netherlands
Prof. J. M. Asua
The University of the Basque Country
Institute for Polymer Materials
(POLYMAT)
Paseo Manuel Lardizabal 3
20018 Donostia-San Sebastian
Spain
Dr. R. Bachmann
Bayer AG
ZT-TE-SVT
51368 Leverkusen
Germany
Prof. M. J. Barandiaran
(POLYMAT)
Manuel Lardizabal, 3
Spain
Dr. C. W. M. Bastiaansen
Den Dolech 2
5600 MB Eindhoven
The Netherlands
Prof. D. J. Broer
Philips Research Laboratories
Prof. Holstlaan 4
5656 AA Eindhoven
The Netherlands
and
Den Dolech 2
5600 MB Eindhoven
The Netherlands
and
Dutch Polymer Institute (DPI)
P.O. Box 902
5600 AX Eindhoven
The Netherlands
XXXI
Polymer Technology
and Chemistry
P.O. Box 513
5600 MB Eindhoven
The Netherlands
Prof. B. W. Brooks
Loughborough University
Department of Chemical
Engineering
Loughborough
Leicestershire, LE11 3TU
United Kingdom
Dr. A. Butte`
Swiss Federal Institute of
Technology
Zurich, ETHZ
Institut fur Chemie- und
Bioingenieurwissenschaten
Gruppe Morbidelli
ETH Hoenggerberg/HCI F135
8093 Zurich
Switzerland
Dr. J. P. Congalidis
E.I. du Pont de Nemours and
Company
DuPont Central Research and
Development
Experimental Station
Wilmington, DE 19880
USA
Dr. M. R. P. F. N. Costa
Faculty of Engineering
University of Porto
Rua Roberto Frias, s/n
4200-465 Porto
Portugal
Prof. J. C. de la Cal
(POLYMAT)
Paseo Manuel Lardizabal, 3
Spain
Dr. A. J. de Koning
DSM Research
Oude Postbaan 1
6167 RG Geleen
The Netherlands
Dr. T. W. de Loos
Delft University of Technology
Faculty of Applied Sciences
Department Chemical Technology
Julianalaan 136
2628 BL Delft
The Netherlands
C. de Witz
Philips Research Laboratories
Prof. Holstlaan 4
5656 AA Eindhoven
The Netherlands
Dr. L. J. Evers
DSM Melamine
Oude Postbaan 1
6167 RG Geleen
The Netherlands
Dr. A. Hoand
DSM Coating Resins
Ceintuurbaan 5
8022 AW Zwolle
The Netherlands
Dr. K.-D. Hungenberg
BASF AG
Polymer Technology, B1
67056 Ludwigshafen
Germany
XXXII List of Contributors
Prof. R. A. Hutchinson
Queens University
Dupuis Hall, 19 Division St.
Kingston, Ontario K7M 2G9
Canada
Dr. P. D. Iedema
University of Amsterdam
1018 WV Amsterdam
The Netherlands
Dr. J. F. G. A. Jansen
DSM Research
Oude Postbaan 1
6167 RG Geleen
The Netherlands
Dr. J. A. Juijn
Research Institute
Department QRI
P.O. Box 9600
6800 TC Arnheim
The Netherlands
Dr. M. F. Kemmere
and Chemistry
P.O. Box 513
5600 MB Eindhoven
The Netherlands
Prof. J. T. F. Keurentjes
P.O. Box 513
5600 MB Eindhoven
The Netherlands
N. H. Kolhapure
DuPont Engineering Research and
Technology
1007 N. Market St.
Wilmington, DE 19898-0001
USA
Prof. J. R. Leiza
(POLYMAT)
Paseo Manuel Lardizabal 3
Spain
J. Mattheij
DSM Melamine
Oude Postbaan 1
6167 RG Geleen
The Netherlands
Dr. T. Meyer
Institute of Process Science
EPFL, ISP-GPM
1015 Lausanne
Switzerland
L. J. Molhoek
DSM Coating Resins
Ceintuurbaan 5
8022 AW Zwolle
The Netherlands
Prof. M. Morbidelli
Zurich, ETHZ
Bioingenieurwissenschaften
Gruppe Morbidelli
8093 Zurich
Switzerland
List of Contributors XXXIII
Prof. E. B. Nauman
The Isermann Department of Chemical
and Biological Engineering
Rensselaer Polytechnic Institute
Troy, NY 12180
USA
Dr. Q. T. Nguyen
Laboratory of Polymers (LP)
Ecole Polytechnique Federale
de Lausanne
1015 Lausanne
Switzerland
J. C. Plummer
Laboratory of Composite and Polymer
Technology (LTC)
Ecole Polytechnique Federale
de Lausanne
1015 Lausanne
Switzerland
Dr. J. R. Richards
E. I. du pont de Nemours and Company
DuPont Engineering and Research
Technology
Experimental Station
Wilmington, DE 19880
USA
Dr. C. Sanchez
Den Dolech 2
5600 MB Eindhoven
The Netherlands
and
Dutch Polymer Institute (DPI)
P.O. Box 902
5600 AX Eindhoven
The Netherlands
Prof. P. J. Schoenmakers
Polymer-Analysis Group
(ITS)
Faculty of Science, University of
Amsterdam
1018 WV Amsterdam
The Netherlands
Prof. L. C. Simon
University of Waterloo
200 University Avenue West
Waterloo, Ontario N2L 3G1
Canada
Prof. J. B. P. Soares
University of Waterloo
200 University Avenue West
Waterloo, Ontario N2L 3G1
Canada
Prof. F. Stoessel
Swiss Institute for the Promotion of
Safety and Security
Chemical Process Safety Consulting
Klybeckstrasse 141
WKL-32.322
4002 Basel
Switzerland
Prof. G. Storti
Zurich, ETHZ
Bioingenieurwissenschaften
Gruppe Morbidelli
8093 Zurich
Switzerland
XXXIV List of Contributors
Prof. R. A. T .M. van Benthem
Coating Technology
and Chemistry
P.O. Box 513
5600 MB Eindhoven
The Netherlands
Dr. M. van Duin
DSM Research
Oude Postbaan 1
6167 RG Geleen
The Netherlands
List of Contributors XXXV
1
Polymer Reaction Engineering, an Integrated
Approach
Th. Meyer and J. T. F. Keurentjes
1.1
Polymer Materials
Synthetic polymers can be denoted as the materials of the 20th century. Since
World War II the production volume of polymers has increased by a factor of 50
to a current value of more than 120 million tonnes annually (Figure 1.1). The con-
sumption per capita has also increased over the years to a worldwide average of ap-
proximately 20 kg per annum in the year 2000. In terms of volumetric output, the
production of polymers exceeds that of iron and steel. The enormous growth of
synthetic polymers is due tot the fact that they are lightweight materials, act as in-
sulators for electricity and heat, cover a wide range of properties from soft packag-
ing materials to bers stronger than steel, and allow for relatively easy processing.
ISBN: 3-527-31014-2
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1940 1950 1960 1970 1980 1990 2000
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6
to/an
World Population ,
10
9
people
Consumption,
kg/hab
2010
Fig. 1.1. Polymer production and the evolution of the population since 1940 [1].
1
Moreover, parts with complex shapes can be made at low cost and at high speed by
shaping polymers or monomers in the liquid state.
The polymer market can be divided into thermoplastics and thermosets. The ma-
jor thermoplastics include high-density polyethylene (HDPE), low-density polyeth-
ylene (LDPE), polyethylene terephthalate (PET), polypropylene (PP), polystyrene
(PS and EPS), poly(vinyl chloride) (PVC), polyamide (PA), poly(methyl methacry-
late) (PMMA) and styrene copolymers (ABS, SAN). The most important applica-
tions of thermoplastics are summarized in Table 1.1. The total Western European
demand for thermoplastics was 37.4 million tonnes in 2002, a growth of about 9%
as compared to 2001 [1]. Thermoplastics are used not only in the manufacture of
many typical plastics applications such as packaging and automotive parts, but also
in non-plastic applications such as textile bers and coatings. These non-plastic ap-
plications account for about 14% of all thermoplastics consumed.
The major thermosets include epoxy resins, phenolics, and polyurethanes (PU),
for which the major applications are summarized in Table 1.2. It has to be noted,
Tab. 1.1. Applications and 2002 Western European markets for the major thermoplastics [1].
Thermoplastic Market
[10
3
tonnes]
Applications
LDPE 7935 pallet and agricultural lm, bags, toys, coatings,
containers, pipes
PP 7803 lm, battery cases, microwave-proof containers, crates,
automotive parts, electrical components
PVC 5792 window frames, pipes, ooring, wallpaper, bottles, cling
lm, toys, guttering, cable insulation, credit cards,
medical products
HDPE 5269 containers, toys, housewares, industrial wrappings and
lms, pipes
PET 3234 bottles, textile bers, lm food packaging
PS/EPS 3279 electrical appliances, thermal insulation, tape cassettes,
cups and plates, toys
PA 1399 lm for food packaging (oil, cheese, boil-in-bag), high-
temperature engineering applications, textile bers
ABS/SAN 788 general appliance moldings
PMMA 317 transparent all-weather sheet, electrical insulators,
bathroom units, automotive parts
Tab. 1.2. Applications and 2002 Western European markets for the major thermosets [1].
Thermoset Market [10
3
tonnes] Applications
PU 3089 coatings, nishes, cushions, mattresses, vehicle seats
Phenolics 912 general appliance moldings, adhesives, appliances,
automotive parts, electrical components
Epoxy resins 420 adhesives, automotive components, E&E components,
sports equipment, boats
2 1 Polymer Reaction Engineering, an Integrated Approach
however, that about one-third of the market for thermosets is for relatively small-
scale specialty products. The total Western European market for thermosets was
10.4 million tonnes in 2002, about 1% below the 2001 value.
The major application areas of polymers can be dened as follows (Figure 1.2).
Automotive industry Motorists want high-performing cars combined with reliabil-
ity, safety, comfort, competitive pricing, fuel eciency, and, increasingly, reassur-
ance about the impact on the environment. Lightweight polymeric materials are
increasingly used in this sector (Daimler Benzs Smart is a nice example), also con-
tributing to a 10% reduction in passenger fuel consumption across Europe.
Building and construction Polymeric materials are used in the building and con-
struction sector, for example for insulation, piping, and window frames. In 2002
this sector accounted for 17.6% of the total polymer consumption.
Electrical and electronic industry Many applications in this eld arise from newly
designed polymeric materials, for example for polymeric solar cells and holo-
graphic lms. It is interesting to note that, while the number of applications in
this eld is increasing, the weight of the polymers used per unit is decreasing.
Packaging The packaging sector remains the largest consumer of synthetic poly-
mers, approximately 38% of the total market. This is mainly due to the fact that
these materials are lightweight, exible, and easy to process, and are therefore
increasingly being substituted for other materials. Although polymer packaging
ranks rst in terms of units sold, it is only third if judged on weight.
Agriculture As agricultural applications account for about 2.5% of the total of syn-
thetic polymers consumed in Europe, they play only a marginal role. Irrigation and
Packaging
38.1%
Building and
construction
17.6%
Electrical and
electronics
7.3%
Large industry
5.2%
Automotive
7.0%
Agriculture
2.5%
Domestic
22.3%
Fig. 1.2. Plastic consumption in 2002 by industry sectors in Western Europe [1].
1.1 Polymer Materials 3
drainage systems provide eective solutions to crop growing, and polymeric lms
and greenhouses can increase horticultural production substantially. The use of so-
called super absorbers for increased irrigation eciency in arid areas can be con-
sidered an important emerging market.
1.2
A Short History of Polymer Reaction Engineering
In Table 1.3 a comprehensive overview of the major developments in the polymer
industry is given. In the 19th century, polymers produced by Nature, such as cellu-
lose, Hevea brasiliensis latex (natural rubber), and starch, were processed to manu-
facture useful products. This practice was often based on experimental discoveries.
As an example, in 1839 Goodyear discovered by mistake the sulfur vulcanization of
natural rubber, making it possible for Ford to develop the automotive market. In
those times no polymers were produced synthetically.
Early in the 20th century (1920), the rst empirical description of macromole-
cules was developed by Staudinger [2]. At the same time, new methods were devel-
oped to determine the specic characteristics of these materials. In the 1930s many
research groups (for examples see refs. 37) developed models for the chain length
distribution in batch reactors resulting from dierent polymer chemistries, a meth-
odology that was further developed in the 1940s leading to more complex and com-
prehensive models, some of which are still being used today.
Tab. 1.3. The history of polymers in brief.
19th century natural polymer and derivatives (vulcanized rubber, celluloid)
1920 concept of macromolecules postulated by Staudinger
19301940 rst systematic synthesis of polymers
synthesis of polyamides (nylon) by Carothers at DuPont
discovery of polyethylene at ICI (Fawcett and Gibson)
19401950 synthetic rubbers and synthetic bers
19501960 stereospecic polymerizations by Ziegler and Natta, the birth of
polypropylene
discovery of polymer single crystals (Keller, Fischer, Till)
development of polycarbonate
19601970 discovery of PPO at GE by Hay and commercialization of PPO/PS
blends (Noryl
2
)
19701980 liquid-crystalline polymers
19801990 superstrong bers (Aramid
2
, polyethylene)
functional polymers (conductive, light-emitting)
19902000 metallocene-based catalysts; novel polyolens hybrid systems
(polymer/ceramic, polymer/metals)
2000 Nature-inspired catalysts
synthesis of polymers by bacteria and plants
Around 1940, partly inspired by World War II, a more systematic search for new
synthetic polymer materials as a replacement for scarce natural materials led to the
development of nylon (DuPont) and polyethylene (ICI) [8, 9]. This was followed by
the development of synthetic rubbers and synthetic bers. In the same period,
Denbigh [10] was one of the rst to introduce chemical reaction engineering con-
cepts into polymer science by considering polymerization reactions at both the
chemical and at the process levels. Processes were classied as homocontinuous
and heterocontinuous, depending on the mixing level. This pioneering approach
also acted as a catalyst for the further development of polymer reaction engineer-
ing (PRE).
The development of catalysts based on transition metals by Ziegler and Natta
[11] allowed the development of stereospecic propylene polymerization processes
and ethylene polymerization in the 1950s. Several process schemes were developed
at that time, of which some are still in use. The major problem in process develop-
ment has been to deal with the heat of polymerization, an issue that was solved, for
example, by using an inert solvent as a heat sink or by ashing of monomer fol-
lowed by condensation outside the reactor. In the same period, polycarbonate and
(somewhat later) poly(propylene oxide) (PPO) were developed. The main character-
istic of the polymers developed so far was that they were bulk materials, to be pro-
duced in extremely large quantities.
In the 1970s, a paradigm shift occurred when polymers with more specic prop-
erties started to be produced. This included various liquid crystalline polymers
leading, for example, to the production of superstrong bers such as Aramid
2
/
Kevlar
2
[12]. The development of functional polymers for the conduction of light
and electricity and optical switches also started then [13]. In the near future this
will probably lead to highly eective and exible polymer solar cells [14].
In the 1990s, metallocene catalysts were developed for polyolen production that
surpassed the ZieglerNatta catalysts in terms of selectivity and reactivity [15, 16].
Additionally, various hybrid materials were combining properties of both the poly-
mer (lightweight, exible) and a solid material, which could be metal (conductive)
or ceramic (insulating), leading to materials with specic properties applicable, for
example, as protective coatings [17].
Current developments include the mimicking of nature (enzymes) for the syn-
thesis of quite complex polymers like natural silk. Also, bacteria and plants are be-
ing modied to produce polymers of interest [18]. However, this can be expected
to require polymer reaction engineering developments that are as yet dicult to
foresee.
1.3
The Position of Polymer Reaction Engineering
Traditional chemical reaction engineering has its basis in the application of scien-
tic principles (from disciplines such as chemistry, physics, biology, and mathe-
matics) and engineering knowledge (transfer of heat, mass, and momentum) to
1.3 The Position of Polymer Reaction Engineering 5
the solution of problems of practical, industrial, and societal importance. Since the
1970s, a changing focus in chemical reaction engineering can be observed, which
is summarized in Figure 1.3.
To deal with more stringent requirements in terms of energy consumption re-
quires a shift from heat loss minimization toward novel intensied process con-
cepts that intrinsically require less energy. Safety should now be considered as an
intrinsic plant property rather than a responsive action, and the plant needs to be
exible to be able to respond quickly to changes in the market. Last but not least,
new concepts will be required to provide a basis for sustainable future develop-
ments, that is, the use of renewable resources and processes based on green
solvents. As a result of this changing focus, a shift toward a multidisciplinary
approach can be observed.
For PRE this implies the combination of several disciplines such as polymer
chemistry, thermodynamics, characterization, modeling, safety, mechanics, phys-
ics, and process technology. PRE problems are often of a multi-scale and multi-
functional nature to achieve a multi-objective goal. One particular feature of PRE
is that the scope ranges from the micro scale on a molecular level up to the macro
scale of complete industrial systems. PRE plays a crucial role in the transfer of in-
formation across the boundaries of dierent scale regions and to provide a compre-
hensive and coherent basis for the description of these processes [19].
As depicted in Figure 1.4, there is a direct link between time and size scale, from
which it is obvious that the micro and macro scales are not related to the same
time scale [20]. As an example, molecular dynamics calculations are addressing a
time scale in the order of femto- to nanoseconds, whereas process system integra-
tion evolves on the scale of years. Engineers have traditionally been working at the
meso scale, which is represented by the middle portion of Figure 1.4, using phe-
1980 1990 2000 2010
Integrated heat recovery
Coal, Oil Natural gas Renewable feedstock
Plant operation
Integrated and
inherent safety
Capacity Quality control Flexible production
Water Air
Recycling
Clean processes
Green solvents
From empiricism to strategy Multidisciplinarity
Optimization Intensification
Energy
Raw material
Safety
Market
Pollution
control
Scientific
methodology
Process
Less energy
demanding processes
Fig. 1.3. Changing priorities in industrial chemical engineering research.
nomenological and continuum models. Today these limits are pushed in two direc-
tions, both toward a more fundamental understanding and at the same time to-
ward a more global scale. In the past, the micro-region has traditionally been
the domain of physicists and chemists, whereas the macro-region has been the
eld, rather, of process or plant engineers. Today, it becomes obvious that only us-
ing a multidisciplinary, parallel, and synergetic approach can lead to successful de-
velopments. Polymer reaction engineering will play an essential role as the core
and the coordinator of this complex process.
1.4
Toward Integrated Polymer Reaction Engineering
As will be obvious from the foregoing discussion, PRE is composed of many disci-
plines all linked together. These disciplines can be either mature or emergent, but
they have a common gateway (see Figure 1.5). Although there is not necessarily a
direct connection between them, there exists a common core in which the dierent
disciplines make their own specic contribution to a general objective.
The frontiers in PRE are determined by what we know, understand, and are able
to quantify, and these frontiers are moving with growing knowledge, competences,
and experience. Eorts to push these limits will induce innovative developments
leading to emerging technologies and products, and will also strengthen the multi-
disciplinary approach. In general terms, PRE can be dened as the science that
Time scale
Size scale
Years
Days
Minutes
Milliseconds
Nanoseconds
Picoseconds
Femtoseconds
1 10 100 1m 1mm 1m 1km
Atomic level
Fundamental
Quantum techniques
Quantum chemistry
Molecular level
Elementary reactions
Molecular modeling
Chemical equilibrium
Phenomenological
Models
Microstructure
Continuum
Models
Heterogeneous
Engineering design
Process models
System integration
Environmental, Global
modeling
Fig. 1.4. Activities in PRE with their corresponding time and size scales.
1.4 Toward Integrated Polymer Reaction Engineering 7
brings molecules to an end-use product. We can either consider it like a black box
(Figure 1.6) or we can try to dene the interconnected disciplines that compose
this black box (Figure 1.7). Provided the required product properties can be met,
we expect that sustainability is the common denominator for all the disciplines in-
volved in this process.
The process of transforming raw materials into valuable end-use products is not
a one-way procedure but rather an iterative process in which we try to optimize all
the parameters involved. The selection of the proper chemistry and technology
should include an evaluation of environmental, safety, and economic parameters.
Moreover, questions regarding the possible use of renewable resources and mini-
mizing the energy requirement will have to be answered. Dening PRE in this
manner appears to be very close to the procedure of life cycle analysis (LCA) [21].
Polymer Reaction
Engineering
(PRE)
Polymer chemistry
Reaction kinetics
Process integration
optimization
Inherent safety
Environment
Recycling, Disposal
Novel processes
New products
Materials
Application
Modeling and
simulation
Thermodynamics
Novel processes
Post-reaction
processes
Measurement and control
Materials sciences
Nano-, Micro-
Bio-
Fig. 1.5. The expanding sphere of polymer reaction engineering.
Polymer Reaction
Engineering
Raw materials End use product
Fig. 1.6. PRE as a black box process.
Life cycle analysis is a tool assisting decision making in the engineering process.
LCA includes the information on the history of the materials used, and the dif-
ferent process and raw material alternatives, as well as the nal product require-
ments. LCA is an instrument driven by environmental considerations against a
background of technical and economic specications, and involves the so-called 3-
P concept (people, planet, and prot). The LCA-based PRE methodology (Figure
1.8) [22] leads to an optimization of all the parameters involved and a reduction of
the costs. This seems to be contradictory at rst sight, but integrating all the as-
pects often leads to cost reductions. In our view, the use of this approach will lead
to a sustainable integrated PRE.
1.5
The Disciplines in Polymer Reaction Engineering
The dierent disciplines involved in PRE can be represented using the academia
industry dichotomy (Figure 1.9). The interests of the two types of players are not
identical: the dierences are similar to the dierences in their mission statements.
Nevertheless, we can observe that a great overlap is present in the middle zone,
Integrated PRE
Polymer chemistry
Reaction kinetics
Process integration
optimization
Inherent safety
Environment
Recycling, Disposal
Novel processes
New products
Materials
Application
Modeling and
simulation
Thermodynamics
Novel processes
Post-reaction
processes
Measurement and control
Materials sciences
Nano-, Micro-
Bio-
Raw materials
Energies
Needs
Laws
Economy
Sustainability
Renewable
Products
Profit
Satisfaction
Knowledge
Fig. 1.7. The integrated approach for sustainable PRE.
where interests, tools, and knowledge are similar, thus providing a strong basis for
partnership.
As stated above, PRE is composed of a large number of disciplines, which are
described in more detail in the following chapters of this handbook. These disci-
plines are interconnected by a synergetic and multidisciplinary approach, and com-
processing
synthesis
raw material
product use
recycling
waste
management
Specification
- technical
- economic
- ecologic
- safety
Balances
- energy
- material
- emission
- waste
- sewage
Evaluation leads to closed
loop assessment of costs
Fig. 1.8. Life cycle analysis of parts, methods, products, and systems.
Academia
Industry
Safety
Process
modeling
Molecular
modeling
Reactor design
Measurement
and control
Fundamental
kinetics
Thermodynamics
Quality
assurance
Novel
technologies
Market
economics
Polymer chemistry
Polymer physics
Environment
Applied
modeling
Fig. 1.9. Overlap of industrial and academic disciplines.
mercial products are the nal achievement resulting from this methodology. This
could be expressed by an orthogonal representation (Figure 1.10) where polymer
sciences are linked with engineering sciences. Every type of polymerization will
have its own specic features, models, and engineering aspects involved. From Fig-
ure 1.10 it will be obvious that only teamwork, bringing together several elds of
expertise, can lead to the nal objective.
1.5.1
Polymerization Mechanisms
Polymerization reactions can be classied depending on the reaction mechanism
involved and can be either step-growth or chain-growth. These mechanisms dier
basically with the time scale of the process. In step-growth polymerization (like
polycondensation), the polymer chain growth proceeds slowly from monomer to
dimer, trimer, and so on, until the nal polymer size is formed at high monomer
conversions. Both the chain lifetime and the polymerization time are often in the
order of hours. In chain-growth polymerization (like ionic or free-radical polymer-
ization), macromolecules grow to full size in a much shorter time (seconds being
the order of magnitude) than required for high monomer conversion. High molec-
ular weights are already obtained at low monomer conversion, which is in great
contrast to step-growth polymerizations. Also, unlike step-growth polymerization,
chain-growth polymerization requires the presence of an active center.
Condensation polymers are the result of a condensation reaction between mono-
mers, with or without the formation of a condensation by-product (Chapter 3). Ex-
amples of polymers produced by condensation are polyamide[6.6], (Nylon 6,6) the
result of the intermolecular condensation of hexamethylenediamine and adipic
acid, and polyamide[6], (Nylon 6) which is the product of intramolecular condensa-
tion of a-caprolactam. This type of reaction is generally sensitive to thermodynamic
equilibrium and requires the removal of the by-product, which is often volatile.
Polycondensation
Fig. 1.10. Product-driven PRE, based on an orthogonal
relationship between science and engineering.
The polymers produced by condensation reactions can be either linear or non-
linear, depending on the number of functional groups per monomer. The polymer-
ization process can be performed in bulk (liquid or solid state) or as an interfacial
polymerization.
Free-radical polymerization (FRP) can be performed homogeneously (in bulk, so-
lution, or suspension; Chapters 4 and 5) or heterogeneously (emulsion, precipita-
tion; Chapter 6). The active site is always a radical that can be unstable (classical
FRP) or stabilized as in pseudo-living FRP. Radicals can be formed by the homo-
lytic bond rupture of initiators (molecules sensitive to homolytic cleavage, such as
peroxides, photosensitive molecules, or bisazo compounds) or by complex mecha-
nisms creating radicals from monomer units using thermal or high-energy
sources, such as X-rays, g-irradiation, or UV. This type of polymerization usually
comprises several steps: initiation, propagation, various transfer mechanisms,
and termination.
In ionic polymerizations a cation or anion is the active site (Chapter 7). A heter-
olytic process leads to charged parts of molecules that can induce the polymeriza-
tion by nucleophilic or electrophilic processes. These reactions generally evolve at
low temperatures (even as low as 120
C) due to the high reactivity of ions. Also,

they are very sensitive to impurities present in the monomer or solvent. These re-
actions are not always terminated, so lead to living polymerization. This process is
often used to build tailor-made copolymers.
Coordination polymerizations require a transition metal catalyst (Chapter 8). Poly-
olens are often produced by this kind of reaction where the catalyst (Ziegler
Natta, for example) acts as the active site but also as the steric regulator, which
makes it possible to build polymers with a dened tacticity. Nowadays a great re-
search eort is devoted to the synthesis of new transition metal-based catalysts,
such as metallocenes, to produce new products.
1.5.2
Fundamental and Engineering Sciences
Apart from the various polymerization mechanisms involved, a large number of
other disciplines will have to be involved, according to the matrix depicted in
Figure 1.10.
Thermodynamics is essential to understand the physicochemical properties of
the individual reactants, solvents, and products involved (Chapter 2). Also, it pro-
vides information on the interaction between the various components present in
the reaction mixture, from which phenomena such as phase behavior and parti-
tioning can be derived. This information is usually accessible by using the appro-
priate equation of state for a given system studied. A close collaboration between
chemical physicists, chemists, and chemical engineers is required to take full ad-
vantage of this fundamental knowledge.
Polymer solutions (solid, bulk, solution, complex media) have to be characterized
by several specic analytical tools (Chapter 20). Techniques such as NMR, ESR,
electron microscopy, chromatography, electrophoresis, viscometry, calorimetry, and
laser diraction are widely used to determine polymer properties, often in combi-
nation. The main characteristics being analyzed are the chain length distribution,
degree of branching, composition, tacticity, morphology, particle size, and chemical
and mechanical properties. Polymer mechanics (Chapter 14) usually concerns the
nal product rather than the polymerization reaction. Nevertheless, as polymers
are usually judged on their end-use properties (Chapter 13), the nal product
needs specic and often customer-based analysis. This is described more speci-
cally for two application areas, namely the use of thermosets for coating applica-
tions (Chapter 16) and the production of polymeric bers (Chapter 17).
Measurement and control are indispensable to achievement of a robust and safe
process (Chapter 12). Since the early 1990s, a tremendous eort has been observed
in the development of new in-line analytical techniques, including spectroscopy
(UV, IR, Raman, laser, and so on), ultrasonic sensing, chromatography, and dirac-
tion or electrical methods. New control schemes appear where the reaction is per-
formed just below the constraint limits, independently of the reaction kinetics. All
these techniques tend to lead to safer and more robust processes while increasing
productivity and product quality at the same time.
Safety cannot be treated as a separate discipline as it is already integrated from
the early chemistry and process development (Chapter 11). Safety deals with a wide
variety of technological aspects with respect to the environment (water, air, soil,
and living species). However, economic aspects are usually taken into consider-
ation also. Modern process development intrinsically includes safety and environ-
mental aspects in all stages of the development.
Modeling is probably the tool of excellence for engineers (Chapter 9). It is
used to simulate the reaction and the process system in order to shorten the time
for development. It is based on models that can be physical or chemical, semi-
empirical or empirical, descriptive or more fundamental. To describe the develop-
ment of the molecular weight distribution upon reaction, moment methods or
equations based on population balance are often used.
Scaleup is a widely used term to dene the methodology that allows scaling up
of a process from small to larger scale (Chapter 10). Often the scaleup process be-
gins with a scaledown approach in order to have reliable and representative equip-
ment already at the laboratory scale. Scaleup is always dependent on the system
studied and requires a proper understanding of the performance of process equip-
ment involved at dierent scales. In polymer reaction engineering, heat transfer
and mixing can be considered as two major issues in this perspective. Modern
computing techniques such as computational uid dynamics and process simula-
tion become more and more important in the optimization of process parameters
and the equipment hardware.
Volatile organic compound (VOC) content in the nal product is related to prod-
uct properties and legislation (FDA approval in the USA, for example). All the pro-
cesses aiming to lower the residual VOC content in the product are denoted as re-
movable (Chapter 18). These processes can dier from each other, depending on
the techniques involved. Devolatilization, post-process reaction, and extraction are
some of the methodologies employed for this purpose.
Stability and degradation of polymers (Chapter 15) become relevant especially
during post processing or moulding processes. Temperature, oxidation and me-
chanic stresses are the main contributors to product degradation.
Currently, there is a strong emphasis on the synthesis of novel functional poly-
mers shaped on a nano scale (Chapter 19) and the development of sustainable
production processes (Chapter 21). The latter includes process intensication as a
methodology, the use of green solvents, and the use of renewable resources.
Many of the new processes under development are focusing on one or more of
these topics, for which the use of supercritical uids is currently being imple-
mented on an industrial scale.
1.6
The Future: Product-inspired Polymer Reaction Engineering
Innovation times in industry have shown a steady decrease since the 1970s. Classic
thinking is that process development becomes increasingly important as industry
matures [23]. This is due to the fact that in an early phase of the lifetime of an in-
dustry, when product concepts are still being created, the rate of product innova-
tion exceeds the rate of process innovation. This period continues until a dominant
design has emerged and opportunities for radical product innovation decrease. In
this phase, the shift is toward process innovations to reduce cost price.
The half-time of product innovation (time-to-market) in the early 1970s was
about ten years. Currently, two years is often considered long. This acceleration of
innovation time is the result of competitive pressure in the market. As a rule of
thumb, the rst company to enter the market with a new product can get up to
60% of market share, so there is a high reward for being rst.
As has been discussed above, chemical engineering has been the basis for poly-
mer reaction engineering in the past. In recent discussions, however, it has been
emphasized that a need exists to refocus chemical engineering toward product-
driven process engineering [24, 25]. The thinking about a process should then start
with the customer or consumer: which of the two depends on the structure of the
supply chain. The wishes of the consumer and consumer-perceived product prop-
erties have to be translated into physical and chemical product properties. In this
way, the main physical attributes of a product are determined, including an idea
about the microstructure. Next, a functional analysis is performed to determine
the lowest number of transformations needed to create the product; this is fol-
lowed by a morphological analysis [26]. Finally, a conceptual process design exer-
cise is performed to generate possible process routes to achieve the desired product
properties. This sequence of events is the core of product-inspired polymer reac-
tion engineering. A key characteristic of this approach is the fact that it avoids the
classical unit operation trap, because it does not x the mindset to consider only
traditional reactor design and separation process steps to build a process.
1.7
Concluding Remarks
In the foregoing we have presented a general framework for sustainable polymer
reaction engineering. Its most important characteristic lies in the concerted multi-
disciplinary approach, rather than focusing on individual competencies. Given the
volume of polymer production, it will be of major importance that environmental
and safety issues become an integral part of the development process. In combina-
tion with tools such as life cycle analysis and product-inspired PRE, this will allow
the development of sustainable new polymer processes.
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18 E. R. Howells, Chem. Ind., 1982, 508.
19 A. Penlidis, Can. J. Chem. Eng., 1994,
72, 385.
20 A. Sapre, J. R. Katzer, Ind. Eng.
Chem. Res., 1995, 34, 2202.
21 A. Azapagic, Chem. Eng. J., 1999, 73,
1.
22 P. Eyerer, J. Polym. Eng., 1996, 15,
197.
23 W. J. Abernathy, J. M. Utterback,
Technol. Rev., 1978, 80, 40.
24 E. L. Cussler, G. D. Moggeridge,
Chemical product design, Cambridge
University Press, Cambridge, 2001.
25 E. L. Cussler, J. Wei, AIChE J., 2003,
49, 1072.
26 C. J. King, AIChE Monograph Ser.,
1974, 70, 1.
References 15
2
Polymer Thermodynamics
1
Theodoor W. de Loos
2.1
Introduction
The phase behavior of polymer solutions plays an important role in polymer pro-
duction and processing. Many polymers are produced by solution polymerization.
Solvent choice, solvent recovery and the removal of traces of solvent from the poly-
mer product are important factors in these processes. An example is the produc-
tion of linear low-density polyethylene (LLDPE), which is a copolymer of ethylene
and a 1-alkene. Hydrocarbons are used as solvents in this process. The reactor con-
ditions are limited at high temperature by the onset of a liquidliquid phase split,
characterized by a lower critical solution temperature, and at low temperature by
crystallization of LLDPE. The pressure must be high enough to keep the ethylene
in solution. Another well-known example is the production of low-density polyethy-
lene (LDPE). In this process ethylene is compressed together with an initiator and
the LDPE is formed by radical polymerization. The reactor pressure chosen must
be high enough to dissolve the polymer in its monomer. In practice reactor pres-
sures are higher than 200 MPa. Since the conversion of ethylene to LDPE is incom-
plete, LDPE has to be separated from unreacted ethylene, which is recycled to the
reactor. To save energy this is done by pressure reduction in two steps, which in-
volve a high-pressure vaporliquid ash.
From a thermodynamic point of view polymer solutions are complicated solu-
tions. A polymer is not a single component but a multicomponent mixture charac-
terized by a molecular weight distribution or by average molecular weights, such as
the number-average molecular weight M
n
or the weight-average molecular weight
M
w
. In the case of a copolymer dierent types of copolymers are possible, for ex-
ample random copolymers and block copolymers, and the comonomer content
may vary. Because of their asymmetric nature the entropy of mixing of polymer
solutions is much lower than in the case of a mixture of two low molecular weight
compounds; also, the pure solvent and the polymer have rather dierent free
ISBN: 3-527-31014-2
1) The symbols used in this chapter are listed at
the end of the text, under Notation.
17
volumes. Because of this, polymersolvent systems often show a liquidliquid
phase split.
In this chapter it is not possible to give an in-depth treatment of the thermody-
namics of polymer solutions. For further reading, see Refs. 16.
2.2
Thermodynamics and Phase Behavior of Polymer Solutions
2.2.1
Thermodynamic Principles of Phase Equilibria
The equilibrium conditions for phase equilibria can be derived in the simplest way
using the Gibbs energy G. According to the second law of thermodynamics, the
total Gibbs energy of a closed system at constant temperature and pressure is a
minimum at equilibrium. If this condition is combined with the condition that
the total number of moles of component i is constant in a closed system [Eq. (1),
where n
a
i
is number of moles of component i in phase a], the equilibrium condi-
tions given by Eq. (2) can easily be derived for a system of p phases and N compo-
nents [7].
X
a
n
a
i
constant 1
m
a
i
m
b
i
m
p
i
for i 1; 2; . . . ; N 2
The chemical potential of component i in phase a is dened by Eq. (3), where g is
the molar Gibbs energy.
m
a
i

q
X
i
n
a
i
g
a

qn
a
i
0
B
@
1
C
A
P; T; n
j0i
3
2.2.2
Fugacity and Activity
In the thermodynamic treatment of phase equilibria, auxiliary thermodynamic
functions such as the fugacity coecient and the activity coecient are often
used. These functions are closely related to the Gibbs energy. The fugacity of com-
ponent i in a mixture, f
i
C
, is dened by Eq. (4a) together with (4b).
dm
i
1RT ln f
i
C
at constant T 4a
lim
P!0
f
i
C
P
i
1 4b
18 2 Polymer Thermodynamics
According to this denition, f
i
C
is equal to the partial pressure P
i
in the case of an
ideal gas. The fugacity coecient f
i
C
is dened by Eq. (5) and is a measure of the
deviation from ideal gas behavior.
f
i
C
f
i
C
P
i
5
The fugacity coecient can be calculated from an equation of state by Eq. (6) or (7)
[8].
RT ln f
i
C
P
0
V
i

RT
P

dP 6
RT ln f
i
C

V
y
qP
qn
i

V; T; n
j0i
RT
V
" #
RT ln
X
i
n
i
RT
PV
0
@
1
A
7
According to Eq. (4), the equilibrium relation in Eq. (2) can be replaced by Eq. (8).
f
i
C
a
f
i
C
b
f
i
C
p
for i 1; 2; . . . ; N 8
The activity a
i
is dened as the ratio of f
i
C
and the fugacity of component i in the
standard state f
0
i
at the same P and T [Eq. (9)].
a
i
1
f
i
C
P; T; x
f
0
i
P; T; x
0
9
An ideal solution is dened by Eq. (10).
a
id
i
1x
i
10
The activity coecient of component i, g
i
[Eq. (11)], is a measure of the deviation
from ideal solution behavior, so the fugacity of a nonideal liquid solution can be
written as Eq. (12).
g
i
1
a
i
a
id
i
11
f
i
C
x
i
g
i
f
0
i
12
The activity coecient g
i
can be calculated from a model for the molar excess
Gibbs energy g
E
, Eq. (13).
RT ln g
i

q
X
i
n
i
g
E

qn
i
0
B
@
1
C
A
P; T; n
j0i
13
In this approach the standard state fugacity f
0
i
of a liquid component is usually the
fugacity of the pure liquid component, and is closely related to the vapor pressure
P
sat
i
of that component. On the vapor-pressure curve of a pure component, we have
conditions according to Eqs. (14).
f
L
i
P
sat
i
; T f
V
i
P
sat
i
; T f
V
i
P
sat
i
; TP
sat
i
14
From Eq. (4a) we obtain Eq. (15), where v
L
i
is the molar volume of pure liquid i.
f
L
i
P; T f
L
i
P
sat
i
; T exp
P
P
sat
i
dm
L
i
RT
!
f
L
i
P
sat
i
; T exp
P
P
sat
i
v
L
i
RT
dP
!
15
Combining Eqs. (14) and (15), we get Eq. (16).
f
L
i
P; T f
V
i
P
sat
i
; TP
sat
i
exp
P
P
sat
i
v
L
i
RT
dP
!
16
At low pressure the fugacity coecient and the exponential term are close to 1, so
Eq. (17) holds.
f
L
i
AP
sat
i
17
2.2.3
Equilibrium Conditions
For low-pressure vaporliquid equilibria (VLE) the equilibrium condition of Eq.
(18) is usually written as Eq. (19), in which f
0
i
is calculated with Eq. (16) or (17)
and j
i
C
with Eq. (6) or (7); x
i
and y
i
are the liquid-phase and vapor-phase mole frac-
tion of component i, respectively.
f
i
C
L
f
i
C
V
18
x
i
g
i
f
0
i
y
i
j
i
C
P 19
The truncated virial equation or the ideal gas equation is often used as the equa-
tion of state. In the latter case all fugacity coecients are 1, so the simplest form
of Eq. (19) is Eq. (20).
x
i
g
i
P
sat
i
y
i
P 20
In the case of low-pressure liquidliquid equilibria (LLE) the equilibrium condition
is given by Eq. (21).
f
i
C
0
f
i
C
00
or x
i
g
i
f
0
i

0
x
i
g
i
f
0
i

00
21
The two liquid phases are indicated by prime (
0
) and double prime (
00
). If for both
liquid phases the standard fugacity is chosen as the pure liquid component, Eq.
(21) reduces to Eq. (22).
x
i
g
i
0
x
i
g
i
00
22
For the calculation of high-pressure vaporliquid equilibria or liquidliquid equi-
libria an equation of state is always used for both phases and the equilibrium con-
dition used is given by Eq. (23).
f
i
C
a
f
i
C
b
or x
i
j
i
C
P
a
x
i
j
i
C
P
b
or x
i
j
i
C
a
x
i
j
i
C
b
23
2.2.4
Low-pressure VaporLiquid Equilibria
Since polymers have no vapor pressure and as a consequence the vapor phase does
not contain polymer, the equilibrium conditions for low-pressure vaporliquid
equilibria of polymer solutions as given by Eq. (20) are only applicable to the
solvent s as in Eq. (24), or in a case where the weight fraction of polymer w
p
is
used as a composition variable as in Eq. (25), where W
s
is the weight fraction based
activity coecient of the solvent.
P x
s
g
s
P
sat
s
24
P 1 w
p
W
s
P
sat
s
25
The relation between a mole fraction based activity coecient g
i
and a weight frac-
tion based activity coecient W
i
of component i is given by Eq. (26), where w
i
and
M
i
are the weight fraction and molecular weight of component i, respectively. g
s
and W
s
can be obtained from a correlation of experimental data using a suitable
model or from a predictive model (see Section 2.3).
g
i
W
i
w
i
x
i
M
i
X
N
j 1
w
j
M
j
26
2.2.5
FloryHuggins Theory and LiquidLiquid Equilibria
The FloryHuggins theory of polymer solutions [1] is based on a rigid lattice
model in which a polymer molecule is assumed to consist of r segments of the
size of a solvent molecule. The FloryHuggins expression for the Gibbs energy of
mixing D
mix
G for N
s
moles of solvent and N
p
moles of polymer is given by Eq. (27).
D
mix
G
RT
N
s
ln j
s
N
p
ln j
p
j
s
j
p
N
s
rN
p
w 27
The rst two terms on the right-hand side of Eq. (27) represent the so-called com-
binatorial entropy of mixing, and the third term is an approximation for the en-
thalpy of mixing. In practice w, the FloryHuggins interaction parameter, is used
as an adjustable, temperature-dependent parameter. j
s
and j
p
are the segment
fractions of solvent and polymer, respectively, dened by Eq. (28).
j
s

N
s
N
s
rN
p
and j
p

rN
p
N
s
rN
p
28
According to the original FloryHuggins theory w is given by Eq. (29), in which
e
ss
; e
pp
, and e
sp
are the interaction energies between two solvent molecules, two
polymer segments, and a solvent molecule and a polymer segment, respectively.
w z
2e
sp
e
ss
e
pp
T
29
Often r is approximated by the ratio of the molar volumes of pure liquid polymer
and pure solvent. The segment fractions of solvent and polymer are then equal to
the volume fractions of solvent and polymer, f
s
and f
p
. Equation (27) is derived us-
ing many assumptions and approximations (for a discussion, see Ref. 8), but on
the basis of this rather simple expression many features of the phase behavior of
polymer solutions can be explained. The expressions for the mole fraction based
activity coecients of solvent and polymer are Eqs. (30) and (31), respectively.
ln g
s
ln 1 j
p

j
p
r
!
1
1
r

j
p
j
2
p
w 30
ln g
p
ln1 j
p
r j
p
r 11 j
p
r1 j
p
2
w 31
As can be seen from Eq. (30), the activity coecient of the solvent is strongly de-
pendent on r for low values of r, but at high values of r g
s
becomes practically inde-
pendent of r. This implies that the equilibrium pressure of low-pressure VLE for
polymersolvent systems is hardly dependent on the molecular weight of the
polymer.
In the original formulation of the FloryHuggins theory D
mix
G increases with
decreasing temperature, which leads to a liquidliquid phase split with an upper
critical solution temperature. Per mole of lattice sites, the entropy of mixing of a
polymersolvent system is much less than for a solventsolvent system; because
of this, polymersolvent systems show a stronger tendency to demix than solvent
solvent systems. This is illustrated in Figure 2.1, which shows schematically the
inuence of r on the location and shape of the liquidliquid two-phase region.
The gure shows that with increasing r, the two-phase region increases in size
and becomes more asymmetric. The critical point, the temperature maximum of
the two-phase region, shifts with increasing r to lower values of w, higher tempera-
ture, and lower values of j
p
. At r ythe critical point is found at a limiting value
of w
1
2
, T y, and j
p
0. This follows directly from the critical point conditions
[Eq. (32), where G is the Gibbs energy per mole of lattice sites].
qG
qj
p
!
P; T
q
2
G
qj
2
p
!
0 32
This leads to Eqs. (33) and (34) for the FloryHuggins expression [Eq. (27)].
w
crit
1
2
1
1
r
p

2
33
j
crit
p

1
1
r
p 34
0.00 0.10 0.20 0.30 0.40 0.50 0.60
p
0.40
0.50
0.60
0.70
0.80
0.90
1.00
r=10
r=100
r=1000
Fig. 2.1. Liquidliquid equilibria for polymersolvent systems
at dierent polymer chain lengths r. Calculated from the Flory
Huggins theory.
The theta temperature y is the highest possible upper critical solution temperature
(UCST) within the framework of the FloryHuggins theory.
Many polymersolvent systems, at temperatures above the UCST, show a second
region with liquidliquid immiscibilty (Figure 2.2), which is characterized by the
occurrence of a lower critical solution temperature (LCST) [9]. This phenomenon
can not be explained on the basis of the original FloryHuggins theory. Delmas
and Patterson [10] calculated binary critical curves of polymersolvent systems us-
ing the Flory equation of state [11, 12]. According to these authors the reason for
the occurrence of this LCST is the large dierence in thermal expansion of pure
liquid polymer and pure solvent, which leads to an increasing dierence in free
volume with increasing temperature and an LCST-type liquidliquid phase split at
temperatures below the critical point of the solvent. If the molecular weight of the
polymer is increased, the UCSTand LCSTapproach each other. In some cases, this
can lead to the phase diagram of Figure 2.3, in which the liquidliquid region has
the shape of an hourglass, as in the polystyreneacetone system (Figure 2.4) [13].
However, another possibility is that the UCST and LCST never meet and that each
liquidliquid region shows a (dierent) y temperature for r y. This type of be-
havior is found for polystyrenemethylcyclohexane [14]; see Figure 2.5.
Another type of LCST is connected to specic interactions like hydrogen bond-
ing. This type of LCST is found at temperatures below the UCST. The resulting
phase diagram is presented in Figure 2.6, which shows a closed-loop region of
liquidliquid immiscibility. This type of phase diagram is not predicted by the
original FloryHuggins theory, either.
Solvent Polymer
L
1
+L
2
L
1
+L
2
L
T
p
Fig. 2.2. Liquidliquid equilibria showing a low-temperature
two-phase region with a UCST and a high-temperature two-
phase region with a LCST.
2.2.6
High-pressure LiquidLiquid and VaporLiquid Equilibria
Figure 2.7 shows schematically the phase behavior of a binary polymer solution at
constant composition in a P; T diagram. In the case of curve a, the mixture at low
temperature shows a liquidliquid region characterized by UCST behavior and at
high temperature a liquidliquid region characterized by LCST behavior. Both two-
phase regions are bounded at low pressures by a three-phase liquidliquidvapor
curve, which separates the liquidliquid region from a vaporliquid region. The
curve that separates a liquidliquid region from the one-phase liquid region is
often called a cloud-point curve. The liquidliquidvapor curve is found in many
cases very close to the vapor-pressure curve of the pure solvent because the poly-
mer concentration in the vapor phase and in the solvent-rich liquid phase is low.
Curve b shows the case where the low-temperature liquidliquid region and the
high-temperature liquidliquid region are merged into a single liquidliquid re-
gion. In this case the cloud-point curve shows a pressure minimum. At pressures
below this minimum, hourglass-shaped two-phase regions are found. At higher
pressures the phase behavior is as represented by Figure 2.2. An example of this
behavior is shown by the polystyreneacetone system [15] (see Figure 2.8). In the
case of curve c the cloud point curve is found at much higher pressure and no
longer shows a minimum.
In going from case a to case c, the mutual solubility of polymer and solvent de-
creases. Stronger polymerpolymer or solventsolvent interactions lead to a lower
mutual solubility, while stronger polymersolvent interactions lead to a higher mu-
tual solubility [15]. As discussed in Section 2.2.5, increasing molecular weight of
Solvent Polymer
L
1
+L
2
L
1
+L
2
L
T
L
p
Fig. 2.3. Hourglass-shaped two-phase liquidliquid equilibria.
the polymer also leads to a decrease in mutual solubility for the same polymer
solvent system. An example of this eect is given by Zeman and Patterson [16] for
the polystyreneacetone system.
A similar eect is observed when the chain length of the solvent is increased.
Ehrlich and Kurpen [17] determined cloud-point curves of 5 wt.% LDPE in ethane,
propane, butane, and pentane. These results are reproduced in Figure 2.9, which
shows that with increasing molecular weight of the solvent the cloud-point pres-
sure increases and dP=dT of the cloud-point curves change sign from positive to
negative. Since ethylene is a worse solvent than ethane, the cloud point pres-
sures for the system ethylene LDPE [18, 19] are higher than for the system
Fig. 2.4. Liquidliquid equilibria in the polystyreneacetone
system at the indicated polystyrene molecular weights
(in g mol
1
). Reproduced with permission from Ref. 13.
ethane LDPE. For this type of systems it is not possible to make a clear dis-
tinction between vaporliquid equilibria and liquidliquid equilibria. The poly-
mer-rich phase can be considered to be a liquid phase, but the solvent-rich phase
is liquidlike at low temperature, but vaporlike at high temperature. De Loos et al.
[20] measured cloud-point curves for LLDPE systems plus hexane, plus heptane,
and plus octane (see Figure 2.10). In this case also, the polymer is more soluble
in the higher molecular weight solvent, which is shown by the shift of the LCST-
type cloud-point curve to higher temperatures. An increased degree of branching
of the polymer leads to a better mutual solubility [21].
Fig. 2.5. Liquidliquid equilibria in the polystyrene
methylcyclohexane system at the indicated molecular weights
of polystyrene (in g mol
1
). Reproduced with permission from
Ref. 14.
Solvent Polymer
L
1
+L
2
L
T
p
Fig. 2.6. Closed-loop liquidliquid equilibria.
P
T
a
a
b
c
Fig. 2.7. P; T phase diagram for a constant
composition polymersolvent system: (a)
system with separate low- and high-
temperature regions of demixing; (b) system in
which the low- and high temperature regions
of demixing have merged, showing a minimum
cloud pressure; (c) system in which the low-
and high-temperature regions of demixing have
merged, without a minimum cloud pressure.
The full curves are cloud-point curves; the
broken curves are liquidliquid vapor curves.
The addition of an anti-solvent such as a supercritical gas also produces changes
in the phase diagram to one like Figure 2.7 [2225]. However, in this case the
liquidliquidvapor equilibrium is represented by a region instead of by a curve.
2.3
Activity Coecient Models
In practice the original FloryHuggins theory is not accurate enough for a quanti-
tative representation of polymersolvent phase equilibria. To improve this situation
a concentration-dependent w-parameter can be introduced and also the tempera-
ture dependence of w can be made more complicated than in Eq. (29). The terms
representing the combinatorial entropy of mixing, the rst two terms in Eq. (27),
can be replaced by results from more accurate theories [4, 26] and the dierence
Fig. 2.8. Liquidliquid equilibria in the polystyreneacetone
system at the indicated pressures. M 20400 g mol
1
.
Reproduced with permission from Ref. 16.
in the free volume of polymer and solvent can be accounted for by adding a free
volume contribution [4]. Further, Eq. (27) can be extended to account for the poly-
dispersity of the polymer.
The system-dependent parameters in these models can be adjusted to experi-
mental data or predicted from a group contribution approach [4, 26].
2.3.1
FloryHuggins Theory
For a solution of a polydisperse polymer with m polymer components in one sol-
vent, the FloryHuggins expression for the Gibbs energy of mixing per mole of lat-
Fig. 2.9. Cloud-point isopleths of LDPE in various n-alkane
solvent at 5 wt.% polymer. The short dashlong dash curve is
the solidication boundary of LDPE. Reproduced with
permission from Ref. 17.
tice sites can be written as Eq. (35). The sum is only over the polymer components,
j
i
is the segment fraction of polymer component i, and j
p

P
m
i1
j
i
1 j
s
is the
overall polymer segment fraction.
D
mix
G
RT
j
s
ln j
s

X
m
i1
j
i
r
1
i
ln j
i
j
s
j
p
g
sp
35
g
sp
f T; j
p
36
To avoid confusion with the polymersolvent interaction parameter, the symbol g
sp
[Eq. (36)] is used instead of w, which is independent of concentration. Equations
(37a)(37c) are examples of expressions used for the temperature and composition
dependence of g
sp
[2729].
g
sp
a
b
T
cT dj
p
ej
2
p
37a
g
sp
a
b
c
T
1 dj
p
37b
Fig. 2.10. Cloud-point curves of poly(E-co-1-octene)n-alkane
systems at P 3 MPa. M
n
33 kg mol
1
, M
w
124 kg mol
1
,
M
z
420 kg mol
1
. The systems show LCST phase behavior.
Reproduced with permission from Ref. 20.
g
sp

a
b
T
c ln T
1 dj
p
37c
We can derive Eq. (38) for the solvent, and Eq. (39) for polymer component i,
where r
n
is number-average chain length of the polymer, which is dened by Eq.
(40) and which is proportional to the number-average molecular weight of the
polymer.
lnx
s
g
s
ln j
s
1
1
r
n

j
p
g
sp
j
s
qg
sp
qj
p
!
j
2
p
38
lnx
i
g
i
ln j
i
1
r
i
j
p
r
n
r
i
j
s
r
i
g
sp
j
p
qg
sp
qj
s

j
2
i
39
r
n

X
m
i1
n
i
r
i
X
m
i1
n
i
40
Using Eqs. (37) and (38), vaporliquid and liquidliquid equilibria can be calcu-
lated as discussed above. Reference 5 gives details of liquidliquid equilibrium cal-
culations in polydisperse polymersolvent systems. In Figure 2.11 the experimen-
tally determined phase behavior of three PEGwater systems is compared with the
calculated phase behavior of these systems using Eq. (37c) to represent g
sp
as a
function of temperature and polymer segment fraction. The parameters were tted
to the data [29].
The description of the inuence of pressure on polymersolvent phase behavior
is also possible using a pressure-dependent g
sp
[27, 3032]. However, this approach
is purely empirical.
2.3.2
Hansen Solubility Parameters
According to the regular solution theory of Hildebrand the w-parameter can be ap-
proximated by Eq. (41) [8], where v
s
is the molar volume of the solvent and d
s
and
d
p
are the solubility parameters of solvent and polymer, respectively. Since these
solubility parameters are pure component parameters, Eq. (41) combined with Eq.
(27) results in a predictive model. However, since many simplications are in-
volved, the results of this model can be considered as only a rough estimate. Fol-
lowing the slogan like dissolves like, a good solvent for a polymer is a solvent for
which d
s
and d
p
have similar values.
w
v
s
RT
d
s
d
p
2
41
Hansen suggested rening the solubility parameter theory by the introduction of
contributions from dispersive interactions (d), polar interactions ( p) and hydrogen
bond formation (hb), as in Eq. (42) [33].
w
v
s
RT
d
s; d
d
p; d
2
d
s; p
d
p; p
2
d
s; hb
d
p; hb
2
42
Recently, Lindvig et al. [34, 35] showed that Eq. (42) systematically overestimates
the innite dilution activity coecient of the solvent and proposed an alternative
expression, Eq. (43).
w a
v
s
RT
d
s; d
d
p; d
2
0:25d
s; p
d
p; p
2
0:25d
s; hb
d
p; hb
2
43
Fig. 2.11. Closed-loop liquidliquid equilibria in the PEG
water system. Symbols: experimental data, M 3:35 kg mol
1
(0), M 8 kg/mol (5), M 15 kg/mol (4); curves tted using
Eq. (37c). Reproduced with permission from Ref. 29.
These authors showed that for a number of polymersolvent system with a 0:6
this method performs similarly to group contribution methods using volume frac-
tions to represent the segment fractions in the FloryHuggins model. Values of
solubility parameters are tabulated by Barton [36].
2.3.3
Correlation of Solvent Activities
The combination of Eq. (35) with one of the Eqs. (36) or similar empirical equa-
tions is not very successful for describing the phase behavior of polymersolvent
systems with strong interactive species and of systems which only dier in mo-
lecular weight. Since the mid-1990s activity coecient models have been proposed
based on a combination of the FloryHuggins type of expression for the combina-
torial entropy of mixing and segment-based local composition models to account
for the contribution from energetic interactions (the residual contribution to the
activity coecient).
In 1993 Chen [37] proposed a correlative model that used a combination of the
FloryHuggins expression for the combinatorial entropy of mixing and the non-
random two-liquid (NRTL) theory [38]. The same approach was followed by Wu
et al. [39]. These authors used Freeds expression [41, 42] for the combinatorial
entropy of mixing, which is more accurate than the FloryHuggins expression, in
combination with the NRTL theory. The nonrandom factor model of Haghtalab
and Vera [42] was modied by Zafarini-Moattar and Sadeghi [43] for polymer solu-
tions. In 2004, Pedrosa et al. [44] suggested use of the UNIQUAC theory [45] in-
stead of the NRTL theory and tested various combinations of combinatorial con-
tributions and residual contributions using a database of 70 low-pressure VLE
systems. These authors have concluded that the combination of a segment-based
NRTL or UNIQUAC residual term with a good combinatorial term is able to pro-
duce the best correlations of experimental VLE data and can also be used to predict
the inuence of the molecular weight of the polymer on polymersolvent VLE.
As an example we will give here the expression for the activity coecient of the
solvent for a model which combines the p free-volume combinatorial term with a
segment-based Wu-NRTL residual term [44]. The p free-volume combinatorial
term combines combinatorial contributions and free-volume contributions [45].
The activity coecient of the solvent is given by Eq. (44).
ln g
s
ln g
combfv
s
ln g
res
s
44
The combinatorial/free-volume term is given by Eq. (45).
ln g
combfv
s
ln
f
fv
s
x
s
1
f
fv
s
x
s
45
The free-volume fraction f
fv
s
is calculated from Eq. (46).
f
fv
i

x
i
v
fv
i
X
j
x
j
v
fv
i
46
The free volume of a component is dened by Eq. (47), where v
i
is the molar
volume of liquid component i, v
i; vdW
is the hard-core volume or van der Waals
volume of this component and can be calculated using the Bondi tables [46], and
p is a correction factor, which is calculated from Eq. (48) in the p free-volume
model [45].
v
fv
i
v
i
v
i; vdW
p
47
p 1
v
s
v
p
48
The residual term is given by Eq. (49) together with Eqs. (50), where a
sp
and a
ps
are
adjustable interaction parameters, a is the NRTL-nonrandomness parameter,
which was xed by Pedrosa et al. at 0.4.
ln g
res
s
q
s
X
2
p
t
ps
G
2
ps
X
s
X
p
G
ps
2

t
sp
G
2
sp
X
p
X
s
G
sp
2
" #
49
t
ij
exp
a
ij
RT

and G
ij
expat
ij
50
X
i
is the eective mole fraction of segments of species i and q
i
is the eective seg-
ment number of species i, which are given by Eqs. (51) and (52); r
s
1 and r
p
r.
X
i

x
i
q
i
X
j
x
j
q
j
51
q
i
r
i
1 2a 1
1
r
i
!
52
2.3.4
Group Contribution Models
Thermodynamic properties can be predicted from group contribution methods.
In these models molecules are divided in functional groups. Group contribution
models for activity coecients consider the interactions between functional groups
rather than between molecules. Since the number of functional groups is much
lower than the number of possible molecules composed of these groups, only a
limited number of group interaction parameters have to be known to describe a
large number of systems. These group interactions are obtained from regression
of experimental data. This makes the group contribution methods purely predic-
tive. However, since details of molecular structure are not considered, group contri-
bution methods for activity coecients are in general less accurate than correlative
models.
Oishi and Prausnitz [47] proposed writing the solvent activity coecient for
polymersolvent systems as the sum of three terms [Eq. (53)].
ln g
s
ln g
comb
s
ln g
fv
s
ln g
res
s
53
The combinatorial contribution g
comb
s
accounts for dierences in size and shape
of the molecules. The free-volume contribution g
fv
s
accounts for changes in free
volume due to mixing, caused by the large dierence between the free volumes of
pure solvent and polymer. For ordinary liquid mixtures in far from critical condi-
tions, this term is usually negligible. The residual contribution g
res
s
accounts for
energy interactions. In the approach of Oishi and Prausnitz, the combinatorial con-
tribution is represented by the StavermanGuggenheim expression, a modication
of the FloryHuggins equation, also used in the UNIFAC group contribution
model [48]; for the residual contribution also, the corresponding expression of the
UNIFAC model is used. The free-volume contribution is calculated from the Flory
equation of state [49]. This group contribution model and those of Chen et al. [50]
and Danner and High [51] are discussed in Ref. 4. Here we will discuss the en-
tropic free volume model of Elbro et al. [52] and Kontogeorgis et al. [53], and the
group contribution Flory (GCFlory) model of Bogdanic et al. [54, 55], which is a
modication of the model of Chen et al. [50].
In the entropic-free volume model, the activity coecient of the solvent is given
by Eqs. (44)(48) with p 1 [52]. The residual contribution is represented by the
residual contribution of the UNIFAC model with temperature-dependent interac-
tion parameters [53]. The liquid molar volumes needed for the calculation of the
free volume of a component can be taken from experiment or calculated from the
Tait equation [4] or by the group contribution method of Elbro et al. [56]. This
model is relatively easy to use.
In the GCFlory model, the solvent activity coecient is calculated from Eq.
(53).
The combinatorial term is calculated by means of the original FloryHuggins ex-
pression, Eq. (54).
ln g
comb
i
ln
f
i
x
i
1
f
i
x
i
54
The free-volume and residual terms are calculated from a modication of the orig-
inal Flory equation of state, Eq. (55), where ~vv is the reduced volume, dened by Eq.
(56).
P
RT
v
~ vv
1/3
C
~ vv
1/3
1

E
attr
v
55
~ vv
v
v
56
The molar hard-core v
is calculated from the pure component hard-core molar

volumes v
i
using a linear mixing rule [Eq. (57)]. The same type of mixing rule is
used for the number of external degrees of freedom parameter C [Eq. (58)].
v

X
i
x
i
v
i
57
C
X
i
x
i
C
i
58
The pure component hard-core volumes and C parameters are calculated from the
group contribution expressions in Eqs. (59) and (60),
v
i
21:9662
X
m
u
i
m
R
m
59
C
i

X
n
u
i
n
C
T0; n
C
T; n
1
T

1
T
0
!
X
n
R
n
X
m
R
m
C
0
n
60
where u
i
n
is the number of groups of type n in molecule i and T
0
is a reference
temperature. R
n
is the normalized van der Waals volume of group n as used in
the UNIFAC method. The attraction term E
attr
is related to the UNIFAC model
by Eq. (61), z is the lattice coordination number, chosen to be equal to 10, and q
i
,
the surface area of molecule i, is given by Eq. (62)
E
attr
X
i
1
2
zq
i
x
i
e
ii

X
j
y
j
expDe
ji
/RTDe
ji
X
k
y
k
expDe
ki
/RT
2
6
6
6
4
3
7
7
7
5
3R ln
~ vv
1/3
1
~ vv

X
i
x
i
X
n
u
i
n
C
T; n

61
q
i

X
n
v
i
n
Q
n
62
Q
n
is the normalized van der Waals surface of group n, as in UNIFAC. The inter-
action energy parameters e
ji
and De
ji
are given by Eqs. (63), in which e
0
ij
is calcu-
lated from a group contribution expression [Eq. (64), together with Eq. (65)].
e
ij

e
0
ij
~ vv
and De
ij
e
ij
e
ii
63
e
0
ji

X
m
y
i
m
X
n
y
j
n
e
nm
64
e
nm
e
nn
e
mm
1/2
De
nm
65
In these expressions the volume fraction f
i
of molecule i, the segment fraction y
i
of molecule i, and the segment fraction y
i
n
of n in molecule i are dened by Eqs.
(66)(68).
f
i

x
i
v
i
X
j
x
j
v
j
66
y
i

x
i
q
i
X
j
x
j
q
j
67
y
i
n

u
i
n
Q
n
X
m
u
i
m
Q
m
68
Note that indices m and n refer to groups m and n, and i and j to molecules i
and j.
The resulting expressions for the free-volume contribution and the residual con-
tribution in the activity coecient are Eqs. (69) and (70).
ln g
fv
i
31 C
i
ln
~ vv
1/3
i
1
~ vv
1/3
1
!
C
i
ln
~ vv
i
~ vv
69
ln g
res
i

1
2
zq
i
2
4
1
RT
e
ii
~ vv e
ii
~ vv
i
1 ln
X
j
y
j
expDe
ji
/RT
X
j
y
j
expDe
ji
/RT
X
k
y
k
expDe
ki
/RT
3
5
70
To apply this method, the liquid molar volumes of the mixture and of the pure
components need to be known. At a given pressure and temperature these values
can be calculated from the equation of state. However, since e
ji
according to Eq.
(63) is volume-dependent, this involves an iterative procedure similar to that
described by Danner and High [4] for the method of Chen et al. [50]. Figure
2.12 shows the experimental solvent activity of the system poly(propylene oxide)
benzene at 347.85 K compared to the correlation by UNIQUAC and predictions by
the GCFlory model. The result of the correlation is almost perfect. The predicted
solvent activities by the GCFlory model are also very close to the experimental
values. In Figure 2.13 a comparison is shown of experimental solvent activity
coecients at innite dilution and predictions by the GCFlory model [54] for
homopolymersolvent systems, demonstrating that the results of predictions are
good. The predictions for copolymer solutions are slightly worse [55].
2.4
Equation of State Models
High-pressure phase equilibria in systems of polymers, solvents, and supercritical
gases are in almost all cases modeled using equations of state. A review of equa-
tions of state for polymer systems, including a discussion of their theoretical back-
ground, has been given by Lambert et al. [6]. One of the rst equations of state that
was used to model the high-pressure phase behavior of polymersolvent systems
was the Flory equation of state [11, 12]. Patterson and Delmas [10] showed that
this equation of state can be used to describe both LCST and UCSTphase behavior.
The perturbed hard-chain theory (PCHT) was developed by Prausnitz and co-
workers [5759]. It can be considered as an improvement of the approach of Flory
Fig. 2.12. Activity of benzene in the poly(propylene oxide)
benzene system at 347.85 K. M
n
500 kg mol
1
. Symbols:
experimental data; curves: UNIQUAC correlation and GCFlory
prediction. Reproduced with permission from Ref. 54.
and co-workers and can be used to model the phase behavior of mixtures of small
and large molecules, including polymers, over a wide range of pressure and tem-
perature [5760]. Here, we will discuss only the two equations of state methods:
the relatively simple SanchezLacombe (SL) lattice uid model [61, 62], and the
statistical associating-uid theory (SAFT) [63, 64], which has now become one of
the standard equations of state for polymer solutions.
2.4.1
The SanchezLacombe Lattice Fluid Theory
Like the FloryHuggins model, the SanchezLacombe lattice uid theory is based
on the assumption that segments of solvent molecules and polymer molecules oc-
cupy the lattice sites of a rigid lattice, but vacant lattice sites are also allowed. The
number of vacant lattice sites, and as a consequence the total number of lattice
sites, are pressure-dependent, and in this way compressibility is introduced.
log
exp
l
o
g

c
a
l
Fig. 2.13. Comparison of calculated activity coecients at
innite dilution using the GCFlory model with experimental
values for many polymersolvent systems. Reproduced with
The resulting equation of state for a pure component is given by Eq. (71).
~ pp~ vv
~
TT
1
r
1 ~ vv ln 1
1
~ vv
!
1
~ vv
~
TT
71
The reduced volume ~ vv, the reduced pressure ~ pp, and the reduced temperature
~
TT are
dened by Eqs. (72a)(72c).
~ vv
v
v

n
0
rn
rn
72a
~ pp
P
P

Pv
72b
~
TT
kT
T
72c
The parameters with an asterisk (
) are the so-called characteristic parameters. In

practice r, the number of segments per molecule, e
, the interaction energy param-

eter, and v
, the molar volume of a lattice site, are used as the independent pure-
component parameters; n is the number of moles of the component and n
0
is the
number of moles of vacant lattice sites. If v is the volume per mole of segments,
the total volume of the system is given by V nrv. For high molecular weights r
is large, so it can be concluded from Eq. (71) that the density of polymer melts is
not very dependent on molecular weight and that the PVT behavior of polymer
melts follows the corresponding states principle (see Figure 2.14) [62].
For mixtures the same equation of state is used, but the characteristic parame-
ters r; e
, and v
are composition-dependent. Neau [65] gives an overview of dier-

ent mixing rules proposed in the literature. Often-used mixing rules are given in
Eqs. (73)(75). In Eq. (75) k
ij
is an adjustable binary interaction parameter which
equals zero for i j and which can tted to binary experimental data.
r
X
x
i
r
i
73
v

X
j
i
v
i
74
e

XX
j
i
j
j
ii
e
jj
q
1 k
ij
75
The segment fraction j
i
of component i is given by Eq. (76).
j
i

x
i
r
i
X
x
i
r
i
76
Neau [65] also showed that the expressions for the chemical potential used in
earlier literature to calculate phase equilibria are thermodynamically inconsistent.
According to Neau, the correct expression for the fugacity coecient for the SL
model is Eq. (77).
Fig. 2.14. Corresponding states behavior of various liquid
polymer PVT data according to the SanchezLacombe model.
Symbols represent experimental data; curves are calculated
from Eq. (71). Reproduced with permission from Ref. 62.
ln ^ jj
i
ln z r
i
2
1
~ vv
~
TT
ln 1
1
~ vv
!
z 1
X
x
j
r
j
!
nr
v
qv
qn
i

n
j
0n
i
" #
1
~ vv
~
TT
nr
e
qe
qn
i

nj 0n
i
" #
77
The compressibility factor z is given by Eq. (78).
z
Pv
RT

~ pp~ vv
~
TT
r 78
In Figure 2.15 [66] experimental isothermal cloud-point curves of the linear low
density polyethylene hexane system are compared with the results of a t of
these data using the SanchezLacombe equation of state. The pure component
parameters of hexane were calculated from the critical point of hexane and its
acentric factor [67]. The pure component parameters of the polymer were obtained
from a simultaneous t of PVT data and the data presented in Figure 2.15. The
equations solved were those described by Koak and Heidemann [68]. The binary
interaction parameter was linearly dependent on temperature. The polymer was
0
1
2
3
4
5
6
7
8
9
10
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35
Weight fraction LLDPE
P

/

M
P
a
450 K
470 K
490 K
Critical Point
Cloud Point
Spinodal
Critical Point
Fig. 2.15. Isothermal cloud-point curves of LLDPE n-hexane.
Symbols: experiments; curves: modied SanchezLacombe t.
[66].
represented by 36 pseudo-components. The SL theory is very well able to describe
the experimental phase behavior.
2.4.2
Statistical Associating-uid Theory
The statistical associating-uid theory (SAFT) developed by Chapman et al. [63, 64]
is based on the thermodynamic perturbation theory of Wertheim [69]. Since it
rst appeared, many dierent versions of SAFT have been published. The dierent
SAFT versions and their application have been reviewed by Muller and Gubbins
[70].
For polymer solutions the SAFT version of Huang and Radosz [71, 72] is the
most widely used. In 2000, a promising new version of SAFT for polymer solutions
called PC-SAFT (perturbed chain-SAFT), was proposed by Gross and Sadowski
[73]. Here we will restrict ourselves to these two SAFT versions.
The basics of both equations of state are equal, and can be written as separate
contributions to the molar Helmholtz energy a. The molar residual Helmholtz en-
ergy a
res
, which is the dierence between the molar Helmholtz energy of the sys-
tem and the molar Heltmholtz energy of the same system in the ideal gas state in
the same conditions of temperature, pressure, and composition, is calculated as
the sum of the contributions of a hard chain term a
hc
, a dispersion term a
disp
, and
an association term a
assoc
[Eq. (79)].
a
res
a a
ig
a
hc
a
disp
a
assoc
79
From this expression the pressure and chemical potential can be derived [Eqs.
(80) and (81), respectively] using standard thermodynamic relationships
(A
P
n
i
a).
p
qA
qV

T; n
80
m
i

qA
qn
i

V; T; n
j0i
81
For polymer solutions the association term is normally not used. The two SAFT
versions discussed here do not explicitly account for polarity and dier only in the
way the dispersion contributions are calculated.
2.4.2.1 SAFT and PC-SAFT Hard Chain Term
In the molecular picture behind SAFT a chain consists of m
i
hard-sphere seg-
ments. These hard-sphere segments are bonded by covalent bonds. The hard-
sphere term of both SAFT versions is the sum of two contributions: a hard-sphere
contribution and a term due the connectivity of these hard-sphere segments, as
given by Eq. (82), where m is the average chain length of the molecules in the mix-
ture [Eq. (83)] [64].
a
hc
RT
m
a
hs
RT

a
chain
RT
82
m
X
x
i
m
i
83
The hard-sphere contribution a
hs
is represented by the BoublikMansoori hard-
sphere equation of state for mixtures of hard spheres, Eq. (84) [74, 75].
a
hs
RT

6
pr
z
3
2
3z
1
z
2
z
3
3z
1
z
2
z
2
3
z
3
1 z
3
2

z
3
2
z
2
3
z
0

ln1 z
3
" #
84
In this equation z
k
is given by Eq. (85), where r is the number density, d
ii
is
the temperature-dependent hard-sphere diameter obtained from Eq. (86); m
i
, the
hard-sphere diameter s
i
, and the energy parameter e
i
are pure component pa-
rameters.
z
k

p
6
r
X
x
i
m
i
d
ii
k
85
d
ii
T s
i
1 0:12 exp
3e
i
kT
!
86
The chain term a
chain
is given by Eq. (87), where gd
ii
hs
is the so-called hard-
sphere radial distribution function at close contact [Eq. (88)] [74, 75].
a
chain
RT

X
x
i
1 m
i
lngd
ii
hs
87
g
hs
ij

1
1 z
3

d
i
d
j
d
i
d
j
3z
2
1 z
3

d
i
d
j
d
i
d
j

2
3z
2
2
1 z
3
3
88
2.4.2.2 SAFT Dispersion Term
In the Huang and Radosz version of SAFT [71, 72] the ChenKreglewski disper-
sion term is used. This term is obtained from a t to the physical property data of
argon and is given by Eq. (89) [76], where t is a constant equal to 0.74048. The con-
stants D
ij
are given by Chen and Kreglewski [76].
a
disp
RT

X
4
i1
X
9
j 1
D
ij
u
kT
!
i
z
3
t
!
j
89
For mixtures, the van der Waals one-uid mixing rules or the volume fraction mix-
ing rules can be used.
The van der Waals mixing rules are given by Eq. (90), where the combining rules
are Eqs. (91) and (92), in which k
ij
is an adjustable binary interaction parameter.
u
kT

X
i
X
j
x
i
x
j
u
ij
kT
!
d
3
ij
X
i
X
j
x
i
x
j
d
3
ij
90
d
ij

d
i
d
j
2
91
u
ij
1 k
ij
u
ii
u
jj
p
92
The volume fraction mixing rules are given by Eq. (93), with volume fractions de-
ned by Eq. (94).
u
kT

X
i
X
j
f
i
f
j
u
ij
kT
93
f
i

x
i
m
i
d
3
i
X
j
x
j
m
j
d
3
j
94
The combing rule for u
ij
is again given by Eq. (92).
2.4.2.3 The PC-SAFT Dispersion Term
In SAFT the dispersion term represents the interactions between individual seg-
ments, while in PC-SAFT the dispersion term represents the interactions of chains
of segments. The expression for a
disp
derived by Gross and Sadowski is Eq. (95),
where the terms on the right-hand side are dened by Eqs. (96) and (97).
a
disp
RT

a
1
RT

a
2
RT
95
a
1
RT
2prm
2
u
kT

s
3
X
6
i0
a
i
mh
i
96
a
2
RT
prm 1 m
8h 2h
2
1 h
4
1 m
20h 27h
2
12h
3
2h
4
1 h
2
2 h
2
" #
1
m
2
u
kT

2
s
3
X
6
i0
b
i
mh
i
97
The reduced uid density h is dened by Eq. (98), in which N
Av
is Avogadros
number.
h
pN
Av
6
rmd
3
98
The parameters a
i
and b
i
are dependent on m, as Eqs. (99) and (100) state.
a
i
m a
0i

m 1
m
a
1i

m 1m 2
m
2
a
2i
99
b
i
m b
0i

m 1
m
b
1i

m 1m 2
m
2
b
2i
100
The constants a
0i
b
2i
are tted to the thermophysical properties of n-alkanes and
are given by Gross and Sadowski [73].
2.4.2.4 SAFT and PC-SAFT Applications
Both SAFT and PC-SAFT contain pure component parameters: the energy parame-
ter e or u, the hard-sphere diameter s, or the hard-sphere volume v
00
, and the num-
ber of segments m per molecule. For small (solvent) molecules these parameters
are obtained from a t of vapor pressure data and saturated liquid volume data.
Since they do not have a vapor pressure, this t is not possible for polymers, and
the pure component polymer parameters are obtained from a t to PVT data of the
molten polymer or from a t to PVT data and binary phase equilibrium data. For
the description of a mixture one needs one binary interaction parameter k
ij
per
binary, which has to be tted to phase equilibrium data. If necessary, k
ij
can be
made temperature-dependent. In general, phase equilibria are very sensitive to
the k
ij
value.
In Figure 2.16 [77], experimental results from a system of ethylene HDPE are
compared with modeling results using SAFT and SanchezLacombe models. In
both cases k
ij
is taken to be linearly dependent on temperature. Due to the polydis-
persity of the polymer, the cloud-point curves show a dip in which the critical point
is located. If in the modeling the polymer is assumed to be monodisperse, this
behavior cannot be reproduced. The gure shows that both SAFT and Sanchez
Lacombe models give a reasonable description of the experimental phase behavior,
although at high and low polymer concentrations the deviations become larger.
The same system was modeled by Tumakaka et al. [78] using SAFT and PC-
SAFT. The results are presented in Figure 2.17, which clearly shows that in this
case PC-SAFT gives a better result than SAFT. In the same paper these authors
present PC-SAFT modeling results for LDPE solvent systems at constant poly-
mer concentration. The pure LDPE parameters were tted to the experimental
data of ethane LDPE. These parameters were subsequently used to describe the
LDPE ethane, propene, propane, butane, and 1-butene systems, using a
temperature-independent k
ij
. The results are very good (see Figure 2.18), but it
should be kept in mind that the modeling is restricted to one polymer concen-
tration.
2.4.2.5 Extension to Copolymers
For the modeling of the phase behavior of copolymersolvent systems, the copoly-
mer can be treated as a homopolymer with eective pure component parameters.
Examples of this approach are given by McHugh and co-workers [79, 80]. The dis-
advantage of this approach is that the pure component polymer parameters depend
on the type and composition of the copolymer. Pure component polymer parame-
ters are obtained from binary polymersolvent phase equilibrium data. With these
parameters it is possible to model the phase behavior of the same polymer with
another solvent.
A better approach is the copolymer SAFT approach of Radosz and co-workers
[8183], in which the copolymer parameters are estimated on the basis of the mo-
lecular weight and structure only. For an AB-type copolymer there are three binary
interaction parameters, the interaction parameters between A segments and seg-
ments of the solvent molecule, the interaction parameter between B segments
Fig. 2.16. Isothermal cloudpoint curves of the
HDPE ethylene system. M
n
43 kg mol
1
, M
w
118
kg mol
1
, M
z
231 kg mol
1
. Symbols: experimental data;
curves: modeling results: (a) SAFT model; (b) Sanchez
Lacombe model. Reproduced with permission from Ref. 77.
and segments of the solvent molecule, and the interaction parameter between A
and B segments. The rst two binary interaction parameters can be obtained from
the phase behavior of the two homopolymer systems, while the third has to be
tted to some copolymersolvent data. Once these parameters are known, predic-
tions can be made for copolymersolvent systems with the same type of copolymer
but with a dierent copolymer composition. The same approach was followed by
Gross et al. [84] for the PC-SAFT model. The result is known as copolymer PC-
SAFT. The two parameters that characterize the polymer structure are the fraction
of type A segments in the polymer molecule and the bonding fraction which gives
the fraction of bonds between segment types A and B. The original literature gives
details.
Figures 2.19 and 2.20 show experimental cloud-point curves and PC-SAFT mod-
eling of the ethylene poly(E-co-EA) and ethane poly(E-co-BA) systems, respec-
tively [85], at a polymer concentration of 5 wt.%. The model correctly predicts
the change in the location of the cloud point with changing comonomer concentra-
tion in the polymer. Especially interesting is the ethylene poly(E-co-EA) system,
in that the curve of cloud-point pressure as a function of the EA concentration in
the polymer shows a minimum. This behavior is correctly described by the model.
Fig. 2.17. Isothermal cloud-point curves of the
HDPE ethylene system. M
n
43 kg mol
1
, M
w
118
kg mol
1
, M
z
231 kg mol
1
. Symbols: experimental data;
curves: modeling results. Reproduced with permission from
Ref. 78.
2.5
Conclusions
Polymersolvent systems behave in many respects in the same way as systems of
low molecular weight components. Dierences between polymersolvent systems
and low molecular weight systems are mainly caused by the fact that polymers
have no vapor pressure, that polymers are composed of many components of
dierent molecular weights, and that there is a large dierence between the free
volumes of the solvent and of the polymer.
The thermodynamic models for polymersolvent systems are less advanced than
for systems of low molecular weight compounds. In general low-pressure vapor
liquid equilibria can be described very well with a variety of models. Once the ad-
justable parameters in these models are tted to experimental data, reliable predic-
tions can be made for other conditions, for example at a dierent temperature or
for a system with the same solvent and the same type of polymer with a dierent
Fig. 2.18. Constant composition cloud-point curves of LDPE
solvent systems at 5 wt.% polymer. Symbols: experimental
data; curves: modeling results using PC-SAFT with one
temperature-independent k
ij
for each system. Reproduced with
molecular weight. Vaporliquid-equilibria can be predicted with dierent group
contribution models. Most recent models give reliable predictions of comparable
accuracy for dierent polymersolvent systems. A disadvantage of this type of
model is that the parameters for the groups of interest should be available.
In general the thermodynamic modeling of low-pressure liquidliquid equilibria
is more dicult than for vaporliquid equilibria. This also holds for polymer
solvent systems. Reliable prediction methods are not available. The correlation of
liquidliquid data using the extended FloryHuggins type models [2729] gives
reasonably good results. Again, once the adjustable parameters in these models
are known, predictions can be made for other conditions.
High-pressure uid-phase equilibria can only be modeled using equations of
state. However, the equation of state models contain adjustable binary interaction
parameters that have to be tted to data. Small variations in these parameters in
general have a large inuence on the predicted phase equilibria. The most promis-
ing models for high-pressure phase equilibria of polymer solutions are the SAFT
and the PC-SAFT ones.
Fig. 2.19. Constant composition cloud-point
curves for poly(E-co-EA)ethylene systems with
dierent repeat-unit compositions at 5 wt.%
polymer. The copolymer molecular weight is in
the range 113157 kg mol
1
. Symbols:
experimental data; curves: PC-SAFT
calculations. Reproduced with permission from
Ref. 85.
2.5 Conclusions 51
Notation
Symbols
a activity, molar Helmholtz energy
A Helmholtz energy
C number of external degrees of freedom
d temperature-dependent hard-sphere diameter
D constant
f
C
fugacity
g molar Gibbs energy; interaction parameter; radial distribution
function
G Gibbs energy
G
ij
NRTL parameter
G Gibbs energy per mole of lattice sites
k Boltzmanns constant
k
ij
binary interaction parameter
m number of polymer components; number of segments
M molecular weight
n number of moles
Fig. 2.20. Constant composition cloud-point
curves for poly(E-co-BA)ethylene systems with
dierent repeat-unit compositions at 5 wt.%
polymer. The copolymer molecular weight is in
the range 155283 kg mol
1
. Symbols:
experimental data; curves: PC-SAFT
calculations. Reproduced with permission from
Ref. 85.
N number of components
p correction factor
P pressure
q eective segment number; surface area
Q normalized van der Waals surface
r number of segments in a molecule
r
n
number-average chain length
R gas constant
R
m
; R
n
normalized van der Waals volume
T absolute temperature
u energy parameter
v molar volume
V volume
w weight fraction
x; y mole fraction
X segment fraction
z lattice coordination number; compressibility factor
Greek
a NRTL nonrandomness parameter
a; b; p phase
g activity coecient (mole fraction basis)
d solubility parameter; density
e energy parameter
y theta temperature; segment fraction
j segment fraction; volume fraction
f
C
fugacity coecient
m chemical potential
W activity coecient (weight fraction basis)
s temperature-independent hard-sphere diameter
t NRTL interaction parameter; constant in SAFT
z density-related variable [Eq. (85)]
h reduced density
u number of groups
w interaction parameter
Subscripts
d dispersion
hb hydrogen bonding
i; j component
mix mixing
p polymer; polar
s solvent
vdW van der Waals
Notation 53
Superscripts
0 standard state
hard core, indicates characteristic parameter

@ reduced
assoc association
attr attraction
chain chain formation contribution
comb combinatorial
crit critical
disp dispersion
E excess
fv free volume
hc hard chain
hs hard sphere
id ideal mixture
ig ideal gas
L liquid
res residual
sat saturated
V gas; vapor
Acronyms
LCST lower critical solution temperature
LDPE low-density polyethylene
LLDPE linear low-density polyethylene
LLE liquidliquid equilibria
NRTL nonrandom two-liquid
PCHT perturbed hard-chain theory
poly(E-co-BA) poly(ethylene-co-BA)
poly(E-co-EA) poly(ethylene-co-EA)
SAFT statistical associating-uid theory
SL SanchezLacombe lattice uid model
UCST upper critical solution temperature
VLE vaporliquid equilibria
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3
Polycondensation
1
Mario Rui P. F. N. Costa and Rolf Bachmann
3.1
Basic Concepts
3.1.1
A Brief History
The concept of producing larger molecules starting from smaller ones containing
suitable groups (such as carboxyls and hydroxyls), by reaction to create a bond be-
tween inert chemical moieties by splitting o a smaller molecule (a condensation),
can be traced back to the middle of the nineteenth century [1]. It was discovered
when preparing oligomers of ethylene glycol, but, in spite of the good impact the
work had at that time, it fell into oblivion a little later. Phenolformaldehyde (in
the form of resins and varnishes) was the rst commercial product (in 1907) con-
sisting of an entirely synthetic polymer [2]; its formation was also an example of
polycondensation; but this early development was purely empirical and contrib-
uted very little to scientic progress.
Staudingers concept of the existence of macromolecules came two decades later
[3]. It paved the way to the systematic study aimed at producing synthetic bers
carried out by Carothers at DuPont in the late 1920s and early 1930s [4], from
which stems the still-used concepts of addition and condensation polymerizations.
In his famous book, Flory [5] justly criticized this terminology, since closely
related polymerization mechanisms involving reactions of groups with active hy-
drogen atoms with epoxides and isocyanates do not lead to the splitting of a by-
product; he proposed a classication into step growth and chain growth poly-
merization. These expressions became widely used, even if they are quite vague;
much better would be random and sequential polymerization [6].
A survey of important examples of polycondensation reactions can be found in
Table 3.1.
ISBN: 3-527-31014-2
57
In some polycondensations, new functional groups are created by reactions of
the monomers. Thus, methylol end groups are formed by the initial reactions of
formaldehyde with other monomers, and their condensation reactions shown
in the last two rows of Table 3.1 occur in later stages of formaldehyde/urea and
formaldehyde/phenol polymerizations (see Section 3.3.4).
Tab. 3.1. A survey of technically important polycondensation reactions.
Functional groups or monomers Connecting group By-product
aCOOH
Carboxylic acid
aOH
hydroxyl
aCOOa
ester
H
2
O
aCOOR
Ester
aOH
hydroxyl
aCOOa
ester
RaOH
aCOOH
Carboxylic acid
aNH
2
primary amine
aCONHa
amide
H
2
O
ClCOCl/aCOCl
Phosgene/chloroformate
aOH
hydroxyl
O
C
O O
carbonate
HCl
Na
2
S/aSNa
Di-sodium sulde
monomer/sodium sulde
end group
aCl
chloro end group (as in
ClC
6
H
4
Cl)
aSa
sulde
NaCl
NaOa
Sodium alkoxide/phenoxide,
e.g.,
NaO C
CH
3
CH
3
ONa
aCl
chloro end group, e.g.,
Cl S
O
O
Cl
aOa
ether
NaCl
aNbCbO
Isocyanate
aOH
hydroxyl
O
C
NH O
urethane
none
aNbCbO
Isocyanate
aNH
2
primary amine
O
C
NH NH
urea
none
CH
O
CH
2
1,2-epoxide
aNHa
secondary amine CH
OH
CH
2
N
b-hydroxy-t-amine
none
aCH
2
OH
Methylol
(NH
2
)
2
CO/NH
2
CONHa
urea/N-alkylurea
O
C
NH CH
2
NH
N,N
/
-dialkylurea
H
2
O
AraCH
2
OH
Aromatic methylol
Ar
/
aCH
2
OH
aromatic methylol
AraCH
2
aAr
/
HCHO
58 3 Polycondensation
3.1.2
Molecular Weight Growth and Carothers Equation
Carothers was mainly interested in polyesterications, and later in polyamidations,
of compounds with the structures AXA and BYB, or sometimes AXB, in which X
and Y are inert chemical moieties whereas A and B are the active carboxyl and hy-
droxyl or amine groups, giving rise to a connecting ester or amide group Z and
splitting o a by-product (water) W [Eq. (1)].
A B Z W (1)
If reacting groups A and B do not belong to the same molecule, and thus do not
create a ring, this reaction leads to a decrease of one polymer molecule (compris-
ing the starting monomers).
A count of the polymer molecules and their mass in the system can easily be
carried out with the help of p, the conversion of reference groups A. Starting with
1 mol of monomer AXB, the remaining moles of polymer are 1 p. Polymer mass
per mole of AXB is equal to its molecular weight M
AXB
, minus the mass lost in by-
product formation, p M
W
, yielding Eq. (2), allowing the number-average molecu-
lar weight (mass of polymer/moles of polymer) to be predicted.
M
n
=
M
AXB
pM
W
1 p
(2)
With two monomers, on introduction of the initial stoichiometric ratio
r = [B[
0
/[A[
0
between mole concentrations of groups A and B, a similar reasoning
leads to Eq. (3).
M
n
=
M
AXA
rM
BYB
2pM
W
1 r 2p
(3)
High molecular weights (say, above 20 000, needed for use as bers) are possible
only by reaching high conversions when monomer molecular weights are a few
hundreds. With two dierent monomers, stoichiometric ratios very close to unity
are also needed. Well-known relationships for number-average degree of polymer-
ization x
n
are obtained from Eqs. (2) and (3) by replacing the molecular weights of
monomers by 1 and the molecular weight of by-product by 0.
The eect of ring formation on M
n
of open chain molecules can be taken into
account by introducing p
c
, the conversion of end groups yielding rings, in Eqs.
(2) and (3). For instance, when there are two monomers AXA and BYB, Eq. (4) is
obtained.
M
n
=
M
AXA
(1 p
c
) (r p
c
)M
BYB
2(p p
c
)M
W
1 r 2(p p
c
)
(4)
Prediction of p
c
and the average molecular weight of rings is not a trivial task.
Carothers has stated that the fraction of rings in bulk polycondensations is negligi-
ble, except when ve- or six-membered rings (or higher in the case of rings con-
taining Si, P, and similar heavier elements lower in the periodic table) can result.
Recent experimental results show this concept is not valid in the case of irrevers-
ible polycondensations (see Section 3.1.7).
Monomers with three or more functional groups lead to the formation of
branched polymers. A network of macroscopic dimensions (a gel) appears for
high enough conversions and monomer branching. In Figure 3.1 are presented
classical predictions (see Section 3.4.3), of average degrees of polymerization and
weight fraction of nite molecules (sol fraction) for the single monomer polycon-
densations of XA
3
and XA
2
. Notice that, in contrast with linear polycondensations,
which require high conversions for obtaining high values of x
n
, low-value maxima
(4 if f = 3) at gel point are observed with these nonlinear polycondensations.
Close to full conversion, the sol is nearly pure unconverted monomer.
Stockmayer [7] has obtained the distribution for the fractions of the initial mono-
mer units present in each nite polymer molecules (Eq. (5), where P
x
is the set of
isomers with x repeating units X).
x[P
x
[/[X[ =
f ( fx x)!
x!( fx 2x 2)!
xp
x1
(1 p)
x( f 2)2
(5)
Fig. 3.1. Average degrees of polymerization and sol fraction in
XA
f
polycondensations without intramolecular reaction, versus
conversion p of A groups with monomer functionalities f = 2
and f = 3, for equilibrium or batch reaction starting from
monomer.
If the functionality f = 2, the even more notorious SchulzFlory [8] distribution is
obtained [Eq. (6)].
x[P
x
[/[X[ = x(1 p)
2
p
x1
(6)
This latter distribution has a relative maximum for x Gx
n
, in contrast to the gen-
eral Stockmayer distribution, which decreases monotonically (see Figure 3.2).
More complex chemical systems lead to molecular weight distributions that are
qualitatively similar: linear polycondensations have most often geometrical or
nearly geometrical distributions with polydispersities M
w
/M
n
close to 2, whereas
nonlinear polycondensations lead to extremely broad distributions near the gel
point, but always dominated in number and even in weight by the lower molecular
weight species.
This chapter concentrates on processes for making either high molecular weight,
mainly linear polymers, or else low molecular weight, branched oligomers which
will be later used to form networks. In any case, consideration of initial stoichiom-
etry, and possible change of functionality due to side reactions, is essential to pre-
dict average molecular weights, and to avoid premature gelation in the processes
described here.
It is also possible to prepare low molecular weight mixtures of ring molecules for
further reactive processing (using, for instance, anion polymerization), starting
Fig. 3.2. Equilibrium distributions of monomer units x [P
x
[=[X[
for XA
f
polycondensations without intramolecular reaction
versus conversion p of A groups with monomer functionalities
f = 2 and 3.
with monomers [8] or even with recycled polymer [9], by dilution with inert sol-
vents and a suitable catalyst (see also Section 3.1.7). The discussion of these other-
wise interesting processes falls outside the scope of this chapter.
3.1.3
The Principle of Equal Reactivity and the Prediction of the Evolution of Functional
Group Concentrations
Carothers successful synthesis of high molecular weight, aliphatic polyesters could
only be carried out thanks to his care in reducing the eect of the hydrolysis reac-
tion through use of high vacuum. Further research carried out by his former col-
laborator P. J. Flory in order to assess the eect of molecular weight on chemical
kinetics would eventually lead to the establishment of the principle of equal reac-
tivity. A parallel research, which also has contributed to the establishment of the
same concept and to the prediction of equilibrium chain length distribution
(CLD), has been led by G. V. Schulz [10] in Germany.
Assuming there is no mutual interference of end groups in the same molecule
(which does often happen with groups attached to aromatic rings), the specic rate
of consumption, R
A
, of end groups A by an irreversible reaction reaction with
groups B can be written as Eq. (7).
R
A
= k[A[[B[ (7)
Equation (7) states that a single apparent second-order rate constant k should de-
scribe all intermolecular reactions of the involved groups A and B for a certain con-
centration of catalyst(s) (which may be A or B themselves) and solvent, regardless
of the polymer molecule to which they belong. A change of composition of the re-
action medium will often cause k also to change.
If the reaction is reversible, a more general expression [Eq. (8)] for R
A
should be
used.
R
A
= k[A[[B[ k
Z
[Z[ (8)
In the case where, as often happens, a by-product W exists, the apparent rst-order
reverse rate constant k
Z
is related, through Eq. (9), to apparent equilibrium ratio K
and by-product concentration [W[.
k
Z
= k[W[/K (9)
3.1.4
Eect of Reaction Media on Equilibrium and Rate Parameters
Polycondensations must be carried out in bulk or with a concentration of solvent
as low as possible (viscosity being the limiting factor) in order to minimize the for-
mation of rings. If the end groups have polarities and/or hydrogen acceptor or do-
nor anities very dierent from the bonds, this is likely to lead to changes in the
value of apparent constant k, which will be observed as a dependence on conver-
sion or stoichiometric ratio.
Known examples are the apparent increase in reactivity with conversion in ester-
ications and the strong eect of water concentration on apparent equilibrium and
rate constants in amidation systems (see Sections 3.3.1 and 3.3.3 respectively).
Should some thermodynamic model of the chemical system be available, knowl-
edge of activity coecients g of chemical groups A; B; Z and by-product W would
allow the apparent equilibrium ratio K to be related to the thermodynamic K
0
(a
true constant, a function only of temperature) through Eq. (10).
K = K
0
g
A
g
B
g
Z
g
W
=
[Z[[W[
[A[[B[
(10)
This kind of computation can be done using the UNIFAC contribution group
method [11], but its empirical character and lack of available parameters at high
temperatures limit drastically its usefulness.
Solvent or bulk media eects can be modeled by taking advantage of group con-
tribution methods [12]. Multiple kinetic experiments with dierent media compo-
sitions are needed in order to compare the free energy of interaction involving the
hypothetical transition state group (see Ref. 13 for an example). No such studies
have ever been tried with polymerization reactions.
Progress in computational quantum mechanics should ultimately make the
practical use of these correction methods more widespread.
In nonlinear polycondensations, it is possible to observe a limiting conversion,
the topological limit [14] when unreacted groups in network are too far apart to
meet. Rate constants will fall before reaching the topological limit if glass transi-
tion temperature T
g
is attained (the glass eect). This situation occurs with many
thermosetting systems of practical interest, epoxies being the most studied, as dis-
cussed in the reviews by Mita and Horie [15] and Dusek [14].
A new theory for describing this phenomenon, leaving aside the long-used free
volume concept, was recently put forward by Corezzi et al. [16]. It is based upon
the AdamGibbs [17] entropy theory of glass transition. Formation of more cova-
lent bonds by polymerization decreases the number of available statistical congu-
rations of the chemical system, thus decreasing congurational entropy, suggest-
ing Eq. (11) relating structural relaxation time t
r
to number-average degree of
polymerization x
n
.
t
r
= t
0
exp[b
g
(T)x
n
[
b
g
=
b
g0
T T
0
(11)
Function b
g
(T) is empirical and could be dierent from that in Eq. (11) [16]. There
is for the moment no published use of this theory to t apparent kinetic constants.
A possible suggestion is the following (untested) correlation with yet another two
parameters, k
0
and C
g
, based on the Rabinowitch equation for diusional eects
on chemical reactions [Eq. (12)].
1/k = 1/k
0
C
g
t
r
(12)
In Duseks terminology, diusion control of chemical reactions may be specic,
when the bond formation rate depends on the mobilities of individual reacting
molecules or substructures, or else nonspecic, when the reaction rate depends
only on the average properties of the system.
Experimental evidence points toward prevalence of nonspecic rate control: for
instance, gel conversion in epoxide resin cure is the same regardless of glass eect
[18].
Lacking a better alternative, an empirical dependence of rate parameters on con-
version, for a given starting composition, must be tried. Examples of this approach
will be discussed along with their respective chemical systems (bulk polyester and
polyamide formation). It is seen that the glass eect could be taken into account
using a similar procedure.
3.1.5
Polycondensation Reactions with Substitution Eects
When the reaction of a functional group changes the reactivity of its neighbors, a
substitution eect exists.
A rst-shell substitution eect (FSSE) is the simplest kind of departure from
ideal behavior. It is the situation where reactivity is aected only by the reaction of
the functional groups attached to the same monomer unit. FSSEs are encountered
in many polycondensations, as reactivities of functional groups in monomers are
often dierent from the reactivities of end groups in polymers because of mutual
steric, resonance, or electrostatic interactions.
For instance, a glycol HOaXaOH shows no substitution eect in an esterica-
tion reaction if the reactivity of the hydroxyls in aCOOaXaOH is the same: a single
kind of group aOH needs to be considered and the description of the reaction
scheme is much simpler.
A second-shell substitution eect (SSSE) occurs when the reactivity of a func-
tional group is aected by the reaction of all the groups attached not only to the
same monomer unit, but also to the units linked to that one. This behavior has
been recognized in urea/formaldehyde formation (see Section 3.3.4.2).
Linear polycondensations AXA BYB with FSSEs in both root units X and Y are
examples found in some important processes, such as the esterication of tereph-
thalic acid and ethylene glycol leading to poly(ethylene terephthalate) (PET). Four
dierent rate constants k
i
are needed to describe forward reactions, and possibly an
equal number of apparent rate constants (k
Z
i
, i = 1 . . . 4) are required to describe
reverse reactions:
A
XA
B
YB
T
k1
k
Z
1
A
XZY
B W A
XA
B
YZ
T
k2
k
Z
2
A
XZY
Z W
A
XZ
B
YB
T
k3
k
Z
3
B
YZX
Z W A
XZ
B
YZ
T
k
4
k
Z
4
Z
XZY
Z W
(13)
Recall that apparent rst-order rate constants of the reverse reactions k
Z
i
are related
to the apparent second-order rate constants of the forward reactions k
i
through the
apparent equilibrium ratios K
i
and the concentrations of by-product:
K
i
=
k
i
k
Z
i
[W[
(14)
If there is no by-product, as happens with isocyanate hydroxyl reactions, [W[ = 1
(dimensionless) should be used in Eq. (14).
This example illustrates several diculties encountered in modeling reversible
polycondensation reactions with substitution eects. A major problem is the possi-
ble change in the nature of bonds because another bond connecting a dierent
unit has been destroyed. There is no closed set of rate equations in terms of
the concentrations of functional groups [AXA[; [BYB[; [Z
D
[; [Z
A
[; [Z
B
[, and [Z
P
[,
even with the help of the two stoichiometric restrictions [X[ = [AXA[ [Z
D
[
[Z
A
[ [Z
P
[ and [Y[ = [BYB[ [Z
D
[ [Z
B
[ [Z
P
[. Introduction of more complex
chemical entities does not alleviate the problem.
For instance, sequence Z
B
XZ
B
(a particular kind of monad, a repeating unit X
with its pendent chemical groups) is formed by destruction of either of the sequen-
ces Z
B
XZ
P
YZ
P
or Z
B
XZ
P
YZ
A
(which are dyads, sets of two connected repeating
units) by reverse reactions at the rightmost Z group as written above. In order to
predict the concentrations of monads, one needs the concentrations of dyads; this
demands knowledge of the concentrations of triads, and so on. This hierarchy of
equations can not be broken without obtaining the whole chain length distribu-
tion; for further details see Section 3.4.5.
In fact, the above kinetic model considers SSSEs for the reverse reaction.
An FSSE model taking into account reverse reaction must consider equality
of rate constants of reverse reactions k
Z
1
= k
Z
2
= k
Z
3
= k
Z
4
= k
Z
. Since [Z
A
[ =
2[AXZ
A
YZ
A
XA[ [AXZ
A
YZ
P
[ and [Z
B
[ = 2[BYZ
B
XZ
B
YB[ [BYZ
B
XZ
P
[, rates of
formation of groups can be written as shown in Eqs. (15).
R
AXA
= 4k
1
[AXA[[BYB[ 2k
2
[AXA[([Z
D
[ [Z
B
[) k
Z
([Z
D
[ [Z
A
[)
R
BYB
= 4k
1
[AXA[[BYB[ 2k
3
[BYB[([Z
D
[ [Z
A
[) k
Z
([Z
D
[ [Z
B
[)
R
ZD
= 4k
1
[AXA[[BYB[ [Z
D
[[2k
2
[AXA[ 2k
3
[BYB[
k
4
(2[Z
D
[ [Z
A
[ [Z
B
[)[ k
Z
([Z
D
[ [Z
A
[ [Z
B
[)
(15)
R
ZA
= 2k
2
[AXA[([Z
D
[ [Z
B
[) 2k
4
[Z
D
[
2
[Z
A
[(2k
3
[BYB[ k
4
[Z
B
[) 2k
Z
[Z
A
[
R
ZB
= 2k
3
[BYB[([Z
D
[ [Z
A
[) 2k
4
[Z
D
[
2
[Z
B
[(2k
2
[AXA[ k
4
[Z
A
[) 2k
Z
[Z
B
[
In conclusion, descriptions of substitution eects not only require knowledge of
more kinetic parameters, but also may lead to added mathematical diculties,
even for just the prediction of basic characteristics of the chemical system, such
as the concentrations of functional groups.
3.1.6
Exchange Reactions
Exchange reactions without formation of by-products, such as the acidolysis and
aminolysis reactions present in polyamidations, do not increase number-average
molecular weight, but can be an important cause of relaxation of chain length dis-
tributions toward the equilibrium. Kotliar has presented a general review of these
reactions [19].
Direct bond exchanges in the complete absence of by-product (such as amide
amide exchange) are at best very slow (if they indeed exist) and, as these reactions
can be safely neglected, only exchange reactions involving an end group and a
bond should be of any importance. The exchange of bonds Z
1
and Z
2
(necessarily
formed with a common by-product W), can be described through Eqs. (16).
XA YC T
k1
k
Z
1
XZ
1
Y W XB YC T
k2
k
Z
2
XZ
2
Y W
XA X
/
Z
2
Y T
k
E
12
k
E
21
XZ
1
Y X
/
B
(16)
These reactions modify the counts of functional groups of similar chemical nature
(for example, distinguishable kinds of amides/amines/carboxylic acids). If there
is only a single kind of bond, there is no net creation or destruction of func-
tional groups or bonds, but a reshuing of pieces of the reacting molecules takes
place.
In order not to violate the condition of chemical equilibrium, rate constants
of forward and reverse exchange reactions can be related to equilibrium constants
of the condensation reactions in which the same functional groups are involved.
In this example, the equilibrium ratio of the exchange reaction must be in accord
with Eq. (17).
k
E
12
k
E
21
=
K
1
K
2
(17)
This operation will reduce the number of kinetic parameters in the kinetic scheme.
Also, several of the various equilibrium constants can also be related through a rea-
soning due to Gordon and Scantlebury [20] for the XA
f
polycondensation, which
consists of checking the formation of the same nal products through successive
equilibria but with dierent intermediate stages.
3.1.7
Ring-forming Reactions
Prediction of the entropy of cyclization for the gaussian chain molecular model
by Jacobson and Stockmayer [21] could relate rate and equilibrium constants of
intramolecular ring-forming reactions to their analogous intermolecular counter-
parts. Their theory has later been rened [22, 23] as it provides a good test for
statisticalmechanical treatments of chain molecules.
Measured ring concentrations for thermodynamically controlled (reversible) poly-
condensations in bulk are usually only a few percent, so this is not a major factor
in those systems.
For irreversible polycondensations, recent studies by Kricheldorf [24, 25] using
MALDI mass spectroscopy have in several circumstances detected quite an appre-
ciable concentration of ring molecules. Unfortunately, dependence of ionization
and thus of instrumental response factor of polymer molecules on the nature of
the end groups [26] prevents a quantitative exploration of those ndings. But it
can be concluded that extension of kinetic modeling in order to take into account
the presence of rings is more important than was previously acknowledged.
The rationale for this unexpected concentration of rings is the irreversible char-
acter of their formation. Unless there is a slight excess of some of the end groups,
presence of both kinds of end groups in the same molecule will inevitably lead to
competition of ring formation with respect to polycondensation. The limiting fac-
tor for molecular weight increase becomes ring formation, not closeness to stoichi-
ometry of the reagents.
In what follows, C
n
is a ring with n bonds and L
n
is a linear molecule containing
n 1 bonds. The formation of that ring moiety can occur by intramolecular reac-
tion of functional groups, or by a back-biting reaction, analogous to the exchange
reactions discussed in the previous section, according to the schemes represented
in Eqs. (18) and (19).
L
n
k
c
(n)
k
cZ
C
n
W (18)
L
m
C
n
k
aE
k
cE
(n)
L
mn
(19)
Except for small rings, rate constants k
cZ
, representing breakage of bonds in the
ring, and k
aE
, describing the addition of rings to the end of chains through the ex-
change reactions, should be identical to their open-chain counterparts, k
Z
and k
E
respectively. The reverse constants depend on the size of the ring. According to
the JacobsonStockmayer theory, valid for gaussian chains (and therefore only for
rings with at least some tens of bonds, and bulk media or with low solvent concen-
tration) k
c
and k
cE
should be related to the corresponding parameters for intermo-
lecular relations through Eqs. (20)(21).
k
c
j
(n) = k
j
k
c
(n) (20)
k
cE
ij
(n) = k
E
ij
k
c
(n) (21)
k
c
(n) =
1
N
AL
(3/2pnb
2
)
3/2
(22)
In Eq. (22), the small contributions of the distances of the ends of functional
groups b were assimilated to the length of a bond, and N
AL
is the Avogadro
Loschmidt number.
If there is only one kind of bond, an equilibrium constant of cyclization K
c
(n)
can be dened from the equilibrium in Eq. (23).
K
c
(n) =
[C
n
[[L
m
[
[L
nm
[
= k
c
(n)/n (23)
3.1.8
Modeling of Polymerization Schemes
Methods for predicting molecular weight distributions at chemical equilibrium and
for irreversible polycondensations are presented with some detail below; see Sec-
tions 3.4.3 and 3.4.4.
Systems at chemical equilibrium are amenable to description by the domain of
calculus of probabilities known as the theory of branching processes [27]. Batch re-
actions starting from monomers can sometimes be described by the same solu-
tions, increasing the practical importance of such an approach. Exchange reactions
also drive molecular weight distributions toward equilibrium. Many reactions of
great technological interest, such as melt polyesterications, can be tackled using
this approach.
Applicability of statisticalprobabilistic methods far from chemical equilibrium
cannot be guaranteed, and the kinetic approaches described in Sections 3.4.4 and
3.4.5 are a better choice.
Use of statisticalprobabilistic methods for describing polycondensations started
with Flory, who used them to compute the equilibrium chain length distribution of
linear systems and later was able to predict gelation conditions for multifunctional
monomers. Stockmayer [7] could extend this method to the computation of chain
length distributions and average molecular weights of nonlinear polymers.
Gordon [20, 28] recognized that nonlinear polymers in the absence of intramo-
lecular reaction can be described by a GaltonWatson branching process. Relatively
complex chemical systems, presenting substitution eects, became tractable, and
even some properties of polymer networks relevant to rubber elasticity theory [29]
and average radius of gyration [30] as well as other polymer properties [3133]
could be computed.
Alternative approaches to Gordons branching theory have later been developed,
mainly the so-called recursive method [34, 35], which is in a number of ways
simpler to understand and use, but lacks the power of the older theory in many
situations.
Reversible polycondensations can be tackled using the concept of molecular frag-
ments introduced in Section 3.1.5. It is possible to establish closed sets of rate
equations for those fragments in many important cases (the main diculty being
the presence of higher-order substitution eects). For a more detailed discussion,
together with a short analysis of the much simpler case of linear polycondensa-
tions with a single kind of bond (a single monomer AXB or two monomers with
dierent groups AXA BYB), see Section 3.4.5.
It is noteworthy that CLD in those chemical systems (and probably in similar al-
ternating polyesterications and polyamidations) is nearly always fairly close to
equilibrium, the main discrepancies occurring as far as the concentrations of the
rst linear oligomers are concerned. So, a method which predicts those concentra-
tions correctly is what is really needed in practice. The main factor controlling the
CLD should be the presence of multifunctional impurities, which should be care-
fully tracked by the kinetic model.
Prediction of the whole CLD should be possible only with Monte Carlo methods,
with their usual drawbacks [36]. Nevertheless, polycondensations are easier to sim-
ulate by Monte Carlo than other polymerizations, since all reactions have more or
less the same time scale.
These simulations are invaluable for investigating the eect of space correlations
between reacting groups and their eect on ring formation and elastic properties
[37]. Prediction of molecular size distribution (which hopefully can be determined
by size exclusion chromatography) is also a useful result [38] which is dicult to
obtain otherwise.
3.2
Mass Transfer Issues in Polycondensations
This section deals with situations where mass transfer eects of by-products (devo-
latilization, solid-state polymerization) and monomers (interfacial polymerization)
become so important as to cause a spatial change in polymer molecular weight
distributions.
3.2.1
Removal of Volatile By-products
Devolatilization in irreversible polycondensations is carried out in the later stages
of the process and is similar to other polymerizations. For reversible polycondensa-
tions, however, it diers from the devolatilization of other polymers in a number of
ways.
v
Reaction and removal of by-product are intimately connected.
v
Monomers may be removed in substantial quantities.
v
Removal of volatiles takes place during the whole course of the reaction.
In the rst stages of the reaction, reversible polycondensates readily form boiling
liquids and care has to be taken to avoid removal of monomers, foaming, or prod-
uct entrainment.
Equilibrium constants are of the order of unity for polyesters and polycarbon-
ates, and of the order of hundreds for polyamides. In order to obtain end-group
conversions above 0.99, this implies a concentration of by-product [W[ below 10
4
times the concentration of bonds in the former two systems. The high temperature
of the processes increases the vapor pressure of the by-products and their equilib-
rium solubility decreases, but even so partial pressures of some millibars for poly-
ester and polycarbonate processes are required; they may be obtained by using a
combination of vacuum and inert stripping gas. These low partial pressures and
consequently nearly innite dilution often justify the application of Henrys law to
describe the vaporliquid equilibrium according to Eq. (24), in which P
W
is the
equilibrium vapor pressure of by-product W, H
W
is its Henry constant for the poly-
mer melt (in the usual range of 101000 bar), w
W
is mass fraction in the melt, P
S
W
is the vapor pressure of pure W, and W
W
is its weight fraction activity coecient.
P
W
= H
W
w
W
= P
S
W
W
W
w
W
(24)
The second part of Eq. (24) is useful below the critical temperature of the by-
product, when some thermodynamic model is available. For instance, given the
densities of melt and by-product respectively as r
P
; r
W
, FloryHuggins theory leads
to Eq. (25).
W
W
=
r
P
r
W
exp(1 w) (25)
Similar expressions hold for the volatile monomers, which at high dilutions can be
treated independently. At low conversions, the innite dilution is not applicable
and the multicomponent FloryHuggins equation [Eq. (26)], for example, should
be used instead. Here the f
Y
i
are the volume (or segment) fractions of the various
components, i = 1 up to N
Y
being the volatile components and the polymer being
component N
Y
1; the y
Y
i
are their mole fractions, V
Y
i
the molar volumes, and
the w
ij
the binary interaction parameters.
W
Y
i
=
r
P
r
Y
i
exp V
Y
i
NY 1
j =1
f
Y
j
V
Y
j
NY 1
j =1
j0i
f
Y
i
w
ij

f
Y
i
y
Y
i
NY 1
j =1
NY 1
k=j1
y
Y
i
f
Y
k
w
jk
(26)
At high conversions, mass transfer resistance to by-product removal is a key factor,
not because of low diusivities D of the by-products (in the range 10
9
to 10
11
m
2
s
1
), and consequent mass transfer coecients, but because of low interfacial
areas.
Because of the huge increase in viscosity of the melt when the reacting mixture
changes from the initial mixture of monomers/oligomers to high polymer, a possi-
ble solution is the use of dierent continuous stirred reactors (CSTRs) in series,
with dierent kinds of stirrers. Other processes consist of simple unstirred bubble
columns.
In either case, these reacting mixtures at the beginning of the processes resem-
ble boiling liquids. Stirring helps the formation of bubbles by cavitation and breaks
existing bubbles, increasing interfacial area. Inert gas injection will also help (but
loss of volatile monomers becomes more dicult to counterbalance). These mech-
anisms become inecient for high enough molecular weight with the consequent
higher viscosity (above 200 Pa s), and special lm-forming equipment must be
used.
Equipment for devolatilization of residual monomers and solvents without
chemical reaction is used in most polymerization processes, vented extruders be-
ing a common choice. They are also used in the nal stages of reversible polycon-
densations [39], as well as other specially developed devices that we discuss next.
The basic design of these latter systems consists in a partially lled horizontal
cylindrical vessel in which the reaction mixture moves axially with the help of a
screw or a rotor with blades. The impeller periodically extracts part of the bulk
liquid, leaves it exposed as a thin lm to the gas phase for a short time t
f
, and re-
mixes it again with the main stream as it ows toward the outlet.
According to the mechanism of creation of lm, three classes of devices can be
distinguished [4042]:
v
Wiped-lm reactors (WFRs) [43], where the impeller blades throw the polymer
melt against the inner surface of the vessel (Figure 3.3), subjecting it to a high
shear rate (in the range 10
3
10
4
s
1
) in the gaps between their tips and the
wall. This high shear is favorable to conveying pseudoplastic, high-viscosity poly-
mers, but can conversely bring about problems for chains which break under
shear, such as polybutylene terephthalate. Vented extruders work using a similar
principle in their central section (where deeper screws lead to partial lling of
the channel) and their reactor models can be considered a variant of this class.
v
Rotating disk contactors (RDCs) (Figure 3.4), in which the disks periodically dip
into the pool of reacting mixture. The polymer lm they carry is exposed to the
gas phase before being mixed again with the bulk liquid.
v
Falling-strand or falling-lm evaporators.
Fig. 3.3. Diagrammatic representation of a wiped-lm reactor.
The currently used description of homogeneous diusion of volatile by-products in
polymer media during reversible polycondensations is due to Secor [44]. It consid-
ers polymer molecules immobile. The ux of small molecules has a negligible con-
vective contribution; only the diusional ux with respect to the polymer needs
be considered, and the microscopic mass balance of a generic volatile component
(usually, but not always, a by-product) Y
i
and a group A
i
belonging to the polymer
may be written, neglecting density variations, as in Eq. (27).
q[Y
i
[
qt
= D
Y
i
2
[Y
i
[ R
Y
i
q[A
i
[
qt
= R
A
i
(27)
As the resistance to mass transfer in the gas phase may be neglected, the diusive
ux of evaporation
_
NN
Y
i
, in moles per unit area and unit time, will be obtained with
the help of a mass transfer coecient k
fY
i
. There are two equivalent alternative def-
initions [Eq. (28)], one using a driving force in terms of mole concentrations, the
other in terms of activities (asterisks mark a concentration or activity value at the
interface, considered to lie at y = 0).
_
NN
Y
i
= D
Y
i
q[Y
i
[
qy
[y=0
= k
fY
i
([Y
i
[ [Y
i
[
+
) = k
a
fY
i
(a
Yw
a
+
Y
i
) (28)
Combining this expression with the microscopic mass balances in the polymer
lm, it is possible to predict mass transfer coecients for simple geometries and
to take into account possible coupling with chemical reactions. For instance, if the
polymer lm is immobile, has a constant depth L, and mass transfer occurs along
the y direction with a plane geometry, time-averaged mass transfer coecient of
Fig. 3.4. Diagrammatic representation of a rotating disk contactor.
volatile species k
f
i
after an exposure time t
f
would be computed by solving Eq. (27)
with initial and boundary conditions as given in Eqs. (29).
[Y
i
[
[t=0
= [Y
i
[
0
; [A
i
[
[t=0
= [A
i
[
0
[Y
i
[
[y=0
= [Y
i
[
+
;
q[Y
i
[
qy
[y=L
= 0 (29)
k
fY
i
t
f
=
D
Y
i
t
f
0
q[Y
i
[(y; t)
qy
[y=0
dt
[Y
i
[
0
[Y
i
[
+
In view of the kinds of gasliquid contact described above, an obvious model is
provided by the penetration theory (innite depth L), where a portion of uid with
uniform concentration prole is suddenly exposed to the gas phase, and is replaced
by fresh uid after an exposure time t
f
. For an innite lm depth L and negligible
chemical reaction, this yields the well-known result [Eq. (30)] for the time-averaged
mass transfer coecient.
k
fY
i
= 2
D
Y
i
pt
f
(30)
Pell and Davis [45] were the rst to actually measure a diusion coecient for a
volatile by-product of a polycondensation, using PET formation in lms of varying
depth (although obtaining values of D much higher than those nowadays ac-
cepted). An early example of discussion of coupling of diusion/chemical reactions
in these systems may be found in Ref. 46.
The rst model associating the axial transport along the reactor (direction z) with
the cross-ow transfer of volatile by product (direction y) (see Figure 3.5) is due to
Amon and Denson [47] (Ault and Mellichamp [46] considered that all the polymer
was in the lm) and was developed for WFRs. It assumes plug ow in the pool,
which implies a negligible hold-up of the liquid in the lm. A time-averaged mass
Volatile by-product
Polymer outlet
Low M
polymer inlet
y
z=0 z z=L
y
JT
x
Fig. 3.5. Simple model for a WFR.
transfer coecient is obtained at each axial position by solving Eqs. (27) and (29),
and the mass balance of the pool is written as Eqs. (31), where u
z
is the axial su-
percial velocity (volumetric ow rate of polymer Q divided by cross-section area of
the pool) and a
v
is the lm area per unit volume.
u
z
d[Y
i
[
dz
= R
Y
i
k
fY
i
a
v
([Y
i
[ [Y
i
[
+
)
u
z
d[A
i
[
dz
= R
A
i
(31)
[Y
i
[
[z=0
= [Y
i
[
0
Since the main mass transfer area is the lm on the barrel wall, the exposure time
would be calculated [47] through Eq. (32), where d
T
is the inner barrel diameter, L
x
is the lm perimeter (L
x
Gpd
T
, if the nip is small) and _ nn is the screw rotational
speed in rotations per unit time.
t
f
=
L
x
pd
T
_ nn
(32)
A better model [48] takes into account the movement of the lm along the wall
with velocity u
x
= pd
T
_ nn between coordinates x = 0 and x = L
x
and therefore adds
a convection term, leading to Eqs. (33), where the [A
i
[
f
and [Y
i
[
f
are the concentra-
tions of the species in the lm. There is no need to consider cylindrical geometry
for the lm, since its thickness is low.
q[Y
i
[
f
qt
u
x
q[Y
i
[
f
qx
= D
Y
i
q
2
[Y
i
[
f
qy
2
R
Y
i
q[A
i
[
f
qt
u
x
q[A
i
[
f
qx
= R
A
i
q[Y
i
[
qt
u
z
q[Y
i
[
qz
= R
Y
i

u
x
L
L
0
[Y
i
[
f
(t; y) dy u
z
[Y
i
[
q[A
i
[
qt
u
z
q[A
i
[
qz
= R
A
i

u
x
L
L
0
[A
i
[
f
(t; y) dy u
z
[A
i
[ (33)
[Y
i
[
[z=0
= [Y
i
[
0
(t) [A
i
[
[z=0
= [A
i
[
0
(t)
[Y
i
[
f
[x=0
(t; y; z) = [Y
i
[(t; z) [A
i
[
f
[x=0
(t; y; z) = [A
i
[(t; z)
q[Y
i
[
f
qy
[y=L
= 0 [Y
i
[
f
(t; 0) = [Y
i
[
+
With some modications, a model of single-screw vented extruders can also be de-
veloped. We will present here a slightly extended version of the treatment by Rob-
erts [49] and Biesenberger and Sebastian [50]. Fundamental studies on uid me-
chanics and mass transfer without reaction are reported in Refs. 51 and 52.
A scheme of ow and mass transfer in single-screw vented extruders, also illus-
trating some key geometrical parameters, is shown in Figure 3.6.
As polymer ows inside the channel along a trajectory in a helix, with a total
length L
B
/sin y, in which y is the angle of the screw, the coordinate z will be taken
along this helicoidal path. Dimensions of the channel will be L
W
(width) by H
(depth), with a fraction f
L
lled with liquid. As the movement of screw pushes
the polymer pool, a fraction passes through the space between the barrel and the
screw, forming the desired evaporating lm. If the uid is Newtonian, the lm
width is h/2, where h is the clearance. The average transverse velocity of the screw
dragging the lm, v
T
, is given by Eq. (34).
v
T
= pd
T
_ nn sin y (34)
The lm which is wiped from the channel re-enters at a distance d upstream of its
departure point given by Eq. (35) [50] and the time of exposure of the lm t
f
is
given by Eq. (36).
d = pd
T
f
L
cos y (35)
t
f
= (1 f
L
)/ _ nn (36)
The concentrations [A
i
[
f
(z) and [Y
i
[
f
(z) respectively for nonvolatile and volatile
components in the lm, back-mixed at axial position z, are obtained by solving
Eq. (27) for t = t
f
with initial conditions described by Eqs. (37) (a more exact model
would consider convection as in Eq. (33)):
[Y
i
[
[t=0
= [Y
i
[(z d); [A
i
[
[t=0
= [A
i
[(z d) (37)
Unwrapped views:
Film
Fig. 3.6. Scheme of ow and mass transfer in single-screw vented extruders.
Assuming plug ow in the channel (a trivial change would be to add an axial dis-
persion coecient), the mass balances in the channel taking into account also the
devolatilization from the pool (mass transfer coecients k
fpY
i
) thus becomes those
given in Eqs. (38).
u
z
d[Y
i
[
dz
= R
Y
i

v
T
h
f
L
L
W
H
([Y
i
[
f
[Y
i
[)
k
fpY
i
f
L
L
W
([Y
i
[ [Y
i
[
+
)
u
z
d[A
i
[
dz
= R
A
i

v
T
h
f
L
L
W
H
([A
i
[
f
[A
i
[) (38)
[Y
i
[
[z=0
= [Y
i
[
0
[A
i
[
[z=0
= [A
i
[
0
The presence of the delay d may be circumvented by using a Taylor expansion
about z [50] in order to obtain a system of second-order ODE. Also according
to Refs. 49 and 50, the exposure time of the pool may be estimated through Eq.
(39).
t
fP
=
H
pd
T
_ nn sin y
(39)
Another integration of Eq. (27) for t = t
fP
with a trivial modication of Eq. (30) will
provide an estimation of the mass transfer coecients of the pool k
fpY
i
.
Twin-screw extruders have the advantage of being self-cleaning and can work
with extremely high viscosity, above 10
6
Pa s [53], making them a good choice for
polyamide and polyurethane nal stages of reaction, thanks to the possibility of
using reduced space times. Their detailed modeling is more dicult than with
single-screw devices, and few fundamental studies [54] have been carried out.
Rates of mass transfer have been predicted for a co-rotating twin screw using pen-
etration theory and experiments have been done with a transparent device (for
observing whether bubbles were present or not in the devolatilization zone). Ob-
served results of k
f
a
v
were proportional to the speed of rotation to the power of
0.5, as penetration theory predicts, but were three times lower than theoretical pre-
dictions, which has been attributed to the very low liquid hold-up and consequent
lack of coverage.
In contrast to WFRs and vented extruders, use of staged models for describing
rotating disk contactors is a natural choice [55], since the J compartments with liq-
uid hold-ups V
mj
can be approximated as CSTRs. Taking into account the possibil-
ity of back-ow, the overall volume ow rate leaving the jth CSTR, Q
j
, will be di-
vided into a fraction b
j
going back to CSTR j 1 and 1 b
j
going to tank j 1,
except for the rst CSTR, in which b
1
= 0. Also, Q
J1
= 0, and the gas phase will
be considered well mixed with uniform temperature (see Figure 3.7). Thus, mass
balances at a steady state of volatile and nonvolatile components in the jth com-
partment ( j = 1, J) may be written as in Eqs. (40).
Q
j1
(1 b
j1
)[A
i
[
j1
Q
j1
b
j1
[A
i
[
j1
= Q
j
[A
i
[
j
R
A
i
V
mj
Q
j1
(1 b
j1
)[Y
i
[
j1
Q
j1
b
j1
[Y
i
[
j1
= Q
j
[Y
i
[
j
R
Y
i
V
mj
k
fY
ij
a
vj
V
mj
([Y
i
[
j
[Y
i
[
+
)
(40)
Mass transfer coecients can be computed using penetration theory as described
above.
Murakami et al. [56] obtained correlations for hold-up and mixing time in RDCs.
Fractional dead space (between 0 and 18% for their experimental data) can be pre-
dicted from the mixing time. This dead space should obviously be kept to a mini-
mum, because polymer staying there will degrade due to secondary reactions
to possibly discolored or gelled material, and product quality may be seriously
harmed. Local lm thickness and hold-up have been correlated to physical proper-
ties (surface tension, viscosity) and geometrical parameters [57]. Residence time
distribution has been shown to become narrower when viscosity grows [58].
Interfacial area [58] can be correlated with relative lling level H/d
T
and the
number of disk rings per unit length ( J/L
T
) [Eq. (41)].
a
v
=
J
L
T
1:72 1:87H/d
T
0:085 0:955H/d
T
(41)
An experimental study on mass transfer in disk-ring contactors of diameter d
R
using low-viscosity acrylamide solutions as a model uid [60] has led to the corre-
lation of Eq. (42), but this correlation should only be used as a rst approximation
[40], in view of the complexities introduced by polymer viscoelasticity.
Sh =
k
f
d
R
D
= 1:59
d
2
R
_ nn
D

0:5
(42)
Falling-lm or falling-strand devolatilizators receive increasing attention as they re-
quire no heavy and expensive machinery: Polymer is simply pumped through
small slits or holes. Ecient surface renewal is achieved by shear thinning during
the fall [59]; strands and lms become very thin and may be completely depleted of
Fig. 3.7. Staged model of an RDC.
volatiles. Depletion or possible tearing determine the optimal height of strands/
lms for a given viscosity and initial lm diameter. Reaction considerably increases
the eciency of these devices (by a factor of up to ten) as it replenishes the volatile
by-product. Guides to the strands/lms, such as wires, thin rods, or grids, will fur-
ther enhance the role of the reaction while reducing the eect of shear thinning
and tearing.
In all these devices, an additional component of interfacial area is provided by
the gas bubbles, which can result from sparging with inert gas (widely used for
devolatilization without chemical reaction) or from boiling. Observed rates of
mass transfer are often several times higher than predicted [50] and this discrep-
ancy has been linked to the presence of bubbles.
The LaplaceKelvin equation predicts that an isolated gas bubble should redis-
solve if its size is below a critical threshold, and conversely it should grow if its ra-
dius r
b
exceeds the critical value given by Eq. (43) [50], where s is the surface ten-
sion, P
me
is the local pressure over the bubble (it may be simply the hydrostatic
pressure, but in other circumstances it may be controlled by medium elasticity
[61]), and P
b
is the pressure inside the bubble, equal to the sum of the partial vapor
pressures due to inert gases and volatile components if physical equilibrium and
gas-phase ideality hold. So, it is possible that no bubbling occurs if the pressure is
high enough or the content of volatiles is too low, but this is often not the case.
r
bc
=
2s
P
b
P
me
(43)
Bubble nucleation in polymer media is usually heterogeneous [62]. It starts when
shear stress manages to detach the small bubbles which are stuck in cracks and
crevices of vessel walls, internals, or suspended dust. Once the source of heteroge-
neous nucleation is spent, only high supersaturation will restart boiling. Of course,
in many practical situations there are already small air bubbles in the polymer, and
they will start foaming too. Favelukis et al. [63] have conrmed this view, and have
developed a theory for bubble growth which may explain the higher mass transfer
rates obtained with vented extruders and similar devices for high rotation speeds.
A predictive theory for bubble nucleation was developed in this same research [64].
Gestring and Mewes [65] have studied polymer degassing both with and without
bubbling using a transparent drum with a rotating blade (similar to the screw of a
vented extruder). Measured values of mass transfer rates without bubbling are
three times lower than predicted by penetration theory, because neither pool nor
lm is well stirred which could explain the failure of predictions in Ref. 54. Rates
of mass transfer in the presence of foaming were about 40 times higher than in
the bubble-free regime.
Trace devolatilization with the help of a stripper agent has a greatly enhanced ef-
ciency. An important recent result is that, when it forms, foam grows until a
limiting volume is reached, regardless of initial volatile content and presence of
stripper gas [66], and thus the devolatilization section in vented extruders should
have enough room for that expansion, and residence time should also be sucient
to allow the nal density to be reached.
A patent [67] for enhancing mass transfer in this class of reactors proposes
the introduction of inert gas into the polymer in order to force the formation of
bubbles (the forced gas sweeping process). An experimental and theoretical model
has also been presented [68] and will be briey summarized here.
The reactor was a rotating disk contactor for making bisphenol A (BPA) polycar-
bonate. The reactor model uses a staged approach, and the crux is the prediction of
the mass transfer rate of by-product (phenol). The two relationships expressed in
Eqs. (44) for the volume of a gas bubble V
b
as a function of the gas ow rate Q
g
[69] and of its rising velocity u
b
in a laminar regime [70] were the key data.
V
b
=
4p
3

1/4
15mQ
g
2rg

3/4
u
b
=
2gd
b
C
d
1
Q
g
d
b
u
b
V
b

1/2
(44)
C
d
=
16
Re
1
In these equations m; r, respectively, are the viscosity and density of the liquid, g is
the acceleration of gravity, d
b
is the bubble diameter, and C
d
is the drag coecient.
The mass transfer coecient was predicted using penetration theory, and the expo-
sure time was computed [Eq. (45)] as the rising time of a bubble in the melt (at
height h
R
above the gas injection point).
t
f
=
h
R
u
b
(45)
The interfacial area per unit volume was obtained from the number of bubbles N
b
and the melt volume V
m
[Eqs. (46)].
a
v
= pd
2
b
N
b
V
m
N
b
=
Q
g
t
f
V
b
(46)
The observed bubble frequency agreed with the theoretical predictions, as also did
the proles of x
n
versus reaction time.
It is interesting to nish this complex section with such a case study, suggesting
that for some problems classical Chemical Engineering of the 1960s can still
help in present-day industrial and scientic problems.
The design and operation of most polycondensation reactors for devolatilization
of volatile by-products (namely vented extruders) is clearly a very dicult problem
because of the complexity of the ows (with or without foaming). Further progress
is likely to require a heavy use of computational uid dynamics, as simplied
models seem to have arrived at their limits.
3.2.2
Solid-state Polycondensation
Current industrial processes for the production of high molecular weight, linear,
aromatic polyesters and polyamides, for use as plastics and bers, use solid-state
polycondensation (SSP) for their last stages. This is the kind of process that will
be treated in this section: the polycondensation of semi-crystalline, low molecular
weight polymers to high molecular weight ones, occurring below the melting tem-
perature of high polymer, but well above the glass transition temperature. We will
disregard polycondensation of crystalline monomers, which is also covered in the
review by Pilati [71].
Because of the need to provide enough interfacial area to allow the removal of
volatile by-products, the polymer has to be in a powdery form. One of the several
optimization problems of these processes is to specify an economical starting par-
ticle size.
A practical diculty is the possible tendency of the particles to stick, which will
make the process unfeasible. It is counteracted by starting with polymers with suf-
ciently high crystallinity, and by adding glass beads. Another problem may be the
sublimation of oligomers, as in nylon-6, which may clog the bed. A precrystalliza-
tion step for PET, to make it attain at least 40% crystallinity before SSP starts, is
present in industrial processes since early 1970s.
The main reason for using SSP is the achievement of molecular weights higher
than would be possible in melt polycondensation, owing to the selectivity gain of
polycondensation with respect to degradation reactions. Therefore, in a batch SSP,
a maximum in molecular weight versus time is expected, and this maximum will
occur at shorter times and will lead to lower molecular weights as the temperature
is increased.
The key assumptions made in order to interpret SSP are due to Gostoli, Pilati et
al. [72, 73] (see Figure 3.8):
v
All chain end groups belong to the amorphous regions.
v
No reactions occur in crystalline regions.
v
Chemical reactions follow the same kinetics as in melt, taking into account
the change in the volume of the reaction media aecting functional group
concentrations.
v
Equilibrium CLD holds locally.
The overall polydispersity of polymer will be greater than the equilibrium value (2
for linear polycondensations) because of the radial prole of M
n
in the diusion-
controlled regime.
In the same way as in heterogeneous catalysis, eective diusion coecients
D
Y
ie
(for uxes with respect to the total geometric area) are decreased relative to
the values in the melt D
Y
i
because of the obstruction due to the crystalline phase
at a volume fraction f
cr
and because of the tortuosity factor t
D
(which depends on
the structure of the solid, values of 1.5 to 3 being common); the relationship is
given in Eq. (47).
D
Y
ie
= D
Y
i
1 f
cr
t
D
(47)
Notice that volume and mass fractions w
cr
of the crystalline phase are dierent be-
cause of the slight dierence in density with respect to the amorphous phase.
An unavoidable complication is thus the description of the build-up of the crys-
talline phase, which aects mass transfer and chemical reactions by increasing
functional group concentrations in the amorphous phase. The rate of crystalliza-
tion is often described by the Avrami equation [Eq. (48)].
w
cr
= 1 exp(k
cr
t
ncr
) (48)
The exponent n
cr
is a function of nucleation and growth type, which is not constant
for the entire course of crystallization. Mallon and Ray [74] have put forward in-
Fig. 3.8. Phase separation in solid-state polycondensation;
A, B are the end groups, W is volatile by-product.
stead of Avrami equation an empirical rate law in terms of residual amorphous
phase volume fraction.
The microscopic mass balance of polymer functional groups and volatile compo-
nents given in Eqs. (27) has to be modied in order to take into account the vari-
able reaction volume due to polymer crystallization. Here we do not follow the
notation in Ref. 74; rather, we use concentrations and rates of reaction per unit
volume of amorphous phase instead of concentrations per unit volume of particle
[A
i
[
p
= [A
i
[/(1 f
cr
), and so on, in order to use the same kinetic rate laws [Eqs.
(49)] as in the melt.
q[(1 f
cr
)[Y
i
[[
qt
= D
Y
i
1 f
cr
t
D
[Y
i
[

(1 f
cr
)R
Y
i
q[(1 f
cr
)[A
i
[[
qt
= (1 f
cr
)R
A
i
(49)
Examples of the use of this approach with PET and nylon-6,6, including a success-
ful comparison with available experimental data, can be found in Ref. 74.
Industrial-scale SSP is carried out in moving packed bed, uidized bed, and
stirred bed reactors; Mallon and Ray have published a brief discussion of idealized
models of these reactors [75]. Fluidized beds have a serious drawback because of
the high consumption of gas needed to keep the bed in a uidized state, and resi-
dence time distribution is unfavorable to high conversions. Stirred beds in series
are a possible solution, depending on economic details.
A model for SSP of nylon-6,6 in a moving bed reactor, considering its complex
geometry and its start-up and shutdown operation [76], can serve as a guide for
dealing with more complex real-life situations.
3.2.3
Interfacial Polycondensation
Typical chemical systems are fast reactions between two difunctional monomers,
AXA BYB. The rst monomer (diamine, bisphenolate) is dissolved in a water so-
lution (in alkaline media in both cases), and the other monomer, with low water
solubility (acid chloride, phosgene), is usually dissolved in an organic solvent. Ei-
ther the neutral form of AXA is in an appreciable amount (in the case of amines),
or a phase transfer catalyst is needed (as in polycarbonate synthesis), since ionized
forms will not dissolve in the organic phase. A decrease in the pH is often used to
quench interfacial polyamidation.
The chain extension of water dispersions of isocyanates with water-dissolved
amines, in order to make polyurea dispersions, shares some similarities with the
former (amine acid chloride) systems.
Another common feature among these chemical systems is the presence of a
parasite reaction consuming end groups B by reaction with water.
Addition of a monofunctional chain stopper to the organic phase is advisable in
order to control the nal M
n
.
In most cases (namely polyamides and polyureas), the polymer is insoluble in
monomer BYB or in its solvent, and precipitates as soon as it forms, often yielding
a shell through which AXA has to diuse. Polycarbonates are an exception, as they
are completely soluble in the methylene chloride solvent chosen for their produc-
tion. Also, the organic phase is continuous in this latter case, which is a rather ex-
ceptional situation for interfacial polycondensations.
Also with the exception of polycarbonates, interfacial polycondensation is mostly
used in the production of specialty products, such as membranes [8082] and mi-
crocapsules [8387].
Early important contributions on interfacial polycondensations are described by
Morgan [77] as well as in Refs. 78 and 79. These studies show that the reaction
occurs in a layer close to the interface, on the organic side; the adjective interfa-
cial is thus rather misleading. Reaction is very fast and mass transfer resistance
is an important factor.
Models have for a long time concentrated on describing the velocity of con-
sumption of water-soluble monomer and consequent rate of lm growth [8387].
Although a possible framework for describing the simpler case of polycarbo-
nate formation has been presented by Mills [88], the rst attempt at predicting
molecular weight distributions for more typical interfacial polycondensation sys-
tems is due to Karoda, Kulkarni et al. [89, 90], based on experimental data by
Johnson [91]. This work will be the basis of the analysis next presented in this
section.
Assuming an apparent second-order rate constant in the organic phase k of the
order 10
2
to 10
4
m
3
/kmol s [77] and a concentration of functional groups B in
the bulk organic phase [B[
b
= 1 kmol m
3
, the characteristic reaction time for con-
sumption of monomer AXA is of the order of 10
4
to 10
2
s. In the absence of
polymer, the diusion coecient of AXA in organic solvent BYB, assuming a
molecular weight of up to a few hundreds, should be of the order of 10
10
to
10
11
m
2
s
1
, and this yields a characteristic width of reaction zone L
R
= 10
8
to
10
7
m. So, polymerization occurs in a thin shell beneath the lm of precipitated
polymer. There will be no functional groups B at the water interface and a steep
gradient of concentration of monomer BYB will be rapidly established inside the
organic phase.
Instead of solving microscopic mass balances for the concentration proles, Kar-
ode et al. [89, 90] use average concentrations in the reaction zone and consider its
thickness L
R
constant (see Figure 3.9).
Furthermore, the rate of movement of the interface between the organic phase
and the precipitated polymer lm is considered to be slow, so that a pseudo-steady
approximation for the diusion of AXA through the polymer lm and for diusion
of BYB inside the organic phase should be valid. Mass balances of monomers in
the reaction zone and in bulk aqueous and organic phases resulting from these as-
sumptions are given in Eqs. (50).
L
R
d[AXA[
dt
= L
R
R
AXA
D
AXA
H
e
[AXA[
blk
H
i
[AXA[
L
p
L
R
d[BYB[
dt
= L
R
R
BYB
k
f
BYB
([BYB[
blk
[BYB[)
V
aq
d[AXA[
blk
dt
= a
v; aq
D
AXA
H
e
[AXA[
blk
H
i
[AXA[
L
p
(50)
V
org
d[BYB[
blk
dt
= a
v; org
k
f
BYB
([BYB[
blk
[BYB[)
There are two partition coecients H
e
and H
i
for monomer AXA:
v
H
e
is the ratio of bulk concentration in the aqueous phase [AXA[
blk
to concentra-
tion in the outer interface of polymer lm (thickness L
p
).
v
H
i
is the ratio of monomer concentration in the polymer lm to concentration in
the organic phase.
V
aq
and V
org
are the volumes of aqueous and organic phases and a
v; aq
; a
v; org
are
their interfacial areas per unit volume (trivially related). No mass transfer resis-
tance is assumed to exist outside the polymer lm (although it can be easily in-
cluded), but it is considered inside the organic phase, with the help of a mass
transfer coecient k
f
BYB
(which can be obtained by penetration theory). Introduc-
[AXA]
blk
[BYB]
blk
H
e
[AXA]
blk
[AXA]
[BYB]
H
i
[AXA]
L
P
L
R
x
[BYB]
blk
[BYB]
R
e
a
c
t
i
o
n

z
o
n
e

Swollen
polymer
film
Bulk
aqueous
phase
Bulk
organic
phase
Fig. 3.9. Model for interfacial polycondensation.
ing the rates of reaction of polymer species (see Section 3.4.4), their mass balances
can be written as Eq. (51).
d[P
IJ
n
[
dt
= R
P
IJ
n
k
nuc; n
([P
IJ
n
[ [P
IJ
n
[
sat
) I; J = A; B; C (51)
Polymer precipitation is taken into account through the model of Kamide et al. [92]
with a phenomenological rate of nucleation k
nuc; n
(nil for n = 1, taken as indepen-
dent of molecular weight for n > 1) [93]. The saturation concentrations of poly-
mer species are taken as the values of their concentrations in the lower branch of
the spinodal curve for the liquidliquid equilibrium with organic solvent. The ear-
lier paper by Karode et al. [89] considered only spinodal decomposition.
A coherent lm is predicted to form when the sum of projected areas for all
phase-separated polymer nuclei (assumed spherical) is equal to the interfacial
area. Film thickness is predicted through the overall mass balance of precipitated
polymer.
Besides thermodynamic data on the liquidliquid equilibria of polymer/solvent
and hydrophilic monomer polymer/solvent, this model needs the rate of nuclea-
tion k
nuc
, considered as an adjustable parameter, it also tries to t the diusion co-
ecient of monomer in the polymer lm D
AXA
, and, as it postulates a constant
width of the reaction zone, it has also to t the kinetic parameters.
In spite of its limitations in predictive power (a natural consequence of the com-
plexity of the phenomena involved), this approach has given an important new in-
sight on these processes. Film permeation properties should depend on the mode
of phase separation, nucleation giving better crystallinity. Molecular weight de-
pends on the competition between reaction and precipitation of polymer: a more
powerful solvent should lead to higher molecular weight. The existence of a sharp
maximum of average molecular weight as a function of the concentration of mono-
mer in the organic phase when the two monomer uxes toward the reaction zone
are balanced, remarked upon by P. W. Morgan, could at last be explained by this
model 40 years later.
3.3
Polycondensation Processes in Detail
3.3.1
Polyesters
3.3.1.1 Structure and Production Processes
Two kinds of polyesters will be discussed in this section:
v
Linear, crystalline, high molecular weight (M
n
between 15 000 and 100 000), used
as plastics and bers, the most important being poly(ethylene terephthalate)
(PET) and poly(butylene terephthalate) (PBT);
v
Unsaturated low molecular weight (M
n
between 1000 and 10 000), often
branched, used as macromonomers for synthesis of thermosets (polyester res-
ins), or thermosetting materials by themselves (alkyd resins). They are prepared
from several monomers, namely phthalic and maleic anhydrides, adipic acid, iso-
phthalic acid, natural fatty acids or triglycerides, and a great variety of multifunc-
tional alcohols. In a few special cases, they may be saturated and/or linear for
use as macromonomers in the production of polyurethanes or other polymers.
3.3.1.2 Acid-catalyzed Esterication and Alcoholysis
The two main reactions in these processes are esterication and alcoholysis, which
share similar mechanisms, with a hypothetical tetrahedral intermediate.
Reactions between anhydrides and alcohols are much faster than carboxyl
alcohol reaction, and full conversion of anhydrides (unless they are in excess) will
occur in less than one minute while being melted and blended with the rest of
the mixture. This stage is slightly exothermal and care is needed to avoid sudden
boiling of the reacting mixture. Kinetic parameters of this reaction (apart from
selectivities with respect to hydroxyls) are usually not needed.
Acidolysis reactions have a dierent mechanism, involving mixed anhydrides
[94]. Their rate is comparable to the esterication reactions only above 250
C.
Esterication also occurs in high-temperature alcoholysis of aromatic esters, as
carboxyl end groups are formed by side reactions, and should also be considered
in the kinetic modeling of these processes.
In spite of being the rst reaction ever studied [95], esterication has been under
investigation ever since, and much knowledge has accumulated, even if some
points are still less clear. The basic kinetic model for polyesterication was estab-
lished by Flory and is summarized in his classic book [5]. Esterication was shown
to be acid-catalyzed, it is rst-order with respect to hydroxyls and, with respect to
carboxyls, its order is either one in the presence of foreign strong protic acids, or
two in their absence [Eq. (52)].
R
COOH
= k
scat
[OH[[COOH[
2
(no foreign acid)
R
COOH
= k
fcat
[OH[[COOH[[Cat-H[ (strong foreign acid Cat-H)
(52)
However, these rate laws can only be observed at low concentrations of hydroxyl
and carboxyl groups; otherwise a higher dielectric constant, association through
hydrogen bonds, and generic nonidealities will introduce changes in the apparent
values of the kinetic constants in Eq. (52). Experimental verication of these rate
laws is more delicate than it seems at rst sight (the eect of reverse hydrolysis re-
action must be adequately taken into account or eliminated by the experimental
set-up) and has been repeated by Hamann et al. [96], but proposal of other kinetics
has continued. In their extensive review, Fradet and Marechal [97] have found that
the overall order of esterication in the chemical literature is claimed to vary from
zero to six!
It is nevertheless useful to have some relationship, even empirical, that could ex-
tend the validity of Eq. (52) to the whole range of concentrations of functional
groups, and such a relationship (Eq. (53) where p is carboxyl conversion) has been
proposed by Chen and Wu [98, 99].
k = k
A
exp(ap) (53)
In Eq. (53) the empirical parameter a is a function of the initial stoichiometric ratio
r. It was theoretically linked to the dependence of the dissociation equilibrium con-
stant of the carboxylic acid on the dielectric constant of the medium and to the de-
pendence of the latter on the carboxylic acid concentration through conversion p. A
good t of experimental data has been obtained with the parameter a varying in the
range 0.2 to 1.2 both for the self-catalyzed and the foreign acid-catalyzed esterica-
tions of adipic acid with dierent diols.
In their modeling of unsaturated polyester resin formation, Beigzadeh et al.
[100] and Zetterlund et al. [101] have also found the ChenWu relationship more
useful than the rather cumbersome empirical models of Paatero et al. [102] or Leh-
tonen et al. [103]. Zetterlund et al. [101] have also presented interesting experimen-
tal data on the simultaneous self- and cross-catalysis by two carboxyl groups,
namely those formed by the addition of maleic and phthalic anhydride to 1,2
propanediol; they show there is an anti-synergistic eect: that is, the total rate reac-
tion of the two carboxyl groups is lower than the sum of the rates of reaction of the
individual acids with the same concentration and at the same temperature.
3.3.1.3 Catalysis by Metallic Compounds
Self-catalyzed esterication is often too slow to be of practical use, especially be-
cause hydroxyl-terminated polymers are either sought or are a consequence of the
process (aromatic polyesterications are carried out with a large excess of hydroxyls
at the beginning of the process, because of the low solubility of the diacid), and
strong protic acids are not advisable, as they would catalyze polymer hydrolysis if
allowed to remain with the polymer. Even volatile catalysts such as methanesul-
fonic acid are avoided. Therefore, metallic salts are currently used as catalysts,
both for esterication and alcoholysis. Strong bases, such as lithium hydroxide,
can also be used, but for alcoholysis only (as in polycarbonate formation).
Metals in metallic complexes can catalyze esterication and alcoholysis through
two distinct mechanisms [117]:
v
Metals of groups IIIII (such as Zn, Mn, Ce, Pb), usually introduced as carboxy-
lates, complex the oxygen in carbonyl esters preferentially.
v
Metals of groups IIIVI (namely Ti, Sb, Ge, Bi), usually introduced as alkoxides,
dialkyltin oxides R
2
SnO and carboxylates such as dibutyltin dilaurate, coordinate
with the acylic oxygen of esters.
Their activity with respect to esterication and alcoholysis has been compared by
Habib and Malek [105, 106] and Chung [107], who found volcano-shaped relation-
ships with dierent optima of activity of the several metals in terms of metal elec-
tronegativity according to Tanaka [108] for the glycolysis of dimethyl terephthalate
(DMT) and for the polycondensation of bis(2-hydroxyethyl) terephthalate (BHET).
A much more careful analysis [117] has considered the catalyst concentrations
and the dierences between the catalyzed reactions.
There are striking dierences [109, 110] between the two groups of metals as
regards sensitivity to inhibition by carboxyls (which poison the rst group) or by
hydroxyls (which poison the second group). Titanium has the best balance of prop-
erties, because it is little inhibited by carboxyls and hydroxyls (which poison Sb)
and also eciently catalyzes esterication. It is also active at surprisingly low con-
centrations [117].
The choice of catalyst also depends on secondary reactions (Ti causes yellowing),
toxicity (a problem for Sb) and price (expensive Ge will nevertheless yield a white
polymer).
The metal responsible for the catalysis is usually involved in several complexes.
An FTIR/NMR study of alcohol exchange with titanates in bulk or concentrated
solutions in apolar solvents [111] has shown that these compounds are present in
stable dimers, trimers, and other associations. These complexes exchange alkoxide
groups very rapidly, even at temperatures below ambient.
Kinetic models have to take into account both the existence of these polynuclear
complexes and the poisoning phenomena, and are more complicated than for acid-
catalyzed reactions. Alcoholysis of DMT, BHET, and other aromatic and aliphatic
esters is now becoming better understood. A key step was to recognize that in sys-
tems such as DMT ethylene glycol (EG) there are two reversible alcoholysis reac-
tions, one consisting in the attack of methyl esters either by EG or the hydroxyethyl
end groups, the other in the attack of the hydroxyethyl ester groups which produ-
ces oligomers detected by HPLC [Eq. (54)].
HOCH
2
CH
2
OH XCOOCH
3
kEG
kEG=KEG
XCOOCH
2
CH
2
OH CH
3
OH
XCOOCH
2
CH
2
OH XCOOCH
3
kHE
kHE=KHE
XCOOCH
2
CH
2
OOCX CH
3
OH
(54)
Besnoin and Choi [112] were the rst to actually use experimentally measured
oligomer concentrations to validate this kinetic scheme for Zn catalyst, as was
soon conrmed and perfected by others [113117].
These reactions are rst order with respect to the esters and hydroxyls, but the
order with respect to the catalyst becomes zero at catalyst concentrations over a
few millimoles per gram (no power rate law [114]). Moreover, the ratio k
EG
/k
HE
much depends on the catalyst (it may vary from 1 to 5) and even on the catalyst
concentration. Mixtures of divalent metal catalysts can have considerable synergis-
tic eects [117], which cannot be explained unless polynuclear complexes partici-
pate in the reaction.
It is noteworthy that, in the similar system dimethyl 2,6-naphthalenedicarboxy-
late 1,3-propanediol, the reactivity of hydroxyl groups in monomer and in hy-
droxypropyl chain ends is the same [118].
There are also studies for DMT 1,4-butanediol with Ti and divalent metal cata-
lysts, for which an order of one with respect to Ti and the hydroxyl and ester
groups has been reported [119]. The analysis of rate data is more dicult because
of the relatively high importance of the secondary reaction leading to THF forma-
tion (see below).
Models for Ti-catalyzed esterication are still more complex. Titanates are hydro-
lyzed by water and form oligomeric a(RO, R
/
O)aTiOa structures (unless the hy-
droxyl excess is large). These structures are more active than the monomeric tita-
nate [120]. Too much water will lead to a drop in activity [110], probably due to
formation of insoluble products. Order one was found with respect to acid, hy-
droxyl, and Ti (at a concentration of a few parts per million) [121], but there is a
slight inhibition eect by the ester groups.
The increase in activity brought about by vestiges of water has also been ob-
served both for Ti and Zr (this latter is even more active) in the model reaction of
octadecanoic acid octadecanol [122]. No simple rst-order rate law with respect
to hydroxyls and carboxyls was found in that research.
Dialkyltin catalysts (such as dibutyltin dilaurate) have catalytic properties for es-
terication and alcoholysis similar to Ti and Zr [123]. The SnaC bond is fairly sta-
ble, but the upper acceptable temperature limit is around 220
C. On the other
hand, thanks to the added exibility provided by the organic group and the possi-
bility of oligomerization, it is possible to prepare catalysts that are quite insensitive
to deactivation by vestiges of humidity [124]. Nowadays these catalysts are often
used in alkyd resin production.
3.3.1.4 Side Reactions in Aromatic Polyester Production
The important side products formed in nonthermooxidative secondary reactions
in PET formation are acetaldehyde, vinyl end groups, and diethylene glycol (DEG)
units, together with carboxyl end groups. DEG units decrease the melting point,
crystallinity and thermal stability. Acetaldehyde, even at parts-per-million level, is
detectable by its avor in drink bottles. Vinyl esters and acetaldehyde lead to chro-
mophoric products. Carboxyl end groups promote hydrolytic and thermal instabil-
ity. Additionally, these side reactions lead to a decrease in molecular weight, which
is particularly undesirable for product use in markets such as tire cord and soft
drink bottles.
Side reactions can be minimized to a certain extent by choice of operating condi-
tions and catalysis. Knowledge of this chemistry has obvious economic advantages,
and many details (for example, the inuence of catalysts and stabilizers) cannot be
found in the open literature.
Thermal scission of ethylene diester groups is a likely source of carboxyl and
vinyl end groups [125] (Scheme 3.1):
C
O
O
CH
2
CH O
H
C
O
C
OH
O
CH
C
O
+
CH
2
O
Scheme 3.1. Vinyl end group formation from PET.
This is a rst-order reaction, with no eect of catalysts or additives.
Further alcoholysis of vinyl esters yields acetaldehyde [Eq. (a)].
XCOOCHbCH
2
HOCH
2
CH
2
OOCY XCOOCH
2
CH
2
OOCY CH
3
CHO
(a)
DEG units are observed to form mainly in the rst stages of the process. The pres-
ence of a hydroxyl ester group is indispensable, as it can be shown experimentally
that DEG forms in negligible amounts if ethylene glycol is heated alone in the ab-
sence of acid catalysts [126]. Reimschuessel [127] has suggested the attack of ethyl-
ene glycol or a hydroxyethyl end group as a possible source of the DEG moieties
(see Scheme 3.2). The analogous intramolecular etherication is the source of
side product dioxane [125] (see Scheme 3.3).
Poly(butylene terephthalate) is also subject to analogous side reactions [128],
the formation of 1-butenyl end groups (Scheme 3.4) followed by splitting-o of
1,3-butadiene or tetrahydrofuran (Scheme 3.5). This latter reaction is not aected
by the metallic catalyst, but is catalyzed by the carboxyl end groups, making pro-
duction of PBT by direct esterication of terephthalic acid and 1,4-butanediol dis-
advantageous.
3.3.1.5 Side Reactions in the Formation of Unsaturated Polyesters
A recent review on the chemistry of unsaturated polyesters has been published by
Malik et al. [129]. Besides cistrans isomerization [130], the other important side
reaction is Ordelt reaction [131133] (see Scheme 3.6) which increases branching
and consumes double bonds. Both reactions are reversible and acid-catalyzed.
C
O
O
CH
2
CH
2
C
O
OH
O
CH
2
O
C
CH
2
OX
O
CH
2
CH
2
O
CH
2
O
C
CH
2
OX
O
H
+
+
Scheme 3.2. Formation of DEG moieties in PET.
C
O
OCH
2
CH
2
O
CH
2
CH
2
C
O
OH
O
CH
2
CH
2
O
CH
2
CH
2
OH
+
Scheme 3.3. Dioxane formation in PET.
3.3.1.6 Modeling of Processes of Aromatic Polyester Production
Continuous processes are currently used in the manufacture of PET. Several mod-
els have been developed, with the aim of contributing to a better design and opera-
tion. A brief discussion of their main assumptions and predictive capacities fol-
lows. Since polycondensation in solid-state and in lm-forming devices has been
analyzed previously, only the specic aspects of the initial process stages still needs
to be covered.
Earlier models for continuous processes based on DMT [134, 135] study the in-
uence of variables, such as the initial stoichiometric ratio, reactor temperatures,
and average residence times for CSTRs in series connected with distillation col-
umns, on process performance. They show it is possible to optimize conversion
and minimize formation of side products. Even if kinetics and physical equilibria
are now much better known, their qualitative conclusions should still hold.
PBT production, for which no published process models have been found,
should be described by a similar approach.
Yamada et al. [136] and more recently Kang et al. [137] have presented models of
the direct esterication process of terephthalic acid (TPA) with ethylene glycol (Fig-
ure 3.10). As TPA has a low solubility because of its high melting point, the rst
reactor in the train (esterication reactor) is operated at a higher pressure and
C
O
O
CH
2
CH O
H
C
O
C
OH
O
H
2
C CH
C
O
CH
2
CH
2
CH
2
CH
2
CH
2
H
2
C CH
HO
C
O
CH CH
2
+
+
O
Scheme 3.4. Vinyl end group formation from PBT.
C
O
O
CH
2
CH
2
C
OH
O
CH
2
CH
2
HO
O
CH
2
CH
2
CH
2
CH
2
+
Scheme 3.5. THF splitting-o from PBT.
R OH
HC CH
R'OOC COOR''
HC CH
2
COOR'' R'OOC
RO
+
Scheme 3.6. Ordelt reaction.
temperature than the pre-polycondensation reactor in order to counterbalance
this lack of solubility. The calculations show it is also possible to optimize conver-
sion and minimize side reactions by a choice of average reaction times, tempera-
tures, and pressures. There are, however, no actual plant data to validate these con-
clusions. The kinetic model uses a fragment approach similar to what was
recommended in previous sections, although without taking into account the inu-
ence of alcoholysis and acidolysis on monomer concentrations. Also, no thermo-
dynamic model has been used for predicting the solubility of TPA, only an inter-
polation between values in pure ethylene glycol and dierent oligomers.
An integrated view of recent processes for PET has presented by Yao and Ray
[138]. Most of the DEG units are shown to be produced essentially in the esteri-
cation and pre-polycondensation reactors, with very little change afterwards. Mini-
mizing vinyl ester formation, thus improving molecular weight and product qual-
ity, is achieved by decreasing residence time in the nishing wiped-lm reactor,
but increasing the residence time in the solid-state polymerization reactor, which is
operated at a lower temperature under a stream of inert gas.
3.3.1.7 Modeling of Processes for Unsaturated Polyester Production
Nava gives a brief description of the industrial processes [139]. Polyester resins
should ideally be produced with a certain predened viscosity in their solution in
acrylic/vinyl monomers and with a known, reproducible, distribution of double
bonds. Trans double bonds are much more reactive in free-radical polymerization,
and the amounts of each one should be known. Carboxyl end groups are in some
processes further converted to metal carboxylates (typically, by adding MgO) in or-
der to thicken the solution, so it is also important to control their concentration.
Therefore, it is worth developing models for these processes, and a few recent
studies have appeared in this area [101, 104], but for now they only aim at predict-
ing the concentrations of functional groups, which is not a minor task in view of
the large number of parameters needed. Modeling of the full process requires con-
sideration of the losses of volatile monomers (lack of reliable vaporliquid equilib-
ria data is a problem), and the aforementioned problems of taking into account the
low solubility of isophthalic and terephthalic acids are also pending.
Fig. 3.10. Simple model for WFR used for the direct
esterication process of terephthalic acid (TPA) with ethylene
glycol.
Description of the branched structure of the resins is less problematic than in
the case of alkyds, because the conversion of double bonds by Ordelt reaction is in
the range 10 to 20%, so the molecules are almost comb-like and the approxima-
tions used by Yang and Pascault [140] should be reasonable.
Modeling of alkyd resin production is a rather formidable task because of the
high number of distinguishable chemical groups, the branched structure of the
polymer, a nonnegligible amount of intramolecular reaction, and side reactions of
the double bonds in fatty acids. The usual problems found in previously discussed
polyesterications, namely lack of data for liquidvapor and liquidsolid equilibria
and associated mass transfers, are also present.
Industrial processes [141143] use batch stirred reactors, connected to partial
condensers in order to recover volatile glycols. Azeotropic distillation with xylene
(for instance) is often used. Monomers may be added in several steps to over-
come solubility problems. Vacuum and inert gas sparging is also used in dierent
stages. Catalysts (mostly alkyltin salts) are used to convert most of the carboxyl
groups, as specications often require less than 1 mg g
1
KOH acid value. Long
reaction times are sometimes avoided through dierent techniques for eliminating
residual carboxyls.
The same plant usually produces dierent varieties of resins, according, for in-
stance, to fatty acid content. New compositions are often sought in order to im-
prove end use properties or to compensate for uctuations of raw material prices.
Therefore, it is often necessary to look for initial amounts of monomers which sat-
isfy stoichiometric constraints (such as mole ratio and fatty acid content), will not
lead to gelation, and meanwhile keep an acceptably high M
n
(for instance).
An early review of the foundations of the macromolecular chemistry of alkyds
has been presented by Kienle [143] and simple methods for predicting gelation
conversion have been reviewed by Jonason [144]. These predictions are not very ac-
curate, but good data on intramolecular reactions and dierences of reactivity of
functional groups will be needed if better control of physico-chemical properties
is sought.
3.3.2
Polycarbonates
3.3.2.1 General Introduction
Polycarbonates are polyesters of carbonic acid formed by reaction of diols (aro-
matic, aliphatic or a mixture of both) with a derivative of carbonic acid. The rst
preparations of polycarbonates were reported by Einhorn in 1898 [155], by reaction
of phosgene with resorcinol or hydroquinone in a pyridine solution. Bischo and
van Hedenstrom in 1902 [156] obtained the same aromatic polycarbonates via
transesterication with diphenyl carbonate (DPC). Thus the main routes to poly-
carbonates were established early, but the properties of the products seemed unin-
teresting. Around 1930 aliphatic polycarbonates were studied by Carothers and van
Natta [157]. These carbonates have low melting points and thermal resistance and
are not commercially interesting as stand-alone thermoplastics. Low molecular
weight, aliphatic polycarbonates with hydroxy end groups, however, are widely
used as a diol component for the synthesis of polyurethanes and polyurethane
urea elastomers.
Following the work of Whineld and Dickson [158], who in 1941 succeeded
in preparing high molecular weight, high melting polyesters, the chemistry of
polycarbonates was re-examined. This led to the preparation of a linear, high
molecular weight polycarbonate derived from bisphenol A [BPA, or 2,2-di(4-
hydroxyphenyl)propane] by Schnell at Bayer [159, 160] and shortly afterwards by
Fox at General Electric [161]. BPA polycarbonate (BPA-PC) proved to be an out-
standing engineering thermoplastic that diers from the other polyesters in that
it is noncrystalline with a high glass transition temperature (about 150
C) and re-
tains its high transparency and toughness after molding. It has thermal stability up
to over 300
C as well as excellent mechanical, optical, and electrical properties, in-

herent re resistance, and food compatibility. Improvements of several polymer
properties such as heat resistance, melt ow, and birefringence were achieved
with dierent (co)monomers [163, 164]. However, BPA-PC remains the commer-
cially most important polycarbonate.
The original processes phosgenation in pyridine solution and melt
transesterication were soon replaced by interfacial polycondensation with phos-
gene, which proceeds at low temperatures and allows the easy production of high
molecular weight polymer. It still remains the predominant production process al-
though interest in the simpler, nonphosgene-based and environmentally more at-
tractive transesterication process revived in the 1990s; problems with the earlier
melt carbonates, in particular the poor resin color, could be overcome. Polycarbon-
ate demand has enjoyed steady growth and total production capacity in 2003 was
about 2.5 million tons per year. Approximately 12% is produced by transesterica-
tion and the percentage is expected to increase. The presentation here focuses on
the engineering aspects of BPA homopolymer production. Detailed reviews of the
synthesis and application of polycarbonates are given in Refs. 164171.
3.3.2.2 Interfacial Polycondensation
In the interfacial process, BPA and phosgene react at the boundary of two immis-
cible liquids, an aqueous alkaline BPA solution and an organic phase containing
phosgene. The overall reaction is shown in Scheme 3.7.
The synthesis proceeds in two steps: phosgenation of BPA forming oligomeric
carbonates with phenolic and chloroformate end groups; and polycondensation of
the oligomers (see Scheme 3.8). For the phosgenation, BPA is rst dissolved in an
+
NaO
C
CH
3
CH
3
ONa
-2n NaCl
C
CH
3
CH
3
n COCl
2
n
O
C
O
O
n
Scheme 3.7. Overall stoichiometry of bisphenol A polycarbonate formation.
aqueous alkaline solution as sodium bisphenolate, and phosgene is dissolved in a
solvent of chlorinated hydrocarbons (such as dichloromethane and monochloro-
benzene) which also dissolves polycarbonate. The reaction is started by dispersing
the two phases. Alternatively, liquidgas phosgene (boiling point 4
C) is fed into a
slurry of BPA in the presence of an organic solvent. At high BPA concentrations a
fourth solid phase may be present [172]. Part of the phosgene is hydrolyzed with
NaOH to NaCl and Na
2
CO
3
and an excess of phosgene (1020 mol%) is required
to compensate for hydrolysis and provide an excess of chloroformate end groups
for the following reaction step. Reaction temperatures are between 20 and 50
C
and the pH is kept between 9 and 13 by the addition of NaOH.
In the polycondensation step, a monofunctional phenol (such as 35 mol% phe-
nol, p-tert-butylphenol, p-cumylphenol) is added as a chain terminator to control
the molecular weight of the nal polycarbonate. Reaction partners are now end
groups (chloroformate and phenolic aOH; see above) and reaction rates decrease.
The nal polycondensation stages are catalyzed by tertiary amines. The amines re-
act with the chloroformate end groups to form intermediate quaternary acylium
salts which then react with phenolate to form carbonate and OH
ions, hydrolyz-
ing the chloroformate end groups, or to form a urethane in a side reaction [164].
Detailed mechanistic studies of the catalyst reaction were performed by Aquino et
al. [173] and Kosky et al. [174].
Numerous variations of the interfacial process have been published. The reac-
tions can be carried out in batch in stirred tank reactors or continuously in series
of CSTRs and tubular reactors. Intensive mixing with dispersion and redispersion
is required throughout the reaction stages. After the reaction is complete, the brine
phase is separated and the polymer solution washed to remove residual amine and
base. Several processes for devolatilization are in use, including solventless precip-
itation, steam precipitation, spray drying, falling-strand devolatilization, and vac-
uum extrusion in devolatilizing extruders.
Phosgenation is generally mass transfer-limited [175, 176] and its rate depends
on mixing as well as on pH and the volume ratio of the organic and aqueous
phases. Although the polycondensation reaction of end groups is slower, both rates
still show the same dependencies due to the interfacial nature of the reaction. The
following phenomena contribute to the reaction process:
... C *
m
Cl
O
+
... C *
m
Cl
O
+
... C *
m
Cl
O
+
... *
n
Na ... *
m
... *
m
... *
m
NaO
4 NaOH
C
O
...
n
* + NaCl
O
+ NaCl
Na + NaCl + Na
2
CO
3
+ H
2
O
Scheme 3.8. Formation of polycarbonate by interfacial polycondensation.
v
Dispersion of the two phases. Rates always depend on mixing. Eective kinetic
rate constants can be formulated as a function of energy dissipation or interfacial
area.
v
The type of emulsion. Both types of emulsions, oil in water (o/w) as well as water
in oil (w/o), can be found.
v
The partition of phenols between the phases and its pH dependence [177]. Silva
and Kosky [178] studied the reaction of hydrolysis taking into account the dier-
ent phases and the partitioning of BPA between them. Monofunctional phenols
with better solubility in the organic phase show a better eciency as chain termi-
nators.
v
Mass transfer to and across the boundaries.
v
Intrinsic (kinetic) reaction rates.
Due to the low reaction temperature and the use of chain terminator, the molecu-
lar weight distribution in interfacial synthesis is kinetically controlled and may be
far from thermodynamic equilibrium. In two parametric studies Mills [179] and
Munjal [180] have tried to model the full molecular weight distribution of polycar-
bonate. Varying the ratio of mass transfer/kinetic rates, they show how mass trans-
fer limitations can lead to a higher polydispersity or a higher oligomer content.
3.3.2.3 Melt Transesterication
The melt process is based on the transesterication of diphenylcarbonate (DPC)
and BPA (see Scheme 3.9).
The melt process requires no solvent and polycarbonate is produced directly
without the need for cleaning, drying, and devolatilization. The only by-product,
phenol, is removed and can be recycled to the production of DPC or BPA. The pro-
cess, however, requires high temperatures (190320
C) so that the polymer re-

mains molten and the viscosity can still be handled. With improved quality of the
starting materials and improved high-viscosity reactors these temperatures no lon-
ger aect polycarbonate quality and most grades can now be produced via the melt
process. The transesterication is a reversible reaction with an equilibrium con-
stant close to unity, so that the by-product phenol has to be removed for the reac-
tion to proceed. Pressures below 0.1 hPa may have to be applied for the nal stage.
n HO
OH + n OCO
O
O
OC
O
+ 2n OH
n
Scheme 3.9. Formation of bisphenol A polycarbonate by transesterication.
Small amounts of basic catalyst (< 0.01 mol% of alkyl-ammonium, or
phosphonium-salts) are mixed together with the DPC and BPA and the reaction
is started at the lower temperature. Conversion is driven by the removal of phenol
and the pressure is successively reduced while the temperature is increased. Sim-
ple reactors such as CSTRs, tubular reactors or falling-lm evaporators can be used
for the rst stages. Viscosity increases dramatically from 5 mPa s up to 1000 Pa s
as conversion increases and special reactors are needed for dealing with the high
viscosity at high conversions [149151].
The melt process depends on the reaction rates, the thermodynamic phase equi-
librium, and mass transfer between the phases. Detailed mechanistic studies of the
Li-catalyzed melt process have been published by Choi et al. [152], and of the solu-
bility of DPC and phenol in polycarbonate by Webb [153]. The liquidgas equilib-
rium has to take into account at least two components: phenol and DPC.
For a semi-batch operation for the rst stages, optimal variations of pressure and
temperature can be calculated based on the above relationships plus the assump-
tion of phase equilibrium, or on a simple relationship for the mass transfer of
each volatile component Y
i
(Eq. (55), with the mass transfer rates per unit volume
J
i
of component Y
i
, mass transfer coecient of component i k
fi
, interface area per
unit volume a
v
, and equilibrium concentration [Y
i
[
+
at the interface).
J
i
= k
fi
a
v
([Y
i
[ [Y
i
[
+
) (55)
Mass transfer coecients may be obtained by tting to process data. Including
DPC loss, production capacity (reaction time), and unwanted side products in a
cost function, the optimization leads to a balancing of mass transfer and reaction
rate. This means that an optimal process is neither entirely mass-transfer nor ki-
netically controlled. To avoid side reactions that impair product quality, the lowest
temperature that kinetics and mass transfer allow is chosen. The results of the
semi-batch optimization can be transferred to the design of a staged, continuous
process [154].
The balancing of reaction versus mass transfer rate can similarly be applied for
the last stages. The relative DPC loss compared to phenol removal is quite high for
these stages. A high fraction of phenol end groups compared to OH end groups is
desirable for product quality. Therefore, excess DPC has to be used at the begin-
ning of the reaction. Unfortunately, a high fraction of phenol end groups reduces
the concentration of one reaction partner and hence reaction rates [146].
Mass transfer and hence the speed with which phenol can be removed are re-
duced with increasing viscosity. Reactors are needed that provide a high rate of
surface renewal. These may be wiped-lm evaporators, single- or twin-screw ex-
truders, reactors of the rotating disk type or falling-strand evaporators [145, 149,
150]. Whereas the rst three reactor types create surface actively, in falling-strand
evaporators the melt is simply pumped through small holes. High surface renewal
rates are achieved by small holes, but also by shear thinning of the falling strands
[59]. The eect of shear thinning lms can also be achieved in rotating disk reac-
tors with disks that contain holes. Apart from surface renewal, mass transfer is de-
termined by diusion. Measurement of diusion coecients is dicult because of
the parallel reaction. An alternative is the determination of diusion constants us-
ing molecular dynamics simulations [148].
3.3.3
Polyamides
3.3.3.1 Introduction
Since their discovery by Carothers [181], aliphatic polyamides such as nylon-6,6
and nylon-6 are important textile bers and plastics. Similar polyamides produced
by melt reaction of aliphatic diacids diamines, or by hydrolytic polymerization of
lactams, have some interest as engineering plastics, and will also be discussed in
this section.
Aliphatic, low molecular weight, branched polyamides of dimer fatty acids with
di- and triethylenediamine are among the most widely used curing agents for
epoxide resins. The chemistry of their formation is similar to that observed for
the aforementioned crystalline linear polyamides.
Aromatic polyamides are specialty products [182], used for high-performance -
bers and composites, which are produced by solution or interfacial processes from
acid chlorides and amines.
3.3.3.2 Kinetic Modeling
The only published kinetic data on nylon-6,6 reaction are due to Ogata [183, 184],
and there is in general a great scarcity of information on the amide acid reaction.
Much more data are available on nylon-6 formation, such as in Refs. 185187.
Because of the obvious identity in average chemical group composition of both
polymers, it should be possible to reconcile both kinetic laws [188]. However,
nylon-6,6 data have been obtained at high water concentrations and relatively low
temperatures, and data on nylon-6 are in the opposite situation. Degradation
reactions of nylon-6,6 through adipic acid chain ends (see Section 3.3.3.3) compli-
cate the interpretation of kinetic data at higher temperatures. Schaer, McAuley
et al. [189] have recently obtained experimental data on the nylon-6,12 system,
which does not present these problems, and these kinetics are now much better
understood.
Apparent equilibrium and kinetic constants in these systems are seen to depend
on water concentration. It obviously changes the activity coecients of functional
groups, but no thermodynamic model has ever been used to completely describe
the mixture. The activity of water can be directly measured from knowledge of its
vapor pressure, and it has been claimed that a correlation based upon a Flory
Huggins model can predict it [190], but no model exists for taking into account
the group interactions. Some interesting ideas can be found in Ref. 191, but no
actual thermodynamic model has been developed, concentrations of hypothetical
species having been used throughout that paper.
The crux of the treatment by Schaer et al. [189] lies in the empirical correlation
expressed by Eq. (56), where b
A
and m
A
are assumed to be constant parameters;
activity coecients are based on mole fractions.
g
COOH
g
NH2
g
CONH
= b
A
m
A
[H
2
O[ (56)
As the overall composition of the system may be described by two variables, such
as [H
2
O] and [COOH], a dependence on [COOH] might be added in Eq. (56).
However, this is not needed, as no eect of the mole ratio [COOH]/[NH
2
] on the
apparent equilibrium constant has ever been detected. Insertion of the above rela-
tionship into the mass action law provides a relationship between apparent equilib-
rium constant K
a
and true thermodynamic constant K
0
[Eq. (57)].
K
a
= K
0
g
H2O
(b
A
m
A
[H
2
O[) (57)
It is seen that parameter b
A
is absorbed by the unknown thermodynamic constant,
and only the ratio g
A
= m
A
/b
A
can actually be found from experimental data. The
correlations found for the activity coecient of water are given in Eqs. (58).
g
H2O
= exp 9:624
3613
T

(Nylon 6,12)
g
H
2
O
= exp 6:390
2258
T

(Nylon 6,6)
(58)
Choosing a reference temperature T
0
= 549 K, Eq. (57) is rewritten as Eq. (59).
K
a
= K
a0
1 g
A
[H
2
O[
g
H2O
/g
H2O
(T
0
)
exp
DH
R
1
T

1
T
0

K
a0
=
b
A
g
H2O
(T
0
)
exp
DH
RT
0
DS
R

(59)
Parameters describing equilibrium (DH; K
a0
, and g
A
) have been tted simulta-
neously with a mass transfer time constant for water k
m
, appropriate to their exper-
imental set-up, and activation energy E
c
and pre-exponential factors k
c0
or k
u0
de-
scribing forward reaction through a third- or second-order rate law:
R
CONH
= k
c0
exp
E
c
R
1
T

1
T
0

[COOH[ [NH
2
[[COOH[
[H
2
O[[CONH[
K
a

R
CONH
= k
u0
exp
E
c
R
1
T

1
T
0

[NH
2
[[COOH[
[H
2
O[[CONH[
K
a

(60)
The optimum values of parameters for the third-order model are shown in Table
3.2. Their approximate correlation matrix can be found in the same reference. It
shows that parameters describing equilibrium are highly correlated with g
A
, and
the pre-exponential factor is highly correlated with k
m
. Further, there is little
change in parameters for the second-order model, which yields k
u0
= 2:64 10
7
mg mol
1
h
1
and has a similar sum of weighed squared residuals. Thus, it is not
yet possible to determine the reaction order without performing experiments with
excess of diamine or diacid, which have not yet been reported at the time of writ-
ing. The authors state the parameters thus obtained for nylon-6,12 should hold for
the other aliphatic polyamides, just correcting the equilibrium constant, which is
lower by a factor of 0.4 to 0.5 in nylon-6,12 relative to nylon-6,6.
There are several studies concluding that the apparent order of reaction changes
from two to three as conversion grows. The reason might be a nonideality eect
similar to the one observed in esterications.
Miller [192] has carried out an experimental study on aminolysis and acidolysis
reactions using carefully dried model compounds. As in esterications, acidolysis
is slower and is explained by a mechanism involving the formation of intermediate
anhydrides. Its activation energy is 27 kcal mol
1
, whereas aminolysis has the
much smaller activation energy of 13 kcal mol
1
. The rate of aminolysis was
shown to be rst order in carboxylic acid.
These results are valuable not only for dealing with block polymers, but also in
kinetic modeling, particularly with cyclic lactams: a narrow CLD will not occur be-
cause of the reorganization brought about by aminolysis.
Hydrolysis of caprolactam is autocatalytic. Mallon and Ray [191] have suggested
that its initial rate is determined by the presence of impurities.
The same authors have also remarked that the rate constant of addition of capro-
lactam to amine end groups is about what would be expected for an aminolysis
reaction.
It should also be possible to predict the concentrations of higher cyclic
oligomers, but the only usable data concern the equilibrium concentrations, and
experimental conrmation has not yet been possible [191].
3.3.3.3 Nonoxidative Thermal Degradation Reactions
The main degradation reaction of nylon-6 is decarboxylation through interaction
of a carboxyl end group and caprolactam or an amide in the polymer chain (see
Tab. 3.2. Equilibrium and rate parameters for nylon formation.
Parameter Units Estimate 95% condence interval
DH kcal mol
1
1.82 G1.42
K
a0
63.1 G6.2
g
A
g mmol
1
2:03 10
2
G0:45 10
2
E
c
kcal mol
1
22.6 G7.7
k
c0
g
2
mmol
2
h
1
3:19 10
4
G0:71 10
4
k
m
h
1
24.3 G15.4
Scheme 3.10) [193, 194]. A slow deamination reaction has also been shown to
occur.
Nylon-6,6 also degrades in the absence of oxygen, to a much greater extent than
nylon-6, and it eventually gels, as explained by the simplied mechanism in
Scheme 3.11 [195, 196].
Cyclopentanone units are created, with a decrease in molecular weight, either
from carboxyl end groups or by intrachain reaction. Losses of CO
2
and NH
3
lead
to an imbalance of end groups, a nuisance for dyeing, and also to crosslinking.
3.3.3.4 Process Modeling
Recent progress in kinetic and reactor modeling make it possible to assist the reac-
tor design and process operations with unprecedented exactness. A recent analysis
of the nylon-6,6 process [138] looked for improvements based on expansion of the
solid-state polymerization, but the gain was minor compared to what happened
with PET. The reason is the much reduced sensitivity of polyamides to by-product
removal as compared to polyesters, since the equilibrium constant of the former is
much greater.
Since the early 1970s, many researchers have modeled nylon-6 processes [197],
as reviewed by Kumar and Gupta [198]. There is an interesting optimization prob-
lem inherent to this process, which consists in adding just as much water as is
needed to start polymerization, and to get rid of it in the later stages. Because of
C
H
2
C
CH
2
CH
2
CH
2
CH
2
N
O
C
X
O
H
2
C
H
2
C CH
2
CH
2
CH
2
N
C
X
k
1
- H
2
O
k
2
- CO
2
C
H
2
C
CH
2
CH
2
CH
2
CH
2
N
HO
C
X
O
OH
Scheme 3.10. Nonoxidative thermal degradation of nylon-6.
X NH
CH
2
CH
2
CH
2
CH
2
C O
NH Y
k
2
- CO
2
k
3
XNHCO(CH
2
)
4
COOH
k
1
O
C
NH
O
X
+ NH
2
Y
- H
2
O
N
C
O
X
+ 2 NH
2
Z
k
4
N
X
Z Z + 2 NH
3
Scheme 3.11. Nonoxidative thermal degradation of nylon-6,6.
the autocatalytic nature of the caprolactam hydrolysis, back-mixing increases con-
version.
A simple and widely used reactor is the VK column (simplied continuous col-
umn), essentially a vertical tube at atmospheric pressure [193, 199], stirred by the
boiling action of water leaving the reactor mixture in the top zone.
Extensive pilot-plant tests carried by Jacobs and Schweigman [199], and further
data from industrial plant, have lead to a simple model of the VK column, consist-
ing in one or two CSTRs in series, followed by a plug-ow reactor.
Other designs [200] have improved performance by preventing water evapora-
tion at the top of the column through the use of above-atmospheric pressure.
The bottom one-third of the columns has a homogenizing function, not only
physical but also chemical, through the aminolysis reaction [201].
Vacuum stripping with a low residence time is used to eliminate most of the
large amount of caprolactam which remains because of the chemical equilibrium
of the back-biting reaction. An alternative is a hot-water extraction step, which will
also extract higher cyclic oligomers.
3.3.4
Polymerizations with Formaldehyde: Amino Resins (Urea and Melamine) and
Phenolics
3.3.4.1 Formaldehyde Solutions in Water
Formaldehyde is a gas at room temperature. It may be sold as a low molecular
weight, solid polymer (paraformaldehyde), and more conveniently as 37% or 55%
water solutions, which usually contain some methanol. Under such conditions,
nearly all the formaldehyde is transformed into methanediol and higher oligomers
(see Scheme 3.12), usually end-capped by methanol, in order to reduce the average
molecular weight and prevent precipitation of paraformaldehyde.
These reactions are not very fast at room temperature: characteristic reaction
times are of the order of minutes.
The various equilibrium constants have been measured using NMR [202] and a
model describing the vaporliquid equilibrium in that system has been developed.
3.3.4.2 Amino Resins
Reaction between a water solution of formaldehyde with urea, melamine, and sim-
ilar molecules (such as acrylamide) leads to hydroxymethylation of the nitrogens
HCHO + H
2
O HOCH
2
OH
(CH
2
O)
x
OH + HOCH
2
OH (CH
2
O)
x+1
OH + H
2
O
(CH
2
O)
x
OH+ HOCH
2
OCH
3
(CH
2
O)
x+1
OCH
3
+ CH
3
OH
HCHO + CH
3
OH HOCH
2
OCH
3
Scheme 3.12. Formaldehyde/water/methanol equilibria.
[Eq. (b)] and further condensations produce the so-called amino resins [Eq. (c)], of
which 80% are based on urea [203], the rest being nearly all produced from mela-
mine (1).
XaNH
2
HCHO XaNHaCH
2
OH (b)
XaNHaCH
2
OH YaNH
2
XaNHaCH
2
Y H
2
O (c)
Since melamine is made from urea and ammonia, it is more expensive. Mela-
mine resins are therefore chosen when one can get an appreciable benet from
their better hydrolytic or thermal resistance.
Ureaformaldehyde (UF) resins are mainly used as adhesives for wood. Lami-
nated sheets (tables and counter tops) are a major application for melamine resins,
which stay in the outer decorative surface. Molding compounds, their rst big ap-
plication, is still a major market, taking advantage of their extreme hardness and
heat resistance. Coatings, textile nishing, paper additives, leather tanning and
foundry binders, for which methanol- or butanol-etheried resins are usually em-
ployed, are important markets discussed in Ref. 203.
A major problem with the use of UF resins is their formaldehyde emission due
to hydrolysis. Formation of melamine resins is much less reversible and therefore
food contact with them is allowed.
Besides earlier classic data on the kinetics of reactions between urea, formalde-
hyde, and UF oligomers by de Jong and de Jonge [204206], only experiments by
Price et al. [207] at higher temperatures in a sealed reactor are of immediate use to
establish a kinetic model of the chemical system. Kumar and Sood [208] have pro-
posed an FSSE model for the early stage of this polycondensation. A modied ver-
sion of that model introduces the groups presented in Scheme 3.14, where their
ve urea monads U
0
. . . U
4
have been kept but three formaldehyde monads have
been used instead of two. Formation of tetrasubstituted urea is known to be negli-
gible.
Both de Jong and de Jonge, and Price et al., have considered that hydrolysis
reactions are unimolecular. Kumar and Sood [208] have considered it could be bi-
molecular, which seems to be reasonable. Available experimental data could not de-
cide for any of the alternatives, since the water concentration was always the same;
this matter needs to be solved, because higher initial concentrations of formalde-
N
N
N
NH
2
NH
2
H
2
N
1
Scheme 3.13. Melamine.
hyde are often used nowadays. Chemical transformations according to this new
model are shown in Scheme 3.15.
A possible simplication consists in distinguishing only rate constants of for-
ward reactions according to the number of hydrogens involved, and therefore
k
1
= 2k
2
= 4k
5
and k
3
= k
4
, k
6
= 2k
7
= 4k
10
and k
8
= k
9
, reducing the number of
unknown parameters.
Since the only information in the experimental data of Price et al. [207] is form-
aldehyde concentration versus time, it is not possible to estimate rate constants k
6
to k
10
from them. Although only at low temperatures, rate constants k
1
; k
3
, and k
h1
(this one measured from the rate of formation/hydrolysis of both monomethylol
urea and dimethylolurea) are nevertheless available from other sources, such as
Ref. 209. A crucial check of the FSSE hypothesis is the equality of the rst-order
hydrolysis constants of methylol groups in mono- and dimethylolurea: the rate con-
stants per mole of the chemical substances should be double for dimethylolurea.
The value of this ratio is 1.68, standard deviation 0.42, for 15 values reported by
Landqvist with dierent buers (pH 6, 7, 9.2, 10) at temperatures 20, 30 and 40
C.
U
0
=
O
C
NH
2
H
2
N
F
0
=
O
C
H H
U
2
=
O
C
NH- -HN
U
3
=
O
C
N H
2
N
U
4
=
O
C
N -HN
U
1
=
O
C
NH- H
2
N
F
1
= -CH
2
OH F
2
= -CH
2
-
Scheme 3.14. Monads in the FSSE model of urea/formaldehyde polycondensation.
W F U F U W F U F U
W F U F U W F U F U
W F U F U W F U F U
W F U F U W F U F U
W F U F U W F U F U
h h
h h
h h
h h
h h
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
k
+ +

+ + +

+
+ +

+ + +

+
+ +

+ + +

+
+ +

+ + +

+
+ +

+ + +

+
2 4 1 3 1 4 0 3
2 4 1 2 1 4 0 2
2 3 1 1 1 3 0 1
2 2 1 1 1 2 0 1
2 1 1 0 1 1 0 0
2
10
1
5
2
9
1
4
2
8
1
5
2
7
1
2
2
6
1
1
Scheme 3.15. Kinetic scheme of FSSE model of urea/formaldehyde polycondensation.
However, that ratio is 6.9 according to de Jong and de Jonge; the activation energy
of the hydrolysis is the same (20 kcal mol
1
), though, according to both research
studies.
The equilibrium constants of the rst and second hydroxymethylations of urea
are, respectively, 990 and 253 at 35
C, and there is a decrease of about 3 in the for-

ward rate constants of the successive substitutions. Interestingly, the rate con-
stants for the reaction of methylenediurea with formaldehyde or monomethylo-
lurea are identical, respectively, to those observed for urea formaldehyde and
urea monomethylolurea [210, 211].
So, there seems to be enough evidence to take FSSEs into account for urea, but
unfortunately it seems there might be no such thing as a single aCH
2
OH group,
and SSSEs should be needed for fully describing this chemistry.
For simplicity, we will keep using the above model in the discussion.
Rate constants are known to depend on pH (although not much between pH 4
and 9); there is catalysis by OH
and H
, so these constants should be written as

in Eq. (61) [204].
k
i
= k
0
i
k
OH
i
OH
| k
H
i
H
| (61)
Rate constants k
6
to k
10
in this scheme can be estimated from data of reactions in
acid media between urea, mono- and dimethylolurea [206]. In the same work, re-
action between methylols was found negligible (the temperature was at most
50
C). For these reactions, the terms k

0
i
; k
OH
i
can be neglected; the reactions are
very slow at pH > 4.
More recent work has concentrated on analysis supported by quantitative
13
C
NMR [212216] and size exclusion chromatography [217] has completed this view
of the chemistry. At high temperatures and alkaline pH, methylol groups form
methylol ether bridges and uron rings 2 (Scheme 3.16).
The preparation and possible industrial uses of uron UF resins may be found in
Ref. 218. NMR shows that these intra- or intermolecular ether bonds are destroyed
with liberation of formaldehyde at acid pH.
O
C
N HOCH
2
N
2
O
C
NH-CH
2
OCH
2
N N
O
C
N
+ H
2
O
C
N
CH
2
O
CH
2
N
O
C
N
HOCH
2
O
CH
2
N
O
H
+ H
2
O
2
Scheme 3.16. Reactions at alkaline pH in urea/formaldehyde polycondensation.
Another question, that should not be overlooked, is the incomplete solubility of
the polymer in water. Except at low conversions, the reaction medium resembles a
colloidal dispersion [219]. Gelation may be physical, before or instead of being
chemical [220].
Amino resins are nearly always made in batch processes, consisting of thermo-
stated reaction kettles connected to a condenser. The current method of synthesis
has three stages [221]:
v
synthesis of methylolated oligomers at pH 8 to 8.5;
v
acid condensation at pH 4 to 5;
v
addition of urea to decrease the nal stoichiometric ratio to 1 to 1.3.
The goal is to reduce formaldehyde emissions [222], while keeping the properties
of products (such as wood panels) at an acceptable level. Since the formaldehyde/
urea molar ratio had to be decreased, the process has also become more dicult to
control.
Modeling of the process has increased its potential importance in this context,
but the diculties of putting it into practice are considerable, because of the daunt-
ing complexity of the chemistry. Notice that it should be integrated with the mod-
eling of the cure stage (a complex combination of heat, mass, and mechanical
modeling, in the case of wood panel manufacture). Cure is performed with ammo-
nium chloride as catalyst, which also acts as a formaldehyde scavenger. Its chemis-
try is not fully understood, because of the much higher temperatures than in resin
synthesis, which lead possibly to ladder structures.
Melamine resins have a similar chemistry, the main dierence being the re-
duced importance of hydrolysis reactions. They are prepared using two stages, al-
kaline addition of formaldehyde, and acid polycondensation.
The initial stage of the melamine/formaldehyde reaction has been studied by
Nastke et al. [223], who succeeded in providing evidence not only of hydroxymethy-
lation, but also of the formation of methylene and methylene ether bridges using
polarography. The functionality of melamine is six, with a negative substitution ef-
fect of about 40% [224, 225].
As with UF, formaldehyde addition is acid- and base-catalyzed (sensitive to pH),
and equilibrium constants are 100 to 200. Methylene bridges are also formed only
at acid pH. Direct analysis of methylene ether bridges has also been performed by
NMR [226].
A simplied model (no reaction reversibility) of melamineformaldehyde forma-
tion based on Tomitas kinetic scheme [225] has been presented [227] and after-
wards extended to reaction in a CSTR [228], also considering reaction reversibility.
There is no experimental validation, but it is noteworthy for the use of a program
to calculate the CLD of a nonlinear reversible polycondensation in order to over-
come the astronomical number of reaction possibilities in the rates of formation
of individual oligomers.
3.3.4.3 Phenolic Resins
Two subclasses have to be distinguished [229]:
v
resols, which are highly branched, low molecular weight (1501500) polymers
with a formaldehyde/phenol stoichiometric ratio between 1.2 to 3, formed at al-
kaline pH;
v
novolacs, made at acid pH, with a formaldehyde/phenol stoichiometric ratio be-
tween 0.5 and 0.8, which have a dierent and much less branched structure than
resols. They are low molecular weight (5005000) thermoplastics, further cross-
linked with hexamethylenetetramine.
Phenolic resins are mainly used as wood adhesives, laminates, molded parts, insu-
lating varnishes, abrasives, and rigid foams.
Novolacs can be made using either strong acid catalysts (sulfuric acid is pre-
ferred) or at pH 4 to 7 using carboxylates of divalent metals (such as Zn, Mn,
Mg). These catalysts complex phenol and methanediol and lead to formation of o-
methylolphenol in a rst step. Subsequent addition steps may also be ortho-
directed (Scheme 3.17), or more randomly distributed (in the case of Zn).
Novolacs prepared with acid catalysts have a more random structure. The
branching density is low because nonterminal rings are less reactive. This is
caused by molecular coiling, which is especially important in high ortho-novolacs.
Phenol groups tend to associate through hydrogen bonds and change the mole-
cular conformation (Scheme 3.18). Nonterminal units are often assumed to stay
- H
2
O
M
2+
O
OH
CH
2
OH
H
CH
2
OH
OH
- M
2+
- H
2
O
- M
2+
+ OH
OH
OH
CH
2
...
Scheme 3.17. Formation of ortho-directed methylene bridges.
O
O
CH
2
O
CH
2
O
CH
2
O
CH
2
CH
2
H
H
H
H
O
H
H
Scheme 3.18. Hypothetical intramolecular hydrogen bonds in novolac resins.
preferentially inside the molecular coils and decrease their reactivity because of
this.
Mathematical models describing formation of novolacs both in batch and contin-
uous reactors have been developed by Frontini et al. [230] and Kumar et al. [231].
They consider the existence of at most one methylol group per molecule, and lump
together all isomers with the same unit counts. A Monte Carlo method [232] can
also be used in order to obtain a more detailed description at molecular level.
The initial addition of formaldehyde to phenol in alkaline media could for the
rst time be successfully described, thanks to Zavitsas and collaborators [233]. Re-
sol formation in further reactions is a complex process, owing to the several dier-
ent aromatic reaction sites and substitution eects [234]; a total of 19 can be distin-
guished [235, 236]. Concentrations of fragments have been computed, assuming
irreversible reactions. Number-average and weight-average molecular weights have
been predicted using the recursive approach. Experimental determination of the
necessary structural and kinetic parameters is a huge task, which requires exten-
sive use of
13
C NMR and synthesis of model compounds. The research informa-
tion [237, 238] allows modeling of these reacting systems to be elaborated with
better chemical support. Fairly good agreement of model and experimentally mea-
sured functional group concentrations in resol formation at various stoichiometric
ratios has been claimed [239] and it is expected that a trustworthy quantitative de-
scription of these systems may eventually be achieved. Validation of these predic-
tions is plagued by experimental diculties, and has mainly been carried out
through measurement of individual oligomer and functional group concentrations.
Reaction is exothermal (DH = 80 kJ mol
1
). Heat of reaction is removed using
water reux, sometimes with a small amount of inert solvent (aromatics are inert
only if they carry deactivating groups), and relatively small batch reactors ( 2 to 10
m
3
) are usually preferred.
Resol reactors have been the subject of studies, such as Ref. 240, concerning op-
eration in accident situations. In novolac production, formaldehyde can be fed con-
tinuously in order to increase safety.
3.3.5
Epoxy Resins
The three-membered cyclic ether group oxirane, a 1,2-epoxide, or an epoxy group
reacts with substances containing an active hydrogen group, such as amines, phe-
nols, and carboxylic acids, or can be polymerized with anion or cation initiators,
therefore yielding a great variety of potentially useful polymers. Nearly all of them
are thermosetting, and used as coatings and adhesives. Their cure processes,
which should be considered in close connection with the method of producing
the nal material, will not be discussed in this section. Instead, a brief review
of processes to make the macromonomers containing epoxy groups, the so-called
epoxy resins, will be presented.
The most widely used epoxy resins are formed through the reaction between
epichlorohydrin (ECH; 3 in Scheme 3.19) and bisphenol A.
The so-called tay process consists in the two-phase reaction of an alkaline so-
lution of bisphenol A with ECH in stoichiometric excess [241]. The main reaction
as described above is accompanied by side reactions, such as hydrolysis and alco-
holysis of chlorine and epoxides in ECH. These reactions create molecules with
functionality one or even zero, and must of course be minimized.
The kinetics has been studied by Enikolopyan et al. [242] and Gao [243], among
others. Branching formation occurs to a low extent and can usually be neglected;
the reaction can be described as a linear irreversible polycondensation AXA BYC,
with A = aOH, B = aCl, and C = epoxide (ECH and oligomers have dierent
reactivities).
The similar epoxidation of novolacs with ECH has been additionally studied by
Oyanguren and Williams [244]. In this system, intramolecular ring formation has
been measured.
The so-called advancement process consists in the melt reaction of bisphenol
A (or a similar monomer) with a bifunctional epoxy resin in the presence of a cat-
alyst, with the goal of producing a higher molecular weight, bifunctional, epoxy
resin. This process leads to branching, due to the reaction of the pendent hydroxyl
group with epoxide, and eventually gelation occurs. Its kinetics has recently been
studied by Smith and Ishida [276]. The activation energy of the branching reaction
was found to be higher (20 as compared to 18 kcal mol
1
) than that of chain exten-
sion, and both constants have been determined both for the catalyzed and noncata-
lyzed reaction.
3.3.6
Polyurethanes and Polyureas
Urethane polymers were discovered by Baeyer in 1937 [246, 247], using the addi-
tion of alcohols to isocyanates leading to carbamates (or urethanes), 4 in Scheme
3.20.
ClCH
2
CH
O
CH
2
+
HO
C
CH
3
CH
3
OH
-NaCl
CH
2
O
CHCH
2
O C
CH
3
CH
3
OCH
2
CH
O
CH
2
OCH
2
CHCH
2
O C
CH
3
CH
3
n
3
Scheme 3.19. Formation of epoxy resin by reaction of bisphenol A with epichlorohydrin.
R NCO + HO R' R N
C
H
O
O R'
4
Scheme 3.20. Addition of alcohols to isocyanates.
The analogous, much faster, reaction with primary amines produces N-
substituted ureas 5 (Scheme 3.21).
Reaction with water produces an amine and carbon dioxide through an unstable
carbamic acid intermediate (Scheme 3.22).
As the amine reacts again with isocyanate, this reaction will lead to branching, as
will consecutive reactions with carbamates, leading to allophanates 6 (Scheme
3.23) and with ureas, leading to biurets 7 (Scheme 3.24).
Trimerization of isocyanates, leading to the thermostable isocyanurate ring 8,
occurs with basic catalysts (multifunctional amines, carboxylates, alkoxides, and
so on) through allophanate intermediates [252254] (Scheme 3.25).
Isocyanate groups also react to form uretdiones 9. This is an equilibrium reac-
tion, which is mainly important at high isocyanate concentration (Scheme 3.26).
Most urethane polymers are thermosets [247, 248]. They are mainly used in the
production of foams, taking advantage of the reaction of water and of the pre-
cipitation of insoluble ureas, which stabilize the foam even before the system
R NCO + H
2
N R' R N
C
H
O
NH R'
5
Scheme 3.21. Addition of primary amines to isocyanates.
R NCO + H
2
O R N
C
H
O
O H
R N
H
H
+ CO
2
Scheme 3.22. Reaction of water with isocyanates.
R NCO R N
C
C
O
O R'
R N
C
H
O
O R'
+
O
N R
H
6
Scheme 3.23. Reaction of urethanes with isocyanates leading to allophanates.
R NCO R N
C
C
O
NH R'
R N
C
H
O
NH R'
+
O
N R
H
7
Scheme 3.24. Reaction of ureas with isocyanates leading to biurets.
gels chemically. Amine- or hydroxyethyl-capped branched polyols of molecular
weight of the order of a few thousands are preferred. They are most often star-
shaped poly(oxypropylene), in combination with shorter polyols such as glycerine,
additives such as surfactants and demolding agents, blowing agents, and water.
Rigid foams use more branched polyols than do exible foams.
Another important use is the fabrication of plastics by RIM (reaction injection
molding) (see Figure 3.11), which exploits the very fast reaction which can be
R NCO
R N
C
C
O
O R'
+
O
N H
R
N
N
N
O
O O
R
R
R
R' OH +
R N
C
C
O
O
N C
R
O
N R
H
R'
O
8
Scheme 3.25. Formation of isocyanurates.
R NCO
C
N
C
N
O
O
R R 2
9
Scheme 3.26. Formation of uretdiones.
Fig. 3.11. Scheme for an RIM machine with a jet impingement
mix-head (on a very exaggerated scale), in its recirculation and
injection modes.
achieved either with amines or with hydroxyls, in the presence of catalysts such as
dibutyltin carboxylates, tertiary amines, or a combination of the two [250]. The ex-
cellent book by Macosko [249] extensively covers this technology, which is particu-
larly well adapted to the fabrication of big, at, molded parts, and also to complex
elastomeric objects (viscosity is very low during mold lling). The whole produc-
tion cycle can take less than one minute from injection to demolding.
As with the other thermosets in this chapter, these processes will not be dis-
cussed in this section. We will nevertheless give a few hints of the reaction engi-
neering of the production of polymers and macromonomers based on this chemis-
try; other relevant uses are adhesives, binders, coatings, thermoplastic elastomers,
and bers.
The catalysis of isocyanate reactions has been extensively studied because of
its critical importance in many of these processes. Noncatalyzed (or rather, self-
catalyzed) reactions may sometimes be fast enough in practice: isocyanate reac-
tions with amines are so fast that only recent studies using stopped-ow methods
could lead to useful data [255, 256], metallic or tertiary amine catalysts being inef-
fective in this case.
As often happens with polymerization reactions, simple rate laws can seldom
describe the whole course of reaction because of catalysis or inhibition by the
urethane groups formed or by the initial reagents. Self-association of metallic cata-
lysts, or their loose complexation by products or reagents, also prevents correlation
of rates of reaction by simple proportionality or even power-law relations. Catalysis
of isocyanate reaction with hydroxyls [250, 251] is by far the best understood.
It might be thought that modeling of polyurethane processes would be relatively
straightforward, given that reactions are mostly irreversible and the methods de-
scribed in Section 3.4.4 should deal with them without diculties.
In reality, allophanate and biuret formation is reversible at temperatures above
130
C [252]. Formation of isocyanurates causes a reorganization of the CLD akin

to what happens in reversible polycondensations because of exchange reactions.
Many polyurethanes are block polymers prepared with a diisocyanate, a short
diol such as 1,4-butanediol or 1,6-hexanediol, or a diamine (the chain extender),
and a diol with molecular weight between 500 and 4000, based on a polyether,
polyester, polycarbonate, poly(butadiene) or other. Most often, the preparation is
performed in two steps: rstly, reaction of the longer polyol with the isocyanate,
then with the chain extender in the second stage.
An important and desirable feature of polyurethanes and polyureas is the phase
separation of the small isocyanate/chain extender blocks, which is possible pro-
vided the thermodynamics is favorable: this means a high enough concentration
and chain length of hard blocks. These hard blocks act as physical crosslinks
at a temperature lower than their melting point, and thermoplastic elastomers (in-
cluding elastic bers) can therefore be obtained.
From the point of view of the prediction of structure, this brings about a complex
problem, which shares some characteristics with solid-state polycondensation, and
has been tackled through the use of Monte Carlo methods [257, 258, 259].
Reactors for these processes range from simple batch or continuous stirred tank
reactors for very low molecular weight or solvent-based processes, to tubular reac-
tors with static mixers or extruders. Owing to the strong exothermicity of the main
reaction, cooling has to be used in order to prevent side reactions from becoming
too important.
Many processes at low temperature and in homogeneous phase can nevertheless
be analyzed through the methods described in Section 3.4.4, as they now stand.
3.4
Modeling of Complex Polycondensation Reactions
3.4.1
Overview
Rate equations allowing the prediction of concentrations of reactive groups, includ-
ing more complex molecular fragments (monads, dyads and so on) from mass bal-
ance equations are established in Section 3.4.2 for irreversible reactions or systems
with at most FSSEs if reversible reactions exist. Stoichiometric coecients are in-
troduced in order to obtain a fairly general formalism, later exploited in Section
3.4.4.
Knowledge of the distributions of numbers of bonds connecting repeating units
makes it possible to describe molecular structure at chemical equilibrium. In Sec-
tion 3.4.3, the main results concerning molecular weights and network properties
of chemical systems verifying FSSEs are presented, using the theory of branching
processes. The presence of rings is also allowed. The results of Section 3.4.2 are
useful in order to predict average numbers of bonds for each monad, needed for
predicting average molecular weights.
Irreversible polycondensations can be tackled quite easily using a general kinetic
approach developed in Section 3.4.4, allowing prediction of average molecular
weights before or after gelation, and even molecular weight distributions (lumping
together isomers with the same numbers of groups).
Prediction of molecular weight distributions for reversible, linear, alternating
polycondensation is discussed in Section 3.4.5. Mathematical diculties grow con-
siderably in the presence of SSSEs. There seems to be no alternative to Monte
Carlo methods for dealing with reversible nonlinear polycondensations or even lin-
ear polycondensations where more than two kinds of bonds are present.
3.4.2
Description of Reactions in Polycondensations of Several Monomers with
Substitution Eects
The goal of this section is to present a general nomenclature of chemical entities
and reactions which provides a concise form for writing the rate equations and
mass balances of chemical species. The existence of substitution eects seriously
complicates the task, because the same molecular entity has to be labeled in a dif-
ferent way, not because it has intrinsically changed, but because its neighbors have
reacted.
We introduce the following nomenclature for the species (monomer units or
functional groups) and vectors h; g; e storing their indices:
X
h
i
monomer units, h
i
A 1 . . . N
X
A
g
i
; A
g
i
functional groups which react forming bond Z
R
i
; indices g
i
; g
i
A
1 . . . N
A
W
e
i
by-products, e
i
A 1 . . . N
W
Z
R
i
bonds, i A 1 . . . N
R
Z
e
i
; Z
e
i
half-bonds, e
i
; e
i
A 1 . . . N
Z
The N
A
functional (or end) groups A
i
will be distinguished (even if chemically sim-
ilar) according to the monomer unit X
h
i
where they are attached. h is yet another
vector of indices, with size N
A
.
N
R
reactions involving pairs of functional groups create connections between
monomer units, possibly (with the well-known exceptions of epoxides and isocya-
nate reactions) also forming by-products. A total number N
W
of by-products W
i
will be considered for the sake of generality. By-product W
e
i
is formed by the reac-
tion between functional groups A
g
i
and A
g
i
creating the bond Z
R
i
.
Vectors e; g
and g
have sizes N
R
. This denition allows for more than one pos-
sible kind of bond between two given monomer units, as happens for instance if a
carboxylic acid reacts with glycerol, which possesses distinguishable primary and
secondary hydroxyls.
In some of these N
R
reactions, such as in the case of self-condensations of sila-
nols in silicone formation and of methylols in formaldehyde polymerizations, an
end group may react with itself. The number of such reactions in this subset will
be dened as N
Rs
.
For each bond, it is useful to dene a positive sense in the direction of the unit
with higher or equal index, which will be coincident for the N
Rs
reactions consid-
ered above. So, there is a total number of N
Z
= 2N
R
N
Rs
kinds of directed bonds
Z
i
, incident on monomer units X
z
i
; the set of monomer units and bonds are the
vertices and edges of a directed graph (or digraph). Vector z, of size N
Z
, therefore
contains the indices of the repeating units to which each directed bond points.
There is a one-to-one correspondence between directed bonds and half-bonds
hanging from the repeating units at each side.
The directed bonds associated with Z
R
i
will be named Z
e
i
and Z
e
i
, using yet an-
other pair of vectors of indices, e
and e
, of sizes N
Z
. Hence, the vectors z and h,
dening respectively their incident and adjacent monomer units, will be related
through h
g
i
= z
e
i
and h
g
i
= z
e
i
.
In order to avoid multiple levels of indexing in equations, the notation given by
Eqs. (62) (loosely inspired by indirect addressing of computer assembly languages)
will be used hereafter.
A
g
i
1A
[i[
Z
e
i
1Z
[i[
W
e
i
1W
[i[
X
h
i
1X
[iA[
X
z
i
1X
[iZ[
(62)
For the N
R
reactions which create new bonds from functional groups and also (very
often) a by-product, we will introduce apparent second-order rate constants of the
forward reaction (k
i
, i = 1; N
R
), as well as apparent rst-order rate constants of the
backward reactions (k
Z
i
), related to the former through the equilibrium ratios K
i
and the concentration of the corresponding by-product, if it exists, according to
Eq. (63).
k
Z
i
=
[W
[i[
[
K
i
k
i
(63)
This may look rather articial, but it helps in situations such as the thermal de-
composition of urethanes or ureas, which are rst-order reactions. By convention,
in such cases we will introduce a nil by-product W
0
(assuming that the indices are
counted starting from one) with a constant unit concentration.
If the groups react independently, by denition there is no substitution eect. The
condensation reaction creating a bond (the same as two half-bonds) can be written
as Eq. (64).
A
[i[
A
[i[
T
k
i
k
Z
i
Z
[i[
Z
[i[
W
[i[
(64)
To account for rst-shell substitution eects (FSSEs), a more general expression
[Eq. (65)] can be written, using stoichiometric coecients n:
NA
n=1
(n
A
in
n
A
in
)A
n

NW
n=1
n
W
in
W
n

NZ
n=1
(n
Z
in
n
Z
in
)Z
n
= 0 (65)
n
A
in
; n
Z
in
correspond, respectively, to functional groups A
n
and oriented bonds Z
n
coming out of the monomer unit in which stood A
[i[
, and a similar convention is
used for n
A
in
; n
Z
in
.
No FSSE means that, for every reaction i, n
A
ig
i
= n
A
ig
i
= 1, n
Z
ie
i
= n
Z
ie
i
= 1, and,
moreover, all other stoichiometric coecients are nil. Likewise, it is useful to intro-
duce the stoichiometric coecients of by-products, n
W
in
.
This trick only works with FSSEs. Higher-order substitution eects (see Sections
3.1.5 and 3.4.5) are much more dicult to describe.
In the absence of FSSEs, the exchange of bonds Z
R
i
and Z
R
j
, necessarily forming
the same by-product (e
i
= e
j
), can be described through Eqs. (66).
X
A
[i[
X
Z
[ j[
Z
[ j[
X
k
E
ij
k
E
ji
X
Z
[i[
Z
[i[
X
A
[ j[
X
A
[i[
X
Z
[ j[
Z
[ j[
X
k
E
ij
k
E
ji
X
Z
[i[
Z
[i[
X
A
[ j[
X
(66)
In the presence of FSSEs, they would be written with an algebraic notation as in
Eqs. (67).
NA
n=1
(n
AE
ijn
n
AE
ijn
n
AE
jin
)A
n

NZ
n=1
(n
ZE
ijn
n
ZE
ijn
n
ZE
ijn
)Z
n
= 0
NA
n=1
(n
AE
ijn
n
AE
ijn
n
AE
ijn
)A
n

NZ
n=1
(n
ZE
ijn
n
ZE
ijn
n
ZE
ijn
)Z
n
= 0
(67)
Stoichiometric coecients n
AE
ijn
; n
ZE
ijn
are the changes in numbers of functional
groups A
n
and bonds Z
n
, respectively, connected to the root unit X
where either
A
[i[
or A
[i[
were attached, and n
AE
ijn
; n
ZE
ijn
; n
AE
ijn
; n
ZE
ijn
are the changes in
numbers of functional groups A
n
and bonds Z
n
, respectively, connected to the root
unit X
where stood the living group A

[ j[
or A
[ j[
. The other stoichiometric coef-
cients n
AE
ijn
; n
ZE
ijn
; n
AE
ijn
; n
ZE
ijn
are the changes in the numbers of groups
attached to root unit X
which gets connected to the unit where stood the attack-

ing group, and they are nil if there are no substitution eects.
The above reactions modify the counts of functional groups of similar chemical
nature (for example, distinguishable kinds of amides/amines/carboxylic acids). If
there is only a single kind of bond, there is no net creation or destruction of func-
tional groups or bonds, as shown by the cancellation of the stoichiometric coe-
cients in Eq. (67), but a reshuing of pieces of the reacting molecules takes place.
Rates of production by chemical reaction of the various groups are obtained us-
ing Eqs. (68)(70).
R
An
=
NR
i=1
(n
A
in
n
A
in
)(k
i
[A
[i[
[[A
[i[
[ k
Z
i
[Z
[i[
[)
NR
i=1
NR
j =i1
d
e
j
e
i
[k
E
ij
[A
[i[
[[Z
[ j[
[(n
EA
ijn
n
EA
ijn
n
EA
ijn
)
k
E
ji
[A
[ j[
[[Z
[i[
[(n
EA
jin
n
EA
jin
n
EA
jin
)[ (68)
R
Zn
=
NR
i=1
(n
Z
in
n
Z
in
)(k
i
[A
[i[
[[A
[i[
[ k
Z
i
[Z
[i[
[)
NR
i=1
NR
j =i1
d
ej
e
i
[k
E
ij
[A
[i[
[[Z
[ j[
[(n
ZA
ijn
n
ZA
ijn
n
ZA
ijn
)
k
E
ji
[A
[ j[
[[Z
[i[
[(n
ZA
jin
n
ZA
jin
n
ZA
jin
)[ (69)
R
Wn
=
N
R
i=1
k
i
n
W
in
([A
[i[
[[A
[i[
[ k
Z
i
[Z
[i[
[) (70)
The reaction volume changes mostly because of by-product removal, and little be-
cause of density changes. The relative rate of change of reaction volume R
V
can be
estimated as the sum of products of the molar volume of by-products by their rate
of elimination by phase change.
The mass balances of the functional groups in a batch reactor can thus be writ-
ten as Eqs. (71).
d[A
n
[
dt
= R
An
R
V
[A
n
[
d[Z
n
[
dt
= R
Z
n
R
V
[Z
n
[
(71)
A convenient way of computing the concentrations of groups at chemical equilib-
rium consists in integrating the system of ODE [Eq. (71)] until close to steady
state.
3.4.3
Equilibrium Polycondensations with Several Monomers
Instead of the elegant but often error-prone Gordons notation, we will introduce a
more straightforward description, hopefully easier to translate into computer pro-
grams. The goal is to obtain a set of formulae for predicting average molecular
weights, molecular weight distributions, and other polymer properties, valid for ge-
neric chemical systems.
These computations assume there is some way of predicting how molecular
fragments (usually monads, unless higher-order substitution eects have to be
tackled) are mutually connected. More specically, it is necessary to know the dis-
tributions of the numbers of bonds connecting the fragments, for each kind of frag-
ment. In fact, one may need only some of the moments of the aforementioned dis-
tributions for making a few calculations.
A kinetic method may be used for this prediction, but mainly as a means to
avoid solving equations derived from mass action laws for concentrations of frag-
ments. This has been one of our motivations for presenting the formalism in Sec-
tion 3.4.2.
Each directed bond Z
i
is supposed to start a pendent chain V
i
(x
Z
; x
A
) with
counts of end groups and directed bonds x
A
and x
Z
, respectively. Notice that the
molecular graphs have to be considered as digraphs, otherwise x
Z
would be mean-
ingless: it would be impossible to know the counts of the monomer units accord-
ing to their chemical nature.
All isomeric trees with the same counts of groups are lumped into the same
chemical species leading to vector count distributions with N
ZA
= N
Z
N
A
inde-
pendent variables.
Vectors of dummy Laplace variables s
A
and s
Z
will be associated with the counts
of unreacted groups and directed bonds. Variables s
A
and s
Z
will be often ranged
together as subvectors of a vector s, of size N
ZA
.
Vector x
X
containing the counts of the monomer units can be obtained from x
Z
through Eq. (72).
x
X
= (Z
ZX
)
t
x
Z
(72)
Z
ZX
is a matrix containing the incidence vectors z dened by Eq. (73).
Z
ZX
ij
=
1 if j = z
i
0 if j 0z
i
(73)
The chemical system is further described through knowledge of the molar frac-
tions of monomers or monomer units, y
X
i
, (summing to 1) and of the molecu-
lar weights of monomer units, unreacted groups, and half-bonds, respectively
M
X
i
; M
A
i
and M
Z
i
. Hence, the molecular weight M[V
i
(x
Z
; x
A
)[ of a tree V
i
(x
Z
; x
A
)
can be computed through Eq. (74).
M[V
i
(x
Z
; x
A
)[ =
NZ
j =1
(M
X
[ jZ[
M
Z
j
)x
Z
j

NA
j =1
M
A
j
x
A
j
(74)
X
i
(x
Z
; x
A
) is, according to the concept introduced in Section 3.1.5, a monad with
vectors of group counts x
Z
and x
A
. Its concentration, normalized by the concentra-
tion of repeating units X
i
, can be thought of as a probability: the probability that a
certain repeating unit is attached to those counts of groups, as stated in Eq. (75).
PX
i
is connected to x
Z
; x
A
groups = [X
i
(x
Z
; x
A
)[/[X
i
[ (75)
Let F
X
i
(s
Z
; s
A
); F
A
i
(s
Z
; s
A
) and F
Z
i
(s
Z
; s
A
) be the probability generating functions
(pgf ) of the counts of the dierent kinds of connecting and unreacted functional
groups directly linked to a unit X
i
, an unreacted group A
i
or a directed bond Z
i
[Eq. (76)].
F
J
(s
Z
; s
A
) =
y
xZ
1
=0

y
xZ
N
Z
=0
y
xA
1
=0

y
xA
N
A
=0
y
xA
N
A
=0
PJ is connected to x
Z
; x
A
groupss
xZ
1
Z1
s
xA
N
A
AN
A
J = X
i
; A
i
; Z
i
(76)
These pgf values are mutually related through Eqs. (77) and (78), in which 1
N
means a vector with N components equal to 1.
F
Aj
(s) = s
1
Aj
qF
X
[ jA[
q log s
Aj
qF
X
[ jA[
q log s
Aj
[s=1N
ZA
= s
1
Aj
L
X
[ jA[
Aj
(s)/l
X
[ jA[
Aj
(77)
F
Z
j
(s) = s
1
Zj
qF
X
[ jZ[
q log s
Z
j
qF
X
[ jZ[
q log s
z
j
[s=1N
ZA
= s
1
Zj
L
X
[ jZ[
Zj
(s)/l
X
[ jZ[
Zj
(78)
Notice the use of L with lower indexes for the derivatives of the pgf values with
respect to the logarithms of dummy Laplace parameters, as well as of l for their
moments, a useful convention which will be encountered often in the rest of this
chapter.
If a pgf relative to the count of monomer units is desired, for a vector of dummy
Laplace variables s
X
, it can be found by obtaining the pgf with respect to the counts
of directed bonds with Eq. (79).
s
Z
= Z
ZX
s
X
(79)
The average numbers of bonds Z
j
; l
X
i
Zj
, and of unreacted functional groups A
j
; l
X
i
Aj
,
attached to a monomer unit X
i
, will be often needed, and can be obtained using
Eqs. (80) and (81).
l
X
i
Zj
=
qF
X
i
q log s
Z
j
[s=1N
ZA
(80)
l
X
i
A
j
=
qF
X
i
q log s
A
j
[s=1N
ZA
(81)
The mass of polymer per mole of monomer units, M
P
, can therefore be computed
using Eq. (82).
M
P
=
NX
i=1
y
X
i
M
X
i

NZ
j =1
l
X
i
Z
j
M
Zj

NA
j =1
l
X
i
A
j
M
Aj

(82)
For the classic self-polycondensation of XA
f
, with equal and independent groups
A; p, the conversion of A groups, is introduced in Eqs. (83).
F
X
= [(1 p)s
A
ps
Z
[
f
F
Z
= F
A
= [(1 p)s
A
ps
Z
[
f 1
l
X
Z
= f p l
X
A
= f (1 p)
(83)
M
P
= M
X
f pM
Z
f (1 p)M
A
Expressions for the less trivial case XA
f
YB
g
C illustrated diagrammatically
in Figure 3.12, A reacting with B or C, B not reacting with C (such as adipic
acid glycerol, f = g = 2), with constant reactivity of end groups A; B, or C, are
presented in Table 3.3.
Group counts have multinomial distributions for these simple systems and can
be easily related to conversions of functional groups (which are the probabilities of
reaction).
The theory of branching processes leads to a system of N
Z
algebraic equations
[Eqs. (84)] for the pgf of pendent trees of the dierent kinds:
V
i
(s
Z
; s
A
) = s
Z
i
F
Z
i
[V(s
Z
; s
A
); s
A
[ i = 1; . . . ; N
Z
(84)
The vector v of the N
Z
probabilities of extinction (the fractions of nite pendent
chains) v = V(1
NZA
) contains the solutions of system (84) for s = 1
NZA
.
Gelation occurs when system (84) has a double root v = 1
NZA
for s = 1
NZA
, imply-
ing that its Jacobian becomes nil [Eq. (85)].
qF
Z
i
qn
j

I
= [[L
Z
i
z
j
(1
NZA
)[ I[ = 0 (85)
For the polycondensation of a single monomer, this leads to the well-known result
of Eq. (86).
Fig. 3.12. Example of proposed notation: polycondensation XA
2
YB
2
C.
Tab. 3.3. Probability generating functions F describing polycondensation XA
f
YB
g
C and its
gelation condition.
F
X
=
F
XX
F
XY

[(1 p
A
)s
A
p
AB
s
ZAB
p
AC
s
ZAC
[
f
[(1 p
B
)s
B
p
B
s
ZBA
[
g
[(1 p
C
)s
C
p
C
s
ZCA
[

F
Z
=
F
ZAB
F
ZAC
F
ZBA
F
ZCA
[(1 p
B
)s
B
p
B
s
ZBA
[
g1
[(1 p
C
)s
C
p
C
s
ZCA
[
[(1 p
B
)s
B
p
B
s
ZBA
[
g
[(1 p
A
)s
A
p
AB
s
ZAB
p
AC
s
ZAC
[
f 1
[(1 p
A
)s
A
p
AB
s
ZAB
p
AC
s
ZAC
[
f 1
F
A
=
F
AA
F
AB
F
AC
[(1 p
A
)s
A
p
AB
s
ZAB
p
AC
s
ZAC
[
f 1
[(1 p
B
)s
B
p
B
s
ZBA
[
g1
[(1 p
C
)s
C
p
C
s
ZCA
[
[(1 p
B
)s
B
p
B
s
ZBA
[
g
Gelation condition gp
Bg
p
ACg
(g 1) p
Bg
p
ABg
p
Cg
p
ABg
=
1
f 1
p
g
=
1
f 1
(86)
Prediction of the gel point for XA
f
YB
g
C is also presented in Table 3.3.
The pgf values of trees starting with a prescribed monomer unit X
i
, an unreacted
group A
i
, or a directed bond Z
i
, are obtained from the theory of branching pro-
cesses through Eqs. (87) and (88).
G
Y
i
(s
Z
; s
A
) = s
Y
i
F
Y
i
[V(s
Z
; s
A
); s
A
[ Y = Z; A (87)
G
X
i
(s
x
; s
A
) = s
X
i
F
X
i
[V(Z
ZX
s
X
; s
A
); s
A
[ (88)
The chain length or molecular weight distribution of polymer is usually described
primarily with the help of the molar concentration of species with x monomer
units, [P
x
[, in which x is the degree of polymerization. Since we are dealing with
several kinds of units, an overall degree of polymerization can be dened, which is
the sum of the degrees of polymerization corresponding to the various monomer
units (the components of vector x
X
). Notice that vector x
Z
with the counts of di-
rected bonds has more information about the molecular composition.
There is a basic diculty when trying to use Eqs. (87) and (88): they provide pgf
values of monomer units or groups, not directly molar concentrations of polymer
molecules, even as generating functions. These latter will have to be computed rel-
ative to the molar concentrations of the various groups or monomer units, and
thus will come multiplied also by the number of those groups in the distributions.
For instance, if there is only one kind of monomer unit and so just one kind of
directed bond, G
X
as computed by Eq. (88) will provide the generating function of
x[P
x
[/[X[ with respect to x; for an alternating polycondensation of two monomers,
G
X1
(s
Z1
; s
Z2
) as computed by Eq. (88) will provide the generating function of
x
1
[P(x
1
; x
2
)[/[X
1
[ with respect to x
1
and x
2
.
Fractions of units and groups of the various kinds in nite molecules (in sol),
after gelation, y
SX
i
; y
SZ
i
and y
SA
i
, can be computed by replacing s = 1
NZA
in the
above equations to give Eq. (89).
y
SY
i
= F
Y
i
(v; 1
NA
) Y = X; Z; A (89)
Prediction of the elastic properties of networks using rubber elasticity theory is
based upon the knowledge of concentrations of elastically active network junctions
(EANJs) and chains (EANCs), respectively m
e
and n
e
[260, 261]. EANJs are the inter-
section of at least three chains leading to the gel, whereas EANCs are the chains
linking EANJs (see Figure 3.13).
These concentrations can be easily predicted, given the probabilities of extinction
and the moments with respect to the numbers of pendent chains as previously de-
ned. Dening x
Zy
as the count of innite pendent chains and the correspondent
dummy Laplace variable as s
Z
y
, its pgf for the chains stemming out of a monomer
unit X
i
is F
X
i
[v s
Zy
(1
NZ
v); 1
NA
[, and so m
e
and n
e
can be computed using Eqs.
(90) and (91).
m
e
=
N
X
i=1
[X
i
[
1 F
X
i
(v; 1
NA
)
N
Z
j =1
n
j
(1 n
j
)L
X
i
Z
j
(v; 1
NA
)
1
2
NZ
j =1
NZ
k=1
n
j
n
k
(1 n
j
)(1 n
k
)L
X
i
Zj Z
k
(v; 1
NA
)
(90)
n
e
=
1
2
NX
i=1
[X
i
[
NZ
j =1
[l
X
i
Zj
n
j
(1 n
j
)L
X
i
Zj
(v; 1
NA
)[
NZ
j =1
NZ
k=1
n
j
n
k
(1 n
j
)(1 n
k
)L
X
i
Z
j
Z
k
(v; 1
N
A
)
(91)
For instance, assuming the so-called phantom network model, shear modulus
G
e
would be predicted for gaussian chains to be given by Eq. (92).
G
e
= RT(n
e
m
e
) (92)
In the presence of gel, it is convenient to introduce the pgf of nite pendent chains,
named
^
VV
i
(s
Z
; s
A
), and the pgf of counts of nite pendent chains connected to units
or groups, which can be found using Eqs. (93) and (94).
Finite pendent chain
Infinite pendent
chain
Junction
EANJ
EANC
EANJ
Chain connecting to gel
Fig. 3.13. Elastically active and inactive junctions and chains in a polymer network.
^
FF
Y
i
(s
Z
; s
A
) = F
Y
i
(n
1
s
Z1
; . . . ; n
NZ
s
ZNZ
; s
A
)/y
SY
i
= F
Y
i
(v5s
Z
; s
A
)/y
SY
i
Y = X; Z; A (93)
^
VV
i
(s
Z
; s
A
) = s
Z
i
^
FF
Z
i
[
^
VV(s
Z
; s
A
); s
A
[ i = 1; N
Z
(94)
So, the various pgf values with respect to the dierent kinds of groups in the
molecules of the sol,
^
GG
X
i
(s
Z
; s
A
);
^
GG
Z
i
(s
Z
; s
A
);
^
GG
A
i
(s
Z
; s
A
), can be computed using
Eqs. (95).
^
GG
Y
i
(s
Z
; s
A
) =
^
FF
Y
i
^
VV(s
Z
; s
A
); s
A
| Y = X; Z; A (95)
After computing the probabilities of extinction, the moments in Eq. (96) can be
evaluated.
^
ll
Y
i
Zj ...Z
k
= L
Y
i
Zj ...Z
k
(v; 1
NA
)/y
SY
i
Y = Z; A (96)
Pgf values of nite pendent chains with respect to molecular weight, for which the
dummy Laplace variable associated with molecular weight is s
M
, can be found from
Eq. (97) (notice the conventional use of a power of a scalar to a vector):
^
VV
M
i
(s
M
) =
^
VV
i
(s
MZ
1
M
X[1Z[
M
; . . . ; s
MZ
N
Z
M
X[N
Z
Z[
M
; s
MA
1
M
; . . . ; s
MA
N
A
M
) =
^
VV
i
(s
MzMXz
M
; s
MA
M
)
(97)
Prediction of average molecular weights is now possible by introducing G
M
(s
M
),
the pgf values of the mass fractions of the polymer molecules in the sol, w
i
, with
respect to their molecular weight M
i
, dened below; the index i in the innite sum
sweeps all nite polymer molecules.
G
M
(s
M
) =
y
i=1
s
M
i
M
w
i
=
Y=X; Z; A
NY
i=1
w
Y
i
s
MY
i
M
^
FF
Y
i
[
^
VV
M
(s
M
); s
MA
M
[ (98)
The mass fractions of the units and groups in Eq. (98) above are relative to the
mass of the sol.
The weight fraction of the sol w
S
, relative to the overall mass of the polymer
computed by Eq. (82), is therefore given by Eqs. (99)(102).
w
S
=
NX
i=1
y
X
i
y
SX
i
M
X
i

NZ
j =1
^
ll
X
i
Zj
M
Zj

NA
j =1
^
ll
X
i
A
j
M
Aj

M
P
(99)
w
X
i
=
y
X
i
y
SX
i
M
X
i
M
P
w
S
(100)
w
Z
i
=
M
Z
i
NX
j =1
y
X
j
y
SX
j
^
ll
Xj
Z
i
M
P
w
S
(101)
w
A
i
=
M
A
i
NX
j =1
y
Xj
y
SX
i
^
ll
X
j
A
i
M
P
w
S
(102)
Before carrying out the evaluation of distributions and average molecular weights,
a special reasoning must be carried out in order to compute number-average mo-
lecular weight and degrees of polymerization. When it is taken into account that,
with the reaction of every pair of end groups in nite molecules, one polymer mol-
ecule is consumed, the number of moles of polymer molecules per mole of mono-
mer units before gelation is given by Eq. (103).
y
P
= 1
1
2
NX
i=1
y
X
i
NZ
j =1
l
X
i
Zj
(103)
After gelation, the more general expression [Eq. (104)] is needed.
y
P
=
NX
i=1
y
X
i
y
SX
i
1
1
2
NZ
j =1
^
ll
X
i
Zj

(104)
The number-average molecular weight of the sol can thereafter be computed
through Eq. (105).
M
n
=
NX
i=1
y
X
i
y
SX
i
M
X
i

NZ
j =1
M
Z
i
^
ll
X
i
Z
j
NA
j =1
M
A
i
^
ll
X
i
A
j

NX
i=1
y
X
i
y
SX
i
1
1
2
NZ
j =1
^
ll
X
i
Zj
(105)
An expression for the number-average degree of polymerization of the sol follows
from Eq. (105) by setting the molecular weights of monomer units equal to one
and the molecular weights of bonds and unreacted groups equal to zero [Eq. (106)].
x
n
=
NX
i=1
y
X
i
y
SX
i
N
X
i=1
y
X
i
y
SX
i
1
1
2
N
Z
j =1
^
ll
X
i
Z
j
(106)
The moments with respect to molecular weight l
M
; l
MM
, and so on, can be now
obtained through dierentiation of Eq. (98) with respect to log s
M
and setting
s
M
= 1. First of all, the systems of linear algebraic equations (107)(113) must be
solved.
[m
Z
i
[ = [d
j
i

^
ll
Z
i
Z
j
[
1
[M
Z
i
M
X
[iZ[
[ (107)
[m
A
i
[ = [d
j
i

^
ll
Z
i
Zj
[
1
[
^
ll
A
i
Zj
[[M
A
i
[ (108)
[m
ZZ
i
[ = [d
j
i

^
ll
Z
i
Z
j
[
1
2(M
Z
i
M
X
[iZ[
)
NZ
l =1
m
Z
l
^
ll
Z
i
Z
l
NZ
l =1
NZ
m=1
m
Z
l
m
Z
m
^
ll
Z
i
Z
l
Zm

(109)
[m
ZA
i
[ = [d
j
i

^
ll
Z
i
Zj
[
1
(M
Z
i
M
X
X[iZ[
)
NA
m=1
M
Am
^
ll
Z
i
A
k
NZ
l =1
NA
m=1
m
Z
l
M
Am
^
ll
Z
i
Z
l
Am

(110)
[m
AA
i
[ = [d
j
i

^
ll
Z
i
Z
j
[
1
NZ
l =1
NA
m=1
m
A
l
M
Am
^
ll
Z
i
Z
l
Am

NA
l =1
NA
m=1
M
A
l
M
Am
^
ll
Z
i
A
l
Am

(111)
[m
MZX
i
[ = [d
j
i

^
ll
Z
i
Z
j
[
1
[(M
X
[iZ[
M
Z
i
)
2
[ (112)
[m
MA
i
[ = [d
j
i

^
ll
Z
i
Zj
[
1
[M
2
A
i
[ (113)
Weight-average and z-average molecular weights are now obtained explicitly
through Eqs. (114) and (115).
l
M
=
qG
M
q log s
M
[s
M
=1
= M
w
=
Y=X; Z; A
N
Y
i=1
w
Y
i
M
Y
i

N
Z
j =1
(m
Z
j
m
A
j
)
^
ll
Y
i
Z
j
N
A
j =1
M
Aj
^
ll
Y
i
A
j

(114)
l
MM
= M
w
M
Z
=
Y=X; Z; A
NY
i=1
w
Y
i
M
2
Y
i
2M
Y
i
NZ
j =1
(m
Z
j
m
A
j
)
^
ll
Y
i
Zj

NA
j =1
M
A
j
^
ll
Y
i
Zj

NZ
j =1
NZ
k=1
(m
Z
j
m
A
j
)(m
Z
k
m
A
k
)
^
ll
Y
i
Zj Z
k
NZ
j =1
(m
ZZ
j
2m
ZA
j
m
AA
j
m
MXZ
j
m
MA
j
)
^
ll
Y
i
Z
j
2
NZ
j =1
NA
k=1
(m
Z
j
m
A
j
)M
A
k
^
ll
Y
i
Zj A
k
NA
j =1
NA
k=1
M
Aj
M
A
k
^
ll
Y
i
A
j
A
k
NA
j =1
M
2
A
j
^
ll
Y
i
A
j
(115)
Except for extremely simple polycondensations, formulae for predicting average
molecular weights are very cumbersome and numerical evaluation is a must.
The weight-average and z-average degrees of polymerization, x
w
and x
z
, are
obtained in the same way as for number-average degrees of polymerization: the
molecular weights of the monomer units are set equal to one and the molecular
weights of bonds and unreacted groups are set equal to zero. For the polyconden-
sation of a single monomer XA
f
, this leads to Eqs. (116) and (117).
x
w
=
1 p(2v 1)
1 p[1 v( f 2)[
(116)
x
z
= 1
2f pv f p
2
v( f 1)(1 p pv)
f 2
(1 p 2pv)[1 p( f 1)(1 p pv)
f 2
[
( f 1)( f 2)p
2
v
2
(1 p 2pv)[1 p( f 1)(1 p pv)
f 2
[
2
(117)
The number-average degree of polymerization x
n
is obtained through a stoichio-
metric reasoning as previously discussed [Eq. (118)].
x
n
=
1 p pv
1 p pv(1 f /2)
(118)
Values of average degrees of polymerization versus conversion of end groups p
shown for f = 2 and f = 3 in Figure 3.1 have been computed using the above
expressions.
Pgf values of the various distributions with respect to the counts of monomer
units, bonds, or unreacted functional groups can be obtained from Eq. (98) by set-
ting equal to one the molecular weight of the species in question and to zero the
molecular weights of all the other species. Analytical inversion by computing deriv-
atives with respect to dummy Laplace variables on s = 0 is feasible with the sim-
plest chemical systems, for which the resulting recurrence formulae are not too
complex, as happens with the Stockmayer distribution.
Numerical inversion of generating functions of the concentration distributions is
usually a better way to predict them. Unless the cost of evaluating G(s) =
y
x=0
s
x
[P
x
[
is too high and more sophisticated methods based upon Laplace transform inver-
sion are needed, an accurate evaluation can be obtained using the method inde-
pendently developed by Mills [262] and ourselves [263] (see also Ref. 264 for a thor-
ough analysis of round-o and truncation errors of similar approaches). It consists
in computing the inversion contour integral on a circle C in a complex plane cen-
tered on the origin with radius [s[ slightly below 1, using the trapezium rule and
Fast Fourier Transform for evaluating the sums [Eq. (119)].
[P
x
[ =
[s[
x
N
N1
m=0
exp
2pimx
N

G(s
m
)
y
n=1
[P
xNn
[[s[
Nn
(119)
The second term in Eq. (119) can be neglected for large enough N or small enough
[s[. A recent surge on this approach has led to exploitation of other more complex
but hopefully more ecient methods [265], mainly developed for Laplace trans-
form inversion, and so more adapted to high average molecular weights. The error
of those formulae is more complex to control, unlike Eq. (119).
Besides molecular weight distribution, it is also possible to access readily some
information about the distribution of molecular sizes and other polymer proper-
ties, such as the angular dependence of light scattering intensity. The evaluation
of averages involving the distances of every pair of monomer units is required,
and a starting point for that purpose is the evaluation of the trail generating func-
tions [3133], allowing the counting of path lengths.
Equilibrium polycondensation of a single monomer XA
f
taking FSSEs into
account has been analyzed by Gordon and Scantlebury [268] using TBP, and exper-
imental results concerning the POCl
3
/P
2
O
5
system have been successfully de-
scribed. More general calculations are better carried out using the method de-
scribed by Kuchanov et al. [267], summarized below for the polycondensation of
XA
f
(but only in the absence of gel).
Chemical equilibrium will be attained in two hypothetical stages:
1. All the rings are formed, but no fused rings, such as naphthalene, are allowed
and molecules look like cactus [266]. The fraction of repeating units X in
rings of size n (n = 1; y) at the end of this stage is assumed to be y
Xc
(n), sum-
ming 1 y
c
, which will be found afterwards from mass action laws. No other
reactions of functional groups A occur.
2. The unreacted monomer and the rings start a polycondensation with an innity
of monomers with a single group A and dierent functionalities, which are f for
the unreacted monomer coming from stage 1 and n( f 2) 1 for the rings.
Dening s
Cn
as the dummy Laplace variables associated to the counts of rings
(including s
C0
for the count of units X in the chains connecting rings) and s
Zl
as the variable counting the bonds not belonging to rings, the generating func-
tion of the trees with either a ring or a unit not belonging to any ring can be
found from TBP as shown in Eqs. (120).
V = F
Zl
(V) = b
0
s
C0
[s
A
(1 a
r
) a
r
V[
f 1
y
n=1
b
n
s
Cn
[s
A
(1 a
r
) a
r
V[
n( f 2)1
G = (1 y
c
)s
C0
[s
A
(1 a
r
) a
r
V[
f
y
n=1
y
Xc
(n)s
Cn
[s
A
(1 a
r
) a
r
V[
n( f 2)
b
0
=
f (1 y
c
)
f 2y
c
; b
n
=
( f 2)y
Xc
(n)
f 2y
c
(120)
A pgf for the counts of repeating units X will result from substituting s
C0
in Eq.
(120) by s
X
and s
Cn
by s
n
X
. Variable a
r
in the expressions (120) is the probability of
reaction of the unreacted functional groups after ring formation in stage 1. It is
necessary to eliminate it, and to introduce the mass action laws for the rings. This
last step is not straightforward, as it requires the application of graph theory in or-
der to compute the concentrations of linear polymer molecules [L
n
[ in Eq. (23).
The nal result, which reduces to the distribution found by Jacobson and Stock-
mayer in their classic paper [21] for f = 2, is Eq. (121).
[P
x
[ = [X[( f 2y
c
)
[x( f 1)[!a
x1
r
(1 a
r
)
x( f 2)2
x![x( f 2) 2[!
f (1 y
c
)
f 2y
c

x
y
Xc
(n) =
nK
c
(n)
[X[
q
n
; q =
f ( f 1)a
r
(1 y
c
)
f 2y
c
y
n=1
nK
c
(n)q
n
= [X[ y
c
; y
c
=
f (p a
r
)
2(1 a
r
)
(121)
A solution is also known for the analogous system of the alternating polycondensa-
tion XA
f
YB
g
[267].
Dilution with an inert solvent will make [X] decrease without aecting the cycli-
zation constants much, and the fraction of rings will increase, until it becomes
practically unity, a phenomenon which has experimental support obtained using
polysiloxanes as model polymers. In bulk systems, the fraction of rings is usually
only a few per cent.
With nonlinear polycondensations of aliphatic monomers, gel points in bulk are
aected by a few per cent due to cyclizations, and elastic properties are also af-
fected (that eect using TBP has been modeled by Dusek et al. [269]). Application
of the approach described above could lead to improved modeling where small
numbers of rings are present.
Taking cyclizations into account raises the question of introducing information
about the spatial location of atoms in models of network formation. The classic ge-
lation theory described here considers a uniform distribution in space of all the
chemical properties. Stauer, one of the main contributors to the progress of per-
colation theory, has strongly criticized this view, claiming that Gordons theory is
inapplicable in the vicinity of gel point [270]. Gordon has not accepted that argu-
ment [271], claiming his theory to be universal and capable of describing gel for-
mation in any homogeneous system.
A new theory, starting with classic gelation theory and using TBP as a particular
case, has been developed by Kuchanov [272, 273], and considers the molecular
graphs to be embedded in ordinary three-dimensional space not in a lattice, as
is usually done in percolation theory. Generating functions are replaced by generat-
ing functionals of the ensemble of positions of the functional groups and repeating
units. Dependence of space coordinates is eventually eliminated by averaging, so
the algebraic equations become integral equations. In spite of its power, it has not
become a widely used instrument for dealing with real complex chemical sys-
tems, and we leave it here only for reference, as even a basic but comprehensible
description would be too extensive.
3.4.4
Kinetic Modeling of Irreversible Polycondensations
In his pioneering study of nonlinear polycondensation [7], Stockmayer has already
checked his statistical solution [Eq. (5)] by solving the mass balance equations in a
batch reactor for the concentrations of functional groups A and the set of isomeric
polymer molecules P
x
with x repeating units X [Eqs. (122)].
d[P
x
[
dt
= k
1
2
x1
y=1
[ y( f 2) 2[[(x y)( f 2)
2[[P
y
[[P
xy
[ [A[[x( f 2) 2[[P
x
[
d[A[
dt
= k[A[
2
; [P
x
[
[t=0
= [X[; [A[
[t=0
= f [X[
(122)
The two solutions are identical. Hence, for a long time no importance was attrib-
uted to the use of a kinetic approach for describing batch polycondensations start-
ing from monomers, and the statistical approach was preferred. Of course, chemi-
cal engineers had to deal with semi-batch and continuous stirred tank reactors
where the statistical approach, although possible, is cumbersome and error-prone,
so a few papers appeared in the 1960s dealing with kinetically controlled linear
polycondensations [274276].
In reality, Kuchanov [277, 278] has shown that,with polycondensations present-
ing FSSEs, kinetic and statistical approaches give distinct results for average mo-
lecular weights and gel points. Dusek [279] has pointed out that this behavior is
even more visible when dealing with polyadditions (linear polyaddition leads to a
Poisson CLD, whereas a simplistic use of a statistical approach would lead to a
geometrical/SchulzFlory CLD) and has conrmed this result using Monte Carlo
simulation of XA
f
polycondensation with FSSEs [280]. Sarmoria and Miller [35]
have tried to extend the recursive approach to systems presenting FSSE by con-
sidering network building starting from dyads and larger fragments. But chemical
systems can be found in which this latter idea does not provide useful results
[281], so that use of statistical approaches outside the description of chemical equi-
librium now seems more like a waste of time.
Kuchanovs kinetic approach divides polymer molecules into classes P(x) having
a vectorial count of groups x. In this approach, groups A
n
should include not
only the unreacted functional groups, but also the bonds and repeating units, and
even larger molecular fragments when needed. We will use N
XZA
as the number of
kinds of groups in that generalized sense.
It is possible to obtain a rate equation for the members of each class by adding
the contributions of the various condensation reactions, leading to a version of
Smoluchowskis coagulation equation.
Ring-forming reactions involving functional groups in the same monomer can
be described by a simple extension of the preceding FSSE model, just by consider-
ing unimolecular reactions and new fake functional groups, which are pairs of
groups [Eq. (123)].
A
[i
+
[

k
+
i
NXZA
n=1
n
+
in
A
n
i = 1; N
+
R
(123)
The rate of formation of groups requires a modication of Eq. (68), since it is no
longer possible to include breakage or exchange reactions. Adding the unimolecu-
lar reactions dened above, the new general rate equation becomes Eq. (124).
R
An
=
NR
i=1
(n
in
n
in
)k
i
[A
[i[
[[A
[i[
[
N
+
R
i=1
n
+
in
k
i
[A
[i
+
[
[ (124)
The multiple sums in the rate of formation of P(x), which will not be presented,
are simplied through consideration of its generating function [Eqs. (125), (126)]
G
RP
(s) =
N
R
i=1
k
i
G
ni
G
ni
qG
q log s
[i[
qG
q log s
[i[
qG
q log s
[i[
[A
[i[
[
qG
q log s
[i[
[A
[i[
[

N
+
R
i=1
k
+
i
qG
q log s
[i
+
[
(G
+
ni
1) (125)
where
G
J
ni
=
NXZA
n=1
s
n
J
in
n
J = ; ;
+
(126)
Equation (125) replaces a similar expression in Ref. 282 with the advantage of
considering only the reactions actually taking place, and not every combination of
pairs of unreacted groups, which does not make sense now, as repeating units are
also A
n
moieties.
Insertion of Eq. (125) into mass balance equations, such as a continuous stirred
tank reactor (CSTR) with constant volume, leads to a nonlinear rst-order PDE
[Eq. (127)].
qG
qt
=
N
R
i=1
k
i
G
ni
G
ni
qG
q log s
[i[
qG
q log s
[i[
qG
q log s
[i[
[A
[i[
[
qG
q log s
[i[
[A
[i[
[

N
+
R
i=1
k
+
i
qG
q log s
[i
+
[
(G
+
ni
1) R
V
G
G
F
(s) G(s)
t
G(s)
[t=0
= G
0
(s) (127)
Solution of the above equation by the method of characteristics [283] is described
in Ref. 282, earlier examples being found in Refs. 284286. They will not be repro-
duced here, for the sake of brevity. If G(s) is to be evaluated, in order to take advan-
tage of the numerical inversion formula Eq. (119), or if average degrees of polymer-
ization in the presence of gel have to be predicted, numerical solution of Eq. (127)
leads to a two-point boundary solution problem with twice as many unknowns
as the number of derivative terms log s
n
(the number of active groups in the
polymer).
A much simpler problem, as Galina was apparently the rst to remark [287], is
the prediction of the moments of [P
x
[ with respect to the counts of groups, l
P
mn...
, in
the absence of gel. Dierentiation of Eq. (126) with respect to log s
n
and setting
s = 1
NZXA
leads to an ODE system with known initial conditions, which has a
straightforward numerical solution [Eq. (128)].
dl
P
jk
dt
=
NR
m=1
k
m
[(n
mk
n
mk
)(n
mj
n
mj
)[A
[m[
[[A
[m[
[
(n
mj
n
mj
)(l
P
[m[k
[A
[m[
[ l
P
[m[k
[A
[m[
[)
(n
mk
n
mk
)(l
P
[m[ j
[A
[m[
[ L
P
[m[ j
[A
[m[
[) l
P
[m[ j
l
P
[m[k
l
P
[m[ j
l
P
[m[k
[
N
+
R
m=1
k
+
m
(l
P
[m
+
[ j
n
+
mk
l
P
[m
+
[k
n
+
mj
[A
[m
+
[
[n
+
mj
n
+
mk
)
l
P
jkF
l
P
jk
t
R
V
l
P
jk
(128)
As there is no gel, a rate equation for the overall concentration of polymer [P[
(zeroth-order moment) is obtained from Eq. (126), setting s = 1
NZXA
[Eqs. (129)].
q[P[
qt
=
NR
i=1
k
i
[A
[i[
[[A
[i[
[ R
V
[P[
[P[
f
[P[
t
[P[
[t=0
= [P[
0
(129)
Number-average and weight-average molecular weights are found by the well-
known expressions (130).
M
n
=
NZXA
n=1
M
A
n
[A
n
[
[P[
M
w
=
NZXA
m=1
NZXA
n=1
M
A
m
M
A
n
l
P
mn
NZXA
n=1
M
An
[A
n
[
(130)
This approach can only deal with ring-forming reactions either for a limited num-
ber of the smallest rings, or alternatively, for linear polycondensations. The impor-
tant practical case of the irreversible polycondensation of AXA BYB BYC (C
being an inert group) leads to the rate laws in Eqs. (131) for the molecules with
the six possible combinations of end groups P
AA
n
; P
AB
n
; . . . P
CC
n
and rings C
n
, where
index n counts the most frequent kind of repeating units in the molecule:
R
P
AA
n
= k 4
n1
m=1
[P
AA
m
[[P
AA
nm
[ 2
n1
m=1
[P
AA
m
[[P
AB
nm
[ 2[P
AA
n
[[B[

R
P
BB
n
= k 4
n1
m=1
[P
BB
m
[[P
BB
nm
[ 2
n1
m=1
[P
BB
m
[[P
AB
nm
[ 2[P
BB
n
[[A[

R
P
AB
n
= k 4
n
m=1
[P
AA
m
[[P
BB
nm1
[
n1
m=1
[P
AB
m
[[P
AB
nm
[ [P
AB
n
[([A[ [B[)

k
c
(n)[P
AB
n
[
R
Cn
= k
c
(n)[P
AB
n
[
R
P
AC
n
= k 2
n
m=1
[P
AA
m
[[P
BC
nm1
[
n1
m=1
[P
AB
m
[[P
AC
nm
[ [P
AC
n
[[B[

R
P
BC
n
= k 2
n1
m=1
[P
BB
m
[[P
AC
nm
[
n1
m=1
[P
AB
m
[[P
BC
nm
[ [P
BC
n
[[A[

R
P
CC
n
= k
n1
m=1
[P
AC
m
[[P
BC
nm
[
R
A
= R
B
= k[A[[B[
y
n=1
k
c
(n)[P
AB
n
[ (131)
Modern computers will not have much diculty with the brute force approach
of solving the mass balances after inserting the above relationships for n = 1 up
to an upper value N of a few hundreds or even thousands (notice that this implies
11N
2
O(N) multiplications and sums every time this set of rates of reaction is
evaluated). A relatively large value of N is needed if the mole ratio is close to one,
in order that extrapolation of CLD and evaluation of the innite sum using the last
equation of Eqs. (131) may be done accurately. A more elegant method uses gener-
ating functions [288] and avoids the problem of the lack of closure of the above
equations for any nite N.
When the kinetic approach was at an early stage, it was thought that it could pro-
vide no information about polymer or network properties. More recently, a descrip-
tion of batch polycondensation using TBP which is rigorously equivalent to the one
obtained by the kinetic approach was found [289], taking into account the times of
birth of molecules, so that the fundamental restriction does not hold. Through
more elementary reasonings, it is nevertheless possible to estimate probabilities
of extinction and thus network elastic properties [282] or average radius of gyration
[290].
3.4.5
Kinetic Modeling of Linear Reversible Polycondensations
The reversible alternating polycondensation with FSSEs in both monomers (see
Section 3.1.5), disregarding exchange reactions, is a convenient case study for dis-
cussing problems of modeling this kind of systems. It can be described by the rate
laws of Eqs. (132) and (133).
R
P
AA
1
= 4k
1
[P
AA
1
[[P
BB
1
[ 2k
2
[P
AA
1
[([P
AB
1
[ [Z
B
[) k
Z
1
[P
AB
1
[ k
Z
2
[Z
A
[
R
P
BB
1
= 4k
1
[P
AA
1
[[P
BB
1
[ 2k
3
[P
BB
1
[([P
AB
1
[ [Z
A
[) k
Z
1
[P
AB
1
[ k
Z
3
[Z
B
[
R
P
AB
1
= 4k
1
[P
AA
1
[[P
BB
1
[ [P
AB
1
[[2k
2
[P
AA
2
[ 2k
3
[P
BB
1
[
k
4
(2[P
AB
1
[ [Z
A
[ [Z
B
[)[ k
Z
1
[P
AB
1
[ 2k
Z
2
[P
AA
2
[ 2k
Z
3
[P
BB
2
[
(132)
2k
Z
4
([Z
A
[ [Z
B
[ 2[P
AA
2
[ 2[P
BB
2
[)
n b2:
R
P
AA
n
= 2k
2
[P
AA
1
[[P
AB
n1
[ 2k
4
n2
m=1
[P
AB
m
[[P
AA
nm
[ 2[P
AA
n
[[2k
3
[P
BB
1
[ k
4
([P
AB
1
[ [Z
B
[)[
[P
AA
n
[[2k
Z
2
2k
Z
4
(n 2)[ k
Z
3
[P
AB
n
[ k
Z
4
[Z
A
[
n
m=2
([P
AB
m
[ 2[P
AA
m
[)

R
P
BB
n
= 2k
3
[P
BB
1
[[P
AB
n1
[ 2k
4
n2
m=1
[P
AB
m
[[P
BB
nm
[ 2[P
BB
n
[[2k
2
[P
AA
1
[ k
4
([P
AB
1
[ [Z
A
[)[
[P
BB
n
[[2k
Z
3
2k
Z
4
(n 2)[ k
Z
2
[P
AB
n
[ k
Z
4
[Z
B
[
n
m=2
([P
AB
m
[ 2[P
BB
m
[)

R
P
AB
n
= 4k
2
[P
AA
1
[[P
BB
n
[ 4k
3
[P
BB
1
[[P
AA
n
[
k
4
n1
m=1
[P
AB
m
[[P
AB
nm
[ 4
n1
m=2
[P
AA
m
[[P
BB
nm1
[

[P
AB
n
[[2k
2
[P
AA
1
[ 2k
3
[P
BB
1
[ k
4
(2[P
AB
1
[
[Z
A
[ [Z
B
[) k
Z
2
k
Z
3
k
Z
4
(2n 3)[ 2k
Z
2
[P
AA
n1
[ 2k
Z
3
[P
BB
n1
[
k
Z
4
[Z
A
[ [Z
B
[ 2
n
m=2
[P
AB
n
[ 2
n1
m=2
([P
AA
m
[ [P
BB
m
[)

(133)
It may be observed from these expressions that, in general, it is not possible to ob-
tain a closed nite set of rate equations for the rst oligomers rate equations for
oligomers with chain length n always depend on concentrations of oligomers with
chain length n 1. Only when the rate constants of reverse equations are equal
do the above expressions simplify (FSSE for reverse reaction), and the above-
mentioned diculty disappears.
On introduction of generating functions of the CLD, dened in Eq. (134), the
concentrations of end groups, trimers, and tetramers conform with Eqs. (134) and
(135).
G
AA
=
y
n=2
s
n2
[P
AA
n
[ G
BB
=
y
n=2
s
n2
[P
BB
n
[ G
AB
=
y
n=2
s
n2
[P
AB
n
[ (134)
[Z
A
[ = 2G
AA
(1) G
AB
(1) [Z
B
[ = 2G
BB
(1) G
AB
(1)
[P
AA
2
[ = G
AA
(0) [P
BB
2
[ = G
BB
(0) [P
AB
2
[ = G
AB
(0)
(135)
The rate equations in terms of those generating functions become Eqs. (136).
R
GAA
= 2k
2
[P
AA
1
[(sG
AB
[P
AB
1
[) k
4
s
2
G
AA
G
AB
2G
AA
[2k
3
[P
BB
1
[
k
4
([P
AB
1
[ [Z
B
[)[ 2k
Z
2
G
AA
2k
Z
4
s
qG
AA
qs
k
Z
3
G
AB
k
Z
4
[Z
A
[ 2G
AA
G
AB
1 s
R
GBB
= 2k
3
[P
BB
1
[(sG
AB
[P
AB
1
[) k
4
s
2
G
BB
G
AB
2G
BB
[2k
2
[P
AA
1
[
k
4
([P
AB
1
[ [Z
A
[)[ 2k
Z
3
G
BB
2k
Z
4
s
qG
BB
qs
k
Z
2
G
AB
k
Z
4
[Z
B
[ 2G
BB
G
AB
1 s
R
GAB
= 4k
2
[P
AA
1
[G
BB
4k
3
[P
BB
1
[G
AA
k
4
[2[P
AB
1
[(sG
AB
[P
AB
1
[)
s
2
G
2
AB
4sG
AA
G
BB
[ [2k
2
[P
AA
1
[ 2k
3
[P
BB
1
[ k
4
(2[P
AB
1
[ [Z
A
[ [Z
B
[)
k
Z
2
k
Z
3
k
Z
4
[G
AB
2k
Z
4
s
qG
AB
qs
k
Z
4
[Z
A
[ [Z
B
[ 2(G
AB
G
AA
G
AB
)
1 s
2(k
Z
2
k
Z
4
)
G
AA
[P
AA
2
[
s
2(k
Z
3
k
Z
4
)
G
BB
[P
BB
2
[
s
(136)
Rate laws for [Z
A
[ and [Z
B
[ become Eq. (137):
R
ZA
= 2k
2
[P
AA
1
[([Z
B
[ 2[P
AB
1
[) 2k
3
[P
BB
1
[[Z
A
[ k
4
(2[P
AB
1
[
2
[Z
A
[[Z
B
[)
k
Z
2
([Z
A
[ 2[P
AA
2
[) k
Z
3
([Z
B
[ 2[P
BB
2
[)
k
Z
4
[X[ [Y[
5
2
([Z
A
[ [Z
B
[) [P
AA
1
[ [P
BB
1
[ 2[P
AB
1
[

R
ZB
= 2k
2
[P
AA
1
[[Z
B
[ 2k
3
[P
BB
1
[([Z
A
[ 2[P
AB
1
[) k
4
(2[P
AB
1
[
2
[Z
A
[[Z
B
[)
k
Z
2
([Z
A
[ 2[P
AA
2
[) k
Z
3
([Z
B
[ 2[P
BB
2
[)
k
Z
4
[X[ [Y[
5
2
([Z
A
[ [Z
B
[) [P
AA
1
[ [P
BB
1
[ 2[P
AB
1
[

(137)
A rate law for by-product [Eq. (138)] is usually required.
R
W
= 4k
1
[P
AA
1
[[P
BB
1
[ 2k
2
[P
AA
1
[[Z
A
[ 2k
3
[P
BB
1
[[Z
A
[ k
4
[Z
A
[[Z
B
[ k
Z
1
[P
AB
1
[
k
Z
2
[Z
A
[ k
Z
3
[Z
B
[ k
Z
4
y
n=2
[(2n 4)([P
AA
n
[ [P
BB
n
[) (2n 3)[P
AB
n
[[
= 4k
1
[P
AA
1
[[P
BB
1
[ 2k
2
[P
AA
1
[[Z
A
[ 2k
3
[P
BB
1
[[Z
A
[ k
4
[Z
A
[[Z
B
[
k
Z
1
[P
AB
1
[ k
Z
2
[Z
A
[ k
Z
3
[Z
B
[
k
Z
4
[X[ [Y[
3
2
([Z
A
[ [Z
B
[) [P
AA
1
[ [P
BB
1
[ 2[P
AB
1
[

(138)
Insertion of these rate laws in mass balances of ideal reactors (batch/plug ow or
transient CSTR) leads to systems of semi-linear, rst-order, partial dierential
equations, with a single family of characteristics [Eq. (139)].
ds
dt
= 2sk
Z
4
(139)
The relationship of Eq. (138) allows integration along characteristics, relating ini-
tial values G
AA
(0; s
0
); G
AB
(0; s
0
), and G
BB
(0; s
0
) to G
AA
(t; s); G
AB
(t; s), and G
BB
(t; s),
but a serious problem remains: integration along characteristics and prediction of
concentration of rst oligomers have to be done at the same time.
Only the solution with equal reactivity has been published [291]. A sketch of an
iterative method to solve this more complex problem is described below (no actual
calculations have been published at the time of writing).
1. Two auxiliary characteristics s
(t) = s
(t), starting at s
= e
s
[s
0
[ and s
=
e
s
[s
0
[, respectively, for t = 0, are introduced in order to provide an accurate nu-
merical estimation of oligomer concentrations through Eq. (140).
G
I
(0) =
G
I
(s
) G
I
(s
)
2
O(e
2
s
) I = AA; BB; AB (140)
Parameter e
s
should be a small value (say 10
6
to 10
8
). Owing to Eq. (139), it is
easy to relate the auxiliary characteristics to the main characteristic s(t) start-
ing with s = s
0
through Eq. (141).
s
(t) = s
(t) = e
s
s(t) (141)
2. The resolution of a system of ODE comprising Eq. (139), the balances of end
groups Z
A
, Z
B
, by-product W and dierential equations for G
AA
(t; s), G
AB
(t; s),
G
BB
(t; s), G
AA
(t; s
), G
AB
(t; s
), G
BB
(t; s
), G
AA
(t; s
), G
AB
(t; s
) and G
BB
(t; s
),
will eventually allow the evaluation of all unknown variables of this problem.
As s
0
is to be found iteratively in order that the characteristic starting with
s = s
0
will attain the prescribed value of s at the prescribed time t, this is a
boundary value problem, but very straightforward to solve.
If there are more than two functional groups per repeating unit, the approach de-
scribed above is no longer useful, as there is no simple way of describing forma-
tion of chemical species through breaking of larger ones, owing to their branched
structure.
Nevertheless, in most situations resembling industrial practice, such as CSTRs
in series, the CLD of these chemical systems will stay close to equilibrium (see
Ref. 291). The distributions of monads depend only on the equilibrium ratios and
it is not necessary to use models with SSSEs for the reverse reactions (the source of
the most challenging mathematical problems), as the same distributions will be
found using equal values of the rate constants of the reverse reaction.
Notation
1
N
vector with N components equal to one
a
v
lm area per unit volume [m
1
]
b length of a Kuhn segment connecting two half-bonds in the same
repeating unit [m]
b
A
empirical parameter in Eq. (56) (dimensionless)
C
d
drag coecient (dimensionless)
C
g
parameter in Eq. (12) [s
1
]
D binary diusivity [m
2
s
1
]
d
b
bubble diameter [m]
d
R
diameter of ring (in a RDC devolatilizer) [m]
d
T
inner diameter of tube, or of the barrel of an extruder [m]
E
c
activation energy of amidation reaction [J mol
1
]
e
i
index of by-product formed by reaction leading to bond Z
R
i
; no by-
product if it is nil
e
i
; e
i
indices of half-bonds of bond Z
R
i
F
X
i
(s
Z
; s
A
); F
A
i
(s
Z
; s
A
); F
Z
i
(s
Z
; s
A
) probability generating functions (pgf ) of the
counts of the dierent kinds of connecting and unreacted functional
groups directly linked to, respectively, a monomer unit X
i
, an un-
reacted group A
i
, or a half-bond Z
i
f monomer functionality (number of functional groups it contains)
G
e
equilibrium zero strain shear modulus of polymer network [Pa]
G(s) moment generating function of molar concentrations of polymer mol-
ecules with respect to their counts of monomer units and unreacted
functional groups
G
J
ni
generating functions of stoichiometric coecients of reaction
i ( J = ; ;
+
), as dened by Eq. (126)
G
X
i
(s
X
; s
A
); G
A
i
(s
X
; s
A
); G
Z
i
(s
X
; s
A
) pgf of trees starting, respectively, with a pre-
scribed monomer unit X
i
, an unreacted group A
i
, or a half-bond Z
i
G
M
(s
M
) pgf of mass fractions of polymer molecules in a sol
g acceleration due to gravity [m s
2
]
g
A
ratio m
A
/b
A
[m
3
mol
1
]
g
i
; g
i
indices of functional groups A
g
i
; A
g
i
reacting to create bond Z
i
H depth of liquid in the channel of a vented extruder [m]
H
e
; H
i
partition coecients of hydrophilic monomer in interfacial polymer-
ization relating, respectively, the bulk concentration in the water
phase and the concentration in the outer interface of the polymer
lm, and the concentrations in organic phase in the two interfaces of
polymer lm (dimensionless)
H
W
Henry constant of component W in terms of pressure versus weight
fraction [Pa]
h clearance between the screw and barrel in a vented extruder [m]
h
i
index of a repeating unit carrying functional group A
i
h
R
height of the liquid above the gas injection point in an RDC [m]
J number of compartments in a staged model of an RDC devolatilizer
J
j
mass transfer rate per unit volume of component j [mol m
3
s
1
]
K apparent equilibrium ratio of bond formation from end groups
(dimensionless)
K
0
thermodynamic equilibrium constant of bond formation from end
groups (dimensionless)
Notation 137
K
a
apparent equilibrium ratio of amidation (dimensionless)
K
a0
reference value of the apparent equilibrium ratio of amidation
(dimensionless)
K
c
(n) apparent equilibrium ratio of cyclization [mol m
3
]
k apparent second-order rate constant [m
3
mol
1
s
1
]
k
0
parameter in Eq. (12) [m
3
mol
1
s
1
]
k
A
empirical parameter in ChenWu relation, Eq. (53) [mol m
3
s
1
]
k
aE
rate constant of breakage of a bond in a ring molecule through reac-
tion with a functional group [mol m
3
s
1
]
k
c
(n) rst-order rate constant of L
n
cyclization [s
1
]
k
cE
(n) rate constant of formation of C
n
by the back-biting cyclization reaction
[s
1
]
k
cr
rate coecient of crystallization in Avrami equation [s
ncr
] (see below)
k
cZ
apparent rst-order rate constant of breakage of a bond in a ring
molecule [s
1
]
k
c0
third-order pre-exponential factors of amidation rate constant
[kg
2
mol
2
s
1
]
k
fY
i
mass transfer coecient of species Y
i
in terms of molar concentra-
tions [m s
1
]
k
a
fY
i
mass transfer coecient of species Y
i
in terms of activities
[mol m
2
s
1
]
k
0
i
noncatalytic contribution to the rate constant in Eq. (61) [mol m
3
s
1
]
k
E
ij
rate constant of exchange reaction forming bond Z
R
i
and destroying
bond Z
R
j
k
E
ij
; k
E
ij
rate constants of exchange reaction forming bond Z
R
i
and replacing
bond Z
R
j
, when the attacking group is, respectively, A
[i[
or A
[i[
k
H
i
acid-catalyzed reaction constant in Eq. (61) [m
6
mol
2
s
1
]
k
OH
i
catalytic term of hydroxyls in Eq. (61) [m
6
mol
2
s
1
]
k
m
water mass transfer rate constant [s
1
]
k
nuc; n
rate coecients of nucleation of polymer species with chain length n
[s
1
]
k
scat
; k
fcat
rate constants of self-catalyzed and foreign acid-catalyzed esterication
[m
6
mol
2
s
1
]
k
u0
second-order pre-exponential factor of amidation rate constant
[m
3
mol
1
s
1
]
k
Z
apparent rst-order rate constant of bond group breakage [s
1
]
k
Z
i
apparent rst-order rate constant of breakage of bond group Z
R
i
[s
1
]
k
+
i
rst-order rate constant of intramolecular reaction i destroying group
A
[i
+
[
[s
1
]
L lm thickness [m]
L
p
thickness of polymer lm in interfacial polymerization [m]
L
R
thickness of reaction zone [m]
L
W
width of the channel in an extruder [m]
L
x
lm perimeter [m]
M relative molecular weight
M
i
relative molecular weight of generic polymer species i, where i is an
arbitrary index
M
n
=
y
i=1
M
i
[P
i
[
y
i=1
[P
i
[ number-average molecular weight of polymer
M
P
mass of polymer per mole of monomer units [kg mol
1
]
M
W
relative molecular weight of by-product W
M
w
=
y
i=1
M
2
i
[P
i
[
y
i=1
M
i
[P
i
[ weight-average molecular weight of polymer
M
z
=
y
i=1
M
3
i
[P
i
[
y
i=1
M
2
i
[P
i
[ z-average molecular weight of polymer
m
A
empirical parameter in Eq. (56) [mol
1
m
3
]
N
A
number of functional (or end) groups
N
AL
AvogadroLoschmidt number [mol
1
]
N
b
number of bubbles
_
NN
j
ux of component j [mol m
2
s
1
]
N
R
number of distinctive chemical bonds
N
Rs
number of symmetrical chemical bonds
N
X
number of kinds of monomer units
N
W
number of by-products
N
Y
number of volatile (or precipitating) components
N
Z
number of half-bonds
N
ZA
= N
Z
N
A
overall number of kinds of functional groups and half-bonds
N
ZXA
= N
Z
N
X
N
A
overall number of kinds of functional groups, monomer
units, and half-bonds
_ nn screw rotational speed (as rotations per unit time) [s
1
]
n
cr
Avrami exponent
P
b
pressure inside a bubble [Pa]
P
me
local pressure over a bubble [Pa]
P
W
vapor pressure of W [Pa]
P
S
W
vapor pressure of pure W [Pa]
p conversion of reference functional groups A
p
c
conversion of functional groups A having given rise to rings
Q volumetric ow rate of polymer [m
3
s
1
]
Q
g
volumetric ow rate of gas [m
3
s
1
]
R ideal gas constant [J mol
1
K
1
]
Re Reynolds number for the rising movement of a bubble
R
j
rate of formation by chemical reaction of species j [mol m
3
s
1
]
R
V
combined relative rate of change of reaction volume by chemical reac-
tion and transfer of by-product [s
1
]
r stoichiometric ratio in alternating polycondensations
r
b
radius of a bubble [m]
s vector of dummy Laplace variables associating s
A
and s
Z
(dened
below)
Notation 139
s
A
vector of dummy Laplace variables associated with the counts of un-
reacted functional groups
s
Cn
dummy Laplace variables associated with the counts of rings (includ-
ing s
C0
for the count of units X in the chains connecting rings) for the
equilibrium polycondensation of a single monomer XA
f
s
M
dummy Laplace variable associated with molecular weight
s
Z
vector of dummy Laplace variables associated with the counts of half-
bonds
s
Zy
dummy Laplace variable associated with x
Zy
s
Zl
dummy Laplace variable associated with the counts of bonds not be-
longing to rings for the equilibrium polycondensation of a single
monomer XA
f
T absolute temperature [K]
T
0
reference temperature [K]
t time [s]
t
f
exposure time [s]
t
fP
exposure time of liquid in the pool of a vented extruder [s]
u
b
bubble rising speed [m s
1
]
u
x
; u
z
average velocity in directions x; z [m s
1
]
V volume of reacting mixture [m
3
]
V
b
volume of a bubble [m
3
]
V
i
(s
Z
; s
A
) pgf of pendent chains V
i
^
VV
i
(s
Z
; s
A
) pgf of nite pendent chains V
i
V
j
molar volume of species j [m
3
mol
1
]
^
VV
M
i
(s
M
) pgf of nite pendent chains V
i
with respect to molecular weight
V
m
overall melt volume [m
3
]
V
mj
volume of liquid in compartment j in a staged model of an RDC devo-
latilizer [m
3
]
v vector of the N
Z
probabilities of extinction (the fractions of nite pen-
dent chains)
v
T
average transverse velocity of the screw dragging the lm [m s
1
]
w
cr
weight fraction of crystalline material
w
j
weight fraction of j
w
S
weight fraction of the sol, relative to the overall mass of the polymer
x degree of polymerization, the number of repeating units in a polymer
molecule
x coordinate along the perimeter, when discussing mass transfer from a
liquid owing over a cylindrical wall [m]
x
A
vector storing the counts of functional groups
x
i
degree of polymerization of generic polymer species i, where i is an
arbitrary index
x
n
=
y
i=1
x
i
[P
i
[
y
i=1
[P
i
[ number-average degree of polymerization of polymer
x
w
=
y
i=1
x
2
i
[P
i
[
y
i=1
x
i
[P
i
[ weight-average degree of polymerization of polymer
x
X
vector containing the counts of monomer units
x
Z
vector storing the counts of half-bonds
x
Zy
number of innite pendent chains connected to a junction
y Cartesian coordinate normal to the interface [m]
y
c
overall molar fraction of repeating units X in rings for a single mono-
mer polycondensation
y
P
number of moles of polymer molecules per mole of monomer units
before gelation
y
SX
i
; y
SZ
i
and y
SA
i
fractions of units and groups of the various kinds in nite
molecules (in a sol), after gelation
y
Xc
(n) molar fraction of repeating units X in rings of size n for a single
monomer y
X
i
molar fractions of monomers or monomer units
polycondensation
Z
ZX
matrix dened in Eq. (73) from incidence vectors z dened below
z Cartesian coordinate parallel to the interface [m]
z
i
index of the monomer unit to which half-bond Z
i
points
Greek
a empirical parameter of ChenWu relation [Eq. (53)] (dimensionless)
a
r
probability of reaction of unreacted functional groups after ring for-
mation in the rst stage (absence of open-chain molecules) of a hypo-
thetical two-stage equilibration of XA
f
b
g
; b
g0
parameters in Eq. (11) describing the glass eect [K]
b
j
fraction of volume ow rate in compartment j going to the preceding
compartment j 1
g
j
activity coecient of species j
w
ij
FloryHuggins parameter (multicomponent mixture)
DH enthalpy of reaction [J mol
1
]
DS entropy of reaction [J mol
1
K
1
]
d upstream distance of re-entry of lm wiped by the screw in a vented
extruder [m]
e
s
small starting value of s in characteristic line
y screw angle
k
c
(n) ratio of rate constants of similar intramolecular and intermolecular
reactions [mol m
3
]
L
I
J...K
(s) =
q . . . qF
I
q log s
J
. . . q log s
K
derivatives of pgf F
I
(s) (or other moment gener-
ating functions) with respect to logarithms of dummy Laplace
parameters
l
I
J...K
=
q . . . qF
I
q log s
J
. . . q log s
K
(1
N
) =
y
x1 =0
. . .
y
xN =0
x
J
. . . x
J
I(x) moments of distribu-
tions, where F
I
(s) is the moment generating function of vector distri-
bution I(x)
Notation 141
l
M
; l
MM
rst and second moments of molecular weight of distribution of
polymer
m dynamic viscosity [N m
1
s
1
]
m
e
concentrations of elastically active network junctions (EANJ)
[mol m
3
]
n stoichiometric coecient (the change in number of moles caused by
chemical reaction)
n
A
in
; n
Z
in
stoichiometric coecients of functional groups A
n
and oriented bonds
Z
n
coming out of the monomer unit in which A
[i[
was situated for
the reaction forming Z
R
i
n
A
in
; n
Z
in
stoichiometric coecients of functional groups A
n
and oriented bonds
Z
n
coming out of the monomer unit in which A
[i[
was situated for
the reaction forming Z
R
i
n
AE
ijn
; n
ZE
ijn
changes in numbers of functional groups A
n
and bonds Z
n
, respec-
tively, connected to the root unit X
where either A
[i[
or A
[i[
were
attached, for the exchange reaction forming Z
R
i
at the expense of Z
R
j
n
AE
ijn
; n
ZE
ijn
; n
AE
ijn
; n
ZE
ijn
changes in numbers of functional groups A
n
and bonds Z
n
, respectively, connected to the root unit X
where the
living group A
[ j[
or A
[ j[
was situated, for the exchange reaction
forming Z
R
i
at the expense of Z
R
j
n
AE
ijn
; n
ZE
ijn
; n
AE
ijn
; n
ZE
ijn
changes in numbers of groups attached to the
root unit X
which gets connected to the unit where the attacking

group was situated, for the exchange reaction forming Z
R
i
at the ex-
pense of Z
R
j
n
W
in
stoichiometric coecients of by-products for the reaction forming Z
R
i
n
+
in
stoichiometric coecient of group A
n
for the ith intramolecular
reaction
n
e
concentration of elastically active network chains [mol m
3
]
r
j
density of j [kg m
3
]
s surface tension [N m
1
]
t space time based upon feed ow rate, V
m
/Q
F
for a CSTR [s]
t
r
structural relaxation time [s]
t
0
parameter in Eq. (11) [s]
t
D
tortuosity for by-product diusion in a solid polymer particle
(dimensionless)
f
cr
volume fraction of crystalline material
f
j
volume fraction of j
f
L
fraction of channel extruder lled with liquid
w FloryHuggins parameter (binary mixture) (dimensionless)
W
W
weight fraction activity coecient of W
Chemical symbols
A; B functional groups
A
g
i
1A
[i[
; A
g
i
1A
[i[
functional groups reacting in bond Z
R
i
formation
A
j
active component (molecular species or fragment) j; nonvolatile,
nonprecipitating
C
n
ring molecule with n bonds
L
n
linear polymer molecule with n 1 bonds and a pair of active end
groups
L
T
length of tube
P
i
generic polymer species, where i is an arbitrary index
P
IJ
n
linear polymer molecule with end groups I and J and n repeating
units of the most frequent kind
[U[ molar concentration of species U
V
i
(x
Z
; x
A
) pendent chain starting with a half-bond Z
i
and containing vector
counts of bonds and functional groups, respectively, x
Z
and x
A
W by-product of condensation reaction
W
e
i
1W
[i[
by-product of condensation reaction leading to bond Z
R
i
X; Y monomer units
X
h
i
1X
[iA[
monomer unit carrying functional group A
i
X
z
i
1X
[iZ[
monomer unit to which each half-bond Z
i
points
Y
j
volatile (or precipitating) component j
Z bond group; Z
R
i
is the ith distinctive bond in the chemical system
Z
A
bond group in fragment AXZ
A
YZ (polycondensation AXA BYB)
Z
B
bond group in fragment BYZ
B
XZ (polycondensation AXA BYB)
Z
D
bond group in dimer AXZ
D
YB (polycondensation AXA BYB)
Z
e
i
1Z
[i[
; Z
e
i
1Z
[i[
half-bonds of bond Z
R
i
Z
P
bond group in fragment ZXZ
P
Z (polycondensation AXA BYB)
Subscripts
aq aqueous
b of a bubble
blk bulk
c critical
cr crystalline
F in feed
g at gel point
org organic
sat at saturation
Superscripts
* used for describing values of concentration at the interface
x average value of x
Acronyms
BHET bis(2-hydroxyethyl) terephthalate
BPA bisphenol A
Notation 143
CLD chain length distribution
CSTR continuous stirred tank reactor
DEG diethylene glycol
DMT dimethyl terephthalate
DPC diphenyl carbonate
EANC elastically active network chains, the chains connecting EANJs (see
below)
EANJ elastically active network junctions, the intersection of at least three
chains leading to a gel
ECH epichlorohydrin
EG ethylene glycol
FSSE rst-shell substitution eect
ODE ordinary dierential equation
PBT poly(butylene terephthalate)
PDE partial dierential equation
PET poly(ethylene terephthalate)
pgf probability generating function
RDC rotating disk contactor
RIM reaction injection molding
SSP solid-state polycondensation
SSSE second-shell substitution eect
TBP theory of branching processes
TPA terephthalic acid
UF ureaformaldehyde polymer
WFR wiped-lm reactor
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4
Free-radical Polymerization: Homogeneous
1
Robin A. Hutchinson
Free-radical polymerization (FRP) is one of the most important commercial pro-
cesses for preparing high molecular weight polymers. It can be applied to almost
all vinyl monomers under mild reaction conditions over a wide temperature range
and, although requiring the absence of oxygen, is tolerant of water. Multiple mono-
mers can be easily copolymerized via FRP, leading to the preparation of an endless
range of copolymers with properties dependent on the proportion of the incorpo-
rated comonomers. This chapter will provide an overview of the kinetics and mech-
anisms, and the techniques used to construct mathematical representations of
bulk and solution FRP. The description will also serve as a good base for the sus-
pension and emulsion FRP chapters that follow.
4.1
FRP Properties and Applications
Polymers produced via free-radical chemistry include the following major families:
v
Low-density polyethylene (LDPE) and copolymers, used primarily in lms and
packaging applications. LDPE has density of <0.94 g cm
3
, and is produced via
high-pressure free-radical polymerization; polyethylenes of higher density (and
polypropylene) are produced via transition metal catalysis, as described else-
where (see Chapter 8).
v
Poly(vinyl chloride) and copolymers, used primarily to produce pipe and ttings,
ooring material, and lms and sheet.
v
Polystyrene and its co- and terpolymers with acrylonitrile and butadiene. Homo-
polymer is used for packaging and containers, while the acrylonitrile-containing
polymers are used for various molded products in the appliance, electronics, and
ISBN: 3-527-31014-2
153
automotive industries. Styrenebutadiene is the most widely used synthetic
rubber.
v
Acrylic- and methacrylic-based polymers. Poly(methyl methacrylate) (PMMA),
due to its transparency and weatherability, is used extensively in signs, lighting
xtures, and windows. Polyacrylates and copolymers are used extensively in the
adhesives and coatings markets, and are also combined with acrylonitrile to
make acrylic bers.
v
Poly(vinyl acetate) and copolymers, used extensively in adhesives, coatings, and
paper and textile treatment.
v
Fluoropolymers including polytetrauoroethylene and copolymers, used widely
in the wire and cable industry. They also have many specialty applications as
coatings due to their inertness and low-surface tension.
In addition to these major product families, there exist many other smaller-volume
(but often high-value) polymeric products synthesized via free-radical chemistry.
These products are manufactured via heterogeneous (emulsion, suspension) or
homogeneous (bulk, solution) polymerization in a wide range of reactor congura-
tions ranging from tubular to well-mixed tanks (and everything in between) in pro-
cesses that may be continuous, batch, or semi-batch. FRP kinetics together with re-
actor design and operating conditions controls the composition and architecture of
the polymer produced. As with other chemistries, the nal product consists of a
mixture of polymer chains with varying length, composition, and structural proper-
ties such as branch points and branch lengths. The processing and end-use proper-
ties of the polymer depend upon the distributions of these characteristics, not just
the average values. Thus it is necessary to develop methods to relate the fundamen-
tal kinetic mechanisms of free-radical polymerization to these distributed charac-
teristics.
4.2
Chain Initiation
Free-radical polymerization, like other chain growth mechanisms, involves the se-
quential addition of vinyl monomers to an active center. The dening characteristic
of FRP is that the active centers are free radicals. Each growing polymeric radical
increases in size rapidly; a typical chain is initiated, grows to high molecular
weight, and is terminated in the time scale of, at most, a few seconds. When the
macromolecule stops growing it cannot generally react further (barring side reac-
tions), and is considered dead. These dead chains have a residence time of mi-
nutes or hours in the polymerization reactor, and the nal polymer product is an
intimate mixture of chains formed under time and/or spatially varying conditions.
The free radicals that initiate polymerization are in most cases generated by ther-
mal or photochemical homolytic cleavage of covalent bonds. Commercial initiators
include azo and peroxy compounds. The driving force for the dissociation of azo
154 4 Free-radical Polymerization: Homogeneous
initiators is the formation of the stable nitrogen molecule and resonance stabilized
tertiary radicals, as shown for 2,2
/
-azobisisobutyronitrile (AIBN) in Scheme 4.1.
Many types of peroxides (R-O-O-R
/
) are also utilized, including diacyl peroxides,
peroxydicarbonates, peroxyesters, dialkyl peroxides, and inorganic peroxides such
as persulfate, the latter being used mainly in water-based systems. The rate of per-
oxide decomposition as well as the subsequent reaction pathway is greatly aected
by the nature of the peroxide chemical structure, as illustrated for tert-butyl perox-
yesters in Scheme 4.2. Pathway (a), the formation of an acyloxy and an alkoxy rad-
ical via single bond scission, is favored for structures in which the carbon atom in
the a-position to the carbonyl group is primary (for example, tert-butyl peroxyace-
tate, R = CH
3
). Pathway (b), concerted two-bond scission, occurs for secondary
and tertiary peroxyesters (for example, tert-butyl peroxypivalate, R = C(CH
3
)
3
) [1,
2]. The tert-butoxy radical formed in both pathways may decompose to acetone
and a methyl radical, or abstract a hydrogen atom to form tert-butanol.
The exact nature of the decomposition pathway is important, as it plays a role in
the eciency of the primary radicals in initiating new polymer chains. When an
initiator decomposes, the primary radicals are nearest neighbors surrounded by a
cage of other molecules through which they must diuse to escape from each
other before they recombine. Once one radical leaves the cage it is extremely un-
likely that the pair will encounter each other again. In-cage reactions for pathway
(a) in Scheme 4.2 will lead to the re-formation of the original initiator molecule,
while the in-cage reactions for pathway (b) lead to the formation of an ether which
is not capable of forming free radicals by another dissociation step.
In general, peroxide decomposition can yield both carbon- and oxygen-centered
primary radicals that add to the carboncarbon double monomer bond to form a
new propagating chain, abstract hydrogen atoms from other molecules (including
N N CH
3
CH
3
C
C H
3
CH
3
CN N
C CH
3
CH
3
CN
N
2 + 2
Scheme 4.1. Decomposition of AIBN.
O
O CH
3
O
CH
3
CH
3
R
R O
O
+
O CH
3
CH
3
CH
3
+
O CH
3
CH
3
CH
3
CO
2
+
(a)
(b)
R
.
Scheme 4.2. Decomposition of tert-butyl peroxyesters. The
preferred pathway depends on the nature of the R substituent.
4.2 Chain Initiation 155
polymer) in the system, or recombine to form inactive compounds. The relative
rates of these processes are dependent on both the nature of the primary radicals
and the monomer system. The mechanistic pathway followed will inuence end-
group structures of the polymeric products, aecting nal properties such as ther-
mal stability. Further details on initiator decomposition kinetics and mechanistic
pathways can be found in the excellent monograph by Moad and Solomon [3].
The above discussion highlights the fact that the simple initiation process of
most polymer texts is the exception rather than the rule, with the fraction of pri-
mary radicals that initiate a new polymer chain a complex function of the reaction
system. Nonetheless, the kinetic treatment is usually simplied by the introduction
of a fractional initiator eciency ( f ), formally dened by Eq. (1), where n is the
number of moles of primary radicals generated per mole of initiator; n = 2 for
most common initiators.
f =
Initiation Rate of Propagating Chains
n(Rate of Initiator Disappearance)
(1)
The initiator eciency is normally in the range 0.40.9, with a low value indicating
inecient usage of the initiator and potentially a high formation rate of undesired
by-products.
The kinetic descriptions in this chapter are developed for thermal unimolecular
scission of a compound to yield two radicals, as this is the most common means of
generating radicals in industrial systems. Thermal initiation of monomers is an ad-
ditional mechanism capable of forming primary radicals at higher temperatures, as
discussed for styrene (see Section 4.3.1.3). Other initiation systems are also avail-
able, and bear a brief mention at this point. Initiators with multiple peroxide link-
ages (n > 2) have been the subject of recent academic study [4]. Photoinitiators
that produce radicals by ultraviolet irradiation are commonly used to initiate cross-
linking and curing reactions in polymeric systems, as the rate of initiation can be
controlled through the intensity and location of the light source. And nally, a re-
dox (reductionoxidation) process is often used to initiate chains in emulsion poly-
merization (see Chapter 6).
4.3
Polymerization Mechanisms and Kinetics
It is important to achieve an understanding of how the basic FRP mechanisms
control polymerization rate and average polymer chain length. This section starts
with the derivation of appropriate kinetic expressions for a single monomer
system. Complicating (but industrially important) secondary reactions are then
introduced, followed by the extension to multi-monomer systems. Dispersed
throughout are up-to-date estimates for important free-radical polymerization rate
coecients, and descriptions of how they are obtained experimentally.
4.3.1
Homopolymerization
Many commercial polymers, including polystyrene, PMMA, and LDPE, are synthe-
sized via homogeneous free-radical polymerization of a single monomer. Homo-
polymer properties are controlled by average chain length and chain-length distri-
bution as well as, in some cases, structural characteristics such as branching level.
4.3.1.1 Basic Mechanisms
The basic set of FRP mechanisms includes initiation, propagation, termination,
and transfer to monomer and solvent or transfer agent, as shown in Scheme 4.3.
The subscript n denotes the number of monomeric units in growing polymer
radicals (P
n
) and dead polymer chains (D
n
). Each reaction has an associated kinetic
rate law expression and a specic rate coecient. The free-radical initiator (I) un-
imolecularly decomposes (with rate coecient k
d
) to form two primary radicals (I
+
)
with eciency f. Chain initiation occurs when the primary radical adds to mono-
mer M, and chain growth continues via successive addition of monomer units to
the radical center (chain propagation, with rate coecient k
p
). Bimolecular cou-
pling of two growing chains results in the loss of two radicals from the system
and the formation of either one (termination by combination, k
tc
) or two (termina-
tion by disproportionation, k
td
) dead polymer chains. Chain stoppage may also oc-
cur via a transfer mechanism, where the growing radical abstracts a weakly bonded
Initiator Decomposition 2 I f I

Chain Initiation
1
I M P
+
Chain Propagation
1 n n
P M P
+
+
Chain Termination
By Combination
n m n+m
P P D +
By Disproportionation
n m n m
P P D D + +
Chain Transfer
To Monomer
*
*
1
n
P M D M
M M P
+ +
+

To Solvent or Agent
*
*
1
n
P S D S
S M P
+ +
+
mon
tr
mon
i
k
k
sol
tr
sol
i
k
d
k
p
k
tc
k
td
k
i
k
n
n
k
Scheme 4.3. Basic free-radical homopolymerization mechanism.
atom (usually hydrogen) from monomer or other molecules (solvent or chain-
transfer agent, denoted by S) in the system to generate a dead polymer chain as
well as a new radical that initiates another polymer chain.
A key assumption implicit in the formulation of Scheme 4.3 is that the rates
of propagation, transfer, and termination reactions are independent of n, the
length(s) of the radical(s) involved. It is known that propagation and likely transfer
reactions involving very short chains (n = 1; 2; 3) are faster by a factor of 10 than
addition to long-chain radicals [5], but this eect diminishes rapidly with chain
length and has a negligible eect on the overall kinetics of the system. Chain ter-
mination, the coupling of two polymeric radicals, is a very fast chemical process
that is controlled by the rate at which the two radicals nd each other in the reac-
tion system. The nature of this diusion control makes termination the most com-
plex reaction in the polymerization process since the apparent rate coecient can
vary greatly with system conditions such as monomer conversion and solution vis-
cosity (see Section 4.3.3). Although termination may also exhibit some chain-
length dependence, most engineering treatments of FRP neglect this complex de-
pendence. For further discussion of the individual mechanisms of Scheme 4.3 and
their rate coecients, see Section 4.3.1.2.
The set of rate laws that can be written from Scheme 4.3 is given by Eqs. (2)(6).
Initiator Decomposition R
d
= k
d
[I[ (2)
Chain Initiation R
init
= 2f k
d
[I[ (3)
Chain Propagation R
p
= k
p
[M[[P
tot
[ (4)
Chain Termination R
term
= (k
tc
k
td
)[P
tot
[
2
= k
t
[P
tot
[
2
(5)
Chain Transfer R
tr
= (k
mon
tr
[M[ k
sol
tr
[S[)[P
tot
[ (6)
Here P
tot
represents the concentration of all polymer radicals in the system [Eq.
(7)].
[P
tot
[ =
X
y
n=1
[P
n
[ (7)
In some literature the right-hand side of the termination rate expression [Eq. (5)] is
written as 2k
t
[P
tot
[
2
. The mode of termination combination or disproportionation
has no eect on the overall termination rate, and thus the two events can also be
expressed by the nomenclature of Eq. (8), where d is the fraction of the termination
events that occur by disproportionation.
k
t
= k
tc
k
td
; d =
k
td
k
tc
k
td
(8)
The following assumptions are widely accepted and usually valid in FRP systems:
v
The small radical species I
+
; M
+
, and S
+
are not consumed by side reactions and
do not accumulate in the system, but are converted to polymeric radicals with
100% eciency. Thus, the total rate of polymer radical formation is given by
(R
init
R
tr
). The net formation of polymeric radicals is R
init
, since transfer
events both consume and create a polymeric radical species.
v
With a continuous source of new radicals in the system, an equilibrium is
achieved instantaneously between radical generation and consumption, such
that R
init
= R
term
. This characteristic, proven to be true for almost all FRP condi-
tions [6], is a result of the fast dynamics of radical reactions compared to that of
the overall polymerization system. Often referred to as radical stationarity or the
quasi-steady-state assumption (QSSA), it leads to the well-known analytical expres-
sion for total radical concentration [Eq. (9)].
[P
tot
[ =
R
init
k
t

1=2
=
2f k
d
[I[
k
t

1=2
(9)
v
The consumption of monomer by chain-initiation or transfer events is negligible
compared to that by propagation. This result, called the long-chain hypothesis
(LCH), must be true if high molecular weight polymer is being produced. Thus
the rate of polymerization (disappearance of monomer) can be taken as equal to
the rate of propagation (R
pol
= R
p
) with the rate of heat generation proportional
to the rate of this exothermic reaction.
Under these (generally valid) assumptions, the classic expressions for rate of poly-
merization (R
pol
), kinetic chain length (u, the average number of monomer units
on a living chain), and instantaneous degree of polymerization (DP
inst
n
, the average
number of monomer units on a dead polymer chain formed at any instant) are
given in Eqs. (10)(12), respectively.
R
pol
= k
p
[M[[P
tot
[ = k
p
[M[
2f k
d
[I[
k
t

1=2
(10)
u =
R
p
R
term
R
tr
=
k
p
[M[
k
t
[P
tot
[ k
mon
tr
[M[ k
sol
tr
[S[
(11)
DP
inst
n
=
k
p
[M[
(k
td
0:5k
tc
)[P
tot
[ k
mon
tr
[M[ k
sol
tr
[S[
(12)
The dierence between Eqs. (11) and (12) arises because termination by combina-
tion yields a single polymer chain such that the chain length of dead polymer
formed (DP
inst
n
) is greater than the chain length of polymer radicals (u) in the sys-
tem at the same instant.
Table 4.1 lists the range of concentration and rate coecient values typically en-
countered in homogeneous free-radical polymerization systems at low conversion.
These can be combined with Eqs. (9)(12) to illustrate the tradeos involved be-
tween the desire for high throughput (R
pol
) and the need to produce high MW
(DP
n
) polymer.
v
The denominator of Eq. (12), the rate of dead chain formation, must be of the
order 10
5
10
8
chains L
1
s
1
in order to produce polymer with a DP
n
of
10
2
10
4
. Individual polymer radicals exist on average only for a fraction of a sec-
ond, as calculated by the expression u=(k
p
[M[). Thus after the rst few seconds of
polymerization, the concentration of dead polymer chains is higher than that of
polymeric radicals, and by the end of a typical polymerization the concentration
of dead chains is orders of magnitude higher than [P
tot
]. Final polymer MW and
MWD (molecular weight distribution) are controlled by how the concentrations
and kinetic coecients in Eq. (12) vary with polymer conversion.
v
The theoretical MW limit for a system is controlled by transfer events, and is cal-
culated by setting [P
tot
] to zero in Eq. (12). For bulk FRP with no solvent, limiting
values of DP
n
are 10
4
10
6
. However, this theoretical limit can only be ap-
proached in homogeneous FRP by reducing rates of polymerization to extremely
low levels. For most systems both termination and transfer events play an impor-
tant role in controlling polymer MW.
v
To produce high MW polymer (DP
n
of 10
2
10
4
) it is necessary to keep total rad-
ical concentration low, so that [P
tot
] is of the order 10
8
10
6
mol L
1
. This dic-
tates the choice of initiator such that R
init
(the product of k
d
and [I]) is also of
order 10
8
10
6
mol L
1
s
1
.
v
Transfer can occur to monomer, solvent or any other species in the system. In
some cases, chain-transfer agents are added deliberately to limit and control poly-
mer DP
n
. These agents are generally chosen such that the rate of abstraction is
much higher than that which occurs with monomer or solvent (k
tr
=k
p
= 10
3
10
0
) and thus can be added in trace quantities (f1 mol L
1
). The use of transfer
agents allows for independent manipulation and control of R
pol
and DP
n
, but is
only possible if the desired MW is less than that achieved for the corresponding
transfer-free reaction.
Tab. 4.1. Typical values of coecients and concentrations in
low-conversion homogeneous FRP systems.
Coecient/Concentration Typical range
k
d
[s
1
] 10
6
10
4
f 0.40.9
k
p
[L mol
1
s
1
] 10
2
10
4
k
t
[L mol
1
s
1
]
[a]
10
6
10
8
k
mon
tr
=k
p
10
6
10
4
k
sol
tr
=k
p
10
6
10
3
[I] [mol L
1
] 10
4
10
2
[M] [mol L
1
] 110
[S] [mol L
1
] 110
[a]
At low conversion.
v
Initial rates of polymerization (monomer consumption rates) at low conversion
are of order 10
4
10
2
mol L
1
s
1
. Approximately 10
3
10
5
s are required to
take a batch system to complete conversion. Faster rates can be achieved by in-
creasing R
init
, but at the expense of decreased polymer MW. Achievable values
of R
pol
are also often limited by the heat removal capabilities of the reactor sys-
tem, as the heat released by monomer addition is of the order 50100 kJ mol
1
.
It should be cautioned that these statements are generalities for a typical FRP sys-
tem. Rate coecients vary with monomer, initiator, and solvent choice (see Section
4.3.1.2) as well as polymerization conditions, and the kinetic treatment is compli-
cated by the occurrence of side reactions (Section 4.3.1.3) and the variation of k
t
with conversion and other system conditions (Section 4.3.3). These factors necessi-
tate the use of more-powerful modeling techniques to quantitatively describe FRP
systems (Section 4.4). Nonetheless, Eqs. (9)(12) provide an idea of the factors con-
trolling rate and MW, and are very useful for a qualitative examination of FRP
systems.
4.3.1.2 Kinetic Coecients
The coupling of polymer MW and polymerization rate is further illustrated via re-
arrangement of Eq. (12) to give Eq. (13).
1
DP
inst
n
=
0:5k
tc
[P
tot
[
k
p
[M[

k
td
[P
tot
[
k
p
[M[

k
mon
tr
k
p
k
sol
tr
[S[
k
p
[M[
=
0:5k
tc
R
pol
k
2
p
[M[
2

k
td
R
pol
k
2
p
[M[
2

k
mon
tr
k
p
k
sol
tr
[S[
k
p
[M[
(13)
R
pol
[Eq. (10)] and DP
n
are both dependent on k
2
p
=k
t
, with DP
n
also a function of
mode of termination (disproportionation versus combination) and chain transfer.
Although R
pol
and DP
n
are easily measured experimentally, it is not possible to re-
solve the quantities into estimates for individual rate coecients. Even the estima-
tion of the ratio k
2
p
=k
t
from R
pol
requires independent knowledge of initiator char-
acteristics f and k
d
, and the assumption that radicals are not being consumed or
retarded by adventitious impurities in the system. These factors have led to consid-
erable scatter in rate coecients reported in the literature (for example, Ref. 7), es-
pecially for individual rate coecients [8, 9]. Yet individual values, and knowledge
of how they vary with temperature, are required for model development and an ac-
curate representation of multi-monomer systems. The emergence of specialized
experimental techniques since 1988 has greatly improved this situation and led to
an improved understanding of free-radical polymerization kinetics. The following
discussion highlights some of these advances, as well as summarizing key FRP
rate coecients as expressed by the Arrhenius law [Eq. (14)].
k
i
= A
i
exp((E
i
0:1DV
i
P)=RT) (14)
Activation energies (E
i
) and volumes (DV
i
) are reported with units of kJ mol
1
and
cm
3
mol
1
respectively, with T in K and P in bar. All second-order rate coecients
are reported with units of L mol
1
s
1
.
Initiation Thermal scission of an initiator is the most common means of generat-
ing radicals in FRP (see Section 4.2). This unimolecular reaction is characterized
by a rst-order rate coecient (k
d
, s
1
) so that, for a constant-volume batch system,
Eq. (2) may be integrated to yield Eq. (15), with [I[
0
the initial concentration at
t = 0.
[I[ = [I[
0
exp(k
d
t) (15)
The decomposition kinetics is often expressed by the half-life of the initiator, the
time needed for the concentration to decrease to half of its initial value [Eq. (16)].
t
1=2
= (ln 2)=k
d
(16)
The requirements for an initiator can vary widely: an initiator with a half-life of 10
h might be used in an academic study so that [I] does not change signicantly dur-
ing the course of an experiment, while an initiator used for high-pressure ethylene
polymerization typically has a half-life on the order of a few seconds. Activation en-
ergies for thermal homolysis of peroxide and azo compounds are in the range of
100150 kJ mol
1
, and thus decomposition rates are very temperature-sensitive:
the t
1=2
of benzoyl peroxide drops from 13 h at 70
C to 0.4 h at 100
C. The depen-
dence on pressure is much less, in the range of 0 to 15 cm
3
mol
1
[1, 2], but still
important for high-pressure LDPE systems. Special care must be taken in handling
and transport of thermal initiators, especially those with faster decomposition
rates.
Values of k
d
at a particular temperature and pressure can be determined by mea-
suring initiator concentration as a function of reaction time using a technique such
as infrared spectroscopy. The experimental diculty increases as half-life shortens,
where special care must be taken to eliminate transient nonisothermal eects. De-
composition kinetics are summarized for a wide range of initiators in the Polymer
Handbook [7] and in trade literature available from commercial suppliers. Of spe-
cial note is the recent work of Buback and co-workers that systematically examines
not only how E
d
and DV
d
vary with alkyl substituent for the peroxyester family
(Scheme 4.2), but also how the substituent choice aects the decomposition path-
way and initiator eciency [1, 2].
Propagation In general, chain growth or propagation proceeds in a highly selec-
tive manner to yield a polymer chain consisting of head-to-tail linkages (Scheme
4.4). In order for high polymer to be formed the propagating radical must not be
too stable: addition must occur at a suciently high rate in comparison with com-
peting transfer and termination events.
A number of nonsteady polymerization rate techniques have been introduced to
measure k
p
, many prone to signicant error [8, 9]. The introduction of a new
method, that couples pulsed-laser-induced polymerization (PLP) with size exclu-
sion chromatographic (SEC) analysis of the resulting polymer [10], has greatly im-
proved the reliability of k
p
data. In this technique, a mixture of monomer and pho-
toinitiator is illuminated by short laser pulses separated by a time of t
0
, typically
0.010.2 s. Propagation and termination (but no initiation) occur between pulses,
with the radical concentration and the rate of termination both decreasing with
time according to Eq. (5). Those growing macroradicals formed by a laser pulse
which escape termination will all have the same chain length (within a narrow
Poisson distribution) that increases with time. There is a high probability that
these surviving radicals will be terminated at t
0
, when a new population of short
radicals are generated by the next laser pulse. Thus, a signicant fraction of dead
chains formed have a chain length DP
0
corresponding to a lifetime of t
0
seconds
[Eq. (17)].
DP
0
= k
p
[M[t
0
(17)
Since radicals have a certain probability of surviving the laser ash and of terminat-
ing at a later pulse, the relative concentration of polymer with chain lengths
2DP
0
; 3DP
0
; . . . is also increased. As a result, PLP produces a well-structured
MWD with peaks at chain lengths of DP
0
and its multiples, as shown in Figure
4.1. With known values for t
0
and [M] (kept constant, as samples are pulsed only
long enough to allow a conversion of 13%), Eq. (17) yields a direct estimate of k
p
from the experimentally-determined value of DP
0
.
PLP-SEC has proven to be a very simple and robust experimental technique for
determining k
p
and its temperature dependence, provided adequate care is taken
with SEC analysis. Data collected from various research laboratories around the
world have been compiled in a series of papers for styrene [11] and methacrylates
[1214]. These papers provide benchmark k
p
data for these monomer systems, il-
lustrate the good agreement between facilities (typically 1020%), and make rec-
ommendations for best experimental practices.
Table 4.2 summarizes the Arrhenius parameters for free-radical propagation of
a wide range of monomers, as determined by PLP-SEC. An extensive review by
Beuermann and Buback [15] contains further discussion and data for additional
monomers. The data for acrylates are limited, due to measurement diculties aris-
ing from additional secondary mechanisms that occur (see Section 4.3.1.3). What
CH
2
C
R
2
R
1
+ C H
2
R
2
R
1
CH
2
C
R
2
R
1
C
R
1
R
2
CH
2
Scheme 4.4. Free-radical chain propagation.
is striking is not only the large variation in k
p
and activation energies between
monomer families, but also the similar behavior within a monomer family. All
methacrylates exhibit a similar temperature (E
p
of 21 to 23 kJ mol
1
) and pressure
(DV
p
of 15 to 17 cm
3
mol
1
) dependence, and the k
p
values for alkyl methacry-
lates at 50
C increase with increasing size of the alkyl ester group (methyl to do-
decyl) by a factor of less than 2. The alkyl acrylate family exhibits exactly the same
trends, although the activation energies (17 to 18 kJ mol
1
) and volumes (10 to
12 cm
3
mol
1
) are lower than for methacrylates, and the values of k
p
at 50
C
0
0.2
0.4
0.6
0.8
1
1.2
3.5 4 4.5 5 5.5 6 6.5
Log MW
w
t

l
o
g
(
M
W
)
DP
0
2DP
0
Fig. 4.1. A typical PLP-generated MWD, as measured by SEC
for poly(butyl methacrylate) produced by PLP of bulk butyl
methacrylate at 25
C and a laser repetition rate of 10 Hz. DP

0
is determined from the inection point of the peak, obtained by
dierentiating the distribution.
Tab. 4.2. Arrhenius k
p
parameters for various monomers determined by PLP-SEC.
[a]
Monomer E
p
[ kJ mol
C1
]
DV
p
[cm
3
mol
C1
]
A
p
[L mol
C1
s
C1
]
k
p
at 50
C/1 atm
[L mol
C1
s
C1
]
Ethylene 34.3 27.0 1:88 10
7
54
Styrene 32.5 12.1 4:27 10
7
238
Methyl methacrylate 22.4 16.7 2:67 10
6
648
Butyl methacrylate 22.9 16.5 3:78 10
6
757
Dodecyl methacrylate 21.0 16.0 2:50 10
6
995
Glycidyl methacrylate 22.9 15.0 6:19 10
6
1230
Cyclohexyl methacrylate 23.0 16.2 6:29 10
6
1204
2-Hydroxypropyl
methacrylate
20.8 n.d. 3:51 10
6
1504
Vinyl acetate 20.7 10.7 1:47 10
7
6625
Methyl acrylate 17.7 11.7 1:66 10
7
22 900
Butyl acrylate 17.4 n.d. 1:81 10
7
27 900
Dodecyl acrylate 17.0 11.7 1:79 10
7
32 000
[a]
All values taken from Ref. 15; n.d., not determined.
are 30 to 40 times greater. The propagation behavior is aected more signicantly
by electron-donating or -withdrawing substituents present in functional monomers
such as glycidyl and 2-hydroxypropyl methacrylates. The PLP-SEC method has also
been utilized to show that there is little to no solvent inuence on propagation ki-
netics of most monomers [15]. However, the propagation kinetics of acrylic acid in
water is a strong function of concentration, a result that may be explained by a
change in local monomer concentration around the propagating radical center
[16].
With accurate estimates of k
p
now available, the possibility of correlating the co-
ecient with the structural characteristics of the propagating radicals and mono-
mers is receiving attention. While some progress has been made in relating activa-
tion energy to reaction enthalpy corrected for polar and resonance factors [17],
more work is required for quantitative predictions.
Termination With independent measures of k
p
available, k
t
can now be estimated
from the lumped ratio of k
2
p
=k
t
. Specialized techniques involving pulsed-laser-
induced polymerization have also been developed to yield accurate estimates of
the ratio k
p
=k
t
[15]. Termination rates in FRP are always diusion-controlled so
that the apparent value of k
t
depends on the conditions under which it has been
measured, including the lengths of the radicals involved in the reaction. Nonethe-
less, the assumption of chain-length independence is usually made for modeling
of commercial FRP systems, since the errors introduced are not large. For a more
detailed discussion of the diusion-controlled nature of the termination reaction,
including its strong conversion dependence, see Section 4.3.3.
Most measurements of k
t
have been carried out at low monomer conversion,
and thus it is useful to tabulate available data in this regime. Signicant scatter,
as much as an order of magnitude, is found in the data contained in the Polymer
Handbook [7], as reected in the vinyl acetate k
t
data in Table 4.3. The uncertainty
Tab. 4.3. Arrhenius k
t
parameters for various monomers.
[a]
Monomer E
t
[ kJ mol
C1
]
DV
t
[cm
3
mol
C1
]
A
t
[L mol
C1
s
C1
]
k
t
at 50
C/1 atm
[L mol
C1
s
C1
]
Ethylene 4.6 15.6 1:6 10
9
2:9 10
8
Styrene 6.5 14 2:2 10
9
2:0 10
8
Methyl methacrylate 4.1 15 4:3 10
8
9:4 10
7
Butyl methacrylate 4.1
[b]
15
[b]
8:5 10
7
1:9 10
7
Dodecyl methacrylate 4.1
[b]
15
[b]
2:8 10
7
6:2 10
6
Vinyl acetate (550) 10
7[c]
Methyl acrylate 6.7 20 6:0 10
9
5:1 10
8
Butyl acrylate 4.0 16 5:1 10
8
1:2 10
8
Dodecyl acrylate 1.7 21 2:1 10
7
1:1 10
7
[a]
All values taken from Ref. 15, unless otherwise indicated.
[b]
Assumed equal to MMA value.
[c]
From Ref. 7.
arises from a number of measurement and interpretation factors [18]. The rest of
the data in Table 4.3 are based on PLP studies, and have a higher level of accuracy
(within a factor of 2); these are taken from the recent review by Beuermann and
Buback [15], adjusted to conform to the convention used in Eq. (5) for the ter-
mination rate. Note the large dierence in magnitude between values for sty-
rene, methyl methacrylate, and methyl acrylate (k
t
of 1 10
8
5 10
8
L mol
1
s
1
)
and values for dodecyl acrylate and dodecyl methacrylate (@0:5 10
7
1 10
7
L mol
1
s
1
). This has been attributed to dierences in segmental diusion rates
and/or steric hindrance of the large ester side groups. The reported activation
energies and volumes are consistent with the diusion-controlled nature of the
reaction.
The mode of termination is also of importance, as it aects the molecular archi-
tecture of the polymer formed, and thus some of its properties. Polymer polydis-
persity (M
w
/M
n
) is 1.5 if all chains are terminated by combination of two radicals,
and 2 if chains are terminated by disproportionation or chain transfer. As shown in
Scheme 4.5, termination by combination results in head-to-head linkages in the
polymer chain, whereas disproportionation results in the formation of an unsatu-
rated end group that may undergo further reaction.
The relative importance of termination by disproportionation versus combina-
tion expressed by d [Eq. (8)] is dicult to measure. The value depends largely on
the structure of the monomer: d is in the range of 0.50.8 for a-methylvinyl mono-
mers such as the methacrylates and 0.050.2 for styrene and acrylates [3]. A weak
temperature dependency has been proposed, but is dicult to verify within the
scatter of the data [19].
Chain transfer Chain transfer in radical polymerization involves the transfer of
the radical center from a polymeric radical to another molecule. It can occur to all
of the substances present in the polymerization system, and always causes a reduc-
tion in u and DP
inst
n
. Scheme 4.3 includes only transfer to monomer and solvent (or
added transfer agent), but transfer to initiator and dead polymer can also occur.
The former is often neglected since [I] is small relative to the concentration of
other species, while the latter can be an important reaction impacting MWD and
CH
2
C
R
2
R
1
+
C
R
1
R
2
CH
2
C
R
1
R
2
CH
2
CH
2
C
R
2
R
1
CH
R
1
R
2
CH
2
C
R
1
R
2
CH
+
Scheme 4.5. Free-radical chain termination by combination and disproportionation.
nal polymer properties (see Section 4.3.1.3). As well as reducing chain length, the
fragments from the transfer reactions (I
+
and M
+
in Scheme 4.3) are incorporated
as end groups in the nal polymer product.
The rate and MW equations in Section 4.3.1.1 were derived assuming that the
radicals formed by transfer reinitiate new polymeric radicals quickly, within about
the same time period as that required for a propagation step (k
mon
i
Ak
sol
i
Ak
p
).
This assumption is valid for transfer to most species, and can be veried by exam-
ining whether addition of the transfer agent has an eect on polymerization rate.
If the low-conversion polymerization rate is signicantly decreased, the species is
classied as a retarding agent or inhibitor, and Eqs. (9)(13) no longer describe
the kinetics of the system; see Section 4.3.1.3.
The chain-transfer ability of a compound can be studied by varying its concentra-
tion while holding all other variables xed. By stopping the reaction at very low
conversion such that concentrations and diusion-controlled k
t
values (and thus
R
pol
and DP
inst
n
) are kept constant, Eq. (13) can be rearranged as Eq. (18).
1
DP
n
=
1
(DP
n
)
0
k
sol
tr
[S[
k
p
[M[
(18)
A plot of 1=DP
n
against [S[=[M[ should yield a straight line with slope k
sol
tr
=k
p
and
intercept 1=(DP
n
)
0
, where (DP
n
)
0
is the average chain length measured in the ab-
sence of transfer agent. The form of this equation leads to the denition of a chain-
transfer constant C for each species, including monomer, in Eq. (19).
C
sol
tr
=
k
sol
tr
k
p
; C
mon
tr
=
k
mon
tr
k
p
(19)
It is these ratios and their temperature dependence that are tabulated in standard
references (for example, Ref. 7).
Solvent/transfer agent For some homogeneous FRP systems, solvent is added not
for its chain-transfer ability, but as a diluent to control viscosity and/or heat trans-
fer. In other systems, a small amount of chain-transfer agent (CTA) is added spe-
cically to control and reduce the MW of the polymer. Thus values for C
sol
tr
may
vary widely from a low of 10
6
10
4
to a high of 10
1
10
1
, depending on the
number of weakly bonded atoms (generally hydrogen or halogen) on the transfer
agent and their ease of abstraction. For very active compounds (for example, thiols
and halogenated compounds) with C
sol
tr
> 10
1
it is necessary to account for the
consumption of CTA during the course of the polymerization, since a changing ra-
tio of [S[=[M[ will cause a corresponding drift in polymer MW. In such cases care-
ful control of CTA addition to the system is required. If it is added at higher con-
centrations, telomerization (formation of low-MW species) will occur rather than
polymerization.
Table 4.4 summarizes values for a few typical solvents and CTA compounds at
50
C. Most organic compounds have low transfer rates (C

sol
tr
of 10
6
10
4
) so that
transfer is important only when they are present in high concentration (that is, as
solvent). They tend to be more reactive toward a radical such as ethylene or vinyl
acetate than a resonance-stabilized radical such as that of styrene. For a given
radical type, aliphatic compounds that yield tertiary radicals will be more eec-
tive transfer agents than those that produce secondary radicals. Halomethanes
and thiols, used as MW-controlling agents due to their high transfer rates, re-
act faster with nucleophilic radicals such as styrene or vinyl acetate than with
(meth)acrylates. Abstraction reactions from organic solvents generally have higher
activation energies than propagation, with (E
tr
E
p
) in the range of 2050 kJ mol
1
[21, 22]. The Polymer Handbook [7] and the monograph by Moad and Solomon [3]
provide a summary of available data for a wider range of monomerCTA (solvent)
pairings.
Monomer Transfer to monomer cannot be avoided, and the maximum upper limit
of chain length that can be achieved in a polymerization is C
mon
tr
, assuming the ab-
sence of all other transfer and termination events. The details of the mechanism
depend upon the specic monomer involved. For monomers that contain aliphatic
hydrogens such as vinyl acetate and (meth)acrylates, the transfer process involves
H-atom abstraction to form an unsaturated new radical, as shown for vinyl acetate
in Scheme 4.6. The polymer chain that grows from this radical thus contains an
unsaturated end group that may undergo further reaction. Transfer to monomer
rates are generally very low, and are dicult to measure experimentally since the
ratio with propagation (R
mon
tr
=R
p
) is independent of [M]. Table 4.5 summarizes
Tab. 4.4. Transfer constants (k
sol
tr
=k
p
) to solvents and transfer agents at 50
C.
[a]
Styrene Methyl
methacrylate
Methyl
acrylate
Vinyl
acetate
Ethylene
[ b]
Benzene 2 10
6
4 10
6
2 10
5
1 10
4
9 10
4[b]
Toluene 1 10
5
2 10
5
1 10
4
2 10
3
1:3 10
2[b]
Ethyl acetate 5 10
4
1 10
5
6 10
5
2 10
4
5 10
3[b]
Triethylamine 5 10
4
8 10
4
4 10
2
4 10
2
1:8 10
2[b]
CCl
4
1 10
2
2 10
4
2 10
4
0.8 1.0
[b]
1-Butanethiol 20 0.6 1.5 50 6.0
[b]
[a]
Representative values at 50
C [7]; there can be an order of

magnitude range in literature data.
[b]
Ethylene values at 130
C and 1360 atm [20].

CH
2
C
H
O C CH
3
O
+ C H
2
C
H
O C CH
3
O
CH
2
CH
2
O C CH
3
O
+ C H
2
C
H
O C CH
2
O
Scheme 4.6. Free-radical chain transfer to monomer (vinyl acetate).
the range of values found in the literature. C
mon
tr
increases with temperature, with
(E
mon
tr
E
p
) in the range of 1040 kJ mol
1
.
4.3.1.3 Additional Mechanisms
The basic mechanisms of Scheme 4.3 are common to and occur in every FRP
system. Other mechanisms are more system specic, dependent not only on the
choice of monomer but also the process operating conditions. These additional
mechanisms complicate the kinetic analysis and often play an important role in
controlling polymerization rate and polymer structure under typical industrial op-
erating conditions.
Thermal initiation Primary radicals in most FRP systems are generated by scis-
sion of an added initiator. Free-radical polymerizations can also be initiated by the
monomer itself, or by reactions involving trace impurities in the system. Generally
the rate of radical generation by these processes is very low negligible compared
with R
init
from the added initiator. Styrene, however, exhibits signicant thermal
polymerization at temperatures of 100
C or more. Indeed, it is not necessary to

add initiator to styrenic systems at high temperatures, as the rate of thermal initia-
tion is sucient to make an industrially viable process [26]. Acrylates and metha-
crylates have also been reported to undergo thermal polymerization, but at a signif-
icantly slower rate than styrene.
The mechanism behind the thermal polymerization of styrene is still under de-
bate, but is believed to involve the reversible formation of a dimeric species by a
DielsAlder reaction, followed by the subsequent hydrogen transfer to a third sty-
rene molecule to form two radicals that can initiate polymerization (Scheme 4.7).
This complex mechanism can be approximated by a third-order dependency on sty-
rene concentration [Eq. (20)] [27].
3M
k
therm
2I
+
R
therm
= k
therm
[M[
3
; k
therm
L
2
mol
2
s

= 2:2 10
5
exp(114:8=RT) (20)
Tab. 4.5. Transfer constants (k
mon
tr
=k
p
) to monomer.
[a]
C
mon
tr
E
tr
CE
p
[ kJ mol
C1
] Reference
Styrene 5 10
5
7
Methyl methacrylate 2 10
5
23.7 23
Butyl acrylate 6 10
5
15.2 24
Vinyl acetate 2 10
4
7
Ethylene
[b]
4 10
4[b]
43.9 25
[a]
Representative values at 50
C, unless otherwise noted; values

reported in Ref. 7 can show an order of magnitude range.
[b]
At 250
C and 2000 bar.

This expression from the mid-1970s has stood the test of time, although the pre-
exponential factor has been increased by a factor of 23 to t 260340
C data ob-
tained in a more recent study [26].
Retardation and inhibition Some substances retard or suppress free-radical poly-
merization by reacting with primary or polymer radicals to yield nonradical prod-
ucts or radicals that are too stable to add further monomer. By decreasing the
concentration of reactive radicals in the system, polymerization rate is slowed (re-
tardation) or stopped completely (inhibition).
Phenolic inhibitors (for example, hydroquinone, monomethylhydroquinone) are
commonly added to monomers at parts-per-million levels in order to prevent poly-
merization during transport and storage by rapidly and eectively scavenging any
radicals (Eq. (21), in which R
+
represents I
+
or P
n
) that may form.
R
+
Z
k
inhib
dead products; R
inhib
= k
inhib
([P
tot
[ [I
+
[)[Z[ (21)
Ideally an inhibitor (Z) stops all polymerization until completely consumed
(R
inhib
gR
p
), at which time polymerization proceeds at a normal rate, as shown
schematically in Figure 4.2. In many academic studies, monomer is distilled or
passed over a column to remove inhibitor before polymerization. This purication
is not done in industry if the concentration of inhibitor in the monomer is much
lower than the concentration of initiator added to the system, since the excess of
initiator-generated radicals quickly consumes the inhibitor.
Retardation, the slowing of polymerization rate by consumption of radicals, can
take dierent forms and thus must be considered on a case-by-case basis. If R
inhib
is of similar magnitude to R
p
, polymerization will proceed at a lower rate until all
of the retarding species is consumed (curve a in Figure 4.2). The kinetic ex-
pressions (Section 4.3.1.1) cannot be applied since termination is no longer the
+
+
CH
+
CH
Scheme 4.7. Thermal initiation of styrene.
sole mechanism of radical consumption; application of radical stationarity yields
R
init
= R
term
R
inhib
.
A dierent form of retardation occurs when a radical species formed from trans-
fer (S
+
in Scheme 4.3) reinitiates at a slow rate. In addition to the slower reaction
rate with monomer to form a polymer radical, the termination of S
+
with other
radicals in the system may also need to be considered (Scheme 4.8). Explicit bal-
ances must be written for S
+
, and the extra mechanisms must be included when
deriving expressions for [P
tot
], R
pol
, and DP
n
. As solvent/transfer agent is generally
not completely consumed, the retardation eect will last the duration of the poly-
merization (curve b in Figure 4.2). The degree of retardation depends on the
value of k
sol
i
, which can vary with monomer type; many carbon-centered radicals
show much lower reactivity toward vinyl esters (for example, vinyl acetate) than
(meth)acrylates [3].
Oxygen inhibits or retards vinyl polymerizations by the formation of peroxy rad-
icals that are generally unreactive. However, subsequent monomer addition can oc-
cur in some systems; this copolymerization forms polymeric peroxides that aect
the thermal stability of the nal polymer product. Good practice requires the re-
moval of air by sparging or freezethaw cycles before a reaction is started, and ex-
clusion of air during polymerization by operating under an inert atmosphere (for
example, nitrogen) or reuxing solvent.
b
a
C
o
n
v
e
r
s
i
o
n
Retardation
Normal
Polymerization
Time
Inhibition
Fig. 4.2. Conversiontime plots for normal, retarded, and
inhibited free-radical polymerizations. Retardation cases a and
b are described in the text.
*
*
1
*
n
n n
P S D S
S M P
S P D
+ +
+
+
sol
tr
k
sol
i
k
sol
t
k
n
Scheme 4.8. Retardation of polymerization by solvent or transfer agent.
Depropagation The addition of a radical to a double bond the propagation
reaction is potentially a reversible process [Eq. (22)].
P
n
M =
kp
k
dep
P
n1
; R
dep
= k
dep
[P
tot
[ (22)
The relative importance of the reverse reaction is governed by the free energy
change, DG
p
= DH
p
TDS
p
, where DH
p
represents the enthalpy and DS
p
repre-
sents the entropy change upon propagation; polymerization can only occur sponta-
neously when DG
p
is negative. With most common monomers, depropagation is
negligible at typical reaction temperatures. For some systems, however, the en-
thalpy and entropy terms for propagation are delicately balanced so that depropa-
gation has a signicant eect on polymerization rate (R
pol
) at higher temperatures
[Eqs. (23)].
R
pol
= R
p
R
dep
= (k
p
[M[ k
dep
)[P
tot
[ = k
e
p
[M[[P
tot
[
k
e
p
= k
p

k
dep
[M[
(23)
Examining the reaction from a thermodynamic viewpoint leads to the denition of
[M[
eq
, the monomer concentration for a particular temperature at which the eec-
tive propagation rate coecient (k
e
p
) and polymerization rate become zero [Eq.
(24)].
K
eq
=
k
p
k
dep
= exp
DG
p
RT

= exp
DH
p
RT

DS
p
R

=
1
[M[
eq
(24)
This equation can also be rearranged to Eq. (25), to dene the ceiling temperature
T
c
at which, for a given monomer concentration, the polymerization rate becomes
zero:
T
c
=
DH
p
DS
p
R ln[M[
(25)
It also provides a link between the thermodynamic and kinetic coecients accord-
ing to Eqs. (26).
DH
p
= E
p
E
dep
; DS
p
= R ln
A
p
A
dep

R ln([M[) (26)
Values of DH
p
for common monomers are tabulated in Table 4.6; an expanded list
may be found in Ref. 7. DS
p
is more dicult to measure experimentally, but is typ-
ically in the range of 100 to 140 J mol
1
K
1
. Table 4.6 also contains estimates
of T
c
calculated at [M[ = 1 mol L
1
. Ethylene, vinyl acetate, and acrylates have very
high values, and depropagation does not occur under viable polymerization condi-
tions. Styrene has a slightly lower ceiling temperature and depropagation must be
considered above 250
C. This temperature range, while higher than that generally

employed for styrene polymerization, is used for some commercial processes [26].
The addition of a methyl group to a monomer greatly reduces T
c
, as seen by
comparing values for a-methylstyrene to styrene and methacrylates to acrylates.
Figure 4.3 is a plot of k
e
p
measured for dodecyl methacrylate (bulk monomer) by
the PLP-SEC technique [28]. At 180
C, the highest temperature examined, k

e
p
is
4000 L mol
1
s
1
, less than half of the k
p
value of 9400 L mol
1
s
1
extrapolated
from the lower-temperature data. With known Arrhenius coecients for propaga-
tion (Table 4.2), the temperature dependence of k
dep
may be estimated directly from
Tab. 4.6. Depropagation behavior of common monomers.
CDH
p
[ kJ mol
C1
]
[a]
T
c
[
C]
[ b]
a-Methylstyrene 35 19
Styrene 73 335
Methyl methacrylate 56 194
Methyl acrylate 80 394
Vinyl acetate 88 460
Ethylene 102 577
[a]
From Ref. 7.
[b]
Calculated for [M[ = 1 mol L
1
, assuming DS
p
= 120 J mol
1
K
1
.
2.4
2.6
2.8
3
3.2
3.4
3.6
3.8
4
2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6
1000/T (K
-1
)
l
o
g
[
k
p
e
f
f

(
L
/
m
o
l
-
s
)
]
Fig. 4.3. Eective propagation rate coecient for bulk dodecyl
methacrylate measured by PLP. The line indicates the forward
rate coecient (k
p
) calculated according to the Arrhenius
parameters of Table 4.2. Experimental data are taken from
Ref. 28.
these data. The corresponding values for DH
p
(54 kJ mol
1
) and DS
p
(123
J mol
1
K
1
) agree well with thermodynamic estimates. The depropagation behav-
ior of many methacrylate monomers is similar [28], and depropagation must be
considered at temperatures above 120
C, especially for systems with low monomer

concentration [29].
Long-chain branching All of the mechanisms presented to this point do not
change the basic linear architecture of the polymer chains, with each repeat unit
linked to two others. Branched polymers, those in which the repeat units are not
linked solely in a linear array, can have signicantly dierent physical properties
than their linear counterpoints, depending upon the number and distribution of
the branches along the polymer backbone as well as their length. Understanding
the mechanisms by which these branches are formed, therefore, is a key compo-
nent to manipulation and control of polymer structure. Branches can be formed
either by intramolecular reactions, discussed in the next subsection, or intermolec-
ular reactions. The reaction of a polymeric radical with another polymer chain, or
long-chain branching, can occur by three distinct mechanisms. The common feature
is the re-activation of a dead polymer chain. As well as creating branched struc-
tures, these reactions signicantly broaden the polymer chain-length distribution.
Intermolecular transfer to polymer The transfer of a radical center from a polymeric
radical to another polymer chain is shown in Scheme 4.9. Addition of monomer
to the mid-chain radical produces a polymer with a branch point, with the length
controlled by the number of propagation events before chain transfer or radical
radical termination occurs. An additional subscript can be added to track the num-
ber of long-chain branches formed [Eq. (27)].
P
n; b
D
m; c
mk
pol
tr
D
n; b
P
m; c1
; R
pol
tr
= k
pol
tr
[P
tot
[m
1
(27)
This reaction does not change the number of monomer units that have been poly-
merized or the number of polymer chains in the system, and thus has no eect on
DP
n
. The rate expression in Eq. (27) is written assuming that all repeat units on all
CH
2
C
H
R
1
+
C
R
1
H
CH
2
CH
2 CH
2
CH
2
R
1
+
C
R
1
CH
2
CH
2
C
R
1
CH
2
CH
2
+
C H
2
CH
R
1
C
R
1
C H
2
CH
2
CH
2
CH R
1
Scheme 4.9. Long-chain branch formation by chain transfer to polymer.
dead polymer chains have an equal probability of reaction, as represented by m
1
, the
total concentration of polymerized monomer units in the system [Eq. (28)].
m
1
=
X
y
n=1
X
y
b=0
n[D
n; b
[ (28)
Note that the reaction is not proportional to the number of chains in the system,
but to the number of repeat units contained in the chains. This has two important
consequences. First, the importance of transfer to polymer increases with polymer
conversion (x
p
) in the system, as seen in Eq. (29) by looking at the ratio of branch-
ing to monomer consumption.
R
pol
tr
R
pol
=
k
pol
tr
[P
tot
[m
1
k
p
[P
tot
[[M[
=
k
pol
tr
x
p
k
p
(1 x
p
)
(29)
Thus polymerizations operating at high monomer conversion will have signi-
cantly higher branching than low-conversion systems. Second, longer polymer
chains those with more repeat units are more likely to participate in a branch-
ing reaction than short chains. Since the re-activated chains increase in length
through subsequent propagation, this leads to a broadening of the molecular
weight distribution reected by an increase in the weight-average MW (M
w
); even
low levels of branching can increase polydispersity values (M
w
/M
n
) to 515 com-
pared to 23 for linear polymers.
As well as conversion, the importance of transfer to polymer depends upon the
monomer system. The reaction can be important in systems with very reactive rad-
icals such as ethylene [3032], vinyl acetate [3335], and acrylate [36, 37] polymer-
izations, but seldom occurs in styrene and methacrylate systems. Transfer to poly-
mer usually occurs via abstraction of a methine hydrogen as shown in Scheme 4.9,
but may also involve other easily abstracted H-atoms, such as the acetate methyl
hydrogens on poly(vinyl acetate). Transfer constants to polymer (C
pol
tr
= k
pol
tr
=k
p
)
are not as readily determined as other transfer constants because the process does
not decrease DP
n
. Long-chain branching (LCB) levels are usually quite low, less
than 2 per 1000 repeat units, making it dicult to employ NMR. Indirect methods
such as multi-detector SEC [32, 38] are often used, leading to a signicant scatter
in reported C
pol
tr
values [7]. Like other transfer events, the relative importance in-
creases with temperature.
Reaction with unsaturated polymer chains Termination by disproportionation, trans-
fer to monomer, and chain scission (discussed later in this section) create polymer
chains with terminal unsaturation (denoted in Eq. (30) by D
=
). These reactive
chains, sometimes called macromonomers, can add to a growing radical to form a
long-chain branch.
P
n; b
D
=
m; c
k
pol
p
P
nm; bc1
; R
pol
p
= k
pol
p
[P
tot
[[D
=
tot
[ (30)
This reaction is fundamentally dierent than transfer to polymer in several re-
spects. It is an addition rather than a transfer (H-abstraction) reaction (Scheme
4.10). The reaction rate is dependent on the number of unsaturated chain ends
rather than the number of repeat units in the chains so that its importance relative
to propagation is controlled by the ratio [D
=
tot
[=[M[ according to Eq. (31).
R
pol
p
R
pol
=
k
pol
p
[P
tot
[[D
=
tot
[
k
p
[P
tot
[[M[
(31)
Unlike transfer to polymer, the mechanism combines two polymer chains (and
all of their repeat units) into one, aecting both DP
n
and DP
w
. Reaction with
terminally unsaturated chains can be important in vinyl acetate [33] and higher-
temperature methacrylate [3] polymerizations.
Reaction with multifunctional monomers Another way to introduce branching is
through addition of a multifunctional monomer to the polymer system. An exam-
ple is the addition of small levels of ethylene glycol dimethacrylate (EGDMA) to
methyl methacrylate (MMA), as shown in Scheme 4.11. Reaction of the rst dou-
CH
2
C
R
2
R
1
+ C H
2
C
R
1
CH
2
C
R
1
C
R
1
R
2
CH
2
Scheme 4.10. Long-chain branch formation by addition to a
terminally unsaturated polymer chain.
+
CH
2
C
C H
3
C
O OCH
3
C
C H
3
C
O O CH
2
C H
2
CH
2
O
C
CH
3
C
O
CH
2
CH
2
C
C H
3
C
O O CH
2
CH
2
O
C
CH
3
C
O
CH
2
CH
2
C
CH
3
C
O O
CH
2
CH
2
O
C
CH
3
C
O
C H
2
+
CH
2
C
C H
3
C
O OCH
3
CH
2
O
C
CH
3
C
O
CH
2
C CH
2
C H
3
C
O O CH
3
C H
2
O
CH
2
C
CH
3
C
O
Scheme 4.11. Addition of ethylene glycol dimethacrylate to a
methyl methacrylate radical. The pendent double bond is
attacked by another polymer radical to form a crosslink.
ble bond incorporates EGDMA in the PMMA chain, with the second reactive site
remaining as a pendent double bond. Reaction of this pendent bond with another
polymer radical creates a branched structure termed a crosslink, since the branch
is tetrafunctional rather than trifunctional in nature.
The addition of a small amount of difunctional monomer such as EGDMA to
MMA [39, 40] or divinylbenzene to styrene is a means to increase polymer MW
without decreasing radical concentration. Addition of higher levels leads to an in-
terconnected branched, or network, polymer.
Short-chain branching (intramolecular transfer to polymer) Intramolecular H-atom
abstraction, often called back-biting, occurs via the formation of a six-membered
ring, as shown in Scheme 4.12 for butyl acrylate (nBA). Monomer addition to the
resulting interior radical leaves a short-chain branch (SCB) consisting of two repeat
units. This mechanism has long been known important for high-pressure LDPE
production at 150300
C [30], where the number of short-chain branches is in

the range of 2050 per 1000 ethylene repeat units. This level of SCB signicantly
decreases the polyethylene crystallinity and gives LDPE some of its unique proper-
ties; LDPE density is 0.92 g cm
3
compared to 0.98 g cm
3
for linear polyethylene.
Multiple back-biting events lead to other SCB structures; in addition to the com-
mon butyl branch in LDPE, ethyl and 2-ethylhexyl branches have been identied
using
13
C NMR [30, 41, 42].
In ethylene/nBA copolymerization it is observed that the methine hydrogens on
nBA units in the polymer chain are much more susceptible to abstraction than hy-
drogen abstraction from a CH
2
unit in the backbone [43]. This result, along with
the observed high concentration of branch points formed at conditions of very low
polymer concentration during nBA homopolymerization [36], indicates that the in-
tramolecular (back-biting) mechanism is also important in acrylate polymeriza-
tions. There is strong evidence to suggest that monomer addition to the resulting
mid-chain radical, due to its higher stability, is much lower than addition to a
chain-end radical [44]. Thus the mechanism aects nBA polymerization rate as
well as polymer structure [37]. The same type of back-biting reaction has also
R
CH
CH
C
CH
C H
COOBu
COOBu
COOBu
COOBu
COOBu
H
R
CH
CH
C
CH
CH
COOBu
COOBu
COOBu
COOBu
COOBu
H
Scheme 4.12. Formation of a mid-chain radical by
intramolecular chain transfer to polymer. Monomer addition to
the new radical structure creates a short-chain branch in the
polymer.
been shown to occur during styrene polymerization at high temperatures (260
340
C) [26].
Chain scission The radical structure formed by intra- or intermolecular transfer
to polymer is less reactive than a chain-end radical. Under higher-temperature con-
ditions, the radical can undergo b-fragmentation (chain scission) as shown in
Scheme 4.13 for butyl acrylate [45]. The scission can occur in either direction,
yielding a short-chain radical or a short-chain unsaturated trimer species. As well
as lowering polymer MW, the scission event produces an unsaturated chain end
that can react further, as discussed previously (see Scheme 4.10).
Scission events can occur in any system where mid-chain radicals are formed.
However, scission is more temperature-activated than H-abstraction and thus be-
comes important only at elevated temperatures. The reaction is not believed to oc-
cur during butyl acrylate polymerization at 75
C [37], but is shown to be important

at 140
C [29, 45]. Scission is a dominant mechanism in styrene polymerizations

at 260340
C [26], and also occurs during LDPE production [30]. Scission of mid-
chain radicals formed via intermolecular transfer to polymer can have a signicant
eect on the breadth and the shape of polymer MWD [46].
Kinetic treatment of these more complex mechanisms is often dicult. Equa-
tions (32)(34) are a network of reactions developed to treat intramolecular trans-
fer, short-chain branch formation, and b-scission for butyl acrylate polymerization
[47].
P
n

k
bb
Q
n
; R
bb
= k
bb
[P
tot
[ (32)
Q
n
M
k
tert
p
P
n1
SCB; R
SCB
= k
tert
p
[M[[Q
tot
[ (33)
Q
n
0:5kb
D
=
n2
P
2
Q
n
0:5kb
P
n3
D
=
3
; R
b
= k
b
[Q
tot
[
(34)
The kinetic coecients are estimated by measuring the level of quaternary carbons
(equated to short-chain branch level) and terminal unsaturations (D
=
) by NMR.
CH
CH
C
CH
CH
COOBu
COOBu COOBu
COOBu
COOBu
H
CH
CH
C
CH
2
COOBu COOBu
COOBu
+ C H CH
2
COOBu COOBu
CH
CH
COOBu COOBu
C H CH
2
COOBu COOBu
C
C H
2
COOBu
+
Scheme 4.13. b-Scission of butyl acrylate mid-chain radical.
Termination of the mid-chain radical (Q
n
) is also considered in the scheme. While
the mechanism provides improved understanding of this complex system, many
questions still remain: does the mid-chain radical terminate at the same rate as
chain-end radicals; what is the reactivity of the unsaturated chain end; and does
the mid-chain radical scission with equal probability in each direction? The reac-
tion engineering challenge is to consider the set of mechanisms required to repre-
sent the basic rate behavior and polymer architecture of the system without intro-
ducing unneeded complexity.
4.3.2
Copolymerization
Reaction of two or more monomers by free radical polymerization is an eective
way of altering the balance of properties of commercial products. Addition of the
polar monomer acrylonitrile to styrene (or methyl acrylate to ethylene) produces a
polymer that combines the strength of the base homopolymer with much im-
proved oil and grease resistance. The adhesive and cohesive properties of coatings
resins are balanced by controlling the mix and relative proportions of monomers in
the recipe.
FRP leads to the formation of statistical copolymers, where the arrangement of
monomers within the chains is dictated purely by kinetic factors. However, reactiv-
ity of a monomer in copolymerization cannot be predicted from its behavior in ho-
mopolymerization. Vinyl acetate polymerizes about 30 times more quickly than
styrene (see Table 4.2), yet the product is almost pure polystyrene if the two mono-
mers are copolymerized together in a 50:50 mixture. a-Methylstyrene cannot be ho-
mopolymerized to form high-MW polymer due to its low ceiling temperature (see
Table 4.6), yet is readily incorporated into copolymer at elevated temperatures.
These and other similar observations can be understood by considering copolymer-
ization mechanisms and kinetics.
4.3.2.1 Basic Mechanisms
In copolymerization, the presence of more than one type of monomer adds an ex-
tra degree of complexity to the kinetics. The dierent monomers form dierent
radical structures, and the relative rates of chain growth depend on the structure
of both monomer and radical. It is these propagation mechanisms that control
polymer composition (the relative amounts of each monomer unit incorporated
into the copolymer) and sequence distribution (the way in which these monomer
units are arranged within the chain). Developing a set of mechanisms to describe
how radical structure aects termination and transfer rates is required to represent
copolymer chain length and molecular weight distributions.
The most common treatment of free radical copolymerization kinetics assumes
that the reactivity of the polymer radical depends solely on the nature of its termi-
nal monomer unit; that is, that the identity of the penultimate unit on the radical
does not aect its reactivity. This assumption provides a good representation of
polymer composition and sequence distribution, but not necessarily polymeriza-
tion rate (see Section 4.3.2.2). This so-called terminal model is widely used to model
free-radical copolymerization according to the set of mechanisms in Scheme 4.14.
In this scheme monomer-j (denoted by M
j
) adds to the initiator primary radical
to form a polymer radical of type-j and unit length. The dead polymer and radical-i
chains of length n (D
n
and P
i
n
) are made up of a mixture of the monomer types in
the system, with their relative amounts governed by the copolymer composition
equation developed below. Chain growth occurs by addition of M
j
to radical-i (P
i
n
)
with the propagation rate coecient k
p
ij
dependent on both radical and monomer
type. The rate coecients for transfer and termination reactions can also be depen-
dent on the nature of the radical center, as indicated by subscripts. However, since
radicalradical termination is a diusion-controlled reaction, the rate coecient
can usually be assumed to be independent of radical type, such that k
cop
t
= k
t
ij
for
all i and j.
Most of the kinetic coecients in Scheme 4.14 are binary parameters, dependent
on the radical and monomer type. Thus the polymerization behavior of three or
more monomers can be estimated reliably from knowledge of the corresponding
binary copolymerizations. For a two-monomer system assuming the long-chain hy-
pothesis, the consumption rates of the two monomers are written as in Eqs. (35).
R
pol1
= k
p11
[P
1
tot
[[M
1
[ k
p21
[P
2
tot
[[M
1
[
R
pol2
= k
p12
[P
1
tot
[[M
2
[ k
p22
[P
2
tot
[[M
2
[
(35)
Initiator Decomposition 2 I f I

Chain Initiation
1
j
j
I M P
+
Chain Propagation
1
i
n j n
P M P
+
+
Chain Termination
By Combination
i
n m n m
P P D
+
+
By Disproportionation
i j
n m n m
P P D D + +
Chain Transfer
To Monomer
1
i
n j n
P M D P + +
To Solvent or Agent
1
*
*
i
n n
j
j
P S D S
S M P
+ +
+
d
k
i
j
k
p
ij
k
tc
ij
k
td
ij
k
mon
tr
ij
k
sol
tr
i
k
sol
i
j
k
j
j
j
Scheme 4.14. Basic free-radical copolymerization mechanism,
assuming terminal radical kinetics.
where P
i
tot
represents the concentration of all polymer radicals of type-i in the sys-
tem [Eq. (36)].
[P
i
tot
[ =
X
y
n=1
[P
i
n
[ (36)
The ratio of the two consumption rates dictates the instantaneous composition
(F
inst
p
i
) of the polymer being formed [Eq. (37)].
F
inst
p1
F
inst
p2
=
R
pol1
R
pol2
=
k
p11
[P
1
tot
[[M
1
[ k
p21
[P
2
tot
[[M
1
[
k
p12
[P
1
tot
[[M
2
[ k
p22
[P
2
tot
[[M
2
[
(37)
Application of the quasi-steady-state assumption yields the ratio of the radical types
as in Eq. (38), and substitution and rearrangement leads to the well-known poly-
mer composition equation [Eq. (39)], where f
1
and f
2
are the mole fractions of M
1
and M
2
in the monomer mixture, and monomer reactivity ratios r
1
and r
2
are de-
ned as k
p11
=k
p12
and k
p22
=k
p21
.
[P
1
tot
[
[P
2
tot
[
=
k
p21
[M
1
[
k
p12
[M
2
[
(38)
F
inst
p1
=
r
1
f
2
1
f
1
f
2
r
1
f
2
1
2 f
1
f
2
r
2
f
2
2
(39)
Equation (39) denes the composition of the copolymer formed at any instant dur-
ing polymerization, and is dependent only on the ratios of the propagation rate co-
ecients and not on their absolute values.
Copolymer properties depend on the distribution of the monomer units along
the chain as well as the average composition. Reactivity ratios also control copoly-
mer sequence distribution. The probability P
11
that an M
1
unit follows an M
1
unit
in the copolymer is equal to the rate of M
1
M
1
formation divided by the sum of the
rates of all additions to radical-1 [Eq. (40)].
P
11
=
k
p11
[P
1
tot
[[M
1
[
k
p11
[P
1
tot
[[M
1
[ k
p12
[P
1
tot
[[M
2
[
=
r
1
f
1
r
1
f
1
f
2
(40)
The probability P
12
that an M
2
unit follows an M
1
P
12
= 1 P
11
=
f
2
r
1
f
1
f
2
(41)
Similar expressions, Eqs. (42) and (43), can be derived for addition to radical-2:
P
22
=
k
p22
[P
2
tot
[[M
2
[
k
p22
[P
2
tot
[[M
2
[ k
p21
[P
2
tot
[[M
1
[
=
r
2
f
2
r
2
f
2
f
1
(42)
P
21
= 1 P
22
=
f
1
r
2
f
2
f
1
(43)
These probabilities can be used to calculate N(M
1
; n
i
), the fraction of all M
1
se-
quences that are exactly n
i
units long. This is simply the probability of having
(n
i
1)M
1
M
1
linkages followed by an M
1
M
2
linkage, according to Eq. (44).
N(M
1
; n
i
) = P
n
i
1
11
P
12
; N(M
2
; n
j
) = P
nj 1
22
P
21
(44)
Thus the fraction of M
1
sequences that consists of an isolated M
1
unit is P
12
, the
fraction that consists of isolated M
1
M
1
diads is P
11
P
12
, the fraction of triads is
P
2
11
P
12
, and so forth. The number-average length of M
1
sequences (N
1
) is given by
Eq. (45) and the fraction of all M
1
units contained in a sequence of length n
i
is
n
i
P
n
i
1
11
P
2
12
; that is, the fraction of M
1
contained in isolated diads is 2P
11
P
2
12
.
N
1
=
1
1 P
11
=
1
P
12
; N
2
=
1
1 P
22
=
1
P
21
(45)
Implicit in these expressions is the approximation, valid for long-chain polymer,
that the number of M
1
M
2
linkages in a chain is equal to the number of M
2
M
1
link-
ages. Thus the ratio of M
1
to M
2
units in the chain must equal the ratio of the re-
spective average sequence lengths [Eq. (46)].
F
inst
p1
F
inst
p2
=
N
1
N
2
(46)
Substitution and rearrangement of this equation yields the polymer composition
equation, Eq. (39). Thus it is possible to estimate reactivity ratios for binary copoly-
mers from triad distributions measured by NMR analysis.
While copolymer composition and sequence distribution are only functions of
the reactivity ratios, the same is not true for polymerization rate. The overall rate
of monomer consumption is given by Eq. (47), where [M
tot
] indicates the total
monomer concentration ([M
1
[ [M
2
[).
R
pol
= k
p11
[P
1
tot
[[M
1
[ k
p21
[P
2
tot
[[M
1
[ k
p12
[P
1
tot
[[M
2
[ k
p22
[P
2
tot
[[M
2
[
=
X
2
i=1
X
2
j =1
k
p
ij
f
r
i
f
j
!
[P
tot
[[M
tot
[ (47)
The fraction of radical-i in the system, f
r
i
[Eq. (48)] can be calculated from Eq. (38).
f
r
i
=
P
i
tot
P
1
tot
P
2
tot
=
P
i
tot
P
tot
(48)
[P
tot
], the total radical concentration, is calculated from an overall radical balance
similar to Eq. (9) and given by Eq. (49).
[P
tot
[ =
R
init
k
cop
t

1=2
=
2f k
d
[I[
k
cop
t

1=2
(49)
The form of Eq. (47) is analogous to the homopolymerization rate expression [Eq.
(10)], with a copolymer-averaged rate coecient for propagation (generalized for a
system with N
mon
dierent monomers) dened in Eq. (50).
k
cop
p
=
X
Nmon
i=1
X
Nmon
j =1
k
p
ij
f
r
i
f
j
(50)
For a two-monomer system, application of the QSSA [Eq. (38)] and simplication
lead to Eq. (51).
k
cop
p
=
r
1
f
2
1
2f
1
f
2
r
2
f
2
2
(r
1
f
1
=k
p11
) (r
2
f
2
=k
p22
)
(51)
Using Eqs. (47)(51), the copolymerization reaction rate can be analyzed as for
homopolymerization (see Section 4.3.1.4), with k
cop
p
now a function of monomer
composition.
4.3.2.2 Kinetic Coecients
The traditional method for determining reactivity ratios involves determination of
copolymer composition for a range of monomer feeds at very low conversion; that
is, measuring F
p1
as a function of f
1
. NMR measurement of sequence distributions
provides additional information about chain microstructure, but suers from
greater experimental noise and signal assignment uncertainty from tacticity ef-
fects. There is a large body of published r
1
r
2
data for monomer pairings, summar-
ized in Ref. 7. The scatter for these ratios is much less than found in k
p
and k
t
data, but care still must be exercised when extracting values from this and similar
compilations. Some error can arise from the methodology used to estimate r
1
and
r
2
from F
p1
versus f
1
data. The estimation is best accomplished by nonlinear least
squares techniques [48, 49], and a statistical analysis also provides a guide to the
optimal monomer compositions at which experimentation should be performed
to improve the estimates [48]. Error can also occur if polymer conversion is su-
ciently high for f
1
to deviate signicantly from the zero-conversion value (in which
case an integrated form of Eq. (39) must be used [50]), or if the experimental sys-
tem does not remain homogeneous (often observed with acid monomers).
There are only a few systems for which the terminal model upon which Eq. (39)
is based does not provide a good description of copolymer composition. The result-
ing polymers exhibit an alternating structure (for example, styrenemaleic anhy-
dride), or the observed reactivity ratios in the system vary with monomer concen-
tration or solvent choice. Since they often include a polar monomer with strong
electron-withdrawing or electron-donating properties, alternative kinetic models
that include the formation of monomer complexes have been developed to repre-
sent these systems [3, 51]. The majority of systems, however, are well behaved
and well represented by the terminal model. Table 4.7 summarizes values of reac-
tivity ratios for styrene, alkyl methacrylate, alkyl acrylate, and vinyl acetate systems.
Reactivity ratios for alkyl methacrylates and acrylates (for example, methyl, butyl,
dodecyl) exhibit a family type behavior, with the composition data of various sys-
tems tted well by a single curve [52]. Values for ethylene copolymer systems at
typical production conditions are summarized in Table 4.8: While r
1
(1 = ethylene)
values for alkyl methacrylates, alkyl acrylates, acrylic acid, and methacrylic acid
could not be distinguished within experimental error [53], there were signicant
dierences in the r
2
values [54].
It is informative to consider some of the implications of these values. In Figure
4.4 the relationship between polymer and monomer composition is plotted for var-
ious copolymer systems:
Tab. 4.7. Monomer reactivity ratios at 50
C
[a]
, r
1
is tabulated horizontally and r
2
vertically.
Monomer-1 Monomer-2
Styrene Methacrylate Acrylate Vinyl acetate
Styrene 0.6 0.8 40
Alkyl methacrylate 0.4 2.2 20
Alkyl acrylate 0.2 0.4 6
Vinyl acetate 0.02 0.03 0.03
[a]
Representative values Ref. 7.
Tab. 4.8. Monomer reactivity ratios for ethylene (monomer-1)
systems at 240
C and 2000 bar [53, 54].

Monomer-2 r
1
r
2
Alkyl methacrylates 0.058 7
Methacrylic acid 0.058 11
Alkyl acrylates 0.058 4
Acrylic acid 0.058 8
Vinyl acetate
[a]
1.0 1.0
[a]
From Ref. 7.
v
For the case where r
1
= r
2
= 1:0 (ethylenevinyl acetate; methacrylate
methacrylate), the monomers have equal reactivity to propagation and will be
incorporated into polymer at the same ratio as they are in the monomer phase
(F
p1
= f
1
).
v
Where r
1
> 1 and r
2
< 1, the copolymer will always be richer in monomer-1 than
in the monomer phase, so that monomer-1 will become depleted in a batch poly-
merization. The further the reactivity ratios deviate from unity, the greater the
deviation between polymer and monomer composition. Systems that exhibit
this behavior include methacrylateacrylate polymerizations, and styrene, meth-
acrylates, or acrylates polymerized with vinyl acetate or ethylene.
v
With both r
1
and r
2
less than unity (styreneacrylate, styrenemethacrylate),
cross-propagation is favored over homopropagation and the copolymer tends
toward an alternating structure. The system has an azeotropic composition at
which the copolymer composition is exactly equal to the monomer composition.
Reactivity ratios exhibit a weak temperature dependence that is often dicult to
measure. With increasing temperature, the ratios tend to approach unity as dem-
onstrated for styrenebutyl acrylate [55], butyl acrylatemethyl methacrylate [56],
and ethylene copolymer systems [53, 54]. The temperature dependence of the latter
agrees well with activation energies reported for addition of monomers to small
radicals [57].
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
f
1
F
p
1
MMA-Sty
MMA-MA
MMA-VAc
Eth-VAc
Fig. 4.4. Relationship between monomer composition f
1
and
corresponding instantaneous polymer composition F
inst
p1
for
various monomer pairings (MMA = methyl methacrylate,
Sty = styrene, MA = methyl acrylate, VAc = vinyl acetate,
Eth = ethylene).
While the terminal model eectively represents copolymer composition for most
systems, it does not provide as good of a description of polymerization propaga-
tion behavior. Rate abnormalities have previously been attributed to termination
reactions and represented by introducing physically unrealistic cross-termination
mechanisms [58]. Careful experimental work by Fukuda and co-workers [51], how-
ever, demonstrated that the rate deviations are due to the inadequacy of the ter-
minal model to describe propagation, with further evidence obtained by applica-
tion of the PLP-SEC technique to measure k
cop
p
. Many common systems show
deviation from terminal propagation kinetics, including styrenemethacrylate [51,
59], styreneacrylate [60, 61], and acrylatemethacrylate [52, 62] systems. As
shown in Figure 4.5, the measured k
cop
p
values can be higher or lower than the ter-
minal model predictions, with the deviation substantial in some cases.
The implicit penultimate unit eect model, which accounts for the inuence
of the penultimate monomer unit of the growing polymer radical on the propaga-
tion kinetics [51], provides a good representation of this behavior [Eqs. (52)].
k
cop
p
=
r
1
f
2
1
2f
1
f
2
r
2
f
2
2
(r
1
f
1
=k
p11
) (r
2
f
2
=k
p22
)
k
p11
=
k
p111
[r
1
f
1
f
2
[
r
1
f
1
[ f
2
=s
1
[
k
p22
=
k
p222
[r
2
f
2
f
1
[
r
2
f
2
[ f
1
=s
2
[
(52)
10.0
100.0
1000.0
10000.0
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
f
1
(MMA)
k
p
c
o
p

(
L
/
m
o
l
-
s
)
Fig. 4.5. Relationship between monomer composition f
1
and
corresponding copolymer-averaged propagation rate coecient,
k
cop
p
. Lines are calculated assuming terminal-model kinetics and
points are experimental data for: MMAnBA (, e) [62] and
MMAstyrene (- - -, C) [59] at 20
C.
The extra parameters s
1
and s
2
, called radical reactivity ratios, capture the eect of
the penultimate unit on the addition rate of monomer [Eqs. (53)].
s
1
=
k
p211
k
p111
s
2
=
k
p122
k
p222
(53)
A value of greater than unity for s
i
indicates that a comonomer unit-j in the penul-
timate position increases the addition rate of monomer-i to radical-i compared to
the homopolymerization case.
The kinetics of diusion-controlled termination in copolymerization is also di-
cult to study. The original interpretation of low-conversion rate data was based on a
chemically controlled model utilizing a cross-termination factor [Eq. (54)].
k
cop
t
=
X
Nmon
i=1
X
Nmon
j =1
k
t
ij
f
r
i
f
rj
; F =
k
t12
k
t11
k
t22
(54)
Assuming terminal propagation kinetics, the best t for F was found to be much
greater than unity for styrenemethacrylate, styreneacrylate, and other systems
such that k
cop
t
was greater than either homotermination value. When the deviation
of propagation kinetics from the terminal model is taken into account, however,
the estimates for k
cop
t
become well behaved and bounded by the homotermina-
tion values [51]. A penultimate model [51, 63] that accounts for the inuence
of polymer composition on segmental diusion is required to t recent acrylate
methacrylate low-conversion k
cop
t
data [63, 64]. In order to use this representation
(Eq. (55), with the cross-termination coecients k
t12; 12
and k
t21; 21
tted to experi-
mental data), it is necessary to track the four possible penultimate radical types in
the system, with f
r
ij
(i; j = 1; 2) the penultimate radical fraction.
(k
cop
t
)
0:5
= k
0:5
t11; 11
f
r11
k
0:5
t21; 21
f
r21
k
0:5
t22; 22
f
r22
k
0:5
t12; 12
f
r12
(55)
While the terminal model and reactivity ratios provide a good description of copoly-
mer composition, the kinetic studies summarized in this section indicate that ad-
ditional parameters and penultimate radical fractions are required to represent k
cop
p
and k
cop
t
. (For a discussion of transfer to monomer in copolymer systems, see Ref.
65.) These mechanistic complexities are often not considered when developing
FRP models for polymer reaction engineering applications. It is expected that this
situation will change as more data become available.
4.3.2.3 Additional Mechanisms
The secondary mechanisms presented for homopolymerization in Section 4.3.1.3
also occur in multi-monomer systems. The kinetics of depropagation, chain trans-
fer to polymer, and chain scission are strongly inuenced by not only the nature of
the monomer and terminal radical, but also the penultimate unit on the polymer
radical.
Depropagation It is not possible to produce high MW homopolymer close to the
ceiling temperature of the monomer (see Eq. (25) and Table 4.6). Addition of a
non-depropagating monomer (M
2
) to the system disrupts this behavior, as illus-
trated by Scheme 4.15. Depropagation of radical-1 becomes a competitive process
with addition of monomer-2, with monomer-1 units at the radical end becoming
irreversibly trapped in the growing chain as soon as monomer-2 adds. Further-
more, depropagation of monomer-1 will occur only if an M
1
unit is also in the pen-
ultimate position; depropagation to the less-stable M
2
radical can be assumed to be
unlikely (k
dep21
A0). Thus MMA can be successfully copolymerized with ethylene at
290
C [57], and a-methylstyrene with various comonomers at temperatures well

above its ceiling temperature [66, 67].
Depropagation in copolymerization aects polymer composition, sequence prob-
abilities, and polymerization rate. With Scheme 4.15, the relative rates of monomer
consumption are given by Eq. (56) (compare with Eq. (37) in the absence of depro-
pagation).
F
inst
p1
F
inst
p2
=
R
pol1
R
pol2
=
k
p11
[P
1
tot
[[M
1
[ k
p21
[P
2
tot
[[M
1
[ k
dep11
f
r11
f
r11
f
r21
[P
1
tot
[
k
p12
[P
1
tot
[[M
2
[ k
p22
[P
2
tot
[[M
2
[
(56)
The ratio f
r11
=( f
r11
f
r21
) accounts for the fraction of radical-1 that ends in a 11
diad. The eect of depropagation becomes larger as total monomer concentration
decreases and as the fraction of the depropagating monomer in the system in-
creases. Lowry [68] rst derived the composition expressions for the situation
where only one monomer depropagates, and general expressions have been devel-
oped for the situation where all four of the propagation reactions are reversible
[66, 69]. Depropagation must be considered when examining the kinetics of
starved-feed semi-batch copolymerization involving methacrylates at the higher-
temperature conditions typically used to produce acrylic coatings [29, 70].
Chain transfer to polymer The rate of chain transfer to polymer is dependent on
both the reactivity of the radical and the abstractability of the hydrogen atom on
the monomer unit in the polymer chain. For the case of intermolecular chain
transfer (long-chain branching), this is represented by Eq. (57), where m
j
1
repre-
sents the total concentration of polymerized monomer-j units in the system and
1 1 1 1
1 2 1 2
2 2 2 2
2 1 2 1
~~~ ~~~
~~~ ~~~
~~~ ~~~
~~~ ~~~
M M M M
M M M M
M M M M
M M M M
+
+
+
+
.
.
.
11
p
k
11
dep
k
12
p
k
22
p
k
21
p
k

.
Scheme 4.15. Depropagation in copolymerization for the case
where M
2
does not depropagate and M
1
depropagates only
when an M
1
-unit is in the penultimate position.
n
j
represents the number of monomer-j units on a particular chain of length n
[Eqs. (58)].
P
i
n; b
D
m; c
mj k
pol
tr
ij
D
n; b
P
j
m; c1
; R
pol
tr
=
X
Nmon
i=1
X
Nmon
j =1
k
pol
tr
ij
[P
i
tot
[m
j
1
(57)
m
j
1
=
X
y
n=1
X
y
b=0
n
j
[D
n; b
[; n =
X
Nmon
j =1
n
j
(58)
Active radicals (ethylene, acrylate, vinyl acetate) are more likely to abstract from a
polymer chain than styrenic or methacrylate radicals, and acrylate and vinyl acetate
monomer units on a chain are more likely to have an H-atom abstracted. Thus it is
not uncommon for the intermolecular transfer to polymer rate of one pairing (for
example, acrylate radical to acrylate monomer unit) to dominate the system, with
the overall transfer rate R
pol
tr
decreasing rapidly with increasing content of the less-
reactive monomer.
The situation is more complicated in the case of intramolecular transfer, which
occurs through the formation of a six-membered ring. In the case of acrylate (1)/
methacrylate (2), it can be assumed that the methacrylate radical is not reactive
enough to back-bite and that the acrylate radical can only abstract hydrogen if the
antepenultimate unit on the chain is also an acrylate unit. Thus back-biting can oc-
cur only for two monomer sequences (M
1
M
1
M
1
and M
1
M
2
M
1
) at the radical end,
as shown in Scheme 4.16 [70]. The overall back-biting rate must be corrected for
the sequence probabilities [Eqs. (40)(43)] at the chain end, according to Eq. (59).
C
CH
C H
COOBu
COOBu
COOBu
H
C
COOBu
R
C
CH
CH
COOBu
COOBu
COOBu
H
C
COOBu
R
C
C
C
C H
COOBu
COOBu
COOBu
COOBu
H
C H
3
R
C
C
CH
COOBu
COOBu
COOBu
C H
3
H
C
COOBu
R
Scheme 4.16. Back-biting reaction in high temperature
copolymerization of butyl acrylate and butyl methacrylate
(R = H or CH
3
).
R
bb
= k
bb
[P
1
tot
[(P
11
P
11
P
12
P
21
) (59)
Back-biting mechanisms have also been examined for styrene/acrylate [71] and
ethylene copolymer systems [43].
Chain scission There is evidence that the rate of b-fragmentation of a mid-chain
radical is aected by the nature of the units adjacent to the mid-chain radical. Har-
ada et al. [72] studied the copolymerization of cyclohexyl acrylate and methyl meth-
acrylate at high temperatures. As in Scheme 4.16, H-abstraction only happens to
the acrylate unit. If the adjacent units are acrylate and methacrylate, two types of
fragmentation with dierent reaction rates are possible, as illustrated in Scheme
4.17. It was observed that the number of the unsaturated end groups per chain is
increased by increasing the methacrylate content in the polymerization. Thus it
was deduced that fragmentation greatly favors the generation of tertiary (methacry-
late chain end) radical species, a result in agreement with the high rate of fragmen-
tation observed in methacrylate macromonomer systems [73].
Fragmentation after intramolecular transfer results in the formation of a long-
chain radical and trimer species or a dimer radical and an unsaturated dead chain
(Scheme 4.13). Consideration of all possible pathways and structures becomes
complex, but the resulting model requires no additional parameters from the ho-
mopolymerization back-biting/scission case and provides a good representation of
high temperature acrylatemethacrylate copolymerization [70].
4.3.3
Diusion-controlled Reactions
The kinetic schemes in this chapter have been written assuming that k
t
is indepen-
dent of the sizes of the radicals involved in the termination reaction. This is not
CH
2
C
CH
2
C
CH
2
C H
CH
3
CO
2
CH
3
CO
2
CH
3
CO
2
CH
3
CH
2
C
CH
3
CO
2
CH
3
+
C H
2
C
CH
2
C H
CO
2
CH
3
CO
2
CH
3
CH
2
C
CH
2
C
CH
2
CH
3
CO
2
CH
3
CO
2
CH
3
+
C H
CO
2
CH
3
fast
slow
Scheme 4.17. Fragmentation of a mid-chain radical with
adjacent MA and MMA units (after Ref. 72).
strictly true, since the termination rate is limited by the rates at which the radical
ends can encounter each other. For a diusion-controlled reaction, the apparent
rate coecient is aected not only by pressure and temperature, but also by system
viscosity (a function of solvent, polymer concentration, and MW) and the lengths
of the two terminating radicals. This complex behavior, as well as experimental dif-
culties in measuring k
t
, has led to a large scatter in reported values, even at low
conversion [7]. Through the application of pulsed-laser experimental techniques
[15] and a critical examination of available data [18], the situation is starting to
improve.
For most commercial free radical polymerization, the errors involved by neglect-
ing the dependence of k
t
on radical chain length are not large. The change in k
t
with conversion (increasing viscosity), however, cannot be neglected. Figure 4.6
shows the three to four orders of magnitude decrease in k
t
typically observed. The
shape of the curve reects the changing nature of the rate-controlling diusion
mechanism. The usual division is as follows:
v
Low conversion: the system viscosity is still low, and the two chains diuse to-
gether quickly. The rate of reaction is controlled by segmental diusion, the in-
ternal reorganization of the chain that is required to bring the reactive ends to-
gether. In this region k
t
is of the order of 10
8
L mol
1
s
1
for many common
monomers (Table 4.3), with the value remaining relatively constant up to 10
20% conversion. Solvent choice can have a signicant eect on the value [18].
1.0E+02
1.0E+03
1.0E+04
1.0E+05
1.0E+06
1.0E+07
1.0E+08
1.0E+09
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Conversion
k
t

(
L
/
m
o
l
-
s
)
MMA
nBA
DA
Fig. 4.6. Typical variation of k
t
with conversion for methyl
methacrylate (MMA), butyl acrylate (nBA), and dodecyl acrylate
(DA). Based upon data from [15].
Lower values of 10
6
L mol
1
s
1
for dodecyl (meth)acrylate is attributed to shield-
ing of the radicals by the long-chain dodecyl ester groups; for these monomers k
t
remains relatively constant up to 60% conversion [64]. Even lower k
t
values are
measured for termination during polymerization of sterically hindered mono-
mers such as the itaconates [74] and acrylate trimer species [44]. The variation
of low-conversion k
t
with polymer composition in copolymer systems can be rep-
resented by Eq. (55).
v
Medium to high conversion: the large increase in system viscosity with polymer
formation leads to a change in the controlling mechanism. The rate of reaction is
controlled by how quickly the two chains nd each other among the tangle of
dead polymer chains in the system. This so-called center-of-mass or translational
diusion mechanism is complex, aected by the lengths of the reacting chains
as well as the system viscosity. The value of k
t
can drop by several orders of mag-
nitude in this regime.
v
Very high conversion: at high conversion, the system may become so viscous that
the polymer radicals move more quickly through propagation (addition of new
monomer units) than by translation. This phenomenon, called reaction diu-
sion, leads to a second plateau region in the k
t
versus conversion plot, with k
t
proportional to k
p
(1 x
p
). If the glass transition temperature of the reaction
mixture exceeds the reaction temperature, the propagation reaction and apparent
initiator eciency [75] may also become diusion-controlled.
The overall behavior of k
t
with conversion is often modeled as a composite of the
various diusional processes [Eq. (60)].
1
k
t
=
1
k
t; SD
1
k
t; TD
k
t; RD
(60)
The subscripts SD; TD, and RD refer to segmental diusion, translational diu-
sion, and reaction diusion. k
t; SD
can be set to the low conversion values summar-
ized in Table 4.3, and k
t; RD
is set proportional to propagation, with proportionality
coecient C
RD
tted to experimental data [Eq. (61)].
k
t; RD
= C
RD
k
p
(1 x
p
) (61)
Many semi-empirical approaches have been used to model k
t; TD
as a function of
system viscosity, conversion, or free volume. The latter treatment relates the chain
diusivity to the system free volume v
f
by Eq. (62), with parameters C
i
tted to ex-
perimental data.
k
t; TD
zC
1
exp(C
2
v
f
) (62)
This eect of polymer MW on system viscosity may be captured by expressing C
1
as a function of M
w
. It is observed experimentally that addition of a powerful
chain-transfer agent to MMA lowers polymer MW and system viscosity, thereby in-
creasing k
t
, while addition of a small amount of EGDMA crosslinking agent has
the opposite eect [39]. Details and variations of this modeling approach can be
found in the literature [40, 7679].
A good model for k
t
is necessary to capture the timeconversion behavior in ho-
mogeneous batch FRP systems. The large decrease in k
t
at intermediate conver-
sion results in an increase in radical concentration [Eq. (9)] and a corresponding
increase in R
pol
[Eq. (10)] that causes an upward curvature in the timeconversion
plot (Figure 4.7). This accelerated rate is accompanied by a large heat release that
can be dicult to remove from the viscous reaction system. The severity of the gel
eect is directly related to the magnitude of the decrease in k
t
, as seen by compar-
ing the nBA and MMA rate proles in the gure. The decrease also leads to an in-
crease in DP
inst
n
[Eq. (13)] for systems where MW is controlled by termination.
4.4
Polymer Reaction Engineering
The design of an industrial polymerization process begins with a clear under-
standing of objectives and an appreciation of constraints. Design and operation
requirements are very dierent for a process manufacturing several grades of a
high-volume commodity homopolymer, and one that produces dozens of dier-
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 500 1000 1500 2000
time (s)
C
o
n
v
e
r
s
i
o
n
MMA
nBA
Fig. 4.7. Typical timeconversion plots for methyl methacrylate
and butyl acrylate batch polymerizations. The sharp increase in
rate seen for MMA, known as the gel eect, is due to the large
decrease in k
t
with conversion.
ent (and often new) low-volume higher-value products of varying composition
and structure. Typical product specications for a homogeneous FRP process
may include average molecular weight/molecular weight distribution, copolymer
composition/copolymer composition distribution, degree of branching/branching
distribution, and sequence length distribution. Depending on the nature of the
product, any of these properties can simultaneously be product specications.
However, the polymer is ultimately not sold on basic structural characteristics but
rather on end-use properties. This poses the challenge of relating structural fea-
tures to properties. Invariably the end-use properties are a product of not one but
several structural features; therefore establishing relationships is a complex task,
and the ensuing relationships are usually restricted to a narrow range of materials.
Establishing structureproperty relationships remains an active area of research.
Together with an understanding of the key properties and their desired values is
a need to understand quantitatively how much variation is acceptable for each
property. In an industrial polymerization environment, there will naturally be
some degree of process variability that will translate into product variability. Know-
ing the extent to which deviations from the target value of a property aect the
manufacturers ability to sell that product is a critical piece of design information.
Unlike many chemical systems, o-spec polymeric material cannot be easily re-
cycled or altered by downstream unit-operations. The diculty of characterizing
polymer structure on-line makes design of a robust easy-to-operate process espe-
cially important.
Design of a process involves several decisions such as the type of reactor used,
the ow and contacting patterns for the reagents, the choice of homogeneous ver-
sus heterogeneous process types, and so on. Heat removal and mixing issues are
two key factors that strongly inuence design and operation of homogeneous FRP
processes.
Heat removal Free-radical polymerizations are highly exothermic, with adiabatic
temperature rises for bulk monomers typically @200500
C. (Values of DH
p
for
common monomers are tabulated in Table 4.6.) In addition, the overall activation
energy for a radical polymerization, calculated from the activation energies of
initiation, propagation, and termination [see Eq. (10)] is on the order of 80 G15
kJ mol
1
. The sudden and dramatic increase in the heat produced in the gel-eect
region can result in loss of eective temperature control. If there is a process dis-
turbance leading to a thermal runaway condition, the heat generation rate can ex-
ceed the heat removal rate to such an extent that the reaction behaves close to adia-
batically. The resulting temperature increase can pose serious safety concerns such
as reactor overpressurization and possible explosion, requiring processes to be
designed to safely release the pressure prior to failure (rupture) of the process
equipment.
Heat removal is also an important issue to consider during process scale-up. As
reactor size increases, the system dynamics become increasingly slow, and there-
fore it takes longer for desired changes (for example decreasing the reactor temper-
ature) to occur. This may in itself not be a serious problem, provided the reactor
cooling system is able to maintain control, albeit at a higher than desired tempera-
ture. However, large variations in the temperature prole can translate into dier-
ences in the nal product properties, particularly molecular weight distribution.
The monograph by Biesenberger and Sebastian [80] provides an excellent discus-
sion of thermal eects, including thermal runaway.
Mixing Mixing can directly aect the kinetics, molecular weight, and composition
in radical polymerizations by homogenizing local concentration gradients, but it
can also indirectly play an important role through its role in reducing thermal gra-
dients in a reactor. In small-scale experiments, most transport phenomena (heat
transfer, mixing) occur suciently fast for overall behavior to be dictated primarily
by reaction kinetics. However, as scale increases, kinetic and transport eects be-
come increasingly coupled. Homogeneous FRP reactions oer a particularly chal-
lenging problem because of the large increase in viscosity accompanying the
conversion from bulk monomer (@1 cp for liquids) to polymer (>10
5
cp). The in-
crease in viscosity can greatly aect the reaction kinetics (see Section 4.3.3) as well
as the heat removal and quality of mixing in the system. Some processes are de-
signed to not require mixing. For example, PMMA can be polymerized in large
sheets. By having large surface areas available for heat transfer, adequate tempera-
ture control is achieved without the need to provide mixing during polymerization.
Other bulk polymerizations (for example, styrene) employ more than one reactor
in series, since dierent reactor congurations and agitators will be required as
the viscosity increases. Solution polymerizations oer low viscosity but the trend
in industry is to eliminate (or greatly reduce) the use of organic solvents. Mixing
can also be an issue at lower viscosities such as those found in LDPE systems,
where the high-temperature conditions make for very fast reactions (for example,
initiator half-life of <1 s) on the order of characteristic mixing times.
4.4.1
Types of Industrial Reactors
There are three major classications of chemical processes, categorized by the
method by which the reactants are added to the reaction vessel. Varying the
contacting pattern can dramatically alter the local reaction conditions (for exam-
ple, concentrations of individual species, including monomers, initiators, chain-
transfer agents, and so on), and is therefore a potentially powerful design tool for
controlling properties such as molecular weight distribution, copolymer composi-
tion distribution, and degree of branching. Because of the ability to manipulate lo-
cal monomer concentrations, the rate of polymerization can also be controlled,
thereby providing safer and more robust operation.
4.4.1.1 Batch Processes
All of the reactants are added to the reactor prior to starting the polymerization. No
material is added to or removed from the reactor during operation. When the poly-
merization is complete, the contents are discharged and the reactor prepared for
the next batch. Batch polymerizations are the simplest to run, but oer the least
control over the polymerization. For polymerizations with more than one mono-
mer, the relative consumption rates of the dierent monomers will be governed
by their respective reactivities, possibly resulting in broad copolymer composition
distributions and inhomogeneous product. Another feature of batch polymeriza-
tions is that reactant concentrations change throughout the polymerization. Molec-
ular weight distribution drift is therefore a common phenomenon and can lead to
very broad distributions in the nal product. From an economic perspective, batch
polymerizations suer from downtime between batches, although much progress
has been made in automating many of the reactant weighing, charging, and dis-
charging steps to minimize this interval. Automation has also improved reproduci-
bility of batch reactions. For operations where changes to the formulation or the
polymerization conditions are common, batch processes have the advantage of be-
ing exible and readily adaptable to new products.
4.4.1.2 Semi-batch Processes
These processes (also called semi-continuous) are similar to batch processes, ex-
cept that reactants can be added and/or products removed during the polymeriza-
tion. Usually only a portion of the total reactant charge is initially fed into the reac-
tor. The polymerization is then started, and reactants are added during reaction in
order to control a desired property (for example molecular weight distribution, co-
polymer composition distribution) or the reaction rate. Any reactant can be fed,
and it is common practice to add monomer(s), initiators, and/or chain-transfer
agents. Two of the most common applications for semi-batch operation in homo-
geneous FRP are control of copolymer composition distribution and control of re-
action rate. In a batch reaction, copolymer composition drifts according to the in-
herent reactivities of the monomers. However in semi-batch operation, drift can be
substantially reduced by maintaining a (near) constant concentration ratio of the
respective monomers in the reactor. Production of low molecular weight co- or ter-
polymers (for example coatings) is also readily done using this type of approach.
Initiator and monomers are continuously fed in the desired ratio to provide com-
position and MW control while maintaining starved conditions (low monomer con-
centration) in the reactor. This mode of operation also ensures that at any time the
monomer concentration in the reactor is low, and therefore the maximum poten-
tial hazard in the event of a thermal runaway reaction is minimized. A potential
concern with operating in a starved mode is that polymer concentrations are high,
resulting in higher rates of transfer to polymer and branching reactions.
4.4.1.3 Continuous Processes
Reactants are fed, and products and unconsumed reactants are removed, continu-
ously. The process may take place in a single reactor or in a train (series) of reac-
tors in which the monomer conversion is gradually increased. Most continuous
processes are operated at steady-state conditions, meaning all reactant concentra-
tions and process conditions (temperature, pressure, and so on) are time-invariant.
This can be an enormous advantage for certain types of properties if the reactor is
also well mixed (no spatial variations); because concentrations are constant, there
is no molecular weight distribution drift, and no composition distribution drift.
Thus, narrower molecular weight distributions can be produced in a well-mixed
continuous reactor for linear polymer systems than in batch systems. Branching
reactions, however, broaden the MWD in a well-mixed continuous reactor to a
greater extent than in a batch system due to the residence time distribution [80,
81]. For large-volume polymers with a limited number of variations to the polymer-
ization conditions (for example, formulation changes), continuous processes are
favored because of their low operating cost, high throughput rates, more uniform
product quality, and simplicity of operation.
4.4.2
Mathematical Modeling of FRP Kinetics
Mathematical modeling is a powerful methodology to improve the understanding
and operation of polymer processes. A good process model can be used to predict
the inuence of operating conditions on reaction rate and polymer properties, to
guide (along with appropriate experimentation) the selection and optimization of
standard operating conditions for existing and new polymer grades, to guide pro-
cess development from lab to pilot-plant to full-scale production, to help discrimi-
nate between kinetic and physical (for example, heat and mass transfer) eects, to
perform design and safety studies, to train plant personnel, and to understand and
optimize transitions and other dynamic behavior (that is, process control).
The modeling approach and level of detail should be dictated by the application.
Whereas an empirical model linking measured inputs and outputs may be the best
solution for control of an existing industrial reactor, it would be totally inappropri-
ate for design of a new process or to choose operating conditions for a new poly-
mer grade. On the other hand, it makes little sense to develop a model that can
predict detailed polymer architecture for control purposes when the only measure
of polymer structure is a melt index value obtained from the lab two hours after
the sample was produced. While empirical modeling has its uses, the focus of
this section is the development of fundamental models based upon rst-principles
descriptions of chemical and physical phenomena. Although a perfect description
of an actual process is, in the end, an unattainable goal, the attempt often leads to
valuable insights that can aid process and product development, scale-up, and opti-
mization. Techniques to model the FRP mechanisms and kinetics of Section 4.3
are presented rst, followed by a discussion of issues related to reactor modeling.
Wherever possible, examples have been selected to emphasize industrial applica-
tion. Although a few historical references are included, the main focus is on advan-
ces made since the mid-1990s.
The objective of kinetic modeling is to build a description of how polymer archi-
tecture and polymerization rate depend on reaction conditions (temperature, pres-
sure) and species concentrations from a dened set of kinetic mechanisms; a dy-
namic model is required to examine how properties change as a function of time.
The mechanisms to be included in a model depend upon its end-use. For simple
mass and energy balances, it is only necessary to consider those that consume
monomer, initiator, and radicals initiation, propagation, and radicalradical ter-
mination. To track polymer molecular weight, all mechanisms that include radical
transfer must also be included. Additional balances are needed to follow other mo-
lecular properties, such as the density of short- or long-chain branches, end-group
functionality, and the creation and reaction of terminal double bonds.
4.4.2.1 Method of Moments
The equations in Section 4.3, while useful for examining rate of polymerization
and instantaneous chain length, are not written in an appropriate form for substi-
tuting into a generalized reactor model. In addition, they do not provide a means
of tracking higher MW averages that are strongly aected by long-chain branching
reactions. One of the challenges in modeling polymerization systems is how to re-
duce a very large number of individual species (living and dead chains with lengths
from 1 to >10
5
, often with other distributed attributes such as the number of
branch points) to a tractable solution. The classical approach to this problem is
to reduce the system of equations through denition of the principal moments
of the various distributions [82]. Construction of moment balances allows the
tracking of average polymer properties: for molecular weight this would be M
n
(number-average), M
w
(weight-average), and possibly M
z
, and for branched sys-
tems it is possible to track the number-average (B
n
) and weight-average (B
w
) num-
ber of branches per chain. Only the basics of the mathematical treatment for a ho-
mopolymerization system will be given here: more details can be found in recent
comprehensive reviews [83, 84].
Consider a free radical system that includes the basic set of mechanisms shown
in Scheme 4.3 as well as long-chain branching [Eq. (27)]. The moments for the rad-
ical (l
j
) and dead (z
j
) polymer distributions are dened in Eqs. (63) and (64).
l
j
=
X
y
n=1
n
j
[P
n
[ (63)
v
j
=
X
y
n=1
n
j
[D
n
[ (64)
It is also helpful to dene moments for the bulk polymer (m
j
), the total polymer in
the system including live radicals [Eq. (65)].
m
j
=
X
y
n=1
n
j
([D
n
[ [P
n
[) (65)
With [D
n
[ g[P
n
[ there is little dierence in magnitude between m
j
and z
j
. Its intro-
duction, however, eliminates the moment closure problem created by the LCB
mechanism [40, 81, 85]. Many of the moments have precise physical meanings.
The zeroth live moment, l
0
, is the concentration of polymer radicals in the system
(denoted by [P
tot
] in Section 4.3), and the rst live moment, l
1
, is the concentration
of monomer units contained in all growing radicals. Similarly, m
0
is the concentra-
tion of all polymer chains in the system, and m
1
is the concentration of monomer
units bound in all polymer chains. These moment denitions collapse the innite
set of equations for polymeric species into a manageable subset used to calculate
MW averages, where m
w
is the molecular weight of the monomeric repeat unit
[Eqs. (66)].
M
n
= m
w
m
1
m
0
; M
w
= m
w
m
2
m
1
; M
z
= m
w
m
3
m
2
(66)
For this example, equations for the kinetic expressions for m
0
; m
1
, and m
2
will be
developed for the calculation of M
n
and M
w
.
The rst step is to formulate balances for live radicals, dead chains, and total
chains of length n, accounting for all of the consumption and generation terms
from the kinetic mechanisms [Eqs. (67)(69)].
R
Pn
= 2f k
d
[I[ k
mon
tr
[M[
X
y
j =1
[P
j
[ k
sol
tr
[S[
X
y
j =1
[P
j
[
( )
d(n 1)
k
p
[M[([P
n1
[ [P
n
[)
k
mon
tr
[M[ k
sol
tr
[S[ (k
td
k
tc
)
X
y
j =1
[P
j
[
( )
[P
n
[
k
pol
tr
n[D
n
[
X
y
j =1
[P
j
[ k
pol
tr
[P
n
[
X
y
j =1
j[D
j
[ (67)
R
Dn
= k
mon
tr
[M[ k
sol
tr
[S[ k
td
X
y
j =1
[P
j
[
( )
[P
n
[
1
2
k
tc
X
n1
j =1
[P
j
[[P
nj
[
k
pol
tr
[P
n
[
X
y
j =1
j[D
j
[ k
pol
tr
n[D
n
[
X
y
j =1
[P
j
[ (68)
R
P
n
D
n
= 2f k
d
[I[ k
mon
tr
[M[
X
y
j =1
[P
j
[ k
sol
tr
[S[
X
y
j =1
[P
j
[
( )
d(n 1)
k
p
[M[([P
n1
[ [P
n
[)
k
tc
X
y
j =1
[P
j
[
!
[P
n
[
1
2
k
tc
X
n1
j =1
[P
j
[[P
nj
[ (69)
The origin of the various terms in these balances should be evident by looking
at the mechanisms of Scheme 4.3 and Eq. (27). The Kronecker delta function
[d(x) = 1 if x = 0 and s(x) = 0 if x 00] accounts for the generation of new poly-
meric radicals (P
1
), and the terms for transfer to polymer account for the probabil-
ity that transfer to a certain chain D
n
is proportional to chain length n. The expres-
sion for termination by combination accounts for the possibility of creating D
n
from any combination of two smaller radical fragments whose lengths sum to n.
The next step in the procedure is to substitute these species balances into the
moment denitions in Eqs. (63)(65). The use of generating functions [82, 86, 87]
eliminates the tedium (and possible errors) of performing the required series sum-
mations, and leads to Eqs. (70)(78) for the moments.
Live moments:
R
l0
= 2 f k
d
[I[ (k
td
k
tc
)l
2
0
(70)
R
l1
= 2f k
d
[I[ k
mon
tr
[M[l
0
k
sol
tr
[S[l
0
k
p
[M[l
0
k
mon
tr
[M[ k
sol
tr
[S[ (k
td
k
tc
)l
0
l
1
k
pol
tr
(l
0
v
2
l
1
v
1
) (71)
R
l2
= 2f k
d
[I[ k
mon
tr
[M[l
0
k
sol
tr
[S[l
0
k
p
[M[(l
0
2l
1
)
k
mon
tr
[M[ k
sol
tr
[S[ (k
td
k
tc
)l
0
l
2
k
pol
tr
(l
0
v
3
l
2
v
1
) (72)
Dead moments:
R
v
0
= k
mon
tr
[M[l
0
k
sol
tr
[S[l
0
k
td
l
2
0

1
2
k
tc
l
2
0
(73)
R
v
1
= k
mon
tr
[M[ k
sol
tr
[S[ (k
td
k
tc
)l
0
l
1
k
pol
tr
(l
0
v
2
l
1
v
1
) (74)
R
v
2
= k
mon
tr
[M[ k
sol
tr
[S[ (k
td
k
tc
)l
0
l
2
k
tc
l
2
1
k
pol
tr
(l
0
v
3
l
2
v
1
) (75)
Bulk moments:
R
m
0
= 2f k
d
[I[ k
mon
tr
[M[l
0
k
sol
tr
[S[l
0

1
2
k
tc
l
2
0
(76)
R
m
1
= 2f k
d
[I[ k
mon
tr
[M[l
0
k
sol
tr
[S[l
0
k
p
[M[l
0
(77)
R
m
2
= 2f k
d
[I[ k
mon
tr
[M[l
0
k
sol
tr
[S[l
0
k
p
[M[(l
0
2l
1
) k
tc
l
2
1
(78)
The set of moment expressions to be considered consists of either the live and dead
moments [Eqs. (70)(75)] or the live and bulk moments [Eqs. (70), (71) and (76)
(78)], substituting m
1
and m
2
for z
1
and z
2
in Eq. (71). Choice of the former, while it
is common practice in the literature, suers from the problem that the equations
for l
2
and z
2
depend on z
3
. The Hulburt and Kutz [88] method is often used to ap-
proximate z
3
, assuming that the molecular weight distribution can be represented
by a truncated series of Laguerre polynomials by using a gamma distribution
weighting function [Eq. (79)].
v
3
=
v
2
v
0
v
1
(2v
0
v
2
v
2
1
) (79)
Using the bulk moments not only eliminates the need for this approximation, but
also reduces the set of equations by one, since Eq. (72) is not required to solve for
M
w
. An additional balance [Eq. (80)] can be added to either set of equations to track
the concentration of LCB formed by the transfer to polymer mechanism,
R
LCB
= k
pol
tr
l
0
m
1
(80)
Thus, a set of six equations [Eqs. (70), (71), (76)(78), and (80)] can be used to col-
lapse the molecular weight distribution into its principle averages to calculate M
n
,
M
w
, and LCB density.
The set of moment equations developed here can be extended to include addi-
tional complex mechanisms, such as reactivity of terminal double bonds [Eq. (30),
Scheme 4.10] [81], crosslinking (Scheme 4.11) [40], and chain b-scission following
intermolecular H-abstraction [89]. The methodology can also be extended to co-
polymerization systems, either by dening copolymer-averaged rate coecients as
in Eqs. (50) and (54) [6, 8587], or by dening additional moment quantities (for
examples, see Refs. 40, 81, 85). Furthermore, since it is easy to implement as part
of larger-scale reactor modeling, it is the standard methodology used in process
simulation packages (see, for example, Refs. 90, 91). For discussion regarding the
nal step of model development, substitution of the kinetic expressions for the mo-
ments into reactor balances, see Section 4.4.3.
4.4.2.2 Modeling of Distributions
The major limitation of models based on the method of moments is that they only
track average quantities. While adequate for most situations, more detail may be
needed if the objective of the study is to improve our knowledge of the kinetics
for example, to examine the combined eect of chain-scission and long-chain
branching on polymer architecture, or to incorporate chain-length dependent ter-
mination kinetics into the mechanistic scheme. In such cases, the kinetic and
modeling assumptions can be tested more rigorously through a detailed compari-
son with full molecular weight distributions (MWDs) measured experimentally.
Recent advances in modeling tools now make it possible to simulate the complete
MWD, as well as how a second distributed quantity (for example, LCB) varies with
chain length.
The modeling of complete MWDs has long been possible for linear polymer sys-
tems, that is, those without any branching. In the absence of long-chain branching
and employing the QSSA, a recursive relationship can be derived for P
n
and D
n
from Eqs. (67) and (68), leading to Eqs. (81) and (82) for the weight-fraction distri-
bution of polymer formed at any instant in time [92].
w
inst
n
= (t 0:5(n 1)b(t b))(t b)n
1
1 b t

n
(81)
t =
k
td
[l
0
[ k
mon
tr
[M[ k
sol
tr
[S[
k
p
[M[
; b =
k
tc
[l
0
[
k
p
[M[
(82)
Assuming the formation of long-chain polymer (t b f1), the values for instanta-
neous DP
n
and DP
w
are given by Eqs. (83).
DP
inst
n
=
1
t 0:5b
; DP
inst
w
=
2t 3b
(t b)
2
(83)
The instantaneous PDI is 2 for a system where there is no termination by combi-
nation (b = 0), and 1.5 if termination by combination is the only chain-ending
mechanism (t = 0). These expressions can be integrated to follow the evolution of
the MWD with time or conversion and compare against experimental data, as was
done by Balke and Hamielec [92] for batch isothermal FRP of MMA.
Unfortunately, the methodology cannot be easily extended to branched systems,
due to the interaction of the polymer radical and dead polymer chain distributions
through reaction (for example, H-abstraction, terminal double bond polymeriza-
tion, crosslinking). The methods for modeling MWDs with branching can be di-
vided into three main groups. The rst, utilizing Monte Carlo techniques, has
been greatly advanced through the eorts of Tobita. Assuming a given set of
mechanisms, the probabilities of connections between primary polymer molecules
(the linear chain that would exist if all of its branch points were severed) is calcu-
lated, and the resulting MWD solved using Monte Carlo techniques [93].
A second group of models is based upon the numerical fractionation concept
developed by Teymour and Campbell [94]. This seminal work identies a succes-
sion of branched polymer generations based on the degree of complexity of
their architecture, tracking the population of chains in each generation using
the method of moments. The complete MWD is approximated by combining the
MWDs for individual generations which themselves are reconstructed from the
leading moments assuming a distributional form. Numerical fractionation was
specically developed to examine the problem of gel formation in polymer sys-
tems. Thus, the generations were dened to follow the geometric progression in
chain length caused by connection of two molecules in the same generation: while
chains from the zeroth generation progress to the rst generation by participating
in a branching event, a chain from the rst generation can only progress to the sec-
ond by joining (through crosslinking, terminal double bond polymerization, or ter-
mination by combination) with another molecule from the same generation [94]. It
has been shown that this classication scheme leads, in certain cases, to errors in
the shape of the overall MWD: through comparison with distributions calculated
by rigorous numerical solution, Butte et al. [95] have shown that the denition of
generations proposed by Teymour and Campbell can create an articial high MW
shoulder due to the accumulation of chains with a wide distribution of the number
of branches (and thus high polydispersity) in the rst branched generation. The
authors conclude that a more accurate approximation is obtained by classifying
the chains according to their number of branches. Both Monte Carlo [96] and a
modied numerical fractionation technique [95] can also be used to calculate the
LCB number as a function of chain length, an important quantity often presented
experimentally.
The commercial software Predici
2
package uses yet another numerical tech-
nique, calculating MWDs using a discrete Galerkin technique with variable grid
and variable order [97]. In 2000, the package was extended to follow branch point
concentrations as a function of chain length through the introduction of balance
equations [98]. The possibility of performing these tasks calculation of complete
MWD as well as LCB distribution in a commercial software package is especially
noteworthy because it makes it possible for a wider range of practitioners to per-
form detailed kinetic modeling. These new modeling capabilities, in combination
with improved characterization techniques, will hasten progress to a better under-
standing and representation of complex polymer architecture [46, 99].
4.4.3
Reactor Modeling
The kinetic expressions of Section 4.4.2 are substituted into overall material and
energy balances to construct a model to represent an FRP process. For a well-
mixed reactor system, Eqs. (84)(89) comprise the general system of equations for
homopolymerization.
d(V[M[)
dt
= (q
in
[M
in
[) (q
out
[M[) VR
pol
(84)
d(V[I[)
dt
= (q
in
[I
in
[) (q
out
[I[) VR
d
(85)
d(V[S[)
dt
= (q
in
[S
in
[) (q
out
[S[) VR
sol
tr
(86)
d(V[l
i
[)
dt
= (q
in
[l
i; in
[) (q
out
[l
i
[) VR
l
i
(87)
d(V[m
i
[)
dt
= (q
in
[m
i; in
[) (q
out
[m
i
[) VR
m
i
(88)
d(Vrc
p
(T T
ref
))
dt
= (q
in
(rc
p
)
in
(T
in
T
ref
)) (q
out
(rc
p
)
out
(T T
ref
))
(DH
p
)VR
pol
Q (89)
In these balances, which must be accompanied by appropriate initial conditions
and a volume balance, V is the reactor volume, q
in
and q
out
are the inlet and outlet
volumetric ow rates, r and c
p
are the density and heat capacity of the mixture, and
Q is the rate of heat removal from the reactor system. The various source terms
have been presented earlier: Eq. (10) for the monomer and energy balance, Eq. (2)
for the initiator balance, R
sol
tr
= k
sol
tr
[S[l
0
in the solvent balance, Eqs. (70) and (71)
for the live moment balances, and Eqs. (76)(78) for the bulk moment balances.
4.4.3.1 Batch Polymerization
Inow and outow terms are set to zero, but the change in volume with conver-
sion must be considered for the constant-mass system [Eq. (90)].
dV
dt
=
V
r
dr
dt
(90)
Volume contraction due to the dierence in polymer and monomer densities can
be as high as 20% for bulk polymerization, and should not be neglected when solv-
ing the material balances. Solution of the initiator balance and substitution into
the monomer balance lead to a dierential equation for conversion, Eq. (91), where
the volume contraction factor is dened as e = (r
nal
r
0
)=r
nal
where r
nal
is the
system density at 100% conversion of monomer to polymer and r
0
is the initial
density of the system.
dx
p
dt
=
k
p
k
1=2
t
!
2f k
d
[I[
0
1 ex
p
!
1=2
(1 x
p
) exp
k
d
t
2

(91)
4.4.3.2 Continuous Polymerization
Equations (84)(89) can be solved to provide a description of the dynamic behavior
of a continuous well-stirred system. Analytical solutions may be derived for the
steady-state case by setting all derivative terms to zero. Assuming no inow of rad-
icals, Eq. (92) results for l
0
.
(q
out
[l
0
[) = V(2f k
d
[I[ k
t
[l
0
[
2
) (92)
For most cases, the radical lifetime is much shorter than the average residence
time. Thus outow of radicals can be neglected, resulting in the familiar expres-
sion, Eq. (93), for l
0
.
[l
0
[ =
2f k
d
[I[
k
t

1=2
(93)
[I] can be calculated from the steady-state solution of Eq. (83), namely Eq. (94),
where y = V=q
out
is the reactor residence time and e = (r
out
r
in
)=r
out
is the frac-
tional density change between inlet and outlet streams.
[I[ =
q
in
[I
in
[
q
out
Vk
d
=
[I
in
[
(1 yk
d
)(1 e)
(94)
Substitution of these expressions into the monomer balance leads to a nonlinear
relationship between conversion and y [Eq. (95)].
x
p
= yk
p
l
0
= y
k
p
k
1=2
t
!
2f k
d
[I
in
[
(1 e)(1 yk
d
)

1=2
(95)
Assuming no inow of polymer into the reactor and the long-chain hypothesis, the
steady-state values for DP
n
and DP
w
in the absence of LCB (k
pol
tr
= 0) are given by
Eq. (83). LCB and reaction with terminal double bonds broaden the MWD signi-
cantly [81].
4.4.3.3 Complex Flowsheets
These are often constructed to represent systems with nonideal mixing and fast re-
action. A classic example is the high-pressure high-temperature free radical pro-
duction of ethylene copolymers, generally conducted in a homogeneous phase con-
sisting largely of supercritical ethylene monomer. These conditions make for very
fast reactions (for example, initiator half-life of <1 s), promote numerous side re-
actions (long-chain branching, short-chain branching, and chain scission), and in-
troduce the potential of thermal runaway. Recent models of these systems combine
a detailed description of polymerization kinetics with a complex owsheet of con-
tinuous well-mixed tanks in series with recycle to represent mixing in a multizone,
multifeed autoclave reactor [100102]. Models for multifeed tubular systems also
include heat transfer and pressure drop along the length of the system [103]. The
general strategy is to tune the model (based upon a set of proposed kinetic
mechanisms captured by the method of moments) by tting kinetic coecients
and mixing and heat transfer parameters to a set of industrial data, and then to
use the model to interpret and optimize industrial operating conditions. Advances
in computing power have allowed the complexity of these models to increase.
4.4.3.4 Computational Fluid Dynamics (CFD)
CFD simulation is emerging as an alternative and more fundamental approach to
examining polymerization systems with complex mixing and reaction. Once again,
much of the work is focused on high-pressure ethylene polymerization systems.
A major challenge is incorporating both macromixing (turbulent diusion and
convection) as well as micromixing (molecular diusion) into the representation
[104]. The rst eorts in this area [104, 105] concern themselves with the predic-
tion of temperature and conversion proles in the reactors; to simplify the calcula-
tional load they consider only initiation, propagation, and termination reactions.
More recently, Kolhapure and Fox [106] incorporated a more complete kinetic
scheme to allow the prediction of polymer MW, polydispersity, and average branch-
ing number. These CFD studies can point the way to improved reactor design and
operation; for example, by examining the importance of initiator distribution at the
injection point, and dening conditions for stable reactor operation [106]. An arti-
cle in 2000 discussed the implementation of CFD calculations within a process
simulation package [107]. Although not yet applied to polymerization systems,
this advancement shows enormous promise.
4.4.3.5 Model-based Control
Model-based control of polymerization systems has also garnered its share of atten-
tion. The goal of these eorts is the development of robust strategies to guide and
control the manufacture of polymer safely and reproducibly in the face of unmea-
sured disturbances and frequent product grade transitions. The main challenge in
controlling polymerization systems is the lack of on-line measurements of polymer
structure. A review by Congalidis and Richards [108] provides a good summary of
literature focusing on this dicult issue; for further discussion, see Chapter 12 of
this book. In most cases, the implementation of detailed fundamental models is
not warranted for control application. However, simple models can often be com-
bined with limited on-line measurements (for example, in Refs. 109112) to im-
prove control performance. Fundamental models can also be used to test empirical
models developed for control purposes [113].
4.5
Summary
Polymer reaction engineering issues can pose major challenges for industrial-scale
polymer synthesis. As reactor size increases, transport phenomena such as heat
and mass transfer become more dicult, and large-scale homogeneous FRP pro-
cesses are often limited by transport eects. In many cases, the nal reaction rate,
molecular weight, and copolymer composition are determined by the coupled ef-
fects of reaction kinetics and transport phenomena. Mathematical modeling, in
conjunction with a strong experimental program, is a powerful means to improve
our mechanistic and process understanding. The use of empirical models has util-
ity in the control of polymerization reactors, and can be an important contributor
to product quality and process robustness. Continuing development of new mea-
surement techniques, together with an ability to relate measurements to functional
properties, will be a critical area of future research.
While many current free-radical polymerization processes have been in indus-
trial use for years, the next several years may see the emergence of new industrial
technologies. Promising technologies for homogeneous FRP include living radical
polymerization chemistries and polymerization in supercritical carbon dioxide.
The adoption of new technology requires identifying an application or product for
which the new technology is clearly advantaged, and successfully overcoming the
numerous scaleup challenges in converting the process to industrial scale. These
processes will require a detailed understanding of polymerization kinetics com-
bined with fundamental reaction engineering principles.
Notation
A
i
pre-exponential factor for mechanism-i
C
XXX
tr
ratio of chain-transfer rate coecient (k
XXX
tr
, XXX = mon, pol, sol) to
propagation [Eq. (19)]
c
p
heat capacity [kJ kg
1
K
1
]
D
=
n
dead polymer chain of length n with terminal unsaturation
D
n; b
dead polymer chain of length n with b branch points
DP
n
number-average degree of polymerization
DP
w
weight-average degree of polymerization
E
i
activation energy for mechanism-i [kJ mol
1
]
F
inst
p
i
mole fraction of monomer-i contained in polymer chains being formed
f initiator eciency [Eq. (1)]
f
i
mole fraction of monomer-i in the monomer mixture
f
r
i
mole fraction of polymer radicals ending in monomer unit-i
f
r
ij
mole fraction of polymer radicals ending in monomer unit-j with pen-
ultimate unit-i
[I] initiator concentration [mol L
1
]
K
eq
equilibrium propagationdepropagation constant
k
bb
rate coecient for intramolecular H-abstraction [s
1
]
k
d
rate coecient for initiation decomposition [s
1
]
k
dep
rate coecient for depropagation [s
1
]
k
i
rate coecient for primary-radical initiation [L mol
1
s
1
]
k
inhib
rate coecient for inhibition [L mol
1
s
1
]
k
p
rate coecient for propagation [L mol
1
s
1
]
k
p
ij
rate coecient for addition of monomer-j to radical-i [L mol
1
s
1
]
k
p
ijk
rate coecient for addition of monomer-k to penultimate radical-ij
[L mol
1
s
1
]
k
cop
p
copolymer-averaged propagation rate coecient [L mol
1
s
1
]
k
e
p
eective propagation rate coecient, corrected for depropagation
[L mol
1
s
1
]
k
pol
p
rate coecient for radical addition to a terminally-unsaturated chain
[L mol
1
s
1
]
k
tert
p
addition rate of monomer to mid-chain radical [L mol
1
s
1
]
k
t
rate coecient for termination [combination disproportionation)
[L mol
1
s
1
]
k
cop
t
copolymer-averaged termination rate coecient [L mol
1
s
1
]
k
tc
rate coecient for termination by combination [L mol
1
s
1
]
k
td
rate coecient for termination by disproportionation [L mol
1
s
1
]
k
therm
rate coecient for thermal initiation of styrene [L
2
mol
2
s
1
]
k
XXX
tr
rate coecient for transfer to species XXX (mon, pol, sol) [L mol
1
s
1
]
k
b
rate coecient for radical b-scission [s
1
]
[M] monomer concentration [mol L
1
]
[M]
eq
equilibrium monomer concentration [mol L
1
]
M
n
number-average molecular weight [g mol
1
]
M
w
weight-average molecular weight [g mol
1
]
m
w
molecular weight of the reaction mixture [g mol
1
]
N
i
number-average length of monomer-i sequences
N(M
i
; n
j
) fraction of monomer-i sequences that are exactly n
j
units in length
P
ij
probability of unit-j following unit-i in a polymer chain
Notation 207
P
n
polymer radical of length n
P
n; b
polymer radical of length n with b branch points
[P
tot
] total concentration of radicals [mol L
1
]
[P
i
tot
] total concentration of polymer radicals of type-i [mol L
1
]
Q
n
mid-chain polymer radical of length-n (formed by intramolecular or in-
termolecular H-abstraction)
q
in
reactor inlet volumetric ow [L s
1
]
q
out
reactor outlet volumetric ow [L s
1
]
R
d
rate of initiator disappearance [mol L
1
s
1
]
R
dep
rate of depropagation [mol L
1
s
1
]
R
inhib
rate of inhibition [mol L
1
s
1
]
R
init
rate of radical generation from initiator [mol L
1
s
1
]
R
LCB
rate of long-chain branch formation [mol L
1
s
1
]
R
p
rate of propagation [mol L
1
s
1
]
R
pol
p
addition rate of terminally unsaturated polymer chains mol L
1
s
1
]
R
pol
total rate of monomer consumption [mol L
1
s
1
]
R
term
rate of radicalradical termination [mol L
1
s
1
]
R
therm
rate of thermal initiation of styrene [mol L
1
s
1
]
R
XXX
tr
rate of transfer to species XXX (mon, pol, sol) [mol L
1
s
1
]
R
l
i
rate of change of moment l
i
[mol L
1
s
1
]
r
i
monomer reactivity ratio for radical-i (for example, r
1
= k
p11
=k
p12
)
[S] solvent (transfer agent) concentration [mol L
1
]
s
i
radical reactivity ratio for monomer-i in the penultimate copolymeriza-
tion model (for example, s
1
= k
p211
=k
p111
)
T temperature [K]
T
c
ceiling temperature of monomer [
C]
t
1=2
initiator half-life [s
1
]
V reactor volume [L]
w
n
weight fraction of chains of length-n
x
p
fractional monomer conversion to polymer
[Z] inhibitor concentration [mol L
1
]
Greek
b ratio of chain termination (combination) to propagation [Eq. (82)]
DG
p
free energy change of polymerization [kJ mol
1
]
DH
p
heat of polymerization [kJ mol
1
]
DS
p
entropy of polymerization [J mol
1
K
1
]
DV
i
activation volume for mechanism-i [cm
3
mol
1
]
d fraction of termination by disproportionation
e volume contraction factor
z
k
kth moment of the dead polymer chains [mol L
1
]
y average residence time [s]
l
k
kth moment of the polymer radicals [mol L
1
]
m
k
kth moment of the total (dead radical) polymer chains [mol L
1
]
n kinetic chain length of polymer radicals
r density [kg L
1
]
t ratio of chain termination (disproportionation) and transfer to propaga-
tion [Eq. (82)]
u average number of monomer units on a living chain
F copolymerization cross-termination factor
Acronyms
AIBN 2,2
/
-azobisisobutyronitrile
BMA butyl methacrylate
CFD computational uid dynamics
CTA chain-transfer agent
DMA dodecyl methacrylate
EGDMA ethylene glycol dimethacrylate
FRP free radical polymerization
LCB long-chain branching
LCH long-chain hypothesis
MA methyl acrylate
MMA methyl methacrylate
MW molecular weight
MWD molecular weight distribution
nBA Butyl acrylate
PDI polydispersity index (M
w
/M
n
)
PLP pulsed-laser polymerization
PMMA poly(methyl methacrylate)
QSSA quasi-steady-state assumption
SCB short-chain branching
SEC size exclusion chromatography
Sty styrene
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5
Free-radical Polymerization: Suspension
1
B. W. Brooks
5.1
Key Features of Suspension Polymerization
Many important polymers are made commercially via suspension polymerization
of vinyl monomers. These include poly(vinyl chloride), poly(methyl methacrylate),
expandable polystyrene, styreneacrylonitrile copolymers and a variety of ion-
exchange resins and specialist materials. The annual polymer production from sus-
pension processes is very high.
5.1.1
Basic Ideas
There are two key requirements for any commercial free radical polymerization
process. The polymerization rate must be reasonably high and the polymer prod-
uct must have the correct molecular weight distribution. The conditions that are
necessary to achieve those goals can be predicted from the kinetics of homoge-
neous free radical polymerization (see Chapter 4). But those conditions cannot be
obtained easily in large-scale production when bulk processes are used. Uniform
mixing and temperature control are dicult to achieve because the high heat
of polymerization is combined with a large viscosity of the reaction medium. As
most polymers are poor thermal conductors, heat transfer from large reactors is
usually poor because the ratio of surface area to volume decreases as the reaction
mass increases.
In suspension polymerization, drops of a monomer-containing phase are dis-
persed in a continuous liquid phase. Monomer solubility in the continuous phase
is often low and polymer is produced inside the drops. Although the drop viscosity
increases with monomer conversion, the eective viscosity of the suspension re-
mains low and ecient agitation is possible. The ratio of surface area to volume
for small drops is relatively high and local heat transfer is good. If the continuous
ISBN: 3-527-31014-2
213
phase is aqueous and well mixed, heat transfer from the reactor is also good. That
permits eective control of temperature and of those variables which depend on
temperature, which include reaction rates, polymer molecular weight, and copoly-
mer composition.
Suspension stability is maintained by good agitation and by the use of drop
stabilizers. Removal of the stabilizing agents, after polymerization, may not be
complete and some contamination of the nal product is sometimes inevitable.
Suspension polymerization usually requires larger reactor volumes than bulk pro-
cesses because the vessels often contain about 50% of the continuous phase. Sus-
pension polymerization has been reviewed previously by Munzer and Trommsdor
[1], Bieringer et al. [2], Warson [3], Brooks [4], Yuan et al. [5], Vivaldo-Lima et al.
[6], and Arshady [7].
5.1.2
Essential Process Components
The chemical events that occur inside drops of the dispersed phase are similar to
those found in bulk polymerization. The drops contain monomer (or monomers),
radical generators (often called initiators), and polymer. Sometimes chain-transfer
agents are added also. The continuous phase is often regarded as chemically inert,
but drop stabilizers are usually present in it and, in some cases, those stabilizers
participate in the polymerization process. For a discussion of stabilizer types, see
Section 5.2.1.
5.1.3
Polymerization Kinetics
Higher conversions of monomers can be accommodated more readily in suspen-
sion processes than in bulk processes because suspensions are more mobile than
molten polymers. Therefore, simple rate expressions may not be applicable be-
cause the values of some rate coecients diminish at high polymer concentrations
(see Section 5.3.2).
It is often assumed that the polymerization chemistry which occurs in the dis-
persed phase is identical to that which occurs in the equivalent bulk process. That
assumption may be valid if the monomers and initiator are virtually insoluble in
the continuous phase. Then, polymerization rates, molecular weight distributions,
and copolymer compositions can be predicted from conventional kinetic schemes.
But drop stabilizers may react with species inside the drops (for example, to form
graft copolymers).
When all the monomers in a suspension polymerization are virtually immiscible
with the continuous phase, then the instantaneous copolymer composition can be
predicted from idealized relationships which apply to homogeneous systems. How-
ever, the use of those relationships is not straightforward if one, or more, of the
monomers is partially soluble in the continuous phase, because the actual compo-
sition of the drops may then be unknown. The eective monomer concentrations,
214 5 Free-radical Polymerization: Suspension
which should be used in these relationships, might be predicted if the appropriate
partition coecients for the two phases can be obtained. That is not often possible
but models that allow for water solubility of monomers have been developed for
the copolymerization of vinyl chloride and vinyl acetate [8] and for the copolymer-
ization of styrene and acrylonitrile [9].
Apparent reactivity ratios obtained directly from suspension polymerization ex-
periments may not be identical to those expected from the equivalent bulk pro-
cesses if some monomer migrates to the continuous phase. Ashady et al. [10]
found values for reactivity ratios that were not expected from results observed in
bulk or solution copolymerization. Izumi and Kitagawa [11] showed that reactivity
ratios for suspension copolymerization, of acrylonitrile and methyl acrylate, were
dierent from those obtained from either solution or emulsion polymerization.
Table 5.1 compares reactivity ratios obtained from solution copolymerization with
those observed in suspension copolymerization.
If the initiator in suspension polymerization is slightly soluble in water, then
simultaneous emulsion polymerization may occur when free stabilizer remains in
the continuous phase [12, 13].
5.1.4
FluidFluid Dispersions and Reactor Type
Batch, or semi-batch, reactors are often used for suspension polymerization on an
industrial scale. Dispersions in tubular ow reactors are dicult to maintain and a
continuous stirred tank would produce drops containing partially polymerized ma-
terial that would coalesce in the receiving equipment. However, new types of ow
reactors are being developed for suspension polymerization (see Section 5.4.1).
Many of the published studies on drop behavior in agitated liquidliquid disper-
sions are applicable to suspension polymerization. But sometimes their use is lim-
ited because they do not account for changing physical properties of drops or for
the presence of drop stabilizers.
Tab. 5.1. Apparent reactivity ratios in solution and suspension copolymerization (reproduced
with permission from Ref. 4).
Monomer 1 AS AN VC MMA
Monomer 2 S MA VA MAA
r
1
(soln) 1.18 1.02 1.68 0.35
r
2
(soln) 0.85 0.7 0.23 1.63
r
1
(susp) 1.0 0.75 2.47 0.63
r
2
(susp) 1.0 1.54 1.99 1.07
Temp [
C] 60 50 70 69
Abbreviations: AS, p-acetoxystyrene; S, styrene; AN, acrylonitrile; MA,
methyl acrylate; VC, vinyl chloride; VA, vinyl acetate, MMA, methyl
methacrylate; MAA, methacrylic acid.
5.1 Key Features of Suspension Polymerization 215
5.1.5
Uses of Products from Suspension Polymerization
Advantages of suspension polymerization are not restricted to temperature control.
Some polymers, such as poly(vinyl chloride) (PVC), are immiscible with their
monomers. Subsequent polymer coagulation makes bulk processes dicult to con-
trol. In suspension polymerization, however, that problem is avoided. There, coag-
ulation is largely conned to the drop interiors and aggregation of polymerizing
drops is restricted. That is why suspension polymerization is used for the large-
scale production of PVC. In that case, the initial drop diameters, and the nal par-
ticle sizes, range between 10 and 100 mm.
If a polymer product is required in particulate form, then suspension polymer-
ization is especially suitable. The energy required to disperse monomer drops is
lower than that required to break up the nished polymer. Also, drop size control
before polymerization is easier to achieve than particle size manipulation of granu-
lated polymer. Suspension polymerization provides a good route to functionalized
particles such as those used in ion-exchange resins. Expandable polystyrene beads
are also made by suspension polymerization. When a product is to be used in
bead form, initial drop diameters can be as large as 12 mm [1].
5.2
Stability and Size Control of Drops
For many applications, the size range of the nal product particles is very impor-
tant. For example, bead diameters aect ow rates through ion-exchange columns.
But particle size can also be important when the polymer is to be converted to a
macroscopic object. Heat transfer rates to polymer particles during extrusion and
mass transfer rates of plasticizers in particulate polymers both depend on particle
size.
During suspension polymerization, drop size depends on the physical properties
of the two phases, the phase ratio, the nature of the suspension ow, and the con-
dition of the phase interface. Interfacial tension and drop stability depend largely
on the nature of the drop stabilizer. If no stabilizer were used to protect the drops,
the suspension would be unstable and the nal polymer particles would reach an
undesirable size.
The adsorption of stabilizer molecules at the interface between monomer and
the continuous phase reduces the interfacial tension and hence reduces the energy
required to form drops. Drop stability against coalescence depends largely on the
ability of the stabilizer to form a thin protective lm at the interface. That gives
the drops better elastic properties [14]. The eect of the elastic properties is en-
hanced by increasing the concentration of the suspending agent, until a certain
surface coverage of the drops is reached. At that point, a critical surface coverage
is established and a further increase in the suspending agent concentration will
have a very little eect on the drop stability [15].
5.2.1
Stabilizer Types
Many drop stabilizers in suspension polymerization are water-miscible polymers.
These materials are sometimes called protective colloids. They include naturally oc-
curring substances, such as gelatin and pectin, and a wide range of synthetic poly-
mers such as partially hydrolyzed poly(vinyl acetate)s. Modied natural products
such as cellulose ether derivatives are also widely used. Munzer and Trommsdor
provide a detailed list of patented stabilizers [1]. Polymeric stabilizers do not all act
in the same way but steric eects are often important [16]. Although transfer of
stabilizer molecules from the continuous phase to the drop surfaces can some-
times be fast, the development of drop stability may be slow [17]. That may arise
because rearrangement of stabilizer molecules on the drop surface is necessary.
Water-miscible polymers are not expected to be good drop stabilizers when the con-
tinuous phase is nonaqueous (see Section 5.5).
Partially hydrolyzed poly(vinyl acetate) (PVA), a common stabilizer, is often
called poly(vinyl alcohol), but that is a misnomer because not all the acetate groups
are hydrolyzed. The extent of hydrolysis (DH) has signicant eects on the behav-
ior of the PVA. This is especially important in the suspension polymerization of
vinyl chloride. PVA with a DH between 70% and 80% is a good stabilizer for drops
in aqueous media. Drops retain their integrity even when agitation levels are re-
duced [18]. But when the DH is less than 60%, drop sizes become sensitive to re-
duction in agitation intensity [18]. Although PVAs with a low DH are poor drop
stabilizers in aqueous media, they are still useful because they aect product mor-
phology by inuencing events inside the vinyl chloride drops (see Section 5.3.3).
Attempts have been made to measure the distribution of the stabilizer between
the two phases and the interface [19]. PVA often becomes grafted onto polymer
that is formed inside the drops, leading to the formation of a skin on the nal
particle surface. This is important because subsequent removal of the skin is not
easy.
Although organic substances are commonly used as drop stabilizers, it is well
known that some particulate inorganic solids can also stabilize drops in suspen-
sion [20]. There are many reports of inorganic solids (such as calcium phosphate,
aluminium hydroxide, and zinc phosphate) being used in the suspension polymer-
ization of styrene [1]. In some cases, small amounts of surfactants (such as sodium
alkylsulfonates) are added to assist the dispersion of those solids. The eect of elec-
trolytes can also be important [21]. Inorganic stabilizers are advantageous when
only low levels of contamination are required because they can sometimes be re-
moved eectively from the nal polymer particles. Also, inorganic particles are
able to stabilize relatively large drops, such as those formed in the manufacture of
expandable polystyrene beads.
Although some inorganic solids are eective stabilizers for drops in suspen-
sion polymerization, other solids are not stabilizers and may even be destabilizers.
OShima and Tanaka [22] suggested that the contact angle between dispersed liq-
uid and inorganic solid is a crucial factor in determining whether an inorganic
solid is a stabilizer or a destabilizer in suspension polymerization. Solids that pro-
vide a relatively large contact angle (such as aluminium hydroxide) would be stabil-
izers in aqueous media. In contrast, those which have a relatively small contact
angle (such as carbon black) would tend to be destabilizers. In practical operation,
the contact angle will probably vary with any given inorganic solid if dierent
monomers are used. In many cases it is not easy to measure contact angles.
Two theories, screen theory and coverage theory, have been suggested to explain the
mechanism of drop stabilization by inorganic solids [21]. According to the screen
theory, nely divided inorganic solids which are dispersed in water form a screen.
Dispersed monomer drops smaller than the mesh of the screen are free to move
through the meshes, while those bigger than the mesh cannot pass through the
meshes and are stopped from coalescing further. In the coverage theory, it is sug-
gested that dispersed inorganic solids cover the surfaces of monomer drops and
form a layer which prevents drop coalescence. Both theories are plausible but
many workers believe that the stabilization is obtained mainly by a coverage eect.
However, not all inorganic solids are adsorbed by the monomer drops. When Wol-
ters et al. [23] used hydroxyapatite and calcium carbonate in the suspension poly-
merization of styrene, the adsorption equilibrium was found to be far on the side
of desorption. Also, Wang and Brooks [24] noticed that many of their stabilizing
particles settled on the bottom of the vessel when stirring of a liquidliquid disper-
sion ceased.
If some particles remain in the continuous phase, it is not feasible for the cover-
age theory to provide a description for every case of suspension polymerization in
which an inorganic solid is used as a stabilizer. Wang and Brooks suggested a
crowding theory which takes account of the dynamic eects of stabilizer particles
[24]. In that model, particles are not required to be permanently adsorbed on drop
surfaces but they become eective when two drops come close together. Although
crowding theory does not explain all the observations, it is compatible with a wide
range of experimental results. The addition of surfactants often improves the dis-
persion action of the ne particles, but it is possible to stabilize dispersions solely
with mono-sized spherical colloidal particles [25].
5.2.2
Drop Breakage Mechanisms
In an agitated suspension, the dispersed phase can be broken into small drops
when its surface is disrupted. That disruption can be caused either by frictional
forces (via viscous shear) or by inertial forces (via turbulence) [26]. The ratio of
the external disrupting force to the interfacial tension force is often expressed as
the Weber number, We. Drop deformation increases as We increases. When We ex-
ceeds a critical value, a drop will break into smaller drops.
The uids in agitated vessels are often turbulent. If the turbulence in local re-
gions can be regarded as isotropic, a criterion for the drop breakage mechanism
can be developed [26, 27]. In turbulent ow, random eddies are superimposed on
the main ow. Eddy sizes are inuenced by the location of the vessel walls and are
restricted by the impeller diameter [28]. Kinetic energy is transferred to smaller
eddies in a sequential fashion, until it reaches the smallest ones. This transfer is
assumed to occur without energy dissipation. However, when the kinetic energy
reaches the small eddies, it is dissipated as heat to overcome the viscous forces.
In theories of local isotropy, it is assumed that the small eddies are statistically
independent of each other. Velocity uctuations are determined by the local rate
of energy dissipation per unit mass of uid (e) and by the kinematic viscosity (n).
Kolmogorov [29], by dimensional reasoning, derived an expression [Eq. (1)] for
the length of the smallest eddy (h).
h n
3=4
e
1=4
1
Rushton et al. [30] suggested that local isotropy could exist when the Reynolds
number is >10
4
. The macroscale of turbulence, L (approximately equal to the im-
peller diameter), is then much larger than the microscale of turbulence. Here, the
Reynolds number (Re) is dened by Eq. (2), where N is the impeller speed, D is the
impeller diameter, and n is the kinematic viscosity of the dispersion.
Re ND
2
=n ND
2
r=m 2
Pressure uctuations can deform the drops and they may break if the inertial
forces exceed the interfacial tension forces. Kolmogoro [27] and Hinze [31] de-
rived an expression for the maximum drop diameter, d
max
, that should be observed
when turbulence is isotropic. Here, d gh and the viscous forces may be neglected
in comparison with the inertial forces; d
max
, can then be related to a critical Weber
number, We
crit
, by Eq. (3).
We
crit
r
c
u
2
dd=s 3
The inertial forces are related to e. Thus, We
crit
We
crit
C
1
r
c
e
2=3
d
5=3
max
=s 4
Rushton et al. [30] showed that Eq. (5) holds, so that Eqs. (6) [32] and (7) follow.
e C
3
N
3
D
2
5
d
max
C
4
s=r
c
3=5
N
6=5
D
4=5
6
d
max
=D C
4
We
0:6
7
In order to use this expression, it is often necessary to relate d
max
(which is dicult
to measure) to the Sauter mean diameter, d
32
(which is more readily determined).
A linear relationship between d
32
and d
max
has been demonstrated by Sprow [33],
Coulaloglou and Tavlarides [28], Kuriyama et al. [34], and Zerfa and Brooks [35].
In the suspension polymerization of vinyl chloride, Zerfa and Brooks found the
relationship in Eq. (8).
d
32
d
0:58
max
8
Equation (6) has been veried with a large number of liquidliquid dispersions
where the volume fraction of the dispersed phase is not high, that is, in non-
coalescing systems [28]. But, unlike many laboratory studies, real suspension poly-
merizations are operated with a high volume fraction of dispersed phase, j. Then,
drop coalescence and breakage happen simultaneously and damping of the turbu-
lent uctuations may occur. To allow for this, a factor f j is often introduced into
Eq. (7). Experimental expressions for f j are reviewed by Yuan et al. [5], and by
Zerfa and Brooks [35]. The latter workers showed that, in the suspension polymer-
ization of vinyl chloride, d
32
was given by Eq. (9).
d
32
=D 0:0273:06jWe
0:6
9
Equation (9) applied when values of j ranged between 0.01 and 0.4, as shown in
Figure 5.1. An expression with similar form is given by Borwankar et al. [15].
When drop coalescence is signicant, Shinnar [32] showed that there will be a
minimum drop size, d
min
, that is proportional to N
0:75
. The extent of drop coales-
cence is reduced by addition of an appropriate drop stabilizer. If the surface cover-
age of the drops by the stabilizer exceeds a critical value then the dispersion can
remain stable after agitation ceases [15].
It must be remembered that correlations between average drop sizes and We
only apply at steady state. The steady-state drop size distribution (DSD) can take
some time to become established [18, 3638]. That may not be a serious problem
with nonreacting dispersions but, in suspension polymerization, the physical prop-

0 10 20 30
0
10
20
30
0.01
0.05
0.1
0.2
0.3
0.4
Volume fraction of dispersed phase
d
3
2
/
D

(

x

1
0
4
)
0.027(1 + 3.06 )We
- 0.6
( x 10
4
)
Fig. 5.1. Correlation of vinyl chloride drop size with volume
fraction j and Weber number We. Reproduced by permission of
Elsevier Science Ltd. From Ref. 35.
erties change with time so that the DSD can continue to change during the process
[37].
When the diameter of the drops is less than the Kolmogorov length h, stresses
from viscous shear will be much larger than those from inertial eects. Drop
breakage is then the result of viscous shear [26]. Here, again, a drop will break if
the deformation variable, sometimes described as a generalized Weber group [31],
exceeds a critical value [39]. Taylor showed [40] that the extent of drop distortion,
before breakup, depended on the ratio of phase viscosities (Eq. (10), where m
d
and
m
c
are the viscosities of the dispersed and the continuous phase, respectively).
We
crit
m
c
qu=qrd=s f
1
m
d
=m
c
10
Shinnar and Church [26, 32] demonstrated that for locally isotropic ow where
qu=qr
2
e=n, d
max
is given by Eqs. (11) and (12).
d
max
sn
1=2
c
=m
c
e
1=2
f m
d
=m
c
11
d
max
zsn
1=2
c
=m
c
N
3=2
D
1
f m
d
=m
c
12
When viscosity-increasing agents were present in the continuous phase for the sus-
pension copolymerization of styrene and divinylbenzene, Jegat et al. [41] found
that drop breakage could occur via viscous shear when ow in the suspension was
turbulent. In that case, the Kolmogorov length would have been larger that that
found when low-viscosity aqueous solutions are used.
The form taken by f m
d
=m
c
depends on the nature of the ow. In laminar ow,
the contributions of rotational and elongational components can be expressed via
the value of a parameter a, which ranges between 0 and 1. For simple shear a 0,
and for pure elongational (hyperbolic) ow a 1 [43]. With low a values, We
crit
(now equivalent to the critical capillary number Ca
crit
) passes through a minimum
as m
d
=m
c
increases. After the minimum is reached, relatively small increases in
m
d
=m
c
are accompanied by large increases in We
crit
. When a 0, We
crit
tends to
an innitely high value if m
d
=m
c
> 4 so that drop breakage no longer occurs [42,
43]; see Figure 5.2.
Correlations that are found in idealized laboratory studies only provide rough
guides to events that occur in commercial reactors. Local ow in large stirred ves-
sels is often ill dened. Also, drop breakage can produce more than two new drops.
Chatzi and Kiparissides [44] suggested that the formation of a daughter drop is ac-
companied by the formation of a number of smaller satellite drops. Drop stabi-
lizers inuence turbulence near drop surfaces and non-Newtonian behavior leads
to further complications. Therefore, it is not surprising that the many published
studies on drop behavior in liquidliquid suspensions lead to a variety of dierent
results. Leng and Quarderer [39] found that d
max
depended on N
0:8
. By using data
from the literature, for the suspension polymerization of methyl methacrylate, they
also showed that d
max
depended on m
0:5
c
when drop breakage occurred by viscous
shear. Presumably, the drop size was not able to respond to changes in m
d
=m
c
that
would have occurred during polymerization. However, average drop size was found
to be a linear function of interfacial tension, as expected, when viscous shear was
important. Borwankar et al. [15] suggested that the relationship between d
max
and
agitator speed may depend on agitator type.
When polymer-containing drops are broken, their elastic properties must be
taken into account. Arai et al. [45] derived a correlation for drop breakup from a
Voigt model to represent the elastic properties. The validity of the correlation was
conrmed experimentally using a dispersed phase with a wide range of viscosity.
Wang and Calabrese [46] carried out experiments with drops made from well-
characterized model uids. They showed that the inuence of interfacial tension
on drop breakage decreased as the dispersed-phase viscosity increased.
5.2.3
Drop Coalescence
The volume fraction of drops in commercial suspension polymerization reactors is
usually high and drop coalescence cannot be ignored. In liquidliquid dispersions
the drop size distributions (DSDs) depend on the breakage and on coalescence
processes.
From experiments in which both drop breakage and coalescence occurred, Kuri-
yama et al. [34] found that drop sizes reached a steady value within an hour, when
the initial drop viscosity was low. But with a high drop viscosity, the drop size re-
duction continued for longer periods of time and the nal drop size was higher.
Although model, nonreacting, uids were used for those experiments, the results
are relevant to suspension polymerization. In their study of drop coalescence in the
suspension polymerization of styrene, Konno et al. [47] found that the Sauter
mean diameter increased as the polymer viscosity increased. They also concluded
that the stabilizer does not eectively prevent the coalescence of drops with diame-
ters larger than d
max
.
The overall rate of drop coalescence is related to the collision frequency of the
drops and to the coalescence eciency. By comparing drop collisions in agitated
0
0.4
0.8
1.2
1.6
0 1 2 3 4
log
C
a
c
r
i
t
A
B
10
(viscosity ratio) + 3
Fig. 5.2. Critical capillary number against log
10
of viscosity
ratio (m
d
=m
c
) for laminar ow. (A) a 0 (simple shear ow);
(B) a 1 (hyperbolic ow). Data from Refs. 42 and 43.
dispersions with molecular collisions in homogeneous uids, previous workers
have developed expressions for collision rates between drops of dierent sizes [48,
49]. If drops adhere for sucient time to allow them to deform, and to permit
drainage of the continuous phase that is trapped between them, then coalescence
may occur [26]. By taking account of these events, expressions can be obtained for
the coalescence eciency [50]. Expressions, for coalescence and for collision rates
are not easy to use because they often contain parameters that are dicult to quan-
tify. Alvarez et al. [50] constructed a model for drop breakage and coalescence, in
the suspension polymerization of styrene, which takes account of viscosity eects.
That model assumes that breakage of a drop, exposed to a turbulent ow eld, is a
result of uctuations with a wavelength equal to the drop diameter. Fluctuations
with wavelengths that are smaller or larger than the drop diameter do not lead to
drop breakage.
5.2.4
Drop Size Distributions
Even when expressions for drop breakage and coalescence rates are available, their
successful use must allow for variations of turbulence intensity within the reactor.
Maggioris et al. [51] describe a two-compartment population balance model for an
agitated suspension polymerization reactor. That model distinguishes between the
impeller region and the remainder of the reactor. Both regions are assumed to be
well mixed and CFD simulations predicted drop size distributions that were com-
patible with experimental results from nonpolymerizing model liquidliquid dis-
persions. For some combinations of stabilizer type and stirrer speed, bimodal
drop size distributions were predicted by the model and found in the experiments.
Yang et al. [52] showed how the size distribution of nonreacting styrene drops
changed with agitation time. Bimodality developed and the relative size of the two
peaks in the distribution depended on the amount of drop stabilizer that was used.
Calabrese et al. [46, 53] showed that, in dilute agitated suspensions for which co-
alescence is negligible, the equilibrium drop size distribution broadened consider-
ably as dispersed-phase viscosity increased.
If no chemical reaction occurs, then the rates of drop breakage and drop coales-
cence eventually become equal and a stable DSD is obtained [54]. Considerable
periods of time might be required for that to occur [18], especially when the drops
have a high viscosity [55]. But, in the case of suspension polymerization, the phys-
ical properties of the drops change with monomer conversion. In a batch process,
early increases in drop viscosity reduce the rates of breakage and coalescence be-
fore a steady-state DSD can be established. Then, the DSD continues to change,
and the average drop size increases, as the polymer content of the drops increases.
Consequently, the nal particle size distribution (PSD) is quite dierent from the
steady-state DSD that would be expected from nonpolymerizing drops. That was
shown to be the case by Jahanzad et al. [37] in the suspension polymerization of
methyl methacrylate. There, the DSDs of polymerizing drops were broader than
that of the DSDs in the corresponding nonpolymerizing monomer drops. But the
average drop size in the nonpolymerizing drops was only slightly smaller than that
in the polymerizing suspension when a large amount of stabilizer was used, be-
cause excess stabilizer reduced drop coalescence in both systems. Similar results
were obtained by Konno et al. [47]. With smaller amounts of stabilizer, a growth
stage exists in which drop coalescence continues when drop breakage rates are
low [50]. The increase in average drop size can be substantial and continues until
the identication point is reached when drop viscosity is too high to permit further
drop coalescence. Jahanzad et al. [37] also showed that, although the diameters of
most drops and particles ranged between 10 and 300 mm, a second peak appeared
in the particle size distribution. The average diameter of particles that accounted
for that second peak was about 1 mm. Most of those smaller particles probably de-
veloped from satellite drops which are formed during the breakage process. The
existence of small satellite drops is compatible with the ideas of Chatzi and Kiparis-
sides [44] and with the work of Sathyagal et al. [56]. But some of the very small
particles could have been formed directly in the aqueous phase because the water
solubility of the free radical initiator (lauroyl peroxide) may be high enough to in-
duce some emulsion polymerization. That can by important with monomers that
are more water-soluble, such as methyl methacrylate, vinyl acetate, and vinyl chlo-
ride. If emulsion polymerization becomes prevalent, then a signicant amount of
the drop stabilizer will be adsorbed on the surfaces of the small particles. The
amount of stabilizer that is available to stabilize the drops is then reduced [57].
In batch reactors, the rate of drop coalescence is aected by changes in drop
viscosity. Therefore, any induced kinetic eects that alter the polymer molecular
weight (and, thereby, change the viscosity) could inuence the coalescence rate
and the DSD. Promoting chain transfer is one way for that to happen.
When drop viscosity remains low, coalescence events can depend on the nature
of the drop stabilizer. Low viscosities may be encountered when the polymers, or
copolymers, are immiscible with their monomers. The polymers then precipitate
inside the drops and their apparent viscosity does not increase substantially until
appreciable conversions have been attained. That is the case with the suspension
polymerization of vinyl chloride. When hydrolyzed poly(vinyl acetate) (PVA) is
used as the drop stabilizer, Zerfa and Brooks [18] showed that DSDs depended on
stirrer speed. With good PVA stabilizers, that had a high degree of hydrolysis, a
reduction in stirrer speed had little eect on the DSD, as shown in Figure 5.3. But
when a poor PVA stabilizer, with a low degree of hydrolysis, was used, a reduc-
tion in stirrer speed led to a broadening of the DSD. There, the DSD became sim-
ilar to that expected when the stirrer speed was maintained at its lowest value,
as shown in Figure 5.4. Clearly, the good stabilizer protected the drops from
coalescence.
5.2.5
Drop Mixing
Most of the coalescence events described in Section 5.2.3 occur when drops have a
uniform chemical composition, but sometimes it is necessary to add material to a
reactor in which a suspension already exists. That can happen if control of copoly-
mer composition is important. In batch operation, copolymer composition usually
changes with overall conversion because monomers react at dierent rates [58].
This drift in copolymer composition may be limited by adding one of the mono-
A
0
50
100
150
200
15 35 55 75 95
Drop diameter (microns)
B
0
50
100
150
200
15 35 55 75 95
C
0
50
100
150
200
15 35 55 75 95
D
r
o
p

n
u
m
b
e
r
D
r
o
p

n
u
m
b
e
r
D
r
o
p

n
u
m
b
e
r
Fig. 5.3. Change in drop size with stirrer speed with PVA
72.5% hydrolyzed. (A) N 350 rpm (5.8 s
1
); (B) N 650
rpm (10.8 s
1
); (C) N reduced from 650 to 350 rpm. Data from
Ref. 18.
mers to the reactor incrementally (that is, by using a semi-batch procedure). But,
when new dispersible material is added to an existing suspension, the new mate-
rial and existing drops can remain segregated for a signicant period of time.
Then, new drops may form with a monomer composition that diers from that of
A
0
50
100
150
200
15 35 55 75 95
B
0
50
100
150
200
15 35 55 75 95
C
0
50
100
150
200
15 35 55 75 95 115
D
r
o
p

n
u
m
b
e
r
D
r
o
p

n
u
m
b
e
r
D
r
o
p

n
u
m
b
e
r
Fig. 5.4. Change in drop size with stirrer speed with PVA 55%
hydrolyzed. (A) N 350 rpm (5.8 s
1
); (B) N 650 rpm
(10.8 s
1
); (C) N reduced from 650 to 350 rpm. Data from
Ref. [18].
the original drops. The new monomer cannot mix with existing drops (which con-
tain the initiator and have adsorbed most of the drop stabilizer). Adding extra drop
stabilizer, with the new monomer, might not be helpful because there is the dan-
ger of stabilizing new drops with the wrong monomer composition that contain
little, or no, radical generator.
Hashim and Brooks [59] studied the addition of styrene to a suspension of stabi-
lized drops. The drops were composed of polystyrene solutions in styrene. The ini-
tial drop viscosity aected the drop size and the rate of coalescence between drops.
As the dispersed-phase viscosity increased, the drop size distribution broadened; at
some stirrer speeds, the mixing rate increased. It appears that there is a critical
drop size which determines the coalescence eciency. Above that size, the drop
mixing rate increases as the drop viscosity decreases. Below the critical drop size,
the mixing rate is inuenced noticeably by the drop size; as the drop size increases,
the coalescence rate also increases.
Drop mixing may become an issue when volatile monomers are used. The en-
thalpy of polymerization for most of the vinyl monomers that are used in suspen-
sion polymerization ranges between 30 and 90 kJ mol
1
. Therefore, a high heat re-
moval rate is usually necessary to maintain a constant reactor temperature. This is
dicult to achieve by heat transfer through the reactor walls in commercial opera-
tions because large reactors have a relatively small surface area to volume ratio.
Heat removal can be improved by allowing the monomer to vaporize. The vapor
is then condensed, cooled, and returned to the reactor as a liquid. If the polymer-
ization process is to be maintained, drops of returning monomer must gain access
to initiator and drop stabilizer. With the suspension polymerization of vinyl chlo-
ride, Zerfa and Brooks [60] found that monomer returning from a reux con-
denser formed drops that acquired initiator without the need for coalescence with
existing stabilized drops. The presence of small particles, formed by simultaneous
emulsion polymerization, appeared to provide a mechanism for transfer of initiator
(bis(4-t-butylcyclohexyl) peroxy dicarbonate) through the continuous phase. With
high reux rates, the drop size distribution became bimodal whereas, in the ab-
sence of reux, a monomodal DSD is expected [60]. New drops, from reuxed
monomer, had limited access to the drop stabilizer (PVA) and were larger than
the old drops.
A special drop mixing problem arises with the suspension polymerization of
vinyl chloride. Because the monomer is very reactive and has a high enthalpy of
polymerization, operators are reluctant to mix initiator in the monomer before a
suspension is formed. Therefore, as a safety precaution, the initiator is often dis-
persed in the aqueous phase of a stabilized suspension. Then the subsequent mix-
ing of monomer and initiator can be quite slow. Zerfa and Brooks [61, 62] showed
that many monomer drops remained uninitiated when monomer in other drops
had polymerized to a considerable extent. That did not happen when initiator was
dissolved in the monomer before it was dispersed: see Figure 5.5. This nonuni-
formity in drop behavior aected the nal polymer properties. Also, addition of ini-
tiator via the aqueous phase promoted simultaneous emulsion polymerization and
modied the PSD. Drop mixing rates were quantied by using dyed monomer
drops in the experiments. The mixing rate was found to depend on both the con-
centration of the PVA and the grade that was used [61].
5.3
Events at High Monomer Conversion
Suspension polymerization provides a practical method of achieving high mono-
mer conversions. Therefore, studies of polymerization and drop behavior that deal
with events at low monomer conversion may not be applicable to suspension poly-
merization.
Fig. 5.5. Eect of the method of initiator
addition to vinyl chloride: (A) initiator
predissolved in drop phase; (B) initiator
predispersed in continuous phase. Panels:
1, 5 min; 2, 20 min; 3, 60 min. N 350 rpm
(5.8 s
1
); j 0:1; PVA concentration 0.06%.
Reproduced by permission of John Wiley &
Sons, Inc. From Ref. 62.
5.3.1
Breakage of Highly Viscous Drops
In batch reactors drop breakage and coalescence are aected by the polymerization
process because the viscosity of the polymerizing uid often increases. Many as-
pects of the interaction of drop behavior with the polymerization process have
been discussed already (see Section 5.2).
5.3.2
Polymerization Kinetics in Viscous Drops
Free radical polymerization kinetics has received much attention and many aspects
of the process are well understood (see Chapter 4). Most academic investigations
have been carried out in idealized conditions where the extent of monomer con-
version is low. The classical expression for the rate of polymerization (R
p
), in a
single-phase reaction, is Eq. (13), where k
p
is the propagation rate coecient, C
M
is monomer concentration, R
i
is the initiation rate and k
t
is the termination rate
coecient [63].
R
p
k
p
C
M
R
i
=k
t
1=2
13
If radicals are generated by the thermal decomposition of an added initiator then,
at steady-state conditions, Eq. (14) applies, where f is an eciency factor, k
d
is the
initiator decomposition rate coecient and C
I
is the initiator concentration.
R
i
2f k
d
C
I
14
Chain termination is often diusion-controlled and the value of k
t
diminishes sub-
stantially as the polymer concentration increases. At high polymer concentrations,
k
p
decreases also [64]. The reduction in k
t
leads to an increase in the polymeriza-
tion rate, a phenomenon often described as a gel eect.
Although most workers agree that the chain termination reaction is diusion-
controlled, reliable quantitative relationships between the rate coecients and
measurable properties of the reaction medium are not generally available. Radical
diusion can depend on solution viscosity, polymer volume fraction and polymer
molecular weight. The latter three entities are interrelated in complicated ways;
meaningful experiments, which may relate them to the rate coecients, are not
easy to devise [65]. However, Brooks et al. showed that eects of viscosity changes
on polymerization rate could be distinguished from the eects of polymer volume
fraction [66]. In some cases, the value of f may also depend on polymer content
[67].
The value of k
d
can often be determined independently but traditional steady-
state experiments give values for k
p
=k
0:5
t
and do not provide separate values for k
p
and k
t
. This restriction becomes a problem for reactor modeling because, in the
presence of polymer, both k
p
and k
t
diminish (even in isothermal conditions).
Pulse laser techniques, combined with accurate molecular weight measurement,
have been used to determine independent values for k
p
but those techniques are
only feasible in the absence of preformed polymer [68, 69].
When a gel eect is observed, kinetic analysis can be dicult because k
t
be-
comes dependent on chain length [70] and the pseudo-steady state assumption
may not be valid [71]. Tefera et al. [72] showed that, when a high monomer conver-
sion is attained, a number of dierent models for the gel and glass eects gave an
adequate description of isothermal timeconversion data over the entire conver-
sion range for a single type and loading of initiator. But models that ignored the
eect of polymer molecular weight on the diusion of macro radicals failed to de-
scribe the timeconversion data if the concentration of the initiator varied. It has
been shown that autoacceleration in free radical polymerization can be observed
even when low molecular weight polymer is being formed, indicating that chain
entanglements are not necessary for a gel eect to occur [73].
In practice, isothermal conditions are not always maintained in suspension poly-
merization and temperature increases can lead to a marked reduction in initiator
concentration. As the monomer conversion increases, the glass transition temper-
ature of the polymer solution also increases and the drops can become glassy. The
chain propagation reaction then becomes diusion-controlled and the value of k
p
decreases signicantly. An increase in reaction temperature may become necessary
in order to achieve complete monomer conversion. Although most workers agree
that k
p
is reduced at high monomer conversions, Faldi et al. [74] have suggested
that diusion control may not be the only reason for that to occur. Qin et al. [75]
developed a three-stage model to account for the gel and glass eects. The match
with experimental data, for methyl methacrylate and styrene polymerizations, up to
high monomer conversion was satisfactory for isothermal conditions. Achilias and
Kiparissides [76] showed, however, that data for polymerization of those mono-
mers were compatible with a model that did not require break points for the gel
and glass eects. The initiator eciency, f , has been shown to depend on the size
of the initiator radicals at high monomer conversion [76].
If crosslinking or copolymer precipitation occurs, bulk polymerization may be
dicult to handle. A suspension process may then be the only feasible way in
which the copolymerization can be carried out [4]. Suspension processes also pro-
vide a means of investigating copolymerization kinetics at high conversion. The
monomer sequence in styrenemethyl methacrylate copolymers at high conver-
sion have been found to dier from those observed at low conversion [77].
5.3.3
Consequences of Polymer Precipitation Inside Drops
Polymers that are insoluble in their monomers will precipitate during polymeriza-
tion. The resulting fouling problems that occur in bulk polymerization are greatly
reduced by using suspension polymerization. This is one of the reasons for
choosing a suspension process for PVC manufacture, as discussed previously (see
Section 5.1.5). Manipulation of polymer precipitation, inside the drops, during
polymerization can inuence the properties of the nal product, especially the po-
rosity, which in the case of PVC aects the ability of the polymer to take up plasti-
cizers. Structural changes that occur inside the drops of polymerizing vinyl chlo-
ride monomer (VCM) have been discussed by a number of authors [78, 79].
PVC starts to precipitate from the monomer phase when the conversion exceeds
0.1% conversion, forming a separate polymer-rich phase inside the drops. The pre-
cipitating polymer aggregates to form unstable microdomains, which aggregate
further to give domains. Subsequent aggregation of domains results in the for-
mation of primary particles. The primary particles grow by polymerization within
them and by buildup of microdomains or domains on their surfaces. Eventually
multiple contacts lead to the formation of a continuous network of primary par-
ticles throughout the polymer particle/monomer droplet; see Figure 5.6. At about
70% conversion the monomer-rich phase disappears and further polymerization
occurs in the polymer-rich phase [80, 81]. The nal polymer grains have irregular
shapes, unlike particles that form from polymers that are completely miscible with
their monomers. Some components of the drop stabilizers are chosen because they
are miscible with the monomer and they can inuence the agglomeration of pri-
mary particles [82]. Those components are sometimes called secondary suspend-
ing agents (SSAs).
As a direct consequence of the process described above, and of the density dier-
ence between PVC and VCM, PVC grains have a complicated morphology and they
can be highly porous. The particle size, the PSD, the morphological characteristics,
and the degree of porosity of PVC grains depend on polymerization conditions.
These include the agitation in the reactor, the type and concentration of suspend-
Fig. 5.6. Schematic representation of polymer formation inside vinyl chloride drops.
ing agent(s), the secondary suspending agents, the polymerization temperature,
the monomer conversion, and the ratio of monomer to water.
Eects of agitation on the mean particle size of PVC resins have been studied by
many researchers, using dierent reactor capacities, and many correlations have
been developed [83, 84]. The eects of agitation on PVC porosity have also received
much attention [80]. As with the suspension polymerization of other monomers,
the choice of suspending agent(s) aects the particle size distribution of the nal
polymer. In the case of PVC, however, the suspending agents also aect the sub-
structure and porosity of the particles. The primary suspending agent system is
often based on PVA, substituted cellulose, or a mixture of the two. Wolf and
Schuessler [85] concluded that the plasticizer absorption (which depends on po-
rosity) of the resulting PVC was related to the surface activity of the suspending
agent, regardless of type. Ormondroyd [86] demonstrated the eect of PVA struc-
ture on the particle size, cold plasticizer absorption, and bulk density of the PVC
produced. Cheng [87] and Cheng and Langsam [88] used hydroxypropyl methylcel-
lulose (HPMC) as a suspending agent and analyzed the inuence of molecular
weight and chemical structure of the cellulose on the particle morphology of the
resulting PVC. Cebollada et al. [81] showed how HPMC structure and concentra-
tion inuenced the particle properties of PVC. SSAs are regularly used in the pro-
duction of suspension PVC to impart higher porosity to the PVC grains. That
improves the subsequent uptake of plasticizer and also promotes the removal of
unreacted VCM at the end of polymerization. PVA with a low degree of hydrolysis
and nonionic surfactants, such as sorbitan monolaurate, have been used commer-
cially as SSAs [89]. The mechanism by which such SSAs function is not entirely
clear [80, 9092].
When nonionic surfactants, such as Span85, Span60 and Span20, are used as
SSAs, with PVA as the main stabilizer, the mean particle size of PVC resins in-
creases quickly as the concentration of nonionic surfactant increases [82]. The
degree of agglomeration of primary particles increases with polymerization tem-
perature and with conversion. A nonionic surfactant with a greater hydrophile-
lyophile balance (HLB) value is more eective in raising the particle size [82].
The increase in the mean particle size of the nal PVC is probably caused by in-
creased coalescence of VCM/PVC droplets during the polymerization process, as a
result of a lowering of water-drop interfacial tension by the SSA. Nonionic surfac-
tants such as Span20, Span60, and Span85 have more anity with VCM than the
PVA has, and they will be absorbed faster than PVA on the VCM/water interface.
Part of the interface, which would otherwise be occupied by PVA molecules, will
become occupied by nonionic surfactant molecules. Thus, the colloid protective
ability of the composite suspending agent would decrease because the nonionic
surfactants with a low molecular weight have a lower colloid protective ability
than that of PVA. In some cases, graft copolymers of PVA and PVC form a skin
(or membrane) around the polymer particles [93]. Zerfa and Brooks [60] showed
that, at low monomer conversion, PVC porosity increases if a high monomer reux
rate is used. Porosity, surface roughness, and particle shape were found to depend
on the origin of the PVA [62]. Particle shape can also be inuenced by the method
of initiator addition [62]. High conversions of VCM are not always desirable be-
cause the porosity of PVC particles usually decreases linearly with monomer con-
version, as shown in Figure 5.7 [60, 82].
When a nonionic surfactant is used as an SSA, in conjunction with PVA, the
porosity of PVC increases as the concentration of nonionic surfactant increases.
Here, increased porosity may be the result of incomplete drop coalescence creating
voids at the sites where droplets are not well contacted [82]. Nonionic surfactant
with a lower HLB value (hence with a higher anity for VCM and a higher solubil-
ity in VCM) is more eective in raising the product porosity. The surface of pri-
mary particle aggregates becomes coarser as surfactant is added [82]. This could
be the consequence of an altering interfacial tension between the PVC-rich phase
and the monomer. That might be expected to decrease the contact deformation of
the primary particles and increase the pore space. When nonionic SSAs are used,
PVC porosity decreases linearly with an increase of polymerization temperature
[82]. The porosity increases as the concentration of nonionic surfactant increases,
and a surfactant with a lower HLB value is more eective in raising the porosity.
The increase in porosity may be caused by a combination of increased coalescence
of VCM/PVC droplets and the nonionic surfactants steric eect inside the droplets
[82]. Bao et al. showed that particle morphology and PVC properties can be con-
trolled by using blends of PVA suspending agents with diering degrees of hydro-
lysis [94]. The use of PVA, with a low degree of hydrolysis, as an SSA increased
particle porosity in the suspension copolymerization of vinyl chloride and propy-
lene [95]. In that case, the SSA was more soluble in the organic phase than the pri-
mary stabilizer (a cellulose ether).
In vinyl chloride polymerization, particle porosity facilitates the subsequent up-
take of plasticizers, but in other cases particle porosity is induced to enhance access
to functional groups within the polymer. That is useful when polymer beads are
required for use in ion-exchange columns, or in analytical instruments. A diene
comonomer can be added to a monomer, to promote crosslinking and phase sepa-
20
30
40
50
60
70
80
90
100
0 20 40 60 80 100
Polymerisation conversion (%)
C
P
A

(
g

D
O
P
/
1
0
0
g

P
V
C
)
Fig. 5.7. Eect of polymerization conversion on the cold
plasticizer absorption (CPA) of PVC. Reproduced by permission
of John Wiley & Sons, Inc. From Ref. 82.
ration inside the drops [9699]. Appropriate functional groups can be incorporated
in the monomers.
5.4
Reaction Engineering for Suspension Polymerization
The discussion above (see Sections 5.2 and 5.3) provides guidelines for the design
of suspension polymerization processes on an industrial scale. However, extrapo-
lating from idealized small-scale studies to full-scale commercial operation is not
straightforward. Maintenance of uniform reactor conditions cannot be guaranteed
inside large reactors and controlled heat transfer from reactors can be dicult.
5.4.1
Dispersion Maintenance and Reactor Choice
Many suspension polymerization processes employ stirred vessels. Oldshue et al.
[100] showed that agitator type and vessel geometry have an important inuence
on internal liquid ow. This must be taken into account in the design of large ves-
sels for suspension polymerization. Maggioris et al. [51] and Vivaldo-Lima et al.
[101] devised two-compartment population balance models to account for the large
spatial variations of the local turbulent kinetic energy. These permit the prediction
of drop size evolution in a suspension polymerization reactor with a high volume
fraction of dispersed phase. Basic expressions were modied to allow for evolving
physical properties of the suspension. Maggioris et al. [51] showed that it was fea-
sible to estimate the volume ratio of the impeller and circulation regions, the ratio
of turbulent dissipation rates, and the exchange ow rate of the two compartments
at dierent agitation rates and continuous-phase viscosities. Although many indus-
trial suspension polymerizations are described as batch processes, they are not
genuine batch operations because some material enters the reactor after polymer-
ization has started. In some cases, substantial reux of monomers occurs and con-
densed monomer returns to the reactor continuously. In others, a semi-batch pro-
cess is used to control product composition. In both these situations, unconverted
monomer with low viscosity is being mixed with drops of higher viscosity. The com-
plexities of these mixing processes have been discussed above; see Section 5.2.5.
Reactor congurations other than conventional stirred tanks have been proposed
for suspension polymerization. Draft tubes, or internal loops, can be used for
suspension polymerization [102], but drop size changes can occur [103] and ow
patterns may be complicated [104]. Tanaka et al. [105] used a loop reactor for the
suspension polymerization of styrene. They employed a double agitation method
to control the transient droplet diameter distribution and the nal particle size dis-
tribution. Ni et al. [106] developed an oscillatory baed reactor for batch suspen-
sion polymerization of methyl methacrylate. Fluid mixing was achieved by eddies
that are generated when a uid passes through a set of equally spaced, stationary,
orice baes that are located inside a tube. Periodically formed vortices were con-
trolled by choosing appropriate values for oscillation frequency, oscillation ampli-
tude, bae diameter, and bae spacing. The nal particle size distribution and
polymer molecular weight were comparable with those of a product obtained
from a conventional stirred tank reactor.
Although most industrial polymerization processes are batch or semi-batch oper-
ations, some continuous-ow processes have been proposed [107]. Use of ow re-
actors may aect the nature of the drop size distribution and the molecular weight
distribution. If ow through a back-mixed region occurs, the drops will be subject
to a distribution of residence times and the nature of the mixing for the dispersed
phase is important. Baade et al. [108] and Taylor and Reichert [109] showed that
complete segregation of drops, in the suspension polymerization of vinyl acetate,
produced an increase in polymer molecular weight. Also, the distribution of mo-
lecular weights became broader than that expected in a batch reactor. Complete
mixing of the drops gave a molecular weight distribution which was narrower than
that found in batch reactors. An oscillatory baed reactor can also be used for
continuous-ow suspension polymerization. Ni et al. [110] describe the eect of
superimposed oscillations on the main ow through a tube. Radial mixing of the
uid occurs but near plug-ow is obtained. A constant level of turbulence intensity
in the reactor can lead to particle size distributions similar to those expected from a
batch reactor.
5.4.2
Agitation and Heat Transfer in Suspensions
In single-phase processes, reactor agitation inuences the rate of heat transfer to,
and from, the surroundings and determines the quality of mixing. With suspen-
sion polymerization reactors, the agitation must also be good enough to generate,
and to maintain, a two-phase dispersion. When conventional stirred tanks are
used, a standard reactor geometry may be adequate to promote convective heat
transfer. Here, the height of the total suspension (H), the impeller diameter (D)
and the clearance underneath the impeller (G) are related to the tank diameter
(T) as follows:
HAT
DAT=3
GAT=3
The use of baes limits nonuniformity in the turbulence and restricts vortex for-
mation. Vortices are undesirable because the centrifugal eect favors drop congre-
gation and may promote unwanted drop coalescence. That can lead to polymer
deposition either on the agitator or the reactor walls (depending on the relative
density of the aqueous and nonaqueous phases). When vertical baes are close to
the walls their width (B) is often given by:
BAT=10
With suspension polymerization, reactor fouling is sometimes a problem. In such
cases, it can be helpful to have a small gap between the outer bae edge and the
reactor wall. That may reduce accumulation of coagulated solids at the wallbae
junction.
Some form of turbine impeller is often suitable for suspension polymerization
when the apparent viscosity of the suspension is not very high. But the power in-
put to the suspension, via the impeller, must be sucient to create and to maintain
the required drop size distribution. The required stirrer speed for the appropriate
turbulence level can be estimated from Eqs. (6)(7) (see Section 5.2.2). But, in real-
ity, the turbulence will not be uniform. Drop breakage and drop coalescence may
occur in dierent regions of the reactor [5]. The necessary power input can be pre-
dicted from correlations between the power number and the Reynolds number
[30]. However, those correlations are usually developed for single-phase uids and
care must be taken when using them for suspensions, where the eective viscosity
of the suspension may be unknown. The Reynolds number in most large-scale sus-
pension polymerization reactors is usually high enough to generate turbulent ow,
and in that region the use of baes increases the required power input.
Heat removal from suspension polymerization reactors can be a problem, espe-
cially after the startup period in batch operation when a gel eect causes auto-
acceleration in the polymerization. If the monomers are volatile at the working
pressure of the reactor, then some heat can be removed relatively quickly by mono-
mer vaporization (as discussed above for vinyl chloride polymerization; see Section
5.2.5). When most of the heat transfer occurs via a cooling jacket, special strategies
may be necessary to manage the heat transfer. Pinto and Giudici [111] suggested
that a mixture of initiators, with dierent half-lives and activation energies, could
be used. Then it may become possible to match the heat generation rate with the
cooling capacity of the reactor jacket. The feasibility of such an approach depends
on the accuracy of the reactor model that is used. Mejdell et al. [112] showed that
the reaction rates predicted from models for the industrial suspension polymeriza-
tion of vinyl chloride were subject to signicant noise because the heat capacity of
the suspension was large and the resolution of temperature measurements was
limited. If the reactor cooling capacity is chosen to cope with heat generation rates
in the later stages of batch operation, when autoacceleration occurs, then the heat
removal capacity of the reactor will not be fully utilized in the early stages of the
polymerization. Longeway and Witenhafer [113] suggested that the reactor could
be operated at a higher temperature in the early stages, to make full use of the
cooling capacity. They constructed a model that predicted a reduction in total reac-
tion time for a given monomer conversion. It should be remembered that the over-
all heat transfer coecient for a jacketed reactor depends on the nature of the wall
material. Transfer coecients for stainless steel reactors are approximately double
the coecients found for glass-lined carbon steel reactors [114].
It is commonly assumed that, in suspension polymerization, heat transfer be-
tween polymerizing drops and the continuous phase is rapid and both phases
have the same temperature. However, Lazrak and Ricard [115] showed that, with
methyl methacrylate polymerization, the internal temperature of drops could be
higher than that of their surroundings when drop diameters exceeded 1 mm. Tem-
perature dierences were large enough to cause changes to polymer quality.
5.4.3
Scaleup Limitations with Suspension Polymerization
Many aspects of scaleup (or scaledown) of suspension polymerization reactors are
similar to those encountered with other polymerization processes. These concern
parameters that control polymerization rate, product composition, and polymer
molecular weight. In the case of suspension polymerization, however, special con-
sideration must be given to maintaining the required drop/particle size distribu-
tion. In the case of VCM polymerization, the maintenance of particle porosity is
also an issue. In principle, correlations between dimensionless entities, such as
the Weber number correlations (see Section 5.2.2), should help reactor designers
to relate observations in laboratory experiments to events that occur on a large
scale. But, even if fundamental requirements for drop breakage and drop coales-
cence are known (which is not always the case), it is dicult to ensure similarity
of conditions inside reactors with greatly diering sizes. Some key relationships
are discussed by Yuan et al. [5] and by Leng and Quarderer [39]. Scaleup criteria
should allow for any variations of volumetric phase ratio that may occur. Some-
times those can be included in modications to the Weber number correlations
(see Section 5.2).
In addition to the problem of matching turbulence homogeneity in reactors of
dierent sizes, there can be a serious diculty in maintaining constant average tur-
bulence intensities. This arises because a high Reynolds number (Re ND
2
r=m) is
easier to achieve in a large reactor than in a small reactor. Often, it not practical to
use a stirrer speed, in a small reactor, which is high enough to compensate for the
relatively small value of D
2
. A good estimate for the physical properties of the
whole suspension is necessary in order to predict values for the Reynolds number.
When the suspension viscosity is high, it is possible for the uid in a large reactor
to be fully turbulent but for the uid in a small reactor to be in the transition re-
gion (between laminar and turbulent ow). In such cases, the drop breakage mech-
anism can change with reactor size. Scaleup is most likely to be successful when
the reactors have a similar basic shape. An unbaed spherical laboratory reactor
will not behave in the same way as a large baed cylindrical reactor. When drop
formation depends on reactors with a special geometry, such as that required for
a crossow membrane [16] or a pulsed column [106], then new scaleup criteria
may become necessary.
Heat transfer rates per unit mass of suspension increase as reactor size
decreases. Consequently, it may not be possible to achieve the same time
temperature prole in a large reactor as is obtained with a small reactor, especially
when autoacceleration occurs. If some heat transfer occurs via monomer evapora-
tion, then the rate of monomer reux can depend on reactor size. In the case of
VCM polymerization, this can result in particle porosity changing with reactor
size (see Section 5.3.3).
5.4.4
Reactor Safety with Suspension Processes
The potential for thermal runaway exists with most commercial free-radical poly-
merization processes that employ batch reactors. This arises because the heat of
reaction is high and there is no eective steady state. Although temperature con-
trol in suspension polymerization reactors is often better that that found in bulk
polymerization, the possibility of thermal runaway cannot be ignored. This was
demonstrated by Nemeth and Thyrion [116] who showed that very sharp tempera-
ture rises could occur in the suspension polymerization of styrene, largely because
spontaneous free-radical generation occurs with that particular monomer as the
temperature increases. When models are used to predict temperature rises in poly-
merization reactors, it is important to allow for small changes that occur in the
physical properties of the polymerizing uid. Otherwise, large overestimates of
temperature rises are obtained [117].
Axial mixing throughout the reactor is particularly important when the density
of the continuous phase lies between the density of the monomer and the density
of the polymer. In those cases the polymerizing drops may gradually sink during
the process. If good mixing is not maintained, highly viscous drops can accumu-
late and coalesce at the bottom of the reactor. The process then reverts to a bulk
polymerization, with all its inherent disadvantages. Such a potential risk arises
with suspension polymerization of styrene in the production of pre-expanded
beads. Even though styrene has a relatively high boiling point, the reactor is main-
tained at a positive pressure because a volatile blowing agent (for example, pen-
tane) must remain in the drop phase. If the suspension fails, heat transfer from
the coalesced drops is quickly reduced and the temperature of the polymerizing
mass begins to rise. The subsequent increase in vapor pressure of the water can
cause the total pressure to reach unsafe values. Disaster may be avoided if a pres-
sure release device (for example, a bursting disk) functions well, but it is essential
that the design, and location, of such a device do not permit excessive fouling by
polymer deposits. Regular reactor cleaning is important.
In small-scale suspension polymerization, inhibitors are often removed from the
monomer before it is dispersed in the continuous phase. In large-scale operation,
however, the inhibitor may not be removed. Its presence lowers the risk of prema-
ture polymerization, which can be dangerous when large amounts of monomer are
being handled. Consequently, the particle size distribution obtained from the large
reactor may dier from that in the small reactor because drop breakage can occur
before signicant amounts of polymer are formed (that is, when the drop viscosity
is still relatively low).
5.4.5
Component Addition during Polymerization
Scaleup often involves more than an increase in reactor size. Even when geometric
similarity is maintained, it may be dicult to reproduce exact laboratory proce-
dures when a large reactor is used. Many scaleup criteria do not apply to tran-
sient events because they employ relationships that assume steady-state conditions.
Thus, the time required to disperse added material may depend on reactor size.
That can be important in suspension polymerization where new material is added
to the continuous phase but it is required to reach the dispersed phase or the phase
interface. The new material may include fresh monomer(s), blowing agents, or
modiers for polymer properties. At startup conditions, the initial dispersion of
drop stabilizers and initiator may require dierent amounts of time with reactors
of dierent sizes. Consequently, the DSD and nal PSD may depend on the scale
of operation, because polymerization (and a change in drop properties) occurs dur-
ing the drop creation process.
5.5
Inverse Suspension Polymerization
When a water-miscible polymer is to be made via a suspension process, the con-
tinuous phase is a water-immiscible uid, often a hydrocarbon. In such circum-
stances the adjective inverse is often used to identify the process [118]. The drop
phase is often an aqueous monomer solution which contains a water-soluble initi-
ator. Inverse processes that produce very small polymer particles are sometimes
referred to as inverse emulsion polymerization but that is often a misnomer
because the polymerization mechanism is not always analogous to conventional
emulsion polymerization. A more accurate expression is either inverse microsus-
pension or inverse dispersion polymerization. Here, as with conventional sus-
pension polymerization, the polymerization reaction occurs inside the monomer-
containing drops. The drop stabilizers are initially dispersed in the continuous
(nonaqueous phase). If particulate solids are used for drop stabilization, the sur-
faces of the small particles must be rendered hydrophobic. Inverse dispersion poly-
merization is used to make water-soluble polymers and copolymers from mono-
mers such as acrylic acid, acylamide, and methacrylic acid. These polymers are
used in water treatment and as thickening agents for textile applications. Beads
of polysaccharides can also be made in inverse suspensions but, in those cases,
the polymers are usually preformed before the suspension is created. Physical
changes, rather than polymerization reactions, occur in the drops. Conventional
stirred reactors are usually used for inverse suspension polymerization and the
drop size distribution can be fairly wide. However, Ni et al. [119] found that good
control of DSD and PSD could be achieved in the inverse-phase suspension poly-
merization of acrylamide by using an oscillatory baed reactor.
5.5.1
Initiator Types
The thermal decomposition of single-component initiators (such as inorganic per-
sulfates) can be used to generate the free radicals in the aqueous drops, but in
5.5 Inverse Suspension Polymerization 239
some cases a redox initiator system is used. Redox reactions produce free radicals
at relatively low temperatures, which is advantageous when the polymerization is
very fast at higher temperatures. This type of polymerization is not always strictly
analogous to simple conventional suspension polymerization. In some circum-
stances, there is evidence to suggest that the polymerization rate is diminished
when large amounts of an oil-soluble surfactant are used to stabilize the monomer
drops, and that a small amount of polymerization occurs in the oil phase [120].
The polymerization kinetics can be complicated when redox systems are used
and the mechanism of radical generation may depend on the specic reductant
oxidant pair that is chosen [121].
5.5.2
Drop Mixing with Redox Initiators
At least one of the two major components of a redox initiator (reductant or oxidant)
must be segregated from the monomer while the suspension is being formed.
Otherwise, polymerization would begin before the desired DSD was attained.
Often, drops of an aqueous solution of monomer and oxidant are initially dis-
persed in an oil and stabilized with an appropriate agent. Then aqueous reductant
is added to start the reaction [122, 121]. Therefore, the initial suspension has two
types of aqueous drops which must become mixed before polymerization can be-
gin. Liu and Brooks [123] used a freezefracture technique with electron micros-
copy to show how large reductant drops became mixed with small monomer-
containing oxidant drops in the early stages of acrylic acid polymerization (Figure
5.8). The actual volumes and concentrations used for the two aqueous solutions af-
fect the rate of viscosity increase in the drops and the polymerization rate [124].
5.6
Future Developments
Future work on suspension polymerization will be concerned with new products
and with new processes. Much of the new work on recipes and product properties
is material-specic and will continue to appear in the patent literature. The devel-
opment of new processes requires further fundamental investigation. Improve-
ments to existing processes need closer attention to ways in which reactors are
operated. These should include the following aspects.
5.6.1
Developing Startup Procedures for Batch and Semi-batch Reactors
Suspension polymerization can rarely be described as a conventional batch process
because uniform physical conditions cannot be created instantly. The way in which
the ingredients are brought together can aect the polymer properties. Therefore,
improvements in the control of product quality may depend on developing better
reactor startup procedures. The initial sequence in which the initiator and drop sta-
bilizer are put into the reactor can aect copolymer composition and polymeriza-
tion rates because inter-drop mixing can be restricted during polymerization. That
is especially important when the initiator and monomer are not premixed before
entry to the reactor. Good control of copolymer composition will continue to be dif-
cult when monomer reactivity ratios vary widely. If late addition of some mono-
mer is used to maintain constant composition at high conversions, then drop seg-
regation must be overcome. Here, a careful choice of drop stabilizer, and possibly
the use of solvents, may be helpful.
Desirable changes in PSD may be obtained by exercising better control of drop
viscosity in the initial drop formation stage. That might be achieved by careful use
of radical inhibitors which reduce initial polymerization rates (and associated vis-
cosity increases) and allow the initial DSD to develop in a desired way. The deci-
sion to remove (or not remove) radical inhibitors from monomers, before they are
put into the reactor, should not be made in an arbitrary way. Radical inhibitors that
dissolve preferentially in the continuous phase might also be used to eliminate the
initial formation of emulsion particles. That could be important because those
emulsion particles, which represent a small mass fraction of the drop phase, have
Fig. 5.8. Inverse dispersion polymerization of acrylic acid.
Freezefracture SEM image of dispersion 2 min after adding
aqueous reductant. Reproduced by permission of Elsevier
Science Ltd. From Ref. 123.
5.6 Future Developments 241
a large surface area and they can distort the distribution of drop stabilizer during
the initial drop development stage.
5.6.2
Maintaining Turbulence Uniformity in Batch Reactors
Turbulence in conventional stirred vessels is far from uniform and prediction
(or control) of DSD is dicult. Thus, the nal PSD is often very wide. That is un-
desirable when the nal particles are used directly (for example, in ion-exchange
resins). In those cases, a narrow PSD is often required. New reactor geometries
and agitation methods could ensure the correct values for the overall Reynolds
and Weber numbers and also give more uniform distribution of turbulence condi-
tions. That will lead to a lower proportion of o-specication material. Here, the
use of new reactors, such as the oscillatory baed reactor, could be helpful.
5.6.3
Developing Viable Continuous-ow Processes
Continuous-ow reactors are often developed to produce high tonnages with low
reactor maintenance but, with suspension polymerization, continuous-ow reac-
tors could oer other advantages. If near plug-ow conditions could be attained,
the drop formation and polymerization stages could be separated to give better
control of the DSD. Also, temperature programming would become feasible so
that variation of drop viscosity with monomer conversion could be manipulated
to achieve better control of drop coalescence and of the nal PSD. For a
continuous-ow reactor to operate successfully the following conditions must be
attained simultaneously: a suitable residence time (often a few hours); small re-
gions of localized turbulence; restricted overall back-mixing; and good heat trans-
fer. New designs of oscillatory baed reactors [106] may make such processes fea-
sible on an industrial scale.
5.6.4
Quantitative Allowance for the Eects of Changes in the Properties of the Continuous
Phase
In suspension polymerization, the continuous phase is often regarded as inert.
Consequently, events that occur in that phase are sometimes neglected, even when
they are potentially important. The overall Reynolds number is often high enough
to ensure that drop breakage is via turbulence and that conventional Weber num-
ber correlations apply. But when the volume fraction of drops is high, or when a
signicant fraction of the drop stabilizer remains in the continuous phase, the
eective viscosity of the suspension becomes high. Then, the Kolmorgorov length
may exceed the drop diameter, and drop breakage via viscous shear becomes im-
portant. More work is required to determine the relationships between drop sizes
and agitation conditions when the uid ow is not fully turbulent. Maintenance
of uniform viscous shear (as opposed to maintenance of uniform turbulence)
throughout the reactor will bring a new set of challenges.
As more complex copolymers are developed, the range of monomer properties in
any one recipe will widen. The chances of all monomers being insoluble in the
continuous phase are small. Therefore the eects of monomer distribution be-
tween the phases, especially on the copolymer composition, will be important. Pre-
diction of phase distribution is not easy in systems that are thermodynamically
nonideal and it may become necessary to develop new sensors that monitor the
composition of the continuous phase.
5.6.5
Further Study of the Role of Secondary Suspending Agents
The porosity and structure of polymer particles are important for many product
applications. Then, the use of SSAs is often important. However, to gain a better
understanding of their role, it is necessary to determine what fraction of those
stabilizers is inside drops of the dispersed phase and how they aect structure in-
side the particles. The importance of grafting of SSAs to the polymer should be
claried.
5.6.6
Further Characterization of Stabilizers from Inorganic Powders
Particulate stabilizers will continue to have a place in suspension polymerization
because they can often be removed after polymerization, but our understanding of
their action is far from complete. Some of the theories do not always agree with
experimental results. Further systematic studies are required to determine the ef-
fect of the size and surface condition of the stabilizer particles on their ability to
stabilize drops. Also, the location of those particles at the end of polymerization
is important. In some cases, it may be advantageous to treat stabilizer particles
so that they remain with the polymer product in order to confer some desirable
property.
Notation
B bae width [m]
C
1
; C
3
; C
4
constants (dimensionless)
C
I
initiator concentration [mol m
3
]
C
M
monomer concentration [mol m
3
]
d drop diameter [m]
d
max
maximum drop diameter [m]
d
min
minimum drop diameter [m]
d
32
Sauter mean diameter [m]
D impeller diameter [m]
Notation 243
f eciency factor (dimensionless)
G clearance underneath impeller [m]
H height of the total suspension [m]
k
d
initiator decomposition rate coecient [s
1
]
k
p
propagation rate coecient [m
3
mol
1
s
1
]
k
t
termination rate coecient [m
3
mol
1
s
1
]
N impeller speed [s
1
]
Re Reynolds number (dimensionless)
R
i
initiation rate [mol m
3
s
1
]
R
p
polymerization rate [mol m
3
s
1
]
T tank diameter [m]
We Weber number (dimensionless)
We
crit
critical Weber number (dimensionless)
Greek
a parameter to dene ow (dimensionless)
e local energy dissipation rate per unit mass of uid [m
2
s
3
]
h Kolmogorov length [m]
m viscosity [kg m
1
s
1
]
n kinematic viscosity [m
2
s
1
]
r density [kg m
3
]
s interfacial tension [kg m
2
]
j volume fraction of dispersed phase (dimensionless)
Subscripts
c continuous phase
d dispersed phase
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6
Emulsion Polymerization
1
Jose C. de la Cal, Jose R. Leiza, Jose M. Asua, Alessandro Butte`,
Giuseppe Storti, and Massimo Morbidelli
6.1
Introduction
Emulsion polymerization leads to the production of a ne dispersion of a polymer
in a continuous medium, which most often is water; the dispersion is called latex.
With a worldwide annual production in excess of 20 million tonnes, emulsion
polymerization is used in the production of a wide range of specialty polymers,
including adhesives, paints, binders for nonwoven fabrics, additives for paper, tex-
tiles, and construction materials, impact modiers for plastic matrices, and diag-
nostic tests and drug delivery systems [14]. The development of this industry
has been due to both the possibility of producing polymers with unique properties
and the environmental concerns and governmental regulations relating to substitu-
tion of solvent-based system by waterborne products.
In a scenario of reduction of margins, increasing competition, and public sensi-
tivity to environmental issues, emulsion polymer producers are forced to achieve
ecient production of high-quality materials in a consistent, safe, and environ-
mentally friendly way. Emulsion polymers are products-by-process whose main
properties are determined during polymerization. A critical point is to know how
these process variables aect the nal properties of the product. One possibility
is to consider the reactor as a black box and to develop empirical relationships
between process variables and product properties. Long-term success can only be
guaranteed by applying knowledge-based strategies that use the polymer micro-
structure (here, the term microstructure is used in a broad sense, including aspects
such as copolymer composition, molecular weight distribution (MWD), branching,
crosslinking, gel fraction, particle morphology, and particle size distribution (PSD)
of the dispersion) as a link between the reactor variables and the nal properties
(Figure 6.1).
The implementation of the approach illustrated in Figure 6.1 has important eco-
ISBN: 3-527-31014-2
249
nomic implications and is scientically challenging. On the one hand, the needs/
opportunities of the market, expressed as desired properties of the nal product,
should be translated in terms of the desired polymer microstructure. This requires
quantitative microstructure/properties relationships. On the other hand, this poly-
mer microstructure should be achieved in the reactor. This involves a deep under-
standing of the emulsion polymerization process, the highest level of under-
standing being the development of predictive mathematical models. In addition,
ecient, safe, and consistent production requires accurate on-line monitoring, op-
timization, and control. Last but not least, ecient methods for removal of residual
monomer and volatile organic compounds (VOCs) should be developed to produce
environmentally friendly products.
This chapter is focused on the challenge of achieving the ecient, safe, and
consistent production of emulsion polymers of the desired microstructure. First,
the main features of emulsion polymerization are discussed in Sections 6.2 and
6.3. Sections 6.46.7 are devoted to the understanding of the kinetics of the pro-
cess. Finally, the emulsion polymer reaction engineering is addressed in Sections
6.86.11.
6.2
Features of Emulsion Polymerization
6.2.1
Description of the Process
Table 6.1 presents a typical formulation for emulsion polymerization. The polymer
is mainly made out of a mixture of hard monomers (leading to polymers with a
high glass transition temperature, T
g
; for example, styrene) and soft monomers
(low T
g
; for example, butyl acrylate) of low solubility in water. In addition, small
amounts of functional monomers such as acrylic and methacrylic acids are in-
cluded in the formulation as they provide some special characteristics, such as im-
proved adhesion. Crosslinking agents and chain-transfer agents (CTAs) are used to
control the molecular weight distribution of the polymer.
Fig. 6.1. Polymer properties as a function of formulation and process type.
250 6 Emulsion Polymerization
Typically, emulsion polymerization is carried out in stirred-tank reactors, which
commonly operate in a semicontinuous mode, although both batch and continu-
ous operations are also used.
In a batch emulsion polymerization, the mixture of monomers is dispersed in
water using emulsiers. The monomer droplets are stabilized by the surfactant
adsorbed on their surface. In principle, any type of surfactant may be used, but in
practice anionic surfactants, nonionic surfactants, and mixtures thereof account for
the great majority of the systems used. The available surfactant partitions between
the surface of the monomer droplets and the aqueous phase; in most formula-
tions, the amount of surfactant exceeds that needed to completely cover the mono-
mer droplets and saturate the aqueous phase. The excess of surfactant forms
micelles that are swollen with monomer (Figure 6.2(a)).
Polymerization is commonly initiated by water-soluble initiators (both ther-
mal, for example, potassium persulfate, and redox, for example, tert-butyl
hydroperoxide/ascorbic acid) although oil-soluble initiators (for example, AIBN)
may also be used. When a water-soluble initiator such as potassium persulfate is
added to the monomer dispersion, radicals are formed and as these radicals are
too hydrophilic to enter the organic phases of the systems, they react with the
monomer dissolved in the aqueous phase, forming oligoradicals. The growth rate
of the oligoradicals is generally modest because of the low concentration of mono-
mer in the aqueous phase. After adding some monomer units, the oligoradicals be-
come hydrophobic enough to be able to enter the micelles (entry into the mono-
mer droplets is not likely because their total surface area is about three orders of
magnitude smaller than that of the micelles). Because of the high concentration
of monomer in the micelle, the oligoradical that has entered the micelle grows
Tab. 6.1. Typical formulation for emulsion polymerization.
Ingredient Content [wt.%]
Monomer(s)
styrene
methyl methacrylate
vinyl chloride
vinyl acetate
butadiene
butyl acrylate
2-ethylhexyl acrylate
Veova 10
ethylene
(meth)acrylic acid
crosslinking monomers
5055
Deionized water 45
Initiators 0.5
Emulsiers 0.53
Chain-transfer agents
fast, forming a polymer chain. The new species formed upon entry of a radical into
a micelle is considered to be a polymer particle. The process of formation of poly-
mer particles by entry of radicals into micelles is called heterogeneous nucleation
[5]. The oligoradicals that do not enter into micelles will continue growing in the
aqueous phase, and upon reaching some critical length they become too hydropho-
bic and precipitate. The emulsier present in the system will adsorb onto the
newly formed interface, thus stabilizing the polymer. Then, monomer will diuse
into the new polymer particle. The process of formation of polymer particles by
precipitation of oligoradicals is called homogeneous nucleation [6]. Both homoge-
Fig. 6.2. Intervals in the batch emulsion polymerization.
neous and heterogeneous nucleation may be operative in a given system. In gen-
eral, homogeneous nucleation is predominant for monomers of relatively high
water solubility (for example, methyl methacrylate 1.5 g/100 g of water and
vinyl acetate 2.5 g/100 g of water) and heterogeneous nucleation is predominant
for water-insoluble monomers (for example, styrene 0.045 g/100 g of water).
Irrespective of the mechanism of particle nucleation (heterogeneous or homoge-
neous) the newly formed particles are very small and suer a tremendous increase
in surface area upon particle growth. It is arguable that the emulsier molecules
may diuse fast enough to adsorb on the surface of these fast-growing particles,
stabilizing them [79]. Therefore, in the so-called mechanism of coagulative nucle-
ation, the species formed by entry of radicals into micelles and by precipitation of
growing radicals in the aqueous phase are considered to be precursor particles that
only become stable upon growth by coagulation and polymerization.
During nucleation, monomer droplets, monomer swollen micelles, and mono-
mer swollen polymer particles coexist in the reactor (Figure 6.2(b)). Polymer
particles compete eciently for radicals, and hence monomer is consumed by po-
lymerization inside the polymer particles. It is worth mentioning that polymeriza-
tion proceeds according to the same mechanisms as are discussed in Chapter 4 for
free-radical polymerization in homogeneous systems. The monomer that is con-
sumed by polymerization in the polymer particles is replaced by monomer that dif-
fuses from the monomer droplets through the aqueous phase. Therefore, the size
of the particles increases and that of the monomer droplets decreases. The number
of micelles decreases because they become polymer particles upon entry of a radi-
cal and also because they are destroyed to provide surfactant to stabilize the in-
creasing surface area of the growing polymer particles. After some time, all the
micelles disappear. This is considered to be the end of the nucleation; only limited
formation of new particles may occur after this point because heterogeneous nucle-
ation is not possible and there is no free surfactant available in the system to stabi-
lize the particles formed by homogeneous nucleation. The stage of the batch emul-
sion polymerization in which particle nucleation occurs is called Interval I. At the
end of Interval I, which typically occurs at a monomer conversion of about 510%
(depending on the surfactant/monomer ratio), 10
17
10
18
particles per liter are
formed. Unless coagulation occurs, the number of particles remains constant dur-
ing the rest of the process.
In Interval II, the system is composed of monomer droplets and polymer par-
ticles (Figure 6.2(c)). The monomer consumed by polymerization in the polymer
particles is replaced by monomer that diuses from the monomer droplets
through the aqueous phase. The mass-transfer rate of monomers with water solu-
bility equal or greater than that of styrene (0.045 g/100 g of water) is substantially
higher than the polymerization rate, and hence monomer partitions between the
dierent phases of the system according to the thermodynamic equilibrium.
Therefore, in the presence of monomer droplets, the concentration of the mono-
mer in the polymer particles reaches a maximum value. As discussed below (see
Section 6.4.1), this saturation value arises from the energy (interfacial tension)
needed to increase the surface area of the polymer particles upon swelling. Conse-
quently, the monomer concentration in the polymer particles is roughly constant
during Interval II. The transport of reactants (monomers, chain-transfer agents)
with water solubility lower than that of the styrene from monomer droplets to poly-
mer particles may be diusionally limited.
Because of the polymerization and monomer transport, the polymer particles
grow in size, and after some time the monomer droplets disappear. This marks
the end of Interval II. The monomer conversion at which Interval II ends depends
on the capability of the polymer particle to be swollen by monomer. The higher the
maximum swelling, the earlier the monomer droplets disappear. In general, the
more water-soluble the monomer, the higher the maximum swelling, and hence
the lower the monomer conversion at the end of Interval II. Thus, the transition
from Interval II to Interval III occurs at about 40% conversion for styrene and at
about 15% conversion for vinyl acetate. This means that most monomer polymer-
izes in Interval III (Figure 6.2(d)). In this interval, monomer concentration in the
polymer particles decreases continuously. The nal product is a waterborne, con-
centrated (5060 wt.% solids) dispersion of tiny (80500 nm in diameter) polymer
particles called latex.
In a semicontinuous reactor in which monomers, surfactant, initiator, and water
may be continuously fed into the reactor, emulsion polymerization does not follow
the sequence of events described above. Thus, slow monomer feed and fast surfac-
tant feed may lead to a system composed of polymer particles and micelles (Figure
6.3(a)). The system will contain only monomer-swollen polymer particles if both
monomer and surfactant are fed slowly (Figure 6.3(b)). On the other hand, a fast
monomer feed and a low surfactant feed will lead to a system containing monomer
droplets and polymer particles (Figure 6.3(c)).
6.2.2
Radical Compartmentalization
From a mechanistic point of view, the compartmentalization of radicals among a
huge number of polymer particles is likely to be the most distinctive feature of
emulsion polymerization. This refers to the fact that the radicals are distributed
among the dierent particles, and hence radicals in dierent particles cannot ter-
minate between them. Consequently, the overall concentration of radicals is higher
than in homogeneous (bulk and solution) free-radical polymerization, leading to a
higher polymerization rate. In addition, the compartmentalization of radicals in a
large number of particles results in a longer lifetime of the radicals, which leads to
higher molecular weights.
6.2.3
Advantages of Emulsion Polymerization
Free-radical polymerization is a very exothermic process, liable to suer thermal
runaways. Compared with bulk and solution polymerization, emulsion polymeriza-
tion is advantageous because the low viscosity of the latex allows high heat re-
moval rates. In addition, because of its high heat capacity, the water absorbs large
amounts of heat with only a moderate increase in temperature. This allows combi-
nation of high polymerization rates and good temperature control. Compared with
solution polymerization, emulsion polymerization is environmentally friendly, as
water is used as the reaction medium. In addition, the low viscosity of the system
allows easy removal of both unreacted monomer and VOCs. Because of the com-
partmentalization of the radicals, emulsion polymerization overcomes the limita-
Fig. 6.3. Species present in semicontinuous emulsion polymerization.
tions imposed by the kinetics of bulk and solution polymerization, and high poly-
merization rates and high molecular weights can be achieved simultaneously.
Some valuable products with applications in paper coating, leather treatment,
binders for nonwoven fabrics, additives for paper, textiles and construction ma-
terials, impact modiers for plastic matrices, and diagnostic tests and drug delivery
systems, can only be produced by emulsion polymerization. In addition, when
needed (for example, for rubber for tires) latexes are easy to process into dry poly-
mer. The main disadvantage of emulsion polymerization is that the product con-
tains emulsier and residues of initiator, which give it water sensitivity.
6.3
Alternative Polymerization Techniques
Dispersed polymers are also achieved by inverse emulsion polymerization, minie-
mulsion polymerization, dispersion polymerization, and microemulsion polymer-
ization. Inverse emulsion polymerization is used in the preparation of solvent-
based dispersions of polymers produced from water-soluble monomers. The
process is similar to conventional emulsion polymerization but the dispersed
phase is an aqueous solution of the monomer and the continuous phase is an or-
ganic solvent [10]. In miniemulsion polymerization [11], the size of the monomer
droplets is substantially reduced (d
d
= 501000 nm) by combining a suitable emul-
sier and an ecient emulsication apparatus, and stabilizing the resulting mono-
mer miniemulsion against diusional degradation by using a costabilizer (hydro-
phobic, low molecular weight compound). The available surfactant adsorbs on
the large surface area of the droplets, and hence no micelles are formed. When
the initiator is added to the system, the radicals enter the monomer droplets,
which become polymer particles. Droplet nucleation minimizes the diusional
limitations encountered in conventional emulsion polymerization and allows the
incorporation of water-insoluble compounds (monomers, polymers, catalysts, cata-
lytic chain-transfer agents, inorganic materials, agents for controlled radical poly-
merization) in the reaction loci. In the last few years, plenty of new applications
have been discovered. These applications include:
v
production of high-solids, low-viscosity latexes;
v
stable operation in continuous polymerization reactors;
v
controlled radical polymerization in dispersed media;
v
catalytic polymerization;
v
encapsulation of inorganic solids;
v
incorporation of hydrophobic monomers;
v
production of hybrid polymer particles;
v
miniemulsion polymerization in nonaqueous media;
v
anionic polymerization;
v
step polymerization in aqueous dispersed media;
v
production of low molecular weight polymers in dispersed media;
v
preparation of latexes with special particle morphology.
In dispersion polymerization [12], the monomers, the initiator and the stabilizer
(or stabilizer precursor) are dissolved in a solvent which is not a solvent for the
polymer (Figure 6.4(a)). Polymerization starts in a homogeneous phase and the
polymer is precipitated, forming unstable nuclei (Figure 6.4(b)). The nuclei are sta-
bilized by the stabilizer present in the system (Figure 6.4(c)). This stabilizer may be
included in the formulation or formed in the reactor by grafting onto the stabilizer
precursor (the case shown in Figure 6.4). Nucleation ends when the number of sta-
ble polymer particles increases to a point at which all new nuclei are captured by
the existing stable particles. Because of the compartmentalization of the radicals
among the polymer particles, the polymerization locus changes from the continu-
ous to the dispersed phase. Dispersion polymerization allows the production of
monodispersed micron-size particles, which are too large for emulsion polymeriza-
tion and too small for suspension polymerization.
Microemulsion polymerization [13] involves the polymerization of oil-in-water
and water-in-oil monomer microemulsions. Microemulsions are thermodynami-
cally stable and isotropic dispersions, whose stability is due to the very low in-
terfacial tension achieved using appropriate emulsiers. Particle nucleation occurs
upon entry of a radical into a microemulsion droplet. Microemulsion polymeriza-
tion allows the production of particles smaller than those obtained by emulsion po-
lymerization. This leads to a higher number of polymer particles, which results in
a more compartmentalized system. Under these conditions the lifetime of the poly-
mer chains increases, leading to ultra-high molecular weights.
Fig. 6.4. Dispersion polymerization.
6.3 Alternative Polymerization Techniques 257
6.4
Kinetics of Emulsion Polymerization
Conventional emulsion polymerization occurs in a three-phase system (polymer
particles, aqueous phase, and monomer droplets) and polymerization may, in prin-
ciple, occur in any phase. However, the concentrations of both monomer and radi-
cals in the polymer particles are much higher than those in the aqueous phase (see
below), and hence the extent of the polymerization in the aqueous phase is in most
cases negligible. On the other hand, the concentration of the radicals in the mono-
mer droplets is very low because the monomer droplets are not ecient at captur-
ing the radicals formed in the aqueous phase. The polymerization in the polymer
particles follows the same mechanisms as in bulk polymerization and the rate of
polymerization per polymer particle R
pp
is given by Eq. (1), where k
p
is the propa-
gation rate constant [m
3
mol
1
s
1
], [M[
p
the concentration of monomer in the
polymer particles [mol m
3
], n the average number of radicals per particle and N
A
Avogadros number.
R
pp
= k
p
[M[
p
n
N
A
(mol/particle s) (1)
The overall polymerization rate R
p
takes into account the existence of many poly-
mer particles in the system according to Eq. (2), where N
p
is the number of poly-
mer particles in the reactor, and V the volume of the reactor.
R
p
= k
p
[M[
p
n
N
A
N
p
V
(mol/m
3
s) (2)
Most emulsion polymerization processes involve several monomers. However,
there is considerable evidence that for many polymerization systems, propagation
depends on the nature of the monomer and on the last two units of the growing
chain [14]. The lack of available values for the large number of parameters involved
in this model makes it advisable to use simpler models, such as the terminal
model [15], in which polymerization is governed by the nature of the monomer
and the terminal unit of the growing chain. In this case, the polymerization rate
R
pi
of a given monomer is expressed as Eq. (3), where k
pji
is the propagation rate
constant of radicals with terminal unit j with monomer i [m
3
mol
1
s
1
], and P
j
the time-averaged probability of nding an active chain with ultimate unit of type j
that for a two-monomer system is given by Eq. (4) [16].
R
p
i
=
j
k
p
ji
P
j

[M
i
[
p
n
N
A
N
p
V
(mol/m
3
s) (3)
P
1
=
k
p21
[M
1
[
p
k
p21
[M
1
[
p
k
p12
[M
2
[
p
; P
2
= 1 P
1
(4)
In order to calculate the polymerization rate, [M
i
[
p
; n and N
p
should be available.
6.4.1
Monomer Partitioning
During Intervals I and II of a batch emulsion polymerization, monomers partition
among monomer droplets, aqueous phase, and polymer particles. The monomer
that is consumed by polymerization in the polymer particles is replaced by mono-
mer that diuses from the monomer droplets through the aqueous phase. In Inter-
val III, there are no droplets and the monomer is mostly located in the polymer
particles. In semibatch processes, monomers are continuously fed into the reac-
tor, usually under starved conditions, that is to say at high fractional conversions
(polymer/monomer ratios close to 90:10 (by weight). Under these circumstances,
only the newly fed monomer droplets are present in the reactor and the lifetime
of these droplets is short because the monomers diuse through the aqueous
phase to the polymer particles, where they are consumed by polymerization. The
concentration of monomer in the polymer particles depends on the relative values
of mass-transfer and polymerization rates. Except for poorly emulsied, highly
water-insoluble monomers, the rate of mass-transfer is faster than the polymeriza-
tion rate, and hence the concentrations of the monomers in the dierent phases
are given by the thermodynamic equilibrium.
The amount of monomer that can be absorbed in the polymer particles is limited
and the excess of monomer forms droplets. The limiting swelling of the polymer
particles is due to the contribution of the surface energy to the total free energy of
the system. Because of the interfacial tension, the surface energy increases as par-
ticles swell and, at some point, this compensates for the decrease in the free energy
due to the monomerpolymer mixing. From values of the maximum swelling for
homopolymerization [17] (Table 6.2) it can be seen that the higher the water solu-
bility of the monomer, the higher the equilibrium swelling. The swelling equilib-
rium depends on the particle size, but for particle sizes common in emulsion poly-
merization this eect is negligible [18, 19].
For a multimonomer system, the calculation of the concentrations of the
monomers in the dierent phases involves the simultaneous solution of the ther-
modynamic equilibrium equations and the material balances. Several equilibrium
equations may be used, those based on partition coecients [20] and on the
Tab. 6.2. Swelling equilibrium data for homopolymerization
[17].
Monomer f
p
M
[a]
Styrene 0.6
n-Butyl methacrylate 0.6
n-Butyl acrylate 0.65
Methyl methacrylate 0.73
Vinyl acetate 0.85
Methyl acrylate 0.85
[a]
f
p
M
= volume fraction of monomer in the polymer particles.
MortonFloryHuggins equation [21] being the most commonly applied. For a
multimonomer system, the parameters of the MortonFloryHuggins are not usu-
ally available, and it has been shown [22] that for solids contents typical of com-
mercial latexes (>50 wt.%) the use of the MortonFloryHuggins equation does
not provide signicant advantages over the use of partition coecients. In the lat-
ter case, the system of algebraic equations (5) and (6) needs to be solved, where K
j
i
is the partition coecient of monomer i between phase j and the aqueous phase,
f
j
i
the volume fraction of monomer i in phase j, f
w
w
the volume fraction of water in
the aqueous phase, f
p
p
the volume fraction of polymer in the polymer particles,
V
p
the volume of polymer particles, V
d
the volume of monomer droplets, V
w
the
volume of the aqueous phase, and V
i
; V
pol
, and W are the volumes of monomer i,
polymer, and water, respectively.
Equilibrium equations:
K
j
i
=
f
j
i
f
w
i
j = polymer particles; droplets (5)
Material balances:
f
p
p

i
f
p
i
= 1
f
w
w

i
f
w
i
= 1
i
f
d
i
= 1 (6)
V
p
f
p
i
V
d
f
d
i
V
w
f
w
i
= V
i
V
w
f
w
w
= W
V
p
f
p
p
= V
pol
Ecient methods for solving Eqs (5) and (6) are given elsewhere [19, 20].
6.4.2
Average Number of Radicals per Particle
The average number of radicals per particle n is given by Eq. (7).
n =
nN
n
N
n
(7)
Figure 6.5 illustrates the mechanisms controlling n. In most emulsion polymeriza-
tion systems, radicals are produced in the aqueous phase from thermal or redox
initiators. Often, these radicals are too hydrophilic and cannot directly enter the hy-
drophobic phases (polymer particles, monomer droplets, micelles). Therefore, they
must stay in the aqueous phase until they polymerize, thus adding a number of
monomer units and becoming hydrophobic enough to enter the organic phases.
As the concentration of monomer in the aqueous phase is low, the period needed
to reach the critical length for entry may be long and a substantial fraction of
the radicals may terminate in the aqueous phase, resulting in a low initiation e-
ciency. In conventional emulsion polymerization, the total area of the polymer par-
ticles is much larger than that of the monomer droplets; therefore most of the
radicals are captured by the polymer particles. There is some debate about the
mechanism for radical entry; diusional [23] and propagational [24]. The diu-
sional model is more general, whereas the propagational model is a simpler
approach applicable to many homopolymerizations. The rate of radical entry can
also be expressed as Eq. (8), where k
a
is the entry rate coecient [m
3
aqueous phase
mol
1
s
1
] and [R[
w
the concentration of radicals in the aqueous phase
[mol m
3
aqueous phase
].
Rate of entry = k
a
[R[
w
(radicals/particle s) (8)
Equation (8) is a simplication because it assumes that all radicals are able to enter
the polymer particles, but the radicals directly produced from inorganic initiators
are too hydrophilic to be able to enter a hydrophobic phase. On the other hand,
the radicals generated from radical desorption (see below) are hydrophobic and
able to enter the polymer particles regardless of their length.
Once inside the polymer particles, the radicals undergo the classical mecha-
Fig. 6.5. Processes controlling the average number of radicals per particle.
nisms of free-radical polymerization: propagation, termination, chain transfer, and
so on. Obviously, in order to suer a bimolecular termination reaction, the particle
should contain two or more radicals, as radicals in dierent particles cannot termi-
nate between them. The rate of termination in a particle with n radicals is given by
Eq. (9).
Rate of Termination =
2k
t
v
p
N
A
n(n 1) = 2cn(n 1)
radicals
particle s

(9)
One consequence of the compartmentalization of radicals in the particles is that
the overall concentration of radicals in the system is much greater than in solution
and bulk polymerization, and hence the polymerization rate is higher.
Chain-transfer reactions to monomers and chain-transfer agents lead to the for-
mation of small and mobile radicals that can exit the polymer particle. Radical de-
sorption leads to a decrease in the average number of radicals per particle. Equa-
tion (10), where k
d
is the rate coecient for radical exit [Eq. (11)] [25], gives the
rate of radical exit from a population of particles with an average number of radi-
cals per particle n. In Eq. (11), l is an overall mass-transfer rate coecient, g=h the
ratio between the rate of generation of small radicals by chain transfer and the rate
of consumption of these radicals (mostly by propagation), m the partition coe-
cient of the small radicals between the polymer particles and the aqueous phase,
[M[
w
the concentration of monomer in the aqueous phase, k
tw
the termination
rate constant in the aqueous phase, and [R[
w
the concentration of radicals in the
aqueous phase.
Rate of Exit = k
d
n (radicals/particle s) (10)
k
d
= l
gN
A
hm
1
lN
p
lN
p
k
p
[M[
w
2k
tw
[R[
w

(s
1
) (11)
The rate of radical exit from particles with n radicals is the product of k
d(n)
and n
[Eq. (12)], and k
d(n)
Rate of Exit = k
d(n)
n (radicals/particle s) (12)
k
d(n)
= l
gN
A
hm
1
lN
p
n
n
lN
p
k
p
[M[
w
2k
tw
[R[
w
(s
1
) (13)
In Eq. (13), the term n=n takes account of the fact that in particles with n radicals,
the desorption rate is proportional to n but the re-entry of newly desorbed small
radicals is proportional to n.
Because radical entry, exit, and termination are stochastic events, particles have a
dierent number of radicals and the number of radicals in a given particle varies
stochastically with time. Equation (14) gives the population balance of particles
with n radicals; it includes the concentration of radicals in the aqueous phase, and
hence the material balance for these radicals is needed from Eq. (15), where f is
the eciency factor of the initiator radicals, k
I
the rate coecient for initiator de-
composition [s
1
], [I] the concentration of the thermal initiator in the aqueous
phase [mol m
3
aqueous phase
], and k
tw
the termination rate in the aqueous phase
[m
3
aqueous phase
mol
1
s
1
].
dN
n
dt
= k
a
[R[
w
N
n1
k
d(n1)
(n 1)N
n1
c(n 2)(n 1)N
n2
(k
a
[R[
w
N
n
k
d(n)
nN
n
cn(n 1)N
n
)
n = 0; 1; 2; 3 . . . (particles/s) (14)
d[R[
w
dt
= 2f k
I
[I[ k
d
n
N
p
N
A
V
w
2k
tw
[R[
2
w
k
a
[R[
w
N
p
N
A
V
w
(mol/m
3
aqueous phase
s) (15)
For most practical cases, the pseudo steady-state assumption can be applied to the
radicals in the polymer particles and in the aqueous phase. Therefore, Eqs. (14)
and (15) are converted into algebraic equations by making the left-hand sides equal
to zero. The exact solution for n, under pseudo steady-state conditions, has been
given in terms of Bessel functions [26], but their use is not friendly. A simpler
and still accurate equation for n is Eq. (16), with C dened in Eq. (17). [27].
n =
2k
a
[R[
w
k
d
(k
2
d
4k
a
[R[
w
Cc)
0:5
(16)
C =
2(2k
a
[R[
w
k
d
)
2k
a
[R[
w
k
d
c
(17)
Equations (16) and (17) should be solved together with Eq. (15). The solution of
this system of algebraic equations includes the three limiting cases of the pioneer-
ing work of Smith and Ewart [28]. When the exit rate of radicals is zero (k
d
= 0)
and the termination of the entering radical and that existing in the polymer parti-
cle is instantaneous, the average number of radicals per particle is n = 0:5. This is
known as SmithEwart Case 2 and corresponds to systems in which (1) there is no
chain transfer to small molecules (that is, monomers and CTAs) or these small
molecules are highly water insoluble, and (2) the polymer particles are relatively
small (typically d
p
< 200 nm). Because for SmithEwart Case 2 n is constant, the
polymerization rate is directly proportional to the number of polymer particles.
In systems in which the entry rate per particle is limited and the rate of radical
desorption is relatively high (large k
d
), n f0:5. This is known as SmithEwart
Case 1 and corresponds to systems with (1) relatively water-soluble monomers or
relatively water-soluble CTAs, (2) small particles (d
p
< 100 nm), (3) a low rate of
generation of radicals from the initiator, and (4) a large number of particles. Under
these circumstances, n can be easily calculated by means of Eq. (18).
n =
k
a
[R[
w
2k
a
[R[
w
k
d
(18)
Under SmithEwart Case 1 conditions, for a given solids content and if termina-
tion in the aqueous phase is negligible, n o1=N
p
. Therefore, the polymerization
rate is independent of the number of polymer particles. If termination in the aque-
ous phase is signicant, the polymerization rate increases with the number of poly-
mer particles.
For large particles (d
p
> 200 nm), high initiator concentrations or redox initia-
tors, and slow termination rates (gel eect), n g0:5 (SmithEwart Case 3) and n
can be calculated as follows:
n =
k
a
[R[
w
2c

0:5
(19)
For a given solids content under SmithEwart Case 3 kinetics, n is inversely pro-
portional to the number of polymer particles, and hence the polymerization rate
is independent of the number of polymer particles if aqueous-phase termination
is negligible. Otherwise, the polymerization rate increases with N
p
.
6.4.3
Number of Polymer Particles
Particle nucleation may occur through heterogeneous nucleation, homogeneous
nucleation, and coagulative nucleation (Figure 6.6). The rate of particle generation
depends on the mechanism considered.
6.4.3.1 Heterogeneous Nucleation
The rate of formation of polymer particles by heterogeneous nucleation is ex-
pressed by Eq. (20), where R
nuc
is the nucleation rate, k
am
the rate coecient for
radical entry into the micelles, and N
m
the number of micelles in the reactor given
by Eq. (21).
1
V
dN
p
dt
= R
nuc
= k
am
[R[
w
N
m
V
(particles/m
3
s) (20)
N
m
=
(S
w
CMCV
w
)N
A
n
m
(micelles) (21)
In Eq. (21), CMC is the critical micellar concentration [mol m
3
aqueous phase
] and
hence CMC V
w
is the amount of surfactant dissolved in the aqueous phase; n
m
is the aggregation number (average number of molecules of surfactant per mi-
celle); and S
w
[mol] is the amount of surfactant that is in the aqueous phase form-
ing micelles and dissolved in such a phase. S
w
can be calculated by means of the
overall material balance for the surfactant, Eq. (22), where S
T
[mol] is the total
amount of surfactant in the reactor, a
s
[m
2
mol
1
] the parking area that is, the
area of the saturated surface of the polymer particles covered by 1 mol of surfactant
and A
p
[m
2
] the total surface area of the polymer particles given by Eq. (23).
S
w
= S
T

A
p
a
s
(22)
A
p
= 4:83N
0:33
p
V
pol
f
p
p

0:66
(23)
Fig. 6.6. Particle nucleation mechanisms in emulsion polymerization.
Assuming no termination of radicals in the aqueous phase and that during nucle-
ation n = 0:5, Smith and Ewart [28] solved Eqs. (20)(23), obtaining Eq. (24) for
the dependence of the number of particles on surfactant and initiator concentra-
tions, where r
v
[m
3
s
1
] is the volumetric growth rate of one polymer particle.
N
p
V
w

o
2f k
I
[I[N
A
f
p
p
r
v
0:4
a
s
S
T
V
w

0:6
(24)
The fulllment of this equation, in particular the 0.6th power dependence of N
p
with respect S
T
, is often considered as a proof of the occurrence of micellar nucle-
ation. However, one should be aware of the assumptions used in the derivation of
Eq. (24). Actually, when radical desorption is taken into account, the solution of
Eqs (20)(23) leads to Eq. (25) [29, 30], where z approaches unity as the water
solubility of the monomer increases.
N
p
V
w

o
2f k
I
[I[N
A
f
p
p
r
v
1z
a
s
S
T
V
w

z
0:6 az a1 (25)
6.4.3.2 Homogeneous Nucleation
In homogeneous nucleation, particles are formed by precipitation of the growing
oligoradicals once they exceed the critical length that makes them insoluble in
water. The water solubility of the oligoradicals depends on their composition. In
this context, the critical length of the oligoradicals formed from an inorganic
water-soluble initiator such as potassium persulfate (that is, one containing an
inorganic fragment) will be longer than that of the oligoradicals formed from
desorbed radicals that are much more hydrophobic. Therefore, the rate of forma-
tion of particles by homogeneous nucleation, R
nuc
, is the rate of polymerization of
oligoradicals of critical length as expressed by Eq. (26), where [M[
w
is the concen-
tration of monomer in the aqueous phase, and R
jcrit
and M
icrit
are the number of
oligoradicals of critical length (with j
crit
> i
crit
) formed from the initiator and from
desorbed radicals, respectively.
R
nuc
= k
p
[M[
w
(R
jcrit
M
icrit
)
V
(particles/m
3
s) (26)
R
jcrit
and M
icrit
are calculated from the balances of radicals of type R and M in the
aqueous phase assuming that pseudo steady-state conditions apply [Eqs. (27) and
(28)].
R
jcrit
= a
jcritd1
1
a
d1
2
2f k
I
IN
A
k
p
[M[
w
(radicals) (27)
M
icrit
=
k
d
nN
p
k
p
[M[
w
a
icrit
1
(radicals) (28)
In these equations, d is the critical length for entry of radicals generated from the
initiator, a
1
is the probability of propagation of radicals able to enter the polymer
particles (generated from desorbed radicals, and from the initiator, with lengths
equal or greater than d) and a
2
the probability of propagation of radicals generated
from the initiator, with length smaller than d).
These probabilities are given by Eqs. (29) and (30).
a
1
=
k
p
[M[
w
k
p
[M[
w
2k
tw
[R[
w
k
a
N
p
N
A
V
w
k
am
N
m
N
A
V
w
(29)
a
2
=
k
p
[M[
w
k
p
[M[
w
2k
tw
[R[
w
(30)
6.4.3.3 Simultaneous Heterogeneous and Homogeneous Nucleation
In systems including rather water-soluble monomers and surfactant concentra-
tions high enough for micelles to be present, particle nucleation may be formed
by both heterogeneous and homogeneous mechanisms. In this case, the overall
nucleation rate is given by Eq. (31).
R
nuc
= [k
am
[R[
w
N
m
k
p
[M[
w
(R
jcrit
M
icrit
)[
1
V

(particles/m
3
s) (31)
6.4.3.4 Coagulative Nucleation
In this mechanism, the species formed by entry of radicals into micelles and
by self-precipitation of radicals are considered nonstable precursor particles. The
actual particles are formed by coagulation and polymerization growth. The detailed
modeling of coagulative nucleation is rather complex [31, 32]. A simplied model
can be derived by considering that the precursor particles disappear by mutual co-
agulation, that they are captured by the existing polymer particles, and that the rate
of nucleation of mature particles is proportional to a k
4
th power of the precursor
concentration [Eqs. (32) and (33), where k
1
; k
2
; k
3
, and k
4
are adjustable parameters
that depend on the type and amount of surfactant] [33].
dN
pr
dt
= k
am
[R[
w
N
m
k
p
[M[
w
(R
jcrit
M
icrit
) k
1
N
pr
N
p
V
k
2
N
2
pr
V
(32)
R
nuc
= k
3
N
pr
V

k4
(33)
6.5
Molecular Weights
The molecular weight distribution of the polymer has a profound eect on its nal
properties [34, 35]. Emulsion polymerization is a compartmentalized system in
which dierent particles may have a dierent number of radicals. In addition, the
number of radicals in a given particle varies with time. Therefore, the length of the
macromolecules formed in a given particle depends on the number of radicals in
the particle at the moment in which the macromolecule was formed. Furthermore,
the architecture of the polymer formed depends on both the formulation and the
kinetics of the process. Thus, for monofunctional monomers with a polymeriza-
tion scheme that does not include chain transfer to polymer, linear polymers are
obtained. On the other hand, branched and crosslinked polymers are obtained
when multifunctional monomers are included in the formulation and when chain
transfer to polymer is operative.
Mathematical models for the calculation of the molecular weight distribution of
linear [36] and nonlinear [3740] polymers are available, but a detailed discussion
of this issue is out of the scope of the present chapter. Instead, some simplied
equations for the calculation of the molecular weights of linear polymers in the
limiting cases of Smith and Ewart [28] will be presented.
6.5.1
Linear Polymers
As discussed above, the MWD depends on the number of radicals per particle.
Smith and Ewart [28] distinguished three limiting cases: In Case 1 n f0:5; in
Case 2 n = 0:5; and in Case 3 n g0:5. In Cases 1 and 2, the probability of having
particles with more than one radical is almost negligible, and hence the system
may be considered to be formed by particles with no radicals and particles with
one radical (zeroone system). In Case 3, the average number of radicals is large
and the kinetics is close to bulk polymerization.
6.5.1.1 ZeroOne System (SmithEwart Cases 1 and 2)
In a zeroone system, the inactive polymer chains are formed in particles contain-
ing one radical by chain transfer to monomer and by instantaneous termination
upon entry of one radical.
The balance for inactive chains of length m in particles with one radical (N
1
) is
given by Eq. (34), where R
m
is the total number of radicals of length m in particles
N
1
.
dM
m
dt
= k
tr; M
[M[
p
R
m
k
a
[R[
w
R
m
m = 1; 2; 3; . . . (macromolecules/s) (34)
Integration of Eq. (34) allows calculation of the whole molecular weight distribu-
tion. However, this is computationally demanding and often the MWD is repre-
sented in terms of the moments of the distribution, the kth-order moment of the
distribution being dened by Eq. (35).
n
k
=
y
m=1
m
k
M
m
(35)
Combination of Eqs. (34) and (35) yields Eq. (36), where R
uk
is the generation rate
of the kth-order moment of the distribution of inactive chains and m
k
is the kth-
order moment of the distribution of active chains.
R
uk
= (k
tr; M
[M[
p
k
a
[R[
w
)
m
k
V
(36)
The balance for active chains of length m in particles with one radical (N
1
) is ob-
tained from Eq. (37).
dR
m
dt
= k
a
[R[
w
N
0
k
tr; M
[M[
p
R
m
k
d
N
1

d
m=1
k
p
[M[
p
(R
m1
R
m
)
k
tr; M
[M[
p
R
m
k
a
[R[
w
R
m
= 0 (37)
The rst moments of the distribution of active polymer chains can be calculated
from Eq. (37) by applying the pseudo steady-state assumption to the active chains
[Eqs. (38)].
m
0
=
R
m
= N
1
= nN
p
m
1
=
k
a
[R[
w
N
0
(k
tr; M
[M[
p
k
p
[M[
p
k
d
)N
1
k
a
[R[
w
k
tr; M
[M[
p
(38)
m
2
= m
1
1
2k
p
[M[
p
k
a
[R[
w
k
tr; M
[M[
p

The cumulative number-(M
n
) and weight-(M
w
) average molecular weights can be
calculated from the moments of the MWD by means of Eqs. (39), where P
M
is the
average molecular weight of the repeating unit in the polymer chain.
M
n
=
n
1
n
0
P
M
; M
w
=
n
2
n
1
P
M
(39)
On some occasions, it is interesting to know the average molecular weights pro-
duced at a given moment in the process. These instantaneous average molecular
weights can be calculated by means of Eqs. (40).
M
ni
=
R
v1
R
v0
P
M
; M
wi
=
R
v2
R
v1
P
M
(40)
Combination of Eqs. (36), (38), and (40) yields Eqs. (41).
M
ni
=
m
1
m
0
P
M
=
k
a
[R[
w
N
0
(k
tr; M
[M[
p
k
p
[M[
p
k
d
)
k
a
[R[
w
k
tr; M
[M[
p
P
M
A
k
p
[M[
p
k
a
[R[
w
k
tr; M
[M[
p
P
M
(41)
M
wi
=
m
2
m
1
P
M
= 1
2k
p
[M[
p
k
a
[R[
w
k
tr; M
[M[
p
P
M
A2M
ni
For the SmithEwart Case 2, k
a
[R[
w
gk
tr; M
[M[
p
and then Eq. (42) holds.
M
ni
A
k
p
[M[
p
k
a
[R[
w
P
M
(42)
If radical termination in the aqueous phase is negligible, from Eq. (15) we obtain
Eq. (43) and hence Eq. (44).
k
a
[R[
w
= 2f k
I
[I[
N
A
V
w
N
p
(43)
M
ni
A
k
p
[M[
p
2f k
I
[I[N
A
N
p
P
M
V
w
(44)
Consequently the molecular weight, as well as the polymerization rate, increases
with the number of polymer particles, and hence it is possible to increase both R
p
and the molecular weights at the same time by conveniently adjusting the formu-
lation to increase the number of polymer particles. This is a specic feature of
emulsion polymerization that cannot be achieved in any homogeneous (bulk or so-
lution) free-radical polymerization.
For the SmithEwart Case 1, k
tr; M
[M[
p
gk
a
[R[
w
and then Eq. (45) applies.
M
ni
A
k
p
k
tr; M
P
M
(45)
Therefore the molecular weights are controlled by chain-transfer reactions and are
independent of N
p
.
6.5.1.2 Pseudo Bulk System (SmithEwart Case 3)
For SmithEwart Case 3, the number of radicals per particle is large and the kinet-
ics approaches bulk polymerization. In this case, the concentration of radicals in
the polymer particles is given by Eq. (19) and the molecular weight is mainly con-
trolled by chain transfer and bimolecular termination. The rate of generation of
polymer of length m in particles with i radicals is given by Eq. (46).
dM
i
m
dt
= k
tr; M
[M[
p
R
i
m
2c
d
(i 1)R
i
m

c
c
iN
i
(i 1)
n1
k=1
R
i
k
R
i
mk
(macromolecules/s)
(46)
From Eq. (46) the moments of the inactive chains can be calculated according to
Eqs. (47), and the moments of the active chains can be calculated by applying the
pseudo steady state in the material balance of the active radicals [Eqs. (48) and
(49)].
R
n0
= (2c
d
c
c
)
m
2
0
N
p
V
k
tr; M
[M[
p
m
0
V
R
n1
= (2c
d
2c
c
)
m
0
m
1
N
p
V
k
tr; M
[M[
p
m
1
V
(47)
R
n2
= (2c
d
2c
c
)
m
0
m
2
N
p
V
2c
c
m
2
1
N
p
V
k
tr; M
[M[
p
m
2
V
dR
m
dt
= k
a
[R[
w
N
p
k
tr; M
[M[
p
R
m

d
m=1
k
p
[M[
p
(R
m1
R
m
)
k
tr; M
[M[
p
R
m
2
(c
c
c
d
)
N
p
R
m
R
m
= 0 (48)
m
0
=
R
m
= nN
p
=
k
a
[R[
w
N
2
p
2c
d
2c
c

1=2
m
1
=
k
a
[R[
w
N
p
k
p
[M[
p
m
0
k
tr; M
[M[
p
m
0
(2c
d
2c
c
)
m
0
N
p
k
tr; M
[M[
p
A
k
p
[M[
p
m
0
(2c
d
2c
c
)
m
0
N
p
k
tr; M
[M[
p
(49)
m
2
=
k
a
[R[
w
N
p
k
p
[M[
p
(2m
1
m
0
) k
tr; M
[M[
p
m
0
(2c
d
2c
c
)
m
0
N
p
k
tr; M
[M[
p
A
2k
p
[M[
p
m
1
(2c
d
2c
c
)
m
0
N
p
k
tr; M
[M[
p
The instantaneous number and weight-average molecular weights are then given
by Eqs. (50).
M
ni
=
k
p
[M[
p
(2c
d
c
c
)
m
0
N
p
k
tr; M
[M[
p
P
M
(50)
M
wi
=
(2c
d
2c
c
)
m
0
m
2
N
p
2c
c
m
2
1
N
p
k
tr; M
[M[
p
m
2
(2c
d
2c
c
)
m
0
m
1
N
p
k
tr; M
[M[
p
m
1
P
M
If bimolecular termination is predominant, then the instantaneous average molec-
ular weights reduce to Eqs. (51).
M
ni
=
k
p
[M[
p
N
p
(2c
d
c
c
)m
0
P
M
(51)
M
wi
=
m
2
m
1
c
c
m
1
(c
d
c
c
)m
0

P
M
AM
ni
2c
d
c
c
c
d
c
c

1
c
c
2(c
d
c
c
)

P
M
Therefore:
M
wi
= 2M
ni
if bimolecular termination is only by disproportionation; and
M
wi
=
3
2
M
ni
if bimolecular termination is only by combination:
Because for a given polymer content c
c
and c
d
are proportional to N
p
, the molecular
weights are independent of the number of particles.
On the other hand, if chain-transfer reactions are predominant over bimolecular
termination, the instantaneous molecular weights are given by Eqs. (52).
M
ni
=
k
p
k
tr; M
P
M
(52)
M
wi
= 2M
ni
For this case, the molecular weights are also independent of N
p
and depend only
on the ratio k
p
=k
tr; M
, and polydispersity is equal to 2.
6.5.2
Nonlinear Polymers: Branching, Crosslinking, and Gel Formation
In contrast to linear polymers, which, once they are formed, preserve their struc-
ture (molecular size) during the rest of the process, the molecular weight of the
nonlinear polymers evolves throughout the whole process because they may be-
come active and inactive several times during that process. Thus, inactive non-
linear chains formed earlier in the process may become active through either a
chain-transfer reaction to polymer or a propagation to pendent double bonds, fur-
ther polymerizing and modifying their structure. The microstructure of these non-
linear polymers is more complex than that of linear polymers, and besides the
MWD of the polymer, other properties such as the level of branching and cross-
linking density are required to fully characterize the polymer. In addition, large
polymer networks (gel) are formed in some cases.
The accurate calculation of the structure of these nonlinear polymers is not an
easy task in homogeneous systems [41, 42], and it is even more complex in emul-
sion polymerization, because of the compartmentalized nature of the system. Nev-
ertheless, some solutions have been reported [3740, 4346]. The discussion of
these approaches is outside the scope of this chapter.
Branches are formed by chain transfer to polymer (either intermolecular or in-
tramolecular) or by propagation to pendent double bonds (PDBs). Terminal double
bonds may be formed by chain transfer to monomer, termination by dispropor-
tionation, and b-scission at relatively high temperatures. PDBs may also be pres-
ent if multifunctional monomers are used in the formulation. Intermolecular
chain transfer to polymer and propagation to PDBs produces long-chain branches
(LCBs), and intramolecular chain transfer to polymer, so-called backbiting, pro-
duces short-chain branches (SCBs). Chain transfer to polymer occurs through hy-
drogen abstraction either from the backbone or from a side group.
A crosslink point is a tetrafunctional unit that links two polymer chains, namely
an H-shaped structure. The mechanisms leading to tetrafunctional units are:
v
intermolecular chain transfer to polymer followed by bimolecular termination by
combination of branched radicals, or
v
propagation of a growing branched radical on a terminal or pendent double
bond, or
v
polymerization of formulations including multifunctional monomers (often
called crosslinkers).
In the free-radical polymerization of vinylic monomers, gel is formed if the follow-
ing conditions are fullled: (1) a mechanism leading to LCBs is operative, for ex-
ample chain transfer to polymer, and (2) a mechanism that links polymer chains
is also operative, for example termination by combination or propagation to pen-
dent double bonds. Obviously, if multifunctional monomers are homopolymerized
or copolymerized with vinylic monomers, gel is also formed. In this case, the pre-
dominant reaction linking polymer chains and leading to polymeric networks is
the propagation to pendent double bonds of the multifunctional monomers.
Under these circumstances, polymer chains of increasing density of branching
and crosslinking are formed and their molecular weight will rapidly increase, lead-
ing to the formation of gel polymer.
6.6
Particle Morphology
Latexes made out of composite polymer particles, that is, particles containing dif-
ferent phases, present denitive advantages in many applications. Thus, particles
formed by an elastic core and a hard shell are used as impact modiers for poly-
mer matrices. Hard coresoft shell particles are particularly useful for paints be-
cause they have a low minimum lm formation temperature and are not sticky at
higher temperatures. Hollow particles are ecient opaciers, and hybrid polymer
polymer particles, such as epoxyacrylic polymer particles, combine the properties
6.6 Particle Morphology 273
of the constituent polymers in a synergetic way. The properties of these materials
largely depend on the particle morphology.
Figure 6.7 illustrates the processes occurring during formation of the particle
morphology during seeded semicontinuous emulsion polymerization. The reactor
is initially charged with previously formed latex (seed). Then, the new monomer is
fed into the reactor and the conditions are adjusted so that polymerization occurs
inside the existing polymer particles. The position at which each polymer chain is
formed depends on the radical concentration prole inside the polymer particles. If
the entering radicals are anchored to the surface of the polymer particle, the new
polymer chains will be mainly located in the outer layer of the particle. As the con-
centration of the newly formed polymer chains increases, phase separation occurs,
leading to the formation of clusters. Polymerization occurs in the clusters as well
as in the polymer matrix, and therefore both the size and the number of clusters
increase. The resulting system is not thermodynamically stable because of the high
surface energy associated with the large polymerpolymer interfacial area. In order
to minimize the free energy, the clusters migrate toward the equilibrium morphol-
ogy. During this migration, the size of the clusters may vary because of (1) poly-
merization in the cluster, (2) diusion of polymer into or from the cluster, and (3)
coagulation with other clusters. The motion of the clusters is ruled by the balance
between the van der Waals attraction/repulsion forces and the resistance to ow
that arises from the viscous drag. The van der Waals forces between clusters are
always attractive. On the other hand, the van der Waals forces between clusters
and the aqueous phase may be either attractive, bringing the clusters toward the
surface of the particle, and repulsive, bringing the clusters toward the center of
the polymer particle. It is worth mentioning that the van der Waals forces are pro-
Fig. 6.7. Development of particle morphology.
portional to the interfacial tensions. The nal morphology heavily depends on the
kinetics of cluster migration [4749]. Metastable morphologies can be achieved by
working under starved conditions (high internal viscosity of the particles) and pro-
moting grafting reactions (low interfacial tensions). Equilibrium morphologies
may be attained if the internal viscosity of the particle is low, and if the polymers
are very incompatible (high interfacial tensions resulting in high van der Waals
forces). The equilibrium morphology is the one that minimizes the interfacial en-
ergy of the system; it depends on the polymerpolymer and polymerwater inter-
facial tensions [47].
6.7
Living Polymerization in Emulsion
Free-radical polymerization (FRP) is a widespread technique for preparing long-
chain polymers (see Chapter 4). Its success is mainly due to the broad range of
monomers that can be readily polymerized by this technique, to its tolerance to-
ward functional monomers, and to the mild reaction conditions required to run
the polymerization. Moreover, as discussed in the preceding sections in this chap-
ter, emulsion polymerization (and in general every polymerization reaction carried
out using water as the continuous medium) has alleviated all the residual incon-
veniences of FRP. In fact, the corresponding processes do not involve a large de-
mand for organic solvents, they easily achieve large monomer conversions, and
they exhibit reduced problems of heat removal, thus making the process intrinsi-
cally safer.
On the other hand, careful control of the polymer microstructure (in the broad
sense dened in Section 6.1) is still an issue. With reference to the macromolecule
structure (that is, average molecular weight, polydispersity, composition, monomer
sequences, chain architecture, degree of crosslinking, and chain-end functionaliza-
tion), a novel process has recently been proposed with much greater potential in
terms of control capacity: living radical polymerization (LRP). By this specic
process it becomes possible to obtain block copolymers by FRP, lling the gap be-
tween the free-radical polymerization technique and other polymerization techni-
ques such as living anionic or cationic polymerization.
6.7.1
Chemistry of LRP
In conventional FRP, termination mainly by bimolecular combination limits the
chain lifetime to a small fraction of the entire process time. Therefore, changes in
the operating conditions (such as monomer concentration and composition, viscos-
ity, temperature, and so on) aect the structure of the polymer chains produced at
dierent stages of the process, thus increasing the product heterogeneity. In a liv-
ing polymerization, instead, these changes are equally distributed among all the
polymer chains, which grow uniformly during the whole reaction. Moreover, as
the living chains are still able to restart propagating when the monomer is com-
pletely depleted, living polymerization represents a route to the production of block
copolymers by successive additions of monomers, an approach clearly not possible
in FRP.
So far, the only living processes industrially available are anionic and cationic
polymerization [50, 51], which generally suer little or no termination. In these
processes, the initiation step is very fast compared to the process time and, hence,
all the chains start growing almost simultaneously. The degree of polymerization,
DP, increases linearly with monomer conversion and is inversely proportional to
the initiator concentration. At the same time, Poisson-like distributions of the poly-
mer chain length are obtained with nal polydispersity values close to the ideal
value of (1 1/DP). Finally, the polymer retains the ionic end groups till the end
of the polymerization and the reaction is simply restarted by further addition of
monomer. However, this kind of polymerization is often impractical from the in-
dustrial viewpoint, since the main requirements are high purity of all the reactants,
very low temperatures, and the use of solvents. Moreover, it does not work with
several widely used monomers, such as styrene.
On the other hand, as previously pointed out, FRP does not suer the same lim-
itations. It can be applied to a broad range of monomers, nearly all vinyl and vinyl-
idene monomers, it is easily operated in the presence of impurities, such as resid-
ual inhibitor residues and traces of oxygen, and over a wide temperature range [52,
53]. Therefore, it is quite natural to attempt to establish living conditions in such a
process. However, it is not practical to approach such conditions by simply reduc-
ing the radical concentration so as to minimize the rate of bimolecular termination
(a second-order reaction with respect to radical concentration, the propagation be-
ing a rst order reaction). Besides the drawback of the corresponding reduction of
the polymerization rate, this would lead to the production of polymer chains with
extremely high molecular weight, since the instantaneous DP is given by the ratio
between the frequencies of propagation and termination (compare Chapter 4). Us-
ing LRP, this control is instead restored by introducing an additional but reversible
termination reaction with a capping species, generically indicated as X. In this
case, each chain experiences a sequence of activationdeactivation steps and the in-
stantaneous DP grown during the generic active step is given by the ratio between
the rates of propagation and reversible termination (k
p
[M[=k
+
t
[X[, where k
+
t
indi-
cates the rate constant of the reversible termination). If the rate of this new termi-
nation is so large as to be dominant with respect to that of the irreversible termina-
tion reactions and comparable with that of propagation, polymer growth will be
distributed all over the process.
Living polymerization is typically started by introducing into the system an ini-
tiator providing the capping species, indicated as RX. This initiator reactivates it-
self many times and adds some monomer units before going back to the so-called
dormant state in the form R(M)
n
X, where (M)
n
indicates a polymer chain made
of n monomer units. In other words, the living process can be regarded as the in-
sertion of a well-dened number of monomer units between the groups R and X,
which are always acting as polymer chain ends and, thus, dened a priori. The av-
erage DP of the polymer is given by the ratio between the converted monomer,
M
0
X
T
(where X
T
is the monomer conversion and M
0
the initial amount of mono-
mer), and the total number of polymer chains. Note that some irreversibly termi-
nated chains are produced anyhow, since these reactions are always taking place in
competition with the activation/deactivation reactions. If the fraction of terminated
chains remains negligible compared to the initial amount of initiator, RX, this last
value corresponds also to the concentration of the dormant chains in the system
and the DP grows linearly with conversion (DP = M
0
X
T
=RX). Moreover, if the
number of active periods each chain experiences is large enough (that is, if the
number of monomer units added per active period is small enough), the polymer
growth is distributed throughout the duration of the process and all the chains
grow uniformly, leading to low polydispersity of the chain length distributions.
Dierent living mechanisms are available and the main ones are briey enumer-
ated in the following sections.
6.7.1.1 Nitroxide-mediated Polymerization (NMP)
The ability of stable nitroxide radicals to react with carbon-centered radicals and
to act as radical inhibitors was already known at the beginning of the 1980s [54],
when Solomon and co-workers showed that the reversible reaction of nitroxides
with growing polymer chains can be used to produce low-DP polymers [55]. But
it is only in the 1990s with the work of Georges and co-workers [56, 57] that this
novel polymerization technique, and in general LRP, received the attention they
deserved.
This living mechanism [Eq. (a)] consists of the reversible combination of the
growing radical chains, R
n
, and the so-called persistent radical species, X (the ni-
troxide radical group), to form dormant polymer chains, R
n
X:
R
n
X S
k
de
kac
R
n
X (a)
Today, many dierent routes are known which use dierent persistent radicals
[5458]. Among these, TEMPO is by far the most widely used, even though it suf-
fers very limited applicability to monomers unlike styrene, and requires high oper-
ating temperatures (about 120140
C). More recent studies were aimed to reduce

the operating temperature and to broaden the monomer applicability so as to en-
large the spectrum of block copolymers accessible by this technique [58]. Despite
these eorts, the range of application remains quite limited.
6.7.1.2 Atom-transfer Radical Polymerization (ATRP)
Atom-transfer radical polymerization (ATRP) was rst reported by Kato et al. [59]
and by Wang et al. in 1995 [60, 61]. This mechanism is based on the so-called
atom-transfer radical addition reaction, and it is catalyzed by a metal: the homolytic
cleavage of the bond in an organic halide occurs through transfer of the halogen to
the metal complex, accompanied by oxidation of the metal atom. The catalytic cycle
is closed by back-transfer from the transition metal to the nal adduct of the halo-
gen. It is clear that, if the radical produced can undergo a few propagation steps
before participating in the back-transfer, and if this product is still able to undergo
another transfer cycle, this reaction can be used to produce the same exchange be-
tween active and dormant states as is found in NMP. The resulting reversible reac-
tion is represented by Eq. (b), where X indicates the halogen atom, Me
(n)
the metal
with the corresponding oxidation state and Li the ligand.
R
n
XMe
(n1)
=Li S
k
de
kac
R
n
X Me
(n)
=Li (b)
ATRP owes most of its success to its high compatibility with many dierent mono-
mers, such as styrene, acrylates, methacrylates, (meth)acrylamides, and acryloni-
trile, which made this technique readily available for the production of several
new block copolymers [62]. Even though the majority of the work has been done
with copper as the transition metal, styrene ATRP has been carried out using Fe-,
Ru-, Ni-, Pd-, and Co-based systems [62]. Note that ATRP does not require the high
reaction temperature typical of NMP and this is also part of the success of this
polymerization technique. Dierent ligands have been used to solubilize the cop-
per atom and it has been noticed that they not only prepare the copper for the re-
action, but can also modify the reactivity of the metal toward both the activation
and deactivation reactions. Actually, the presence in the system of a metal, the
need for complex ligands to solubilize it, and the deep color typically imparted by
this complex to the nal polymer (if not removed) represent the major drawbacks
of this process. Thus far, chlorine and bromine have been used successfully as the
halogen atoms, whereas iodine gives rise to side reactions [63].
6.7.1.3 Degenerative Transfer (DT)
As mentioned above, in both NMP and ATRP the exchange between the active and
the dormant state is based on a reversible (although dierent) termination mecha-
nism. Therefore, the exchange directly aects the radical concentration. In LRP by
DT, instead, this exchange is carried out by direct transfer of the o-end group be-
tween an active and a dormant chain. When an iodine atom is used as end group,
the reaction can be summarized by Eq. (c), where R
n
I indicates the generic dor-
mant species with iodine.
R
n
R
m
I
kex
R
m
R
n
I (c)
Therefore, the main dierence from the previous two systems is that this living
mechanism does not form new radicals and a conventional initiator is needed to
start and sustain the reaction. The initial amount of this species has to be prop-
erly selected. As a matter of fact, since the living reaction of Eq. (c) is not aecting
the radical concentration, the nal concentration of the chains terminated by bimo-
lecular combination will be half of the initial concentration of initiator. Therefore,
the initial concentration of the species carrying the iodine group (in the following
simply called the transfer agent) determines the nal DP of the polymer, pro-
vided that the initiator concentration is small compared to that of the transfer
agent.
Only a few papers have appeared in the literature dealing with LRP by DT [64
66], and the applications are almost completely limited to the homopolymerization
of styrene. In this case, it was possible to obtain good control of the nal CLD, with
polydispersity values as low as 1.31.4. Better performances are dicult to obtain
with styrene, mainly because of the limited transfer activity of the iodine atoms.
This is the main reason for the very poor results obtained when applying this pro-
cess to the polymerization of acrylates (for example, n-butyl acrylate), and for the
complete lack of control reported for other monomers [6466].
6.7.1.4 Reversible AdditionFragmentation Transfer (RAFT) Polymerization
The RAFT process can be regarded as a special case of degenerative transfer. As
shown in Eq. (d), the reaction proceeds through the direct interaction of an active
and a dormant chain with the formation of a reaction intermediate involving both
chains [67, 68]. At this stage, the reaction can either go back, forming the initial
radical again, or proceed forward with the transfer of the Y = C(Z)Y moiety
from the dormant to the active chain, which is now identied as the transfer
species.
R
n
R
m
YC(Z)Y

k
add
k
()
frag
R
m
YC
.
(Z)YR
n

k
()
frag
R
m
R
n
YC(Z)Y (d)
Note that the best results have been reported when using a sulfur atom as the Y
group [6770]. The process is started by introducing into the system a so-called
RAFT agent, the structure of which can be described as RYC(Z) = Y. The cor-
rect choice of the R group, or leaving group, is of paramount importance, not only
because this is going to be one polymer chain end (the other end being occupied
by the RAFT group), but mainly because it inuences the initial reactivity of the
RAFT agent. From Eq. (d), it is in fact clear that in the rst addition reaction an
intermediate species is formed, having the R group on one side and the polymer
radical on the other. The fate of such a species that is, the probability that the
following fragmentation reaction proceeds backward or forward depends mainly
upon thermodynamic considerations, namely upon which, the polymer radical or
the leaving-group radical, is the more stable. In other words, if the leaving group
generates a radical that is too unstable compared to the polymer radical, the
RAFT is always going to proceed backward, and thus no control is actually
achieved. Similar considerations apply in block polymerization of two monomers,
where the rst block can be regarded as a special case of the R group. Accordingly,
care must be given to the correct choice of which monomer has to be polymerized
rst.
Even though the most satisfactory results have been obtained by RAFT polymer-
ization of styrene (Figure 6.8 shows an example of the application of RAFT to bulk
styrene polymerization, indicating the good control of polymer growth), the pro-
cess is also very eective for many other monomers, such as acrylates and metha-
crylates [6770]. Moreover, the operating temperatures used to carry out this poly-
merization are usually close to those typical of conventional radical polymerization
[6770]. The low temperature, along with the wide range of compatible mono-
mers, makes this mechanism one of the most promising techniques to be applied
on an industrial scale for the production of new materials, in competition with
ATRP. Once more, a signicant drawback is the need to remove the sulfur atoms,
which confer to the nal polymer a deep color ranging from yellow to red, from the
product.
6.7.2
Polymerization of LRP in Homogeneous Systems
As already pointed out, the nal aim of LRP is to strictly control the architecture of
the polymer chain by minimizing the fraction of dead chains in the system while
maintaining uniform growth of the whole population of chains. The homogeneity
of chain lengths is the key factor in homopolymerization and it is usually ex-
pressed in terms of polydispersity ratio, P
d
(dened as the ratio between weight
and number-average molecular weight; P
d
= 1 when all chains are of the same
length). The fraction of dead chains becomes even more important when the pro-
cess is intended to produce block copolymers, in which case terminated homo-
polymer chains represent a signicant drawback with respect to the product qual-
ity. To minimize terminations, dierent strategies are eective for the dierent
living mechanisms, as briey reviewed below.
For clarity, let us start by discussing the application of NMP to a bulk system. As
previously pointed out, a successful LRP requires the termination reaction between
the growing radical chain and the nitroxide (referred to simply as the deactivation
reaction hereafter) to be dominant with respect to bimolecular irreversible termina-
tion. It has been exhaustively demonstrated that, in spite of the fact that these bi-
molecular reactions, deactivation and termination, are both very fast and controlled
Fig. 6.8. Example of application of RAFT to bulk
polymerization of styrene. Left: degree of polymerization (DP)
and polydispersity versus conversion; right: evolution of
molecular weight distribution as measured by GPC [71].
by diusion, deactivation soon becomes the favored reaction path anyway. This is
often referred to as the persistent radical eect [72, 73]. To explain this behavior,
let us rst point out that, because of the nature of NMP, where new radical chains
can be created from dormant ones by activation, this mechanism does not require
a radical initiator. Accordingly, when the reaction starts, dormant chains start to
activate, building up a radical concentration. At the same time, the two bimolecular
termination reactions, termination and deactivation, start to operate. But, while de-
activation simply produces a dormant chain again, termination subtracts polymer
chains from the activation/deactivation equilibrium and, according to simple stoi-
chiometric arguments, trapping radicals (nitroxides) are accumulated. The ulti-
mate eect of this accumulation of trapping radicals is that deactivation becomes
faster and faster, thus shortening the active lifetime of the active radicals and their
concentration, but also decreasing the nal amount of irreversibly terminated
chains. Fischer et al. derived Eq. (53) to evaluate the concentration of radicals for
an NMP [72], where (RX)
0
is the initial concentration of dormant chains.
R =
k
ac
(RX)
0
3k
de
k
t
t

1=3
(53)
This equation conrms that the radical concentration steadily decreases in time.
Albeit the living action in ATRP takes place by a dierent reaction mechanism,
the same arguments presented above for NMP can be used. It can be easily veried
that the concentration of the metal in the reduced form, Me
(n)
[compare the corre-
sponding reaction scheme, Eq. (b)], remains roughly constant during the whole
process, and therefore the activation process can be approximated as a monomolec-
ular process as in NMP.
On the other hand, degenerative transfer and RAFT are characterized by com-
pletely dierent kinetics when the polymerization is performed in a homogeneous
system. Given the nature of the living mechanism of these two systems, based on a
transfer reaction, radical concentration is not aected by the living system. Thus,
the persistent radical eect is totally absent and the kinetics of DT and RAFT is
identical to that of a conventional nonliving system. Accordingly, an initiator is
necessary to sustain the reaction and the concentration of radical chains is set by
the equilibrium between initiation and bimolecular termination; that is, the well
known formula in Eq. (54), where R
i
represents the rate of radical generation,
holds in this case also.
R = (R
i
=k
t
)
1=2
(54)
No matter which is the living mechanism under consideration, it is fundamental
to keep the radical concentration as low as possible to ensure a nal fraction of
dead chains which is negligible with respect to the dormant polymer. In a bulk or
solution polymerization, the nal concentration of dead chains is a function of the
radical concentration only: high polymerization rates correspond to high dead
chain concentrations. It can be shown [72] that the time needed to obtain 90% con-
version after proper tuning of the process parameters so as to obtain a dened frac-
tion of dead chains, f, is given by Eq. (55), where the factor C is dierent for the
dierent living mechanisms (NMP/ATRP: C = 4=3; RAFT/DT: C = 1).
t
90; f
= C
k
t
(ln 10)
2
fk
2
p
(RX)
0
(55)
Using typical parameter values for styrene homopolymerization at 80
C, reaction
times of the order of magnitude of 100 h are needed to have f = 0:05. Even if it
can be shown that low polydispersity values can be achieved also at higher f values
(>0.20.3) [72, 73], these values cannot be accepted in copolymerization. While
increased reaction temperatures and thus propagation rates generally should pro-
mote smaller dead chain contents [compare Eq (55)], in the case of styrenic copoly-
mers this leads to limited improvements only, since undesired side reactions nega-
tively aecting the polymer quality (such as chain transfer and thermal initiation)
become more and more important.
6.7.3
Kinetics of LRP in Heterogeneous Systems
A possible way out of this problem comes from the application of LRP to segre-
gated systems, namely emulsion polymerization. Let us focus on a system charac-
terized by the presence of very small polymer particles and a water-soluble initiator.
When a radical is formed and, after a few propagation steps, absorbs or enters a
particle without radicals, this same radical goes on propagating until the particle
experiences a second entry. At this point, given the very small size of the particle
and the diusion-limited nature of the termination reaction, the two radicals react
with each other almost instantaneously to produce a dead chain. Thus, the particle
goes back to a state without radicals until another entry takes place. This particular
kinetic condition is often referred to as a zeroone system (compare Section 6.5)
and, under the assumption of negligible radical desorption, the corresponding av-
erage number of active chains per particle is equal to 0.5 (SmithEwart Case 2).
Kinetic behavior similar to that of a zeroone system is readily established with
DT and RAFT as living mechanisms [74]. Since a transfer reaction is taking place
in both cases, the same kinetics as in a nonliving process is again operative. There-
fore, the fraction of dead chains in the system can be adjusted by tuning the fre-
quency of entry properly, while the transfer reaction rate independently controls
the homogeneity of polymer growth. It is again important to notice that in emul-
sion polymerization the rate of formation of dead chains by irreversible termina-
tion is regulated by the frequency of entry only, while the polymerization rate is
not aected. Accordingly, in principle it is possible to maintain the same high
polymerization rates typical of emulsion systems, while keeping under control the
ratio between dormant and dead chains, and thus the nal quality of the polymer.
The corresponding time evolution of the number of active chains per particle, i, is
therefore as sketched in Figure 6.9(a). Note that the living reactions are not in-
volved at all. Accordingly, the average number of active chains per particle remains
close to 0.5.
Comparable propagation rates are not found when using NMP or ATRP [74, 75].
Referring once more to NMP for simplicity, it is not possible to have one radical
per particle for a signicant time period, since each activation event will produce
a transient and a persistent radical: keeping in mind the extremely small size of a
typical polymer particle produced in emulsion, the radicals recombine almost im-
mediately. In other words, the principle behind radical segregation cannot hold
when NMP is active, since two radicals are generated each time an activation reac-
tion occurs in the particle. Note that the average time particles spend with zero and
one radical is 1=f
a
and 1=f
d
, respectively, the frequencies of activation and deactiva-
tion being f
a
= k
ac
[RX[
p
and f
d
= k
de
[X[
p
. This reduction of the polymerization rate
cannot be counteracted by increasing the rate of the activation reaction: when f
a
approaches f
d
, a second activation is more likely to take place instead of a deactiva-
tion, the probability of this event being equal to f
a
=( f
a
f
d
). Accordingly, the two
transient radicals may terminate with each other and accumulate two persistent
radicals in the particle, thus increasing the frequency of deactivation. In other
words, each particle accumulates persistent radicals till the rate of the second acti-
vation becomes small enough (that is, when f
a
f f
d
), and the average number of
radicals per particle has a value much smaller than 0.5, that typical of DT and
RAFT in emulsion. Note that, when f
a
f f
d
, this average number of radicals can
be readily estimated as f
a
=f
d
. Actually, it has been shown that the process kinetics
approaches that of the corresponding bulk process, thus canceling the advantages
of operating in emulsion from a kinetic point of view [75]. The corresponding
sketch of the time evolution of the number of active chains per particle is shown
in Figure 6.9(b). An average value of active chains per particle, much smaller than
0.5, is readily veried.
Fig. 6.9. Expected kinetics for LRP in emulsion: (a) RAFT/DT;
(b) NMP/ATRP. i = number of radicals per particle;
r; f
c
; f
ac
; f
de
= frequencies of radical entry, bimolecular
termination, activation, and deactivation, respectively.
6.7.4
Application of LRP in Heterogeneous Systems
6.7.4.1 Ab-initio Emulsion Polymerization
Besides the kinetic considerations illustrated in Section 6.7.3, performing a LRP by
ab-initio emulsion polymerization is still the objective of major research eorts by
many groups, mainly because this process is generally simpler and more commer-
cially established, albeit less versatile, than other emulsion processes. Nonetheless,
this process turns out to be much more complicated than others (for example,
miniemulsion) when applied to LRP, since the multiphase environment greatly
complicates the global kinetics of the process. The need to have the RX species,
which is generally very hydrophobic, inside the polymeric reaction locus demands
fast material transport of this species out of the monomer droplets, where it is ini-
tially stored, across the water phase to the polymer particles, where the reaction
actually takes place. This transport must satisfy two fundamental requirements
[74]: (1) RX must be readily available in the particles so that all the chains can start
growing from the beginning of the process, and (2) RX must be uniformly dis-
tributed among all the particles.
Despite the initial rather unsuccessful eorts to conduct an NMP in emulsion,
mainly due to stability problems, this process proved to give good results [76].
Great care must be put into the choice of the nitroxide: the use of nitroxides that
are too hydrophobic leads to uncontrolled reactions, while nitroxides that are too
hydrophilic lead to long induction periods, mainly due to the signicant duration
of LRP in water [77]. It has also been observed that polymerization in the mono-
mer droplets plays a fundamental role. Although this always happens to a small
extent also in non-LRP, the impact of this process is very limited, due to the large
dierence in radical concentrations (and therefore reaction rates) between mono-
mer droplets and polymer particles. On the contrary, in systems like NMP and
ATRP, segregation is not eective at enhancing the radical concentration in the
polymer particles, and thus polymerization in monomer droplets proceeds as in
particles [78].
Unfortunately ATRP, which is more versatile than NMP, can with diculty be
applied to ab-initio emulsion polymerization, mainly because its chemistry, which
involves one more species (the metalligand complex), becomes even more com-
plicated [79]. Earlier attempts failed just because anionic surfactants reacted with
the metal [80]. However, switching to nonionic ones did not bring substantial
improvements. Micron-sized particles were often observed, with the exception of
n-butyl methacrylate (BMA), where submicron particles were obtained, although
rather susceptible to coagulation [81].
As shown earlier, the RAFT mechanism is better suited to emulsion polymeriza-
tion, where it is possible to exploit the segregation typical of these systems. How-
ever, even in this case, its application to ab-initio emulsion polymerization did not
enjoy much success. The reasons for such behavior are always the same: (1) poor
transport of very hydrophobic species from monomer droplets to particles, and (2)
the possible occurrence of some polymerization in the monomer droplets that
makes these species even more insoluble [82]. A notable exception is again the
polymerization of BMA [83]. As for NMLP, more water-soluble RAFT agents failed
to solve the problem, since they mainly move the polymerization into the water
phase. A simple solution to this problem could come from the use of surface-active
RAFT agents. These are suciently water-soluble to diuse fast across water, but
their surface activity is high enough to keep them away from the aqueous-phase
chemistry. The best example of such a species is represented by xanthates [84],
even though they suer from low activity in controlling the polymer growth. The
poor results in terms of polydispersity are even worse because these RAFT agents
remain anchored to the surface, although this can turn out to be an eective way to
produce coreshell particles.
6.7.4.2 Miniemulsion Polymerization
Among dierent alternatives, a very eective way to operate an LRP in segregated
systems is indeed miniemulsion. In this case, small monomer droplets are the pri-
mary locus of reaction and all the diculties from interphase transfer vanish, since
monomer and all the other hydrophobic species required to run an LRP are already
in the main reaction locus. However, further diculties have been reported, such
as incomplete droplet nucleation and colloidal stability problems [74, 82, 85]. More
subtle is the evidence of instabilities in the miniemulsion due to the kinetics of
LRP. In contrast to conventional systems, where long chains are created from the
beginning, in LRP all the polymer chains are short initially. This might lead to
superswelling states of the droplets and, eventually, to destabilization [86].
Despite these diculties, literature abounds with examples of styrene miniemul-
sion polymerizations by NMP; all show good control of the MWD and the afore-
mentioned problem of slow polymerization rates [76]. Due to the improvements
in nitroxide eciency, studies involving polymerization of acrylates have also ap-
peared [87]. However, a fast buildup of nitroxides is often observed in this case,
which depresses the polymerization rate. A possible solution is represented by the
removal of the excess of nitroxides, which has also given good results in styrene
polymerization [87].
ATRP is also very eective when applied to miniemulsion systems. Still, care is
needed in the choice of surfactant (nonionic) and ligand (not too water-soluble).
Also, it proved eective to run a so-called reverse ATRP, that is, starting from
the metal in the oxidized form, since the original metal complex (such as Cu(I))
is rather sensitive to oxidation during miniemulsion formation by sonication
[88].
Finally, RAFT also has been successfully applied to miniemulsion polymeriza-
tion with several monomers [82]. Figure 6.10 shows a typical result of a block co-
polymerization of MMA and styrene, which proved to give good control of polymer
growth together with high polymerization rates. Still, some problems remain un-
solved. Among them is the evidence of long induction times, generally attributed
to high desorption rates as a consequence of the initial exchange reaction to very
short species. This has been shown to be easily solved by using oligomeric RAFT
agents [74].
6.8
Emulsion Polymerization Reactors
Emulsion polymers are products-by-process whose microstructure and proper-
ties are determined during the polymerization. Therefore, the reactor type, the op-
eration mode, and the control strategy play a key role in achieving an ecient, safe,
and consistent production of high-quality emulsion polymers.
6.8.1
Reactor Types and Processes
In principle, both stirred-tank reactors and tubular reactors, and combinations
thereof, may be employed.
6.8.1.1 Stirred-tank Reactors
The stirred-tank reactor is the reactor most commonly used in emulsion polymer-
ization. This reactor may operate in batch, semibatch, or continuous mode.
A batch reactor is a closed system in which time is the only independent vari-
able. The batch operation can be used for small-scale production of homopolymers
from monomers with a relatively low heat of polymerization. However, the draw-
backs associated with this type of operation limit its industrial use. These draw-
backs are:
v
Control of the polymer properties is impracticable.
v
Productivity is low, considering the load, unload, and cleaning times.
v
Because all of the monomer is initially charged into the reactor, the heat genera-
tion rate is high and the control of the reactor temperature is very dicult.
v
Batch-to-batch variations due to irreproducible particle nucleation may jeopardize
product consistency. The use of seeded polymerization mitigates the problem.
Fig. 6.10. Example of application of RAFT to miniemulsion
polymerization for the formation of poly(methyl methacrylate)-
b-polystyrene [74]. Left: conversion prole; right: evolution of
molecular weight distribution as measured by GPC.
In semibatch operation, some fraction of the reactants (the initial charge) is
charged into the reactor initially, and the rest of the formulation is fed in con-
tinuously over a period of time. Most commercial emulsion products are manu-
factured in semibatch reactors. The main characteristic of this process is its
great exibility. By varying the composition and amount of the initial charge,
as well as the composition and ow rates of the feeds, both temperature and poly-
mer quality can be controlled. A wide range of products are accessible using this
technique, which allows any polymer property to be tailored, including copolymer
composition, molecular weight distribution, polymer architecture, particle mor-
phology, and particle size distribution. In addition, a large portfolio of products
can be produced with a single reactor. The main drawback of this operation mode
is the relatively low productivity, which is being compensated by using larger
reactors.
In continuous operation mode, both feed and euent streams ow continu-
ously. The main characteristic of a continuous stirred tank reactor (CSTR) is the
broad residence time distribution (RTD), which is characterized by a decreasing ex-
ponential function. The same behavior describes the age of the particles in the re-
actor and hence the particle size distribution (PSD) at the exit. Therefore, it is not
possible to obtain narrow monodisperse latexes using a single CSTR. In addition,
CSTRs are liable to suer intermittent nucleations [89, 90] that lead to multimodal
PSDs. This may be alleviated by using a tubular reactor before the CSTR, in which
polymer particles are formed in a smooth way [91]. On the other hand, the copoly-
mer composition is quite constant, even though it is dierent from that of the feed.
The broad RTD together with the problem of heat removal in large stirred tanks
make it dicult to achieve high conversions in a single tank. An arrangement of
multiple stirred tanks in series allows better heat removal and presents a narrower
residence time distribution, which in turn leads to a narrower PSD. Moreover,
copolymer composition and molecular weight can be controlled by intermediate
feeds of monomer or chain-transfer agents. CSTRs in series are used for high-
tonnage productions such as styrenebutadiene rubber (SBR), but are not well
adapted to the production of specialties because of the diculties associated
with grade transitions.
6.8.1.2 Tubular Reactors
From a safety point of view, tubular reactors are advantageous because they have a
large area/volume ratio and hence the heat removal capacity is higher than that of
the CSTR.
A continuous plug-ow reactor is somewhat similar to a batch stirred-tank reac-
tor, where reaction time is equivalent to the space time (t) in the tube. For this re-
actor type, grade transition between dierent polymer grades is instantaneous, but
the control of polymer properties is almost impracticable. An important disadvan-
tage of the tubular reactor is the inadequate mixing that can lead to phase separa-
tion, reactor plugging, and wall fouling [92]. Several modications have been per-
formed to improve radial mixing and minimize the associated problems, but to
date tubular reactors have not been widely utilized for industrial production. The
most important modied tubular reactors include loop reactors, pulsed-ow reac-
tors, wicker-tube reactors, and CouetteTaylor ow reactors.
The continuous-loop reactor is probably the only tubular reactor used in com-
mercial production of emulsion polymers [93, 94] and its use is limited to produc-
tion of vinyl acetate homopolymers and copolymers (with ethylene and Veova 10)
[9597]. A continuous-loop reactor consists of a tubular loop that connects the inlet
and the outlet of a recycle pump. The macromixing of such reactors is between
that of plug-ow and well-mixed reactors. Commonly, the loop recirculation rate
is signicantly greater than the feed rate. Under these circumstances, the resi-
dence time distribution is very close to that of a CSTR [98]. Its high heat-transfer
area/reactor volume ratio allows ecient heat removal and hence high conversions
in short residence times can be achieved. This results in a substantial reduction in
the reactor volume. The main disadvantage of this reactor is that highly mechani-
cally stable formulations are required to prevent shear-induced coagulation at high
recycling rates.
Pulsed-ow reactors consist basically of a column in which a periodic external
pulsation is provided. The goal of the pulsed ow regime is to achieve highly eec-
tive mixing, minimizing phase segregation, wall fouling, and tube plugging [99,
100]. The introduction of sieved plates, Raschig rings, or baes is reported to im-
prove mixing [101, 102]. However, these internal elements may be sources of coag-
ulation, and cleaning coagulum from these reactors will be very dicult.
The wicker-tube reactor consists of a coiled tube which meanders between solid,
xed, cylindrical supports. The heat removal capacity is high and it is claimed that
the multiple changes in ow direction allow the production of a polymer disper-
sion with a very low coagulum content [103, 104].
The CouetteTaylor reactor consists of two concentric cylinders of which the
outer one is xed and jacketed, while the inner one rotates as a stirrer. In this
way, the reaction takes place in the annulus formed between the two cylinders.
For a specic conguration, if the inner cylinder exceeds a certain speed the uid
inside the gap develops counter-rotating toroidal vortices. The boundaries of the
vortices represent a barrier for axial mixing, while radial mixing inside each vortex
is good. Consequently the CouetteTaylor reactor may be modeled as a hydro-
dynamically formed train of continuous stirred tank reactors. Good radial mixing,
which reduces phase segregation and plugging, and high heat removal capacity are
the main characteristics of these reactors [105108].
6.8.2
Reactor Equipment
Despite the availability of dierent reactors, commercial emulsion polymerization
is mostly carried out in stirred-tank reactors or in reactors that have a similar
macromixing behavior, such as the loop reactor. The mixing problems associated
with tubular reactors, together with a lack of exibility in controlling product prop-
erties, lowers the attractiveness of tubular reactors for commercial production.
Therefore the discussion will be limited to stirred-tank reactors.
The stirred-tank reactors used for the production of emulsion polymers have
sizes ranging from 5 to 50 m
3
. Stainless steel vessels with a height/diameter ratio
between 1.1 and 1.3:1 are usually employed. These reactors must be equipped for
mixing and heat transfer.
6.8.2.1 Mixing
For agitator selection it is critical to dene correctly the mixing requirements. In
practice, the most common cause of agitator failure is not miscalculation of the
power or rotational speed, but incorrect denition of the agitator main task. In
emulsion polymerization, the mixing equipment must ensure that the tasks of
emulsication and blending are performed well, and it must facilitate mass and
heat transfer without causing coagulation [109].
The power consumption of an impeller is the product of the pumping capacity
(circulation ow rate) and the velocity head, which is directly related to shear rate
and turbulence. Depending on the type and size of the impeller, either the ow or
the turbulence can be favored [110]. Axial ow impellers usually produce a uid
motion that is downward at the central axis of the vessel and upward in the wall
region. They are designed to produce a high ow/power ratio with little turbulent
loss. The designs of axial-ow impellers are derived from three-blade propellers.
Radial-ow turbines produce a radial uid motion from the impeller to the wall,
where the radial ow separates into an upper and a lower circulation loop. They
are characterized by a relatively low ow/power ratio, with much of the energy dis-
sipated by turbulence around the impeller. Radial-ow turbines have at blades or
a disk with at blades.
In emulsion polymerization, a high shear rate may cause coagulation. However,
a certain amount of turbulence is required for emulsication and to avoid phase
segregation. Moreover, high uid circulation is needed in order to guarantee
the macroscopic uniformity and to enhance mass and heat transfer. In this way,
mixed-ow turbines with features of both radial and axial ow can be useful. The
most common of these impellers is the 45
angled blade turbine. Multiple impel-

lers on the same shaft can also be employed.
In any case, the agitation requirements in emulsion polymerization are often re-
lated to the operation mode. In batch operations, vigorous agitation is required in
the initial stages to avoid monomer segregation and promote good phase disper-
sion. Later on, a lower agitation intensity is needed to avoid shear-induced coagula-
tion. In semicontinuous operations, multiple impellers are normally used to en-
sure agitation as the level goes up. In addition, it is very important for mixing of
the entering reactants to be instantaneous: this requires a high circulation ow
rate. If neat monomer is fed in, a certain amount of turbulence is required to facil-
itate dispersion. This requirement may be avoided by feeding a pre-emulsion. The
location of the addition point of the reactants is important, to avoid monomer
pools and other problems derived from the accumulation of initiators, which in-
creases ionic strength and thus promotes coagulation, and the accumulation of
emulsiers, which leads to local nucleations and/or occulations. Continuous op-
eration requires mixing characteristics similar to those of the semibatch process.
Empirical correlations for the key aspects of mixing, such as power consump-
tion, emulsication, liquid circulation, and mixing time, can be found elsewhere
[111]. The advances in computational uid dynamics (CFD) combined with new
techniques of measuring the local ow pattern are likely to transform the whole
eld.
6.8.2.2 Heat Transfer
Polymerization reactions are highly exothermic and the heat generated must be
removed in order to control reactor temperature. In commercial emulsion poly-
merization, the heat removal rate from the reactor is often the factor limiting pro-
ductivity. Both safety and product quality depend on the heat removal capacity of
the reactor. For industrial reactors, it is often not sucient to operate with a simple
cooling jacket and other devices must be incorporated in the design [112]:
v
improved jacket design to increase turbulence, and hence the heat-transfer co-
ecient (dimpled, half-pipe);
v
cooled baes (the use of internal coils is not an option because they tend to in-
crease fouling and coagulation);
v
external loop heat exchangers for the reaction medium in this case, a mechan-
ically stable formulation is required; external heat exchangers can be used also to
cool the feedstreams in continuous and semicontinuous operations;
v
reux condensers.
Increasing the agitation speed to increase the internal heat-transfer coecient is
not an option because a high impeller speed can lead to coagulum formation.
In any case, heat-transfer requirements are largely determined by the operation
mode. Batch is the most critical operation because high polymerization rates are
achieved due to the high monomer concentration. In semibatch mode, the heat
generated can be easily controlled by the monomer feed rate. In these reactors, ex-
tra cooling is provided by the cold feed. In continuous mode, the continuous cold
feed facilitates the control of the reactor temperature, particularly when the reactor
temperature is high.
6.9
Reaction Engineering
Independently of the operation mode (batch, semibatch, or continuous), in well-
mixed stirred-tank reactors the properties do not vary signicantly with the posi-
tion in the reactor, and time is the only independent variable. Therefore, the neces-
sary balances for the reactor design may be made at macroscopic level that is, for
the reactor as a whole.
6.9.1
Mass Balances
Considering inlet and outlet streams in the reactor, the mass balance [Eq. (56)] for
any species i results,
dN
i
dt
= F
ie
F
is
(R
i
)V (56)
where N
i
[mol] is the total amount of compound i in the reactor; F
ie
[mol s
1
] the
inlet molar ow rate of component i; F
is
[mol s
1
] the outlet molar ow rate of i,
(R
i
) [mol s
1
m
3
] the net generation rate of i in the reactor, and V [m
3
] the reactor
volume.
Equation (56) applies for the particular combination of monomers, initiator,
water, and emulsier, and for amounts of each polymerized monomer. Equation
(56) also applies to the number of polymer particles and of precursor particles
and the moments of the molecular weight distribution, although in those cases
units other than moles should be used. The specic forms of the net generation
rates are discussed below. Usually, the polymerization rate of monomer j is ex-
pressed as the rate of monomer consumption (R
pj
), and hence (R
Mj
) = R
pj
.
For batch processes, F
ie
= F
is
= 0, and for semicontinuous operation F
is
= 0. For
the continuous operation F
is
can be calculated from Eq. (57), where V is constant
in a continuous operation and Q
s
is the volumetric outlet ow rate.
F
is
= Q
s
N
i
V
(57)
In emulsion polymerization, the density of the reaction medium does not change
signicantly. Therefore, the volumetric inlet and outlet ow rates can be consid-
ered to be the same. The advance of the polymerization is usually given in terms
of the conversion X
i
of monomer i [Eq. (58)]. Here Polymer
i
and Monomer
i
are ei-
ther in grams or in moles.
X
i
=
Polymer
i
Polymer
i
Monomer
i

in the reactor
(58)
When more than one monomer is polymerized, an overall conversion can be calcu-
lated from Eq. (59), where X
T
can be gravimetric or molar depending on the units
used for Polymer
i
and Monomer
i
(grams or moles, respectively).
X
T
=
Polymer
i
Polymer
i

Monomer
i
in the reactor
(59)
The calculation of the monomer conversion depends on the operation mode. Table
6.3 summarizes the expressions for the dierent reactors. The instantaneous co-
polymer composition refers to the composition of the copolymer that is being
formed at a given time. Referred to monomer 1 this composition is given by Eq.
(60), where R
pi
is the polymerization rate of monomer i.
y
1i
=
R
p1
R
pi
(60)
The cumulative composition is the average composition of the copolymer formed
up to a given time, as stated in Eq. (61), where N
poli
is the amount [mol] of mono-
mer i polymerized.
y
1cum
=
N
pol1
N
poli
(61)
In continuous operations under steady-state conditions, y
1i
= y
1cum
during the
whole process.
6.9.2
Heat Balance
Assuming that the energy balance for the reacting systems is essentially an en-
thalpy balance, this reduces to Eq. (62), where c
pi
and c
pie
[J mol
1
K
1
] are the
heat capacity of compound i in the reactor and under the entry conditions, respec-
tively. R
pi
[mol m
3
s
1
] is the polymerization rate of monomer i, (DH
ri
) [J mol
1
]
Tab. 6.3. Usual conversion denitions.
[a]
Conversion Batch Semicontinuous Continuous
(steady state)
Fractional conversion of monomer i
N
i0
N
i
N
i0
N
i0

F
ie
dt N
i
N
i0

F
ie
dt
F
ie
F
is
F
ie
Overall fractional conversion
(N
i0
N
i
)
N
i0
(N
i0

F
ie
dt N
i
)
(N
i0

F
ie
dt)
(F
ie
F
is
)
F
ie
Overall global conversion
(N
i0

F
ie
dt N
i
)
N
Ti
[a]
N
i0
= number of moles of monomer i at time zero; N
Ti
= the total
amount of monomer i [mol] to be fed in a semicontinuous operation.
In order to calculate the gravimetric conversions, it is necessary to
multiply each term by the molecular weight of the corresponding
monomer.
is the polymerization heat of monomer i under the reactor conditions, T [K] is
the reactor temperature, T
e
[K] the temperature of the feeds, Q
loss
[J s
1
] the heat
losses to the surroundings (for example, through the reactor lid), Q
stirring
[J s
1
]
the heat produced by the agitator, and Q
transfer
[J s
1
] the heat removed through
the heat removal devices (cooling jacket, cooling baes, external heat exchanger
and reux condenser).
N
i
c
pi
dT
dt
=
R
pi
(DH
ri
)V
F
ie
c
pie
(T T
e
)
Q
transfer
Q
loss
Q
stirring
(62)
For heat removal through the cooling jacket Q
transfer
is given by Eq. (63), where U
[J m
2
s
1
K
1
] is the overall heat-transfer coecient, A [m
2
] the total heat-
transfer area and DT
ml
the logarithmic mean temperature dierence between the
cooling uid and the reaction medium.
Q
transfer
= UADT
ml
(63)
DT
ml
is given by Eq. (64), where T
we
and T
ws
[K] are the inlet and outlet tempera-
tures of the cooling uid (normally water) in the jacket. If T
we
AT
ws
then
DT
ml
A(T T
w
).
DT
ml
=
(T T
we
) (T T
ws
)
ln
(T T
we
)
(T T
ws
)
(64)
The overall heat-transfer coecient includes several resistances in series, but the
internal resistance usually controls the heat-transfer rate (h
i
AU). The internal
heat-transfer coecient is a function of several factors such as the impeller type
and dimensions, the impeller speed, the reactor diameter, and physical properties
of the uid. Empirical correlations based on dimensionless groups can be used.
Equation (65) presents the usual form of these expressions [111], where Nu; Pr
and Re are the Nusselt, Prandtl, and Reynolds numbers, j and j
w
the viscosity of
the reaction medium at the reactor and wall temperatures respectively, and a; b; c,
and d are constants.
Nu = a Re
b
Pr
c
j
j
w

d
(65)
Due to changes in the properties of the reaction media (for example, viscosity) the
overall heat-transfer coecient changes during the process. In semicontinuous op-
eration, the heat-transfer area varies during the operation.
A practical method to determine the heat transferred in any cooling device is to
measure the ow rate and the inlet and outlet temperatures of the cooling uid,
which are related by Eq. (66) where _ mm
w
[kg s
1
] is the mass ow rate and c
pw
[J kg
1
K
1
] the heat capacity.
Q
transfer
= _ mm
w
c
pw
(T
we
T
ws
) (66)
Combination of Eqs. (62) and (63) or (66) allows the estimation of the polymeriza-
tion rate from temperature measurements. This method, which is called reaction
calorimetry (see Section 6.10.1.6), is a powerful noninvasive on-line monitoring
technique and it has been extensively applied to polymerization reactors [113, 114].
6.9.3
Polymer Particle Population Balance (Particle Size Distribution)
Particle size distribution strongly aects rheology [115], which in turn inuences
heat removal rate, mixing, mass transfer, and stability of the latex. On many occa-
sions all of these aspects determine the scaleup and the feasibility of the operation.
In addition, particle size distribution aects lm formation and some application
properties [116, 117].
There are several ways in which the PSD can be represented, and often this de-
pends on the method used to measure it. Thus, histograms are used when the
PSD is determined by transmission electron microscopy. However, the mathemat-
ical analysis is simpler if the PSD is dened in terms of the number density of
polymer particles of unswollen volume v [m
3
particle
], n(v). The units of n(v) are the
number of particles per unit of unswollen volume of particle. From this denition,
the number of particles with unswollen volumes between v
1
and v
2
is given by Eq.
(67), and the total number of particles by Eq. (68).
N
p
(v
1
v
2
) =
v2
v1
n(v) dv (67)
N
p
=
y
0
n(v) dv (68)
Equation (69) gives the macroscopic population balance for a CSTR, where the left-
hand side accounts for the accumulation of particles in the reactor, the rst term
on the right-hand side accounts for the entry of particles into the reactor, the sec-
ond for the exit of particles from the reactor, the third for the formation and loss of
particles of unswollen volume v due to particle growth, the fourth for the loss of
particles by coagulation with other particles and the fth term accounts for the for-
mation of particles of unswollen volume v by particle coagulation. In Eq. (69) n(v)
and n
e
(v) are the reactor and inlet number density of polymer particles, Q
s
[m
3
s
1
]
is the volumetric ow rate, V [m
3
] the reactor volume, r
v
(v) [m
3
particle
s
1
] the volu-
metric growth rate of each particle of volume v, k(v; v
/
) the coagulation rate con-
stant for particles of volumes v and v
/
, and v
0
the volume of particles formed by
nucleation.
qn(v)
qt
=
Q
s
V
n
e
(v)
Q
s
V
n(v)
qr
v
(v)n(v)
qv

n(v)
V
y
v0
k(v; v
/
)n(v
/
) dv
/
1
2V
vv0
v0
k(v v
/
; v
/
)n(v v
/
)n(v
/
) dv
/
(69)
This equation is a partial-dierential-integral equation and the nucleation term is
best incorporated as a boundary condition at volume v
0
as in Eq. (70) [118], where
R
nuc
is the nucleation rate given by Eqs. (20), (26), (31), and (33).
n(v
0
) =
R
nuc
r
v
(v
0
)
V (70)
The rst and second terms on the right-hand side of Eq. (69) should be removed
for batch reactors, as well as for semicontinuous reactors to which no particles are
fed. On the other hand, the coagulation terms may be neglected for stable formu-
lations. Equations (69) and (70) are conveniently solved by using orthogonal collo-
cation [119, 120].
6.9.4
Scaleup
The main objective of scaleup is to reproduce the laboratory results in commercial-
scale reactors in such a way that the end-use polymer properties can be main-
tained. In this way, a successful scaleup takes place when the latex is produced on
a large scale at planned rates, at the projected manufacturing cost, and to the de-
sired quality standards [121]. To achieve this goal, knowledge of the mechanisms
that control the reactor behavior and the product properties is required [122].
Then, the design variables that aect these controlling mechanisms must be main-
tained constant from the smaller scale to the commercial equipment. In theory,
this could be done by applying the principle of similarity by means of dimen-
sionless groups characterizing the phenomena of interest. However, when several
mechanisms are involved in the process, it is impossible to maintain all the dimen-
sionless groups constant simultaneously. In this case, it is very important to know
which similarities to keep and which to sacrice.
The ow into the vessel, together with heat and mass transfer, must be con-
sidered in emulsion polymerization reactors because all of these mechanisms can
have a great inuence on polymer properties and reactor behavior. Unfortunately,
the mixing and heat-transfer parameters do not scale equally. In Table 6.4 several
scale factors are shown for a change from a 50 L pilot-scale vessel to a full-scale
vessel of 50 m
3
. The calculated values assume geometric similarity with a constant
impeller/tank diameter ratio and a constant height/tank diameter ratio. This table
shows, in dierent columns the change in selected parameters when one of them
is held constant.
It is often essential to maintain the same rate of heat transfer in the large-scale
unit. Nevertheless this scaleup criterion is impractical because it demands exces-
sive impeller tip speeds and high power costs. For this reason, to compensate the
negative eect in the heat-transfer rate when another scaleup criterion is selected,
additional cooling devices are necessary in most cases [123].
With respect to mixing characteristics, it is very important to identify the param-
eters that have a major eect on the polymer properties. This task is dicult in
emulsion polymerization, where mixing aects several polymer properties. Mono-
mer droplet and particle size, mass transfer between the dierent phases, coagula-
tion and kinetics may be aected by mixing parameters. The power per volume or
the tip speed are the more usual scaleup criteria, but an adequate combination of
several mixing parameters can be better to maintain product quality. In some
cases, changes in the formulation can be utilized to maintain dynamic similarity.
Changes in viscosity during the process aect mixing, and scaleup becomes more
dicult. Intermediate pilot plant experiments are required in most cases to make a
successful scaleup. Computational uid dynamics will probably transform scaleup
in the near future.
6.10
On-line Monitoring in Emulsion Polymerization Reactors
In the production of dispersed polymers, the main objectives to be fullled are:
v
Safety: The reactor temperature must be kept under safe limits to avoid thermal
runaways. In addition, violation of environmental regulations both in the plant
environment and in the nished products must be avoided.
Tab. 6.4. Several scale factors during scaleup.
Parameter
[a]
Pilot scale
(50 L)
Plant scale of 50 m
3
(scaleup procedure)
P (power) 1 10
3
10
8
100 10
5
0.1
N (impeller rpm) 1 0.21 10 0.1 1 0.01
Q (impeller ow) 1 215 10
4
100 10
3
10
P=V (power/volume) 1 1 10
5
0.1 100 0.0001
q=V (heat transfer rate/volume) 1 0.08 1 0.05 0.21 0.01
ND (tip speed) 1 2.1 100 1 10 0.1
Q=Q
S
(impeller ow/feed rate) 1 0.21 10 0.1 1 0.01
Q=H (impeller ow/head) 1 46.8 1 100 10 10
3
Re (Reynolds number) 1 21.5 10
3
10 100 1
[a]
Units are as given in the Notation section.
v
Production rate: The goal is to maximize the production rate of the available
reactors.
v
Product quality: The required quality is given by the end-use properties such as
viscosity, scrub resistance, tensile strength, exibility, elasticity, toughness, and
glosss.
In order to implement the process conditions that lead to the required specica-
tions of safety, production rate, and product quality, it is necessary to develop suit-
able control strategies. Reaction control strategies rely on both ecient monitoring
techniques and state estimation and ltering techniques. In this section the main
focus is on the instrumentation available for monitoring emulsion polymerization
reactors. Detailed reviews for on-line monitoring techniques for polymerization re-
actors are available [124126].
Polymer latexes are products-by-process, and therefore the required structural
and morphological properties of the polymer that yield the adequate end-use prop-
erties are produced in the reactor. In polymer latexes the properties that one would
like to control during the polymerization include: monomer(s) conversion, copoly-
mer composition, MWD, PSD, particle morphology, branching and crosslinking,
gel content, and particle size distribution. Not all of these properties can be moni-
tored on-line, although some can be made observable by combining available
measurements and mathematical models. Examples of observable properties are
copolymer composition by means of calorimetric or density measurements [127
129] and instantaneous molecular weights from measurements of unreacted
monomer and CTAs (gas chromatography [130] or reaction calorimetry [131] in
linear polymers).
Other properties, such as molecular weight distribution of nonlinear polymers
and particle morphology, are currently neither measurable nor observable.
6.10.1
On-line Sensor Selection
One of the issues when monitoring an emulsion polymerization reactor is selec-
tion of the most appropriate technique [124, 126]. For instance, monomer conver-
sion and copolymer composition can be monitored on-line by means of densim-
etry, refractive index, gas chromatography, calorimetry, ultrasound, uorescence,
ultraviolet reection, and other spectroscopic methods such as Raman, mid-range
infrared, and near-infrared.
Figure 6.11 can be used as a guide for the selection of a technique for monitor-
ing monomer conversion and copolymer composition. The main idea behind this
plot is the fact that the amount of information provided by the available techniques
is dierent and furthermore, the implementation of these techniques involves dif-
ferent degrees of diculty (including here robustness in a harsh environment,
maintenance, and know-how required). The ideal technique would be located
in the upper left-hand corner, but unfortunately no such technique is currently
available.
In the rest of Section 6.10.1, a brief description of the monitoring techniques
shown in Figure 6.11 will be presented, emphasizing the advantages and disadvan-
tages of each one, and nally examples of application for emulsion polymerization
reactors will be given.
6.10.1.1 Latex Gas Chromatography
In this technique, a latex sample from the reactor is rst diluted and then injected
into the GC to analyze unreacted monomers and CTAs [132, 133]. Although suc-
cessful implementation of this technique for latexes with a high solids content
has been reported [134], the setup is liable to suer clogging. Additional disadvan-
tages of this monitoring technique include the time delays associated with the
analysis itself when multicomponent copolymerizations are monitored. This draw-
back can be partially alleviated by using capillary columns and modern gas chro-
matography equipment with reduced analysis time.
6.10.1.2 Head-space Gas Chromatography
This GC-based monitoring technique circumvents the lack of robustness of the
latex GC technique by analyzing the reactor head-space [135, 136]. However, the
estimation of the monomer concentrations in the polymer particles requires that
equilibrium between the latex and gas phase is attained. In addition, the values of
the equilibrium parameters are required, which introduces an additional uncer-
tainty to the measurements. Note also that formulation ingredients such as CTAs
are not measurable by this means.
6.10.1.3 Densimetry
This technique is based on the density change that occurs when monomer is con-
verted to polymer. This dierence, which is obviously a maximum in bulk polymer-
ization, allows emulsion polymerizations of relatively high solids content to be ac-
curately monitored [137]. The main disadvantage of on-line densimetry is that, as
for latex GC, a sample of the reaction medium must be introduced in the thermo-
stated measurement cell and the system is liable to suer clogging. A further dis-
Fig. 6.11. Guideline chart for sensor selection.
advantage of densimetry is that it provides only overall conversion measurements
for copolymerization, and hence partial conversions and copolymer compositions
must be inferred using a model [129]. An advantage of densimetry in comparison
to GC is that there is no delay in the measurement of density, which can be moni-
tored almost continuously.
6.10.1.4 Ultrasound
The principle of ultrasound relies on the propagation of the ultrasonic wave pres-
sure. The measurable properties are the ultrasonic velocity and the attenuation of
the wave, which are a function of the medium where the wave propagates and
hence of the density, viscosity, and compressibility. The attenuation measurements
are not very reliable for on-line monitoring because the attenuation of the wave in
dispersed systems is complex and depends on the dispersion medium, the viscous
losses within the particles and at the interface between the particle and the contin-
uous phase, thermal losses, sound scattering in dispersed media, and the dynamic
relaxation of the polymeric material [138, 139]. Furthermore, there are technical
problems in measuring the attenuation at high solids and the presence of gas
bubbles can make the measurements dicult. Sound propagation velocity is better
suited to monitor emulsion polymerization reactors and it has been proven in sys-
tems with high conversion and high solids content [140142]. In principle, the
main advantages of this technique are that it is noninvasive in nature (although
care should be taken with emitterreceiver transducers located inside the reactor),
it is fast and cheap, and, in addition to monomer conversion, other latex properties
such as particle size, monomer solubilities, and critical micellar concentration can
also be measured [141].
The main disadvantage is that to exploit the information on the sound veloc-
ity and attenuation fully, calibration is required to obtain accurate predictions of
monomer conversion or other properties such as particle size because the theo-
retical models linking those characteristics to sound propagation velocity are not
predictive.
Nevertheless, on-line sound velocity is one of the more promising techniques for
monitoring industrial-size polymerization reactors because of the fast and robust
measurement and easy maintenance at a relatively low cost.
6.10.1.5 Spectroscopic Techniques
Since the mid-1990s, there has been plenty of activity regarding the use of spectro-
scopic techniques for on-line evaluation of polymer properties [143146]. This has
been possible due to the recent development of ber-optic probes, which allow in-
situ measurements in remote and harsh environments (high temperatures, pres-
sures, toxic environments, and so on). An additional advantage is that a ber-optic
probe can be installed in an existing reactor within a short time without expensive
modications. Fluorescent, ultraviolet (UV), infrared (IR), near-infrared (NIR),
mid-infrared (MIR) and Raman spectroscopic techniques can be used for poly-
merization reaction monitoring. These can be divided between absorption- and
emission-based techniques. IR, NIR, and MIR are absorption-based.
IR is not well suited to monitor polymerizations in dispersed media because
water gives a strong absorption, and hence important bands are overlapped or
hidden by that of the water. In addition, transmission through ber-optics is still
relatively poor in the infrared region, which makes IR not as suitable as other tech-
niques for remote monitoring.
NIR spectroscopy corresponds to the spectral region 140004000 cm
1
. The
main advantages of NIR are that no sample preparation is required and that the
NIR signal can be easily transmitted through ber-optics made of silica, which
have a low cost. The main disadvantage of NIR comes from the fact that in this re-
gion, absorption bands are broad because they do correspond not to specic bonds
or groups of molecules, but to combinations of them. This makes the accurate
quantitative analysis dicult. Furthermore, the detection of the minor compounds
in polymerization formulations is not easy. Although NIR has been used to moni-
tor emulsion polymerization reactions [147], diculties due both to broad bands
associated with water absorption and to the eect of the particle size have been re-
ported [141, 148, 149]. Another diculty of NIR is the short penetration depth of
the NIR signal. Furthermore, the presence of big monomer droplets might cause
inaccuracies in the quantitative analysis due to inhomogeneous sampling of the
reactor by the NIR probe.
The MIR spectral region is from 4000 to 400 cm
1
. This region is very rich in
fundamental absorptions and hence the potential of this technique is high. How-
ever, the use of MIR spectroscopy to monitor emulsion polymerization reactors is
scarce, mainly because remote monitoring is not possible at low cost as currently
only a few exotic materials are known to be able to transmit in this region. In addi-
tion, water is absorbed in this region and it may hide bands that are important for
further analysis.
Raman spectroscopy is an emission-based technique. Although conventional dis-
persive Raman spectroscopy (laser wavelengths between 500 and 700 nm) has not
been successfully used to monitor polymerization reactions due to the tremendous
eect of uorescence on the spectra, FT-Raman (laser wavelength in the NIR re-
gion, 1034 nm) or modern dispersive Raman equipments (laser wavelengths over
800 nm) overcome this diculty. Currently, Raman spectroscopy can be considered
as the spectroscopic technique with the greater potential to monitor polymerization
reactors, and especially emulsion polymerization reactors, in situ. Raman spectros-
copy presents several advantages over the absorption techniques (MIR and NIR).
The most important ones are:
v
Water is a weak scatterer and hence Raman is well suited to monitor polymeriza-
tion in dispersed media.
v
It is very sensitive to CbC bonds. This makes it possible to follow, with high ac-
curacy, the disappearance of monomer by polymerization.
v
Low-cost ber-optic technology can be used to monitor polymerization reactors
remotely.
v
The penetration depth of the Raman signal is greater than for NIR and hence in
emulsion polymerization interference by monomer droplets can be avoided.
Figure 6.12 shows an example of monitoring a semibatch emulsion polymerization
of MMA/BA of high solids content (55 wt.%) by means of on-line FT-Raman spec-
troscopy [150]. It should be pointed out that this monomer system was challenging
because the chemical structures of the monomers are very similar, and hence most
of the bands overlap. Chemometric (partial least squares, PLS) analysis was neces-
a)
0
0.001
0.002
0.003
0.004
0.005
0.006
0 0.2 0.4 0.6 0.8 1
Conversion
W
e
i
g
h
t

F
r
a
c
t
i
o
n

M
M
A

b)
0
0.01
0.02
0.03
0.04
0.05
0 0.2 0.4 0.6 0.8 1
Conversion
W
e
i
g
h
t

F
r
a
c
t
i
o
n

B
A
Fig. 6.12. On-line monitoring of a seeded semibatch emulsion
copolymerization of MMA/BA. Evolution of (a) MMA; (b) BA.
sary to quantitatively determine the concentrations of monomers and the solids
content. Furthermore, in some cases nonlinear calibration techniques are neces-
sary because PLS, a multivariate linear calibration, may not be sucient if the
degree of nonlinearity between the spectra and the properties of interest is sig-
nicant.
6.10.1.6 Reaction Calorimetry
Reaction calorimetry is probably the cheapest, easiest, and most robust monitoring
technique for polymerization reactors, due to the large enthalpy of polymerization
of most monomers. The technique is noninvasive (basically, only temperature sen-
sors are required), and it is industrially applicable [151, 152]. It yields continuous
information on the heat released by polymerization and hence it is also very useful
for safety issues. The main drawback is that only overall polymerization rates can
be obtained. Consequently, the determination of the individual rates requires esti-
mation techniques [114, 153155].
Reaction calorimetry is based on the energy balance in the reactor, given by Eq.
(71),
N
i
c
pi
dT
dt
= Q
r
Q
feed
Q
transfer
Q
loss
Q
stirring
(71)
where the term on the left-hand side is the heat accumulated in the reactor, Q
r
is
the heat generation rate due to polymerization, Q
feed
is the sensible heat genera-
c)
10
20
30
40
50
60
0 0.2 0.4 0.6 0.8 1
S
o
l
i
d
s

C
o
n
t
e
n
t

(
%
)
Conversion
Fig. 6.12. (c) solids content. g, gravimetry and gas chromatography; , FT-Raman.
tion rate due to the feeding of reagents into the reactor, Q
transfer
is the heat ow
across the reactor wall, and Q
loss
and Q
stirring
represent the rate of heat losses and
of heating due to stirring, respectively. The generation rate of the heat of reaction,
Q
r
, can be calculated from the other terms, provided that these can be calculated
with sucient accuracy. In emulsion polymerization reactors, the largest of these
terms is Q
transfer
.
In heat-ow calorimetry, Q
transfer
is calculated from the measurements of the re-
actor (T) and jacket (T
w
) temperatures by applying Eq. (72), where U is the overall
heat-transfer coecient and A the heat-transfer area.
Q
transfer
= UA(T T
w
) (72)
The implementation of heat-ow calorimetry requires knowledge of the evolution
of U. This is the weakest point of this technique.
In heat-balance calorimetry, eqs. (71) and (72) are coupled with the energy bal-
ance in the jacket to produce Eq. (73), where m
w
is the mass of cooling uid in
the jacket, _ mm
w
the mass ow rate of cooling uid in the jacket, c
pw
its specic heat
capacity, T
we
the inlet jacket temperature and T
ws
the outlet jacket temperature.
m
w
c
pw
dT
ws
dt
= UA(T
ws
T) _ mm
w
c
pw
(T
we
T
ws
) (73)
Heat-balance calorimetry allows the simultaneous estimation of U and Q
r
, pro-
vided that T
we
T
ws
could be accurately measured. Therefore, heat-balance calo-
rimetry is best suited for large-scale industrial reactors because a signicant dier-
ence between the jacket inlet and outlet temperatures is necessary, and this is the
case in industrial reactors. The advantage of this approach is that a-priori informa-
tion of the overall heat-transfer coecient is not necessary and hence it is more
robust and reliable than heat-ow calorimetry.
Oscillation calorimetry also allows simultaneous determination of the heat of re-
action and the overall heat-transfer coecient from temperature measurements of
the reactor and the jacket. This is done by taking advantage of the dierent dynam-
ics of heat transfer (fast) and heat of the reaction (slow) when an oscillation of
either the reactor or jacket temperature is created articially. The analysis of the os-
cillatory temperature signals allows calculatation of the UA term and Q
r
simulta-
neously [156, 157]. The oscillation of the jacket and reactor temperatures can be
achieved in dierent ways, but perhaps the most practical one is by imposing a si-
nusoidal oscillation in the set-point of the reactor temperature. This approach can
only be applied to small reactors (<20 L) with high ow rates of the cooling uid,
because the oscillating signal is strongly attenuated as the reactor size increases.
The higher reactor time-constants make the estimation of Q
r
and UA very uncer-
tain [158].
The amount of free monomer and the copolymer composition in emulsion poly-
merization reactors can be inferred from measurement of the heat of reaction, Q
r
[127, 128]. Figure 6.13(a) shows the evolution of the free monomer concentration
as inferred from on-line reaction calorimetry compared with the o-line measure-
ment (gravimetry and gas chromatography) for a VAc/BA/AA high solids content
semibatch emulsion polymerization. In Figure 6.13(b), the estimation of the ter-
polymer composition from calorimetric measurements is compared with NMR
and GC measurements for a VAc/MMA/BA emulsion terpolymerization [159].
a)
0
50
100
150
200
250
300
350
0 50 100 150 200 250 300 350
Gravimetry
Chromatography
Calorimetry
F
r
e
e

M
o
n
o
m
e
r

(
g
)
Time (min)
b)
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0
T
e
r
p
o
l
y
m
e
r

C
o
m
p
o
s
i
t
i
o
n
Conversion
VAc
MMA
BA
________
Calorimetry
Full Points GC
Open Points NMR
Fig. 6.13. On-line monitoring of emulsion polymerization
reactor by means of calorimetric measurements: (a) free
monomer in VAc/BA/AA semibatch emulsion polymerization;
(b) terpolymer composition in the VAc/MMA/BA semibatch
emulsion polymerization.
6.11
Control of Emulsion Polymerization Reactors
The objective of reactor control is to achieve an ecient, safe, and consistent pro-
duction of high-quality materials. The quality of the emulsion polymers is given by
its end-use properties such as mechanical strength; tack, peel, and shear resis-
tances; brightness; impact strength; weatherability; drawability; and elastic modu-
lus. These end-use properties depend on the molecular and morphological prop-
erties of the latex, which are the variables that can be controlled in the reactor.
Therefore, the relationship between the structural and morphological properties
of the polymer latex and the end-use properties is required to establish which are
the characteristics of the polymer latex to be produced/controlled in the reactor
(Figure 6.1). The development of rst-principle structureproperties relation-
ships is very challenging as the basis is not yet well established. Thus, the cur-
rent industrial practice is a trial and error methodology. In order to reduce this
time-consuming methodology semiempirical approaches can be used. An example
of this type of approach was recently reported to relate the MWD of an acrylic latex
of a given composition and the adhesive properties [160, 161].
However, this relationship only provides a way to estimate the end-use properties
from a given microstructural property (MWD in the example); in practice, one
would like to know the microstructure that will yield a given set of end-use proper-
ties (see Figure 6.14). This can be achieved by inverting the model using appropri-
ate techniques of optimization or neural networks [160, 161].
Once the desired molecular and morphological properties of the latex are estab-
lished, a closed-loop control strategy can be implemented. A typical closed-loop
control strategy used to control copolymer composition and molecular weight dis-
tribution is shown in Figure 6.14.
In the control scheme, x are state variables of the polymerization reactor, y are
measurable properties of the polymer latex, y
meas
are properties that are monitored
on-line, and u are the manipulated variables of the process (basically ow rates of
monomers and chain-transfer agents).
Fig. 6.14. Closed-loop control strategy for optimal control of
composition and MWD in emulsion polymerization reactors.
The closed-loop control strategy requires calculation of the set-point, that is, the
trajectories or proles of the state variables as a function of a measured variable
(overall conversion). These proles can be calculated by means of an optimization
algorithm. In what follows, a brief description of the calculation of the optimal tra-
jectories for copolymer composition and the MWD control is presented. The goal
of the optimization algorithm is to calculate the set-point trajectories of the state
(controlled) variables that ensure the production of an emulsion polymer of the de-
sired copolymer composition and MWD in the minimum process time. To achieve
this goal, the objective function to be minimized is as expressed in Eq. (74), where
R
p
is the polymerization rate and X
T
is the overall conversion.
Min
[M[p
1
0
1
R
p
dX
T

(74)
The minimization of Eq. (74) is subjected to the following constraints:
Constraint 1: product composition and MWD The polymer produced must have
the desired copolymer composition and the nal MWD.
The condition to produce a latex with a given copolymer composition is that the
ratio of the monomer concentrations in the polymer particles must be kept at
the value that ensures the production of the desired composition. This comono-
mer ratio can be calculated from the MayoLewis equation, Eq. (75), where r
1
and
r
2
are the reactivity ratios and y
1i
is the instantaneous composition referred to
monomer 1.
[M
1
[
p
[M
2
[
p
=
(2y
1i
1) G(2y
1i
1)
2
4r
1
(y
1i
1)y
1i
r
2
1=2
2r
1
(y
1i
1)
(75)
The calculation of the condition to produce a latex with a given MWD is based on
the fact that for linear polymers produced by free-radical polymerization, the poly-
mer chains do not suer any modication once they are formed. This opens the
possibility of decomposing the desired nal MWD in a series of instantaneous
MWDs to be produced at dierent stages of the reaction [130]. When chain trans-
fer to a CTA is the main termination event, each of those MWDs can be character-
ized by the number-average chain length, X
ni
, according to Eq. (76).
X
ni
=
k
p1
[M
1
[
p
k
p2
[M
2
[
p
k
tr; CTA
[CTA[
p
(76)
Therefore the problem reduces to calculating the sequence of the values of X
ni
that
provide the desired nal MWD. In order to calculate the X
ni
values that should be
produced at each value of X
T
, the nal MWD is discretized as in Eq. (77), where
X
Tf
is the nal overall conversion; X
ni
j
is the instantaneous number-average chain
length produced in the conversion increment j, W
j
(n) is the instantaneous MWD
produced in the conversion increment j, and k is the number of increments into
which X
Tf
is divided.
W
+
c
(n) =
1
X
Tf
k
j =1
W
j
(n)DX
Tj
=
DX
T
X
Tf
k
j =1
n
X
nij
exp
n
X
nij

(77)
Note that in the discretization the most probable distribution is used because, if
chain transfer to CTAs is the main termination event, the instantaneously formed
polymer obeys this distribution (polydispersity index = 2).
For a given number of conversion increments, the required values of X
ni
j
can be
calculated by minimizing the Eq. (78), where W
d
c
(n) and W
+
c
(n) are the desired
and the calculated MWDs.
Min
X
ni
n
[W
d
c
(n) W
+
c
(n)[
2

(78)
This is a nonlinear optimization in which the number of values of n should be
greater than the number of conversion increments. A priori any MWD, W
d
c
(n),
with polydispersity index equal or greater than 2 can be prepared by this method.
Strictly speaking, the maximum molecular weight achievable with this technique is
that produced with the minimum amount of CTA that ensures the termination by
chain transfer to CTAs is the main termination event. In practice, this is very close
to the molecular weight obtained without CTA. On the other hand, MWDs contain-
ing very low molecular weights may require the use of amounts of CTA that exceed
the maximum allowable quantities (usually lower than 1 wt.% based on monomer)
used in industrial practice. The minimization of Eq. (78) provides the values of X
ni
j
to be produced at dierent DX
T
[Eq. (79)].
X
ni
o
[M
1
[
p
[M
2
[
p
[CTA[
p
= f (X
T
) (79)
Equations (75) and (79) are used as the constraints in the optimization algorithm
to produce a copolymer of constant instantaneous composition Y
1i
and a given
MWD, W
d
c
(n).
Constraint 2: Safety considerations Polymerizations are exothermic processes that
can cause runaways, so the maximum amounts of the monomer that can be pres-
ent in the reactor should be limited for safety reasons. Therefore, to design safe
processes an analysis of the risk parameters must be made in order to obtain the
limits in reaction conditions for safe operation: namely, the limits in monomer
concentration and temperature that ensure that the pressure buildup in the reactor
will not exceed the maximum pressure that the reactor can withstand. The risk
parameters are the onset temperature, the adiabatic temperature increase, and the
maximum temperature and pressure that may be reached during a polymerization
process under adiabatic conditions. To assess risk parameters, adiabatic calorime-
ters of low thermal inertia (phi-factor, F, less than 15%) are used.
The onset temperature of the polymerization reaction, T
onset
, is dened as the
temperature at which the self-heating rate is equal to a given arbitrary onset crite-
rion. This criterion depends on the sensitivity of the equipment and is used as a
reference to calculate the adiabatic temperature increase, DT, which depends on
the total amount of monomer in the formulation, M
iTOT
, the heat of polymeriza-
tion (DH
ri
), and the heat capacity of the reaction medium according to Eq. (80),
where N
i
and c
pi
are the amount and the heat capacity, respectively, of each reagent
i present in the reaction medium.
DT =
i
M
iTOT
(DH
ri
)
i
N
i
c
pi
(80)
The adiabatic temperature increase, DT, is calculated for the experiments carried
out in the adiabatic calorimeters by subtracting the T
onset
from the maximum tem-
perature achieved, T
max
.
DT = T
max
T
onset
(81)
Thus, the dependence of the risk parameters on process variables such as the
monomer concentration in the polymer particles, particle size, solids content and
initiator/monomer ratio are of paramount importance to establish the safe regions
of operation of an emulsion polymerization reactor, and furthermore to develop op-
timal control strategies under safe conditions.
A typical result obtained in an adiabatic calorimeter for an emulsion polymeriza-
tion reaction is shown in Figure 6.15. From the evolution of the temperature, the
onset of the adiabatic reaction and the maximum temperature achieved can be de-
termined. Therefore, adiabatic temperature increases under these conditions can
be easily calculated. The evolution of the pressure provides an indication of the
maximum pressure reached.
Figure 6.16 shows the evolution of the risk parameters as a function of
the polymer/monomer ratio for the emulsion polymerization of VAc/BA/AA
(78.5:18.5:3) as obtained in a VSP2 reactor (Fauske & Associates). The particle size
of the seed and the initiator/monomer ratio were the same in all the experiments.
The plot shows that the onset temperature decreases as the monomer concentra-
tion in the polymer particles increases. T
max
; DT, and pressure (the latter not
shown) increase upon increasing the monomer content. The analysis can
be extended for other process variables such as solids content, particle size, and
initiator/monomer ratios.
An example of the safety limits for the VAc/BA/AA emulsion polymerization
system is shown in Figure 6.17. The plot, which is based on the data displayed in
Figure 6.16, is constructed assuming that the polymerization will be carried out at
80
C (T
work
) and that the maximum temperature allowed to run the process, T
limit
,
is 100
C. Note that this temperature must be calculated on the basis of the maxi-
mum pressure that the reactor can withstand, and is also a function of the process
variables.
The graph shows that the region of polymer/monomer ratio below 3:1 (concen-
tration of monomer in the polymer particles higher than [M[
p
= 2:90 mol L
1
) will
not be safe. In other words, if higher monomer concentrations are used in the
process and the cooling system fails, there is a risk of exceeding the T
limit
tempera-
a)
20
40
60
80
100
120
0 50 100 150 200 250 300
T

(
C
)
time (min)
b)
0,5
1
1,5
2
2,5
3
3,5
4
0 50 100 150 200 250 300
P

(
a
t
m
)
time (min)
Fig. 6.15. Time evolution of (a) temperature; (b) pressure
during emulsion polymerization of VAc/BA/AA (78.5:18.5:3)
with initial monomer/polymer ratio = 50:50; initiator/monomer
ratio = 0.002 wt.%; nal solids content = 50 wt.%; seed
particle size = 156 nm.
0
20
40
60
80
100
120
140
0 2 4 6 8 10
Tonset
T
Tmax
T
e
m
p
e
r
a
t
u
r
e

(
C
)
Polymer/Monomer
Fig. 6.16. Evolution of the risk parameters as a function of the
polymer/monomer ratio for a VAc/BA/AA emulsion
polymerization of high solids content.
0
20
40
60
80
100
120
140
0 2 4 6 8 10
T
e
m
p
e
r
a
t
u
r
e

(
C
)
Polymer / Monomer
T
work
+ T
T
limit
T
work
[M]
p
DANGER
SAFE REGION
T
Fig. 6.17. Safety regions for a VAc/BA/AA emulsion
polymerization. Polymerization temperature = 80
C; maximum
temperature allowed for the process = 100
C.
ture (T
work
DT > T
limit
) and the runaway will take place. Above the limit polymer/
mononor = 3 ([M[
p
< 2:90 mol L
1
) the process can be operated safely because in
none of the cases does the [T
work
DT] operating line exceed the limit of the safe
operation temperature.
Constraint 3: Nonremoval of monomer and CTA The monomers and CTA already
charged in the reactor cannot be removed (Eqs. (82)(84), where the subscripts f
and pol stand for free and polymerized amounts, respectively).
d[M
1f
M
1pol
[
dX
T
b0 (82)
d[M
2f
M
2pol
[
dX
T
b0 (83)
d[CTA
f
CTA
pol
[
dX
T
b0 (84)
Constraint 4: Limitation on monomer and CTA addition The maximum amounts
of the monomer and CTA that can be added to the reactor are the total amounts
of these compounds in the formulation, M
1TOT
; M
2TOT
, and CTA
TOT
, respectively
[Eqs. (85)(87)].
M
1f
M
1pol
aM
1TOT
(85)
M
2f
M
2pol
aM
2TOT
(86)
CTA
f
CTA
pol
aCTA
TOT
(87)
The optimization provides the amounts of monomers and CTAs in the reactor at
any overall conversion. These proles are independent of the kinetics of the pro-
cess and can be regarded as master curves. Once the trajectories of the amounts
of monomers and CTAs as a function of the conversion are calculated, the imple-
mentation of the closed-loop strategy (Figure 6.14) reduces to tracking these pro-
les. To do so, on-line measurements of the overall conversion and of the free
amount of monomers and CTA are necessary. Reaction calorimetry plus state esti-
mation is probably the easiest, cheapest, and most robust option from an industrial
perspective.
At each sampling time a nonlinear controller calculates the values of the manip-
ulated variables u (ow rates of monomer and CTA) that must be added during the
sampling interval to ensure tracking of the master trajectories and hence to pro-
duce the desired polymer. A number of nonlinear controllers have been reported
in the literature for this purpose: nonlinear model predictive controllers (NMPCs)
[162], nonlinear geometric controllers (NGCs) [163], and internal model control-
lers (IMCs) [164] being the ones that have gained more attention in the specialized
literature.
An example of the performance of an on-line control strategy like the one de-
picted above is shown in Figures 6.18 and 6.19 [165]. A copolymer with constant
composition, styrene/n-butyl acrylate (S/BA) = 50:50 and a bimodal MWD with
two peaks (50 wt.% of the polymer in each peak) of dierent polydispersities were
sought: M
w1
= 1:05 10
6
and PI
1
= 2:5 and M
w2
= 1:15 10
5
and PI
2
= 3. Fig-
ure 6.18 presents the optimal proles of styrene, n-butyl acrylate, and tert-dodecyl
mercaptan (TDM) to produce the copolymer with the properties mentioned. It can
be seen that to maintain the comonomer ratio the required amount of n-BA was
always greater than that of styrene. Moreover, during the production of the rst
50% of the polymer, the amount of TDM required was low since the mode with
the high molecular weight was prepared rst; at 50% conversion, a sudden addi-
tion of TDM was required to start producing the low molecular-weight mode. Fig-
ure 6.19 presents a comparison between the desired and obtained copolymer com-
position and MWD during the controlled experiment.
Notation
A total heat-transfer area [m
2
]
A
p
total surface area of the polymer particles [m
2
]
a
s
saturated surface of the polymer particles covered by 1 mol of surfactant
[m
2
mol
1
]
c overall termination rate coecient in the polymer particles [Eq. (9)] [s
1
]
c
c
rate coecient for bimolecular termination by combination [s
1
]
0
0.5
1
1.5
2
0
0.003
0.006
0.009
0.012
0.015
0 0.2 0.4 0.6 0.8 1
Butyl acrylate
Styrene
CTA
T
o
t
a
l

a
m
o
u
n
t
s

o
f

m
o
n
o
m
e
r
s

(
m
o
l
/
L
)
T
o
t
a
l

a
m
o
u
n
t

o
f

C
T
A

(
m
o
l
/
L
)
Overall Conversion
Fig. 6.18. Optimal trajectories for the amount of monomer
and CTA to produce S/n-BA = 50:50 copolymer with a bimodal
MWD.
c
d
rate coecient for bimolecular termination by disproportionation [s
1
]
CMC critical micellar concentration [mol m
3
]
c
pi
heat capacity of compound i in the reactor [J mol
1
K
1
]
c
pie
heat capacity of compound i under the entry conditions [J mol
1
K
1
]
c
pw
heat capacity of the cooling uid [J kg
1
K
1
]
[CTA[
p
concentration of CTA in polymer particle [mol m
3
]
CTA
f
free amount of CTA in the reactor [mol]
a)
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0

C
o
p
o
l
y
m
e
r

C
o
m
p
o
s
i
t
i
o
n
Overall Conversion
b)

0.0
0.1
0.2
0.3
0.4
0.5
0.6
3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
Desired
X=0.18
X=0.47
X=0.60
X=0.77
X=0.96
d
f
/
d
l
o
g
(
M
w
)
log (M
w
)
Fig. 6.19. Experimental results of the on-line controlled
emulsion polymerization of S/n-BA: (a) cumulative copolymer
composition; (b) MWD produced at dierent conversions.
Notation 313
CTA
pol
amount of CTA polymerized [mol]
CTA
TOT
total amount of CTA in the formulation [mol]
D impeller diameter [m]
d
d
diameter of the monomer droplets [nm]
d
p
diameter of the polymer particles [nm]
f eciency factor of the initiator radicals
f
ac
frequency of activation in living polymerization [s
1
]
f
c
frequency of bimolecular termination [s
1
]
f
de
frequency of deactivation in living polymerization [s
1
]
F
ie
inlet molar ow rate of component i [mol s
1
]
F
is
outlet molar ow rate of component i [mol s
1
]
H velocity head [J kg
1
]
h
i
internal heat-transfer coecient [J m
2
s
1
K
1
]
(DH
ri
) polymerization heat of monomer i under the reactor conditions [J mol
1
]
I amount of initiator [mol]
[I] concentration of initiator in the aqueous phase [mol m
3
]
i
crit
critical length of the oligoradicals formed from desorbed radicals
j
crit
critical length of the oligoradicals formed from initiator
K
j
i
partition coecient of monomer i between the phase j and the aqueous
phase.
k(v; v
/
) coagulation rate constant for particles of volumes v and v
/
[m
3
particle
1
s
1
]
k
a
entry rate coecient [m
3
mol
1
s
1
]
k
ac
activation rate coecient in NMP or ATRP [s
1
or m
3
mol
1
s
1
]
k
add
addition rate coecient in RAFT [m
3
mol
1
s
1
]
k
am
rate coecient for radical entry into the micelles [m
3
mol
1
s
1
]
k
d
rate coecient for radical exit [s
1
]
k
d
(n) rate coecient of radical exit from particles with n radicals [s
1
]
k
de
deactivation rate coecient in NMP or ATRP [m
3
mol
1
s
1
]
k
ex
exchange rate coecient in DT [m
3
mol
1
s
1
]
k
()
frag
fragmentation rate coecient in RAFT, backward reaction [s
1
]
k
()
frag
fragmentation rate coecient in RAFT, forward reaction [s
1
]
k
I
rate coecient for initiator decomposition [s
1
]
k
p
propagation rate constant [m
3
mol
1
s
1
]
k
pi
average propagation rate constant of monomer i in copolymerization
[m
3
mol
1
s
1
]
k
pji
propagation rate constant of radicals with terminal unit j with monomer
i [m
3
mol
1
s
1
]
k
t
termination rate coecient in the polymer particles [m
3
mol
1
s
1
]
k
+
t
reversible termination rate coecient in living polymerization
[m
3
mol
1
s
1
]
k
tr; CTA
average chain transfer to CTA rate constant in copolymerization
[m
3
mol
1
s
1
]
k
tr; M
chain transfer to monomer rate coecient [m
3
mol
1
s
1
]
k
tw
termination rate coecient in the aqueous phase [m
3
mol
1
s
1
]
m partition coecient of small radicals between polymer particles and the
aqueous phase [Eq. (11)]
M
icrit
number of oligoradicals of critical length formed from desorbed radicals
M
if
amount of free monomer i in the reactor [mol]
M
ipol
amount of monomer i polymerized [mol]
[M
i
[
p
concentration of monomer i in the polymer particles [mol m
3
]
M
iTOT
total amount of monomer i in the formulation [mol]
M
m
number of inactive chains of length m
M
i
m
number of inactive chains of length m in particles with i radicals
M
n
cumulative number-average molecular weight
M
ni
instantaneous number-average molecular weight
[M[
p
monomer concentration in the polymer particles [mol/m
3
]
m
w
mass of the cooling uid in the jacket [Kg]
_ mm
w
mass ow rate of the cooling uid [Kg/s]
M
w
cumulative weight-average molecular weight
M
wi
instantaneous weight-average molecular weight
[M[
w
monomer concentration in the aqueous phase [mol/m
3
]
N impeller rpm
n number of radicals in a particle
n average number of radicals per particle
N
A
Avogadros number
n(v) number of polymer particles per unit of unswollen volume of particle
[particles m
3
particle
]
n
e
(v) inlet number density of polymer particles [particles m
3
particle
]
N
i
total amount of compound i in the reactor [mol]
N
i0
moles of monomer i in the reactor at time zero [mol]
n
m
aggregation number of surfactant [molecules/micelle]
N
m
number of micelles
N
n
number of polymer particles with n radicals
N
p
number of polymer particles
N
poli
moles of monomer i polymerized [mol]
N
pr
number of precursor particles
N
Ti
total amount of monomer i to be feed in a semicontinuous operation
[mol]
Nu Nusselt dimensionless number
P impeller power consumption [J s
1
]
P
j
time-averaged probability of nding an active chain with ultimate unit of
type j
P
M
average molecular weight of the repeating unit in the polymer chain
Pr Prandtl dimensionless number
q heat transfer rate [J s
1
]
Q impeller ow [m
3
s
1
]
Q
feed
sensible heat generation rate due to feeding into the reactor [J s
1
]
Q
loss
rate of heat losses to the surroundings [J s
1
]
Q
r
heat generation rate by polymerization reaction [J s
1
]
Notation 315
Q
s
volumetric ow rate [m
3
s
1
]
Q
stirring
rate of heat production by the agitator [J s
1
]
Q
transfer
heat removal rate [J s
1
]
Re Reynolds dimensionless number
R
i
net generation rate of component i [mol m
3
s
1
]
r
i
reactivity ratio of monomer i
R
jcrit
number of oligoradicals of critical length formed from initiator
R
m
number of radicals of length m
R
i
m
number of radicals of length m in particles with i radicals
R
nuc
nucleation rate of polymer particles [particles m
3
s
1
]
R
p
overall polymerization rate [mol m
3
s
1
]
R
pi
polymerization rate of monomer i [mol m
3
s
1
]
R
pp
polymerization rate per polymer particle [mol particles
1
s
1
]
RX amount of the capping species in controlled polymerization [mol]
r
v
volumetric growth rate of one polymer particle [m
3
s
1
]
r
v
(v) volumetric growth rate of a particle of volume v [m
3
s
1
]
R
nk
generation rate of the kth moment of the distribution of inactive chains
[R[
w
concentration of radicals in the aqueous phase [mol m
3
]
S
T
total amount of surfactant in the reactor [mol]
S
w
amount of surfactant in the aqueous phase [mol]
t reaction time [s]
T reactor temperature [K]
DT adiabatic temperature increase
T
e
temperature of the feed [K]
T
g
glass transition temperature [K]
T
lim
maximum temperature achievable for a safe operation [K]
T
max
maximum temperature obtained during an adiabatic polymerization
reaction [K]
DT
ml
logarithmic mean temperature dierence
T
onset
temperature at which the polymerization start under adiabatic condi-
tions [K]
T
w
jacket temperature [K]
T
we
inlet temperature of the cooling uid in the jacket [K]
T
ws
outlet temperature of the cooling uid in the jacket [K]
U overall heat-transfer coecient [J m
2
s
1
K
1
]
V reactor volume [m
3
]
V
i
volume of monomer i [m
3
]
V
d
volume of the droplet phase [m
3
]
V
w
volume of the aqueous phase [m
3
]
V
p
volume of the polymer particles [m
3
]
v
p
volume of a swollen polymer particle [m
3
]
V
pol
volume of polymer [m
3
]
W volume of water [m
3
]
W
+
c
(n) cumulative weight MWD
W
d
c
(n) desired cumulative MWD
W
j
(n) instantaneous weight MWD of the polymer formed at conversion incre-
ment j
[X] concentration of living agent in controlled polymerization [mol m
3
]
X
i
conversion of monomer i
X
ni
instantaneous number-average chain length
X
nij
instantaneous number-average chain length of the polymer formed in
conversion increment j
X
T
overall conversion
X
Tf
nal overall conversion
DX
Tj
jth overall conversion increment
y
1cum
cumulative copolymer composition referred to monomer 1
y
1i
instantaneous copolymer composition referred to monomer 1
Greek
a
1
parameter of Eq. (29)
a
2
parameter of Eq. (30)
g generation rate of small radicals by chain transfer [Eq. (11)] [mol m
5
]
d critical length for entry of radicals generated from the initiator
h consumption rate of small radicals generated by chain transfer [Eq. (11)]
[m
2
]
l overall mass-transfer rate coecient [m
3
s
1
]
m
k
kth-order moment of the distribution of active chains
n
k
kth-order moment of the distribution of inactive chains
r frequency of radical entry [s
1
]
t space time [s]
j viscosity of the reaction medium at the reactor temperature [kg m
1
s
1
]
F fraction of the heat of reaction used to heat the reactor walls
f
P
M
volume fraction of monomer in the polymer particles
f
j
i
volume fraction of monomer i in phase j
f
P
p
volume fraction of polymer in the polymer particles
f
w
w
volume fraction of water in the aqueous phase
C parameter of Eq. (17)
j
w
viscosity of the reaction medium at the wall temperature [kg m
1
s
1
]
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7
Ionic Polymerization
1
Klaus-Dieter Hungenberg
This chapter will deal with ionic chain growth polymerization for monomers which
are of some industrial importance. It will deal mainly with those polymer reaction
engineering aspects which are relevant for designing processes and products. As it
cannot cover the entire subject, the systems dealt with are chosen as examples of
the most important features of ionic polymerization.
7.1
Introduction
There are several recent monographs [17] on anionic and cationic polymerization
covering various mechanistic, kinetic and preparative aspects, so here just some
fundamental issues which are relevant for reaction engineering will be discussed.
Like free-radical polymerization ionic polymerization is also a chain polyaddi-
tion. After the formation of an active center (radical, anionic, or cationic species),
monomer molecules are added to this active center to form long-chain molecules.
However, from a kinetic point of view there are two major dierences between rad-
ical and ionic polymerization.
The rst dierence is that free-radical polymerization is monomer-based, which
means that the kinetics is (almost) exclusively determined by the monomer M.
Once a radical R
+
is formed and added to the monomer molecule to build the
growing chain R- - -M
+
, the reactivity of this growing chain in all reactions is deter-
mined by the nature of the monomer irrespective of the nature of the initiating
radical, which just forms the tail of that growing chain. So, from a practical point
of view, in radical polymerization it is sucient to determine the kinetic scheme
and parameters and their dependences on the system variables temperature and
pressure for a monomer system with one kind of radical initiator. Furthermore,
all active radical centers from one monomer are identical, and they are hardly in-
ISBN: 3-527-31014-2
323
uenced by the nature of the surroundings, nor by the solvent nor by penultimate
units of the chain; at least, the inuences of penultimate units [8] or solvents [9]
are quite small. In contrast, ionic polymerization is site-based: that is, the nature
of the active center strongly depends on the nature of the initiator. Propagation is
by monomer insertion at an ion pair [Eq. (1) or (2)], where the counter ion comes
from the initiator system.
@@P
n
X
M @@P
n1
X
(1)
or
@@P
n
Y
M @@P
n1
Y
(2)
So the kinetic scheme and parameters not only depend on M, but they may dier
considerably according to the initiator used. Furthermore, the active centers are
not uniform as in free-radical polymerization, but because of their ionic nature
there usually exists a complex chemical equilibrium between dierent species,
even if the initiator has a unique structure. This equilibrium [Eq. (3)] between
free ions, solvent-separated ion pairs, contact ion pairs, covalent polarized bonds,
and between associated and non-associated species, as well as the concentration of
these species strongly depend on the polarity or solvating power of the solvent sys-
tem, the solvent itself, and the presence of other salts.
X
==Y
; Y
X
d
Y
d
1=n (XY)
n
(3)
All these species can in principle participate in all the reactions with dierent rate
coecients. These facts make ionic polymerizations dicult to access for kinetic
modeling from a practical point of view in an industrial environment.
There is another important dierence between free-radical and ionic polymeriza-
tion. In free-radical polymerization, there are system-immanent, unavoidable ter-
mination reactions, the bimolecular disproportionation and combination between
two radicals. Because these termination reactions are very fast (k
t
= 10
7
10
9
M
1
s
1
) compared to propagation (k
p
= 10
0
10
3
M
1
s
1
) and radical formation
by initiator decomposition (k
d
= 10
3
10
1
s
1
) the pseudo-steady-state hypothesis
can be applied.
In ionic systems, in general, there are no such system-immanent termination re-
actions between species carrying the kinetic chain and, if there are reactions which
terminate the active species, they often occur on a similar time scale to initiation
and propagation, or they are even slower.
Examples of such reactions, which irreversibly terminate the kinetic chain, are
elimination reactions where the eliminated species is not able to re-initiate the po-
lymerization, such as in the elimination of LiH or NaH during anionic polymeriza-
tion of styrene or butadiene [1013]. In cationic polymerization, the collapse of ion
pairs to covalent species, as in reaction (4) where the CaF bond is too strong for
the ion pair to be reformed again, is a true termination reaction.
324 7 Ionic Polymerization
@@CH
2
C
HPh PF
6
@@CH
2
CHPhaF PF
5
(4)
Many other similar eliminations are not true termination reactions, but are trans-
fer reactions, when the eliminated species can re-initiate a new chain, as in reac-
tion (5).
@@CH
2
aC
(CH
3
)
2
; SO
3
H
@@CH
2
aC(CH
3
)bCH
2
H
2
SO
4
(5)
So, ionic polymerization oers the possibility, by proper choice of the reaction con-
ditions, of running as a living polymerization. Living polymerization in its pure
form is dened not only by the absence of any termination reaction destroying
the active center, but also by the absence of any transfer reaction, so that the kinetic
chain length and the length of the individual chain are the same and increase lin-
early with conversion.
However, especially in many cationic systems, the active center may be preserved
throughout the reaction, but transfer reactions to other molecules such as mono-
mers, polymers, solvent, and so on may stop the individual chain and initiate a
new growing chain [Eqs. (6)(8)].
- - -P
+
n
M - - -P
+
n1
propagation (6)
- - -P
+
n
T - - -P
n
T
+
transfer (7)
T
+
M - - -P
+
1
re-initiation (8)
So, the growth of the individual chains may be terminated by transfer reactions.
The active center itself is preserved, but a new chain is started. Thus, transfer reac-
tions change the molecular weight of the polymer, but they do not change the con-
centration of active centers. The conversion kinetics is only changed by transfer re-
actions if the re-initiation is much slower than the propagation step.
Another dierence between free-radical and ionic polymerization that must also
be kept in mind is economic rather than scientic. Most of the monomers can be
polymerized by radical or ionic mechanisms (see Table 7.1), but in most cases the
requirement for purity of monomers and solvents in ionic polymerization is much
higher, and initiators are more expensive, so ionic polymerization is chosen only if
the monomers do not polymerize by a radical pathway, or if ionic polymerization
oers other advantages, such as access to molecular structures like block copoly-
mers or specially designed molecular weight distributions.
7.2
Anionic Polymerization
Anionic polymerization involves a wide variety of reactions leading to high molec-
ular weight molecules with the participation of an anionic species. The most
important systems are those for the anionic polymerization of diene rubbers [14
16], styrenic polymers, and block copolymers of styrene and dienes [1721] as well
as the ring-opening polymerization of cyclic ethers, lactones, or lactams. Here es-
pecially, polymers from ethylene oxide and propylene oxide are important as base
materials for polyurethanes [2224].
7.2.1
Anionic Polymerization of Hydrocarbon Monomers Living Polymerization
There are two main reasons why anionic polymerization of hydrocarbon mono-
mers such as styrene, a-methylstyrene, butadiene, isoprene, and so on has gained
scientic and industrial importance:
v
These monomers may be polymerized under such conditions that termination
and transfer reactions are absent, resulting in a so-called living polymerization.
v
The microstructure of the polydienes so produced can be varied over a wide
range.
So the microstructure of dienes strongly depends on the counter ion (see Table
7.2.) and the solvent or the presence of additives, which are capable of shifting the
equilibrium in Eq. (3) from the right to the left (see Table 7.3.). An attempt to ra-
tionalize the inuence of polar additives on the microstructure is given in Ref. 25.
Generally, the vinyl content increases with the fraction of free ions.
7.2.1.1 Association Behavior/Kinetics
There are numerous publications [1, 5, 6] dealing with the equilibrium of Eq. (3)
between free ions as one extreme possibility for the structure of the initiating and/
Tab. 7.1. Monomers with dierent initiation mechanisms.
Monomers Type of initiation
Radical Cationic Anionic
Ethylene
a-Olens
1,1-Dialkyl olens
1,3-Dienes
Styrene, a-methylstyrene
Halogenated olens
Vinyl esters
Acrylates, methacrylates
Acrylonitrile, methacrylonitrile
Acrylamide, methacrylamide
Vinyl ethers
N-Vinylcarbazole
N-Vinylpyrrolidone
Aldehydes, ketones
or polymerizing species, and aggregation of more or less covalently bonded species
as the other extreme. All these species may participate in the polymerization, and
the rates for the same reaction may dier by several orders of magnitude depend-
ing on the species involved. For example, the propagation rate coecient for
anionic polymerization of styrene in THF at 25
C is 8 10
4
M
1
s
1
for the free
ion, 200 M
1
s
1
for the ion pair [26], and values of 0.0155 and 0.024 M
0:5
s
1
are reported [27, 28] for the overall propagation rate coecient k
p
K
1=2
of the
equilibrium system from monomeric and dimeric polystyryllithium in benzene
and cyclohexane.
In particular, the question of association in lithium-based polymerization in non-
polar solvents, one of the most important industrial systems, and the determina-
tion of the kinetic scheme and parameters, are still under debate. In general, the
association behavior is formulated as in Eq. (9), where n gives the association num-
ber, which generally is between 2 and 6, depending on the structure of P (mono-
mer or initiator), solvent, and temperature (see Table 7.4).
(PaLi)
n

Kass
nPaLi (9)
Tab. 7.2. Microstructure of polybutadienes produced in hydrocarbon solvent with dierent
counter ions (from [25a]).
Alkali metal cis-1,4 [ %] trans-1,4 [ %] 1,2 [ %]
Li 35 52 13
Na 10 25 65
K 15 40 45
Rb 7 31 62
Cs 6 35 59
Tab. 7.3. Vinyl content of polybutadienes produced in hydrocarbon solvent with butyllithium as
initiator with dierent additives (from [28a]).
Additive Molar ratio additive/lithium 1,2 [ %]
Diethyl ether 10:1 16
Diethyl ether 5:1 10
THF 6:1 43
THF 3:1 25
THF 1:1 17
Diglyme 4:1 87
Diglyme 2:1 85
Diglyme 1:1 78
With the assumption that association is high and the concentration of the mono-
meric species is low, the concentration of the monomeric species is given by Eq.
(10), where PaLi is either the initiating lithium alkyl or the propagating species.
[PaLi[ =
K
ass
n
[PaLi[
0

1=n
(10)
Assuming that the associated species are not reactive, or at least they are much less
reactive than the non-associated one, the reaction rates for initiation and propaga-
tion are given by Eq. (11), where k is either k
i
or k
p
.
r = k[PaLi[[M[ = k
K
ass
n

1=n
[PaLi[
1=n
0
[M[ = k
obs
[PaLi[
1=n
0
[M[ (11)
This correlation of the association number with the reciprocal of the reaction order
may be too simple. Extensive discussions on this subject are summarized in Refs.
1, 5, 6, and 2933. Here, just an overview of the various interpretations is given
without trying to judge which is the right one, but in every case of ionic polymer-
ization, when one is trying to set up a realistic mechanistic process model, similar
questions must be answered. Therefore the anionic polymerization of hydrocarbon
monomers in hydrocarbon solvents, which is one of the best-investigated anionic
Tab. 7.4. Association number for dierent Li organyls.
[a]
Li alkyl Solvent n
n-BuLi benzene 66.3
cyclohexane 6
THF 22.8
sec-BuLi cyclohexane 4
benzene 4
THF 1.1
t-BuLi benzene 4
hexane 4
Menthyl-Li cyclohexane 2
Benzyl-Li benzene 2
THF 1
Poly(styryl)-Li benzene 2
cyclohexane 2
hexane 2
Poly(isoprenyl)-Li benzene 2
hexane 2
cyclohexane 24
Poly(butadienyl)-Li cyclohexane 24.3
benzene 23.7
hexane 2
[a]
Compilation of data given in Ref. 6, pp. 16, 20, 138.
systems, is used here as an example to point out which aspects may become impor-
tant for reactor and process layout.
One reason for the debate is the high sensitivity of ionic systems to impurities,
which may cause experimental errors leading to various interpretations of the data.
However, from a mechanistic point of view also there are arguments that this sim-
ple correlation does not seem to be a general rule. For styrene with t-butyllithium
initiation is reported to be independent of monomer concentration [34]; for dienes
various orders are reported with dierences between fractional reaction order and
degree of aggregation (see Table 7.1 in Ref. 6). Furthermore, cross-aggregation be-
tween initiating and propagating species is likely to occur and must be consid-
ered, as well as intermediate equilibria between hexamers, tetramers, dimers, and
monomers. In Ref. 35 this problem is addressed for the cross-association of styryl-
and butadienyllithium. There are a number of recent publications reporting much
higher association numbers of up to 100 and more [3639], which are under dis-
cussion [40, 41]. Bywater discussed [42, 43] the diculties in separating K
ass
and
k
p
. Nevertheless, there are some reports on the separate determination of K
ass
,
[4447], which however are contradictory. With the exception of those in Ref. 47,
most of the data are from investigations at rather low temperatures (< 30
C) com-
pared to industrial conditions, which are at considerably higher temperatures (60
100
C). So, extrapolating the association behavior from low to higher temperatures
may cause errors.
In addition it must be stated that Eq. (10) is only valid if the concentration of
non-associated species is low. Otherwise the equilibrium of Eq. (9) must be consid-
ered a priori: for example, for n = 2 in the case of styrene, the concentration of
non-associated PaLi is given by Eq. (12).
[PaLi[ =
K
ass
4

K
ass
4

2
K
ass
2
[PaLi[
0
(12)
Figure 7.1 gives the temperature dependence of K
ass
and k
p
for styrene from Ref.
44. When the fraction a
of non-associated polystyryllithium is calculated with the

0.00000001
0.00001
0.01
10
10000
10000000
0.0025 0.003 0.0035 0.004
1/T / 1/K
K
a
s
s

/

M
0.001
0.1
10
1000
k
p

/

M
-
1

s
-
1
Fig. 7.1. Association equilibrium constant K
ass
and propagation rate constant k
p
as f (T) [44].
simplication in Eq. (10) and the correct solution in Eq. (12), Figure 7.2 shows that
there may be considerable deviations for values of K
ass
= 10
5
M and higher. So,
for industrial temperatures the fraction of associated species may be rather low
and a rst-order kinetic law with respect to lithium concentration may result [10,
33].
Table 7.5 gives some examples of the temperature dependence of the propaga-
tion rate coecient for Li-initiated styrene polymerization according to Eq. (11)
with n = 2. From Figure 7.3 it can be seen that there are deviations of one order
of magnitude between the results of dierent authors, even when considering the
same solvent and a rather limited temperature range of 460
C. In Ref. 48 data for

styrene and butadiene are given up to 70
C assuming n = 2 for styrene and n = 2

or 4 for butadiene. More diculties will arise when extrapolating to higher temper-
atures and tackling the problem of temperature dependence of the association be-
havior. In Ref. 10 an attempt is made to describe the propagation over a wider tem-
0.001
0.01
0.1
1
10
0.000001 0.0001 0.01 1
Kass / M
Fig. 7.2. Fraction a of non-associated species as a function

of K
ass
for dimerization for various polystyryllithium
concentrations (b, 0.0001 M; , 0.001 M; , 0.01 M). Broken
lines: exact solution according to Eq. (12); full lines:
approximate solution according to Eq. (10).
Tab. 7.5. Literature values for propagation rate coecient k
/
p
= k
p
(K=2)
0:5
for Li-initiated
styrene polymerization in hydrocarbon solvents.
kO
p; 0
[M
C0:5
s
C1
] E
a
[kJ mol
C1
] Solvent Temperature [
C] Ref.
4:5 10
8
60.3 none 2050 49
2:6 10
9
64.0 none 421 50
2:9 10
11
78.6 cyclohexane 3050 51
5:2 10
8
60.3 benzene 1030 27
5:1 10
7
56.9 toluene 2050 52
6:8 10
8
63.6 toluene 3060 53
perature range, from 10
C up to 100
C, with k
p
= 1 10
11
e
7900=T
M
1
s
1
and
K = 3:2 10
38
e
27600=T
M according to Eq. (12), which collapses to a simple rst-
order kinetic with respect to initiator above 40
C.
There is no judgment on the quality of the various results, but this overview can
serve as an example for the diculties in ionic polymerization kinetics in general,
and careful checking of literature kinetic data is strongly recommended before they
are used for reactor layout.
This somewhat extensive discussion on the association behavior of lithium-
initiated polymerization, the best-investigated ionic system, shows the diculties
in kinetic modeling of ionic polymerization. Contrary to free-radical polymeriza-
tion, the existence of all possible dierent species must be considered for every sys-
tem under investigation.
7.2.1.2 Molecular Weight Distribution of Living Polymers
The living nature of the anionic polymerization of hydrocarbon monomers has
been revealed by Szwarc [54, 55]. There is still an ongoing debate on the exact def-
inition of living polymerization [5, 6, 5557]. For the scope of this chapter we will
refer pragmatically to living polymers if the active end groups of the individual
chains retain the propensity of growth for at least as long a period as needed for
the completion of the intended synthesis [5]: that is, initiation and propagation
[(Eqs. (13) and (14)] are the only reactions, irreversible termination and transfer re-
actions being absent.
0.0001
0.001
0.01
0.1
1
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036 0.0037
1/T / K
-1
k
p
1
/
2
K

/

M
-
1
s
-
1

acc. to [49]
acc. to [50]
acc. to [51]
acc. to [27]
acc. to [53]
acc. to [52]
Fig. 7.3. Comparison of literature values for propagation rate
coecient k
/
p
= k
p
(K=2)
0:5
for lithum-initiated styrene
polymerization in hydrocarbon solvents.
I M P
1
initiation (13)
P
1
M P
i1
propagation (14)
In the sense of this denition, the associated species discussed above can also be
called living, even if they do not participate in a propagation reaction, but they are
in equilibrium with the active non-associated species on a much shorter time scale
than the overall reaction. For simplicity, in the following discussion the association
is not considered explicitly, but if it is known quantitatively it can be considered by
making the rate coecients a function of [PaLi].
From the reactions in Eqs. (13) and (14), the set of dierential equations (15)
(20) can be derived.
d[I[
dt
= k
i
[I[[M[ (15)
d[M[
dt
= k
i
[I[[M[ k
p
[M[
y
i=1
[P
i
[ = R
P
(16)
d[P
1
[
dt
= k
i
[I[[M[ k
p
[P
1
[[M[ (17)
d[P
i
[
dt
= k
p
[P
i1
[[M[ k
p
[P
i
[[M[ (18)
y
i=1
[P
i
[ = [I[
0
[I[ (19)
y
i=1
i[P
i
[ = [M[
0
[M[ (20)
For fast initiation (k
i
gk
p
), all initiator is transferred to growing chains immedi-
ately, so monomer conversion and the kinetic chain length are given by Eqs. (21)
(23).
[M[ = [M[
0
e
kp[I [
0
t
(21)
n =
[M[
0
[M[
[I[
0
=
[M[
0
[M[
0
e
kP[I [
0
t
[I[
0
= x
M
[M[
0
[I[
0
(22)
with
y
i=1
[P
i
[ = [I[
0
(23)
The resulting frequency distribution h(i) of chain lengths i can be derived by solv-
ing the system of dierential equations sequentially starting with [P
1
[
t=0
= [I[
0
and the denition of the kinetic chain length given above [Eq. (24)].
h(i) =
[P
i
[
[P
i
[
=
[P
i
[
[I[
0
=
n
(i1)
e
n
(i 1)!
(24)
The weight distribution is given by Eq. (25).
w(i) =
n
(i1)
e
n
(i 1)!(n 1)
(25)
The average number- and weight-average degrees of polymerization and the poly-
dispersity for this Poisson distribution are given by Eqs. (26)(28).
P
n
=
[M[
0
[M[
[I[
0
= 1 n (26)
P
w
= 1 n
n
1 n
A1 P
n
(27)
D =
P
w
P
n
A1 (28)
If, however, k
i
gk
p
does not hold, meaning if the initiation rate coecient is in
the order of k
p
or even less, there is no immediate conversion of initiator to grow-
ing chains and the simplication of Eq. (23) becomes invalid and must be replaced
by Eq. (19). The solution for this general case is given in Refs. 58 and 59. From
Eqs. (15) and (16), the variation of monomer conversion as a function of initiator
conversion is given by Eq. (29) with r = k
p
=k
i
> 1.
[M[ [M[
0
= (1 r)([I[ [I[
0
) r[I[
0
ln
[I[
[I[
0
(29)
The variation of M and I with time cannot be solved analytically in this case, but
must be found numerically. The frequency and weight distributions of the so-
called Gold distribution are given by Eqs. (30) and (31), with R = r 1, q = r=R
and u = (r 1) ln([I[
0
=[I[). The averages of this distribution are given by Eqs.
(32) and (33).
h(i) =
[N
i
[
y
i=1
[N
i
[
=
r
R

i
e
qu
y
j =i
u
j
j!
r(1 e
u=R
)
(30)
w(i) =
i[N
i
[
y
i=1
i[N
i
[
=
r
r 1

i
e
ru=(r1)
y
j =i
u
j
j!
(1 r)(1 e
u=R
)
ru
R

(31)
P
n
=
(1 r)(1 e
u=(r1)
)
ru
r 1
(1 e
u=(r1)
)
(32)
P
w
=
ru
r 1
1 ru
r 1
2ru (2r 1)(r 1)(1 e
u=(r1)
)
(1 r)(1 e
u=(r1)
)
ru
r 1
(33)
A Poisson distribution will also result when using bifunctional initiators [60], with
the peak maximum at 2[M[
0
=[I[
0
. Figure 7.4 gives a comparison of the Poisson dis-
tribution for n = 50 (k
i
> k
p
), the Gold distribution for (k
i
< k
p
, r = k
p
=k
i
= 100),
and the SchulzFlory or most probable distribution resulting from step growth po-
lymerization or free-radical polymerization with termination by disproportionation.
This most probable distribution is given by Eq. (34), where p is the conversion of
end groups in step growth polymerizations or polycondensation or the probability
of propagation in chain growth polymerization.
h(i) = p
i1
(1 p) (34)
The width of the distributions reects the sharpness of the initiation reaction; with
k
i
> k
p
all chains start at the same time and the distribution is very narrow, just
reecting some statistics of monomer addition. If chain initiation is delayed for
some chains (k
i
< k
p
), the distribution is skewed and will become narrower if reac-
0
0.01
0.02
0.03
0.04
0.05
0.06
0 50 100 150 200
i
h
(
i
)
Poisson
Gold
Schulz-Flory
Fig. 7.4. Comparison of various distributions for P
n
= 51:
SchulzFlory distribution with p = 0:98, P
w
= 102; Gold
distribution with r = k
p
=k
i
= 100, u = 86:513, P
w
= 64; and
Poisson distribution for n = 50. The corresponding weight-
averages are 102, 64, and 52.
tion proceeds and more chains will be initiated and propagate. The broadest distri-
bution is the most probable distribution if, as in step growth polymerization, there
is no initiation but only chain propagation.
Slow initiation has some important consequences, which are shown in Figure
7.5. The monomer may be consumed before initiator conversion is complete. This
may be important when using functionalization techniques or synthesizing block
copolymers. Moreover, the polydispersity may be considerably higher than 1, the
value which is usually assumed to be typical for living polymerization and used as
a criterion for livingness.
Besides the reactivity ratio r, the equilibrium between dierent species
associated and non-associated ones or free ions and ion pairs, active and dormant
species which may have dierent reactivities in propagation reactions, can also
have an impact on broadening the molecular weight distribution [6173].
The MWD discussion up to now has concerned batch reactors, but there are also
a number of publications dealing with other reactors. In ideal plug ow reactors
under steady-state conditions, polymers with the same characteristics of the MWD
as in batch reactors are built the time axis is transformed to the length axis of the
plug ow reactor [74, 75], and for fast initiation the MWD is a Poisson distribution.
For laminar plug ow reactors [75, 76] some broadening of the distribution is ob-
served, depending on [M[
0
=[I[
0
and conversion. The long-term stability of laminar
ow tubular reactors is questioned [76], because of the possibility of very long
chains growing near the reactor walls, where the residence time approaches inn-
ity, if radial diusion of the monomer occurs from the inner tube to the walls.
The MWD resulting from semi-batch operations of a stirred tank reactor with
monomer feed under various conditions is treated in Refs. 7782. In a homoge-
neous continuous stirred tank reactor (HCSTR), the steady-state concentrations of
monomer and initiator can be derived from the monomer and initiator mass bal-
1
1.1
1.2
1.3
1.4
0 0.2 0.4 0.6 0.8 1
x
I
D
0
0.2
0.4
0.6
0.8
1
x
M
Fig. 7.5. Polydispersity D and monomer conversion x
M
as a
function of initiator conversion x
I
for r = 10 (full lines) and
r = 100 (broken lines) according to Eqs. (29), (32), and (33).
[I [
0
= 0:101 M, [M[
0
= 3 M. Number- and weight-averages at
x
M
= 1 are 31 and 34 for r = 10, and 51 and 64 for r = 100.
ance, neglecting volume changes, by Eqs. (35) and (36), which must be solved si-
multaneously. [M[
f
and [I[
f
are the feed concentrations, V is the reactor volume,
and v
in; I
; v
in; M
are the volume feed ows of initiator and monomer.
[M[ =
v
in; M
V
[M[
f
t
k
i
[I[ k
P
k
i
[M[
2
[I[t
2
[M[
(35)
[I[ =
v
in; I
V
[I[
f
t
k
i
[M[t 1
(36)
In a CSTR, the narrow Poisson distribution resulting from the chemistry is super-
imposed by the broad residence time distribution of the HCSTR chains can leave
the reactor after seconds of growth as very short chains, but there are also chains
which reside in the reactor for very long time, growing to very long molecules. This
results in a SchulzFlory distribution [83] [Eqs. (37)(40)], where t is the mean
residence time and [M] is the steady state-monomer concentration.
h( j) =
1=t
k
P
[M[t 1=t
k
P
[M[
k
P
[M[ 1=t

j1
(37)
w( j) = j
1=t
k
P
[M[t 1=t

2
k
P
[M[
k
P
[M[ 1=t

j1
(38)
P
n
= 1 k
P
[M[t (39)
P
w
= 1 2k
P
[M[t (40)
Equation (37) is equivalent to Eq. (34) with the propagation probability given by Eq.
(41).
p =
k
P
[M[
k
P
[M[ 1=t
(41)
In a segregated stirred tank reactor (SCSTR) [74] the width of the distribution
ranges from that of an HCSTR for rather low conversion or mean residence time,
up to a value approaching that of a batch reactor for high conversions or long
mean residence times. The inuence of termination, chain transfer, and long-
chain branching in batch and CSTR reactors is described in Refs. 84 and 85.
7.2.1.3 Side Reactions
Pure living polymerization of hydrocarbon monomers usually occurs at low tem-
peratures, where side reactions are not important. At higher temperatures, how-
ever, two side reactions do become important, elimination of LiH and transfer to
compounds with an acidic hydrogen [5, 6, 31, 86, 87].
There have been some investigations on the stability of alkyllithium deriva-
tives and of growing chains. Generally, linear alkyllithiums are more stable than
branched ones, with rst-order decomposition half-lives of 16 h at 8798
C
[88, 89]. From Ref. 89, k
tt
= 1:0 10
10
exp(11798=T) s
1
for s-BuLi and k
tt
=
9:5 10
10
exp(13407=T) s
1
for n-BuLi can be evaluated. As with all rate coe-
cients of ionic polymerization, this elimination also depends on the reaction sys-
tem. The lithium hydride (LiH) elimination from butyllithium in the presence of
polar additives such as lithium butoxide is reported to be several times faster than
from pure lithium alkyl [90, 91], and in ethereal solvents proton abstraction or
ether cleavage may occur [92].
Growing chains such as polydienyl- and polystyryllithium are less stable. For
polystyryllithium, the LiH elimination is followed by proton transfer to another
polystyryllithium [93], resulting in an allylic anion, which is unable to propa-
gate (see Scheme 7.1). The same holds for polystyrylsodium [94]. Quantitative
data for LiH elimination are given in Refs. 13 (k
tt
= 295 e
5280=T
s
1
) and 10
(k
tt
= 3:92 10
6
e
(8700=T)
). In Ref. 95 the inuence of THF was investigated, but
rather similar values were obtained (k
tt
= 2:4 10
6
e
(8459=T)
). It must be noted
that these termination reactions are much slower than propagation, that is to say
the half-life for the active chains is much higher (hours) than the half-life for prop-
agation (seconds) at temperatures of 80
C and higher.
Polybutadienyllithium is somewhat more stable than polystyryllithium (k
tt
=
6:7 10
5
s
1
versus 1:9 10
4
s
1
at 93
C [13]), but contrary to styrene, the side

reactions here may cause coupled and branched polymers [9598].
The other class of important side reactions is transfer to compounds with acidic
hydrogen atoms, such as toluene, ethyl benzene and so on (Scheme 7.2).
Some quantitative data have been given for chain transfer from polystyryllithium
to aromatic solvents [10, 33, 47, 99101], and from polydienyllithium to alkenes
[102, 103] and toluene, and for the inuence of polar additives [104]. There is usu-
ally no eect on the polymerization rate, because the number of active chain ends
B u

Li
Bu

LiH
B u

PsLi
Bu

PsH
Li

+
i
k
tt
i
+
i
+
i
+
-
Scheme 7.1. Termination in anionic polymerization of styrene.
is maintained, but the chain length of the macromolecules, that is, the molecular
weight, is reduced. The presence of transfer reactions limits the production of
block copolymers by sequential addition of monomers to the living chains. How-
ever, in Refs. 33 and 99 it is pointed out that the presence of transfer reactions
may be advantageous, for example, for homopolymerzation of styrene in a CSTR,
because they reduce the amount of initiator necessary to get the desired molecular
weight.
The eect of side reactions, such as termination by monomer, impurities, or
spontaneous termination and transfer to monomer or impurities, on the molecular
weight distribution are dealt with in Refs. 66 and 105119; they generally result in
some broadening of the distribution.
7.2.1.4 Copolymerization
The most important copolymers are those from styrene and butadiene, either as
statistical copolymers or block copolymers. From a kinetic point of view the as-
sociation behavior discussed above becomes even more complex because of the
possible cross-association between the dierent growing chain ends. This issue has
seldom been addressed [35, 120].
But in spite of this complex association behavior, in most cases the simple Mayo
terminal model [Eq. (42)] with two copolymerization parameters, which was devel-
oped originally for free-radical polymerization, is in many cases sucient to de-
scribe anionic copolymerization also.
F
1
=
r
1
f
2
1
f
1
f
2
r
1
f
2
1
2f
1
f
2
r
2
f
2
2
(42)
However, there is one important dierence between free-radical and living anionic
polymerization, and this is the lifetime of the growing chain. This dierence be-
comes important when considering the dependence of copolymer composition on
conversion. Equation (42) gives the copolymer composition or mole fraction F
1
of
monomer M
1
in the polymer as a function of mole fraction f
1
in the monomer
B u Li

B u

Li
Li Li

+
i
k
tr
+
i
+
kp
1
Scheme 7.2. Transfer to ethylbenzene in anionic polymerization of styrene.
feed for incremental conversion. Because of the dierent reactivity of the mono-
mers, usually f
1
and consequently F
1
change with increasing conversion.
In free-radical polymerization, where the lifetime of the growing polymer chain
is in the order of seconds or less, compared to hours for the overall polymerization
reaction, and where new chains are initiated throughout the overall reaction time
by decomposition of radical initiators such as peroxides or azo compounds, those
chains which are initiated at dierent times or levels of conversion will dier in
their composition, but those which are initiated at the same time will have the
same composition. This dierence in composition from chain to chain is called
rst-order chemical heterogeneity.
If, however, as in living polymerization, all chains start at the same time and live
throughout the polymerization, every chain will see all the changes in monomer
feed composition, and consequently the composition will change along the chain
and not from chain to chain. This is known as second-order chemical heteroge-
neity. The dierences between these two kinds of heterogeneities, one between
dierent chains, the other within dierent fractions of one chain, are shown in
Scheme 7.3.
The severity of the chemical heterogeneity strongly depends on the copolymer-
ization parameters. In free-radical polymerization there is just one pair of parame-
ters, which may depend somewhat on temperature, for one pair of monomers;
whereas in ionic polymerization these parameters for every pair of monomers
strongly depend on the counter ion and solvent polarity (see Table 7.6).
These extreme values have a very drastic eect on the shift not only in composi-
tion but also in rates. Taking the absolute rate coecients given by Ohlinger
[35] for Li-initiated copolymerization of butadiene and styrene at 20
C in toluene
(k
SS
= 0:45, k
SB
= 110, k
BB
= 0:084, k
BS
= 0:0066 M
1
s
1
), the resulting overall
R-BBBBBSBB-Li
I-BBBBBSBB
R-BBBBBSBBSBSBSSBS-Li
I-BBBBBSBB
I-SBSBSSBS
R-BBBBBSBBSBSBSSBSSSSSSSSS-Li
I-BBBBBSBB
I-SBSBSSBS
I-SSSSBSSS
Increasing conversion
First-order chemical heterogeneity
Second-order chemical heterogeneity
-
Scheme 7.3. Chemical heterogeneity with increasing
conversion for free-radical (rst-order) and living
polymerization (second-order).
conversion versus time curves are given in Figures 7.6 and 7.7. The interesting fea-
ture is that even though the homopolymerization of styrene is faster than that of
butadiene, during copolymerization nearly all the butadiene is consumed at a
lower rate than in homopolymerization before styrene is incorporated to any appre-
ciable extent, and after the butadiene is consumed the overall polymerization rate
becomes that of pure styrene.
0
0.2
0.4
0.6
0.8
1
0 5000 10000 15000 20000 25000 30000
t / s
c
o
n
v
e
r
s
i
o
n
x
S
= 0
x
S
= 1
x
S
= 0.35
x
S
= 0.65
x
S
= 0.5
Fig. 7.6. Batch copolymerization of styrene and butadiene with
n-butyllithium (1 g) at 20
C in toluene (10 kg) with various

styrene feed fractions x
S
(20 mol monomer overall). Simulation
of overall conversion with data from Ref. 35.
Tab. 7.6. Copolymerization parameters for Li-initiated copolymerization of styrene (= M
1
) and
butadiene (= M
2
).
[a]
T [
C] Solvent r
1
r
2
25 bulk 0.04 11.2
20 toluene 0.004 12.9
30 benzene 0.035 10
50 cyclohexane 0.025 15.1
30 heptane 0.1 7
78 THF 11 0.04
0 THF 0.2 5.3
25 THF 0.3 4
25 diethyl ether 0.4 1.7
[a]
Examples taken from Ref. 6, p. 247.
The reason is that k
SB
has a high value and k
BS
has a low value. This combina-
tion is responsible for nearly all chain ends existing as butadienyllithium ends,
which predominantly propagate by addition of butadiene (k
BB
> k
BS
). If one of the
occasional propagation reactions by addition of styrene gives a styryllithium chain
end, there will be a very fast addition of butadiene to regenerate butadienyllithium
ends. Thus, in a batch copolymerization, very few styrene units are incorporated
into the chains during the rst part of the reaction and they exist as isolated units.
Incorporation of styrene will increase only when nearly all the butadiene is con-
sumed. Overall, therefore, there is a block of nearly pure butadiene with some iso-
lated styrene units, followed by a rather short block where styrene and butadiene
are incorporated at almost the same rates a so-called tapered block, followed by
a nal block of nearly pure styrene (see Scheme 7.3). From Table 7.6 one can see
that a similar but reverse situation is valid in polar solvents; here styrene is con-
sumed rst and then butadiene, but again a copolymer with nearly pure blocks of
homopolymer will result.
7.2.1.5 Tailor-made Polymers by Living Polymerization Optimization
Anionic living polymerization oers a unique opportunity for tailor-made polymers
because all the chains and their living ends are accessible throughout the course of
the reaction. In general, there are two important tasks in tailoring polymers: one
concerns their chemical distribution and the other the molecular weight distribu-
tion.
0
0.2
0.4
0.6
0.8
0 5000 10000 15000 20000 25000 30000
t / s
x
S

i
n
p
o
l
y
m
e
r
x
S
= 0.5
x
S
= 0.65
x
S
= 0.35
Fig. 7.7. Batch copolymerization of styrene and butadiene with
n-butyllithium (1 g) at 20
C in toluene (10 kg) with various

styrene feed fractions x
S
(20 moles monomer overall).
Simulation of mole fraction of styrene in copolymer with data
from Ref. 35.
The structure of copolymers in terms of composition or sequence length distri-
bution may vary between two extremes copolymers with a very high level of
chemical heterogeneity within each chain, and homogeneous copolymers with the
comonomer units randomly distributed along the chain.
The various pathways to block copolymers are described in a number of reviews
and monographs [6, 121127]. In principle, block copolymers are accessible by se-
quential addition of monomers to either monofunctional or bifunctional [128, 129]
initiators (see Scheme 7.4, where the route from a monofunctional initiator to
a three-block copolymer is shown as an example). The amount of undesired by-
products homopolymers or di-block copolymers depends on the reactivity ratios
relative to propagation given in the scheme. These are obviously the ratios for
transfer and termination at higher temperatures, but also the ratios for initiation
and the cross-propagation reactions. From Figure 7.5 and Eq. (29) it can be seen
that the monomer for forming one block may be consumed before the initiator or
the ends of the previously formed block are completely transferred to the ends of
the new block, and so the yield of tri-block copolymers is reduced.
The optimal production of tri-block copolymers in a series of CSTRs, where the
reactors are operated in an isokinetic way, is described in Ref. 130.
To produce a copolymer with a more random structure in spite of the extreme
values of the copolymerization parameters, there are several possibilities. One is
R-S
o
-Li + R-Li
+ m Bu
R-S
o
-Bu
p
-Li + R-Bu
q
-Li + R-Li
+ l S
R-S
o
-Bu
p
-S
r
Li + R-Bu
q
-S
s
-Li + R-S
t
-Li
Reactivity ratios
for side reactions
Dead chains
SSSSSS
SSSSBBBBB + BBBBB
SSSSBBB +
SSSSBBBSSSS
S p
i
k
k
,
Bu p
Bu S
k
k
,
S p
S Bu
k
k
,
R-Li
+ n S
i p
tt
k
k
,
i p
tr
k
k
,
-L + -L
+ m Bu
-L -L +
+ l S
+ -
i
+
S p
i
k
k
,
Bu p
Bu S
k
k
,
S p
S Bu
k
k
,
+ n S
i p
tt
k
k
,
i p
tr
k
k
,
Scheme 7.4. Pathway to SBS tri-block copolymer and possible side products.
to use small amounts of polar additives such as THF, ethers, alkoxides, and so on
as modiers [131, 132], to bring the extreme r-values nearer to unity. Another obvi-
ous method is to polymerize in a continuous stirred tank reactor, where there is
no shift in composition. For the steady state, the copolymerization equation can
be written as a function of feed (index 0) and reactor concentrations [Eq. (43)].
[M
1
[
0
[M
1
[
[M
2
[
0
[M
2
[
=
r
1
[M
1
[
[M
2
[
1
r
2
[M
2
[
[M
1
[
1
(43)
A third possibility is model-based feed control [133], where butadiene is fed to a
mixture of styrene and butadiene in such a way that a certain monomer ratio is
maintained.
The other important task is to tailor the molecular weight distribution of the
polymer, and especially for this task the livingness in anionic polymerization is
advantageous [134]. Optimized reactor operations for broadened or bimodal distri-
butions in a tubular reactor are described in Refs. 135 and 136. Semi-batch opera-
tion with a programmed initiator feed [137, 138] and oscillating feeds to homoge-
neous CSTRs oer the possibility of a wide range of MWDs [139144].
7.2.1.6 Industrial Aspects Production of Living Polymers
In general, the requirements for purity of the reagents, solvents, and monomers
are much higher in anionic polymerization than in free-radical polymerization.
Necessary distillations and/or adsorption towers, often with activated aluminum,
increase the costs for feed preparation compared to free-radical processes.
Anionic polymerization of styrene has attracted much attention during recent
years and several publications and patents have been published on this issue. The
main reason for this interest is the high rate of polymerization which can be
achieved compared to free-radical polymerization, and the low content of residual
styrene and oligomers in the nal polymer [145147].
There are several concepts for an anionic process, which in many cases are oper-
ated in an adiabatic or at least non-isothermal mode. Some are using recirculated
loop reactors [148151] or single-pass tubular reactors [75, 152, 153], which may
be segmented [154]. A spray tower [155] has a similar residence time distribution,
but heat removal is by a countercurrent nitrogen stream. Boiling CSTRs are de-
scribed in Refs. 33 and 156. One problem seems to be fouling or gel formation in
regions of the reactor where the ow of living chains is limited [76].
Polybutadiene rubbers are produced either with transition metal catalysts to give
high-cis-butadiene rubber or with lithium alkyls to give medium-cis-butadiene
rubber (see Table 7.7). The latter is mainly used as the rubber component in the
production of HIPS (high impact polystyrene).
These rubbers are generally produced in aliphatic solvents [6, 157159] in a
CSTR or a series of CSTRs. The vinyl content, which is usually about 10% in ali-
phatic solvents, can be varied by the addition of polar compounds (see Table 7.3)
over a wide range.
Copolymers from styrene and butadiene (SBRs) with a more or less random co-
monomer distribution are produced either in an emulsion polymerization process
(cold or hot E-SBR), a free-radical polymerization, which however gives crosslinked
polymers, or in a solution process using lithium initiators (S-SBR). There are con-
tinuous processes [157, 158, 160166] as well as (semi-) batch processes (167, 168)
with a controlled feed of butadiene [133, 169] to maintain a constant monomer ra-
tio. Randomizers are often used [131, 170] to control the comonomer distribution.
Block copolymers and also star-shaped [171] block copolymers from styrene and
dienes are generally produced batch-wise with the monomers added in appropriate
sequences. These sequences depend on the functionality of the initiator (mono- or
bifunctional initiators) [172175], on the use of coupling agents [176, 177], and on
the sharpness of the transition between the various blocks. Another reason for ap-
portioning the monomer feed is the limited heat removal capacity of the reactor.
7.2.2
Anionic Polymerization of Vinyl Monomers Containing Heteroatoms
The possibilities of living polymerization described above have always attracted re-
searchers toward extending this technique to other vinyl monomers such as acryl-
ates (i), methacrylates (ii), cyanoacrylates (iii), nitriles (iv), and vinyl aldehydes or
ketones (v) (see Scheme 7.5). However, almost no industrial applications have
H
COOR
H
H
CH
3
COOR
H
H
COOR
H
H
CN
H
H
H
CN
H
H
H
COR
i ii iii
iv
v
Scheme 7.5. Monomers with heteroatoms for anionic polymerization.
Tab. 7.7. Microstructure of polybutadienes produced in hydrocarbon solvent with dierent
catalyst systems.
Catalyst cis-1,4 [ %] trans-1,4 [ %] 1,2 [ %]
Nd 98 1 1
Co 96 2 2
Ni 96 3 1
Ti 93 3 4
Li 36 52 12
been developed up to now for this group of monomers. Some overviews can be
found in Refs. 5 and 7. An interesting example of the application of these mono-
mers are the cyanoacrylates, which can be polymerized by very weak bases such as
water or skin proteins and which are used as superglues.
The reason for this deciency in application is the presence of side reactions,
which can only be suppressed by proper selection of the structure of the monomer
itself and the reaction conditions, especially the polymerization temperature. The
propagating center in the anionic polymerization of (meth)acrylates is the ester
enolate anion, which is formed according to Eq. (44).
CH
3
H
H COOMe
A
A CH
2
C H
3
O
OMe
+ (44)
The most important side reaction is the attack at the ester group, which can be
inter- or intramolecular [Eqs. (45) and (46)].
CH
3
H
H COOMe
R
CH
3
COR
H
H
Me O
+ + (45)
CH
2
CH
3
CH
3
O
OMe
C H
3 O
OMe
O
C H
3
O
+
CH
2
CH
3
CH
3
O
O
MeO
OMe
C H
3 O
OMe (46)
Another side reaction is the enolization of acrylate polymer chains [Eq. (47)].
A CH
2
C
COOR
H

CH
2
C
COOR

AH
+ +
(47)
Whether these side reactions are termination or transfer reactions depends on the
ability of the anions to re-initiate the polymerization and on the fate of the vinyl
ketone formed in Eq. (45). Generally, this vinyl ketone is rapidly incorporated into
the chain, and a relatively unreactive dormant end group is produced. The alkoxide
from reactions such as Eq. (45) is usually not reactive enough to initiate another
chain.
These side reactions can be suppressed to some extent at temperatures below
0
C, which make them hardly accessible in industrial applications. The t-butyl

group is reported to prevent side reactions. In general, the kinetic formalism for
the heteroatom-containing monomers is the same as that described in Section
7.2.2, but side reactions are more important. Some recent developments in the po-
lymerization of these monomers have been described in Refs. 178 and 179, and
these papers also cover the relevant mechanistic literature.
However, the anionic polymerization of (meth)acrylate monomers has not yet
gained industrial importance.
7.2.3
Anionic Polymerization of Monomers Containing Hetero Double Bonds
Besides monomers containing carboncarbon double bonds, monomers with het-
eroatoms at the double bond can also be polymerized via an anionic mechanism.
The only monomer with some industrial importance is formaldehyde. It is poly-
merized [180] via its carbonoxygen double bond to give polyacetal homopolymer
or polyoxymethylene [Eq. (48)].
nCH
2
O (aCH
2
aOa)
n
(48)
The polymerization is a precipitation polymerization from gaseous formaldehyde
in an inert solvent such as cyclohexane at fairly low temperatures to prevent depoly-
merization reactions. Amines such as tri-n-butyl amine are used as initiators. The
polymer precipitates in the dispersing agent as powder. After completion of the
polymerization, it is necessary to stabilize the hydroxyl end groups, for example
by esterication with acetic anhydride to prevent the unzipping reaction of Eq.
(49).
a(aCH
2
aOa)
n
CH
2
aOH a(aCH
2
aOa)
n1
CH
2
aOH CH
2
O (49)
7.2.4
Anionic Polymerization via Ring Opening
There are a number of heterocyclic monomers, for example, epoxides, cyclic sul-
des, lactones and lactides, lactams, cyclic carbonates, and cyclosiloxanes, which
can be polymerized by ring-opening reactions; many of them can be polymerized
by an anionic as well as by a cationic mechanism. They cannot all be covered here,
but there are a number of monographs and reviews on this subject [181185].
In polymerization via double bonds the driving force for chain growth is the en-
ergy dierence between one double and two single bonds, which in most cases is
high enough to overcome the loss in entropy when going from monomers to poly-
mers. In ring-opening polymerization the number and nature of the bonds remain
the same, and there is just the release of ring strain to make chain growth of cyclic
monomers an exothermic reaction. The Gibbs free energy of polymerization DG
P
is given in Eq. (50).
DG
P
= DH
P
TDS
P
(50)
The equilibrium constant K
P
for the chain growth step P
i
M P
i1
is dened in
Eq. (51) and the equilibrium monomer concentration [M[
e
in Eq. (52).
K
P
=
k
p
k
d
=
[P
i1
[
[P
i
[[M[
e
A
1
[M[
e
(51)
ln[M[
e
= (DH
P
TDS
P
)=RT (52)
For monomer concentrations below this equilibrium concentration, no polymeriza-
tion occurs. As for most polymers, the changes for entropy and enthalpy are both
negative (see Table 7.8), there exists a limiting temperature T
C
above which poly-
merization is thermodynamically forbidden. T
C
is given by Eq. (53), where the
standard state refers to unit concentration.
T
C
=
DH
P
DS
P
=
DH
0
P
DS
0
P
R ln[M[
(53)
From Table 7.8 it can be seen that for most of the cyclic monomers, the reversibil-
ity of the propagation must be taken seriously into account. It has been shown
[186] that, even for a living polymerization without any termination or transfer re-
Tab. 7.8. Standard thermodynamic parameters for some cyclic monomers for anionic
polymerization [182].
Monomer Atoms in ring States
[a]
DH
0
p
[kJ mol
C1
] DS
0
p
[ J mol
C1
K
C1
] [M]
e
[M]
O 3 gc 140 174 4 10
16
O
O 4 lc 82.4 74 3 10
11
O
P
O
O
OMe
5 ss 14 13.5 1:6 10
2
N
H
O
6 lc 7.1 27.6 1.58
O
O O
O 6 ss 22.9 41.1 1:16 10
2
N
H
O
7 lc 13.8 4.6 2:2 10
3
[a]
State of monomer (rst letter) and polymer (second letter): g gaseous, l liquid, s solution, c
condensed.
action but where the propagation step is reversible, the limiting molecular weight
distribution is not a Poisson distribution but a most probable distribution with
D = 2.
As the cyclic monomer and the linear polymer chain consist of the same bonds,
there are two further side reactions which are inherent to the system inter- and
intramolecular chain transfer to polymer (Scheme 7.6).
By intermolecular chain transfer there is no change in P
n
, because the number
of chains remains the same, but a scrambling of the molecular weight distribution
will occur, leading to the most probable MWD as a limiting distribution. Intra-
molecular chain transfer will lead to macrocycles, which also can participate in
propagation reactions. The equilibrium concentration according to the Jacobsen
Stockmayer theory [187] of these non-strained macrocycles of size n is given by
Eq. (54).
[M
n
[
e
=
k
p
(n)
k
p
(n)
An
5=2
(54)
The anionic polymerization of lactams [188, 189] is usually via a so-called activated
anionic mechanism with a two-component catalyst system from a strong base and
an N-acyllactam. It is interesting in the sense that the active center of the growing
chain is an N-acyllactam end group to which a lactamate anion, formed from the
monomer, is added (Scheme 7.7). First, there is H-abstraction from the monomer
to give the lactamate anion. In principle, this anion could add to another lactam
molecule, but this step is rather slow. Instead it will add much faster to the N-
acyllactam activator. A subsequent proton transfer gives the active N-acyllactam
end group and the lactamate anion is regenerated. The chain propagation consists
of the same sequence of elementary reactions.
This activated anionic polymerization is living in the sense that the number of
active centers is preserved; but the inevitable intermolecular chain transfer to poly-
X X X X X
X
X X X X X X
X X X X X
X X X X X
X
X X X X X
X
X X X X X
X X X X X
+
X X X
+
X
X
X
+
+
k
p
k
inter
k
intra
k
intra
Scheme 7.6. Chain growth, inter- and intramolecular transfer in ring-opening polymerization.
mer, here the transamidation, together with the propagationdepropagation of the
cyclic monomer and macrocycles, will broaden the molecular weight distribution
[189].
This polymerization has attracted much attention because it is very fast com-
pared to the hydrolytic polymerization of e-caprolactam, which takes several hours,
whereas the anionic polymerization is complete within minutes, even below the
melting point of the polymer. However, no large-scale process is known [190,
191]. The anionic polymerization of caprolactam is described in melt in extruders
[192, 193], in direct polymerization to bers [194] and in casting and RIM pro-
cesses [195]. The latter processes, particularly, are performed below the melting
temperature, so the equilibrium monomer (and oligomer) concentration is
much lower (13%) compared to the hydrolytic polymerization (1012%), where
a monomer extraction step is necessary.
The polymerization of ethylene oxide was one of the rst living polymerizations
[196]. Polymers from oxiranes, polyoxyalkylenes, are used in a wide range of mo-
N
H
O
B
N
O
N
O
R
O
N
O
N
O
R
O
N
O
N
O
R
O
N
O
N
H
O
N
O
N
H
O
R
O
N
O
N
O
N
H
O O
N
O
*
n

N
H
O O
N
O
*
n

N
O
N
H
O O
N
O
n

N
O
N
H
O
N
O
N
H
O O
NH
O
n

N
O
+
initiation
+
+ +
+
propagation
+
+
Scheme 7.7. Activated anionic mechanism for ring-opening polymerization of lactams.
lecular weights and applications [2224]. The most important ones are rather low
molecular weight polymers, which are used either as nonionic surfactants [197] or
as raw materials for polyurethanes [23, 24].
Scheme 7.8 is a general reaction scheme for the copolymerization of ethylene
oxide and propylene oxide with multifunctional alcohols as initiators.
Usually potassium alkoxides, often from multifunctional alcohols, are used as
initiators. They are formed in a separate step starting from the respective alcohol
and potassium hydroxide. The resulting water must be removed to ensure maxi-
mum conversion to the potassium alkoxide. Remaining water will terminate grow-
ing chains, forming hydroxyl end groups. Chains with alkoxide end groups can
undergo chain transfer reaction with hydroxyl-terminated chains. This proton ex-
change, which may also happen with multifunctional initiator molecules, is the
fastest reaction in this scheme. The acidity of the participating species is rather
similar; the dierences are generally those between primary and secondary hy-
droxyl groups, so the equilibrium constant for the proton exchange is around unity.
O H OH
OH
KOH O H O
OH
O H
2
K
+
O H
O
OH
K
+
O H OH
O
K
+
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
R
O H
2
K
+
K
+
K
+
K
+
K
+
K
+
K
+
K
+
K
+
OH
R
O H
2
O
O
R
n K
+
OH
O
R
m

OH
O
R
n O
O
R
m

K
+
+ +
initiatior formation
+
+
+
+
copolymerization
EO / PO
+
+
Termination
+
+
chain transfer
Scheme 7.8. Anionic ring-opening copolymerization of ethylene and propylene oxide.
This equilibrium between active and non-active chains is very fast, so in general
a Poisson distribution will result. For the case where the rst addition is dierent
from the subsequent ones, either the Gold distribution [58] in Eq. (30) or a distri-
bution given by Weibull [198] can be used. A recursive formula for a more complex
distribution assuming dierent reactivities for each addition of ethylene oxide is
given in Ref. 199.
However, it has been shown that normally the chain length dependence of the
propagation rate coecient is not important, with the exception of the rst unit
[200, 201]. Both distributions can be used to describe ethoxylation reactions [202].
There are a number of recent publications on the kinetics and copolymeriza-
tion kinetics of ethylene and propylene oxide initiated with several alcohols and
KOH [203209]. The copolymerization parameters are generally in the ranges of
r
E
= 24, r
P
= 0.150.3, showing the higher reactivity of ethylene oxide.
One important side reaction, which may occur at higher temperatures, is the iso-
merization of propylene oxide to allyl alcohol [210, 211], leading to an unsaturated
end group (1) which may aect polyurethane production.
R O CH
2
CH CH
2
1
The industrial process [23, 212, 213] of ethoxylation and propoxylation is usually a
semi-batch process. The starter alcohol and KOH are mixed and water is removed
by distillation. In a second step, monomers are fed into the reactor, where the feed
rate is chosen so as to be able to remove the heat of polymerization and to keep the
latent heat of polymerization of unreacted monomers in a safe state. By this pro-
cess, homopolymers and random copolymers are accessible. Block copolymers are
produced by successive feeds of the respective monomers. Catalyst is removed by
addition of acids and subsequent crystallization and ltration of precipitated salts.
An optional fourth step is the removal of volatile compounds by distillation.
7.3
Cationic Polymerization
There are many monomers that can be polymerized via a cationic mechanism (see
Table 7.1), but the most important polymers from an industrial point of view are
homo- and copolymers from isobutene and from some heterocyclic monomers
such as trioxane, tetrahydrofuran, and epoxides. There is a detailed discussion on
the mechanistic features in Refs. 15, 7, and 181183.
7.3.1
Cationic Polymerization of Vinyl Monomers
Cationic polymerization of vinyl monomers is by electrophilic addition of the
monomer to a growing carbenium ion. The reactivity of vinyl monomers in cati-
onic polymerization follows the electron-donating ability of the substituents at the
double bond. Electron-donating substituents increase the nucleophilicity of the
double bond in the addition reaction and stabilize the resulting carbenium ion.
The general order of reactivity in cationic polymerization is given in Eq. (55).
N
C H
2
CH C H
2
CH
OR
CH C H
2
OMe
C H
2
Me
CH C H
2
Me
C H
2
Me
(55)
Initiation is by either strong protonic acids (perchloric acid, triic acid, and so on)
or Lewis acids together with a co-initiator such as BF
3
/H
2
O, AlX
3
/RX. As discussed
for anionic polymerization, for cationic polymerization also several dierent spe-
cies may be involved in propagation, but it has been pointed out (Ref. 2, pp. 190,
205) that the reactivity dierences between the various species carbenium ions
and ion pairs are not very great. Covalent species are not active in propagation.
In general, propagation rate coecients in cationic polymerization are very large.
A very comprehensive review is given in Ref. 214. For isobutene, values of
1:5 10
8
M
1
s
1
are reported at 0 and 78
C [215]. For such high rate coe-

cients the polymerization may become diusion-controlled, which has been ad-
dressed [216] for a tubular reactor.
In cationic polymerization of alkenes, there is an equilibrium between active
ions or ion pairs and inactive covalent species, where the ionization constant is
rather low (10
5
M
1
in the isobutene/BCl
3
system). The dynamics of this equilib-
rium strongly aects the width of the molecular weight distribution. For the se-
quence of reactions [Eq. (56)] the polydispersity of the distribution is given by Eq.
(57) [217], if there are no other side reactions such as transfer or irreversible termi-
nation.
kp
M
H
3
CaCH
kass
kion
H
3
CaCHA
M
(56)
a a
R R
D = P
w
=P
n
= 1 [I[
0
k
p
=k
ass
(57)
Bimodal distributions may result, if free ions and ion pairs have the same reactivity
but dierent lifetimes [218].
However, transfer reactions are nearly unavoidable side reactions in cationic
polymerization and may involve b-proton transfer even to rather weak bases like
the monomer itself, to transfer agents and solvent as well as FriedelCrafts alkyla-
tion of aromatic rings, if monomers like styrene are polymerized. Proton transfer
yields unsaturated chains [Eq. (58)], with the double bond in either the endo or exo
position. These may lead to branched polymers, if the double bonds are accessible
to homo- or copolymerization.
C
+
*
n

A C
+
A
*
n

*
n

+
+
+ (58)
As proton transfer usually has the higher activation energy, the molecular weight
of the polymer decreases with temperature. Tabulated transfer coecients may be
taken from Refs. 219 and 220.
The problem of living or non-living cationic polymerization of alkenes is ad-
dressed in Refs. 220 and 221. It is shown that, depending on the molecular weight,
even for transfer constants up to 5 10
4
the system exhibits the behavior of a liv-
ing system, such as a linear increase of molecular weight with conversion, rather
narrow distributions, and so on.
Copolymerization parameters for cationic polymerization can be found in Refs.
3, 222, and 223. Note that the scattering of data in higher and so the reliability
of copolymerization parameters for cationic polymerization are much less than for
radical polymerization.
Commercial polymers [2, p. 683, 157, 224] from isobutene involve isobutene
homopolymers and butene rubbers. Polyisobutene homopolymers comprise a
wide range of polymers with molecular weights from a few thousand grams per
mole up to 10
6
g mol
1
, and butene rubbers are copolymers of isobutene with
13 mol% of isoprene. High molecular weight homopolymers are produced in the
continuous BASF belt process at 100
C in boiling ethylene to remove the heat of

polymerization. The ethylene evaporates during polymerization and the polymer is
scraped from the belt. Volatiles are removed in twin-screw extruders. Homopoly-
mers and rubbers are also produced in the Exxon slurry process in methyl chloride
at 95
C. The polymerization rate is controlled by initiator feed and cooling is

with liquid ethylene and/or propylene. The polymer slurry is withdrawn from the
top of the reactor and worked up downstream.
Medium and low molecular weight polymers are produced in solution processes
in light hydrocarbons in CSTR reactors or in recirculating tubular (loop) reactors.
The molecular weight is controlled by monomer purity, initiator, water content,
and temperature.
7.3.2
Cationic Ring-opening Polymerization
Monographs and reviews of this subject can be found in Refs. 181185 and 225
227. The most important polymers from cationic ring-opening polymerization are
polyoxyalkylenes with one or four CH
2
groups produced by the polymerization of
trioxane and tetrahydrofuran. The smaller epoxides, ethylene and propylene oxide,
though able to polymerize by a cationic and anionic mechanism, are not polymer-
ized cationically, because of the existence of side reactions leading to dioxane or
dioxolane [228]. In contrast to these smaller homologs, THF and trioxane can only
be polymerized by a cationic mechanism [23, 229].
Initiation can be by strong protonic acids such as perchloric acid and uorosul-
fonic acid, oxonium salts like triethyloxonium (Et
3
O
, A
= BF
4
or SbCl
6
), and
Lewis acids, for example BX
3
, PF
5
, SBF
5
, and so on. Lewis acids usually need a
co-initiator, which in many cases is water, which is present to some extent in
the monomer even after purication. Hetero polyacids of the general formula
H
n
X
m
Mt
z
O
y
with X = P or Si and Mt = Mo; W or V, have gained more and more
importance, especially for THF. The active chain end is usually an oxiranium ion
(2).
O
+
R
2
Ions and ion pairs are both active in propagation, but their respective contribution
usually cannot be distinguished because of the high exchange rates between the
two. Covalent species may reversibly result from association with counter ions
such as CF
3
SO
3
or ClO
4
. They may participate in propagation reactions, but their
reactivity is much less than that of the ionic species (see Table 7.9). A detailed dis-
cussion on the kinetics of propagation for THF is given in Ref. 182.
Because of the low energy gain from ring strain, the equilibrium monomer con-
centration for the ve- and six-membered rings such as THF and trioxane during
polymerization is rather high (see Figure 7.8).
As already discussed (see Section 7.2.4), inter- and intramolecular transfer reac-
tions to polymer are of great importance with regard to the molecular weight dis-
tribution (Scheme 7.6). In complete thermodynamic equilibrium, the conversion
should be given by the equilibrium monomer concentration and the molecular
weight distribution should be the most probable one with D = 2, because of the
intermolecular chain transfer, which is responsible for scrambling of the molecular
Tab. 7.9. Propagation rate coecients for some monomers for ionic and covalent species [2].
Monomer Counter ion Solvent T [
C] Propagating species k
p
[M
C1
s
C1
]
THF CF
3
SO
3
CCl
4
25 ionic
covalent
4 10
2
6 10
5
CH
2
Cl
2
25 ionic
covalent
3:1 10
2
1:7 10
4
CH
3
NO
2
25 ionic
covalent
2:4 10
2
5 10
4
Oxepane CF
3
SO
3
H
3
NO
2
25 covalent
ionic
1:4 10
4
4 10
4
Oxazoline CH
3
C
6
H
4
O
CD
3
CN 40 covalent
ionic
1:9 10
3
1:8 10
5
weight distribution. Intramolecular chain transfer will give macrocycles, the con-
centration of which should be proportional to n
5=2
[Eq. (54)], if ring formation is
reversible and all equilibrium conditions are fullled. Examples of this ideal equi-
librium between linear and cyclic polymers are found for 1,3-dioxolane and sil-
oxanes [230, 231].
However, for THF it has been shown [232] that, even after monomer conversion
has reached the equilibrium concentration, there is still a buildup of cyclic mono-
mers [Eq. (59)]: that is, the system is not yet in equilibrium with respect to macro-
cycles and transfer reactions may still proceed.
O
O
+ O
+
O
O
+
O
+
+
(59)
So, in spite of these transfer reactions, linear polymers with a narrow molecular
weight distribution can be formed by kinetic control, if, as for THF, the transfer
rate coecient to polymer is rather small. Chain growth, and consequently conver-
sion and kinetic chain length, may have reached their equilibrium faster than
the other equilibrium reactions. Depending on reactivity ratios in propagation and
transfer, the polymerization can be stopped at low conversions, yielding the desired
linear and narrow product [233].
In contrast, transfer rates for trioxane to polymer are extremely fast. This can
be seen from the observation that during copolymerization of trioxane with 1,3-
dioxolane, ethylene oxide, and similar comonomers, the comonomer is nearly com-
pletely consumed at an early stage of reaction [229, 234236]. One would therefore
expect longer sequences of these comonomers. However, it has been shown, from
0
0.5
1
1.5
2
2.5
0.0028 0.003 0.0032 0.0034 0.0036
1/T / 1/K
l
n
[
M
]
Fig. 7.8. Equilibrium THF concentration during polymerization according to Ref. 252.
NMR and stability studies, that the comonomers are randomly distributed along
the chains [237, 238]. This is attributed to the fact that intermolecular chain trans-
fer (transacetalization), contrary to THF polymerization, proceeds on a time scale
similar to propagation, and the same holds for the intramolecular chain transfer
leading to cyclic polymer [239, 240]. Cationic polymerization of trioxane is usually
a precipitation polymerization leading to crystalline polymers, and the size of the
macrocycles is determined by the size of the crystalline lamellae [240].
The polymerizationdepolymerization equilibrium is not between the growing
chain and the originally propagating monomer, trioxane, but to formaldehyde [Eq.
(60)] [241, 242]. Thus formaldehyde should be considered as a comonomer [236,
243], which will be accumulated until its equilibrium concentration and pressure
is reached.
RaOCH
2
aOCH
2
aOCH
2
aOaCH
2
TRaOCH
2
aOCH
2
aOaCH
2
CH
2
O (60)
This unzipping depolymerization occurs during polymerization, but it may also oc-
cur under thermal stress with the neutralized polymer; unzipping then starts from
neutral but unstable end groups such as aOH or aCHO or from statistical chain
scission. Unzipping will stop at comonomer units such as those from ethylene ox-
ide, dioxepane, and similar monomers, which are not able to depolymerize, and a
then stable copolymer will result. Homopolymers, which are usually polymerized
anionically from formaldehyde (see Section 7.2.3) will not be stable unless unstable
end groups are transformed to stable ones.
There are several industrial processes for poly-THF and polyoxymethylene.
Cationic polymerization of poly-THF may be batch-wise or continuous [23, 244]
using strong protonic acids in a temperature range of 30
to 60
C, depending
on the desired molecular weight. Newer processes use solid catalysts like zirco-
nium oxide together with acetic anhydride to form poly-THF with two acetate end
groups, which later are hydrolyzed to give the dihydroxy polymer. Other acidic cat-
alysts such as zeolites or acid montmorillonite clay are also described [245247].
The cationic copolymerization of trioxane with ethylene oxide, 1,3-dioxolane, and
suchlike is initiated either with strong protonic acids or Lewis acids, for example
BF
3
. Molecular weight is controlled by the catalyst concentration and monomer
purity, and also by chain transfer agents such as methylal [248], which may lead
to more stable end groups. Most processes are run below the melting temperature
of the polymer (164167
C) in precipitating agents or in bulk, and are carried out

in kneaders or double-screw reactors [249, 250], but there are also some descrip-
tions of melt processes [251].
7.4
Conclusion
Ionic polymerization oers several advantages. In many cases, it is much faster
than free-radical polymerization or polycondensation. This is either because of
very high rate coecients for propagation, especially in the case of cationic poly-
merization, or because of the high stationary concentration of active centers, for
example in living anionic polymerization compared to free-radical polymerization.
Furthermore, because of its site-based nature, it oers more control over the struc-
ture of the resulting polymer by changing the reactivity of the active center when
using dierent counter ions, solvents, complexing agents, or salts as additives. So a
wide range of structural isomers can be obtained, and copolymerization parame-
ters may be varied over a wide range, resulting in structures ranging from block
copolymers to random copolymers from the same pair of monomers, which is not
possible by free-radical polymerization.
However, from a kinetic and modeling point of view, this site-based nature of
ionic polymerization also has some disadvantages. Because the reactivity of the
active center strongly depends on the nature of the initiator and on all the other
factors in the polymerizing system, the kinetic scheme and parameters of every
system are dierent, and so in general they must be determined again for every
change in the system.
The high sensitivity to impurities necessitates much more eort to purify mono-
mers and solvents. This may prevent the wider employment of ionic polymeriza-
tion. Generally, ionic polymerization is used for monomers which cannot be poly-
merized by free radicals, or for the production of polymer structures which are
otherwise not accessible.
Notation
D polydispersity index
f
i
mole fraction of monomer i in the monomer mixture
F
i
mole fraction of monomer i in polymer chains being formed
h(i) frequency distribution of chain length
i degree of polymerization
[I[
f
initiator feed concentration
k
t
rate coecient for termination [M
1
s
1
]
k
tt
rate coecient for thermal termination, for example, LiH elimination
[s
1
]
k
AB
rate coecient for chain propagation [M
1
s
1
] for monomer B
added to chain ending with A
k
ass
rate coecient of association
k
ion
rate coecient of ionization, dissociation
k
p
rate coecient for chain propagation [M
1
s
1
]
k
d
rate coecient for decomposition [s
1
]
k
i
rate coecient for chain initiation [M
1
s
1
]
K equilibrium constant, general
K
ass
equilibrium constant of association
[M] monomer concentration [M]
[M[
eq
equilibrium monomer concentration
Notation 357
[M[
f
monomer feed concentration
M
n
number-average molecular weight [g mol
1
]
M
w
weight-average molecular weight [g mol
1
]
[N
i
[ concentration of polymer chains with degree of polymerization i
n association number or ring size
P
n
number average degree of polymerization
P
w
weight average degree of polymerization
r
1
; r
2
copolymerization parameters according to the terminal model
r ratio of k
p
=k
i
for living polymerization
R
p
rate of propagation [M s
1
]
R gas constant
T temperature
T
C
ceiling temperature
_ vv
in; I
initiator feed ow [L s
1
]
_ vv
in; M
monomer feed ow [Ls
1
]
w(i) mass distribution of chain length
x
M
monomer conversion
x
I
initiator conversion
Greek
DG
p
Gibbs free energy of polymerization
DH
p
enthalpy of polymerization
DS
p
entropy of polymerization
t residence time
n average kinetic chain length
Acronyms
s- (t-, n-)Bu sec.- (tert.-, n-)butyl
CSTR continuous stirred tank reactor
HCSTR homogeneous continuous stirred tank reactor
M, M
+
monomer molecule (
+
, with active center)
T, T
+
transfer agent (
+
, with active center)
THF tetrahydrofuran
PaLi growing polymer chain with lithium counter ion
PsH polystyrene molecule ending with hydrogen
P
i
polymer chain with degree of polymerization i
HIPS high-impact polystyrene
NMR nuclear magnetic resonance
RIM reaction injection molding
SBR styrenebutadiene rubber
SCSTR segregated continuous stirred tank reactor
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8
Coordination Polymerization
1
Joao B. P. Soares and Leonardo C. Simon
8.1
Polyolen Properties and Applications
8.1.1
Introduction
Polyolens are among the most important commodity plastics today due to their
low production costs, reduced environmental impact, and a very wide range of ap-
plications. They are found in products as diverse as prosthetic implants, gas pipe-
lines, automobile parts and accessories, synthetic fabrics, lms, containers, and
toys.
It may seem surprising that polymers composed only of carbon and hydrogen
atoms can be so exible, but the versatility of polyolens can be easily explained
by the way the monomer molecules ethylene, propylene, and higher a-olens
are connected to form the polymer chains. It is true for any polymer, but dramati-
cally so for polyolens, that chain microstructure is the key to understanding their
physical properties.
Polyolens are produced in practically all types of reactor congurations
autoclaves, tubular reactors, loop reactors, uidized-bed reactors making them a
prime choice for polymer reaction engineering studies. Polymerization may take
place in either gas or liquid phases. For liquid-phase reactors, the monomers can
be either liquid (as in the case of propylene and higher a-olens) or dissolved in an
inert diluent. Industrial catalysts for olen polymerization are mainly heteroge-
neous, but some processes also use soluble catalysts. There are many dierent
types of catalysts for olen polymerization and they can be used to synthesize poly-
mer chains with very dierent microstructures and properties.
Despite the fact that polyolens use comparatively simple monomers and have
been around for many years, it can be said with condence that the degree of
sophistication of polyolen manufacturing and characterization techniques has
ISBN: 3-527-31014-2
365
no equal among other synthetic polymers. In this chapter, we will introduce the
reader to this fascinating eld of polymer reaction engineering by giving an over-
view of the dierent scientic and technological aspects related to olen polymer-
ization with coordination catalysts.
8.1.2
Types of Polyolens and Their Properties
Polyethylenes are the commercial polyolens with the highest tonnage. Figure 8.1
compares the molecular structures of some polyethylene resins made by coordina-
tion and free-radical polymerization. (Free-radical polyolens are not the main
topic of this chapter and will be described only in contrast with polyolens made
with coordination catalysts.)
The oldest type of commercial polyolen is low-density polyethylene (LDPE)
made by free-radical polymerization. Low-density polyethylene is made using
supercritical ethylene under severe polymerization conditions in autoclaves
(15002000 atm, 180290
C) or tubular reactors (15003500 atm, 140180
C). Be-
cause of backbiting and chain transfer to polymer reactions, LDPE has both short-
and long-chain branches. These branches decrease the crystallinity and density of
the polymer typically in the range 0.9150.935 g cm
3
and aect several other
mechanical and rheological properties. Low-density polyethylene is used predomi-
nantly for making lms because of its limp feel, transparency, and toughness.
Additionally, the long-chain branches give excellent processability and high melt
tension to LDPE.
High-density polyethylene (HDPE) was rst made with ZieglerNatta catalysts.
When produced as a homopolymer, HDPE has no short-chain branches, but a
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
C
H
H
LDPE LLDPE / VLDPE HDPE
0.96-0.97 g/cm
3
0.915-0.94 g/cm
3
/ 0.88 - 0.912 g/cm
3
0.915-0.935 g/cm
3
Fig. 8.1. Polyethylene microstructures.
366 8 Coordination Polymerization
very small amount of a-olen comonomer can be copolymerized with ethylene
to form short-chain branches that decrease its density. Typically, the density of
HDPE resins is in the range from 0.96 to 0.97 g cm
3
. Since HDPE has few or no
short-chain branches, it has much greater rigidity than LDPE and can be used in
structural applications.
Linear low-density polyethylene (LLDPE) is a copolymer of ethylene and a-olens
(generally 1-butene, 1-hexene, or 1-octene) with densities in the range 0.9150.94
g cm
3
. Products with even lower densities, down to 0.88 g cm
3
, are sometimes
called very low-density polyethylene (VLDPE) but are chemically identical to
LLDPE. Copolymerization of ethylene with increasing amounts of a-olens dis-
rupts the order of the linear polyethylene chains by introducing short-chain
branches. As a consequence, the density, crystallinity, and rigidity of LLDPE are
lower than for HDPE. Linear low-density polyethylene is used predominantly in
lms, and shares the market with LDPE.
Polypropylene is the second most important commercial polyolen. While free-
radical polymerization can only produce atactic polypropylene, ZieglerNatta cata-
lysts can make highly isotactic polypropylene. The chain regularity of isotactic
polypropylene is responsible for its high melting temperature and crystallinity,
making it ideal for injection molding and extrusion applications due to its excellent
rigidity, toughness, and temperature resistance. Metallocene catalysts can produce
several types of polypropylenes with other stereosequences, as illustrated in Figure
8.2 for some representative catalysts. Isotactic polypropylene is by far the leader
among the commercial stereoisomers of polypropylene, but syndiotactic polypropy-
lene and some stereoblock elastomeric polypropylenes made with metallocene cat-
alysts have attracted some interest lately [13].
Olens are commonly polymerized in a single reactor or in two or more reactors
in series. Single reactors are used when a polyolen with more uniform composi-
tion is required, while reactors in series are employed for the commercial produc-
isotactic
syndiotactic
isotactic-
stereoblock
isotactic-
atactic-
stereoblock
hemi-isotactic
atactic
Cp
2
ZrCl
2
Et(Ind)
2
ZrCl
2
iPr(Flu)(Cp)HfCl
2
(NMCp)
2
ZrCl
2
Et(Me
4
Cp)(Ind)TiCl
2
iPr(Cp)(Ind)ZrCl
2
Fig. 8.2. Polypropylene microstructures and some metallocene catalysts used in their synthesis.
tion of homopolymers and copolymers with more elaborate microstructural distri-
butions. A series of reactors allows for signicant exibility during polymerization,
since each reactor can be kept in dierent polymerization conditions to make a
polymer that can be considered a blend of two or more components (reactor
blends). High-impact propylene/ethylene copolymers are the most typical example
of this polymerization technique. Propylene is fed to the rst reactor, producing
isotactic polypropylene particles. A mixture of propylene and ethylene is fed to the
second reactor to make a propyleneethylene amorphous copolymer phase which
is dispersed within the isotactic polypropylene particles already formed. The amor-
phous copolymer fraction is responsible for increasing the impact strength of the
homopolymer matrix formed in the rst reactor, as illustrated in Figure 8.3.
Another important example of polyolens produced with reactors in series com-
prises HDPE resins for pipe applications. It will be shown later that when ethylene
and a-olens are copolymerized with a heterogeneous ZieglerNatta catalyst in a
single reactor, the low molecular weight chains are also the ones that contain the
highest a-olen fraction. For pipe applications this is undesirable because it de-
creases the environmental stress cracking resistance of the polymer [4, 5]. One
way of overcoming this problem is to produce a high molecular weight copolymer
in the rst reactor in the absence of chain-transfer agent and a lower molecular
weight homopolymer in the second reactor in the presence of chain-transfer agent.
Coordination catalysts are also used to make elastomers, notably ethylene
propylenediene (EPDM) rubbers [6]. In this case, homogeneous catalysts are pre-
ferred to heterogeneous ones because they generally produce polymers with a
more uniform distribution of crystallinity. The unreacted double bonds of the
dienes are used during rubber crosslinking reactions. Figure 8.4 shows some typi-
cal examples of dienes used for the manufacture of EPDM rubbers.
PC
TC
PC
TC
catalyst +
diluent
propene
propene + ethene
c.w. c.w.
rubber domains
homopolymer matrix
product
Fig. 8.3. Process for the production of high-impact polypropylene.
8.1.3
The Importance of Proper Microstructural Determination and Control in Polyolens
Since polyolens are composed of only carbon and hydrogen atoms, the way
these atoms are connected in other words, the microstructure of a polyolen
determines their properties. At the most elementary level, the microstructure of a
polyolen is dened by its distributions of molecular weight, chemical composi-
tion, long-chain branching, and stereoregularity. Therefore, determining the micro-
structure of polyolens can be considered the rst and most important step toward
the understanding of their properties.
High-temperature gel permeation chromatography (GPC) is the standard tech-
nique for measuring the molecular weight distribution of polyolens. Since gel
permeation chromatography is a very well-established technique it will not be dis-
cussed here. Several publications provide additional discussions on the GPC tech-
nique [79].
The chemical composition distribution of polyolens is measured (indirectly)
by either temperature rising elution fractionation (Tref ) or crystallization analysis
fractionation (Crystaf ). These two techniques provide similar information on the
chemical composition distribution of polyolens and can be used interchangeably
in the vast majority of cases. Both methods are based on the fact that the crys-
tallizability of HDPE and LLDPE depends strongly on the fraction of a-olen como-
nomer incorporated into the polymer chains, that is, chains with an increased a-
olen fraction have a decreased crystallizability. A similar statement can be made
for polypropylene and other polyolen resins that are made with prochiral mono-
mers: resins with high stereoregularity and regioregularity have higher crystalliz-
abilities than atactic resins.
In Crystaf, polyolen chains are crystallized from a dilute solution by slowly
lowering the solution temperature. Chains with fewer a-olen units crystallize at
higher temperatures, while chains with a higher a-olen fraction crystallize at
lower temperatures. This information is used to generate a Crystaf prole relating
crystallization temperatures to the fraction of polymer that crystallizes at those
5-ethylidene-2-norbornene
1,4-hexadiene
dicyclopentadiene
CH - CH
3
CH
2
= CH - CH
2
- CH = CH - CH
3
Fig. 8.4. Dierent dienes used for the production of EPDM.
temperatures. The Crystaf prole is then converted into the chemical composition
distribution by means of a calibration curve relating the fraction of a-olen in the
copolymer to the crystallization temperature, as illustrated in Figure 8.5. Tempera-
ture rising elution fractionation operates in a similar way to Crystaf, but involves
one additional step, when the chains crystallized during the crystallization period
described above are eluted from the Tref column to generate the Tref prole. A
Tref calibration curve, similar to the Crystaf calibration curve, is used to transform
the Tref curve into the chemical composition distribution. More details of the Tref
and Crystaf analytical procedures can be obtained from many recent publications
[7, 10, 11].
For our purposes in this chapter, it suces to say that the chemical composition
distribution of LLDPE made with heterogeneous ZieglerNatta catalysts is gener-
ally bimodal or multimodal, as illustrated in Figure 8.6. This clearly indicates that
heterogeneous ZieglerNatta catalysts have at least two but probably more
distinct active-site types with dierent reactivity ratios for a-olen incorporation:
one site type produces polymer with a low a-olen content, while the other site
type makes polymer with a much higher a-olen content. The presence of two or
more active sites on heterogeneous ZieglerNatta catalysts is also conrmed by the
fact that they produce polyolens with broad molecular weight distributions and
polydispersities much higher than the theoretical value of 2 that would be expected
for polymers made with coordination catalysts containing a single site type, as will
T
c
Crystaf vessel
-olefin fraction
Cumulative
Crystaf Profile
T
c
w
T
c
d
w
/
d
T
c
Differential
Crystaf Profile
T
c
Calibration Curve
Chemical Composition
Distribution
w
-olefin fraction
Fig. 8.5. Estimation of the chemical composition distribution
of a polyolen using a Crystaf prole and a calibration curve.
be discussed in more detail below. In addition, the chains with the lower a-olen
fractions are also the ones with the higher molecular weight averages, as depicted
in Figure 8.7 [12]. In this way, the distributions of molecular weight and chemical
composition of polyolens made with heterogeneous ZieglerNatta catalysts are al-
ways coupled and are, in fact, considered the ngerprint of these resins.
The molecular weight distribution of polypropylene made with heterogeneous
ZieglerNatta catalysts is also broad, with polydispersities higher than 2. In addi-
tion, some catalysts will also produce polypropylene with a distribution of stereo-
regularities that can be traced back to the presence of multiple active-site types
with distinct stereochemical control characteristics [13].
On the other hand, several homogeneous ZieglerNatta and metallocene cata-
lysts make HDPE, LLDPE, and polypropylene with narrow distribution of chemical
composition and molecular weight with the theoretical polydispersity of 2. The av-
erage a-olen fraction for these polymers is constant and independent of molecular
weight, which conrms that they are made by a single-site catalyst [14]. In fact, the
ability to make polyolens with narrow microstructural distributions, and con-
sequently with a much better control of polymer microstructures and properties,
is one of the main reasons why metallocene catalysts have had such an impact on
the polyolen manufacturing industry since the 1980s.
An equally important contribution of metallocene catalysts to polyolen syn-
thesis is the ability to produce polyethylene and polypropylene with long-chain
branches. These narrow-MWD resins have excellent processability and melt
strength due to the presence of few long-chain branches (often less than 1 per
1000 carbon atoms) and have had a marked impact on the polyolen industry
[15]. The only absolute way of measuring long-chain branches in polyolens is by
carbon-13 nuclear magnetic resonance (
13
C NMR) but, due to the low levels of
long-chain branches generally present in these resins, these measurements are
Easier to crystallize
More difficult
to crystallize
Mol % -olefin comonomer
Crystallization temperature
W
e
i
g
h
t

f
r
a
c
t
i
o
n
Fig. 8.6. Chemical composition distribution of a polyolen
made with a heterogeneous ZieglerNatta catalyst.
very often subject to signicant experimental error. Nonetheless, very good evi-
dence of the presence of long-chain branches can be found by studying the rheo-
logical response of these resins. Long-chain branch formation with polyolens will
be discussed in detail below in Section 8.3.4.
8.2
Catalysts for Olen Polymerization
The class of catalysts we currently call ZieglerNatta was rst used by Ziegler in
1953 to polymerize ethylene at low pressure, and further developed by Natta in
1954 to produce isotactic polypropylene. Both Ziegler and Natta were awarded the
Nobel Prize in chemistry in 1963; since then, this eld has grown incessantly, with
the development of improved catalysts and new industrial processes.
Many other catalysts capable of polymerizing olens have become available since
the original ZieglerNatta catalyst based on crystalline titanium chloride was intro-
duced. More recently, the discovery of soluble metallocene/aluminoxane catalysts
opened the doors to a new revolution in the production of polyolens. These cata-
lyst systems are able to make polyolens in very high yields and with a degree of
microstructural control not possible to achieve using conventional ZieglerNatta
catalysts.
Most industrial processes today still use heterogeneous ZieglerNatta catalysts,
although the market share of metallocene resins is increasing due to the enhanced
x, mole % butene
N
o
r
m
a
l
i
z
e
d

r
e
s
p
o
n
s
e

(
a
.
u
.
)
M
w
0.00
0.06
0.04
0.02
0 2 4 6 8 10
2x10
5
10
5
8x10
4
6x10
4
4x10
4
Fig. 8.7. Average weight-average molecular weight of ethylene
1-butene copolymers made with a heterogeneous ZieglerNatta
catalyst as a function of average 1-butene content [11a].
properties of polyolens made with these catalysts and the fact that polymerization
processes that were originally designed to use ZieglerNatta catalysts can be con-
verted, with minimal changes, to operate with metallocenes the so called drop-
in technology.
Although traditional heterogeneous and homogeneous ZieglerNatta catalysts
are commonly used as the standard example of coordination polymerization, co-
ordination catalysts include any complex of transition metals and organic ligands:
Phillips catalysts are heterogeneous, chromium-based complexes that are not clas-
sied as ZieglerNatta catalysts; metallocenes are complexes of a transition metal
in most cases an early transition metal and cyclopentadienyl or cyclopentadienyl-
derivative ligands; late transition metal catalysts may have a variety of ligands con-
taining heteroatoms, such as phosphorus, nitrogen, or oxygen, directly bonded to
the transition metal.
The active site in coordination catalysts for olen polymerization is, therefore, a
transition metal surrounded by ligands. The catalytic properties depend on the ne
tuning between the transition metal and the ligands in terms of geometry and elec-
tronic character. In most cases the active site is produced by the activation of a
complex called a pre-catalyst, or catalyst precursor. The pre-catalyst is commonly
stable and easy to handle; sometimes it is stable even to moisture and oxygen.
The creation of the active site by reaction of the pre-catalyst with an activator or
cocatalyst is made just prior to its injection in the polymerization reactor or inside
the polymerization reactor itself. The activator alkylates the pre-catalyst complex to
form the active sites and stabilizes the resulting cationic active site. Common acti-
vators are based on organoaluminum or organoborane compounds [16]. Because
the activator works as a Lewis acid (electron acceptor), it is also used to scavenge
polar impurities from the reactor. These impurities are electron donors, such as
oxygen, sulfur and nitrogen compounds, and moisture, that poison the cationic
active site. Figure 8.8 shows a simplied chemical equation for the activation
mechanism and the corresponding equation used for modeling in the Section 8.3.
A
X L
L
A
R L
L
AlR
3
X
C Al C
*
AlR
2
X
2
A = transition metal center (Ti, Zr, Ni, )
L = ligands
X = halogen (Cl, Br)
AlR
3
= alkylaluminum cocatalyst
R = alkyl group (methyl, ethyl)
Fig. 8.8. Catalyst activation by reaction of a pre-catalyst and a cocatalyst.
Polymerization with coordination catalysts proceeds via two main steps: mono-
mer coordination to the active site, and monomer insertion into the growing poly-
mer chain, as illustrated in Figure 8.9. Before insertion, the double bond in the
olen monomer coordinates to the coordination vacancy of the transition metal.
After the olen is inserted into the growing polymer chain, another olen mono-
mer can coordinate to the vacant site; thus the process of insertion is repeated to
increase the size of the polymer chain by one monomer unit at a time until chain
transfer takes place [17]. In the case of copolymerization, there is a competition be-
tween the comonomers to coordinate to the active sites and to be inserted into the
growing polymer chains. Dierent rates of coordination and insertion of comono-
mers determine the nal chemical composition of the copolymer chain.
Insertion of a prochiral a-olen such as propylene creates a chiral carbon bonded
to the active site. Dierently from free-radical polymerization, coordination poly-
merization can be regio- and stereoselective, depending on the design of the li-
gands bonded to the transition metal. Regioselectivity determines the sequence of
12 or 21 insertions while stereoselectivity determines whether the polymer is
isotactic, syndiotactic, or atactic (Figure 8.10).
Several chain-transfer mechanisms are operative in coordination polymerization:
transfer by b-hydride elimination; transfer by b-methyl elimination; transfer to
monomer; transfer to cocatalyst; and transfer to chain-transfer agent commonly
hydrogen or other small molecules. The type of termination reaction determines
the chemical group bound to the active site and the terminal chemical group in the
polymer chain. The rst three types produce unsaturated chain ends, while the last
two types produce saturated chain ends. Figure 8.11 illustrates these ve transfer
mechanisms.
Reaction of the active site with polar impurities deactivates the catalyst. Due to
the cationic nature of the active sites, nucleophilic groups with a lone pair of elec-
A
R L
L
A
R L
L
A
L
L
M P
1
*
C*
R
A
L
L
A
L
L
n M P
1+n
* *
R
n n
P
1
Pol
( )
Fig. 8.9. Monomer coordination and insertion.
trons (generally substances containing oxygen, nitrogen, or sulfur) can coordinate
irreversibly with the active site, causing irreversible catalyst deactivation. Bimo-
lecular catalyst deactivation happens when two active sites form a stable complex
that is inactive for monomer polymerization. This type of bimolecular intermediate
is favored at high catalyst concentrations and is reversible [18]. The term latent
state can be used to describe certain catalytic intermediates that reduce the cata-
lyst activity. The formation of latent states is dicult to probe and the mechanisms
are generally not well understood. Figure 8.12 shows chemical equations for this
catalyst deactivation mechanism.
A
L
L
Pol
A
L
L
2
1 Pol
1
2
A
L
L
Pol
A
L
L
2
1
Pol
1
2
1,2-insertion
2,1-insertion
A
L
L
Pol
A
L
L
Pol
A
L
L
Pol
A
L
L
Pol
Regioselectivity
Stereoselectivity
Fig. 8.10. Regio- and stereoselectivity in coordination polymerization.
chain transfer by -hydride elimination
A
L
L
A
H L
L
A
L
L
Pol
P
r
P
H
D
r
Pol
H
Pol
* *
A
L
L
A
CH
3
L
L
A
L
L
Pol
P
r
P Dr
Pol
CH
3
Pol
* *
A
L
L
A
L
L
Pol
P
r
P
H
Dr
Pol
H
* *
A
L
L
Pol
H
2
H
2
H
2
A
Pol L
L
A
Pol L
L
A
L
L
Pol
P
r
M P
r
D
r
* *
A
Pol L
L
A
L
L R
Pol AlR
2
P
r
Al P
A
D
Al
* *
AlR
3
chain transfer by -methyl elimination
chain transfer to hydrogen
chain transfer to monomer
chain transfer to cocatalyst
Fig. 8.11. Chain termination mechanisms.
A
R L
L
A
R L
L
R
A
L
L
2 C*
2 Cd
Fig. 8.12. Catalyst deactivation by bimolecular reactions.
The catalytic cycle is a convenient graphical way to describe the central role
played by the active site in the mechanism of polymerization. Changes in the na-
ture of the active site will aect the catalytic mechanism and consequently the
activity and the selectivity of the polymerization. Changes in the polymerization re-
actor conditions, such as temperature and monomer concentration, play a vital role
in the catalyst mechanism because they aect the rate constants of each of these
steps. Figure 8.13 shows a catalyst cycle for olen polymerization with coordina-
tion catalysts.
Catalytic activity is a measurement of how fast the monomer can be poly-
merized. Unfortunately, it may be expressed in several ways in the literature,
which very often makes it dicult to compare experimental results from dierent
research groups. A common, but not recommended, way is to express catalyst
activity as the mass of polymer made by one mole of catalyst per unit of time, for
instance kg
polymer
(mol
catalyst
h)
1
. Since polymerization rate is proportional to
monomer concentration, this value of the catalyst activity cannot be used for dier-
ent monomer concentrations. A better way is to normalize the catalyst activity with
respect to the moles of monomer present in the reactor, that is, to express the cat-
alyst activity in units of kg
polymer
(mol
catalyst
h mol
monomer
)
1
. Since the measured
polymerization rate does not necessarily have a rst-order dependence on mono-
mer concentration, this form may also be oversimplied, but it is certainly pref-
erable to the rst one. In addition, since coordination catalysts generally deactivate
during polymerization, one should be very careful when extrapolating these aver-
age catalyst activities to dierent polymerization times. In general, it is advisable
that the complete plot of catalyst activity as a function of polymerization time be
available for the proper quantication of polymerization kinetics with coordination
catalysts. Such proles are illustrated in Figure 8.14 for characteristic polymeriza-
tion cases. Another commonly used parameter when accessing catalyst activity is
the turnover frequency, in time
1
units, which stands for the time necessary for
one monomer insertion to take place.
C
AlR
3
C
M
P
r
* *
P
H
P
H
P
Me
*
*
*
H
2
D
r
M
M
M
D
r
D
r
M
Fig. 8.13. Catalytic cycle for polymerization.
8.2.1
ZieglerNatta, Phillips, and Vanadium Catalysts
The low-pressure ethylene polymerization catalyst introduced by Ziegler was
TiCl
4
/AlR
3
, where R is commonly an alkyl group such as methyl or ethyl. A cata-
lyst for stereospecic polymerization of propylene, TiCl
3
/AlR
3
, was disclosed by
Natta shortly after Zieglers discovery. The active sites for polymerization are
located at the surface and edges of the crystalline structure of titanium chloride.
Dierences of atomic arrangements around the titanium atoms on the titanium
chloride surface aect the chemical properties and consequently the activity and
the selectivity of the polymerization catalyst. First-generation ZieglerNatta cata-
lysts consisted of particulate titanium chloride crystals. Two major advances in het-
erogeneous ZieglerNatta catalysts were the use of supports and internal donors.
Inert supports such as magnesium chloride can improve the morphology of the
nal polymer particle in the reactor, increase catalytic activity by many times, and
consequently decrease the load of transition metal in the nal polymer. Internal
donors help to control the selectivity of the catalyst by blocking certain sites and
therefore are necessary to control polymer structure. The evolution of heteroge-
neous ZieglerNatta catalysts is a truly fascinating story that has been reported in
detail in many references [19, 20].
Phillips catalysts are based on Cr(IV) supported on silica and alumina. The true
structure of the Phillips catalyst is not well understood. A mixture of chromium
oxide and silicon oxide (CrO
3
/SiO
2
) is used to create the active sites. The catalyst
does not require addition of chemical activators before the polymerization, since
the active site is produced prior to the polymerization by thermal activation at
high temperatures (600
C, for instance) [21, 22]. Phillips catalysts are used in

both gas-phase and slurry processes. Polyethylene made with Phillips catalysts
Decay type
Build-up type
polymerization time
p
o
l
y
m
e
r
i
z
a
t
i
o
n

r
a
t
e
Fig. 8.14. Polymerization kinetics with coordination catalysts
showing dierent deactivation rates.
has a very broad molecular weight distribution, with polydispersities ranging from
12 to 24. Interestingly, hydrogen is not an eective chain-transfer agent and gener-
ally decreases catalyst activity.
Vanadium catalysts are used to manufacture ethylenepropylenediene rubbers.
The catalyst is produced by activating a mixture of VCl
3
and VCl
4
with AlR
3
(alky-
laluminum) compounds. Vanadium catalysts are very sensitive to reaction condi-
tions [23]. Changes in the composition of the solvent, polymerization time, and
temperature can aect catalyst activity and selectivity.
8.2.2
Metallocene Catalysts
Metallocene catalysts have structures similar to ferrocene (Cp
2
Fe), which is a
widely known complex with a sandwich structure, where the transition metal
lies between two cyclopentadienyl (Cp) rings. Cp
2
ZrCl
2
(Figure 8.15) is a well
studied example of a metallocene catalyst for olen polymerization. Metallocenes
are soluble and therefore can be used as homogeneous catalysts, but they can also
be supported on inert carriers such as silica, alumina, and magnesium chloride,
among other inorganic and organic supports, and used as heterogeneous catalysts
[24].
The cocatalysts commonly used with ZieglerNatta catalysts (AlEt
2
Cl, AlEt
3
) are
not able to activate metallocene catalysts very well. Even though metallocenes
can be activated with these cocatalysts, they generally deactivate very fast, and
consequently have no commercial interest. The use of bulky activators, such as
methylaluminoxane (MAO), is necessary to produce highly active metallocene cata-
lysts. In fact, it can be said that it was the discovery of MAO as a good cocatalyst
for metallocenes that made possible the metallocene revolution that we are cur-
rently experiencing in polyolen manufacture [25]. Other bulky Lewis acids such
as trispentauorophenylborane (B(C
6
F
5
)
3
) are also very good cocatalysts for metal-
locenes.
A large variety of metallocene catalysts can be obtained by altering the simple
structure of Cp
2
ZrCl
2
. The nature of the transition metal and the structure of the
ligand have a large eect on catalyst behavior. The shape, geometry, and chemical
structure of the ligand can aect the activity and selectivity of the catalyst. The
symmetry imposed by ligands around the active site determines the geometry for
monomer coordination and insertion, and consequently the relative orientation of
catalyst and growing polymer chain. The possibility of variations in the chemical
Zr
Cl
Cl
Fig. 8.15. Structure of a typical metallocene catalyst, Cp
2
ZrCl
2
.
substitutions and/or presence of bridging groups on the cyclopentadienyl rings
creates an endless set of possible structures, especially if substitutions of ligands
with heteroatoms are considered. The size and the type of the bridge connecting
the cyclopentadienyl rings aect the opening on the opposite side of the transition
metal, and consequently the relative rates of the elementary steps in the polymer-
ization mechanism. This eect is called the biting angle. The literature on metal-
locene catalysts is very rich one may even say opulent and thousands of metal-
locene catalyst structures have been documented since the early 1980s [1, 2, 26].
The appropriate selection of ligand structure has a major eect on the selectivity
of the polymerization mechanism. A practical and very interesting example is the
control of tacticity in polypropylene. There are two mechanisms to explain control
of stereoregularity: chain-end or enantiomorphic site control. In the former, the ori-
entation of the growing polymer chain determines the orientation of the monomer
during insertion. In the latter, this orientation is determined by the active site, as
determined by the arrangements between the transition metal and its ligands [27].
Since the stereochemical control of most metallocenes is of the enantiomorphic
type, it is possible to classify them according to the type of polypropylene chain
they will produce based merely on the symmetry of the ligands around the active
site, as elegantly illustrated in Figure 8.16.
Furthermore, certain ligands can change the orientation during the growth of a
polymer chain, for instance oscillating between congurations that produce atactic
and isotactic polypropylene blocks. By the proper choice of polymerization condi-
tions it is possible to produce polypropylenes that have chains varying from mainly
atactic through block atacticisotactic to mainly isotactic congurations [28].
M X X
C
2v
(atactic PP)
Ex: Cp
2
ZrCl
2
M X X
C
s
(meso)
(atactic PP)
Et(Ind)
2
ZrCl
2
M X X
C
2
(racemic)
(isotactic PP)
Ex: Et(Ind)
2
ZrCl
2
M X X
C
s
(syndiotactic PP)
Ex: iPr(Flu)(Cp)HfCl
2
M X X
C
1
(no unequivocal prediction)
Ex: (Flu)(MeCp)ZrCl
2
Fig. 8.16. Symmetry requirements for the production of
polypropylenes with dierent stereoregularities.
Another important class of metallocene catalysts, the half-sandwich metallo-
cenes (Figure 8.17) have a more open structure because only one cyclopentadienyl
ring is coordinated to the transition metal. Catalysts with open structures have very
high reactivity ratios toward the incorporation of longer a-olens and are used for
the production of ethylene/1-octene copolymers [29]. More importantly, these cata-
lysts can form polyolens containing long-chain branches via a mechanism that
is analogous to the copolymerization of long a-olens, as will be described in Sec-
tion 8.3.4.
8.2.3
Late Transition Metal Catalysts
This family of coordination catalysts is characterized by having a transition metal
from groups 8, 9, or 10. A great advantage of some polymerization catalysts based
on late transition metals is that the active sites are more tolerant to polar comono-
mers (and impurities) than the early transition metals used with metallocenes. The
tolerance toward polar comonomers is attributed to the electronic conguration of
the central metal and its interaction with its ligands. This feature is very attractive
for modifying the chemical composition of polyolens by copolymerization with
vinyl alcohols, acrylates, or other vinyl polar comonomers. A few polar functional
groups can signicantly increase the hydrophilicity of polyolens and enhance sev-
eral of their properties, such as dyeability, adhesion, and compatibility with other
polar polymers.
Late transition metal catalysts are very active and produce high molecular weight
polyethylene. The catalyst can be used in homogeneous solution or supported in
inert carriers such as silica. The active site can be generated by activation of a metal
halide complex such as (diimine)NiCl
2
with organoaluminum compounds such as
(CH
3
)
3
Al or MAO. As for metallocenes, the active species are cationic. These cata-
lysts have a well dened structure and in homogeneous systems can behave as
single-site catalysts.
Ti
N
Si
C
H
3
C
CH
3
CH
3
CH
3
CH
3
H
3
C
H
3
C
H
3
C
H
3
C
CH
3
CH
3
Fig. 8.17. A half-sandwich metallocene.
A class of late transition metal catalysts based on Ni and Pd with bulky diimine
ligands has an interesting feature called the chain walking mechanism [30].
With the appropriate choice of ligands and reactor conditions, it is possible to pro-
duce branched polyethylene from pure ethylene without addition of comonomers.
The chain walking mechanism involves simultaneous isomerization and polymer-
ization steps, as indicated in Figure 8.18. Isomerization reactions cause the active
site to move along the growing polymer chain without terminating chain growth.
A short-chain branch is created when monomer insertion takes place after the
active site has moved away from the chain end. The number of carbons in this
short branch equals the number of carbons by which the active site has moved
away from the chain end. Branches from methyl to hexyl or longer are produced
during ethylene polymerization, although methyl branches are predominant [31].
The number of branches produced by the chain walking mechanism can be
controlled by varying the polymerization temperature and monomer concentration.
Increasing the polymerization temperature or decreasing the monomer concen-
tration favors chain walking and increases the number of short-chain branches.
By choice of appropriate polymerization conditions, ethylene can be used to make
polyethylene with properties varying from very low density (highly branched) to
high density (few or no branches).
The molecular weight of polyethylene made with some late transition metal
catalysts based on iron can be very high (> 1 000 000 g mol
1
) [30]. At low tem-
peratures polymerization of a-olens with certain diimineNiCl
2
catalysts behave
as a living polymerization: that is, the number-average molecular weight increases
linearly with polymerization time and the polydispersity index (PDI) is approxi-
mately 1.
Forward
Chain
Walking
Forward
Chain
Walking
A = metal active center
P = polymer chain
A
P P
A
P
A
Backward
Chain
Walking
P
A
Monomer
Insertion
Ethyl Branch
A
P
Chain Walking
followed by Insertion
Insertion
Fig. 8.18. Chain walking mechanism.
8.3
Polymerization Kinetics and Mechanism with Coordination Catalysts
8.3.1
Comparison between Coordination and Free-radical Polymerization
One of the main dierences between the polymerization kinetics with coordination
catalysts and free-radical initiators is that the former depends on the characteristics
of the active site as well as on monomer type, while the latter is almost exclusively
regulated by monomer type. As we will see, even though this may not constitute a
problem for establishing an operative mechanism for coordination polymerization,
it creates a signicant challenge for model parameter estimation.
In free-radical polymerization, the initiator fragment moves away from the grow-
ing chain and therefore can inuence chain growth and termination during only
the rst few monomer insertion steps. Consequently, the values of the polymeriza-
tion kinetic parameters depend mainly on the monomer type, thus permitting the
creation of tables of rate constants and activation energies as a function of mono-
mer type, independently of the type of initiator used during polymerization.
In contrast, in coordination polymerization chain growth and termination take
place by insertion of the monomer or chain-transfer agent into a metalcarbon
bond, as proposed by the Cossee mechanism. Consequently, electrical and steric
eects around the active site aect polymerization kinetics as much as does the
monomer type. The mechanisms of free-radical and coordination polymerization
are contrasted in Figure 8.19.
In this way, rate constants for coordination polymerization depend not only on
the monomer type but also on the nature of the active sites present during poly-
merization. Since the nature of the active sites is a rather complex (and unfortu-
nately poorly understood) function of polymerization conditions such as temper-
ature, catalyst/cocatalyst ratio and type, presence and concentration of catalyst
modiers, and solvent type, among other factors, this makes the determination of
general tables of polymerization rate constants and activation energies for coordi-
nation polymerization virtually impossible. On the other hand, the same phenom-
ena, that is to say those that make it dicult to predict the behavior of coordination
polymerization a priori, are also responsible for the remarkable exibility of coordi-
nation catalysts, since polymers with completely dierent properties can be made
with only a few monomer types by simply varying the way these monomers are
inserted into the polymer chain via active-site design.
8.3.2
Polymerization Kinetics with Single-site Catalysts
8.3.2.1 Homopolymerization
Several metallocene, late transition metal, and homogeneous ZieglerNatta cata-
lysts behave as single-site catalysts, while all heterogeneous ZieglerNatta and
Phillips catalysts have more than one site type. The mechanism for coordination
8.3 Polymerization Kinetics and Mechanism with Coordination Catalysts 383
polymerization can be divided into ve main classes of reaction: catalyst activation
with the cocatalyst; catalyst initiation with monomer; chain propagation; chain
transfer; and poisoning and deactivation [32].
No bimolecular termination reactions termination by combination or
disproportionation as observed in free-radical polymerization take place with co-
ordination catalysts. Some catalysts, under certain polymerization conditions, may
polymerize dead polymer chains containing terminal vinyl unsaturations, leading
to the formation of chains with long-chain branches. We will discuss the mecha-
nism of long-chain branch formation with coordination catalysts in Section 8.3.4.
Coordination catalysts must be activated via reaction with a cocatalyst, which is
generally present in great excess. (In some references, the complex that is reacted
with the cocatalyst is called the pre-catalyst and the product of the reaction between
the pre-catalyst and the cocatalyst is named the catalyst. Even though this termi-
nology is more rigorous, we will adopt the looser terminology by which the transi-
tion metal compound is called the catalyst, even before reaction with the cocata-
lyst.) The cocatalyst/catalyst molar ratio is commonly 5:120:1 for heterogeneous
ZieglerNatta catalysts, but it can be as high as 1000:1 or more for metallocene
catalysts. Little is known, from a quantitative point of view, about the kinetics of
catalyst activation for coordination polymerization. Qualitatively, it has been shown
that the cocatalyst is required to reduce and alkylate the active site. This reaction is
generally assumed to proceed very quickly and to be rst order with respect to cat-
alyst, C, and cocatalyst or activator, Al, to form the active site C
+
[Eq. (1)].
Coordination polymerization is site-based:
Ti
CH
2
- CH
2
CH
2
CH
2
Free-radical polymerization is monomer-based:
R* + M RM*
RM* + M RMM*
R(M)
n
* + M R(M)
n+1
*
Fig. 8.19. Comparison of the monomer propagation step in

free-radical and coordination polymerization.
C Al
ka
C
+
(1)
After the catalyst is activated by reaction with the cocatalyst, it is ready to poly-
merize the monomer, M, forming a living polymer chain P
1
of length 1 [Eq. (2)].
C
+
M
k
i
P
1
(2)
A subsequent monomer propagation reaction with a growing polymer of chain
length r, P
r
, increases its length to r 1 [Eq. (3)].
P
r
M
kp
P
r1
(3)
In general, the rst monomer insertion step is considered to have a dierent reac-
tion rate constant, k
i
, from the subsequent monomer propagation steps, k
p
. Since
in practice these constants are very dicult (if not impossible) to estimate in-
dependently, most kinetic models make the reasonable simplifying assumption
that k
i
Gk
p
.
The most important transfer reactions in coordination polymerization are: (1) b-
hydride elimination; (2) transfer to chain-transfer agent; (3) transfer to monomer;
and (4) transfer to cocatalyst.
b-Hydride elimination is a rst-order reaction in which the hydrogen atom at-
tached to the b-carbon in the living chain is abstracted by the active center, forming
a metal hydride center, C
+
H
, and a dead polymer chain containing a terminal vinyl
unsaturation, D
=
r
[Eq. (4)].
P
r

ktb
C
+
H
D
=
r
(4)
The metal hydride center is available for polymerization and will undergo an initi-
ation reaction in the presence of monomer [Eq. (5)], similarly to that of [Eq. (2)].
C
+
H
M
k
iH
P
1
(5)
The independent estimation of k
i
and k
iH
can be very involved; often the simplify-
ing assumption k
i
Gk
iH
is adopted.
For polypropylene polymerization, b-hydride transfer will produce a dead poly-
mer chain with a vinylidine chain end. On the other hand, vinyl-terminated chains
are produced when b-methyl-transfer reactions take place [Eq. (6)].
P
r

ktbCH
3
C
+
CH3
D
=
r
(6)
Chain-transfer agents are commonly used to control the molecular weight of the
polymer. By far the most common chain-transfer agent used in olen polymeriza-
tion is hydrogen [Eq. (7)].
P
r
H
2

ktH
C
+
H
D
r
(7)
Chain transfer to hydrogen leads to the production of a dead chain with a saturated
chain end, D
r
, and a metal hydride active site that can be initiated with monomer
according to Eq. (5).
Transfer to monomer also occurs during olen polymerization, leading to a
vinyl-terminated chain for the case of polyethylene (and a vinylidine-terminated
chain for the case of polypropylene) [Eq. (8)].
P
r
M
ktM
P
1
D
=
r
(8)
Finally, the cocatalyst may also act as a chain-transfer agent [Eq. (9)]. If the cocata-
lyst is trimethylaluminum, (CH
3
)
3
Al, this elementary step produces a methylated-
active center, which can also be initialized by the monomer in a subsequent step:
P
r
Al
k
tAl
C
+
CH3
D
r; Al
(9)
Coordination catalysts are very sensitive to polar impurities and may also be deac-
tivated due to mono- or bimolecular mechanisms. Even though these elementary
reactions are not very well understood from a quantitative point of view, we will
show next some simple reaction mechanisms proposed to describe them.
Reactions with polar impurities, I, leading to the formation of a deactivated site,
C
d
, and a dead polymer chain have been modeled with the very simple equations
[Eqs. (10) and (11)].
P
r
I
k
dI
C
d
D
r
(10)
C
+
I
k
dI
C
d
(11)
Likewise, monomolecular and bimolecular deactivation reactions have been de-
scribed with the simple kinetic schemes described by Eqs. (12)(14).
P
r

k
d
C
d
D
r
(12)
C
+

k
d
C
d
(13)
2C
+

k
d
2C
d
(14)
These deactivation equations are not easy to prove, but have been successful in de-
scribing several olen polymerization processes with ZieglerNatta and metallo-
cene catalysts.
The term single-site catalyst has a very precise meaning in coordination poly-
merization. From the point of view of catalyst structure, single-site catalysts are
those where all active sites are represented by the same chemical species and have
the same polymerization kinetic parameters. In other words, single-site catalysts
can be represented with a single set of the elementary reactions described by Eqs.
(1)(14) or any other equivalent set of polymerization mechanism equations. From
a polymer microstructure point of view, single-site catalysts will produce linear
polymers that have a theoretical polydispersity of 2 instantaneously. These two con-
ditions are not independent. In fact, the second condition is the consequence of
the rst.
The qualication instantaneously used above should not be taken lightly, since
this may lead to signicant misunderstanding of catalyst behavior. An instanta-
neous property refers to the property of the polymer made at a given instant in
time under a set of invariant polymerization conditions. If these conditions change
throughout the polymerization, so will the instantaneous property under examina-
tion. Therefore, even though polymer made with a single-site coordination catalyst
has a polydispersity of 2 instantaneously, the polydispersity of the accumulated
polymer may be much higher (but never lower) than 2 if reaction conditions are
allowed to vary during the polymerization, as indicated in Figure 8.20 for the case
of decreasing chain-transfer agent concentration as a function of polymerization
time. It is only when the polymerization is operated at steady state that the instan-
taneous properties of the polymer will be equal the accumulated ones.
Polymers made by a mechanism where the chain can either grow by propagation
or terminate by transfer reactions, as quantied by Eqs. (1)(14), follow Florys
most probable chain length distribution [33] [Eq. (15)].
w(r) =
r
r
2
n
exp
r
r
n

(15)
time
time
c
h
a
i
n

t
r
a
n
s
f
e
r

a
g
e
n
t
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1 2 4
log r
w
(
r
)
4.5 3.5 3 2.5 1.5
Fig. 8.20. Instantaneous chain length distributions of a
polymer made with a single-site catalyst when the
concentration of chain transfer agent the reactor decreases with
increasing polymerization time.
In Eq. (15), w(r) is the weight distribution of chains of length r and r
n
is the
number-average chain length of the polymer population. Therefore, from a poly-
mer microstructure point of view, a coordination catalyst is considered to have
only one site type if it produces polymer with a chain length distribution that fol-
lows Eq. (15) instantaneously.
8.3.2.2 Copolymerization
The polymerization model most commonly adopted for olen copolymerization is
the terminal model, particularly for studies of polymerization kinetics. In the ter-
minal model, only the last monomer molecule added to the chain end inuences
polymerization and transfer rates. Besides the fact that it is logically expected, there
is also signicant experimental evidence supporting the terminal model for olen
polymerization. Since monomer propagation and chain-transfer reactions take
place by insertion between the chemical bond formed by the metal in the active
site and the polymer chain end, it is certainly reasonable to assume that both the
nature of the active site and the type of monomer last added to the chain will aect
these reactions. On the other hand, higher-order models such as the penultimate
and pen-penultimate models have not found widespread use in coordination
polymerization.
Copolymerization models are similar to homopolymerization models, with the
added complexity that more polymerization rate constants are required. An ac-
cepted form of the terminal model for the binary copolymerization of olens is
shown in Table 8.1. Notice that, except for the fact that the polymerization rate con-
stants now depend on the monomer and the chain end type, the mechanism is es-
sentially the same as the one described in Section 8.3.2.1 for homopolymerization.
For the case of linear binary copolymers, the instantaneous bivariate chain length
and chemical composition distribution, w(r; y), is described by Stockmayers distri-
bution [Eqs. (16)(19)] [34].
w(r; y) =
r
r
2
n
exp
r
r
n

r
2pk
r
exp
ry
2
2k

(16)
k = F
A
(1 F
A
)
1 4F
A
(1 F
A
)(1 r
A
r
B
)
q
(17)
r
A
=
k
p; AA
k
p; AB
; r
B
=
k
p; BB
k
p; BA
(18)
y = F
A
F
A
(19)
As indicated in Eq. (19), y is the deviation from the average molar fraction of
monomer type A in the copolymer, F
A
. As usual, the instantaneous value of F
A
can be calculated using the molar fraction of monomer A in the reactor, f
A
, and
the reactivity ratios r
A
and r
B
by the MayoLewis equation, Eq. (20) [35].
F
A
=
(r
A
1) f
2
A
f
A
(r
A
r
B
2) f
2
A
2(1 r
B
) f
A
r
B
(20)
In the same way that Florys distribution is the necessary outcome of adopting the
homopolymerization model described by Eqs. (1)(14), Stockmayers distribution
is the consequence of adopting the binary copolymerization mechanism described
in Table 8.1.
The attentive reader may have noticed that Stockmayers distribution is an exten-
sion of Florys distribution for the case of copolymers. In fact, upon integration in
the interval yay ay, Stockmayers distribution reduces to Florys distribu-
tion as demonstrated by Eq. (21).
w(r) =
y
y
r
r
2
n
exp
r
r
n

r
2pk
r
exp
ry
2
2k

dy =
r
r
2
n
exp
r
r
n

(21)
Therefore, the chain length distributions of linear binary (or multicomponent) co-
polymers also follow Florys most probable distribution and have, instantaneously,
a polydispersity of 2.
Tab. 8.1. Terminal model for binary copolymerization of olens.
[a]
Activation C A
ka
C
+
Initiation C
+
A
ki; A
P
1; A
C
+
B
ki; B
P
1; B
Propagation P
r; A
A
kp; AA
P
r1; A
P
r; A
B
kp; AB
P
r1; B
P
r; B
A
kp; BA
P
r1; A
P
r; B
B
kp; BB
P
r1; B
b-Hydride elimination P
r; A

ktb; A
C
+
H
D
=
r; A
P
r; B

ktb; B
C
+
H
D
=
r; B
Transfer to hydrogen P
r; A
H
2

ktH; A
C
+
H
D
r; A
P
r; B
H
2

ktH; B
C
+
H
D
r; B
Transfer to monomer P
r; A
A
kt; AA
P
1; A
D
=
r; A
P
r; A
B
kt; AB
P
1; B
D
=
r; A
P
r; B
A
kt; BA
P
1; A
D
=
r; B
P
r; B
B
kt; BB
P
1; B
D
=
r; B
Transfer to cocatalyst P
r; A
Al
kAl; A
C
+
CH3
D
r; Al
P
r; B
Al
kAl; B
C
+
CH3
D
r; Al
Deactivation with impurities P
r; A
I
kdI; A
C
d
D
r; A
P
r; B
I
k
dI; B
C
d
D
r; B
Monomolecular deactivation P
r; A

kd; A
C
d
D
r; A
P
r; B
kd; B
C
d
D
r; B
[a]
A and B represent the two monomer types. All other symbols are the
same as those used for homopolymerization, but the reaction rate
constants indicate the type of chain end and reacting monomer with
the generic nomenclature k
i; j
where i is the chain end type and j
represents the monomer type.
Similarly, an expression for the chemical composition distribution alone can
be obtained by integrating Eq. (16) over all chain lengths, that is, in the interval
0 ar ay:
w(y) =
y
0
r
r
2
n
exp
r
r
n

r
2pk
r
exp
ry
2
2k

dr =
3
4
2k
r
n
r
1
y
2
r
n
2k
!
5=2
(22)
It is dicult to overestimate the explanatory power contained in these few simple
expressions. Equation (16) teaches us that longer polymer chains also have narrow
chemical composition distributions, as illustrated in Figure 8.21. This result sim-
ply reects the fact that statistical deviations from the average copolymer composi-
tion become less likely as the chain increases in length, as would be expected since
chains with innite length should all have exactly the same average copolymer
composition. Equation (16) also shows that the tendency to form comonomer
blocks (r
A
r
B
y) will necessarily broaden the chemical composition distribution
of copolymers, while the tendency toward monomer alternation (r
A
r
B
1) will
narrow the chemical composition distribution and in the limit make all chains
have the composition F
A
= 0:5, as illustrated in Figure 8.22. In fact, the chemical
composition distribution is best apprehended by plotting Eq. (22) as a function of
the lumped parameter r
n
=k. Figure 8.23 shows that the chemical composition dis-
0
0.001
0.002
0.003
0.004
0.005
0.006
0.007
0.008
0.009
0.01
-0.1 -0.08 -0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08 0.1
y
w
(
r
,
y
)
r = 250
r = 500
r = 1000
Fig. 8.21. Chemical composition distribution for several chain
lengths, as described by Stockmayers bivariate distribution.
Distribution parameters: r
n
= 1000, F
A
= 0:5, r
A
r
B
= 1.
0
0.005
0.01
0.015
0.02
0.025
0.03
0.035
-0.1 -0.08 -0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08 0.1
y
w
(
r
,
y
)
r
1
r
2
= 0.01
r
1
r
2
= 1.0
r
1
r
2
= 5
Fig. 8.22. Chemical composition distribution for the same
chain length and varying r
A
r
B
, as described by Stockmayers
bivariate distribution. Distribution parameters: r
n
= 1000,
F
A
= 0:5, r = 1000.
0
5
10
15
20
25
30
35
40
-0.1 -0.08 -0.06 -0.04 -0.02 0 0.02 0.04 0.06 0.08 0.1
y
w
(
y
)
r
n
/ = 1000
r
n
/ = 2000
r
n
/ = 4000
Fig. 8.23. Chemical composition distribution as a function of
the lumped parameter r
n
=k in Eq. (22).
tribution becomes broader as the value of r
n
=k decreases, reecting the fact that
polymers with shorter number-average chain lengths and a tendency to form
blocks (see Eq. (17): k increases when r
A
r
B
increases) have broader chemical com-
position distributions. In conclusion, the width of the instantaneous chemical
composition distribution of binary copolymers made by coordination polymeriza-
tion is a function of a single lumped parameter r
n
=k and, for a given copolymer
composition, depends only on the number-average chain length and reactivity ratio
product r
A
r
B
.
8.3.3
Polymerization Kinetics with Multiple-site Catalysts
All heterogeneous ZieglerNatta and Phillips catalysts have two or more active-site
types and many soluble ZieglerNatta and metallocene catalysts may also show
multiple-site behavior [36, 37]. In addition, several metallocene catalysts, when
supported on organic and inorganic carriers, may behave like multiple-site cata-
lysts even if they behaved as single-site catalysts in solution polymerization. There-
fore, several of the catalysts used industrially for polyolen manufacturing have in
fact two or more active-site types.
The kinetics of polymerization with multiple-site catalysts is generally consid-
ered to be the same as with single-site catalysts, as described by Eqs. (1)(14) for
homopolymerization and in Table 8.1 for copolymerization, with dierent polymer-
ization kinetic parameters assigned to each site type. In some cases, the polymer-
ization mechanism may be extended to include site transformation steps, where
sites of one type may change into sites of another type, such as the one described
with the reversible reaction in Eq. (23), where D could be a catalyst modier such
as an electron donor, for instance.
C
+
1
D C
+
2
(23)
Since these additional site transformation steps may aect the relative ratio of
site types present in the reactor but do not inuence the general polymerization
behavior with multiple-site catalysts, for the sake of simplicity they will not be fur-
ther considered in this chapter.
It is usually straightforward to detect the presence of multiple-site types on a co-
ordination catalyst because these catalysts will produce polymer with polydispersity
higher than 2 even under invariant polymerization conditions. The simplest way to
visualize this phenomenon is to assume that every dierent site type on a multiple-
site catalyst produces polymers that follow a distinct Florys distribution: that is,
those with a distinct number-average chain length, r
n; i
[38]. In this way, the chain
length distribution for the whole polymer is a combination of distinct Florys dis-
tributions weighted by the mass fraction of polymer made on each site type, m
i
[Eq. (24)].
w(r) =
X
n
i=1
m
i
r
r
2
n; i
exp
r
r
n; i

(24)
The graphical representation of Eq. (24) for a coordination catalyst having three
distinct site types is shown in Figure 8.24. It is important to remember that the
use of Eq. (24) is a direct consequence of assuming that the mechanism of poly-
merization for multiple-site catalysts is described with the same set of equations,
Eqs. (1)(14), used to describe single-site catalysts. In other words, Florys distribu-
tion is the logical consequence of the mechanism adopted for coordination poly-
merization.
For polymers made with multiple-site catalysts, the instantaneous number- and
weight-average chain lengths are given by Eqs. (25) and (26).
r
n
=
X
n
i=1
m
i
r
n; i
!
1
(25)
r
w
= 2
X
n
i=1
m
i
r
n; i
(26)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1 4
log r
w
(
r
)
4.5 3.5 3 2.5 2 1.5
Fig. 8.24. Chain length distribution of a polymer made with a
coordination catalyst containing three dierent active-site types.
See Figure 8.25 for the corresponding chemical composition
distribution. Distribution parameters: r
n; 1
= 500, r
n; 2
= 1000,
r
n; 3
= 2000, m
1
= 0:3, m
2
= 0:3, m
3
= 0:4.
Therefore, the polydispersity index of a polymer made with a catalyst having n site
types is given by Eq. (27), which is always greater than or equal to 2.
PDI =
r
w
r
n
= 2
X
n
i=1
m
i
r
n; i
!
X
n
i=1
m
i
r
n; i
!
(27)
Similarly, the bivariate molecular weight and chemical composition distributions
of binary copolymers made with multiple-site catalysts can be described as a
weighted superposition of Stockmayers distributions [39]. If we consider only the
chemical composition component of the distribution, as described by Eq. (22), the
distribution of polymer made with a multiple-site catalyst becomes Eq. (28).
w(y) =
X
n
i=1
m
i
3
4
2
k
r
n

i
s
1
y
2
i
2
r
n
k

i
!
5=2
(28)
Figure 8.25 shows the chemical composition distribution obtained with Eq. (28) of
a polyolen made with a catalyst having three distinct active-site types, whose
chain length distribution has already been presented in Figure 8.24. Notice the
characteristic bimodal distribution of ethylene/a-olen copolymers made with het-
0
5
10
15
20
25
0.8 0.82 0.84 0.86 0.88 0.9 0.92 0.94 0.96 0.98 1
fraction of ethylene
w

(
f
r
a
c
t
i
o
n

o
f

e
t
h
y
l
e
n
e
)
Fig. 8.25. Chemical composition distribution
of polymer made with a coordination catalyst
containing three dierent active-site types.
See Figure 8.24 for the corresponding chain
length distribution. Distribution parameters:
(r
n
=k)
1
= 2000, (r
n
=k)
2
= 4000,
(r
n
=k)
3
= 8000, F
A; 1
= 0:88, F
A; 2
= 0:90,
F
A; 3
= 0:93, m
1
= 0:3, m
2
= 0:3, m
3
= 0:4.
erogeneous ZieglerNatta catalysts. These two gures illustrate a very important
aspect of olen polymerization with heterogeneous ZieglerNatta catalysts, the
fact that the sites that make polymer chains with higher number-average chain
lengths also have a lower reactivity ratio toward comonomer incorporation. This
seems to be a universal property of heterogeneous ZieglerNatta catalysts and is
dramatically illustrated in Figure 8.26 for the bivariate distribution of chain length
and chemical composition of a model polymer. Much research has been done to
overcome this phenomenon, which can very often be seen as a limitation of heter-
ogeneous ZieglerNatta catalysts, since low molecular weight chains with high a-
olen fractions are easily extracted from the polymer particles and may cause reac-
tor fouling, a high extractable content in lms a serious limitation for food and
medical applications and odor problems during processing.
The multiplicity of active sites on heterogeneous ZieglerNatta and Phillips cata-
lysts is a truly complex phenomenon and other explanations proposed to describe
the observed broad chain length and chemical composition distributions have also
been proposed, but most rely on similar approaches to the one described herein.
The references at the end of the chapter give more information on this topic [40,
41].
8.3.4
Long-chain Branch Formation
The mechanism of long-chain branch (LCB) formation with coordination polymer-
ization catalysts is terminal branching. In this mechanism, a dead polymer chain
containing a terminal unsaturation generally a vinyl group is copolymerized
with a growing polymer chain to form an LCB (Figure 8.27) [15]. We have already
seen that dead polyethylene chains with terminal unsaturations will be formed by
w

(
r
,

y
)
Fig. 8.26. Bivariate distribution of chain
length and chemical composition of a
polymer made with a coordination catalyst
containing three dierent active-site types.
Distribution parameters: r
n; 1
= 500,
r
n; 2
= 1000, r
n; 3
= 2000, F
A; 1
= 0:88,
F
A; 2
= 0:90, F
A; 3
= 0:93, m
1
= 0:3, m
2
= 0:3,
m
3
= 0:4, (r
1
r
2
)
1
= (r
1
r
2
)
2
= (r
1
r
2
)
3
= 1.
b-hydride elimination and transfer to monomer reactions, as described by Eqs. (4)
and (8), respectively. Since these chains can be reincorporated into the growing
polymer chains via LCB-formation reactions, they are frequently called macro-
monomers. Macromonomers can be made in situ via b-hydride elimination and
transfer to monomer reactions or they can be added, as an additional comonomer
type, to the polymerization reactor.
In this way, long-chain branch formation can be seen as a copolymerization reac-
tion with a very long a-olen and, as expected, catalysts that have a high reactivity
ratio toward a-olen incorporation can also form polymers with high LCB con-
tents. Several metallocene catalysts and some homogeneous ZieglerNatta cata-
lysts are eective in forming polymer chains with LCBs. In contrast, heteroge-
neous ZieglerNatta catalysts make only linear polyolens.
The polymerization mechanism described by Eqs. (1)(14) for homopolymeriza-
tion needs to be augmented by only one additional equation, Eq. (29), to include
long-chain branch formation.
P
r; i
D
=
s; j

kLCB
P
rs; ij1
(29)
In Eq. (29), the subscripts i and j indicate the number of LCBs per chain, while the
subscripts r and s are their respective chain lengths. Therefore, when a linear grow-
ing chain (i = 0) reacts with a linear macromonomer ( j = 0), a chain with one LCB
is formed (i j 1 = 1). Similar equations are easily developed for copolymeriza-
tion.
The weight distribution of chain length for polymer populations containing i
LCBs per chain, w(r; i) is given by Eq. (30) [42], in which the parameter t is given
by Eq. (31).
w(r; i) =
1
(2i 1)!
r
2i1
t
2i2
exp(tr) (30)
t =
rate of chain transfer rate of LCB formation
rate of propagation
(31)
Zr B
=
P
r,2
D
s,1
=
P
r+s,4
Zr B
C
H
2
=

C
H
2
Fig. 8.27. Mechanism of long-chain branch formation with coordination catalysts.

Therefore, in the absence of LCB formation, t = 1=r
n
, and Eq. (30) reduces to
Florys most probable distribution, Eq. (15). Figure 8.28 shows the chain length
distribution for several polymer populations with increasing numbers of LCBs per
chain. As expected, the chain length average increases with an increasing number
of LCBs per chain.
An analytical solution for the instantaneous chain length distribution for the
whole polymer produced in a CSTR is also available [Eq. (32)] [15]. The function
I
1
is the modied Bessel function of the rst kind of order 1, given by Eq. (33).
Bessel functions are easily found in mathematical tables and are readily available
is most scientic software applications [43, 44].
w(r) =
(1 a)t exp(rt)
(1 a)

a
I
1
2
rt
1 a

(32)
I
1
(x) =
X
y
k=0
(x=2)
12k
k!G(k 2)
(33)
The parameter a is dened by Eq. (34), where f
=
is the molar fraction of macro-
monomer in the reactor, measured with respect to the total concentration of poly-
mer; s is the reciprocal of the average reactor residence time; k
LCB
is the rate con-
stant for LCB formation; and Y is the concentration of growing polymer chains in
the reactor.
0
0.00005
0.0001
0.00015
0.0002
0.00025
0.0003
0.00035
0.0004
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000
r
w
(
r
,
y
)
Linear
1 LCB
2 LCB
3 LCB
4 LCB
5 LCB
Fig. 8.28. Chain length distributions of the several polymer
populations of branched polyolens made with a single-site
coordination catalyst (1=t = 1000).
a =
f
=
1 s=(k
LCB
Y)
(34)
Figure 8.29 shows how the chain length distribution of the whole polymer is af-
fected by the value of the parameter a. First, notice that a belongs to the interval
[0, 1]. All chains are linear when a = 0 since this implies that either f
=
= 0 (with-
out macromonomers, no LCBs can be formed) or s=(k
LCB
Y) y. The latter con-
dition is obeyed when either s y (that is, the reactor residence time tends to
zero) or k
LCB
Y = 0. Both cases imply that no macromonomers are accumulated
in the reactor. On the other hand, LCB formation is maximal when a = 1, a condi-
tion obeyed only when all dead polymer chains in the reactor contain terminal un-
saturations, f
=
= 1, and the residence time in the reactor is innite, s 0, or the
rate of LCB formation is innite, k
LCB
Y y. Therefore, Eq. (32) captures, in a
very elegant way, all the factors determining LCB formation with a coordination
catalyst.
The parameter a can also be related to the number of LCBs per chain for the
whole polymer, B, by Eq. (35).
B =
a
1 a
(35)
0
0.00005
0.0001
0.00015
0.0002
0.00025
0.0003
0.00035
0 5000 10000 15000 20000 25000 30000 35000 40000
r
w
(
r
)
= 0.1
= 0.3
= 0.5
Fig. 8.29. Overall chain length distribution for branched
polyolens made with a single-site coordination catalyst
(1=t = 1000).
Notice that the average number of LCBs per chain can vary from 0 when a = 0 to
innity when a = 1. Since most long-chain-branched polyolens made with coordi-
nation catalysts are only sparsely branched, with values of B rarely exceeding unity,
the upper limit of the paramter a should be considered only as a theoretical possi-
bility never to be reached in practical situations.
Chain length averages and polydispersity index for the whole polymer can also
be related to the parameters a or B via Eqs. (36)(38).
r
n
=
1
t
(1 2B) (36)
r
w
=
2
t
(1 2B)(1 B) (37)
PDI = 2(1 B) (38)
These equations demonstrate that the polydispersity index of long-chain-branched
polyolens is always greater than 2 and that the chain length averages increase
with an increasing number of LCBs per chain.
It is also interesting to calculate the mass fraction of polymer populations con-
taining i LCBs per chain, m
i
, by Eq. (39).
m
i
=
(2i)!
i!(i 1)!
a
i
(1 a)(2i 1)
(1 a)
2i2
(39)
Notice that, for sparsely branched polymers, most of the chains are linear, but the
number of more highly branched species increases as a 1, as illustrated in Fig-
ure 8.30.
Similarly, an extension [Eq. (40)] of Stockmayers distribution can be derived for
binary copolymers containing LCBs formed by terminal branching [45].
w(r; y; i) =
1
(2i 1)!
r
2i1
t
2i2
exp(rt)
r
2pk
r
exp
ry
2
2k

(40)
These equations give a very accurate portrait of the chain microstructure of these
polyolens. They are, in fact, a window into their chain architecture and can be
very useful in understanding the constitution of these complex polymers.
8.4
Single Particle Models Mass- and Heat-transfer Resistances
Most commercial processes for the manufacture of polyolens use solid catalysts,
such as heterogeneous ZieglerNatta and Phillips catalysts. Many metallocene cat-
alysts have also been supported on inorganic carriers, typically silica, for industrial
use [24]. As in any solid-catalyzed reaction, interparticle and intraparticle mass-
and heat-transfer resistances may become a limiting step in heterogeneous olen
polymerization processes.
Olen polymerization with heterogeneous catalysts has several very distinct char-
acteristics that should be discussed from a qualitative point of view before a more
quantitative treatment is presented. Eective heterogeneous catalysts for olen
polymerization are highly porous, as is usual with most heterogeneous catalysts.
When a fresh catalyst particle is rst fed to the reactor it is evidently free of poly-
mer, but its pores quickly become lled with polymer molecules formed as mono-
mer diuses from the bulk phase in the reactor to the surface of the active sites on
the catalyst pores. At this point, the three alternatives illustrated in Figure 8.31 are
possible: (1) the polymer phase clogs the catalyst pores and inhibits any additional
polymerization from happening; (2) the structure of the catalyst is not strong
enough to resist the expansion forces of the fast-forming polymer chains and ex-
plodes in several smaller particles, generating nes; (3) the growing polymer
chains are capable of fragmenting the catalyst particle in an ordered way and act
as a binder between the catalyst fragments, forming an expanding polymer particle
composed of polymer chains surrounding catalyst fragments.
The last alternative is the only one that has industrial interest; much catalyst re-
search is behind the design of catalyst particles that can be properly fragmented to
form uniform polymer particles. This leads to the so-called replication phenome-
non, whereby the size distribution of the catalyst particles is neatly replicated by
the size distribution of the polymer particles exiting the reactor, as illustrated in
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 0.5 1 1.5 2 2.5 3 4 4.5 5
i (LCB/chain)
m
i
3.5
= 0.05
= 0.1
= 0.2
= 0.4
= 0.8
Fig. 8.30. Mass fraction of chains with i LCB per chain, as a function of the parameter a.
Figure 8.32. Proper replication of the catalyst particles is essential for stable reactor
operation and also for the handling of the polymer particles in post-reactor pro-
cesses. Reactor residence time distribution in CSTRs may have an important eect
on the replication phenomenon; the references at the end of the chapter provide
more details on this subject [4650].
This picture of particle fragmentation and growth has been captured in its most
important details by the multigrain model [36, 5160] which was originally devel-
oped to describe the crystalline structures of TiCl
3
and TiCl
4
/MgCl
2
ZieglerNatta
catalysts, but has also been used extensively to describe metallocene and late tran-
sition metals catalysts supported on inorganic carriers. In the multigrain model,
the polymer particle is divided into two levels of mass-transfer resistances: the mi-
croparticles or primary particles, and the macroparticle or secondary particle. The
secondary particle is the porous catalyst particle itself that is fed to the reactor. It
is considered to be formed by the agglomeration of several nonporous primary
particles having polymerization active sites on their surfaces. As polymer grows
around the primary particles, the secondary particle expands as a function of poly-
merization time and activity. The multigrain model is illustrated in Figure 8.33.
Notice that the multigrain model does not deal directly with the initial seconds
of particle fragmentation, when the catalyst pores are being lled with polymer
chains that start to fragment the catalyst particles. Since many industrial catalysts
are in fact pre-polymerized in milder conditions in a separate reactor before being
fed to the polymerization reactor, this should not be seen as a limitation of the
multigrain model for most industrial applications. Catalyst pre-polymerization in
catalyst particle with
pores clogged with polymer
catalyst fragmentation
and formation of fines
desired expanding
catalyst-polymer
particle
Fig. 8.31. Particle growth and fragmentation for
polymerization with heterogeneous coordination catalysts.
milder conditions is generally recommended to avoid the formation of intraparticle
hot spots and the improper fragmentation of the catalyst particles when subjected
to the more severe polymerization conditions existing in industrial polymeriza-
tion reactors. Several older and some more recent simulation studies deal with
these initial instants of polymerization, but they are beyond the scope of this
chapter. These initial particle-fragmentation models are more interesting for pre-
polymerization studies, since the amount of polymer made during this very short
initial stage is unlikely to have a marked inuence on the overall properties of the
Polymerization
Catalyst Polymer
Particle size
C
u
m
u
l
a
t
i
v
e

%
Fig. 8.32. Replication phenomenon for polymerization with
heterogeneous coordination catalysts.
Secondary Particle
or
Macroparticle
Primary Particle
or
Microparticle
Catalyst
fragment
Growing
polymer
shell
Fig. 8.33. The multigrain model.
polymer produced in the reactor. A 2001 review covers some of these alternative
models [36].
The multigrain model equation for spherical secondary particles is the classic
diusion-reaction equation in a sphere, Eq. (41), where M
s
is the monomer con-
centration in the secondary particle as a function of polymerization time, t, and
radial position, r
s
.
qM
s
qt
=
1
r
2
s
q
qr
s
D
e
r
2
s
qM
s
qr
s

R
V
p
(41)
The eective diusivity in the secondary particle, D
e
, can be estimated using the
conventional expression for eective diusivity in porous heterogeneous catalysts,
Eq. (42), where D
b
is the monomer bulk diusivity in the reaction medium, and e
and t are the void fraction and tortuosity of the polymer particle, respectively. The
fact that both e and t are likely to vary as a function of the degree of fragmentation
and expansion of the secondary particle is certainly one of the diculties in getting
a good estimate for D
e
.
D
e
=
eD
b
t
(42)
Finally, R
V
p
is the average volumetric rate of polymerization in the secondary
particle at a given radial position. Since, in the multigrain model, the polymeriza-
tion is assumed to take place only at the surface of the primary particles, this term
couples the models for the primary and secondary particles.
Equation (41) is subjected to the following boundary conditions given by Eqs. (43)
and (44), where R
s
is the radius of the secondary particle, k
s
is the mass-transfer
coecient in the external lm surrounding the secondary particle, and M
b
is the
monomer concentration in the bulk phase. Equations (43) and (44) are the classic
boundary conditions for heterogeneously catalyzed chemical reactions, namely
symmetry at the center of the particle and stationary convective mass transfer
through the mass-transfer boundary layer surrounding the particle, respectively.
Finally, the initial condition is given by Eq. (45).
qM
s
qr
s
(r
s
= 0; t) = 0 (43)
D
e
qM
s
qr
s
(r
s
= R
s
; t) = k
s
(M
b
M
s
) (44)
M
s
(r
s
; t = 0) = M
0
s
(45)
The initial concentration in the secondary particle, M
0
s
, may be set to zero for a
monomer-free catalyst condition, but this generally leads to sti dierential equa-
tions that may be very hard to solve. It is also common to assume a pseudo-steady-
state concentration at t = 0 to obtain the initial condition for Eq. (41). Unless one
is interested in the monomer proles for the very rst seconds of polymerization,
this approximation generally leads to a system of partial dierential equations that
is simpler to integrate.
Spherical primary particles are modeled with a similar equation [Eq. (46)].
qM
p
qt
=
1
r
2
p
q
qr
p
D
p
r
2
p
qM
p
qr
p

(46)
In Eq. (46), the subscript p refers to values in the primary particles. Equation (47)
has been suggested to estimate the eective diusivity of monomer in the primary
particle, where D
a
is the diusivity of monomer in amorphous polymer and w and i
are correction factors to account for the decrease in diusivity due to chain crystal-
linity and immobilization of the polymer amorphous phase due to the crystallites.
As can be very well imagined, these parameters are also hard to determine and D
p
is generally used as an adjustable parameter in the model.
D
p
=
D
a
wi
(47)
Notice that Eq. (46) does not contain a polymerization reaction term. Because the
multigrain model assumes that polymerization takes place at the surface of the cat-
alyst fragment embedded within the primary particle, the reaction term appears as
one of the two required boundary conditions [Eq. (48)]. Equation (48) states that
the rate of monomer diusion at the surface of the catalyst fragment, R
c
, equals
the rate of monomer consumption due to polymerization at rate of R
c
p
, and Eq.
(49) imposes the condition that the concentration at the surface of the primary par-
ticle equals the equilibrium concentration of monomer absorbed onto the polymer
phase, M
eq
.
4pR
2
c
D
p
qM
p
qr
p
(r
p
= R
c
; t) =
4
3
pR
3
c
R
c
p
(48)
M
p
(r
p
= R
p
; t) = M
eq
aM
s
(49)
The equilibrium concentration of monomer in polymer can be related by Eq. (50)
to the monomer concentration in the secondary particle at a given radial position
and time if a partition coecient, K
MP
, between the two phases is known.
M
eq
=
M
s
K
MP
(50)
The polymerization rate at the surface of the catalyst fragment is given by Eq. (51),
where C
+
is the concentration of active sites at the surface of the catalyst fragment.
R
c
p
= k
p
C
+
M(r
p
= R
c
; t) (51)
Finally, the initial condition for the primary particle is stated in Eq. (52).
M
p
(r
p
; t = 0) = M
0
p
(52)
Once again, a pseudo-steady-state approximation may be adopted to reduce the
stiness of the system of dierential equations for short polymerization times.
The multigrain model also includes a set of equations to describe the temper-
ature proles in the primary and secondary particles. These equations are sum-
marized in Table 8.2. Mathematical models for solving this system of partial dier-
ential equations with moving boundaries are involved and have been discussed in
the literature [36, 5160].
This versatile model has been used extensively to describe polymerization with
heterogeneous ZieglerNatta catalysts. Although it is dicult to make general
statements for such complex systems, it can be said with condence that most
of the mass- and heat-transfer resistances will take place at the beginning of the
polymerization when the concentration of active sites on the secondary particles
is at its maximum. As polymer is formed, it pushes apart the active sites in what
can be visualized as a dilution eect. In this way, as the secondary particle grows,
the catalyst concentration decreases, and naturally intraparticle mass- and heat-
transfer eects become less prevalent. For the same reason, particle hot spots are
more likely to be observed with highly active catalyst particles at the beginning of
the polymerization. This eect is highly undesirable since it may lead to softening
of the polymer phase and result in particle agglomeration and severe reactor foul-
ing, especially in gas-phase reactors.
The equations presented so far for the multigrain model are mass- and energy-
balance equations in a spherical catalyst particle used for conventional hetero-
geneously catalyzed reactions subjected to a moving boundary due to polymer
formation. To predict polymer properties such as chain length and chemical com-
position, these monomer and temperature proles must be coupled with an addi-
tional set of equations that describes polymerization and termination mechanisms
Tab. 8.2. Temperature proles in the primary and secondary particles according to the
multigrain model.
Secondary particle Primary article
r
p
C
p
qT
s
qt
=
1
r
2
s
q
qr
s
k
e
r
2
s
qT
s
qr
s

(DH
p
)R
V
p
r
p
C
p
qT
p
qt
=
1
r
2
p
q
qr
p
k
e
r
2
p
qT
p
qr
p

qT
s
qr
s
(r
s
= 0; t) = 0 4pR
2
c
k
e
qT
p
qr
p
(r
p
= R
p
; t) = (DH
p
)
4
3
pR
3
c
k
e
qT
s
qr
s
(r
s
= R
s
; t) = h(T
b
T
s
) T
p
(r
p
= R
p
; t) = T
s
T
s
(r
s
; t = 0) = T
0
s
T
p
(r
p
; t = 0) = T
0
p
taking place on the surface of the catalyst. The method of moments is generally the
preferred technique used in conjunction with the multigrain model, but its discus-
sion will be deferred to Section 8.5. Instead, we will use Stockmayers bivariate dis-
tribution, Eq. (16), to illustrate how polymer properties can be conveniently pre-
dicted from the multigrain model.
First, it should be remembered that Stockmayers distribution is an instanta-
neous distribution; that is, it describes the distributions of chain length and chem-
ical composition for polymer made at a given instant in time at a given spatial lo-
cation in the reactor. Now, consider the polymerization of ethylene and an a-olen,
1-hexene for instance, taking place in a spherical porous catalyst particle. Hydro-
gen is used as the chain-transfer agent. Assume also that the catalyst has only one
type of active site, as would be observed when supporting a metallocene on a po-
rous silica particle, for instance. The primary and secondary particles at a given in-
stant in time are subject to mass-and heat-transfer resistances that result in radial
monomer concentration and temperature proles. Assuming that ethylene propa-
gates at a much higher rate than 1-hexene and that both have comparable diu-
sivities, the radial prole for ethylene will be much steeper than for 1-hexene. Sim-
ilarly, the radial prole for hydrogen can be assumed to be very at, since the
hydrogen diusivity is high and its reaction rate is low. (Notice that a low reaction
rate of the chain-transfer agent as compared to the polymerization rate for the
monomers is a requirement for the production of high molecular weight poly-
mers.) Given that the monomer concentration and temperature aect the parame-
ters of the Stockmayer distribution, r
n
=k, each radial position i in the secondary
particle is associated with a unique Stockmayers distribution, w
i
(r; y), as depicted
in Figure 8.34. Polymer richer in the slow reacting comonomer, 1-hexene, is pro-
duced near the center of the particle because the molar ratio of 1-hexene/ethylene
increases from the surface to the center of the particle. Likewise, chains with lower
molecular weight are produced at the center of the particle because the molar ratio
of hydrogen/(ethylene 1-hexene) increases from the surface to the center of the
particle. These concentration gradients will, therefore, broaden the distributions
of molecular weight and chemical composition of polymer made with a heteroge-
neous catalyst, even a single-site catalyst, due to the spatial variations of concentra-
tions within the particle.
The summation of all these distributions over the polymer particle, weighted by
the amount of polymer made at each radial position, gives the distribution for the
whole particle at a given instant in time w
p
(r; y), as described by Eq. (53), where
R
p; i
is the rate of polymerization at radial position i and m is the number of radial
positions used in the discretization of the macroparticle.
w
p
(r; y) =
X
m
i=1
R
p; i
w
i
(r; y)
X
m
i=1
R
p; i
(53)
These instantaneous distributions can then be integrated in time to obtain the
cumulative distribution in the reactor per polymer particle, W
p
(r; y) [Eq. (54)].
W
p
(r; y) =
X
m
i=1
R
p; i
w
i
(r; y) dt
X
m
i=1
R
p; i
dt
(54)
For the case of catalysts containing multiple-site types, such as heterogeneous
ZieglerNatta catalysts, a similar approach applies, by dening one Stockmayers
distribution for each active-site type. In this case, the overall distribution of chain
length and chemical composition in the particle at a given instant equals the sum-
mation of the distributions over all site types and all radial positions in the particle
[Eq. (55)], where the subscript j indicates the site type of a catalyst containing n
site types.
C
2
H
4
C
6
H
12
H
2
1 2 3 4
4
1
2
3
0
0.2
0.4
0.6
0.8
1
1.2
1 2 3 4 5
log r
w
(
r
)
0
5
10
15
20
25
30
0.7 0.72 0.74 0.76 0.78 0.8 0.82
fraction of ethylene
w

(
f
r
a
c
t
i
o
n

o
f

e
t
h
y
l
e
n
e
)
1
2
3
4
Fig. 8.34. Using Stockmayers distribution with the multigrain
model to predict the distribution of chain length and chemical
composition of polyolens.
w
p
(r; y) =
X
m
i=1
X
n
j =1
R
p; i; j
w
i; j
(r; y)
X
m
i=1
X
n
j =1
R
p; i; j
(55)
Many other single-particle model formulations exist with lower or higher levels of
sophistication. Most of these models generate qualitative results that are similar to
the ones described in this section. As usual with any modeling eort, the degree of
model sophistication must be justied by the quality of the experimental data avail-
able to support the model assumptions. Our recent (2001) review gives coverage of
these alternative models [36].
8.5
Macroscopic Reactor Modeling Population Balances and the Method of Moments
Population balances coupled with the method of moments can be considered the
method of choice in most olen polymerization simulation models. Population
balances are molar balances (steady-state or dynamic) of all the important chemical
species present in the reactor: living and dead polymer chains, catalyst sites, mono-
mers, and chain-transfer agents. Solving the dynamic population balances for liv-
ing and dead chains of length r allows the recovery of the complete chain length
distribution as a function of polymerization time. Alternatively, instead of solving
the whole population balance, one may use the method of moments to solve for
only a few moments of the chain length distribution, a technique that requires
much less computational eort. In this case, it is possible to model how chain
length averages vary as a function of polymerization time, but the information
about the complete distribution is irretrievably lost for more complex cases.
In this section, we will rst illustrate how to use the method of moments for
homopolymerization and then show how these equations can be easily adapted to
copolymerization using the method of pseudo-kinetic constants.
8.5.1
Homopolymerization
In the following model development, we will use the polymerization kinetics
mechanism described by Eqs. (1)(14) to derive the population balances and mo-
ment equations for homopolymerization with a catalyst containing only one site
type. Catalysts containing two or more site types are handled similarly by dening
a set of equations with distinct polymerization kinetic constants for each dierent
site type.
For living polymer chains of length r b2 made in a CSTR, the dynamic popula-
tion balance can be derived as Eq. (56).
dP
r
dt
= P
in
r
k
p
M(P
r1
P
r
) (k
tb
k
tH
H
2
k
tAl
Al k
tM
M k
dI
I k
d
s)P
r
(56)
In Eq. (56) and in the subsequent ones, the notation x
in
represents the feed ow
rate of a given chemical species to the reactor, and s is the reciprocal of the average
residence time in the CSTR. Notice that Eq. (56) is simply the molar balance for
chains of length r: chains are generated by propagation of a chain of length r 1
or by transfer from a feed stream (coming from a previous reactor in a series of
reactors, for instance), and are consumed by either propagation to chains of length
r 1, by transfer and deactivation reactions leading to dead polymer chains, D
r
, or
by exiting the reactor in an outlet stream.
Similarly, for chains of unit length, Eq. (57) applies.
dP
1
dt
= P
in
1
(k
i
C
+
k
iH
C
i
H
)M k
p
P
1
M
(k
tb
k
tH
H
2
k
tAl
Al k
tM
M k
dI
I k
d
s)P
1
(57)
The population balances for C
+
and C
+
H
are needed to solve Eqs. (56) and (57).
They are given in Eqs. (58) and (59) respectively, where Y
0
=
P
y
r =1
P
r
.
dC
+
dt
= C
+in
k
a
CAl (k
tAl
Al k
tM
M)Y
0
(k
i
M k
dI
I k
d
s)C
+
(58)
dC
+
H
dt
= C
+in
H
(k
tb
k
tH
H)Y
0
(k
iH
M k
dI
I k
d
s)C
+
H
(59)
Often, the reaction between catalyst and cocatalyst is considered instantaneous.
Consequently, the term k
a
CAl can be dropped from Eq. (58) and it is assumed
that C
+
(t
0
) = C(t
0
).
The concentration of deactivated catalyst sites at any time is obtained via a molar
balance [Eq. (60)].
C
d
(t) = C
+
(t
0
) C
+
(t) C
+
H
(t) Y
0
(t) (60)
Population balances for dead polymer chains are also easily derived from the poly-
merization mechanism equation, Eq. (61).
d
^
DD
r
dt
=
dD
r
dt

dD
=
r
dt

dD
r; Al
dt
=
^
DD
in
r
[(k
tH
H
2
k
dI
I k
d
) (k
tb
k
tM
M) k
tAl
Al[P
r
s
^
DD
r
(61)
8.5 Macroscopic Reactor Modeling Population Balances and the Method of Moments 409
In Eq. (61), dead chains with all types of chain ends (D
r
; D
=
r
, and D
r; Al
) have been
combined in a single variable
^
DD
r
for simplicity. Separate population balances for
dead chains with dierent chain end types could also be kept, if necessary.
Molar balances for monomer, chain-transfer agent, impurities, catalysts, and co-
catalyst [Eqs. (62)(66)] are also required to solve the system of ordinary dieren-
tial equations dened by Eqs. (56)(61).
dM
dt
= M
in
(k
p
Y
0
k
tM
Y
0
k
i
C
+
k
iH
C
+
H
s)MGM
in
(k
p
Y
0
s)M (62)
dH
2
dt
= H
in
2
(k
tH
Y
0
s)H
2
(63)
dI
dt
= I
in
[k
dI
(Y
0
C
+
C
+
H
) s[I (64)
dC
dt
= C
in
(k
a
Al s)C (65)
dAl
dt
= Al
in
(k
a
C k
tAl
Y
0
s)Al (66)
Because of the long-chain approximation, the simplication k
p
Y
0
gk
tM
Y
0
k
i
C
+
k
iH
C
+
H
in Eq. (62) is very often applied.
Elegant ways of solving the population balances dened by Eqs. (56)(66) have
been developed to model how the complete chain length distribution of polyolens
varies as a function of polymerization time in batch, semibatch, or continuous re-
actors [61, 62].
When only chain length averages are required, the method of moments is the
most adequate technique for solving this problem. The ith moment, m
(i)
, of a given
distribution, f (x), is dened by Eq. (67).
m
(i)
=
X
x
x
i
f (x) (67)
Therefore, the zeroth moment is simply the total number (or concentration) of liv-
ing polymer chains [Eq. (68)].
Y
(0)
=
X
y
r =1
P
r
= P
1

X
y
r =2
P
r
(68)
Notice that, for coordination polymerization, Y
(0)
will be approximately equal to
the number of active sites at a given time in the reactor, since initiation reactions
tend to be very fast in these systems.
Taking the rst derivative of Eq. (68), one obtains Eq. (69).
dY
(0)
dt
=
dP
1
dt

X
y
r =2
dP
r
dt
(69)
Substituting Eqs. (56) and (57) into Eq. (69) generates the nal expression for the
zeroth moment of living polymer chains in a CSTR. After some algebraic manipu-
lation, Eq. (70) is obtained.
dY
(0)
dt
= Y
(0)in
K
i
M (K
t
K
d
s)Y
(0)
(70)
Here the several kinetic parameters were lumped into the constants K
t
; K
d
, and K
i
according to Eqs. (71)(73), to allow for a more concise notation.
K
t
= k
bt
k
tH
H
2
k
tM
M k
tAl
Al (71)
K
d
= k
d
k
dI
I (72)
K
i
= k
i
C
+
k
iH
C
+
H
(73)
Similarly, the rst moment of the living chains corresponds to the weight of these
chains [Eqs. (74) and (75)].
Y
(1)
=
X
y
r =1
rP
r
= 1 P
1

X
y
r =2
rP
r
(74)
dY
(1)
dt
=
dP
1
dt

X
y
r =2
r
dP
r
dt
(75)
Once again, substituting Eqs. (56) and (57) into Eq. (75) leads to the nal expres-
sion for the rst moment of living polymer chains in a CSTR, Eq. (76).
dY
(1)
dt
= Y
(1)in
K
i
M (K
t
K
d
s)Y
(1)
k
p
MY
(0)
(76)
The equations for the second moment of living polymer, Eqs. (77)(79), are derived
in an analogous manner.
Y
(2)
=
X
y
r =1
r
2
P
r
= 1
2
P
1

X
y
r =2
r
2
P
r
(77)
dY
(2)
dt
=
dP
1
dt

X
y
r =2
r
2
dP
r
dt
(78)
dY
(2)
dt
= Y
(2)in
K
i
M (K
t
K
d
s)Y
(2)
k
p
M(2Y
(1)
Y
(0)
) (79)
A similar procedure leads to the moment equations for the chain length distribu-
tion of dead polymer molecules [Eqs. (80) and (81)].
X
(i)
=
X
y
r =1
r
i
P
r
(80)
dX
(i)
dt
=
X
y
r =2
r
i
dX
r
dt
(81)
Substituting Eq. (61) into Eq. (81) produces the general expression for the ith mo-
ment of the dead polymer chains, Eq. (82).
dX
(i)
dt
= X
(i)in
(K
t
K
d
)(Y
(i)
P
1
) sX
(i)
(82)
Notice that P
1
is subtracted from Y
(i)
for exactness since dead chains of length
1 are simply monomer units and should not be counted as dead polymer chains.
This correction, however, is negligible for high polymers and can be omitted for
most modeling applications.
Equation (70), (76), (79), and (82) can be solved with the molar balances for the
reactants, Eqs. (62) to (66), to calculate the leading moments of the chain length
distribution. The values of the moments, as a function of polymerization time,
can then be used to compute the chain length averages with the expressions de-
scribed below.
The number-average chain length, r
n
, is easily related to the zeroth and rst mo-
ments of the distributions of chain length of living and dead polymer by Eq. (83).
r
n
=
X
y
r =1
r(D
r
P
r
)
X
y
r =1
(D
r
P
r
)
=
X
(1)
Y
(1)
X
(0)
Y
(0)
G
X
(1)
X
(0)
(83)
Since, for most coordination polymerizations, the amount of dead polymer far ex-
ceeds the amount of living polymer in the reactor, the approximation indicated in
Eq. (83) is very commonly used.
The weight-average chain length, r
w
, is likewise obtained from the ratio of the
second to the rst moments of living and dead chains, obtained from Eq. (84).
r
w
=
X
y
r =1
r
2
(D
r
P
r
)
X
y
r =1
r(D
r
P
r
)
=
X
(2)
Y
(2)
X
(1)
Y
(1)
G
X
(2)
X
(1)
(84)
Finally, the polydispersity index, PDI, is given by Eq. (85).
PDI =
r
w
r
n
=
(X
(2)
Y
(2)
)(X
(0)
Y
(0)
)
(X
(1)
Y
(1)
)
2
G
X
(2)
X
(0)
(X
(1)
)
2
(85)
For the case of multiple-site catalysts, population balances are derived for each cat-
alyst site type, and the chain length-averages for the whole polymer are found by
averaging the values calculated for each site type [Eqs. (86) and (87)].
r
n
=
X
n
j =1
(X
(1)
j
Y
(1)
j
)
X
n
j =1
(X
(0)
j
Y
(0)
j
)
G
X
n
j =1
X
(1)
j
X
n
j =1
X
(0)
j
(86)
r
w
=
X
n
j =1
(X
(2)
j
Y
(2)
j
)
X
n
j =1
(X
(1)
j
Y
(1)
j
)
G
X
n
j =1
X
(2)
j
X
n
j =1
X
(1)
j
(87)
Population balances and the method of moments can also be combined with the
multigrain model and other polymer particle growth models. In this case, the pop-
ulation balances are dened for each position in the particle to obtain the radial
proles of chain length averages [36, 5160].
8.5.2
Copolymerization
Population balances for copolymerization can be developed using the polymeriza-
tion kinetics presented in Table 8.1. This approach generates equations that are
similar to the ones obtained for homopolymerization but contain more terms to
account for the eect of chain ends on the kinetics of propagation and termination.
We will rst show how to derive such population balances for living polymer
chains, but instead of applying the same approach to all other species we will intro-
duce the concept of pseudo-kinetic rate constants [63, 64]. When pseudo-kinetic
rate constants are dened, the equations derived for homopolymerization can also
be used for copolymerization with only one minor modication, thus considerably
simplifying the time required for model development.
The population balance for living polymer chains terminating in monomer type
A with r b2 is given by Eq. (88).
dP
r; A
dt
= P
in
r; A
k
p; AA
(P
r1; A
P
r; A
)A k
p; BA
P
r1; B
A k
p; AB
P
r; A
B
(k
tb; A
k
tH; A
H
2
k
tAl; A
Al k
t; AA
A k
t; AB
B k
dI; A
I k
d; A
s)P
r; A
(88)
Similarly, for living polymer chains terminating in monomer type B with r b2,
Eq. (89) applies.
dP
r; B
dt
= P
in
r; B
k
p; BB
(P
r1; B
P
r; B
)B k
p; AB
P
r1; A
B k
p; BA
P
r; B
A
(k
tb; B
k
tH; B
H
2
k
tAl; B
Al k
t; BA
A k
t; BB
B k
dI; B
I k
d; B
s)P
r; B
(89)
Equations (88) and (89) can be added to obtain the dierential equation for P
r
=
P
r; A
P
r; B
, Eq. (90).
dP
r
dt
= P
in
r; A
P
in
r; A
(k
p; AA
P
r1; A
A k
p; AB
P
r1; A
B k
p; BA
P
r1; B
A
k
p; BB
P
r1; B
B) (k
p; AA
P
r; A
A k
p; AB
P
r; A
B k
p; BA
P
r; B
A k
p; BB
P
r; B
B)
(k
tb; A
P
r; A
k
tb; B
P
r; B
) (k
tH; A
P
r; A
k
tH; B
P
r; B
)H
2
(k
tAl; A
P
r; A
k
tAl; B
P
r; B
)Al
(k
t; AA
P
r; AA
A k
t; AB
P
r; A
B k
t; BA
P
r; B
A k
t; BB
P
r; B
B)
(k
dI; A
P
r; A
k
dI; A
P
r; B
)I (k
d; A
P
r; A
k
d; B
P
r; B
) sP
r
(90)
Applying the denitions in Eqs. (90)(93) to Eq. (90), one obtains Eq. (94).
f
A
=
P
r; A
P
r; A
P
r; B
; f
B
= 1 f
A
(91)
f
A
=
A
A B
; f
B
= 1 f
A
(92)
M = A B (93)
dP
r
dt
= P
in
r
(k
p; AA
f
A
f
A
k
p; AB
f
A
f
B
k
p; BA
f
B
f
A
k
p; BB
f
B
f
B
)P
r1
M
(k
p; AA
f
A
f
A
k
p; AB
f
A
f
B
k
p; BA
f
B
f
A
k
p; BB
f
B
f
B
)P
r
M
(k
tb; A
f
A
k
tb; B
f
B
)P
r
(k
tH; A
f
A
k
tH; B
f
B
)P
r
H
2
(k
tAl; A
f
A
k
tAl; B
f
B
)P
r
Al
(k
t; AA
f
A
f
A
k
t; AB
f
A
f
B
k
t; BA
f
B
f
A
k
t; BB
f
B
f
B
)P
r
M
(k
dI; A
f
A
k
dI; A
f
B
)P
r
I (k
d; A
f
A
k
d; B
f
B
)P
r
sP
r
(94)
Equation (94) can be expressed in the more compact form of Eq. (95), where the
pseudo-kinetic constants are dened by Eqs. (96)(102).
dP
r
dt
= P
in
r

^
kk
p
M(P
r1
P
r
) (
^
kk
tb

^
kk
tH
H
2

^
kk
tAl
Al
^
kk
tM
M
^
kk
dI
I
^
kk
d
s)P
r
(95)
^
kk
p
= k
p; AA
f
A
f
A
k
p; AB
f
A
f
B
k
p; BA
f
B
f
A
k
p; BB
f
B
f
B
(96)
^
kk
tb
= k
tb; A
f
A
k
tb; B
f
B
(97)
^
kk
tH
= k
tH; A
f
A
k
tH; B
f
B
(98)
^
kk
tAl
= k
tAl; A
f
A
k
tAl; B
f
B
(99)
^
kk
tM
= k
t; AA
f
A
f
A
k
t; AB
f
A
f
B
k
t; BA
f
B
f
A
k
t; BB
f
B
f
B
(100)
^
kk
dI
= k
dI; A
f
A
k
dI; A
f
B
(101)
^
kk
d
= k
d; A
f
A
k
d; B
f
B
(102)
Notice that Eqs. (56) and (95) are equivalent, with the only dierence that Eq. (95)
uses pseudo-kinetic constants in place of the actual kinetic constants found in Eq.
(56). The beauty of this modeling approach is that it is not necessary to develop
new equations for copolymerization (binary or higher): the equations developed
for homopolymerization, including the moment equations, are equally applicable
to copolymerization, provided that pseudo-kinetic constants are used to replace
the actual polymerization kinetic constants.
To calculate the pseudo-kinetic constants one must know the values of f
A
and f
A
at each polymerization time. Values for f
A
are easily calculated from the molar bal-
ance for the monomers, Eq. (103).
dA
dt
= A
in
(k
i
C
+
k
i; H
C
+
H
)A (k
p; AA
f
A
k
p; BA
f
B
)AY
0
(k
t; AA
f
A
k
t; BA
f
B
)AY
0
sA (103)
Since most of the monomer is consumed in polymerization reactions, Eq. (103) is
commonly reduced to the simpler form of Eq. (104).
dA
dt
= A
in
(k
p; AA
f
A
k
p; BA
f
B
)AY
0
sA (104)
The analogous equation for monomer B is Eq. (105).
dB
dt
= B
in
(k
p; BB
f
B
k
p; AB
f
A
)BY
0
sB (105)
The long-chain approximation can be used to calculate the values of f
A
via Eqs.
(106)(108).
k
p; AB
P
r; A
B = k
p; BA
P
r; B
A (106)
and therefore:
k
p; AB
f
A
f
B
= k
p; BA
f
B
f
A
= k
p; BA
(1 f
A
) f
A
(107)
f
A
=
k
p; BA
f
A
k
p; BA
f
A
k
p; AB
f
B
(108)
The use of Eq. (108) to calculate f
A
assumes that this value is not a function of
chain length; compare Eq. (91). It has been shown that this hypothesis is valid for
high polymers [63, 64].
Finally, the average copolymer composition [Eq. (109)] is easily obtained from
Eqs. (104) and (105).
F
A
=
A
A B
; F
B
= 1 F
A
(109)
8.6
Types of Industrial Reactors
The polymerization of olens with coordination catalysts is performed in a large
variety of polymerization processes and reactor congurations that can be classied
broadly into solution, gas-phase, or slurry processes. In solution processes, both
the catalyst and the polymer are soluble in the reaction medium. These processes
are used to produce most of the commercial EPDM rubbers and some polyethylene
resins. Solution processes are performed in autoclave, tubular, and loop reactors.
In slurry and gas-phase processes, the polymer is formed around heterogeneous
catalyst particles in the way described by the multigrain model. Slurry processes
can be subdivided into slurrydiluent and slurrybulk. In slurrydiluent pro-
cesses, an inert diluent is used to suspend the polymer particles while gaseous
(ethylene and propylene) and liquid (higher a-olens) monomers are fed into the
reactor. On the other hand, only liquid monomer is used in the slurrybulk pro-
cess. Polyethylene and polypropylene can be produced in slurrydiluent reactors,
while slurrybulk reactors are restricted to polypropylene and its copolymers.
Slurry processes involve the use of autoclaves or loop reactors. Gas-phase reactors
are also used to polymerize ethylene, propylene, and higher a-olens. They can be
classied into uidized-bed and stirred-bed reactors. A gaseous stream of mono-
mer and nitrogen uidizes the polymer particles in uidized-bed reactors, while
mechanical stirring is responsible for suspending the polymer particles in gas-
phase stirred-bed reactors. Gas-phase stirred-bed reactors are further subdivided
into horizontal and vertical reactors. These dierent reactor congurations are il-
lustrated in Figure 8.35.
Several polymerization processes use only one reactor, but two or more reactors
can also be operated in series (tandem reactor technology) to produce polyolens
with more complex microstructures [5]. Each reactor in the series is maintained
under dierent operating conditions to produce products that are sometimes called
reactor blends. Although, in principle, the post-reactor blending of dierent
resins could lead to the same product, in reactor blends the chains are mixed on
the molecular scale, permitting better contact between the polymer chains made
in dierent reactors at a lower energy cost.
The oldest example of this procedure is the manufacture of high-impact poly-
propylene, as already described (see Section 8.1.2). Other applications have become
more popular lately, especially for the production of bimodal resins. Figure 8.36
illustrates a tandem process using two gas-phase vertical stirred-tank reactors. Sev-
eral other reactor combinations are used industrially [65]. For heterogeneous pro-
cesses, the rst reactor(s) in the series can be either slurry or gas-phase, but com-
monly the second reactor (or set of reactors) is a gas-phase reactor. This is
especially important when the production of polymers with lower crystallinity
(a)
(b)
(c)
(d)
(e)
Fig. 8.35. Reactor congurations used with olen
polymerization: (a) Autoclave; (b) Loop; (c) Fluidized-bed;
(d) Vertical gas-phase; (e) Horizontal gas-phase.
occurs in the second set of reactors, because this fraction is more easily extracted in
slurry reactors, leading to fouling problems. Of course, these processes should be
operated in such a way as to avoid particle agglomeration caused by the formation
of sticky polymers of lower crystallinity.
For heterogeneous catalysts, tandem reactor technology also relies on the fact
that each polymer particle is in fact a microreactor operated in semibatch mode,
into which monomers and chain-transfer agents are fed continually, while the poly-
mer formed never leaves the microreactor. In this way, polymer populations with
dierent average properties are produced in each reactor and accumulate in the
polymer particle microreactor, as illustrated in Figure 8.37. In theory, an optimal
balance does exist between the fractions of these dierent populations to meet
certain performance criteria. This creates a truly fascinating reactor and product
design problem because the fractions of the dierent polymer populations per par-
ticle will be a function of the residence time distribution in the individual reactors
in the reactor train.
Consider rst the case of two tubular reactors in series, making high-impact
polypropylene. Reactor 1 produces isotactic polypropylene, while random
ethylenepropylene copolymer is made in Reactor 2. Assuming that both reactors
are ideal plug-ow reactors, the residence time of all the polymer particles in each
reactor is exactly the same. Consequently, if the distribution of active sites in the
propylene
ethylene
hydrogen
propylene
ethylene
hydrogen
catalyst
cocatalyst
Reactor 2 Reactor 1
unreacted
monomer
N
2
offgas
powder
silo
Extruder
polymer
pellets
N
2
Fig. 8.36. Example of a gas-phase tandem reactor process.
catalyst particles is uniform, the fractional polypropylene content in the ethylene
propylene copolymer is exactly the same in each polymer particle exiting Reactor 2.
Figure 8.38 illustrates this situation.
A very dierent picture emerges when using two CSTRs in series. Because the
residence time distribution of an ideal CSTR, E(t), with average residence time t
r
,
is given by the usual exponential decay equation [Eq. (110)], then some particles
will leave Reactor 1 after a short time while others will only leave after spending a
considerably longer time in the reactor.
E(t) =
1
t
r
exp
t
t
r

(110)
Since the same will happen in Reactor 2, in the end the ratio of polypropylene to
ethylenepropylene copolymer per particle exiting Reactor 2 will also vary widely,
which may be undesirable in some applications. Some of the reactor congura-
tions shown in Figure 8.35 can reduce this phenomenon, particularly the congu-
ration adopted for the gas-phase horizontal reactor, because the residence time dis-
tribution of this reactor is the equivalent to about three to four CSTRs in series.
(Remember that the residence time of an innite series of ideal CSTRs is that of
a plug-ow reactor.) A more recent solution for this problem, in fact a completely
new alternative to tandem reactor technology, is the multizone reactor that will be
described in more detail below (see Section 8.6.4).
catalyst and
cocatalyst
monomers and
chain transfer
agents
monomers and
chain transfer
agents
Product from
reactor 1
Product from
reactors 1 and 2
(reactor blend)
Fig. 8.37. Production of reactor blends in tandem reactors.
These polymerization processes were originally designed to polymerize olens
with heterogeneous ZieglerNatta catalysts, with the exception of some solution
processes that were designed to work with homogeneous ZieglerNatta catalysts
for the production of EPDM rubbers or some types of polyethylene resins. How-
ever, heterogeneous ZieglerNatta processes can be adapted to the use of metallo-
cene catalysts with minimal changes if the metallocenes are supported on an inert
carrier such as silica. Although some dierences in particle morphology have been
noticed when heterogeneous ZieglerNatta catalysts are replaced by supported
metallocenes, these ZieglerNatta processes are also currently being used with
metallocene catalysts on an industrial scale. In fact, the possibility of using metal-
locenes in conventional ZieglerNatta reactors is one of the main reasons for the
fast adoption of metallocenes by the polyolen manufacturing industry.
8.6.1
Gas-phase Reactors
Gas-phase reactors for olen polymerization are divided into two classes: uidized-
bed reactors and stirred-bed reactors. The stirred-bed reactors can be further clas-
sied into vertical and horizontal.
Fig. 8.38. Reactor blends produced in two plug-ow reactors and two CSTRs in series.
Gas-phase reactors, especially uidized-bed reactors, are the most common con-
guration for the polymerization of ethylene to produce HDPE and LLDPE. They
are also a very common choice for the second reactor in the production of high-
impact polypropylene.
Fluidized-bed reactors were developed by Union Carbide (Unipol Process)
currently Univation and British Petroleum (BP). Some details in their cong-
uration may vary, but their main characteristics are the same. In uidized-bed
reactors, gaseous monomers, chain-transfer agent, inerts, and catalysts are fed con-
tinuously into the reactor. The polymerization temperature should be kept well
below the melting point of the polymer to avoid particle agglomeration, loss of u-
idization, and bed collapse. Since polymer particles are formed in the gas phase in
absence of diluent, there is no need for further separation steps when the product
is exiting the reactor (except for removal of unconverted monomer), which is a
clear advantage of gas-phase processes over slurry and solution processes.
The heat of polymerization can be removed by heat exchangers placed on an ex-
ternal recirculation loop. However, low boiling point hydrocarbons and a-olen co-
monomers can be introduced into the reactor in the liquid phase to absorb the heat
of polymerization by their latent heat of evaporation in an operation procedure
called condensed mode. Since most polymerization reactors are limited by their
heat removal capability, this technique permits a substantial increase in reactor
productivity.
There are two principal designs for stirred-bed gas-phase reactors: vertical (origi-
nally developed by BASF/Targor) and horizontal (originally developed by Amoco
Chisso). These reactors have several of the advantages of uidized-bed reactors but
the polymer bed is suspended by mechanical agitation. Therefore, impeller design
is of the utmost importance in these reactors to avoid reactor fouling and particle
agglomeration. Stirred-bed reactors are generally smaller than uidized-bed reac-
tors, thus permitting grade transition with less production of o-specication ma-
terial. Both vertical and horizontal designs can be operated in condensed mode to
increase productivity. As mentioned above, the narrower residence time distribu-
tion of horizontal gas-phase stirred-bed reactors is advantageous for the production
of reactor blends with a narrow distribution of their dierent components. Narrow
residence time distributions are also useful if frequent grade transitions are re-
quired.
Gas-phase reactors have several advantages, notably:
v
Good temperature control due to high turbulence and heat-transfer coecients,
and heat removal by the latent heat of vaporization of inerts and monomers.
v
Lower operational costs due to lack of diluent recovery operations and, in the
case of uidized-bed reactors, due to the absence of moving parts.
v
Grade exibility for molecular weight control, since hydrogen concentration is
regulated by varying the partial pressure of hydrogen in the reactor. In slurry
and solution reactors, the low solubility of hydrogen in the diluent may reduce
the range of possible molecular weights for a given catalyst.
v
Higher comonomer incorporation (that is, production of copolymer with lower
crystallinity). This is possible since there is no risk of copolymer dissolution in
the reaction medium. However, care should be taken not to form sticky polymer
particles that can lead to particle agglomeration or reactor fouling.
v
The narrower residence time distribution of horizontal stirred-bed reactors leads
to higher yields per pass, formation of less o-specication material, and more
uniform impact copolymers and reactors blends.
Some disadvantages of gas-phase reactors are:
v
For the particular case of uidized-bed reactors, uidization is not a trivial pro-
cess and therefore demands better process control and the design of catalyst par-
ticles that uidize well.
v
Severe fouling and polymer particle agglomeration can occur, with occasional re-
actor shutdown. Fluidized-bed reactors, in particular, are prone to the formation
of polymer sheets on the walls (sheeting) or polymer chunks that may lead
periodic interruption of reactor operation.
v
Fluidized-bed reactors are generally very large, which makes grade transition
more time-consuming and might lead to the production of signicant amounts
of o-specication products.
8.6.2
Slurry Reactors
Slurry processes for olen polymerization are performed in autoclave or loop reac-
tors. Both reactor congurations are rather old and date from the beginning of
commercial olen polymerization. Most rst-generation olen polymerization pro-
cesses used autoclave reactors, while the Phillips process employed a loop reactor.
Slurrydiluent processes use an inert diluent to suspend the polymer particles.
Although the diluent does not directly aect the polymerization, it has been shown
that dierent diluents might change catalyst behavior, probably due to electronic
interaction with the active sites. Gaseous monomers and hydrogen are continu-
ously bubbled through the diluent. Liquid a-olen comonomers, diluent, catalysts,
and cocatalyst are continuously fed into the reactor. Alternatively, liqueed propy-
lene can be fed into the reactor (slurrybulk process). Except from this dierence,
all other conditions are similar to the slurrydiluent process.
Both autoclave and loop reactors have a residence time distribution of CSTRs
(loop reactors are operated at very high recirculation ratios), so they share several
of the same characteristics. There is a tendency nowadays to favor the loop reactor
conguration for the production of polypropylene in slurrybulk mode.
Some advantages of slurry reactors are:
v
Their simplicity of design and low cost make them a common choice for
laboratory-scale studies for screening catalysts and investigation of polymeriza-
tion kinetics, particularly autoclave congurations.
v
The large amount of diluent used (or liquid monomer) acts as a heat sink, per-
mits very good temperature control, and minimizes the risk of runaway polymer-
izations.
v
In loop reactors, the high recirculation rate leads to high turbulence and high
heat-transfer coecients. Additionally, the high heat-transfer area available in
these reactors permits ecient removal of heat of polymerization and therefore
high polymer yields.
However, slurry processes also have several disadvantages, such as:
v
It is necessary to remove the diluent from the polymer formed and recycle it
back to the polymerization reactor after purication, thus increasing operational
costs and environmental hazards.
v
With ZieglerNatta catalysts, molecular weight is generally controlled by transfer
to hydrogen. Since the solubility of hydrogen in the diluent is not very high,
there is less exibility for controlling molecular weight with this type of reactor.
This is not as important for Phillips catalysts, where molecular weight control is
achieved via support treatment, but can become a limiting factor with Ziegler
Natta catalysts. Metallocenes are generally very sensitive to the presence of hydro-
gen and therefore less inuenced by this reduced solubility that ZieglerNatta
catalysts.
v
Less crystalline copolymer chains can dissolve in the diluent particularly
the ethylenepropylene copolymer fraction in high-impact polypropylene
causing fouling and increasing the viscosity of the diluent. Therefore, certain
low-crystallinity grades cannot be produced with these reactors.
It has been speculated that, for the case of metallocene catalysts, some of the limi-
tations encountered with slurry reactors (both CSTR and loop) when producing
copolymers of lower crystallinity can be minimized or completely eliminated. As
discussed above, heterogeneous ZieglerNatta catalysts produce LLDPE with very
broad chemical composition distributions containing low-crystallinity tails. Such
low-crystallinity tails are absent in most polyolens made with metallocene cata-
lysts, thus minimizing the risk of copolymer dissolution during polymerization in
slurry reactors.
8.6.3
Solution Reactors
Solution processes use autoclave, tubular, or loop reactors. As compared to slurry
and gas-phase polymerization, solution processes are commonly operated at a
much higher temperature to keep the polymer dissolved in the reaction medium,
and at much lower average residence times (520 min, as opposed to 14 h). Since
polymerization conditions are more uniform in solutions reactors there are
no inter- and intraparticle heat- and mass-transfer resistances, for instance this
conguration is commonly used for the production of EPDM rubbers with soluble
ZieglerNatta vanadium-based catalysts. Composition homogeneity is a require-
ment of most EPDM rubbers since the formation of populations with higher crys-
tallinity is generally not acceptable in the rubber industry.
Solution reactors can be also used to produce polyethylene resins with soluble
ZieglerNatta or metallocene catalysts.
The short residence time used in solution reactors because of their high opera-
tion temperature is often an advantage during grade transition. The fact that the
polymer is in solution is also benecial for process control, since solution viscosity
can be used as a measure of polymer molecular weight, for instance. However,
high solution viscosities are also a limiting factor for these reactors, reducing the
achievable polymer concentration in solution, especially for high molecular weight
resins. Solution reactors can also operate in a wider range of temperatures than
slurry and gas-phase reactors, for which the temperature should be high enough
RISER
upward
pneumatic
transport
DOWNCOMER
packed bed
moving downward
Catalyst
inlet
Heat exchanger
Gas
fan
Product
discharge
Internal
gas/solid separator
Fig. 8.39. Schematic of a multizone circulating reactor [50].
to permit high polymerization rates but not so high as to soften the polymer and
cause particle agglomeration and reactor fouling. This wider temperature range al-
lows for more exibility in terms of catalyst types and polymer structural control.
In addition, solution reactors can be used to produce polymer from very high to
very low crystallinity, since there are no problems with reactor fouling caused by
sticky low-crystallinity polymers.
8.6.4
Multizone Reactors
The multizone circulating reactor (see Figure 8.39) is a novel concept for propylene
polymerization, developed by Basell. This reactor combines a fast uidization reac-
tor with a moving packed-bed reactor and can produce reactor blends in a single
reactor instead of in a series of reactors [65]. The reactor operates in a cycle: poly-
mer is transferred from the bottom of the xed-bed section (downcomer) to the
bottom of the uidized-bed section (riser). A gas stream, containing monomers
and inerts, conveys the polymer particles to the top of the riser and a centrifugal
separator settles them at the top of the downer. Finally, the particles ow by gravity
from the top to the bottom of the downer, where the cycle is repeated again.
The polymer particles can pass through these two sections of the reactor several
times before exiting the reactor. If these two (or more) zones are kept in dierence
polymerization conditions, a multimodal reactor blend polymer can be produced.
It is claimed that because the polymer particles can be made to circulate between
the dierent reactor zones several times before exiting the reactor, a more uniform
distribution of blend components will result than in an equivalent resin made
on two reactors in series. Of course, this is what would be expected from a reactor
blend made in several reactors in series.
Notation
A monomer type A
Al cocatalyst or activator
B number of LCBs per chain for the whole polymer; monomer type B
C catalyst
C
+
active center
C
+
CH3
methylated active center
C
d
deactivated site
C
+
H
metal hydride center
D catalyst modier (electron donor)
D
a
diusivity of monomer in amorphous polymer [cm
2
s
1
]
D
b
monomer bulk diusivity in the reaction medium [cm
2
s
1
]
D
e
eective diusivity in the secondary particle, [cm
2
s
1
]
D
p
eective diusivity in the primary particle, [cm
2
s
1
]
D
r
dead chain with a saturated chain end
Notation 425
D
=
r
dead polymer chain containing a terminal vinyl unsaturation
^
DD
r
dead polymer chains with all possible types of chain ends
D
r; Al
dead polymer chain formed via a transfer to cocatalyst reaction
E(t) reactor residence time distribution
f
=
molar fraction of macromonomer in the reactor, measured with respect
to the total concentration of polymer
f
A
molar fraction of monomer A in the reactor
F
A
average fraction of comonomer A in the copolymer
H
2
hydrogen
i number of long-chain branches per polymer chain
I polar impurity
I
1
modied Bessel function of the rst kind of order 1
k
a
rate constant for catalyst activation [s
1
]
k
d
rate constant for monomolecular or bimolecular deactivation [s
1
]
K
d
lumped deactivation constant, dened in Eq. (72)
k
dI
rate constant for deactivation by impurity [L mol
1
s
1
]
k
i
initiation rate constant [L mol
1
s
1
]
K
i
lumped initiation constant, dened in Eq. (73)
k
iH
initiation rate constant for a metal-hydride center [L mol
1
s
1
]
k
LCB
rate constant for LCB formation [L mol
1
s
1
]
K
MP
monomer partition coecient between bulk and polymer phases
k
p
propagation rate constant [L mol
1
s
1
]
k
p; ij
propagation rate constant for monomer type i and chain end type j
[L mol
1
s
1
]
k
s
mass-transfer coecient in the external lm surrounding the secondary
particle [cm s
1
]
K
t
lumped chain-transfer constant, dened in Eq. (71)
k
tb
b-hydride elimination rate constant [s
1
]
k
tb-CH3
b-methyl elimination rate constant [s
1
]
k
tAl
rate constant for transfer to cocatalysts [L mol
1
s
1
]
k
tH
rate constant for transfer to hydrogen [L mol
1
s
1
]
k
tM
rate constant for transfer to monomer [L mol
1
s
1
]
m number of radial positions used in the discretization of the macro-
particle
m
i
mass fraction of polymer made on site type i, mass fraction of polymer
with i long-chain branches per chain
M monomer
M
b
monomer concentration in the bulk phase [mol L
1
]
M
eq
equilibrium concentration of monomer absorbed onto the polymer
phase [mol L
1
]
M
p
monomer concentration in the primary particle [mol L
1
]
M
0
p
initial monomer concentration in the primary particle [mol L
1
]
M
s
monomer concentration in the secondary particle [mol L
1
]
M
0
s
initial concentration of monomer in the secondary particle [mol L
1
]
n number of active-site types in a multiple-site catalyst
PDI polydispersity index
PDI polydispersity index for branched polymers
P
r
growing polymer of chain length r
r chain length
r
A
; r
B
reactivity ratios
R
c
radius of the primary particle [cm]
r
n
number-average chain length
r
n
number-average chain length for branched polymers
R
p; i
rate of polymerization at radial position i [mol L
1
s
1
]
R
c
p
polymerization rate at surface of catalyst fragment [mol L
1
s
1
]
R
V
p
average volumetric rate of polymerization in the secondary particle at a
given radial position [mol L
1
s
1
]
r
p
radial coordinate in the primary particle [cm]
r
s
radial coordinate in the secondary particle [cm]
R
s
radius of the secondary particle [cm]
r
w
weight-average chain length
r
w
weight-average chain length for branched polymers
s reciprocal of the average reactor residence time [s
1
]
t polymerization time [s]
t
r
average reactor residence time [s]
w(r) weight distribution of chains of length r (Florys most probable chain
length distribution)
w(r; i) weight distribution of chains of length r containing i long-chain
branches
w(r; y) weight distribution of chains of length r and chemical composition y
(Stockmayers bivariate distribution)
w(r; y; i) weight distribution of chains of length r, chemical composition y, and i
long-chain branches
w(y) weight distribution of chains with chemical composition y
w(r) instantaneous chain length distribution for the whole polymer produced
in a CSTR in the presence of branching reactions
w
p
(r; y) instantaneous distribution of chain length r and chemical composition
y in the polymer particle
W
p
(r; y) cumulative distribution of chain length r and chemical composition y in
the polymer particle
X
(i)
ith moment of the dead polymer chains
y deviation from the average molar fraction of monomer type A in the
copolymer
Y concentration of growing polymer chains in the reactor
Y
(i)
ith moment of the living polymer chains
Greek
a dened in Eq. (34)
e void fraction of the polymer particle
Notation 427
i correction factor to account for the decrease in diusivity due to chain
immobilization of the polymer amorphous phase due to the crystallites
k dened in Eq. (17)
m
(i)
ith moment of a chain length distribution
t dened in Eq. (31); tortuosity of the polymer particle
f
I
fraction of chains terminated in monomer of type i
w correction factor to account for the decrease in diusivity due to chain
crystallinity
Subscripts
i; j site type; number of long-chain branches
r; s chain length
Superscripts
in feed ow rate of a given chemical species to the reactor [mol L
1
s
1
]
^ pseudo-kinetic constant
Acronyms
Cp cyclopentadienyl
Crystaf crystallization analysis fractionation
CSTR continuous stirred-tank reactor
EPDM ethylenepropylenediene rubber
GPC gel permeation chromatography
HDPE high-density polyethylene
LCB long-chain branch
LLDPE linear low-density polyethylene
MAO methylaluminoxane
Tref temperature rising elution fractionation
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9
Mathematical Methods
P. D. Iedema and N. H. Kolhapure
9.1
Introduction
In this chapter some mathematical methods to solve kinetic modeling problems
are explained. A very sound basis for this was already laid many years ago by Flory
[1]. Here, we want to present modern mathematical tools that have recently been
developed through the use of computers. The focus is on the link between kinetic
rate data and reactor type on one hand, and distributive properties in one or
more dimensions on the other. These distributive or microstructural properties
are concerned not only with countable quantities, such as the number of monomer
units in a polymer molecule, but also with structure in the case of branched poly-
mer molecules. With structure, we discuss the connectivity of branch points and
the lengths of the segments between them. In the greater part of the text, reactors
are treated in a simplied manner. We consider continuous and batch reactors, but
all of them ideally mixed. The eect of incomplete mixing (segregation, macro-
and micromixing) is addressed in classical textbooks such as Biesenberger [2] and
Dotson et al. [3]. Some recent attempts to include the impact of micromixing on
distributions are available in the literature [5759], but this eld is still in its in-
fancy. Nevertheless, to still provide a sound basis for issues of mixing, we devote
one section to the use of computational uid dynamics in polymer reaction engi-
neering problems.
The microstructural properties that we address are chain length, number of
monomer units of one kind (copolymer), number of branch points, number of un-
saturated bonds, and number of reactive monomer units (end groups in poly-
condensation). Problems may require solution of one or more of these properties
simultaneously. Here, we will denote this as the dimensionality of the problem
at hand. For instance, growth in addition polymerization can be described by a
simple 1D (chain length) reaction equation and population balance.
R
n
M
kp
R
n1
(1)
ISBN: 3-527-31014-2
431
dR
n
dt
= k
p
M(R
n1
R
n
) (2)
In contrast, growth in polycondensation of a trifunctional monomer A with a bi-
functional monomer B requires a 3D description. The 3D distribution R
n; i; k
, where
subscripts denote chain length, number of A end groups, number of B end groups,
respectively, obeys:
R
n; i; k
R
m; j; l

kc
R
nm; ij1; kl1
(3)
dR
n; i; k
dt
= k
c
X
n1
m=1
X
i
j =0
X
k
l =0
j(k l 1)l(i j 1)R
m; j; l
R
nm; ij1; kl1
(4)
Note that this describes a reaction between single end groups of two dierent
molecules; end group combinations within one (longer) molecule require a similar
approach.
These examples illustrate the importance of the dimensionality of the problem at
hand. In general, low dimensionality can be dealt with using analytical or dieren-
tial methods, while higher dimensionality soon requires a Monte Carlo sampling
approach. Note that all of these methods, except MC, start with a population bal-
ance. Here we will mainly discuss ways to solve such balances of lower or higher
dimensionality. This chapter will start with the description of lower-dimensional
problems and show to what extent these can be successful. This often involves the
reduction of the problem to lower dimensionality, inevitably leading to averaging
over one or more dimensions. The most well-known is the method of moments,
which, however, does not solve full distributions. This is followed by the introduc-
tion of a fairly recent mathematical method based on dierential equations that
does solve full distributions: the Galerkin hp nite element method (FEM). Sub-
sequently, we will present advanced applications of the Galerkin-FEM (G-FEM)
method, being classes and pseudo-distribution modeling. A completely dierent
approach originating from polymer network modeling is then discussed: prob-
ability generating functions. To conclude the methods for countable properties, we
give an overview of full Monte Carlo simulation methods as introduced by Tobita
[1115, 4851], mostly for cases where analytical or dierential equation ap-
proaches fail. A separate section then is spent on very recently developed condi-
tional Monte Carlo methods to synthesize branched architectures. Finally, a section
is devoted on applications of computational uid dynamics in polymer reaction
engineering.
9.2
Discrete Galerkin hp Finite Element Method
The discrete Galerkin hp nite element method (FEM) is a powerful numerical
method to solve chain length distributions for a wide set of polymerization prob-
432 9 Mathematical Methods
lems. It has been implemented in the commercially available package PREDICI.
A great proportion of the problems discussed in this chapter are solved with this
approach. A detailed description of the mathematics of the method is given by
Wulkow [4]. Below the main mathematical features are given following the de-
scription in Ref. 4.
Any set of population balance equations (see, for example, Table 9.2, below) can
be written as a set of countable ordinary dierential equations [Eqs. (5)].
u
/
s
(t) = f
s
u
1
(t); . . . ; u
stot
(t) s = 1; . . . ; s
tot
(5)
Here, the u
s
(t) are the concentrations of all the macromolecules with length n at
time t, represented by vector u
s
(t); s
tot
is the dimension (chain length) of the sys-
tem, for polymer systems typically very large, up to 10
6
. For an approximation u
1
of the solution u(t t) after a time step from t to t t a semi-(linear)-implicit
Euler scheme is applied [Eq. (6), where j = u(t), A is the derivative f
u
(j), and I
the identity matrix].
(I tA)Du = tf (j) (6)
u
1
= j Du
The solution of this equation is approximated by a nite element Galerkin method.
This is realized by a multilevel algorithm, according to which a subdivision of the
s-axis is constructed (see Figure 9.1). On each interval h a local expansion u
j
s
of u
s
is
used, where j is the level number and l is the interval number:
u
j
s
[
h
j
l
=
X
p
j
l
k=0
a
j
kl
t
j
k; l
(s) (7)
j j
p h
1 1
,
j
m
j
m
p h , ( ) ( )
Fig. 9.1. Division of chain length axis into intervals of length
h, where distribution is approximated by Chebyshev
polynomials of order p.
9.2 Discrete Galerkin hp Finite Element Method 433
The polynomials t
j
k; l
are discrete Chebyshev polynomials of degree k. The number
of expansion coecients p
j
l
may dier from interval to interval, such that tting it
to a concentration distribution can be solved by varying grid and order. Note that
this feature gives the name to the method: Galerkin h (varying intervals) p (vary-
ing order). The node-order-distribution on the nal grid is chosen in such a way
that the work necessary to compute the whole distribution is minimal:
D
F
= (h
l
; p
l
) . . . (h
m
; p
m
) (8)
The construction is started with an initial grid D
0
on the interval [0; s
max
], where
s
max
may be very large. It proceeds from level to level by renements or increases
of the order, using information from the previous level. An example is shown in
Figure 9.2.
The Galerkin hp method is very exible, being able to solve simple distributions
with few broad intervals, but also complicated, including multimodal distributions
with steep anks requiring intensive local adaptation. Such adaptations are man-
aged automatically with the method. The algorithm as implemented in PREDICI
utilizes chain length truncation. A truncation index is calculated, being the maxi-
mum chain length up to which a distribution is calculated. From the index for a
calculated distribution, s
old
max
, a new index is calculated from the moments of the
distribution:
s
new
max
=
m
1
m
0
k
m
2
m
0
m
1
m
0

2
s
k = 10 (9)
When higher accuracy is required in tail calculations weight- or w(log s)-based
truncation indices can be calculated, where moments m
0
; m
1
, and m
2
are replaced
by m
k
; m
k1
, and m
k2
, with k = 1 or 2, respectively. For example, a Flory distribution
with average n
n
= 100 is represented until s
max
= 1100. A rst demonstration of
the capabilities of the Galerkin-FEM method will be given in Section 9.4 in a com-
parison with the method of moments. Further and extensive use is made of the
(h
1
,p
1
) (h
2
,p
2
) (h
3
,p
3
) (h
4
,p
4
) (h
5
,p
5
)
(h
1
,p
1
+1) (h
2
,p
2
) (h
3L
,1) (h
3R
,1) (h
4
,p
4
+1) (h
5
,p
5
)
1
max
s
Fig. 9.2. Renement strategy. Orders of intervals (h
1
; p
1
) and
(h
4
; p
4
) increased by 1. Interval (h
3
; p
3
) is split into two
intervals with order 1 (order may be higher according to
optimization strategy). Other intervals remain unchanged.
method in the classes and pseudo-distributions approach, to be discussed in Sec-
tions 9.5 and 9.6.
9.3
Method of Moments
9.3.1
Introduction
The method of moments is the most well-known method for solving polymeriza-
tion problems [13]. The equations are derived from the population balances.
This is realized in a straightforward way for the radical polymerization system of
Table 9.1, a 1D problem. Table 9.2 presents the original population balances and
Table 9.3 the resulting moment equations, up to the 4th moment. The linear part
of this problem can be solved without additional assumptions, but the nonlinear
part leads to a closure problem. This will be discussed next. Some results and a
discussion on the validity of the method will be given in Section 9.4, in a compari-
son with the Galerkin-FEM method.
9.3.2
Linear Polymerization
Suppose we want to describe a recombination reaction of two living copolymer
chains with one dead chain [Eq. (10)], which is a 2D problem.
R
p
n; i
R
s
m; j

kc; ps
P
nm; ij
(10)
The rst subscripts (n; m) denote chain length, the second (i; j) the number of
monomer units of one type per chain; superscripts indicate terminal units, identi-
ed as either monomer 1 or monomer 2, so p = 1 or 2 and s = 1 or 2; k
c; ps
is the
Tab. 9.1. Reaction equations for radical polymerization with transfer to polymer and random
scission by H-abstraction.
Mechanism Reaction equation Rate factor
Initiation I
2
2I v I v M R
1
k
d
; k
i
f
Propagation R
n
M R
n1
k
p
Disproportionation termination R
n
R
m
P
n
P
m
k
td
Recombination termination R
n
R
m
P
nm
k
tc
Transfer to monomer R
n
M P
n
R
1
k
m
Transfer to chain transfer agent S R
n
S P
n
R
1
k
S
Transfer to polymer R
n
P
m
P
n
R
m
LCB k
trp
m
Random scission by H-abstraction R
n
P
m
P
n
R
ml
P
l
k
rs
m
rate coecient for combination between chains with terminal units p and s. The
full population balance reads as [5] (the = duet means that this is one out of
possibly more contributions to the population balance of P
n; i
):
dP
n; i
dt
=
X
2
r =1
X
2
q=1
k
c; ps
X
n1
m=1
X
i
j =0
R
p
m; j
R
s
nm; ij
(11)
The moments of distributions R and P are dened as:
l
p
ab
=
X
y
n=1
X
y
j =1
n
a
i
b
R
p
n; i
m
ab
=
X
y
n=1
X
y
j =1
n
a
i
b
P
n; i
; p = 1; 2 (12)
The population balance of Eq. (11) is expressed in moments by performing the
summations as in Eq. (12) and collecting all the terms. In its most general form
the result can be expressed as [5]:
dm
ab
dt
=
1
2
X
2
p=1
X
2
s=1
k
c; ps
X
a
g=0
X
b
d=0
a
g

b
d

l
r
g; d
l
r
ag; bd
(13)
Usually, when number- and weight-average molecular weights are to be calculated,
Tab. 9.2. (Population) balances for radical polymerization with transfer to polymer and random
t
dM
dt
= M
0
M k
p
tM
X
y
n=1
R
n
= M
0
M k
p
tMl
0
(a)
t
dI
2
dt
= I
20
I
2
k
d
tI
2
(b)
t
dI
dt
= I 2k
d
tI
2
k
i
tIM (c)
t
dS
dt
= S
0
S k
s
tSl
0
(d)
t
dR
1
dt
= R
1
k
i
tIM k
s
tSl
0
k
p
tR
1
M k
rs
tl
0
m
0
(e)
dR
n
dt
= k
p
MR
n
k
p
MR
n1
k
tp
R
n
m
1
k
tp
l
0
P
n
k
rs
l
0
X
y
k=n1
P
k
k
rs
l
0
m
1

(k
tc
k
td
)l
0
R
n
k
s
SR
n
k
m
MR
n
R
n
=t
(f )
dP
n
dt
= k
tp
l
0
nP
n
k
tp
m
1
R
n
k
rs
l
0
X
y
k=n1
P
k
k
rs
m
1
R
n
k
rs
l
0
(n 1)P
n
k
td
l
0
R
n

1
2
k
tc
X
n1
m=1
R
mn
R
m
k
s
SP
n
k
m
MP
n
P
n
=t
(g)
it is sucient to have a; b = 0; 1; 2. Although these forms seem to be complex, they
can be derived straightforwardly and solved without any additional assumption or
model for linear polymerization that is, when rate factors are independent of
chain length, comonomer content, and so on. In fact, contributions to the popula-
tion balances from all other kinetic mechanisms propagation, transfer to solvent
or monomer, disproportionation can be treated in similar but simpler ways. For
linear polymerization the method of moments provides exact solutions for number
Tab. 9.3. Moment equations for radical polymerization with transfer to polymer and random
dl
0
dt
= k
p
MR
1
(k
tc
k
td
)l
2
0
k
s
Sl
0
k
m
Ml
0

1
t
l
0
(a)
dl
1
dt
= k
p
Ml
0
k
tp
m
1
l
1
k
tp
m
2
l
0

1
2
k
rs
l
0
(m
2
m
1
) k
rs
l
0
(m
1
m
0
)
(k
tc
k
td
)l
0
l
1
k
s
Sl
1
1 k
m
Ml
1

1
t
l
1
(b)
dl
2
dt
= 2k
p
Ml
1
k
tp
m
1
l
2
k
tp
m
3
l
0
k
rs
l
0
1
3
m
3

1
2
m
2

1
6
m
1

k
rs
l
2
(m
1
m
0
)
(k
tc
k
td
)l
0
l
2
k
s
Sl
2
k
m
Ml
2

1
t
l
2
(c)
dl
3
dt
= 3k
p
Ml
2
k
tp
m
1
l
3
k
tp
m
4
l
0
k
rs
l
0
1
4
m
4

1
2
m
3

1
4
m
2

k
rs
l
3
(m
1
m
0
)
(k
tc
k
td
)l
0
l
3
k
s
Sl
3
k
m
Ml
3

1
t
l
3
(v)
dl
4
dt
= 4k
p
Ml
3
k
tp
m
1
l
4
k
tp
m
5
l
0
k
rs
l
0
1
5
m
5

1
2
m
4

1
3
m
3

1
30
m
1

k
rs
l
4
(m
1
m
0
) (k
tc
k
td
)l
0
l
4
k
s
Sl
4
k
m
Ml
4

1
t
l
4
(e)
dm
0
dt
= k
rs
l
0
(m
1
2m
0
)
1
2
k
tc
k
td

l
2
0
k
s
Sl
0
k
m
Ml
0

1
t
m
0
(f )
dm
1
dt
= k
rs
l
0
1
2
m
2

1
2
m
1
m
0

k
rs
l
1
(m
1
m
0
) k
rs
l
0
(m
2
m
1
) k
tp
l
1
m
1
k
tp
l
0
m
2
(k
tc
k
td
)l
0
l
1
k
s
Sl
1
k
m
Ml
1

1
t
m
1
(g)
dm
2
dt
= k
rs
l
0
1
3
m
3

1
2
m
2

1
6
m
1
m
0

k
rs
l
2
(m
1
m
0
) k
rs
l
0
(m
3
m
2
) k
tp
l
2
m
1
k
tp
l
0
m
3
k
tc
(l
0
l
2
l
2
1
) k
td
l
0
l
2
k
s
Sl
2
k
m
Ml
2

1
t
m
2
(h)
dm
3
dt
= k
rs
l
0
1
4
m
4

1
2
m
3

1
4
m
2
m
0

k
rs
l
3
(m
1
m
0
) k
rs
l
0
(m
4
m
3
) k
tp
l
3
m
1
k
tp
l
0
m
4
k
t
(l
0
l
3
3l
1
l
2
) k
td
l
0
l
3
k
s
Sl
3
k
m
Ml
3

1
t
m
3
(i)
dm
4
dt
= k
rs
l
0
1
5
m
5

1
2
m
4

1
3
m
3

1
30
m
1
m
0

k
rs
l
4
(m
1
m
0
) k
rs
l
0
(m
5
m
4
)
k
tp
l
4
m
1
k
tp
l
0
m
5
k
t
(l
0
l
4
4l
1
l
3
3l
2
2
) k
td
l
0
l
4
k
s
Sl
4
k
m
Ml
4

1
t
m
4
( j)
and weight averages of molecular weight and copolymer composition. Most well
known are the averages for homopolymerization expressed as:
M
n
= m
0
m
1
m
0
M
w
= m
0
m
2
m
1
(14)
9.3.3
Nonlinear Polymerization
In nonlinear polymerization rate factors depend on chain length or other micro-
structural properties, which leads to special problems when utilizing the method
of moments [6]. We here address transfer to polymer in radical polymerization
leading to long-chain branching (LCB) and random scission. The reaction equation
for transfer to polymer in a 1D formulation with the rate factor proportional to
chain length, k
tp
m is Eq. (15).
R
n
P
m

ktpm
P
n
R
m
(15)
The population balance contribution for dead chains is given by:
dP
n
dt
= k
tp
(m
1
R
n
l
0
nP
n
) m
1
=
X
y
n=1
nP
n
; l
0
=
X
y
n=1
R
n
(16)
Dening moments as in Eq. (12), m
a
=
P
y
n=1
n
a
P
n
, and constructing the moment
equations from Eq. (16) yields:
dm
a
dt
= k
tp
(m
1
l
a
l
0
m
a1
) (17)
This illustrates a typical closure problem. In linear polymerization, dierential
equations of the ath moment contain RHS terms with ath or lower moments,
which allows direct solution of the set. In contrast, as shown by Eq. (17), nonlinear
polymerization leads to higher moments on the RHS. This implies that the set
cannot readily be solved without additional assumptions. Another example is ran-
dom scission of linear dead chains into two living chains (macroradicals):
P
n

krs n
R
m
R
nm
(18)
Again, the rate factor is proportional to chain length. The 1D population balance
reads:
dR
n
dt
= k
rs
X
y
m=n1
nP
n
(19)
Constructing equations for 0th through 4th moments by summing over chain
length leads to:
dl
0
dt
= 0; (20)
dl
1
dt
=
1
2
k
rs
(m
2
m
1
); (21)
dl
2
dt
= k
rs
1
3
m
3

1
2
m
2

1
6
m
1

; (22)
dl
3
dt
= k
rs
1
4
m
4

1
2
m
3

1
4
m
2

; (23)
dl
4
dt
= k
rs
1
5
m
5

1
2
m
4

1
3
m
3

1
30
m
1

: (24)
Hulburt and Katz [7] have developed a method to obtain estimates of the higher
moments in terms of lower ones using a distribution approximation method.
Most previous work has been based on the 3rd-moment closure. A general expres-
sion is constructed for moment m
i
, where l is the highest order of the series of
Laguerre polynomials in the approximation, while a and g are parameters to be
specied:
m
i
=
(i g 1)!
(g 1)!
m
0
(g=a)
i
X
l
m=3
k
m
(g=a)
i
X
m
j =0
(1)
j
m!(m g 1)!(m i g 1 j)!
j!(m j)!(m g 1 j)!
" #
(25)
The series is truncated at l = i 1, so that the computation of m
i
requires the coef-
cient k
i1
. This implies that m
l
and higher moments equal zero. Coecients k
i
follow in their turn from the lower moments m
0...i1
by:
k
i
=
X
i
j =0
(1)
j
(g 1)!
j!(i g 1 j)!
(g=a)
ij
(i j)!
m
ij
; (26)
so k
0
= m
0
. It is further assumed that: a =
m
1
m
0
; g =
a
2
m
2
=m
0
a
2
, which leads to
k
1
= k
2
= 0.
Thus, closure expressions have been obtained for m
3
; m
4
, and m
5
:
m
3
=
m
2
m
0
m
1
(2m
2
m
0
m
2
1
) (27)
m
4
=
(2m
2
1
3m
2
m
0
)(3m
2
1
m
2
6m
2
2
m
0
4m
0
m
1
m
3
)
m
2
0
m
2
1
(28)
m
5
=
(12m
4
1
m
2
42m
2
1
m
2
2
m
0
36m
2
0
m
3
2
20m
3
1
m
0
m
3
30m
1
m
2
0
m
2
m
3
5m
2
1
m
2
0
m
4
)(3m
2
1
4m
2
m
0
)
m
2
0
m
3
1
(29)
9.4
Comparison of Galerkin-FEM and Method of Moments
Certain features of both methods can nicely be illustrated in a simple nonlinear
problem: radical polymerization with transfer to polymer in a continuous stirred-
tank reactor (CSTR) with termination by either disproportionation or recombina-
tion. Data and results are shown in Figures 9.39.5. Typical for the moment
method is the occurrence of a point beyond which no stable solution exists. In
this case this happens for k
tp
= 1000 m
3
(kmol s)
1
for the case with dispropor-
tionation and k
tp
= 160 m
3
(kmol s)
1
when recombination is by the termination
mechanism. In both cases the second moment of dead chains, m
2
, goes to innity
at that point. Such instabilities are not found by the G-FEM method. At higher k
tp
we observe further clear discrepancies, especially for the living chains having much
higher M
w
according to G-FEM. However, the living chain M
w
values are not calcu-
lated correctly in all cases by the G-FEM method. This is best demonstrated by
comparing the chain length distributions (CLDs) of living and dead chains for the
recombination case shown in Figures 9.1 and 9.2. One observes that the CLD tail
of the living chains extends over a much wider range than that of the dead chains.
This is due to the existence of computation limits in the G-FEM PREDICI package:
concentrations P
n
below a specied minimum are put equal to zero. For dead
chains this limit is located at chain lengths of around 10
7
, where concentrations
are more than 10 orders of magnitude smaller than the highest dead chain concen-
trations. Living chain concentrations drop less rapidly with length; in terms of
n
2
R
n
they even rise at high n, and consequently they are calculated up to a higher
limit: n = 10
9
. Now, some of the living chains are produced from dead ones of the
same length through transfer to the polymer. The computation limit of dead
chains is therefore visible as a discontinuity in the living CLD, beyond which it is
no longer calculated correctly. This also results in an error in the total living chain
concentration, l
0
, which ultimately would aect the overall population balance, in-
cluding the dead chain CLD [6]. Checking the monomer balance with the dead
polymer balance (m
1
), one learns that for the case shown the result is still reliable.
For larger k
tp
we see that gradually more of the monomer units polymerized be-
come contained in living chains, of which the CLD is not computed correctly, so
that the overall solution is no longer valid. Estimation procedures for monomer
units contained in tails beyond the computation limit are described by Iedema
et al. [6]. In the case of disproportionation this problem automatically resolves
itself by increasing k
tp
(>1800 m
3
/(kmol s)
1
). This is because living chain concen-
trations increase more rapidly within the computation limit of 10
9
and reach the
same magnitude as the dead chain tail concentrations; see Figure 9.3. Thus, living
and dead CLDs nicely overlap over the whole range and are correctly calculated,
even while a considerable proportion of the monomer units are now polymerized
in living chains.

10
0
10
2
10
4
10
6
10
8
10
10
10
12
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
x 10
-5
kmole/m
3
Chain Length
C
o
n
c
e
n
t
r
a
t
i
o
n
n
2
R
n
Computation
limit P
n
10
0
10
2
10
4
10
6
10
8
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
Chain Length
C
o
n
c
e
n
t
r
a
t
i
o
n
Computation
limit
n
2
P
n
kmole/m
3
Fig. 9.3. Radical polymerization in CSTR with
transfer to polymer. Reactor and kinetic data:
initiator feed: I
2; f
= 5 10
3
kmol m
3
;
monomer feed M
f
= 16:75 kmol m
3
;
residence time: t = 30 s; k
d
= 0:5 1 s
1
;
k
p
= 1:4 10
5
m
3
(kmol s)
1
; k
tc
= 5 10
10
m
3
(kmol s)
1
; k
tp
= 180 m
3
(kmol s)
1
;
conversion x = 0:249. The discontinuity in the
living CLD is due to a vanishing dead chain
concentration.
We conclude that the method of moments yields accurate solutions for all
moments (hence M
n
; M
w
; M
z
) in the case of linear polymerization. In those cases
where Flory distributions form the solution of instantaneous or steady-state poly-
merizations, full CLDs can be constructed as simple combinations of Flory dis-
tributions. This is not possible when distributions are resulting from combina-
tion reactions between other distributions, such as recombination termination. In
nonlinear polymerization the method of moments requires estimation of higher
moments, by which errors are introduced unavoidably. In those situations the
0 20 40 60 80 100 120 140 160 180
10
1
10
2
10
3
10
4
10
5
k
tp
(m
3
/(kmole.s))
M
w
Galerkin-FEM
Moments method
(closure
3
)
Living chains,
recombination termination only
kg/mole
0 20 40 60 80 100 120 140 160 180
0
20
40
60
80
100
120
140
k
tp
(m
3
/(kmole.s))
M
w
Galerkin-FEM
Moments method
(closure
3
)
Dead chains,
recombination termination only
kg/mole
Fig. 9.4. Radical polymerization; for data, see Figure 9.3.
Comparison of Galerkin-FEM and method of moments. The
deviation is strongest for living chains.

0 500 1000 1500 2000 2500 3000
10
0
10
1
10
2
10
3
10
4
10
5
10
6
10
7
k
tp
(m
3
/(kmole.s))
M
w
Galerkin-FEM
Moments method
(closure
3
)
Disproportionation termination only
kg/mole
Dead chains
Living chains
Living
chains
Dead chains
10
5
10
6
10
7
10
8
10
9
0
0.002
0.004
0.006
0.008
0.01
10
0
10
2
10
4
10
6
10
8
10
10
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Chain Length
C
o
n
c
e
n
t
r
a
t
i
o
n
kmole/m
3
Dead
Living
Close-up
Fig. 9.5. Radical polymerization; see Figure 9.3. Termination is
through disproportionation only. The living chain concentration
is the same order of magnitude as the dead chain concentra-
tion at high chain length.
Galerkin-FEM method is preferred, although care must be taken when extremely
long chain lengths have to be calculated.
9.5
Classes Approach
9.5.1
Introduction
The classes approach is applicable to multidimensional problems where the range
of the second and higher dimensions is restricted to a small range. In the examples
of this approach we will discuss presently, these second dimensions are the num-
bers of terminal double bonds (TDBs) on a chain in the case of poly(vinyl acetate)
(PVAc) and the numbers of radical sites on a chain in the case of low-density poly-
ethylene (LDPE). The idea simply is to solve the problem rigorously in the rst
dimension, chain length, for separate classes with a xed value for the second di-
mension. Thus, a 2D problem is reduced to a set of 1D problems, where the size of
the set is determined by the number of values of the second variable the number
of classes for which the solution is desired. Obviously, this is only feasible when
the number of classes is limited, since the equations have to be implemented sep-
arately for each class. A dierent classes approach is followed by Pladis and Kippar-
issides [8], who combined it with a method of moments.
9.5.2
Computing the CLD of Poly(vinyl acetate) for a Maximum of One TDB per Chain
The most general set of reaction equations is given in Table 9.4 in terms of all
three concentration distribution variables chain length, number of TDBs, num-
Tab. 9.4. Reactions for radical polymerization of vinyl acetate.
Initiator dissociation I
2

kd
2I
Initiation I M
ki
R
1; 0; 0
Propagation R
n; i; k
M
kp
R
n1; i; k
Termination by disproportionation
(without TDB creation)
R
n; i; k
R
m; j; l

ktd
P
n; i; k
P
m; j; l
Termination by disproportionation (with TDB creation) R
n; i; k
R
m; j; l

ktd
P
n; i1; k
P
m; j; l
Termination by recombination R
n; i; k
R
m; j; l

ktc
P
nm; ij; kl
n; i; k
M
km
P
n; i; k
R
1; 1; 0
n; i; k
P
m; j; l

ktpm
P
n; i; k
R
m; j; l1
Terminal double bond propagation R
n; i; k
P
m; j; l

kdbj
R
nm; ij1; kl1
Notation: m; n: chain length; i; j: number of terminal double bonds
(TDB) per chain; k; l: number of branches per chain.
ber of branches; hence it is a 3D problem [9]. Most of the equations in the table are
self-evident except the TDB propagation reaction, which deserves closer examina-
tion. It refers to the incorporation of dead chains with a TDB in the growing living
chain. The reaction equation is:
R
n; i; k
P
m; j; l

k
db
j
R
nm; ij1; kl1
(30)
In fact, this represents a combination reaction that sums chain lengths, while
numbers of branches are summed along with the addition of one extra branch cre-
ated by the reaction; TDBs are summed as well, except for one TDB consumed in
the reaction. It is evident that the reactivity of the dead chain inserted is propor-
tional to the number of TDBs it carries. Now, TDB propagation introduces a non-
linearity of a dierent kind than that caused by the step involving transfer to poly-
mer discussed previously. In that case the nonlinearity is due to the dependence of
the transfer rate on chain length, a variable already present in a 1D description of
chain length alone. In contrast, here the rate depends on a second distribution vari-
able, the number of TDBs per chain, which is not dealt with explicitly in the 1D
description of chain length. Mathematically speaking, in order to solve the problem
in one dimension, chain length, one has to solve it in the second dimension, TDB
number, as well. Two methods exist to deal with the TDB-dependent reactivity. The
rst is the classes approach, to be discussed here, and the second is the pseudo-
distribution approach, to be presented in Section 9.6. The full 3D molecular
weightterminal double bond-branching population balance equations belonging
to the reactions as given in Table 9.4 are listed in Table 9.5. Note that this system
is an exact representation of the reactions in Table 9.4, no assumptions have yet
been made, and it is valid for cases with an arbitrary number of TDBs per chain.
In the present case of a CSTR, the complete population balances of all distribu-
tions Q
n
contain an outow term of the general shape Q
n
=t, where t represents
the average residence time (equal to volume/volumetric ow). The overall mo-
ments l
0
and m
1
are dened as usual and in the 3D case follow as:
l
0
=
X
y
i=0
X
y
k=0
X
y
n=1
R
n; i; k
m
1
=
X
y
i=0
X
y
k=0
X
y
n=1
nP
n; i; k
(31)
Since we will not address branching here, the set has to be reduced to 2D, by sum-
mation over the branching index k. The second dimension, the number of TDBs
per chain, is concerned with the manner in which they are created. One of two pos-
sible mechanisms is transfer to monomer, producing a monoradical with a TDB
according to the reaction equation shown in Table 9.4. Subsequent propagation of
this monoradical leads to a chain with a TDB. The second mechanism is dispropor-
tionation, directly leading to chain with a TDB. Now, chains with more than one
terminal double bond can be created in two ways: insertion of chains with a TDB
created by disproportionation termination, or by termination by recombination. If
disproportionation does not lead to reactive TDBs and recombination is absent,
chains may carry one TDB as a maximum, which is the case being generally dealt
with in modeling studies of PVAc [1018]. The specic situation of a maximum
of one TDB per chain here serves as an example of the classes approach, while
the more general case of more than one TDB will be addressed in the context of
pseudo-distribution modeling (Section 9.6). Only two TDB classes are required to
fully describe the problem of one TDB as a maximum: 0 and 1 TDB per chain.
Consequently, population balances for only four distributions have to be solved
R
n
; P
n
; R
=
n
; P
=
n
and this can be done in an exact way without additional assump-
tions. The equations are shown in Table 9.6. The resulting CLDs for a realistic set
of kinetic data are shown in Figure 9.6 for the total dead chain concentrations, with
and without TDB.
9.5.3
Multiradicals in Radical Polymerization
In most models of radical polymerization, living chains are explicitly taken into
account, except for instance in the Monte Carlo simulation approach by Tobita
[1115]. Usually, macroradicals are assumed to possess only one radical site
Tab. 9.5. Full 3D set of population balance equations for radical polymerization of vinyl acetate in living and
dead chain concentration variables R
n; i; k
and P
n; i; k
. (for indices, see Table 9.4); summation over the branching
index k, yielding a 2D formulation of exactly the same form, provides the basis for the TDB classes model.
Initiator dissociation
dI
2
dt
= k
d
I
2

I
2
t
Initiation
dI
dt
= 2k
d
I
2
k
i
MI
I
t
;
dR
1; 0; 0
dt
= k
i
MI
Propagation
dR
n; i; k
dt
= k
p
M(R
n1; i; k
R
n; i; k
)
Termination by
disproportionation
(TDB creation)
dR
n; i; k
dt
= k
td
l
0
R
n; i; k
;
dP
n; i; k
dt
=
1
2
k
td
l
0
(R
n; i1; k
R
n; i; k
)
[a]
Termination by
recombination
dR
n; i; k
dt
= k
tc
l
0
R
n; i; k
;
dP
n; i; k
dt
=
1
2
k
tc
X
n1
m=1
X
i
j =0
X
k
l =0
R
m; j; l
R
nm; ij; kl
Transfer to monomer
dR
n; i; k
dt
= k
m
MR
n; i; k
;
dR
1; 1; 0
dt
= k
m
l
0
M;
dP
n; i; k
dt
= k
m
MR
n; i; k
Transfer to polymer
dR
n; i; k
dt
= k
tp
(l
0
nP
n; i; k1
m
1
R
n; i; k
);
dP
n; i; k
dt
= k
tp
(l
0
nP
n; i; k
m
1
R
n; i; k
)
Terminal double bond
propagation
dR
n; i; k
dt
= k
db
R
n; i; k
X
y
n=1
X
y
i =0
X
y
k=0
iP
n; i; k

X
n1
m=1
X
i1
j =0
X
k
l =0
jP
m; j; l
R
nm; ij1; kl1
!
dP
n; i; k
dt
= k
db
il
0
P
n; i; k
[a]
The rst term between brackets equals zero in the case in which no
account is taken of TDB creation by disproportionation.
Tab. 9.6. Full set of population balance equations for the PVAc problem in the case of a
maximum of one terminal double bond per chain.
Propagation
dR
n
dt
= k
p
M(R
n1
R
n
)
dR
=
n
dt
= k
p
M(R
=
n1
R
=
n
)
Termination by
disproportionation
dR
n
dt
= k
td
l
0
R
n
;
dP
n
dt
= k
td
l
0
R
n
dR
=
n
dt
= k
td
l
0
R
=
n
;
dP
=
n
dt
= k
td
l
0
R
=
n
Transfer to monomer
dR
=
1
dt
= k
m
l
0
M;
dR
=
n
dt
= k
m
MR
=
n
;
dP
=
n
dt
= k
m
MR
=
n
dR
n
dt
= k
m
MR
n
dP
n
dt
= k
m
MR
n
Transfer to polymer
dR
n
dt
= k
tp
(l
0
nP
n
m
1
R
n
);
dP
n
dt
= k
tp
(l
0
nP
n
m
1
R
n
)
dR
=
n
dt
= k
tp
(l
0
nP
=
n
m
1
R
=
n
);
dP
=
n
dt
= k
tp
(l
0
nP
=
n
m
1
R
=
n
)
Terminal double
bond propagation
dR
n
dt
= k
db
R
n
X
y
n=1
P
=
n

X
n1
m=1
P
=
m
R
nm
!
dP
=
n
dt
= k
db
l
0
P
=
n

0
0.2
0.4
0.6
0.8
1
1.2
k
db
= 0
k
db
= 2500 m
3
/(kmole.s)
k
db
= 6200 m
3
/(kmole.s)
k
db
= 31000 m
3
/(kmole.s)
kmole/m
3
) (
2
n n
P P n
=
+
Fig. 9.6. Radical polymerization of vinyl
acetate in a CSTR: sensitivity of chain length
distribution to rate of TDB propagation.
Reactor and kinetic data: initiator feed:
I
2; f
= 3:85 10
3
kmol m
3
; monomer feed
M
f
= 9 kmol m
3
; residence time: t = 4000 s;
k
d
= 9 10
6
s
1
; k
p
= 9500 m
3
(kmol s)
1
;
k
m
= 2:38 m
3
(kmol s)
1
; k
td
= 10
8
m
3
(kmole s)
1
; k
tp
= 5 m
3
(kmol s)
1
;
conversion x = 0:5.
(monoradical assumption). In principle, this is only correct for linear polymeriza-
tion. In nonlinear polymerization, for example, transfer to polymer or TDB propa-
gation, multiradicals can easily be created. For instance, transfer to polymer is fre-
quently assumed to occur only in dead chains, but obviously it also takes place in
living chains. In order to investigate the eects of taking multiradicals into ac-
count, we apply the classes approach. This anticipates the expectation that transi-
tion regimes exist, where the monoradical assumption no longer holds, while the
numbers of radical sites per chain is still low.
We take the example of radical polymerization with transfer to polymer; reaction
and population balance equations are listed in Tables 9.7 and 9.8. Note that the sec-
Tab. 9.7. Reaction equations for radical polymerization of ethylene: 2D chain length
multiradical approach.
Initiator dissociation I
2

kd
2I
Initiation I M
ki
R
1; 1
Propagation R
n; i
M
kpi
R
n1; i
Termination by disproportionation R
n; i
R
m; j
ktdij
R
n; i1
R
m; j1
Termination by recombination R
n; i
R
m; j

ktc ij
R
nm; ij2
n; i
M
kmi
R
n; i1
R
1; 1
Transfer to solvent R
n; i
S
kmi
R
n; i1
R
1; 1
n; i
R
m; j

ktpjm
R
n; i1
R
m; j1
Notation: m; n: chain length; i; j: number of radical sites per chain.
Tab. 9.8. (Population) balance equations for radical polymerization of ethylene: 2D chain
lengthmultiradical approach.
Initiator dissociation
dI
2
dt
= k
d
I
2

I
2
t
Initiation
dI
dt
= 2k
d
I
2
k
i
MI
I
t
;
dR
1; 1
dt
= k
i
MI
Propagation
dR
n; i
dt
= k
p
iM(R
n1; i
R
n; i
)
Termination by
disproportionation
dR
n; i
dt
= k
td
l
0
(i 1)R
n; i1
iR
n; i
Termination by recombination
dR
n; i
dt
=
1
2
k
tc
P
n1
m=1
P
i1
j =1
j(i j 2)R
m; j
R
nm; ij2
Transfer to monomer
dR
n; i
dt
= k
m
M(i 1)R
n; i1
iR
n; i
;
dR
1; 1
dt
= k
m
l
0
M
Transfer to solvent
dR
n; i
dt
= k
s
S(i 1)R
n; i1
iR
n; i
;
dR
1; 1
dt
= k
m
l
0
S
Transfer to polymer
dR
n; i
dt
= k
tp
[l
0
nR
n; i1
R
n; i
l
1
(i 1)R
n; i1
iR
n; i
[
l
a
=
X
y
n=1
X
y
i =0
n
a
R
n; i
ond subscript of R
n; i
denotes the number of radical sites per chain; hence chains
with i = 0 represent what is usually called dead chains. The transfer-to-polymer
reaction is obviously responsible for the creation of multiradicals, as appears from
the term R
n; i1
on the RHS. Two classes models are formulated, one with two
classes (the usual living and dead chains) and one with ve classes (up to four
radical sites per chain). Note that the implementation of the termination reactions
requires the implementation of 4
2
pairs of reaction equations of the form:
R
I
n
R
J
m

ktc IJ
R
IJ2
nm
; R
I
n
R
J
m

k
td
IJ
R
I1
n
R
J1
m
(32)
where R
I
n
denotes the 1D distribution of the class with I radical sites per chain.
Thus we see that many more classes rapidly lead to a huge implementation task
and the classes method is not appropriate for such problems.
We calculated CLDs with the two classes models for various transfer-to-polymer
rates. Up to k
tp
= 500 m
3
(kmol s)
1
results are identical, proving the validity of
the monoradical-assumption in this range. For k
tp
= 5000 m
3
(kmol s)
1
, on the
contrary, we see large dierences, as shown in Figure 9.7. According to the ve-
classes model, chains are much shorter and also conversion is lower. This is due
to dierences in an increase in the reactivity of multiradical chains in dierent
reactions. From the reaction equations we see that propagation increases linearly
with the number of radical sites, but termination with the product of radical sites.
Hence, accounting for multiradicals leads to an increased termination/propagation
ratio and thus to shorter chains and lower conversion under the conditions simu-
lated. Note that the relative heights of the distributions in Figure 9.7 suggest that
for k
tp
= 5000 m
3
(kmol s)
1
even more than ve classes are required for a proper
description.
We conclude, however, that the classes approach in this case produces useful
information on the multiradical issue, even when employing a limited number of
classes.
9.6
Pseudo-distribution Approach
9.6.1
Introduction
This strategy is based on the Galerkin-FEM method. The simultaneous description
of CLD and DBD leads to a two-dimensional problem with the property coordi-
nates chain length and number of branches. In order to avoid the computationally
expensive 2D problem, a mathematical reduction technique is applied to the origi-
nal model, which allows the computation of average branching degrees per chain
length (and the respective variances). For that reason branching moment distribu-
tions are introduced. The population balances for these distributions can be solved
10
0
10
2
10
4
10
6
10
8
10
10
10
12
0
0.1
0.2
0.3
Chain Length n
10
-3
kmole/m
3
n
2
R
n,0
n
2
R
n,0
2-classes model
5-classes model
n
2
R
n,1
n
2
R
n,1
10
4
10
6
10
8
10
10
0
1
2
3
4
5
Chain Length n
10
-3
kmole/m
3
C
o
n
c
e
n
t
r
a
t
i
o
n
n
2
R
n,1
n
2
R
n,1
n
2
R
n,3
n
2
R
n,4
n
2
R
n,2
2-classes model
5-classes model
C
o
n
c
e
n
t
r
a
t
i
o
n
Fig. 9.7. Radical polymerization with transfer
to polymer: multiradical problem. CLDs of
chains with 0 . . . 4 radical sites per chain.
Comparison of two- and ve-classes model.
Accounting for multiradicals leads to lower
conversion and shorter chains. Kinetic data:
k
d
= 0:57 s
1
; k
p
= 1:38 10
5
m
3
(kmol s)
1
;
k
m
= 138 m
3
(kmol s)
1
; k
s
= 790 m
3
(kmol s)
1
; k
tc
= k
td
= 2:82 10
8
m
3
(kmol s)
1
; k
tp
= 5000 m
3
(kmol s)
1
.
as a 1D problem. Thus the original 2D problem is replaced by a series of 1D prob-
lems, getting exact information on averages concerning the second (number of
branches) distribution. The distributions of the original kinetic model will be called
real distributions whereas the additional branching moment distributions are
named pseudo-distributions.
We will introduce this approach in the case of the 2D CLD/DBD computation for
mixed-metallocene polymerization of ethylene. Subsequently, we present applica-
tions of the approach to the 3D problems of radical polymerization of vinyl acetate
(CLD/DBD/number of terminal double bonds distribution), AB radical copolymer-
ization (CLD/comonomer composition distribution/sequence length distribution),
and nally the 2D problem of radical polymerization of polyethylene, where ran-
dom scission is a complicating factor.
9.6.2
CLD/DBD for Mixed-metallocene Polymerization of Ethylene
9.6.2.1 Formulation of Pseudo-distribution Problem
Long branches are created in this system by incorporation of chains with a termi-
nal double bond (TDB) at the catalyst site (constrained-geometry catalyst, CGC)
[1930]. The reaction equations are listed in Table 9.9 and the denitions of the
growing and dead chain branching moment distributions are elucidated in Table
9.10. Note that the 0th branching moment distributions represent the original nor-
mal chain length distributions. From the branching moment distributions F and
C certain averages may be derived. For example, the average number of branches
of chains of length n; B
n
, as well as the branching density, r
n
, can be computed
from the ratio (for each n) of the 1st and 0th branching moment distribution:
Tab. 9.9. Reaction mechanisms and rate coecients.
Reaction Reaction equation Rate coecient
Branching cat. activation and initiation
[a]
C
CGC
C
+
CGC
;
C
+
CGC
M R
b
1; 0
k
a; CGC
k
i; CGC
Linear cat. activation and initiation
[a]
C
lin
C
+
lin
;
C
+
lin
M R
l
1; 0
k
a; lin
k
i; lin
Branching cat. propagation R
b
n; i
M R
b
n1; i
k
p; CGC
Linear cat. propagation R
l
n; i
M R
l
n1; i
k
p; lin
Branching cat. b-hydride elimination R
b
n; i
C
+
CGC
P
b
n; i
k
w; CGC
Linear cat. transfer to monomer R
l
n; i
M C
+
lin
P
l=
n; i
[b]
k
m; lin
branching cat. terminal double bond propagation R
b
n; i
P
=
m; j
R
b
nm; ij1
[b]
k
p; TDB
[a]
Catalyst activation and initiation are taken as one step.
[b]
Note that P
=
n; i
= P
b=
n; i
P
l=
n; i
.
B
n
= C
1
n
=P
n
; r
n
= C
1
n
=(nP
n
) (33)
In fact, F and C represent the moments of the branching distributions of living
and dead chains at the given chain length, n. Thus, the branching polydispersity
D
n
follows from the second branching moment according to:
D
n
=
C
2
n
=C
1
n
C
1
n
=P
n
(34)
In order to derive the balance equations for the branching moment distributions,
the following steps have to be performed [31]:
v
For each reaction step of the kinetic model, the two-dimensional population
balance is derived.
Tab. 9.10. Notation for mixed-metallocene systems.
R
b
n; i
polymer growing on branching catalyst
R
l
n
polymer growing on linear catalyst (0 branches)
P
b=
n; i
; P
l=
n; 0
; P
=
n; i
dead polymer with terminal double bond from branching/linear cat.
and their sum, resp.
P
b
n; i
; P
l
n; 0
; P
n; i
dead polymer without terminal double bond from branching/linear
cat and their sum, resp.
m
=
0
=
X
y
n=1
X
y
i =0
P
=
n; i
m
0
=
X
y
n=1
X
y
i =0
P
n; i
l
b
0
=
X
y
n=1
X
y
i =0
R
b
n; i
l
l
0
=
X
y
n=1
R
l
n
R
b
n
=
X
y
i =0
R
b
n; i
P
b=
n
=
X
y
i =0
P
b=
n; i
P
l=
n
= P
l=
n; 0
P
=
n
=
X
y
i =0
P
=
n; i
P
b
n
=
X
y
i =0
P
b
n; i
P
l
n
= P
l
n; 0
P
n
=
X
y
i =0
P
n; i
F
b1
n
=
X
y
i =0
iR
b
n; i
C
=1
n
=
X
y
i =0
iP
=
n; i
C
1
n
=
X
y
i =0
iP
n; i
F
b2
n
=
X
y
i =0
i
2
R
b
n; i
C
=2
n
=
X
y
i =0
i
2
P
=
n; i
C
2
n
=
X
y
i =0
i
2
P
n; i
v
The two-dimensional balance is reduced to a one-dimensional balance by apply-
ing the above summations over the branching index (in the same type of opera-
tion as obtaining moments from distributions).
v
The resulting terms have to be expressed in terms of the branching moment
distributions and are added to the system of equations.
All equations are solved simultaneously. This procedure can in principle be applied
to any polyreaction model where additional properties have to be considered. The
key is how a certain reaction step changes the additional property.
The total set of balance equations for all the reaction mechanisms involved in
the mixed-metallocene problem is:
dM
dt
= k
i; lin
C
+
lin
k
i; CGC
C
+
CGC
(k
p; lin
k
m; lin
)l
b
0
(k
p; CGC
k
m; CGC
)l
l
0
M
M
0
M
t
(35)
dR
l
n; 0
dt
= k
i; lin
MC
+
lin
d(n 1) k
p; lin
([R
l
n1; 0
R
l
n; 0
)M
(k
b; lin
k
m; lin
M)R
l
n; 0

R
l
n; 0
t
(36)
dR
b
n; i
dt
= k
i; CGC
MC
+
CGC
d(n 1) k
p; CGC
(R
b
n1
R
b
n
)M
(k
b; CGC
k
m; CGC
M)R
b
n; i
k
p; TDB
m
=
0
R
b
n; i

X
n1
m=1
X
i
j =0
P
=
m; j
R
b
nm; ij1
!
R
b
n; i
t
(37)
dP
l=
n; 0
dt
= (k
m; lin
M k
b; lin
)R
l
n; 0
k
p; TDB
P
l=
n; 0
l
b
0

P
l=
n; 0
t
(38)
dP
b=
n; i
dt
= (k
m; CGC
M k
b; CGC
)R
b
n; i
k
p; TDB
P
b=
n; i
l
b
0

P
b=
n; i
t
(39)
dB
dt
= k
p; TDB
m
=
0
l
b
0

B
t
(40)
Here d(i) is the Kroneckers delta function which has value of 1 for i = 0 and 0 for
i 00. Note that growing chains at the linear catalyst do not carry branches; hence
the second index is always zero. Now, we will derive the equations for the pseudo-
distributions in a stepwise manner. Reactions not aecting the number of
branches per chain, that is, those describing propagation, transfer to monomer,
and b-hydride elimination, will be presented rstly. The reaction creating branch-
ing, TDB propagation, is more complex and will be discussed subsequently.
Propagation step In this case the degree of branching is not altered, so this is a
simple step from this point of view. The contribution to the balance of ath branch-
ing moment distributions of living chains in reduced or pseudo-distribution nota-
tion follows, by multiplication with i
a
and taking the summation over the branch-
ing index i:
dF
a
n
dt
=
X
y
i=0
i
a
dR
i
n
dt

= k
p
M(F
a
n1
F
a
n
) (41)
Transfer to monomer, b-hydride elimination Again, the degree of branching is not
aected, hence the contributions to the pseudo-distribution balances of the living
and dead chains are given by:
dF
a
n
dt
= k
m
MF
a
n
;
dC
a
n
dt
= k
m
MF
a
n
; (42)
dF
a
n
dt
= k
b
F
a
n
;
dC
a
n
dt
= k
b
F
a
n
; (43)
TDB propagation The one-dimensional contributions for this mechanism describ-
ing chain length are obtained from the TDB propagation terms in the 2D equa-
tions by summing over the number of branches, i:
dR
b
n
dt
= k
p; TDB
R
b
n
m
=
0
(44)
dP
=
n
dt
= k
p; TDB
P
=
n
l
b
0
(45)
dR
b
n
dt
= k
p; TDB
X
n1
m=1
R
b
n
P
=
nm
(46)
The rst branching moment distribution follows by multiplication of Eqs. (44)(46)
with the number of branches i, and subsequent summation:
dF
b1
n
dt
= k
p; TDB
F
b1
n
m
=
0
(47)
dC
=1
n
dt
= k
p; TDB
C
=1
n
l
b
0
(48)
The production term requires some more extensive algebraic manipulation:
dF
b1
n
dt
= k
p; TDB
X
y
i=0
i
X
n1
m=1
X
i1
j =0
R
b
m; j
P
=
nm; ij1
!
= k
p; TDB
X
n1
m=1
X
y
j =0
R
b
m; j
X
y
i=j
iP
=
nm; ij1
0
@
1
A
= k
p; TDB
X
n1
m=1
X
y
j =0
R
b
m; j
X
y
i=0
(i j 1)P
=
nm; i
!
= k
p; TDB
X
n1
m=1
X
y
j =0
jR
b
m; j
X
y
i=0
P
=
nm; i

X
y
j =0
R
b
m; j
X
y
i=0
(i 1)P
=
nm; i
!
= k
p; TDB
X
n1
m=1
(F
b1
m
P
=
nm
R
b
m
C
=1
nm
R
b
m
P
=
nm
) (49)
The second branching moment distribution follows by multiplication of the TDB
propagation terms in the 2D equations with the squared number of branches i
2
and subsequent summation:
dF
b2
n
dt
= k
p; TDB
F
b2
n
m
=
0
(50)
dC
=2
n
dt
= k
p; TDB
C
=2
n
l
b
0
(51)
The production term again requires some more extensive algebraic manipulation:
dF
b2
n
dt
= k
p; TDB
X
y
i=0
i
2
X
n1
m=1
X
i1
j =0
R
b
m; j
P
=
nm; ij1
!
= k
p; TDB
X
n1
m=1
X
y
j =0
R
b
m; j
X
y
i=j
i
2
P
=
nm; ij1
0
@
1
A
= k
p; TDB
X
n1
m=1
X
y
j =0
R
b
m; j
X
y
i=0
(i j 1)
2
P
=
nm; i
!
= k
p; TDB
X
n1
m=1
X
y
j =0
j
2
R
b
m; j
X
y
i=0
P
=
nm; i

X
y
j =0
R
b
m; j
X
y
i=0
i
2
P
=
nm; i
2
X
y
j =0
jR
b
m; j
X
y
i=0
iP
=
nm; i
2
X
y
j =0
jR
b
m; j
X
y
i=0
P
=
nm; i
2
X
y
j =0
R
b
m; j
X
y
i=0
iP
=
nm; i

X
y
j =0
R
b
m; j
X
y
i=0
P
=
nm; i
0
B
B
B
B
B
B
B
B
B
B
B
@
1
C
C
C
C
C
C
C
C
C
C
C
A
= k
p; TDB
X
n1
m=1
F
b2
m
P
=
nm
R
b
m
C
=2
nm
2F
b1
m
C
=1
nm
2F
b1
m
P
=1
nm
2R
b
m
C
=1
nm
R
b
m
P
=
nm
!
(52)
The principles of the pseudo-distribution model are applicable to any reactor. Re-
sults are presented for a semi-batch reactor using kinetic data from a realistic
mixed-metallocene system in Figure 9.8.
9.6.2.2 Construction of the Full 2D Distribution
The pseudo-distribution approach thus allows us to calculate the 1D CLD and
the average number of branches versus chain length. The question arises of how
to obtain the full bivariate chain lengthnumber of branches distribution from
the pseudo-distribution model. The issue is that construction of branching distri-
butions at each chain length requires an assumption to be made about the shape
of the branching distribution, or more precisely for chains originating from the
branching catalyst (P
b=
n
). For instance, if we suppose that each monomer unit in a
chain of given length has equal probability of being branched, then the branching
distribution can be described by a binomial distribution. However, from the branch-
ing polydispersity as calculated from Eq. (34) we observe that the distribution for
dead chains from the branching catalyst is narrower than a binomial distribution.
An alternative approximation method is required, generating branching distribu-
tions at a given chain length with correct values for both the average number of
branch points N
n
and the branching polydispersity D
n
. A three-parameter binomial
distribution modied by raising of it to a power a
n
(the third parameter) varying
with chain length, the variable power binomial distribution [VPBD] can satisfy
these requirements:
p
n; N
=
n
N

(r
n
)
N
(1 r
n
)
(nN)
& '
an
(53)
Note that in the VPBD the parameter a permits the distribution width to be
changed: a > 1 leads to a narrower distribution. The tting procedure is described
in more detail by Iedema et al. [20]. The VPBD method turns out to yield identical
solutions to the classes (Section 9.5) and pgf (Section 9.7) methods as applied to the
mixed-metallocene problem. The resulting full bivariate CLD/DBD for the case of a
CSTR is shown in Figure 9.9, together with the VPBD t.
We conclude that the pseudo-distribution approach can be applied successfully,
provided a good approximation can be made for the branching distribution at given
chain length from the branching moments. The method is valid for batch reactors
as well, in contrast to, for example, the pgfcascade method (Section 9.7), which is
restricted to steady state reactors. It is to be preferred over classes methods in
cases, like the metallocene one, where the second distribution dimension may as-
sume high values as well.
10
3
10
4
10
5
10
6
10
7
0
0.2
0.4
0.6
0.8
1
1.2
1.4
Molecular Weight
t = 100 s
600 s
d
w
/
d
{
l
o
g
(
M
W
)
}
Semibatch, r
CGC
= 0.2
10
2
10
3
10
4
10
5
0
0.2
0.4
0.6
0.8
1
x 10
-3
Chain Length
B
r
a
n
c
h
i
n
g

d
e
n
s
i
t
y

b
100 s
200 s
300 s
400 s
500 s
600 s
Semibatch, r
CGC
= 0.2
B
a
t
c
h

t
i
m
e
Fig. 9.8. Mixed-metallocene polymerization of
ethylene in a semibatch reactor; branching
(constrained geometry) catalyst: CGC-Ti; linear
catalyst: Et[Ind]
2
ZrCl
2
. Reactor and kinetic
data: initial concentration CGC-Ti: 8 10
7
kmol m
3
; initial concentration Et[Ind]
2
ZrCl
2
:
3:2 10
6
kmol m
3
; monomer molar feed
ow: 8 10
7
kmol s
1
; batch time: 600 s;
k
i; CGC
=k
p; CGC
= k
i; lin
=k
p; lin
= 1; k
p; CGC
[M[ =
k
p; lin
[M[ = 500 s
1
; k
b; CGC
= 0:3 s
1
; k
b; lin
=
0:7 s
1
; k
m; CGC
=k
p; CGC
= 0; k
m; lin
=k
p; lin
=
0:0014; k
H; CGC
= 250 m
3
kmol
1
s
1
;
k
H; lin
= 0; k
p; TDB
= 1750 m
3
kmol
1
s
1
.
9.6.3
CLD/Number of Terminal Double Bonds (TDB) Distribution for Poly(vinyl acetate)
More than one TDB per Chain
9.6.3.1 General Case
This problem has been introduced in the discussion of the classes approach. For
reaction equations and a full set of population balances, see Tables 9.5 and 9.6.
Here, we address the more general problem of more than one TDB per chain [9].
This occurs as a consequence of insertion of TDB chains created by disproportion-
ation or of recombination termination. We start with the full 3D set of Table PVAc2
and then reduce it to a 1D formulation by developing the TDB and branching mo-
ment expressions. The (N; M)th branching-TDB moments or pseudo distributions
for living and dead chains are dened by:
F
N; M
n;:;:
=
X
y
i=0
i
N
X
y
k=0
k
M
R
n; i; k
!
C
N; M
n;:;:
=
X
y
i=0
i
N
X
y
k=0
k
M
P
n; i; k
!
(54)
0
10
20
30
40
10
-12
10
-10
10
-8
10
-4
F
r
a
c
t
i
o
n
Number of Branches N
CSTR
r
CGC
= 0.2
[H
2
] = 1.13 10
-3
kmole/m
3
10
-6
10
-2
50
10
0
10
1
10
2
10
3
10
4
10
5
60
C
h
a
i
n

L
e
n
g
t
h

n
10
1
10
2
10
3
10
4
10
5
2
3
n
a
n
VPBD power
Fig. 9.9. Mixed-metallocene polymerization of
ethylene in a CSTR. Kinetic data are the same
as in Figure 9.8. Residence time CSTR: 300 s;
feed concentrations identical to initial
concentrations in Figure 9.8. Bivariate chain
length/number of branches distribution.
Hydrogen present. Based on molecular weight
distribution and branching distribution from
the Galerkin-FEM model. Assumption: variable
power binomial distribution of number of
branch points at each chain length of dead
chains from CGC-Ti with power a
n
as shown in
the insert. The discontinuity at N = 1 indicates
the existence of a ridge at N = 0, due to the
contribution of branchless chains from
Et[Ind]
2
ZrCl
2
.
Performing the corresponding summations on the equations in Table 9.6, one ob-
tains the (N; M)th moment formulation of Table 9.11. Some of the summation
terms in these equations will not be evaluated for the general (N; M) case, but we
will determine them by assigning values to N and M. Since we will not address
branching, we take M = 0 here, but in principle this can be treated in a similar
way. We will focus now on the TDB moment distributions and successively derive
the model equations for the zeroth, rst, and second moments, or N = 0; 1, and 2.
Solving the model thus essentially means solving the population balances of the
real concentration distributions R
n
and P
n
and the pseudo-distributions F
N; M
n
and
C
N; M
n
.
Tab. 9.11. The general (N; M)th double moment formulation of the population balance equation set of Table
9.10, obtained by multiplying by the TDB number and branching number indices, i
N
and k
M
, and subsequent
summation over these indices.
Propagation
dF
N; M
n
dt
=
d
X
y
i =0
i
N
X
y
k=0
k
M
R
n; i; k
dt
= k
p
M(F
N; M
n1
F
N; M
n
)
Termination by dispropor-
tionation
dF
N; M
n
dt
= k
td
l
0
F
N; M
n
dC
N; M
n
dt
=
1
2
k
td
l
0
X
y
i =0
i
N
X
y
k=0
k
M
R
n; i1; k
F
N; M
n
!
[a]
Termination by recombination
dF
N; M
n
dt
= k
tc
l
0
F
N; M
n
dC
N; M
n
dt
=
1
2
k
tc
X
y
i =0
i
N
X
y
k=0
k
M
X
n1
m=1
X
i
j =0
X
k
l =0
R
m; j; l
R
nm; ij; kl
!
Transfer to monomer
dF
N; M
n
dt
= k
m
MF
N; M
n
;
dF
N; M
1
dt
= k
m
l
0
M
dC
N; M
n
dt
= k
m
MF
N; M
n
Transfer to polymer
dF
N; M
n
dt
= k
tp
l
0
n
X
y
i =0
i
N
X
y
k=0
k
M
P
n; i; k1
m
1
F
N; M
n
!
dC
N; M
n
dt
= k
tp
l
0
n
X
y
i =0
i
N
X
y
k=0
k
M
P
n; i; k1
m
1
F
N; M
n
!
propagation
dF
N; M
n
dt
= k
db
X
y
i =0
i
N
X
y
k=0
k
M
R
n; i; k
X
y
n=1
X
y
j =0
X
y
l =0
iP
n; j; l
X
n1
m=1
X
i1
j =0
X
k
l =0
jP
m; j; l
R
nm; ij1; kl1
0
B
B
B
B
B
@
1
C
C
C
C
C
A
dC
N; M
n
dt
= k
db
l
0
C
(N1); M
n
[a]
The rst term between brackets equals zero in the case where TDB creation by
disproportionation is not accounted for.
The resulting equations for N = 0 and M = 0 are listed in Table 9.12. Here, the
(0; 0)th moments are the usual 1D chain length distribution variables, dened by:
R
n
=
X
y
i=0
X
y
k=0
R
n; i; k
(= F
0; 0
n
) P
n
=
X
y
i=0
X
y
k=0
P
n; i; k
(= C
0; 0
n
) (55)
All of the derivations are straightforward, but the TDB propagation deserves closer
examination. From Table 9.11 we have the general (N; M) formulation in:
dF
N; M
n
dt
= k
db
X
y
i=0
i
N
X
y
k=0
k
M
R
n; i; k
X
y
n=1
X
y
j =0
X
y
l =0
iP
n; j; l

X
n1
m=1
X
i1
j =0
X
k
l =0
jP
m; j; l
R
nm; ij1; kl1
!
(56)
Taking M = 0 and N = 0, the rst term between the brackets can be rewritten as:
X
y
i=0
X
y
k=0
R
n; i; k
X
y
n=1
X
y
i=0
X
y
k=0
iP
n; i; k
!
=
X
y
i=0
X
y
k=0
(R
n; i; k
X
y
n=1
C
1; 0
n
) =
X
y
n=1
C
1; 0
n
!
X
y
i=0
X
y
k=0
R
n; i; k
= R
n
X
y
n=1
C
1; 0
n
(57)
Tab. 9.12. The (0; 0)th moment distribution formulation of the population balance equation set
of Table 9.11 (taking N = 0 and M = 0); this set is solved by the TDB moment distribution
model.
Propagation
dR
n
dt
= k
p
M(R
n1
R
n
)
Termination by
disproportionation
dR
n
dt
= k
td
l
0
R
n
;
dP
n
dt
= k
td
l
0
R
n
Termination by
recombination
dR
n
dt
= k
tc
l
0
R
n
;
dP
n
dt
=
1
2
k
tc
X
n1
m=1
R
m
R
nm
Transfer to monomer
dR
n
dt
= k
m
MR
n
;
dR
1
dt
= k
m
l
0
M
dP
n
dt
= k
m
MR
n
Transfer to polymer
dR
n
dt
= k
tp
(l
0
nP
n
m
1
R
n
);
dP
n
dt
= k
tp
(l
0
nP
n
m
1
R
n
)
propagation
dR
n
dt
= k
db
R
n
X
y
n=1
C
1; 0
n

X
n1
m=1
C
1; 0
m
R
nm
!
;
dP
n
dt
= k
db
l
0
C
1; 0
n
The second term between the brackets can be rewritten as:
X
y
i=0
X
y
k=0
X
n1
m=1
X
i1
j =0
X
k
l =0
jP
m; j; l
R
nm; ij1; kl1
=
X
n1
m=1
X
y
k=0
X
k
l =0
X
y
j =0
jP
m; j; l
X
y
i=j1
R
nm; ij1; kl1
0
@
1
A
8
<
:
9
=
;
=
X
n1
m=1
C
1; 0
m
R
nm
(58)
Thus, we nd the TDB propagation term for the living chains to be given by:
dR
n
dt
= k
db
R
n; i; k
X
y
n=1
C
1; 0
n

X
n1
m=1
C
1; 0
m
R
nm
!
(59)
Applying M = 0 and N = 0 to the dead chains formulation yields:
dP
n
dt
= k
db
l
0
C
1; 0
n
(60)
The RHS expressions of Eqs. (59) and (50) contain higher TDB moment (1; 0) dis-
tributions (C
1; 0
n
) than the (0; 0) moment distributions, R
n
and P
n
, they describe.
Tab. 9.13. The (1; 0)th moment distribution formulation of the population balance equation set of Table 9.11
(taking N = 1 and M = 0); this set is solved by the TDB moment distribution model.
Propagation
dF
1; 0
n
dt
= k
p
M(F
1; 0
n1
F
1; 0
n
)
Termination by dispropor-
tionation
dF
1; 0
n
dt
= k
td
l
0
F
1; 0
n
;
dC
1; 0
n
dt
=
1
2
k
td
l
0
X
y
i =0
iR
n; i1
F
1; 0
n
!
= k
td
l
0
F
1; 0
n

1
2
R
n

[a]
Termination by recom-
bination
dF
1; 0
n
dt
= k
tc
l
0
F
1; 0
n
;
dC
1; 0
n
dt
= k
tc
X
n1
m=1
F
1; 0
m
R
nm
Transfer to monomer
dF
1; 0
n
dt
= k
m
MF
1; 0
n
;
dF
1; 0
1
dt
= k
m
l
0
M;
dC
1; 0
n
dt
= k
m
MF
1; 0
n
Transfer to polymer
dF
1; 0
n
dt
= k
tp
(l
0
nC
1; 0
n
m
1
F
1; 0
n
);
dC
1; 0
n
dt
= k
tp
(l
0
nC
1; 0
n
m
1
F
1; 0
n
)
propagation
dF
1; 0
n
dt
= k
db
F
1; 0
n
X
y
n=1
C
1; 0
n

X
n1
m=1
(C
2; 0
m
R
nm
C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm
)
( )
;
dC
1; 0
n
dt
= k
db
l
0
C
2; 0
n
[a]
The rst term between brackets equals zero in the case where TDB
creation by disproportionation is not accounted for.
This is a direct consequence of the fact that the reactivity of the dead chains de-
pends on the number of TDBs they carry. Hence, at this point we are already con-
fronted with the closure problem present in the TDB moment model, anticipating
that solving these higher moments leads to even higher moments in the equations.
Next, we will derive the higher moment equations. For N = 1 and M = 0 we ob-
tain the set of population balance equations for the pseudo-distributions of order
(1; 0) as listed in Table 9.13.
The termination by recombination equation is derived by developing the sum-
mation term as:
1
2
X
y
i=0
i
X
n1
m=1
X
i
j =0
R
m; j
R
nm; ij
!
=
1
2
X
n1
m=1
X
y
j =0
R
m; j
X
y
i=j
iR
nm; ij
0
@
1
A
=
1
2
X
n1
m=1
X
y
j =0
R
m; j
X
y
i=0
(i j)R
nm; i
!
=
1
2
X
n1
m=1
X
y
j =0
jR
m; j
X
y
i=0
R
nm; i

X
y
j =0
R
m; j
X
y
i=0
iR
nm; i
!
=
1
2
X
n1
m=1
(F
1; 0
m
R
nm
R
m
F
1; 0
nm
) =
X
n1
m=1
F
1; 0
m
R
nm
(61)
This yields for the recombination contribution to the population balance:
dC
1; 0
n
dt
= k
tc
X
n1
m=1
F
1; 0
m
R
nm
(62)
With respect to TDB propagation, with M = 0 and N = 1 the rst term between
brackets becomes that in Eq. (64)
X
y
i=0
X
y
k=0
iR
n; i; k
X
y
n=1
X
y
i=0
X
y
k=0
iP
n; i; k
!
=
X
y
i=0
X
y
k=0
iR
n; i; k
X
y
n=1
C
1; 0
n
!
=
X
y
n=1
C
1; 0
n
!
X
y
i=0
X
y
k=0
iR
n; i; k
= F
1; 0
n
X
y
n=1
C
1; 0
n
(63)
and the second term, somewhat more complicated, becomes
X
y
i=0
i
X
y
k=0
X
n1
m=1
X
i1
j =0
X
k
l =0
jP
m; j; l
R
nm; ij1; kl1
!
=
X
y
i=0
i
X
n1
m=1
X
i
j =0
( jP
m; j
R
nm; ij1
)
( )
=
X
n1
m=1
X
y
j =0
jP
m; j
X
y
i=j1
iR
nm; ij1
0
@
1
A
8
<
:
9
=
;
=
X
n1
m=1
X
y
j =0
jP
m; j
X
y
i=0
(i j 1)R
nm; i
! ( )
=
X
n1
m=1
X
y
j =0
j
2
P
m; j
X
y
i=0
R
nm; i

X
y
j =0
jP
m; j
X
y
i=0
(i 1)R
nm; i
!
=
X
n1
m=1
(C
2; 0
m
R
nm
C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm
) (64)
Thus, we nd the TDB propagation terms for the living and dead chains to be:
dF
1; 0
n
dt
= k
db
F
1; 0
n
X
y
n=1
C
1; 0
n

X
n1
m=1
(C
2; 0
m
R
nm
C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm
)
( )
(65)
dC
1; 0
n
dt
= k
db
l
0
C
2; 0
n
(66)
The higher moments observed earlier on the RHS are seen again.
We nally present the result for one higher moment distribution, N = 2, M = 0,
for which we obtain the set of population balance equations for the pseudo-
distributions of order (2; 0) as listed in Table 9.14.
First, the termination by recombination term is developed:
1
2
X
y
i=0
i
2
X
n1
m=1
X
i
j =0
R
m; j
R
nm; ij
!
=
1
2
X
n1
m=1
X
y
j =0
R
m; j
X
y
i=j
i
2
R
nm; ij
0
@
1
A
=
1
2
X
n1
m=1
X
y
j =0
R
m; j
X
y
i=0
(i j)
2
R
nm; i
!
=
1
2
X
n1
m=1
X
y
j =0
j
2
R
m; j
X
y
i=0
R
nm; i

X
y
j =0
R
m; j
X
y
i=0
i
2
R
nm; i

X
y
j =0
jR
m; j
X
y
i=0
iR
nm; i
!
=
1
2
X
n1
m=1
(F
2; 0
m
R
nm
R
m
F
2; 0
nm
2F
1; 0
m
F
1; 0
nm
) =
X
n1
m=1
(F
2
m
R
nm
F
1; 0
m
F
1; 0
nm
)
(67)
This yields for the recombination contribution to the population balance:
dC
2; 0
n
dt
= k
tc
X
n1
m=1
(F
2
m
R
nm
F
1; 0
m
F
1; 0
nm
) (68)
The rst term in the equation describing TDB propagation is derived in a similar
way to Eq. (62), while the second term follows as:
Tab. 9.14. The (2; 0)th moment distribution formulation of the population balance equation set of Table 9.11
(taking N = 2 and M = 0); this set is solved by the highest TDB moment version of the TDB moment
distribution model.
Propagation
dF
2; 0
n
dt
= k
p
M(F
2; 0
n1
F
2; 0
n
)
Termination by
disproportionation
dF
2; 0
n
dt
= k
td
l
0
F
2; 0
n
;
dC
2; 0
n
dt
=
1
2
k
td
l
0
X
y
i =0
i
2
R
n; i1
F
2; 0
n
!
= k
td
l
0
F
2; 0
n
F
1; 0
n

1
2
R
n

[a]
Termination by
recombination
dF
2; 0
n
dt
= k
tc
l
0
F
2; 0
n
;
dC
2; 0
n
dt
= k
tc
X
n1
m=1
(F
2
m
R
nm
F
1; 0
m
F
1; 0
nm
)
Transfer to monomer
dF
2; 0
n
dt
= k
m
MF
2; 0
n
;
dF
2; 0
1
dt
= k
m
l
0
M
dC
2; 0
n
dt
= k
m
MF
2; 0
n
Transfer to polymer
dF
2; 0
n
dt
= k
tp
(l
0
nC
2; 0
n
m
1
F
2; 0
n
);
dC
2; 0
n
dt
= k
tp
(l
0
nC
2; 0
n
m
1
F
2; 0
n
)
propagation
dF
2; 0
n
dt
= k
db
F
2; 0
n
X
y
n=1
C
1; 0
n
X
n1
m=1
C
3; 0
m
R
nm
C
1; 0
m
F
2; 0
nm
2C
2; 0
m
F
1; 0
nm
2C
2; 0
m
R
nm
2C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm

8
>
>
>
>
<
>
>
>
>
:
9
>
>
>
>
=
>
>
>
>
;
;
dC
2; 0
n
dt
= k
db
l
0
C
3; 0
n
[a]
The rst term between brackets equals zero in the case where TDB
creation by disproportionation is not accounted for.
X
y
i=0
i
X
y
k=0
dR
n; i; k
dt

=
X
y
i=0
i
2
X
y
k=0
X
n1
m=1
X
i1
j =0
X
k
l =0
jP
m; j; l
R
nm; ij1; kl1
!
=
X
y
i=0
i
2
X
n1
m=1
X
i
j =0
( jP
m; j
R
nm; ij1
)
( )
=
X
n1
m=1
X
y
j =0
jP
m; j
X
y
i=j1
i
2
R
nm; ij1
0
@
1
A
8
<
:
9
=
;
=
X
n1
m=1
X
y
j =0
jP
m; j
X
y
i=0
(i j 1)
2
R
nm; i
! ( )
=
X
n1
m=1
(C
3; 0
m
R
nm
C
1; 0
m
F
2; 0
nm
2C
2; 0
m
F
1; 0
nm
2C
2; 0
m
R
nm
2C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm
) (69)
The total contribution of TDB propagation to the population balance is thus given
by:
dF
2; 0
n
dt
= k
db
F
2; 0
n
X
y
n=1
C
1; 0
n
(
X
n1
m=1
C
3; 0
m
R
nm
C
1; 0
m
F
2; 0
nm
2C
2; 0
m
F
1; 0
nm
2C
2; 0
m
R
nm
2C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm

)
(70)
For the dead chains we have:
dC
2; 0
n
dt
= k
db
l
0
C
3; 0
n
(71)
It is obvious that even higher TDB moment distribution balances can be con-
structed, but we will restrict ourselves to the ones developed for up to the second
moments. When applying the TDB moment model, in principle two solution strat-
egies are possible: one using the zeroth and rst TDB moments only and the sec-
ond with zeroth, rst, and second TDB moments. In the rst case we have to nd a
closure relationship for the second moment, and in the second case, one for the
third moment. Below, we show that the system becomes simpler in the case of a
maximum of one TDB per chain.
Closure relations We have adopted a simple form for these relationships:
C
2; 0
n
= D
n
C
1; 0
n
P
n
C
1; 0
n
(72)
C
3; 0
n
= D
/
n
C
2; 0
n
C
1; 0
n
C
2; 0
n
(73)
Here the functions D
n
and D
/
n
are in fact polydispersities of the branching moment
distributions and in principle are to be determined as functions of chain length n.
Inserting these closure relationships in Eqs. (65), (66), and (70), (71), reduces them
to:
dF
1; 0
n
dt
= k
db
F
1; 0
n
X
y
n=1
C
1; 0
n

X
n1
m=1
C
1; 0
m
F
1; 0
nm
D
m
C
1; 0
m
P
m
1

C
1; 0
m
R
nm
!
( )
(65a)
dC
1; 0
n
dt
= k
db
l
0
D
n
C
1; 0
m
P
n
C
1; 0
n
(66a)
dF
2; 0
n
dt
= k
db
F
2; 0
n
X
y
n=1
C
1; 0
n
(
X
n1
m=1
C
1; 0
m
F
2; 0
nm
2C
2; 0
m
F
1; 0
nm
D
/
m
C
2; 0
m
C
1; 0
m
1

C
2; 0
m
R
nm
2C
1; 0
m
F
1; 0
nm
C
1; 0
m
R
nm
2
6
4
3
7
5
9
>
=
>
;
(70a)
dC
2; 0
n
dt
= k
db
l
0
D
/
n
C
2; 0
n
C
1; 0
n
C
1; 0
n
(71a)
An exact determination of D
n
and D
/
n
is not possible, but they can be estimated
from results of other methods, for instance a TDB classes model in regions with
few TDBs per chain.
9.6.3.2 TDB Pseudo-distribution Approach for a Maximum of one TDB per Chain
This case allows a few simplications. Firstly, only the rst TDB moment distribu-
tions, F
1; 0
n
and C
1; 0
n
, have to be solved in addition to the real concentration distri-
butions, since all higher TDB moment distributions are identical to these. Second,
the TDB propagation contributions to the population balances become greatly sim-
plied and their closure problem vanishes, since with C
2; 0
n
= C
1; 0
n
Eqs. (65) and
(66) become:
dF
1; 0
n
dt
= k
db
F
1; 0
n
X
y
n=1
C
1; 0
n

X
n1
m=1
C
1; 0
m
F
1; 0
nm
!
(74)
dC
1; 0
n
dt
= k
db
l
0
C
1; 0
n
(75)
This implies that under the condition of a maximum of one TDB per chain, the
set of population balance equations of the TDB branching moment variant of the
model is solvable without requiring any additional closure assumption. The results
obtained with the pseudo-distribution model are identical to those obtained with
the classes model shown before (see Figure 9.6).
9.6.3.3 TDB Pseudo-distribution Approach for More than one TDB per Chain
It is interesting here to compare results for the case of insertion of disproportiona-
tion-produced TDBs leading to more than one TDB per chain to the case of a
maximum of one TDB per chain. The chain length distributions for the two cases
and high TDB propagation rates are depicted in Figure 9.10 (left-hand side), which
reveals that the CLDs are quite dierent. Most interestingly, for the case of a max-
imum of one TDB per chain, the CLD features a shoulder that becomes higher
with increasing k
db
. This shoulder is absent in the other case, which can be ex-
plained by realizing that here the longer chains become more reactive with length
because of the higher number of TDBs on longer chains (see Figure 9.10, right-
hand side). Since these chains are more reactive they will be consumed by the
TDB propagation reaction more intensively, thereby producing more living chains,
which is consistent with our ndings (see Figure 9.10, left-hand side). When ex-
tending the trend of increasing TDB propagation rate, we would expect a transition
to a situation with vanishing dead chain concentrations, while retaining very few
but extremely long living chains. Thus, we observe the eect of dead chains with
many TDBs acting as crosslinkers between living chains. It should be noted that
under such conditions our model is no longer fully representative. The model
should at least be extended by allowing living chains with TDBs to be subject to
TDB propagation and, consequently, the existence of multiradicals.
The graph on the right in Figure 9.10 shows the numbers of TDBs per chain as a
function of chain length for both cases of TDB production. Here, the contrast is
very sharp. While for the maximum of one TDB per chain case the average num-
ber of TDBs per chain decreases with chain length, in the case of more than one
TDB it increases linearly with n in the double-logarithmic plot. The decrease in
the former case is caused by the simultaneous transfer-to-polymer reaction [9].
The latter implies a reduction to a constant TDB density, the number of TDBs
per monomer unit in a dead chain. As noted before, this results into a linear
increase in dead chain reactivity with chain length, similarly to the transfer-to-
polymer reaction.
Fig. 9.10. Radical polymerization of vinyl
acetate in a CSTR. The reactor and kinetic data
are the same as in Figure 9.6. Left: chain
length distributions for dead and living chains.
The part of the living chain CLD from the TDB
moment model beyond 10
10
is estimated.
Right: numbers of TDBs per chain for various
k
db
.
9.6.4
Radical Polymerization of Ethylene to Low-density Polyethylene (LDPE)
This problem has received considerable attention for a long time. Modeling is com-
plicated, since branching is involved, and the importance of random scission for
LDPE has now been recognized [31, 32, 54]. We address the 2D problem of CLD/
DBD calculation here. The full set of reaction equations is given in Table 9.15, no-
tation in Table 9.16, and population balance equations in Table 9.17. For merely
Tab. 9.15. Reaction mechanisms for LDPE (rst subscript: chain length; second subscript:
number of branch points).
Mechanism Reaction equation Rate factor
Initiation I
2
2Iv Iv M R
1; 0
k
d
; k
i
f
Propagation R
n; i
M R
n1; i
k
p
Disproportionation termination R
n; i
R
m; j
P
n; i
P
m; j
k
td
Recombination termination R
n; i
R
m; j
P
nm; ij
k
tc
n; i
M P
n; i
R
1; 0
k
m
Transfer to chain-transfer agent S R
n; i
S P
n; i
R
1; 0
k
S
n; i
P
m; j
P
n; i
R
m; j1
LCB k
trp
Pre-scission (formation of secondary
macroradicals)
R
n; i
P
m; j
P
n; i
R
+
m; j
k
rs
Scission of macroradicals R
+
n; i
R
nm; ij
P
m; j
k
sec
Tab. 9.16. Notation for LDPE system.
R
n; i
Primary radical chains
R
+
n; i
Secondary radical chains
P
n; i
Dead polymer chains
m
0
=
X
y
n=1
X
y
i =0
P
n; i
l
0
=
X
y
n=1
X
y
i =0
R
n; i
l
+
0
=
X
y
n=1
X
y
i =0
R
+
n; i
R
n
=
X
y
i =0
R
n; i
R
+
n
=
X
y
i =0
R
+
n; i
P
n
=
X
y
i =0
P
n; i
F
1
n
=
X
y
i =0
iR
n; i
F
+1
n
=
X
y
i =0
iR
+
n; i
C
1
n
=
X
y
i =0
iP
n; i
F
2
n
=
X
y
i =0
i
2
R
n; i
F
+2
n
=
X
y
i =0
i
2
R
+
n; i
C
2
n
=
X
y
i =0
i
2
P
n; i
B
n
= C
n
=P
n
number of branches per chain
r
n
= C
n
=(P
n
n). branching density
Tab. 9.17. Population balance equations for LDPE.
2D population balance equations
dR
n; i
dt
= k
p
M(R
n1; i
R
n; i
) (k
td
k
tc
)l
0
R
n; i
k
trp
(nl
0
P
n; i1
m
1
R
n; i
)
(k
m
M k
s
S)R
n; i
k
rs
m
1
R
n; i
k
sec
X
y
m=n1
g(m; n)
X
y
j =i
[ b(m; j; n[i)R
+
m; j
[
8
<
:
9
=
;
(k
m
M k
s
S)l
0
d(n 1)d(i) k
i
f MId(n 1)d(i)
(a)
dP
n; i
dt
= k
td
l
0
R
n; i

1
2
k
tc
X
n1
m=1
X
i
j =0
(R
m; j
R
nm; ij
) k
trp
(nl
0
P
n; i
m
1
R
n; i
)
(k
m
M k
s
S)R
n; i
k
rs
(nl
0
P
n; i
m
1
R
n; i
)
k
sec
X
y
l =n1
g(l; n)
X
y
j =i
[ b(m; j; n[i)R
+
m; j
[
8
<
:
9
=
;
(b)
dR
+
n; i
dt
= nk
rs
l
0
P
n; i
k
sec
R
+
n; i
(c)
1D concentration distribution equations
dR
n
dt
= k
p
M(R
n1
R
n
) (k
td
k
tc
)l
0
R
n
k
trp
(nl
0
P
n
m
1
R
n
) (k
m
M k
s
S)R
n
k
rs
m
1
R
n
k
sec
X
y
m=n1
g(m; n)R
+
l
(k
m
M k
s
S)l
0
d(n 1) k
i
f MId(n 1)
(d)
dP
n
dt
= k
td
l
0
R
n

1
2
k
tc
X
n1
m=1
R
m
R
nm
(k
trp
k
rs
)(m
1
R
n
nl
0
P
n
) (k
m
M k
s
S)R
n
k
sec
X
y
m=n1
g(m; n)R
+
m
(e)
dR
+
n
dt
= nk
rs
l
0
P
n
k
sec
R
+
n
(f )
1D pseudo-distribution equations, 1st branching moment
dF
1
n
dt
=
X
y
i =0
i
dR
n; i
dt

k
p
M(F
1
n1
F
1
n
) (k
M
M k
S
S)F
1
n
(k
td
k
tc
)l
0
F
1
n
k
trp
m
1
F
1
n
l
0
n(C
1
n
P
n
) k
rs
m
1
F
1
n
k
sec
X
y
m=n1
g(m; n)
X
y
j =0
R
+
m; j
X
j
i =0
ib(m; j; n[i)
" # ( )
(k
M
M k
S
S)l
0
d(n 1)
k
i
f Md(n 1)
(g)
dC
1
n
dt
=
X
y
i =0
i
dP
n; N
dt

= (k
M
M k
S
S)F
1
n
k
td
l
0
F
1
n
k
tc
X
n1
m=1
F
1
m
R
nm
(k
trp
k
rs
)(m
1
F
1
n
l
0
nC
1
n
) k
sec
X
y
n=m1
g(n; m)
X
y
j =0
R
+
m; j
X
j
i =0
ib(m; j; n[i)
" # ( )
(h)
dF
+1
n
dt
=
X
y
i =0
i
dR
+
n; i
dt

= nk
rs
l
0
C
1
n
k
sec
F
+1
n
(i)
computational reasons it is assumed that the scission reaction proceeds in two
steps, a pre-scission reaction yielding a secondary macroradical R
+
n; i
, and a subse-
quent breakage of this radical:
P
n; i
R
m; j

krs (n1)
R
+
n; i
P
m; j
(76)
R
+
n; i

ksec
R
nm; ij
P
m; j
(77)
The term (n 1) in the pre-scission equation [Eq. (76)] is due to the fact that we
are dealing with random (pre-)scission here: that is, every CaC bond has equal
probability of being attacked to form a secondary radical. The population balance
contribution from this reaction is similar to that from a transfer-to-polymer reac-
tion (see Table 9.17). The 2D population balance contribution from the actual scis-
sion step reads as (Table 9.17):
dR
n; i
dt
= k
sec
X
y
m=n1
g(m; n)
X
y
j =i
[ b(m; j; n[i)R
+
m; j
[
8
<
:
9
=
;
(78)
Here, the functions g and b are the most general form of probability functions, ex-
pressing the way in which the fragment lengths are distributed (g) and how the
branch points are redistributed on these fragments (b). The function g(m; j; n) de-
scribes the probability that a chain of length n with j branch points breaks into a
fragment with length m, while b(m; j; n[ j) is the conditional probability that a frag-
ment of length m created by scission of a chain n=i carries exactly j branch points.
The fragment length distribution function reects the scission mechanism acting.
Tab. 9.17. (continued)
1D pseudo-distribution equations, 2nd branching moment
dF
2
n
dt
=
X
y
i =0
i
2
dR
n; i
dt

= k
p
M(F
2
n1
F
2
n
) (k
M
M k
S
S)F
2
n
(k
td
k
tc
)l
0
F
2
n
k
trp
m
1
F
2
n
l
0
n(C
2
n
2C
1
n
P
n
)
k
sec
X
y
m=n1
g(m; n)
X
y
j =0
R
+
m; j
X
j
i =0
i
2
b(m; j; n[i)
" # ( )
k
rs
m
1
F
2
n
(k
M
M k
S
S)l
0
d(n 1) k
i
f Md(n 1)
( j)
dC
2
n
dt
=
X
y
i =0
i
2
dP
n; i
dt

= (k
M
M k
S
S)F
2
n
k
td
l
0
F
2
n
k
tc
X
n1
m=1
(F
2
m
R
nm
F
1
m
F
1
nm
)
(k
trp
k
rs
)(m
1
F
2
n
l
0
nC
2
n
) k
sec
X
y
n=m1
g(n; m)
X
y
j =0
R
+
m; j
X
j
i =0
i
2
b(m; j; n[i)
" # ( )
(k)
dF
+2
n
dt
=
X
y
i =0
i
2
dR
+
n; i
dt

= nk
rs
l
0
C
2
n
k
sec
F
+2
n
(l)
The Galerkin-FEM approach allows us to choose any model describing such mech-
anisms, either chemical or mechanical, if they are expressed in terms of fragment
lengths as functions of overall chain length or numbers of branch points [54]. An
overview of such models is given elsewhere [32]. In the most realistic models the
eect of branching and architectures is accounted for; this gives rise to predomi-
nantly long and short fragments. The fundamental problem here, to start with, is
that the second dimension of the 2D population balance problem, the branching
distribution, has to be solved to calculate the rst dimension, CLD. Moreover, not
only the branching distribution, but also the character of the branched architec-
tures, determine the scission function. One way of addressing this problem is
employing an empirical approximation relationship for the fragment length func-
tion g(n; m) found for topological scission of LDPE architectures [33]:
g(n; m) =
1
(2s m)
2

1
(2s n m)
2
X
n1
m=1
1
(2s m)
2

1
(2s n m)
2
( ) (79)
with s the average segment length, according to:
s =
n
n
1 2 + LCB=m
0
(80)
In Eq. (80), LCB is the overall concentration of long chain branches, following
from a balance coupled with the transfer-to-polymer reaction (see Table 9.17). The
fragment length distribution g(n; m) for topological scission is a function of chain
and fragment length only, and independent of the number i of branch points on
the original chain. Note that this is an approximation method that ts to the dier-
ential equation approach. Obviously, it accounts for branching architectures in an
averaged manner. Fully accounting for architectures is not possible with the dier-
ential equation method, since it does not describe connectivity in molecules. Doing
this in more rigorous ways, full [1115] or conditional [3335] Monte Carlo (MC)
simulations can be used (see Section 9.8). We stress here that the strength of the
dierential method discussed here is its ability to implement any function de-
scribing scission in overall molecular dimensions, such as chain length. This is
not readily possible in MC simulations.
In order to solve the one-dimensional chain length distribution problem, the
scission contribution of Eq. (78) is summed over the number of branch points on
fragments, j. By denition
P
i
j =0
b(n; i; m[ j) = 1, so this population balance assumes
a one-dimensional form:
dR
m
dt
= k
sec
X
y
n=m1
g(n; m)R
+
n
(81)
The 1D population balance for the pseudo-distribution or rst branching moment
distribution F
n
follows by taking the rst branching moment of Eq. (78):
d
X
y
j =0
jR
m; j
dt
=
dF
m
dt
= k
sec
X
y
n=m1
g(n; m)
X
y
i=0
R
+
n; i
X
i
j =0
jb(n; i; m[ j)
" # ( )
(82)
Depending on the branch point redistribution function, the term in square brackets
(in fact the expectation value of the number of branches on a fragment) can be
evaluated. Similarly, we nd for the second branching moment expression:
d
X
y
j =0
j
2
R
m; j
dt
=
dF
2
m
dt
= k
sec
X
y
n=m1
g(n; m)
X
y
i=0
R
+
n; i
X
i
j =0
j
2
b(n; i; m[ j)
" # ( )
(83)
The task is now to nd empirical expressions for the rst and second branching
moment summation terms between brackets in Eqs. (82) and (83) similar to Eq.
(79) for the fragment lengths. The shape of these is strongly dependent on the scis-
sion mechanism [32]. Note that nding solutions for this problem is important for
calculation of the branching density and the branching polydispersity as functions
of chain length. From this the shape of the branching distribution at constant
chain length can be estimated, which then produces an estimation of the full
CLD/DBD.
Finally, in Figure 9.11 we show MWDs for two dierent scission models. The
linear scission case assumes scission of unbranched chains. The topological scis-
sion case employs the fragment length function of Eq. (79). A marked dierence is
observed.
9.6.5
Radical Copolymerization
We now address the problem of nding the 3D distribution of chain lengths,
copolymer composition, and sequence length distribution in radical copolymer-
ization. We have several options here. One could be explicitly solving the 3D con-
centration variable at the sequence level, P
seq
n; i; s
, denoting the concentration of se-
quences of length s on chains with a total number of monomer units n (usually
called chain length), and number of monomer units of one kind i. Note that i=n
is then the fractional copolymer composition. We will not do this, but instead
choose a simpler option and solve a dierent 3D concentration variable at the
chain level, P
n; i; s
. Subscripts n and i have the same meaning as in P
seq
n; i; s
, but s
here denotes the number of monomer sequences of one kind. Solving this prob-
lem in the full three dimensions would yield the average sequence length on
chains P
n; i; s
, simply following as i=s. We will show next how to solve the problem
using pseudo-distributions and thus nd the average copolymer composition and
sequence length as a function of chain length, n. Reaction equations are listed in
Table 9.18, notation and denitions in Table 9.19. Note that macroradicals are
specied according to terminal unit, with an upper index A or B.
9.6.5.2 Balance Equations
All the reactions listed in Table 9.18 have contributions to the set of balance equa-
tions. We will give a few examples of the generation of these contributions from
some of the reaction equations.
Tab. 9.18. Reaction equations for radical copolymerization.
Initiation Propagation Termination
I
2

kd
2I R
A
n; i; s
A
kAA
R
A
n1; i1; s
R
A
n; i; s
R
A
m; j; t

kc
P
nm; ij; st
I A
ki
R
A
1; 1; 0
R
B
n; i; s
B
kBB
R
B
n1; i; s
R
B
n; i; s
R
B
m; j; t

kc
P
nm; ij; st
I B
ki
R
B
1; 0; 0
R
A
n; i; s
B
kAB
R
B
n1; i; s
R
A
n; i; s
R
B
m; j; s

kc
P
nm; ij; st
R
B
n; i; s
A
kBA
R
A
n1; i1; s1
1e+0 1e+1 1e+2 1e+3 1e+4 1e+5 1e+6 1e+7 1e+8
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0
0.2
0.4
0.6
0.1
0.3
0.5
10
1
10
0
10
2
10
4
10
6
10
3
10
5
10
7
10
8
Chain Length
d
W
/
d
{
l
o
g
(
n
)
}
Fig. 9.11. Radical polymerization of ethylene in a CSTR. Linear
and topological scission with the same polydispersity of 26 as
experimental MWD from SEC-MALLS [35]. Solid line,
experimental MWD; dash-dot line, topological scission result;
dash-dot-dot line, linear scission result.
BxA-propagation: R
B
n, i, s
BA m
kBA
R
A
nB1, iB1, sB1
In this reaction all the indices in-
crease by 1. The contribution to the balance equations from which the length distri-
bution is calculated simply follows by taking the double sum over i and s:
d
X
y
s=1
X
y
i=1
R
A
n; i; s
!
dt
= k
BA
A
X
y
s=2
X
y
i=2
R
B
n1; i1; s1
= k
BA
AR
B
n1
(84)
For the rst moment distribution of the number of A units we have:
d
X
y
s=1
X
y
i=1
iR
A
n; i; s
!
dt
=
dG
A
n
dt
= k
BA
A
X
y
s=2
X
y
i=2
iR
B
n1; i1; s1
= k
BA
A
X
y
i=2
iR
B
n1; i1
(85)
The last term here contains the two-dimensional distribution multiplied by i:
i.R
B
n1; i1
, which upon summation over i, due to its index (i 1), produces the
sum of two one-dimensional distributions: R
B
n1
and G
B
n1
. Hence, we get:
dG
A
n
dt
= k
BA
A(R
B
n1
G
B
n1
) (86)
Tab. 9.19. Notation and denitions.
Overall moments l
A
0
=
X
y
n=1
X
y
s=1
X
y
i =1
R
A
n; i; s
l
B
0
=
X
y
n=1
X
y
s=1
X
y
i =1
R
B
n; i; s
m
0
=
X
y
n=1
X
y
s=1
X
y
i =1
P
n; i; s
2D concentrations P
n; i
=
X
y
s=1
P
n; i; s
P
n; s
=
X
y
i =1
P
n; i; s
R
A
n
=
X
y
s=1
X
y
i =1
R
A
n; i; s
1D concentrations R
A
n
=
X
y
s=1
X
y
i =1
R
A
n; i; s
R
B
n
=
X
y
s=1
X
y
i =1
R
B
n; i; s
P
n
=
X
y
s=1
X
y
i =1
P
n; i; s
1st moment distributions
of number of A units
G
A
n
=
X
y
s=1
X
y
i =1
iR
A
n; i; s
G
B
n
=
X
y
s=1
X
y
i =1
iR
B
n; i; s
L
n
=
X
y
s=1
X
y
i =1
iP
n; i; s
1st moment distributions
number of A sequences
F
A
n
=
X
y
s=1
s
X
y
i =1
R
A
n; i; s
F
B
n
=
X
y
s=1
s
X
y
i =1
R
B
n; i; s
C
n
=
X
y
s=1
s
X
y
i =1
P
n; i; s
Number of A units per chain as a function of n n
A
n
= L
n
=P
n
Number of A sequences per chain as a function of n s
A
n
= C
n
=P
n
Average sequence length of A as a function of n l
A
n
= n
A
n
=s
A
n
Average sequence length of B as a function of n l
B
n
= (n n
A
n
)=s
A
n
= n
B
n
=s
A
n
Obviously, in this case the problem in obtaining the rst moment distribution of
the number of A sequences is exactly identical to that for the A units, so we have:
dF
A
n
dt
= k
BA
A(R
B
n1
F
B
n1
) (87)
AxA-propagation: R
A
n, i, s
BA m
kAA
R
A
nB1, iB1, s
Here, only two of the three indices in-
crease by 1. The length distribution is again calculated simply by taking the double
sum over i and s which is identical to the length distribution term found in the pre-
vious propagation case, Eq. (84):
d
X
y
s=1
X
y
i=1
R
A
n; i; s
!
dt
= k
AA
A
X
y
s=2
X
y
i=2
R
A
n1; i1; s
= k
AA
AR
A
n1
; (88)
For the rst moment distribution of the number of A units, for this propagation
step we have:
d
X
y
s=1
X
y
i=1
iR
A
n; i; s
!
dt
=
dG
A
n
dt
= k
AA
A
X
y
s=2
X
y
i=2
iR
A
n1; i1; s
= k
AA
A
X
y
i=2
iR
A
n1; i1
; (89)
which again is equal to the one found before, Eq. (85). Hence we end up with an
expression containing two one-dimensional distributions on the right-hand side:
dG
A
n
dt
= k
AA
A(R
A
n1
G
A
n1
) (90)
For this propagation step the situation for the rst moment distribution of A se-
quences is dierent, since we now have
d
X
y
i=1
X
y
s=1
sR
A
n; i; s
!
dt
=
dF
A
n
dt
= k
AA
A
X
y
i=2
X
y
s=2
sR
A
n1; i1; s
= k
AA
A
X
y
s=2
sR
A
n1; s
; (91)
where in the last term the summation over s proceeds with a two-dimensional dis-
tribution R
A
n1; s
simply having s as the index. This yields:
dF
A
n
dt
= k
AA
AF
A
n1
; (92)
containing only one one-dimensional distribution.
BxB propagation R
B
n, i, s
m
kBB
R
B
nB1, i, s
Only the chain length index is increased. Using
a similar argument to previously, we can say that the right-hand side expressions
for both the number of A units and the number of A sequences moment distribu-
tions will produce two-dimensional distributions as intermediate results having i
and s as indices. Summation of these will nally produce expressions like Eq. (92):
dG
B
n
dt
= k
BB
BG
B
n1
(93)
dF
B
n
dt
= k
BB
BF
B
n1
(94)
Termination by combination: R
A
n, i, s
BR
A
m, j, t
m
kc
P
nBm, iBj, sBt
This is the reaction
equation for termination between macroradicals with identical terminal groups.
The balance equation describing the production of dead chains P
n; i; s
is:
dP
n; i; s
dt
=
1
2
k
tAA
X
n1
m=1
X
i1
j =1
X
s1
t=1
(R
A
m; j; t
R
A
nm; ij; st
) (95)
The rst moment distribution of the number of A units leads to:
d
X
y
s=1
X
y
i=1
iP
n; i; s
!
dt
=
dL
n
dt
=
1
2
k
tAA
X
n1
m=1
X
y
i=1
i
X
i1
j =1
X
y
s=1
X
s1
t=1
(R
A
m; j; t
R
A
nm; ij; st
)
( )
=
1
2
k
tAA
X
n1
m=1
X
y
i=1
i
X
i1
j =1
(R
A
m; j
R
A
nm; ij
)
( )
(96)
The last term can be rearranged to give for the rst moment of the number of A
units:
dL
n
dt
=
1
2
k
tAA
X
n1
m=1
X
y
i=1
i
X
i1
j =1
(R
A
m; j
R
A
nm; ij
)
( )
=
1
2
k
tAA
X
n1
m=1
X
y
j =1
R
A
m; j
X
y
i=j
iR
A
nm; ij
0
@
1
A
=
1
2
k
tAA
X
n1
m=1
X
y
j =1
R
A
m; j
X
y
i=0
(i j)R
A
nm; i
!
=
1
2
k
tAA
X
n1
m=1
X
y
j =1
jR
A
m; j
X
y
i=1
R
A
nm; i

X
y
j =1
R
A
m; j
X
y
i=1
iR
A
nm; i
!
=
1
2
k
tAA
X
n1
m=1
(G
A
m
R
A
nm
R
A
m
G
A
nm
) = k
tAA
X
n1
m=1
G
A
m
R
A
nm
(97)
An expression for the contribution from the termination reaction to the rst mo-
ment distribution of the number of A sequences is obtained in an identical
manner:
dC
n
dt
= k
tAA
X
n1
m=1
C
A
m
R
A
nm
(98)
For the termination between B-terminated macroradicals the expressions obtained
are exactly the same as Eqs. (97) and (98). For the reaction between A- and B-
terminated macroradicals we nd:
dL
n
dt
= k
tAB
X
n1
m=1
(G
A
m
R
B
nm
R
A
m
G
B
nm
) (99)
dC
n
dt
= k
tAB
X
n1
m=1
(C
A
m
R
B
nm
R
A
m
C
B
nm
) (100)
The consumption terms for the macroradicals corresponding to the termination
reactions have simpler forms like the balance equation in three dimensions:
dR
A
n; i; s
dt
= k
tAA
R
A
n; i; s
X
n1
m=1
X
i1
j =1
X
s1
t=1
R
A
m; j; t
k
tAB
R
A
n; i; s
X
n1
m=1
X
i1
j =1
X
s1
t=1
R
B
m; j; t
= R
A
n; i; s
(k
tAA
l
A
0
k
tAB
l
B
0
) (101)
From this the moment distribution expressions for the number of A units and for
the number of A sequences easily follow as:
dF
A
n
dt
= F
A
n
(k
tAA
l
A
0
k
tAB
l
B
0
) (102)
dG
A
n
dt
= G
A
n
(k
tAA
l
A
0
k
tAB
l
B
0
) (103)
Once the pseudo-distributions have been solved, the average copolymer composi-
tion n
A
n
=n and sequence lengths l
A
n
can be calculated with the expressions given
in Table 9.19. Note that the average number of B units n
B
n
can simply be derived
from n
A
n
, since n
B
n
= n n
A
n
. For large numbers of sequences per chain we may
further assume that these are equal for both monomers: s
B
n
= s
A
n
. Thus, the average
sequence length for B; l
B
n
, can also be inferred easily. Some illustrative calculations
have been carried out for a batch copolymerization and the results (together with
kinetic and reactor data) are shown in Figure 9.12.

0
0.2
0.4
0.6
0.8
1
10
1
10
2
10
3
10
4
10
5
10
6
Chain length
C
o
p
o
l
y
m
e
r

c
o
m
p
o
s
i
t
i
o
n
A
B
10
1
10
2
10
3
10
4
10
5
10
6
10
-1
10
0
10
1
10
2
10
3
10
4
Chain length
S
e
q
u
e
n
c
e

l
e
n
g
t
h
B
A
Fig. 9.12. Average copolymer composition and
sequence length as functions of chain length
for batch copolymerization. Kinetic data:
k
d
= 6:25 10
3
s
1
; k
i
= 3:75 10
4
m
3
(kmol s)
1
; k
pAA
= 1000 m
3
(kmol s
1
);
k
pAB
= 100 m
3
(kmol s)
1
; k
pAA
= 1000 m
3
(kmol s)
1
; k
pBA
= 10
6
m
3
(kmol s)
1
;
k
pBB
= 10
5
m
3
(kmol s)
1
; k
c
= 3 10
5
m
3
(kmole s)
1
; c
A0
= 2 kmol m
3
; c
B0
= 2
kmol m
3
; c
I0
= 10
2
kmol m
3
; batch time:
400 s. Shorter chains (produced early in the
batch) contain equal amounts of A and B with
sequence lengths of 2.5 on the average. Long
chains (late in the batch) possess more B, with
sequences of up to 2000.
9.7
Probability Generating Functions
9.7.1
Introduction
Probability generating functions (pgf ) are dened as polynomials in the transfor-
mation variable z [where the coecients p
i
represent a probability distribution
(that is, a length distribution)]:
G(z) =
X
y
i=0
p
i
z
i
(104)
Distribution moments and coecients can be obtained from G(z) according to:
m
0
= G(1); m
1
=
qG
qz

z=1
; m
2
=
q
2
G
qz
2
!
z=1
(105)
p
i
=
1
i!
q
i
G
qz
i
!
z=0
(106)
We will discuss pgfs as used in a transformation procedure to solve population bal-
ance equations [3], and as employed in the cascade theory of polymer networks
[3744].
9.7.2
Probability Generating Functions in a Transformation Method
According to the transformation procedure, the population balance equations in
terms of discrete variables (chain length, number of branch points) are trans-
formed into a set of equations in z. The transformed set is solved and subsequently
inverted to the original discrete variable domain. This process makes use of some
interesting properties of certain mathematical expressions as transformed into the
z-domain. Transformations and inversions are tabulated in textbooks [3]. As an ex-
ample we take linear AB step polymerization in a batch reactor with equal initial
end group concentration P
0
:
P
n
P
m

k
P
nm
(107)
dP
n
dt
= k
X
n1
m=1
P
m
P
nm
2kP
n
X
y
n=1
P
n
(108)
The total chain concentration is m
0
=
P
y
n=1
P
n
, so by taking the zeroth moment of
Eq. (106) we obtain Eq. (109), yielding:
dm
0
dt
= k(m
0
)
2
(109)
m
0
= P
0
=(1 ktP
0
) (110)
Since by denition [Eq. (104)] G(1) = m
0
, while the convolution property prescribes:
G
X
n1
m=1
P
m
P
nm
!
= G(P
n
)
2
(111)
Eq. (108) becomes:
dG(z)
dt
= kG
2
(z) 2G(z)G(1) (112)
By putting z = 1, Eq. (110) for the total concentration m
0
is reproduced. To solve
Eq. (112) we rst realize that under initial conditions the pgf is given as: G(z; 0) =
P
0
z; integration then leads to:
G(z) = P
0
G(1)=P
0
2
z=[1 z1 G(1)=P
0
[ (113)
This expression in the z-domain has a standard inverse form in the chain length
domain, which represents a Flory distribution as the well-known solution to this
problem:
P
n
= P
0
G(1)=P
0
2
1 G(1)=P
0
n1
(114)
This pgf transformation procedure is an elegant method that has found many ap-
plications [3]. However, its ability to solve complete distribution problems is re-
stricted to cases where explicit inversion is possible. In other cases only the main
moments can be calculated, which then often can also be realized directly by the
method of moments.
9.7.3
Probability Generating Functions and Cascade Theory
The cascade theory has been developed to deal with problems concerning polymer
network formation [3744]. Consider the polymer network made by polycondensa-
tion of f -functional monomers, represented as a rooted tree in Figure 9.13.
Let end group conversion be given as a; then for a three-functional monomer
the pgf of the connectivity between the zeroth and rst generation is given by:
F
0
(z) = (1 a)
3
3a(1 a)
2
z 3a
2
(1 a)z
2
a
3
z
3
= (1 a az)
3
(115)
Likewise, the pgf for connectivity between rst and second (and all subsequent)
generations is given by:
F
1
(z) = (1 a az)
2
(116)
In general, for f -functional monomers we thus have:
F
0
(z) = (1 a az)
f
F
1
(z) = (1 a az)
f 1
(117)
From the connectivity pgfs at subsequent generation levels the branch point prob-
ability distributions at a certain level can be inferred. For instance, in the example
with f = 3 at level 2 the branch point pgf reads as:
F
0
(z) = (1 a aF
1
)
3
(118)
where F
1
is given by Eq. (116); coecients of z
i
in Eq. (118) represent the proba-
bilities of nding i branch points at level 2. Thus, at an arbitrary level we have:
G
0
(z) = F
0
(F
1
(F
1
(. . . F
1
(z)))) (119)
From Eqs. (117), number- and weight-average chain lengths can be derived using
Eqs. (105) [37], but a more elegant method is to construct self-consistent equations
[45, 46] to solve the pgf. In the three-functional example above, the probabilities of
a given node on an arbitrary generation level being connected to zero, one, or two
(1-)
3
z
0
3(1-)
2
z
1
3
2
(1-)z
2 3
z
3
(1-)
2
z
0
2(1-)z
1 2
z
2
F
1
(z) = (1-+ z)
2
F
0
(z) = (1-+ z)
3
G
e
n
e
r
a
t
i
o
n
0
1
2
Fig. 9.13. Principle of probability generating functions and

cascade theory for a three-functional polymer network.
further nodes are expressed by the coecients for z
0
; z
1
, and z
2
, respectively, in
pgf G(z). In addition, being connected to a further node implies the possibility of
being connected to even further nodes. This possibility is described by the identical
pgf G(z). The connectivity to further nodes if connected to two nodes is expressed
by G
2
(z), since statistics of these connectivities are identical, but independent.
Note that the contributions of further connectivities are thus correctly described
by the coecients of the z terms. The self-consistent equation becomes:
G = (1 a)
2
a(1 a)zG a
2
z
2
G
2
(120)
We will illustrate this procedure on a simple linear step-polymerization ( f = 2) to
obtain the CLD and on single metallocene ethylene polymerization to nd the 2D
distribution of chain lengths and numbers of branch points.
Linear step-polymerization is treated as above with f = 2, yielding the self-
consistent pgf equation:
G = (1 a) azG (121)
and hence:
G = (1 a)=(1 az) (122)
Applying Eqs. (105) to Eq. (121) we nd the number- and weight-average for the
number of links between monomer units, which after adding 1 yields the familiar
expressions for n
n
and n
w
already found by Flory [1]:
n
n
=
qG
qz

z=1
=
a
1 a
1 =
1
1 a
n
w
=
q
2
G
qz
2

z=1
0
qG
qz

z=1
=
a
1 a
0
2a
2
(1 a)
2
1 =
1 a
1 a
(123)
Series expansion in z of Eq. (122) yields for G:
G =
X
y
i=0
(1 a)a
i
z
i
(124)
of which the coecients represent a Flory distribution (1 a)a
i1
, realizing again
that chain length is one more than the number of links. The derivation of the
CLD/DBD 2D distribution for the metallocene system is based on the fact that all
segments between branch points possess the same statistics. The pgf method is
then applied to the connectivity of segments rather than monomer units as in the
polycondensation problem. A pgf is constructed for the probability of nding con-
nectivity points (branch points) on a segment going in a direction opposite to the
growth direction. The self-consistent pgf equation follows from an argument in
which the probability of a segment having a branch point plays a central role. As-
suming steady state and taking the (0; 0)-moment of the population balance equa-
tions (35)(40), we nd this branching probability to equal:
b =
B
B m
=
0
l
0
=
k
b
k
p; TDB
tl
0
(2k
b
t 1)k
p; TDB
l
0
k
b
1=t
(125)
A given segment is connected to an initiation point (hence not to a branch point)
with probability 1 b, and it is connected to a branch point with probability b. In
the case of a branch point the segment is connected to two further segments obey-
ing the same statistics and hence pgf. Thus we have:
G = (1 b) bzG
2
(126)
which has a quadratic form this time, having Eq. (127) as the solution [45]:
G =
1
1 4b(1 b)z
q
2b
(127)
This can be expanded to give:
G =
X
y
i=0
(2i)!
i!(i 1)!
b
i
(1 b)
i1
z
i
(128)
where the coecients for z
i
represent the probability distribution of the numbers
of branch points per molecule. Here, the factor (2i)!=(i 1)! is called the Catalan
number, which has already been derived by Flory [1] and represents the number of
dierent ways a molecule with i branch points can be constructed. Since the num-
ber of segments between branch points plus terminal segments per molecule is
2i 1, obtaining the length distribution further requires the length distribution of
the segments to be taken into account. This should obey a Flory distribution, being
dictated by the competition of propagation on the one hand, and termination by
b-hydride elimination and TDB incorporation on the other. Hence the number-
average segment length and probability distribution of segments with length n
i
follow as:
n
s
n
=
k
p
M
k
b
k
p; TDB
m
=
0
1=t
p
n
=
1
n
s
n
exp
n
i
n
s
n

(129)
From Eq. (129) the probability of nding polymers with i branch points (2i 1
segments) is easily inferred. The conditional probability of polymers with 2i 1
segments, all with a Flory distribution with average n
s
n
, of having total length n is
known to be:
p(n[i) =
n
2i
(n
s
n
)
2i1
(2i)!
exp
n
n
s
n

(130)
This result can be understood as the product of 2i 1 segmental probability distri-
butions [Eq. (129)], leading to n in the exponential, multiplied by a prefactor repre-
senting the number of possibilities of distributing n monomer units among 2i 1
segments. Combining Eqs. (129) and (130) gives the full expression for the 2D dis-
tribution of CLD and DBD:
p(n; i) =
n
2i
(n
s
n
)
2i1
1
i!(i 1)!
b
i
(1 b)
i1
exp
n
n
s
n

(131)
As regards a successful application of the pgf cascade method, we conclude that:
v
connectivity statistics should be identical for all units (monomer units or seg-
ments), and
v
a convenient series expansion of the pgf from the self-consistent equation should
be possible.
9.8
Monte Carlo Simulations
9.8.1
Introduction
This method is employed for problems where analytical or dierential equations
approaches are not feasible in view of high dimensionality, or only lead to approxi-
mate solutions or averages for one or more dimensions. Examples of such limi-
tations have been discussed above. The Galerkin-FEM method in the pseudo-
distribution mode was confronted with closure problems in the case of PVAc with
more than one TDB per chain. The pgf-method is applicable only to systems with
identical statistics of the constituting elements. In principle, Monte Carlo simula-
tion does not suer from such limitations. Here, we will introduce classical MC,
but subsequently mainly discuss some successful applications of advanced MC
methods.
Classical MC simply describes the reactions of single monomer units. In the
case of branching, a reaction event can be either a propagation, a termination or
a branching step, according to the relative probabilities of these reactions. This
method has, for instance, been applied to a single metallocene system for branched
polyethylene to provide the bivariate CLD/DBD [47]. The disadvantage of this
approach is that it requires billions of reaction steps to generate suciently large
populations of molecules, typically 10
6
, to derive accurate statistics. Computation-
ally less demanding is application of MC to larger constituent units than mole-
cules: segments or primary polymers [1115, 47]. In the aforementioned metallo-
cene example this could be realized for a continuous reactor in a simple manner
because of the identical statistical properties of all segments. This increased com-
putation speed by a factor of 15 [47]. However, when the tails of very broad CLDs
are to be described, typically involving concentrations more than six decades lower
than the highest chain concentrations in the system, the numbers of molecules to
be generated become excessive, even with primary polymer sampling. Tobita has
achieved a great improvement in MC sampling in this respect by applying sam-
pling based on weight-fraction instead of number-fraction distributions [1115].
We will now discuss this method as applied on mostly branched radical polymer-
ization systems involving transfer to polymer, terminal double bond incorporation,
recombination termination, and random scission for both continuous and batch
reactors.
9.8.2
Weight-fraction Sampling of Primary Polymers: Batch Reactor, Transfer to Polymer
[48]
A branched molecule is thought to be composed of primary polymers (pps) in
which growth of linear chains has started from monoradicals or from secondary
radical sites at other pps, created by transfer to polymer, and stopped by a certain
termination mechanism. Primary polymers can possess one or more branch points
at which other pps have been growing. Primary polymer sampling is generally
based on the assumption of instantaneous growth of pps. In a batch reactor the
length distribution of such pps is then determined by the kinetic conditions (con-
version) at the birth time, y. The MC process starts with sampling such a birth
time y, and under number-fraction sampling its length is sampled from the (usu-
ally Flory) number-fraction distribution at y. Since molecules may start growing at
any moment, we may (but must not necessarily) consider this rst sampled pp as
the rst one of the whole molecule. The rst pp may, by transfer to polymer reac-
tions, receive one or several branch points in the remaining time between y and
the batch end time c, and thus become attached to pps created at later birth times.
These rst, second, third and further pps may in their turn receive branch points
and become attached to more pps at later stages. The MC process stops when the
last pps no longer obtain branch points.
A slightly modied approach does not regard the rst sampled pp as the rst
one in the molecule. Instead it accounts for the possibility that the rst sampled
pp has started growing from a branch point created on a previously formed pp (be-
tween 0 and y), rather than being initiated from a monoradical. Since in all cases
the connectivity is based on the same values for the branching probability at the
various birth times, the results are identical.
Since most pps are present in short chains, this sampling procedure generates
mostly short molecules; hence a very great many molecules have to be created to
predict long CLD tails accurately. If, instead, one sampled monomer units on pps
and was able to predict their connectivity to other parts of the molecule, then most
molecules generated would have sizes around the maximum of the weight-fraction
distribution. In other words, such a method is signicantly more eective at nd-
ing long CLD tails. This is the rationale of weight-fraction sampling, since the
probability of selecting a monomer unit at random from a pp population is propor-
tional to the length n of the pps. Since in that method a monomer unit is sampled
at random in a molecule, it cannot always be on the rst pp of the molecule. The
MC process consequently proceeds in the second manner described above. The
rst monomer unit sampled at y forms part of a pp in the zeroth generation, as
do the pps to which it (eventually) is connected by branch points from it, on the
one hand, and (eventually) to the pp on which it started growing on, on the other.
The MC algorithm determines the birth times and lengths of pps in subsequent
generations.
We will demonstrate the MC procedure on a very simple radical polymerization
process with transfer to polymer, while disproportionation is the only termination
mechanism (see Figure 9.14). The algorithm employs conversion x, rather than
time, as the independent variable. Consequently, it starts with sampling the birth
conversion x = y of a zeroth-generation pp by sampling a random number be-
tween 0 and end conversion c. Its length is determined by sampling from the
weight-fraction distribution (usually according to Flory):
w
n
(y) =
n
n(y)
2
exp
n
n(y)

(132)
The average chain length n(y) is given by:
n(y) = k
p
M(y)l
0
(y)=k
td
l
0
(y)
2
= k
p
M(y)=k
td
l
0
(y) (133)
pp: brith conversion ,
length from w
n
(), Eq. (132)
branch points sampled with Eq. (138)
with (,) from Eq. (137)
initial unit
pp:
0 < z(0) <
pp with u(0)
< u(0) <
pp with u(1)
u(0) < u(1) <
pp with u(0)
< u(0) <
pp with u(1)
z(0) < u(1) <
pp with u(1)
z(0) < u(1) <
pp:
0 < z(1) < z(0)
brith conversion z(1),
brith conversion z(0),
Fig. 9.14. Monte Carlo sampling of primary polymers and their
connectivity for radical polymerization with transfer to polymer
in a batch reactor. Conversion c, rst pp sampled at birth
conversion x = y.
Sampling can be realized by using the cumulative distribution of w
n
(y), a function
of y; cw
n
(y), with values between 0 and 1, selecting a random number between 0
and 1 (rand(1)), and nding y by requiring that cw
n
(y) = rand(1). A faster method
utilizes the property that sampling twice from the number-fraction distribution
and adding results exactly reproduces a weight-fraction distribution [49]. Sampling
from n
n
can be performed rapidly using the simple formula:
n = ceil[n(y) ln1=rand(1)[ (134)
where ceil denotes the value obtained when rounding a real number to the nearest
higher integer, a standard operation available in most mathematical packages such
as MATLAB. Doing this twice and adding the values generates a weight-fraction
sample value. The probability of receiving branch points for this pp depends on
its average branching density between y and c and is proportional to its now
known length, n. The former can be derived from the monomer and branch points
balance (Table 9.1):
dM
dt
= k
p
l
0
(t)M
dx
dt
= k
p
l
0
(t)(1 x) (135)
dr
dt
= k
tp
l
0
(t) (136)
Combination and integration between y and c yields the average branching den-
sity r(y; c):
dr
dt
= C
tp
1
1 r
r(y; c) = C
tp
ln
1 y
1 c

(137)
The number of branch points m on this pp is sampled from a binomial distribu-
tion containing average branching density r(y; c) and pp length n:
p(m) =
n
m

r
m
r
(nm)
(138)
Sampling can be performed by employing standard random number generators
for a binomial distribution (for example, in MATLAB: m = binornd(n; r)). Next, to
the pps attached at each of these branch points a birth conversion u, y < u < c, and
a length must be assigned. The former should follow from the formation intensity
distribution of branching density over the conversion interval yc as given by
Eq. (137). This implies that we should sample u from the conditional (given that
this branch point exists at a pp formed at y) probability distribution, as expressed by:
CP
a
(u[y) = ln
1 y
1 u

ln
1 y
1 c
0
(139)
The sampling can be performed by selecting a random number between 0 and 1
(rand(1)) and inferring u from it by requiring that CP
a
(a function of u between 0
and 1) equals rand(1). The shape of Eq. (139) is such that on average u is chosen
closer to c than to y. This agrees with the fact that branch formation intensity is
higher at high conversion. The length of the pp grown at x = u is sampled from
the number-fraction distribution:
n
n
(y) =
1
n(y)
exp
n
n(y)

; (140)
since a single chain end (instead of an arbitrary unit on the chain) is chosen at ran-
dom as its starting point. Sampling is easily realized by employing Eq. (133). This
eventually leads to a number of pps in generation 0 with specied birth conver-
sions and lengths. Included in the procedure for this generation is the accounting
for the eventuality of the rst pp [pp(y)] being attached to a pp created earlier, at z,
0 < z < y. This follows from the relative probability of the rst pp of being initi-
ated by a transfer-to-polymer reaction [Eq. (141)].
P
b
= k
tp
l
0
m
1
=(k
tp
l
0
m
1
2k
d
I
2
) = k
tp
m
1
=(k
tp
m
1
k
td
l
0
) (141)
The latter equality follows from the quasi-steady-state-assumption. Note that P
b
in
a batch reactor is a function of conversion. If other transfer mechanisms are pres-
ent, the denominator is extended with the corresponding contributions to the initi-
ation process. Whether or not the pp is attached to another pp indeed follows by
selecting a random number between 0 and 1 and determining whether the in-
equality rand(1) < P
b
is false or true. If connected (true) then the birth conversion
of the earlier pp simply follows from the conditional distribution (given that the
rst sampled pp is created at x = y and grows from an earlier one):
CP
i
(z[y) = z=y (142)
CP
i
is linear with z since from the perspective of the pp created at x = z its proba-
bility of undergoing transfer to polymer is simply linearly proportional to conver-
sion. This implies that all values for the birth conversion between 0 and y are
equally probable. Sampling can be performed in the same way as described for
CP
a
[Eq. (139)]. Finally, the length of the pp grown at x = u is sampled from the
weight-fraction distribution w
n
(z), Eq. (132), since any of the monomer units in
this pp can undergo branching. This then concludes the MC process at generation
0. If this generation has generated new pps attached in either way to the rst one,
the generation number is increased by one. Note that pps attached alongside the
rst pp can only become attached to pps created at higher conversion. In contrast,
the pp (created at x = z) to which (eventually) the pp sampled rst is attached by
its chain end can have further branch points created at birth conversions x > z, but
in addition it can be itself attached to a pp pp (x < z) created earlier; see Figure
9.14. The number of branch points on the pp formed at x = z also follows from
the binomial distribution, Eq. (138), but now with an average branching density
r(z; c) and a length one less than its sampled length, since one of its monomer
units already possesses a branch point (by which its is connected to the rst pp
sampled).
9.8.3
Example
We demonstrate the algorithm with the synthesis of a molecule with 10 branch
points as shown in Figure 9.15. Alongside all the pps between brackets are listed
the generation number, birth conversion, and length, respectively. The rst pp is
sampled at x = y = 0:4 and has length 300 [w
n
distribution, Eq. (132)]. It possesses
three branch points [binomial distribution, Eq. (138)]. Birth conversions of these
three pps are sampled using Eq. (139) to be: u = 0:65; 0:45, and 0.62. The lengths
of the three pps are sampled from the distribution n
n
at these conversions [Eq.
(140)]: 60, 130, and 80, respectively. The pp sampled rst turns out [using probabil-
ity P
b
from Eq. (141)] to be connected to an earlier pp. Birth conversion of this
earlier pp equals z = 0:3, as sampled from CP
i
, Eq. (142). Its length is 230 [w
n
dis-
tribution, Eq. (132)]. This nishes generation 0, which has generated four pps in
total. In the rst generation two of these pps according to Eq. (138) turn out to
(0, 0.4, 300)
(0, 0.45, 130) (0, 0.62, 80)
(1, 0.51, 60)
(2, 0.65, 100)
(0, 0.65, 60)
(1, 0.22, 180)
(1, 0.6, 110)
(2, 0.42, 80)
(0, 0.3, 230)
(1, 0.37, 140)
Fig. 9.15. Example of full Monte Carlo sampling of a branched
molecule for radical polymerization with transfer to polymer.
posses branch points: the one with u = 0:45 (one branch point) and the one with
z = 0:3 (three additional branch points). Primary polymer (0, 0.45, 130) can have
only branch points at later (>0.45) birth conversion: at u = 0:51, length 60. Pri-
mary polymer (0, 0.3, 230) can have branch points at later (>0.3) birth conversion:
u = 0:6, length 110, and u = 0:37, length 140). In addition, Primary polymer (0,
0.3, 230) turns out to be attached [Eq. (142)] to an even earlier (<0.3) pp: birth con-
version 0.22, length 180. This concludes generation 1, which generated four pps in
total. In the second generation only two of these turn out to have one extra branch
point each. After nding birth conversions and lengths for these two, the algo-
rithm stops.
9.8.4
CSTR with Transfer to Polymer [14]
The algorithm is similar to that for the batch reactor, but now the residence time
distribution (RTD) has to be taken into account, while the expressions for the (con-
ditional) probability are also slightly modied. The RTD in terms of the reduced
residence time y = t=t, where t is the average residence time, is given by:
F(y) = exp(y) (143)
In contrast to the batch reactor, here we take the reduced residence time y as the
independent variable. The y of the rst pp is sampled from this distribution [using
sampling formula Eq. (133)], while its length is chosen from the weight-fraction
distribution, w
n
, Eq. (132) [using sampling formula Eq. (133) twice and adding].
Note that in a CSTR this distribution is at steady-state. Essentially, the longer a pp
stays in the reactor, the higher its probability of receiving branch points. Stated an-
other way, the branching density in a pp is proportional to residence time y:
r(y) = ry (144)
This is consistent with Eq. (143) since:
r =
y
0
F(y)r(y) (145)
It follows from the steady-state variants of the balances of monomer and branching
density, Eqs. (135)(137), that the average branching density r is related to (steady-
state) conversion x, according to:
r = C
tp
x=(1 x) (146)
The actual number of branch points on the rst pp again follows from the bino-
mial distribution, Eq. (138). The residence time u of each of these pps that has
grown on the rst pp should be less than y, or 0 < u < y. They are sampled from
the conditional (given the connection to the pp created at y) probability:
CP
a
(u[y) = u=y; (147)
because of the linear dependence on exposure time, branching density being con-
stant. The sampling procedure is identical to that for CP
a
and CP
i
in the batch MC
algorithm. The lengths of these pps follow from the (steady-state) number-fraction
distribution, n
n
, according to Eq. (140), for the same reasons as have been ex-
plained for the batch reactor. The probability that the rst pp has itself been initi-
ated at a secondary radical site on a previously created pp is given by P
b
as formu-
lated in Eq. (141); in a CSTR P
b
is a constant. Previous here means a longer
residence time than y: y < z < y. Residence time z is sampled (as before) from a
conditional probability expression containing the RTD:
CP
i
(z[y) =
1 F(z)
1 F(y)
(148)
Sampling is easily performed by applying Eq. (143) and adding y to the value
found.
9.8.5
Comparison of Galerkin-FEM Classes Model and CSTR with Transfer to Polymer
We implemented the Monte Carlo code in MATLAB and performed simulations
for a CSTR using the kinetic data shown in Figure 9.16. For comparison, calcula-
tions with the Galerkin-FEM two- and ve-classes multiradical models were made.
For a sample of 20,000 molecules good agreement could be observed with the
Galerkin-FEM models. The CLD tail is interesting (Figure 9.17). We observe a sig-
nicant contribution of living chains to the overall concentration in both Galerkin-
FEM models. In both models transfer to polymer of living chains was included,
which in the ve-classes model yielded a considerably higher concentration of liv-
ing chains. It is the overall concentration of the ve-classes model that is most in
line with the MC simulations. We conclude that the two-classes model underesti-
mates the tail and there deviates from the MC results. The extremely large mole-
cules of the tail turned out to be very time-consuming in the MC simulations per-
formed with a code written in MATLAB (not speed-optimized). One molecule with
CL > 10
8
took a time of around 10 min (1.5 GHz Athlon CPU Processor), and the
whole population of 290,000 took several hours. Note that we applied a cut-o
limit: molecules getting beyond 2 10
5
branch points in one generation were
stopped, which happened 40 times in the whole population and led to a maximum
number of branches per molecule of around 2:6 10
6
. The Galerkin-FEM ve-
classes model converged within 30 s. Obviously, the Galerkin-FEM method is
much faster to calculate CLD only. On the other hand, MC simulations provide the
full bivariate CLD/DBD. However, it must be noted that we did not extract the full
architectural information. This would require construction of incidence matrices
[33], which probably limits calculations to around 10,000 branch points in a mole-
cule.
9.8.6
Batch Reactor, Terminal Double Bond Incorporation [15]
The problem of incorporation of chains with a terminal double bond (TDB) exists
in polymerizations discussed above, such as radical polymerization of vinyl acetate
and olen polymerization with a constrained-geometry metallocene catalyst (CGC).
Tobita [15] has developed an MC algorithm for this problem for the PVAc case. It is
assumed that TDBs are created by transfer to monomer only, while recombination
is absent, which results in a maximum of one TDB per chain. We largely follow
Tobitas explanation, but dier in that we will assume that disproportionation is
the termination mechanism, while transfer to solvent and to polymer are not yet
being accounted for. Later we will address the real PVAc problem, which in fact
has two branching mechanisms: TDB propagation and transfer to polymer.
10
0
10
2
10
4
10
6
10
8
10
10
0
0.1
0.2
0.3
0.4
0.5
Chain Length
d
w
/
d
{
l
o
g
(
M
W
)
}
Galerkin-FEM,
5-classes multiradical
Monte Carlo
Fig. 9.16. Good agreement between MC
simulations (290,000 molecules) and Galerkin-
FEM ve-classes model (all living and dead
chains). Reactor and kinetic data: initiator feed
I
2; f
= 5 10
3
kmol m
3
; monomer feed
M
f
= 16:75 kmol m
3
; residence time: t = 30
s; k
d
= 0:5 s
1
; k
p
= 1:4 10
5
m
3
(kmol s)
1
;
k
td
= 5 10
10
m
3
(kmol s)
1
; k
tp
= 2000 m
3
(kmol s)
1
; conversion x = 0:249; average
branching density r = 0:00463; average pp
length n
n
= 144; branching probability
P
b
= 0:679.
Similarly to the MC algorithm for transfer to polymer in a batch reactor, conver-
sion x is employed as the independent variable. The procedure starts in generation
0 by sampling a birth conversion y for the rst pp: 0 < y < c, where c is the end
conversion, while its length follows by sampling from the weight-fraction distribu-
tion w
n
, Eq. (132), then the average chain length n(y) is given by:
n(y) =
k
p
M(y)l
0
(y)
k
m
M(y)l
0
(y) k
td
l
0
(y)
2
=
k
p
M(y)
k
m
M(y) k
td
l
0
(y)
(149)
Now, we consider the possibility that this pp will be incorporated in a pp that
grows later, at u: y < u < c. This depends, in the rst place, on the probability
that the rst pp, grown at x = y, possesses a TDB:
P
TDB
(y) =
k
m
M(y)l
0
(y)
k
m
M(y)l
0
(y) k
td
l
0
(y)
2
=
k
m
M(y)
k
m
M(y) k
td
l
0
(y)
(150)
In the second place, we have to know which fraction of the pps with a TDB grown
at x = y will actually be incorporated as conversion increases, since together with
10
6
10
7
10
8
10
9
0
0.005
0.01
0.015
Chain Length
d
w
/
d
{
l
o
g
(
M
W
)
}
Monte Carlo
GF-2, living
GF-5, living
GF-5, dead
GF-2, dead
GF-2
GF-5
Fig. 9.17. Tail of the CLD of Figure 9.16. At
chain lengths > 10
7
living chain concentra-
tions become of the same order of magnitude
as dead chains. The Galerkin-FEM two-classes
model (no multiradicals) underestimates the
tail. The rapid decline of the MC curve at
3 10
8
is due to the cut-o procedure.
P
TDB
(y) this determines the probability of the randomly chosen pp at x = y becom-
ing connected to a later pp. We should consider what happens to pps with a TDB
after their creation at x = y. A fraction of them is incorporated, but as the rate
at which this happens depends on their concentration, this rate will decrease. In
fact, the fractional decrease of these pps exactly follows the decrease in the fraction
of TDBs of pps created at x = y. The TDB mole-fraction, F
TDB
(y; u), starts at
C
m
= k
m
=k
p
for all birth conversions, so also at x = y, while it decreases according
to the balance describing the TDB consumption starting from y:
dF
TDB
(y; t)
dt
= k
p; TDB
l
0
(t)F
TDB
(y; t) (151)
With Eq. (135) this is transformed in terms of birth conversion u (y < u < c),
giving:
dF
TDB
(y; u)
du
=
C
p; TDB
F
TDB
(y; u)
1 u
; (152)
where C
p; TDB
= k
p; TDB
=k
p
. By integration between y and c one obtains:
F
TDB
(y; c) = C
m
1 c
1 y

Cp; TDB
(153)
Thus, we see that at x = c a fraction
1 c
1 y

Cp; TDB
of TDB chains is still present.
Or, the probability that such pps created at x = y have reacted at x = c to produce
a branch point equals one minus this fraction. The overall probability P
b; TDB
(y; c)
of a randomly chosen pp(y) to be incorporated in a later pp(c) thus becomes that
given by:
P
b; TDB
(y; c) = P
TDB
(y) 1
1 c
1 y

Cp; TDB
( )
(154)
Whether or not it is connected follows by the checking of the inequality rand(1) <
P
b; TDB
(y; c). Now, the birth conversion u at which incorporation takes place has to
be determined. This is realized by using the conditional probability distribution in
u, CP
a; TDB
(u[y), over the interval y to c, namely given that the pp has reacted
during the interval represented by the fraction
1 c
1 y

Cp; TDB
:
CP
b; TDB
(u[y) =
P
b; TDB
(y; u)
P
b; TDB
(y; c)
= 1
1 u
1 y

Cp; TDB
( )
1
1 c
1 y

Cp; TDB
( ) , # "
(155)
Sampling proceeds in the same manner as discussed in the cases with transfer to
polymer [see Eq. (139)]. Connectivity in generation 0 can also occur, when the pp
sampled rst itself incorporates pp chains with a TDB during its growth at x = y.
Obviously, such chains should have been created at birth conversions z before y;
hence 0 < z < y. The probability of receiving branch points in this way in fact
equals the instantaneous branching density r
TDB
(y), which is given by the ratio of
TDB propagation to monomer propagation rate:
r
TDB
(y) =
k
p; TDB
l
0
(y)n
TDB
(y)
k
p
(1 y)M
0
l
0
(y)
=
C
p; TDB
n
TDB
(y)
(1 y)M
0
(156)
Here, n
TDB
(y) is the average concentration of TDBs in the reactor, which follows
from a TDB balance (production and consumption):
dn
TDB
(t)
dt
= k
m
M(t) k
p; TDB
l
0
(t)n
TDB
(t) (157)
With Eq. (135) and M = M
0
(1 y), it follows that:
dn
TDB
(y)
dy
= C
m
M
0

C
p; TDB
n
TDB
(y)
1 y
; (158)
which yields Eq. (159) by integration:
n
TDB
=
C
m
M
0
1 y (1 y)
Cp; TDB
C
p; TDB
1
(159)
With this Eq. (133) becomes:
r
TDB
(y) =
C
p; TDB
C
m
1 (1 y)
C
p; TDB
1
(C
p; TDB
1)
(160)
Given the length of the pp rst sampled and r
TDB
(y), the number of branch points
can be sampled from a binomial distribution, Eq. (138), using a standard binomial
distribution random number generator. This yields a certain number of branch
points connecting the pp to the same number of pps formed earlier, of which birth
conversion and lengths have to be determined. The former follows from the condi-
tional probability that a pp created between 0 and z (0 < z < y) is connected to the
pp growing at x = y, CP
i
(z[y). This probability is proportional to the mole fraction
of TDBs on pps created between 0 and z still present at x = y. The average TDB
mole fraction of these pps at x = y follows from Eq. (153) by integration between
0 and z:
F
TDB
(z; y) =
1
y
z
0
F
TDB
(z; y) dz (161)
Thus, the normalized CP
i
(z[y) becomes:
CP
i
(z[y) =
1
y
z
0
F
TDB
(z; y) dz
1
y
y
0
F
TDB
(z; y) dz
=
1 (1 z)
1Cp; TDB
1 (1 y)
1Cp; TDB
(162)
Conversion births z are determined by sampling as described previously. The
shape of Eq. (162) prescribes that on average z is found to be closer to y than to
0, reecting the fact that pps generated early have a high chance of being incor-
porated by pps earlier than y. The lengths of the pps are sampled from the
number-fraction distribution in the usual manner [Eq. (133)]. This then concludes
generation 0, and the procedure is repeated for higher generations until no more
connections are found.
9.8.7
CSTR, Terminal Double Bond Incorporation
The greatest dierence from the batch reactor is again the taking into account of
the RTD according to the exponential form of Eq. (143). The residence time t (or
reduced RT x = t=t) is taken as the independent variable. The algorithm starts
with the sampling of x and the determination of the length from w
n
with n(y) after
Eq. (149) and the double sampling after Eq. (134). The pp sampled rst may
through its eventual TDB become connected to a pp that starts growing after the
rst one, hence having an RT shorter than x. Similarly to the batch reactor, the
probability of this connectivity is the product of P
TDB; c
, the probability of a ran-
domly chosen pp having a TDB, and a factor denoting the decrease of TDB fraction
F
TDB
due to TDB incorporation. P
TDB; c
follows from Eq. (150), but is a constant in
the CSTR case. The TDB fraction must be considered as a function of residence
time, F
TDB
(t), with starting value F
TDB
(0) = C
m
, as transfer to monomer is the
only source of TDBs. The balance equation for F
TDB
(t):
dF
TDB
(t)
dt
= k
p; TDB
l
0
F
TDB
(t), (163)
which is similar to Eq. (151), with the starting condition, the steady-state equality:
l
0
=
x
k
p
t(1 x)
; (164)
and the denition of the reduced RT leads to:
F
TDB
(x) = C
m
exp C
p; TDB
x
1 x

x
& '
; (165)
This time, the exponential term describes the decline of unreacted TDB with resi-
dence time x; hence one minus this term denotes the fraction of pps having gener-
ated a connection as a function of x. Thus, the probability of an arbitrary pp being
connected as a function of x becomes:
P
TDB
(x) = P
TDB; c
1
F
TDB
(x)
C
m
& '
(166)
The residence time u, 0 < u < x, of the pp connected has to determined next. It
simply follows from the conditional (given that its TDB has reacted) probability
CP
a
(u[x):
CP
a
(u[x) =
P
TDB
(u)
P
TDB
(x)
(167)
The chain length of this pp follows from w
n
.
9.8.8
Incorporation of Recombination Termination [14]
Recombination termination is implemented in the same way in the batch reactor
and in the CSTR. First to note is that termination through recombination happens
to two pps growing simultaneously, which implies that birth conversions or resi-
dence times are identical for the two. The algorithm starts with a check on which
of the new pps created in a certain generation by some mechanism is connected to
another one by recombination. This probability is obtained from the relative reac-
tion rates; for example, in the case of transfer to polymer only:
P
tc
= k
tc
l
2
0
=(k
tc
l
2
0
k
td
l
2
0
k
tp
m
1
l
0
) = k
tc
l
2
0
=(k
tc
l
0
k
td
l
0
k
tp
m
1
) (168)
When recombination is at hand (rand(1) < P
tc
), determination of the birth conver-
sion or residence time is performed in no other way, as before. The total length of
the two pps connected can be found by sampling once from w
n
and once from n
n
,
and addition. The correctness of this can be understood by realizing that the sec-
ond pp can be connected to the rst one only by one chain end.
9.8.9
Incorporation of Random Scission, Linear Chains, Batch Reactor [50]
Here we will follow Tobitas explanation of the MC algorithm for radical polymer-
ization with random scission for nonbranched systems, though it includes recom-
bination termination. Later, the link to branching by transfer to polymer will be
elucidated. Random scission is assumed to happen to dead chains breaking into a
living and a dead fragment. The living fragment starts growing again and will be
terminated by some mechanism such as recombination. This implies that a scis-
sion point acts as an initiation point for a new pp, which further obeys the same
growth statistics as pps growing from initiator radicals or secondary radical sites on
other pps. Scission and subsequent growth may occur several times to pp chains,
so nally they may be constructed of various segments, created at various times.
The construction process of pps undergoing scission and growth steps is de-
picted schematically in Figure 9.18 for the case of a batch reactor. The algorithm
starts by randomly sampling a birth conversion y
0
of Seg-0, the rst pp sampled,
between 0 and end conversion c. For this rst pp we may arbitrarily choose its
growth direction: to the right in Figure 9.18. Now in principle, the length of Seg-0
is sampled from w
n
by sampling twice from n
n
, but this is not denitively the value
it nally will get, since scission may occur. Therefore, the connecting unit between
these two is explicitly considered as the initially selected monomer unit. Next, the
part to the right of this unit is examined and a check is made on whether scission
has taken place. To this end the scission density h (or scission probability of mono-
initially selected unit
Seg-2 Seg-2 Seg-1 Seg-0
P
tc
P
rs
recombination
scission
) | (
0 2 ,rs i
CP
) | (
0 1 ,rs a
CP
end conversion
0
1
b
i
r
t
h

c
o
n
v
e
r
s
i
o
n

Chain length
initiation from
initiation from
scission at
scission at
scission
1
scission
Fig. 9.18. Example of the construction of a linear pp chain
undergoing scission and recombination in radical polymeriza-
tion. The square on the LHS marks the (non-scission) initiation
point of this chain at birth conversion y
2
.
mer units) is dened; its derivation exactly follows that of the branching density in
the case of transfer to polymer. Realizing that
dh
dt
= k
rs
l
0
(t) (169)
and applying Eq. (135), we nd
h(y
0
; c) = C
rs
ln
1 y
0
1 c

(170)
where C
rs
= k
rs
=k
p
, which is similar to Eq. (137). It has been demonstrated [51]
that for equal scission probability h(y
0
; c) of all monomer units in a chain the
number average of fragments equals 1=h(y
0
; c), while its length distribution is
Flory [Eq. (171)].
n
s
n
(y
0
; c) = h(y
0
; c) exph(y
0
; c)n (171)
The scission check can now be performed by comparing the RHS of Seg-0,
n
n
(y
0
; c) from Eq. (140) with n
s
n
(y
0
; c): if n
n
(y
0
) > n
s
n
(y
0
; c), scission has taken
place, otherwise it has not. Given that scission has taken place, the birth conver-
sion y
1
(> y
0
) at which scission takes place is determined by the expression for
the conditional probability distribution, Eq. (139) in view of the similarity be-
tween branching and scission. If scission has taken place, then the probability is
1
2
that the chain end forms the initiation site for a new pp Seg-1 with growth direc-
tion to the right, while its length is sampled from n
n
(y
1
). Seg-1 is checked for scis-
sion using Eqs. (139) and (171). If scission did not happen, termination has taken
place to this segment. It is connected to a further pp by recombination with prob-
ability P
tc
[Eq. (168)]; but in Figure 9.18 it is not connected, so Seg-1 is a terminal
segment at the RHS of the initially selected unit.
Next, the chain part in the direction left of the initial unit on Seg-0 is considered.
Its length is again determined by checking whether scission has taken place [com-
paring lengths from Eqs. (139) and (172)]. If not, then the chain end represents an
initiation site. The probability P
rs
that this is a site following a scission at y
0
is
given by the rate of scission relative to the other reaction rates (compare Eq. (141)
for the branching probability P
b
):
P
rs
(y
0
) =
k
rs
l
0
(y
0
)m
1
(y
0
)
k
rs
l
0
(y
0
)m
1
(y
0
) 2k
d
I
2
(y
0
)
=
k
rs
m
1
(y
0
)
k
rs
m
1
(y
0
) (k
td
k
tc
)l
0
(y
0
)
(172)
Figure 9.18 shows the situation where Seg-0 has grown at a scission point on Seg-
2
/
after scission of the latter at birth conversion y
2
< y
0
, to be selected as a random
number between 0 and y
0
. The growth direction of Seg-2
/
has then to be selected.
There is a probability of
1
2
that it is in the direction indicated, to the LHS. Its length
is determined by comparing lengths with Eqs. (139) and (171). In this case no scis-
sion took place, and hence the possibility of termination by recombination must be
checked, using Eq. (168). Recombination happened to Seg-2
//
, also created at y
2
.
On checking whether scission occurred, this turned out to be not the case, and
thus Seg-2
//
becomes the other terminal end, at the LHS of the initial unit. Note
that the RHS of the pp rst sampled, Seg-0, if it had not undergone scission, might
have been connected to another segment by recombination. Then, the algorithm
would have followed the same lines as for Seg-2.
9.8.10
Combined Scission/Branching
The combined scission/branching algorithm starts in generation 0 with the scis-
sion procedure. Once the linear chain eventually consisting of several segments
with dierent birth conversions has been constructed, the numbers of branch
points on these various segments are determined using the binomial distribution
[Eq. (138)] with the proper branching densities and lengths. To determine whether
scission has taken place on the pps connected via these branch points, the RHS
part of the scission algorithm has to be employed. Eventually, scission did not
take place, and then the check for recombination should be performed. Now, the
terminal at the RHS of the initially selected unit (Seg-1 in Figure 9.18) is always a
free end, so it is never connected. In contrast, the terminal at the LHS has been
assessed as a initiation site not being created by scission. Hence, this site may
have been created either by an initiator radical or at a dead pp backbone by transfer
to polymer, with probability P
b
from Eq. (141). If it is connected to a pp at a smaller
birth conversion (u < y
2
in Figure 9.18), then the scission algorithm is fully re-
peated with the connection point as the initially selected unit. This concludes gen-
eration 0.
9.8.11
Scission in a CSTR
As usual in a CSTR, the independent variable is residence time: in the example of
Figure 9.18, y
0
for Seg-0. Now, the average scission density h is a constant; follow-
ing by a similar argument to that for branching [Eq. (146)] gives:
h = C
rs
x=(1 x) (173)
For individual pps the scission density is a function of residence time (compare Eq.
(144) for branching density):
h(y) = hy (174)
The RTD itself follows Eq. (143). Knowing h(y
0
), the scission check can be made by
comparing lengths from Eqs. (139) and (171). Given that scission has taken place
on the RHS of Seg-0, the shorter residence time y
1
(0 < y
1
< y
0
) at which scission
takes place is determined by a similar expression (Eq. (147)) to that for branching,
giving the conditional scission probability distribution:
CP
a; rs
(y
1
[y
0
) = y
1
=y
0
(175)
The LHS part of the branching algorithm is also slightly modied. The probability
P
rs
of Seg-0 being started on a scission point at Seg-2
/
again follows from Eq. (172),
but it is constant in a CSTR. The residence time y
2
, now longer than y
0
, is sampled
from a conditional probability distribution similar to Eq. (148):
CP
i; rs
(y
2
[y
0
) =
1 F(y
2
)
1 F(y
0
)
(176)
9.9
Prediction of Branched Architectures by Conditional Monte Carlo Sampling
9.9.1
Introduction
Except for the full Monte Carlo simulations, all of the previously described mathe-
matical methods were meant to compute microstructural properties in terms of
countable quantities: number of monomer units (chain length), number of branch
points, and so on. However, when dealing with branched polymer molecules, the
connectivity structure, or topology, is a highly important issue for both character-
ization and properties of branched polymers. It is obvious that, given the number
of monomer units and branch points in a molecule, a high variability exists in to-
pology. This section is devoted to prediction methods of branched architectures.
We present two methods, both based on conditional Monte Carlo sampling, the
rst applicable to radical polymerization with transfer to polymer, the second to
metallocene-catalyzed polymerization of polyolens. Both are applicable to CSTRs
only. Note that the full Monte Carlo method described previously also generates in-
formation on connectivity. It has as such been utilized to predict radii of gyration
[1115, 4851] for radical polymerization systems. In principle, this method can
be extended to other polymerization systems as well. However, conditional MC
methods take full advantage of the fact that it is often much easier to nd the
CLD/DBD, which then makes it possible to focus directly on the more interesting
large molecules with many branch points.
Although topology is less easy to quantify than countable microstructural proper-
ties, highly interesting properties can still be inferred that provide direct character-
izations of branched structures. One of these is the well-known radius of gyration,
and another is a recently introduced topological characterization originating from
rheology: the bivariate seniority/priority distribution [52]. Here, methods will be
described to obtain radius of gyration and seniority/priority values from architec-
tures as synthesized by the algorithms to be described. In all cases architectures
will be represented in descriptive matrices from graph theory [53].
9.9.2
Branched Architectures from Radical Polymerization in a CSTR
For a given combination of chain length and number of branch points (n; N) a
great number of molecular topologies is possible, but the specic chemistry of
radical polymerization leads to a specic probability distribution of topologies.
The synthesis algorithm [33] generates this distribution. Like the full MC method
it is based on the primary polymers (pps) being the linear constitutive elements of
branched molecules (Figure 9.19). A molecule with N branch points is composed
of N 1 pps. The length distribution of pps (Flory) follows in much the same way
i < N i < N+1
End: Architecture
Scission
pp
1
pp
2
pp
3
pp
4
Connection
algorithm
N
Y
Architecture
Start: Seletion of n, N combinations from 3-D n-N-
concentration distribution (Galerkin-FEM)
Selection of N+1 primary
polymers from Flory distribution
Sampling of monomers on pps to determine
time order: pp
1
, pp
2
, pp
3
, ..., pp
N+1
.
Start with pp
1
Connection algorithm: connects
pp
i
to structure containing pp
1...i-1
fragment length
distribution
Rheology:
Seniority/
Priority
Radius of
gyration
Fig. 9.19. Synthesis algorithm for branched architectures in
radical polymerization. Right: algorithm ow diagram. Upper
left: connection of primary polymers. Lower left: a resulting
architecture with specied connectivity structure and lengths
between segments.
9.9 Prediction of Branched Architectures by Conditional Monte Carlo Sampling 503
as in the full MC method [Eq. (140)]. Note that pps are attachable to other ones by
only one terminal. The mechanism making pps attachable at two ends is termina-
tion by recombination, but for the time being this will not be considered. The
method allows for the fact that pps may undergo scission. Note nally that a pri-
mary polymer may carry several branch points. The population of pps thus pro-
duced possesses a length distribution that is controlled by the chemistry of the
system.
The rst step of the algorithm is sampling N 1 pps from the calculated distri-
bution, which is realized by selecting N numbers n
i
at random in the interval
1 < n
i
< n. This generates N 1 intervals 1 n
1
, (n
1
1) n
2
; . . . ; (n
N1
) n
N
;
(n
N
1) n, representing the desired pp lengths. Thus, a length distribution is
obtained that approximates to a Flory distribution for large N and n [33].
The next step is nding the growth time sequence of pps in the molecule to be
composed. This determines which pp may have grown from which other already
existing pp. Notice that pp growth may be regarded as instantaneous in this radical
system. Now, the time order in which pps are sampled is not independent of their
length, since more possibilities exist of attaching smaller pps to a longer one than
of attaching longer pps to a smaller one. This implies that the longer pps of a
molecule, on average, are created before the short ones. In the algorithm, the
early-time preference of long pps is realized by sampling of monomer units on
pps. This is performed by selecting a random number between 1 and n and deter-
mining its location on the sequence of N 1 segments used for pp length sam-
pling. This is the pp rst in time order. It is removed from the sequence and the
sampling is repeated for the remaining segments until the complete time order is
determined.
The connection part of the algorithm is simple after the time order has been de-
termined; see Figure 9.19. The second pp selected is attached to pp
1
; the third may
be attached to pp
1
and pp
2
, and so on. The algorithm accounts for the fact that a
pps probability of receiving a branch point is proportional to its length, which re-
ects branch formation by transfer to polymer. Furthermore, it accounts for the
pps dierences in residence time. A pp early in time order meaning a pp with a
long residence time has a higher chance of receiving branch points than a later
pp. This implies that branch point distribution is heterogeneous, since pps with a
longer residence time possess a higher branching density. However, this is coun-
teracted by the circumstance that within a molecule the pps early in time order
are longer on average. Note further that within a molecule, longer pps are associ-
ated with longer residence times, although obviously within the whole pp popula-
tion in a CSTR no such relationship exists. We should realize here that the sit-
uation for a batch reactor might be dierent. When conditions change in a batch
reactor, the pp length distribution might also change, which should be accounted
for in the sampling procedure. The present algorithm is strictly applicable to a
CSTR, since it assumes one (steady-state) pp length distribution. The algorithm
generates topologies accounting for all the important chemical and reactor condi-
tions inuencing them: the specic n; N combination, pp length distribution, and
coupling procedure representing transfer to polymer. The specic population of
architectures this produces indeed has properties dierent from those exhibited by
the population of all possible architectures [33].
9.9.3
Branched Architectures from Polymerization of Olens with Single and Mixed
Branch-forming Metallocene Catalysts in a CSTR [35]
A polymer with length n and N branches may assume a large number of architec-
tures. Due to the statistical nature of chemistry the architectures may feature large
dierences. We developed a Monte Carlo method virtually synthesizing the poly-
mer according to the proper kinetic rules, which reects the chemistry of the pro-
cess. We rst discuss a method for a single-catalyst system, which is essentially
simpler than the method for a mixed system that will be presented next. Flow dia-
grams are shown in Figure 9.20.
9.9.3.2 Single-catalyst System
In this case the method is based on the separation of the synthesis activities con-
cerning topology and segment lengths. It will be shown next that the topology is
created by a series of insertion events, during which structures with certain num-
bers of branch points are coupled. The probabilities of existence of these structures
are only determined by the numbers of branch points they carry, not by the lengths
of these segments. We can see this by realizing that in the single-catalyst system all
chain segments in a molecule of given n and N should obey the same statistics,
since all of them have grown under the same kinetic conditions. This fact implies
that interchanging any pair of segments does not aect the probability of existence
of a structure as long as it retains the same topology. For a complete architecture
this argument is equally valid. As long as the topology is the same and as long as
the total number of monomer units is constant, all molecules are equally probable.
This implies that we can determine rst the topology and afterward the length of
the segments.
9.9.3.3 Synthesis of Topology
In order to determine the topology of a molecule, as a rst step of the algorithm we
consider the rst insertion of a terminally double-bonded polymer structure into a
growing chain attached to the branching catalyst. The number of branch points on
the inserted chain, N
1
, and the number of branch points on the growing chain (to
be formed after the rst insertion) must add up to N 1. The situation is depicted
in Figure 9.21. Note that with a single catalyst, at steady state in a CSTR, the statis-
tical properties of the inserted chains and growing chains are identical. Insertions
are possible in N 1 dierent ways, each way having its own probability. These
probabilities can be calculated from the two-dimensional chain length/number of
branch points distribution using the following arguments. The frequency of inser-
tion of a species with a terminal double bond is proportional to its concentration.
Therefore, the insertion probability of a polymer chain containing a certain num-

Start
N
N
1
> 0 N
1
N
2
> 0 N
2
Update of topology
(connectivity matrix)
Final topology
(adjacency matrix)
Full incidence matrix
2N + 1 segment
lengths
Segment length
algorithm
Start
N, n
Full architecture
Rheology Radius of gyration
N = N
1
N = N
2
y
n
n
y
Sampling N
1
N 1 from
N
2
= N N
1
(eq 178) ) (
1
b
N P N
Start
N
N
1
> 0
1
N
2
> 0
2
Update of architecture
(connectivity matrix)
N = N
1
N = N
2
Full architecture
Rheology Radius of gyration
y
n
n
y
Sampling N
1
N 1 from
N
2
= N N
1
(eq 183) ) ( ,
1
b
N n P N
Sampling n
1
n 1 from
n
2
= n n
1
(eq 181, for N
1
selected) ) , ( ,
1 1
P N n
b
N n
Sampling k n n
1
-1 from
(eq 184) ) ( 1 ,
1 1
b
N N n n P k
1
,
b
N
f o

b

b
m
,
Fig. 9.20. Flow diagrams of synthesis algorithm for branched
architectures from metallocene-based polymerization. Left:
single-metallocene system. Right: two-catalyst system.

N
1
?
=
N
1
N- N
1
- N- N
1
-1
=
D
ir
e
c
ti
o
n
o
f
g
r
o
w
t
h
N
1
, n
1
N- N
1
-1, n -n
1
-k -1
=
1
=
k
Structure being inserted,
from either catalyst
B
r
a
n
c
h
i
n
g

c
a
t
a
l
y
s
t
Linear
segment
on branching
catalyst
D
ir
e
c
tio
n
o
f g
r
o
w
th
Structure to grow on
branching catalyst
Structure being inserted
B
r
a
n
c
h
i
n
g

c
a
t
a
l
y
s
t
Structure to grow on branching
catalyst
Fig. 9.21. Synthesis algorithm for branched architectures from
metallocene-based polymerization. Left: single-metallocene
system. Right: two-catalyst system.
ber of branches is proportional to that structures concentration Therefore, the
insertion probability of a polymer chain containing a certain number of branch
points, say N
1
, should be proportional to the concentration of chains with N
1
branch points. However, the probability of insertion of a chain with N
1
branch
points is not the only factor playing a role. Additionally we need to know the prob-
ability of the growing chain, after the rst insertion, obtaining precisely that num-
ber of branch points to arrive at N branch points in total: N N
1
1. Now, during
the growth process of a polymer chain, the probability that after the rst insertion
it will receive this particular additional number of branch points is independent of
its growth history. This means that it is independent of whether it grows after the
rst, second, or any other insertion, and it also is independent of the number of
branch points on chains previously inserted. Therefore, the probability that the
polymer will grow to obtain the N N
1
1 additional branch points is simply pro-
portional to the concentration of such chains. Hence, under the condition that a
polymer with N branch points is formed, the probability of a rst insertion with
N
1
branch points equals the normalized product of the concentrations of polymers
with a terminal double bond and N
1
branch points and polymers with N N
1
1
branch points. For the formation of polymers with a terminal double bond this
leads to the conditional branch point probability density function (PDF):
1(N
1
) [ P
N
=
P
N1
P
N1N1
X
N1
j =0
P
j
P
N1j
with P
N
=
X
y
n=1
P
n; N
(177)
Note that here P
n; N
represents the concentration at the branching catalyst CGC
Ti, P
b
n; N
. In this case in the absence of linear catalyst, P
n; N
= P
b
n; N
. For a chain
without a terminal double bond, the branch point probability density function (N-
PDF) is modied to:
1(N
1
)[P
N
=
P
N1
P
N1N1
X
N1
j =0
P
j
P
N1j
(178)
The PDF of Eq. (178) expresses the probability of an insertion of a chain with N
1
branch points under the condition that a polymer with N branch points and a ter-
minal double bond is formed. This formula is symmetrical by denition. It turns
out that this PDF (apart from round-o errors) is identical to the PDF dened in
Eq. (177). This is due to the kinetics of the system, which allows the concentration
of polymers with a terminal double bond to be written as a fraction of the concen-
tration of polymers without terminal double bonds [35], as formulated in:
P
n; N
P
n; N
= c (179)
with c as an arbitrary constant.
The PDF 1(N
1
)[P
N
is a symmetric distribution with peaks at N
1
= 0 and
N
1
= N 1. This implies that the probability of inserting a chain with zero or
N 1 branch points is much higher than that of chains with and intermediate
number of branch points. Once the number of branch points on the chain inserted
is known, the problem is divided into two smaller sub-problems. The architecture
of the inserted chain with N
1
branch points as well as the architecture of the grow-
ing chain with N 1 N
1
branch points must be determined. For both the in-
serted and the growing chain the same line of reasoning can be used as above for
a smaller number of branches, N
1
and N N
1
1, respectively. In our algorithm
the procedure described above in a recursive manner continues until no more
structures with branch points have to be attached. Then the topology is known.
The lengths of the segments are determined in exactly the same manner as for
the radical polymerization case. Note, however, that with N branch points we here
have 2N 1 segments.
9.9.3.4 Mixed-catalyst System
The synthesis of architectures in this case has similarities to, but also marked
dierences from, that of the single-catalyst case. Notice that although the mixed
system algorithm is constructed to deal with those systems, it obviously should be
able to describe the single catalyst correctly as a limiting case as well. In the latter
case both algorithms should lead to the same results. Again, the procedure starts
at the most recent insertion (Figure 9.21) of a branched structure into a growing
structure. Now, the main dierence from the single-catalyst case is that separation
of topology and segment length distribution is no longer possible. This is due to
the fact that in the mixed-catalyst case segments originate from two dierent cata-
lysts and therefore possess dierent statistical properties. This also implies that the
interchange of arbitrary pairs of segments is not allowed now. Hence, the assign-
ment of lengths to segments can no longer be performed in an independent way
and has to be included in the topology generation procedure. This means that for
the structure to be inserted we have to specify both the number of branch points
N
1
, and the chain length n
1
. Note that the inserted structures originate from both
linear and branching catalyst and therefore have mixed statistical properties. The
insertion of a structure can be realized in many dierent ways. The probabilities
of these dierent options follow from the bivariate chain length/number of branch
points distribution in a manner to be explained next. The insertion probability of
a polymer chain containing a certain combination of number of branch points N
1
and chain length n
1
is proportional to this structures concentration: 1
i(nsertion)
=
P
n1; N1
. Note that this concentration includes chains from both catalysts: P
n1; N1
=
P
b
n1; N1
P
l
n1
. Again, knowing these probabilities, 1
i
alone is not sucient to deter-
mine the probabilities of all the dierent options. Additionally we need to know
the probability of the growing structure possessing precisely that number of
branch points to obtain N branch points and n monomer units in total, 1
g(rowing)
.
Now, for a given N
1
and n
1
, several versions of the growing structure can satisfy
this condition, since the insertion can take place at various positions. We denote
this position as the length k of the linear segment between the catalyst site and
the insertion point. The value of k may vary between 2 and n n
1
2, while each
insertion option has its own probability. The sum of all these probabilities yields
the desired growing structure probability, 1
g
. The individual probability for a cer-
tain k should be proportional to the probability of nding a linear segment (zero
branches) with length k at CGCTi, and hence the concentration P
b
k; 0
. In addition,
it should be proportional to the probability of nding a branched structure with
N N
1
1 branch points and length n n
1
k, the concentration P
b
nn1k; NN11
.
Thus, the growing structure probability 1
g
follows as the sum of products:
1
g
=
P
nn11
k=1
P
b
k; 0
P
b
nn1k; NN11
. Again, this can only be done when assuming that
at each time instant the probability of future growth of a structure is completely
independent of its growth history. Hence, under the condition that a polymer
with N branch points and n monomer units is formed, the probability of a rst
insertion with N
1
branch points and n
1
monomer units equals the normalized
product of the probabilities 1
i
and 1
g
. For chains with a terminal double bond
this leads to the bivariate chain length/number of branch points probability density
function (n; N-PDF):
1(n
1
; N
1
)[P
b
n; N
=
P
n1; N1
X
nn11
k=1
P
b
k; 0
P
b
nn1k; NN11
X
n2
i=1
X
N1
j =1
P
i; j
X
ni1
k=1
P
b
k; 0
P
b
nik; Nj1
(180)
The n; N-PDF for chains without TDB likewise is:
1(n
1
; N
1
)[P
b
n; N
=
P
n1; N1
X
nn11
k=1
P
b
k; 0
P
b
nn1k; NN11
X
n2
i=1
X
N1
j =1
P
i; j
X
ni1
k=1
P
b
k; 0
P
b
nik; Nj1
(181)
Again, due to the similarity between the distributions of chains with and without
TDBs [Eq. (179)]. The PDFs possess the same shape. Now, it is instructive to derive
monovariate N-PDFs from the n; N-PDFs. Doing this for the single-catalyst case
should then generate N-PDFs identical to the monovariate N-PDFs as obtained
from the single catalyst algorithm. The N-PDF describing the probability that a
structure with N
1
branch points will be inserted to form a molecule with N branch
points in total is obtained from the n; N-PDF by taking the sum over chain lengths
n
1
:
1(N
1
)[P
b
n; N
=
X
n1
n1=1
1(n
1
; N
1
) [ P
b
n; N
(182)
One may realize that this can be performed for various total chain lengths n. This
implies that in principle this N-PDF 1(N
1
) [ P
b
n; N
is still a function of n. Now, the
monovariate N-PDF created by the single-catalyst algorithm, 1(N
1
) [ P
b
N
, does not
depend on n. A clearly interesting test for the mixed system algorithm is to check
whether it indeed yields an n-independent N-PDF for the single-catalyst system,
which turns out to be the case.
Equations (181) and (182) give the PDFs describing the probability of having
a rst insertion of a branched structure with n
1
monomer units and N
1
branch
points. Hence, this rst step in the algorithm should provide n
1
and N
1
. The
sampling from the bivariate distribution proceeds in two sub-steps. First, N
1
is
sampled from the monovariate N-PDF derived from the bivariate n; N-PDF as de-
scribed above. Secondly, for the sampled N
1
a chain length PDF is extracted from
the full bivariate n; N-PDF as the cross-section at N
1
. From this n-PDF the n
1
is
sampled. The rst step of the algorithm is completed by determining the length
of the linear segment, k. This is realized by sampling from the PDF that describes
the probability of nding such a linear segment of length k. This probability was
already introduced above as being proportional to both the concentration of these
linear segments P
b
k; 0
and the concentration of the complementary branched struc-
tures P
b
nn1k; NN11
. Hence, sampling proceeds from the PDF being formed by
the normalized product of the two concentrations:
1(k)[P
b
nn1; NN11
=
P
b
k; 0
P
b
nn1k; NN11
X
nn11
k=2
P
b
k; 0
P
b
nn1k; NN11
(183)
After the last insertion as the rst step in the algorithm the problem is split into
two sub-problems, the tasks of nding the architectures of the inserted structure
and that of the growing branched structure. These tasks proceed in exactly the
same manner as the rst step and they may each lead to further architecture-
nding steps. For instance, nding the architecture of the inserted chain involves
the derivation of the n; N-PDF 1(n
2
; N
2
)[P
b
n
1
; N
1
. The procedure described above in
a recursive manner continues until no more structures with branch points have to
be attached. Notice that at that instant of time in contrast to the single-system
algorithm not only the topology is known, but also the segment lengths, and
hence the architecture synthesis process is fully complete.
9.9.4
Mathematical Methods for Characterization of Branched Architectures
9.9.4.1 Graph Theoretical Connectivity Matrices
Branched topologies as generated by the conditional Monte Carlo methods de-
scribed in this section are most conveniently represented in matrix forms from
graph theory [33, 53]. We name two of them the adjacency matrix A and the inci-
dence matrix C (see Figure 9.22). They both describe connectivity. Note that in
1
2
3
10
7
5 6
1
2
3
4
5
6
7
8
9
10
1
2
3
Caylee tree
Comb
N = 10
a
b
c
d
e
f i
a
b
c
d
e
f
g
h
i
10
9
8
7
6
5
4
3
2
1
10
9
8
7
6
5
4
3
2
1
10 9 8 7 6 5 4 3 2 1 10 9 8 7 6 5 4 3 2 1
comb
Cayley tree
. 1 . . . . . . . .
1 . 1 . . . . . . .
. 1 . 1 . . . . . .
. . 1 . 1 . . . . .
. . . 1 . 1 . . . .
. . . . 1 . 1 . . .
. . . . . 1 . 1 . .
. . . . . . 1 . 1 .
. . . . . . . 1 . 1
. . . . . . . . 1 .
A
. . . . . . 1 . . .
. . . . . . 1 . . .
. . . . . . . 1 . .
. . . . . . . 1 . .
. . . . . . . . 1 .
. . . . . . . . 1 .
1 1 . . . . . . . 1
. . 1 1 . . . . . 1
. . . . 1 1 . . . 1
. . . . . . 1 1 1 .
A

10
9
8
7
6
5
4
3
2
1
C
10
9
8
7
6
5
4
3
2
1
C
i h g f e d c b a i h g f e d c b a
comb Cayley tree
1 . . . . . . . .
1 1 . . . . . . .
. 1 1 . . . . . .
. . 1 1 . . . . .
. . . 1 1 . . . .
. . . . 1 1 . . .
. . . . . 1 1 . .
. . . . . . 1 1 .
. . . . . . . 1 1
. . . . . . . . 1
1 . . . . . . . .
. 1 . . . . . . .
. . 1 . . . . . .
. . . 1 . . . . .
. . . . 1 . . . .
. . . . . 1 . . .
1 1 . . . . 1 . .
. . 1 1 . . . 1 .
. . . . 1 1 . . 1
. . . . . . 1 1 1

4
9 8
g h
= =
= =
Fig. 9.22. Branched topologies of molecules with N = 10
branch points (terminal segments not shown). Extreme cases:
Cayley tree and comb. Adjacency and incidence matrices, A and
C of the topologies shown, are represented below.
addition to C, a vector of segment lengths corresponding to the segments in the
vector a; b; c; . . . completes the architectural information. The mathematical
methods for characterization to be discussed here are designed in such a way that
they utilize either of these two representations as input.
9.9.4.2 Characterization of Architectures by Radius of Gyration
Molecular architectures can be structurally classied as being more comb-like or
Cayley tree-like. Structure has impact on the radius of gyration, which is larger
for linear molecules than for branched molecules of the same weight (number of
monomer units), since the latter are more compact. The ratio between branched
and linear radius is usually described by a contraction factor. Furthermore, Cay-
ley tree-like structures are more compact than comb-like structures [33, 56]. We
will show here how to obtain the contraction factor from the architectural informa-
tion. The squared radius of gyration hs
2
i is expressed in monomer sizes. Accord-
ing to a statistical-mechanical model [55] it follows from the architecture as repre-
sented in graph theoretical terms, the Kirchho matrix, K, which is derived from
the incidence matrix, C [33]:
hs
2
i = n
1
Tr(L
1
n1
) (184)
Here, n is the number of monomer units and Tr(L
1
n1
) denotes the trace of L
1
n1
,
being the matrix with n 1 reciprocals of the eigenvalues of the Kirchho matrix
K. The full n n sized matrix K is calculated from:
K = CgC
T
(185)
where C
T
is the transpose of C (size (n) (n 1) and g is a vector of length
(n 1) related to the size of monomer units. For the computation of the radius of
gyration, we apply a coarse graining method to save on computational eort to nd
the smallest eigenvalues of K [56]. Thus, the Kirchho matrix reduces in size, now
based on the number of branch points, (2N 2) (2N 2). In this case the vec-
tor g of length (2N 1) contains the N 1 interbranch segment lengths and the
N 2 free arm lengths of the molecule.
It should be realized that the incidence and Kirchho matrices contain purely
topological information (connectivity between branch points). Thus, we see that
the radius of gyration is determined by both topology (K) and segment length dis-
tribution (g). We now dene a purely topological structure qualier topological
radius, based on a topological Kirchho matrix:
K = CC
T
(186)
Note that the combCayley tree ranking of molecules within a certain population
in Eq. (186) is dierent in principle from that in Eq. (185), since the former ex-
cludes segment length eects.
9.9.4.3 Characterization of Architectures by Seniorities and Priorities
Introduction The rheological meaning of the concepts of seniority and priority
has been explained previously elsewhere [46, 52]. Here, we will introduce them as
merely topological qualiers. The seniority s
j
of a segment j is dened as the mo-
lecular distance to the nearest free arm. The seniority of a free arm is 1; the value
for a segment ending on a terminal branch point is 2. Priority is dened as follows.
Each inner segment is connected to two trees, each of these trees having a number
of terminal segments (free arms). The priority is the smaller of these numbers of
terminal segments. Our method of nding the distribution is based on a graph
theoretical representation of branched molecules.
Seniority The seniority of a molecular segment between two branch points (in-
ner segment) is related to the longest chemical path (LCP) of that segment. In
terms of graph theory we say that segments ending on a terminal branch point
(outer segments) are attached to one and all other segments are attached to two
parts of the tree that represents the molecule. The LCP is dened as the highest
number of segments in the path to a terminal segment; the inner segments have
two such LCPs one on each side. In a comb most segments have much longer
LCPs than those in a Cayley tree. The seniority of a segment is dened as the
shorter of the two LCPs of that segment. The seniority of an outer segment is 1;
the value for a segment ending on a terminal branch point is 2. The algorithm
nds the seniority distribution by checking all the possible end-to-end paths of
the molecule while numbering the inner segments according to the order in which
they are passed in the path. (Note that to nd the number of segments with senior-
ity 1, the outer segments, is a trivial problem since any molecule with N branch
points possesses N 2 outer segments).
The following steps are taken in the algorithm:
1. Find the N
t
sets of N
t
terminal branches J
t
by identifying all columns of A, for
which the sum equals 1; start with one vertex J
t
( j), j A 1:N
t
, corresponding to
column J of A.
2. Find adjacent vertices; from a selection of n
j
columns of A, for each of these
columns J( j), j A 1:n
j
, check the nonzero entries being found in n
ij
rows
I(i), i A 1:n
ij
for each j; this produces in total n
i
=
P
nj
j =1
n
ij
row indices I(i),
i A 1:n
i
; thus from a vertex set J( j), j A 1:n
j
, all the vertices adjacent to the
vertices in the set are found and stored in a new vertex set I(i), i A 1:n
i
.
3. Assign sequence numbers to edges; for each of the vertices J( j) a set of n
ij
adja-
cent vertices I(i) is found, associated with n
ij
directed edges pointing from ver-
tex J( j) to vertices I(i); for certain J( j) this is the set of edges e
JI
, where J = J( j)
and I = I(i), i A 1:n
ij
; thus nding the edges e
IJ
for this J( j) means that they
are spotted on a path and should receive a sequence number n
s
; for all other
J( j) other edge sets are found, but all n
i
edges found from one vertex set J( j),
j A 1:n
j
, are assigned the same sequence number; by denition, n
s
equals 2
for the (one) edge found from the starting vertex.
4. Update adjacency matrix; for each I; J pair found in step 2: A(I; J) =
A( J; I) = 0.
5. The new vertex set I(i), i A 1:n
i
, found in step 2 is the starting point for a new
cycle of nding subsequent adjacent vertex sets, but this should happen in the
updated A; thus, the new set of columns follows as J = I(i), where all zero col-
umns in the updated A are left out; the algorithm then repeats steps 25 until A
has only zeros.
6. Collect all sequence numbers for all 2(N 1) edges in both directions, the vec-
tor n
s
(e
ij
); for any directed edge nd maxn
s
(e
ij
); nd the seniority of each
edge by taking the minimum of [maxn
s
(e
ij
); maxn
s
(e
ji
)].
For illustration, the algorithm has been applied to the simple N = 5 problem of
Figure 9.23.
Find terminal branches: N
t
= 3, J
t
= 1 3 5; start with J
t
= 3.
Nonzero entry in column J = 3 is in row 2, hence n
ij
= 1, i = 1, I(1) = 2.
The edge found is e
JI
= e
32
and it assigned the sequence number 1: n
s
(e
32
) = 2.
A is updated with A(2; 3) = A(3; 2) = 0: A =
0 1 0 0 0
1 0 0 1 0
0 0 0 0 0
0 1 0 0 1
0 0 0 1 0
2
6
6
6
6
6
4
3
7
7
7
7
7
5
New vertex set from updated A: J = I = 2; repeat from step 2;
Non-zero entries in column J = 2 are in rows 1 and 4, hence n
ij
= 2, i = 1; 2;
I(1) = 1; I(2) = 4;
The edges found are e
21
and e
24
and they are assigned the sequence number 3:
n
s
(e
21
) = n
s
(e
24
) = 2;
A is updated with A(2; 1) = A(1; 2) = 0 and A(2; 4) = A(4; 2) = 0:
2
1
3
4
5
n
s
(e
32
) = 2
n
s
(e
23
) = [3 4]
n
s
(e
12
) = 2
n
s
(e
21
) = [3 4]
n
s
(e
24
) = [3 3]
n
s
(e
42
) = 3
n
s
(e
54
) = 2
n
s
(e
45
) = [3 4]
S = 2 S = 3
S = 2
S = 2
Fig. 9.23. Sequence numbers per segment for each of the
three possible path sequences through one architectural
alternative of a ve-branch molecule and the resulting
seniorities.
A =
0 0 0 0 0
0 0 0 0 0
0 0 0 0 0
0 0 0 0 1
0 0 0 1 0
2
6
6
6
6
6
4
3
7
7
7
7
7
5
New vertex set from J = I(1) = 1 and I(2) = 4; since column 1 has all zeros, the
new J = 4; repeat from step 2.
Nonzero entry in column J = 4 is in row 5, hence n
ij
= 1, i = 1; I(1) = 5.
The edge found is e
JI
= e
45
and it assigned the sequence number 1: n
s
(e
45
) = 4.
A is updated with A(4; 5) = A(5; 4) = 0, so A has all zeros and the collection of
sequence numbers stops.
This run yields the sequence e
32
e
21
e
24
e
45
with the associated sequence
numbers 2 3 3 4 (see Figure 9.23). Similarly, starting with vertex 1 and vertex
5 yields the sequences e
12
e
23
e
24
e
45
and e
54
e
42
e
21
e
23
with sequence num-
bers 2 3 3 4 and 2 3 4 4, respectively. Collecting the sequence numbers per
edge yields the vectors n
s
(e
ij
) shown in Figure 9.23 and then taking maxima and
minima according to step 6 of the algorithm yields the seniority distribution d
S
.
This seniority algorithm is a transparent one in the sense that it explicitly calcu-
lates the segments longest chemical paths, on which the denition of the seniority
is based. However, it involves a lengthy procedure since the sequence numbering
has to be applied as many times as there are terminal branches. In the case of
N = 1534 (perfect Cayley tree with six generations) this number amounts to 768.
For this reason a faster and simpler algorithm has been developed, in which no ex-
plicit longest chemical path evaluation takes place, but instead a decomposition of
the graph is realized. It consists of the following steps (see Figure 9.24):
1. Find the set of N
t
terminal branches J
t
by identifying all the columns or rows of
A for which the sum equals 1 (asterisk positions in Figure 9.24).
2. Assign seniority values to (terminal) edges; each of the vertices J
t
is adjacent to
a penultimate vertex I
pu
, (some dierent J
t
to the same I
pu
,) so that the set I
pu
may have fewer elements than N
t
: I
pu
aN
t
(in the gure the penultimate
vertices have an asterisk in the second conguration); all vertices J
t
to I
pu
repre-
sent N
t
edges; to all of these edges a seniority value is assigned: S = 2 i
u
,
where i
u
is the updated number of the adjacency matrix (0 the rst time).
3. Update A by putting zeros in rows and columns J
t
. The eect is two-fold: the
original terminal vertices (asterisks in the rst conguration of Figure 9.24) van-
ish, being replaced by new ones (asterisks in the second conguration), but the
structure is also decomposed at certain vertices, namely those marked by an as-
terisk on a non-terminal position. Note that thus all asterisks in fact denote ter-
minal vertices: that is, they have sums of rows and columns equal to 1 in A.
4. Repeat steps 1 through 3 until A is all zeros.
We have ensured that this decomposition algorithm reproduces exactly the same
seniority distributions as the longest chemical path algorithm.
Priority Priority values are found for each segment (again, inner segments only)
by constructing balances of terminal segments on each side of the segments.
An example has been worked out, based on Figure 9.25. The full set of balance
equations reads:
d
s
= {38 11 12 8 4} (incl. ones)
1
2
3
2
2
2
2
2
2
2
2
2
2 2
*
*
*
*
*
*
*
*
*
*
*
3
3
3
*
*
*
*
*
*
*
*
*
3
3
3
3
3
3
3
3
3
*
*
*
*
*
*
*
4
4
4
4
4
4
4
4
*
*
*
5
5
5
5
Fig. 9.24. Decomposition algorithm to nd
seniority distributions for a molecule with
N = 36. The rst conguration has 11 terminal
segments, yielding 11 segments with S = 2.
The rst update produces the second congu-
ration with nine terminal vertices, including
three on positions where the structure is
broken (into four parts); segments adjacent to
these vertices get S = 3. By the second and
third updates similarly the segments with
S = 4 and S = 5 are identied.
2
1
3
4
5
p
32
= 2
p
23
= 5
p
12
= 2
p
21
= 5
p
24
= 4
p
42
= 3
p
54
= 2
p
45
= 5
d
P
= {3 1}
Fig. 9.25. Two-sided and real priorities for one architectural
alternative of a ve-branch molecule.
p
12
= 2 p
24
= p
12
p
32
p
45
= p
24
1
p
32
= 2 p
21
= p
42
p
32
p
42
= p
54
1
p
54
= 2 p
23
= p
42
p
12
These eight equations with eight unknowns can be solved to yield the results
shown in Figure 9.25. Thus the number of free segments on each side of each seg-
ment is obtained. The lower value is the priority of that segment.
In general the set of equations can be written as:
p = B
1
:r where r =
X
2(N1)
j =1
B
ij
1:
Here, B is a matrix of 2(N 1) 2(N 1) coecients that is obtained from the
adjacency matrix A. This yields the two priorities per edge, one for each direction,
of which the smallest value is the priority.
9.10
Computational Fluid Dynamics for Polymerization Reactors
9.10.1
Introduction
Chemically reacting ows in polymerization reactors display complex behavior due
to the interactions between physical and chemical processes. These processes oc-
cur over a wide range of length and time scales, and often result in tight coupling
between uid dynamics and chemistry. Early numerical simulations of these ows
were based on combinations of idealized ow reactor models such as the CSTR,
the plug-ow reactor (PFR) and the batch reactor (BR). These models either ne-
glect radial mass and heat transfer or include only eective transfer coecients,
and solve a system of governing dierential equations as an initial value problem.
They often assume that the reactants are mixed rapidly and thus the concentra-
tions can be considered to be uniform at small scales. For diverse polymerization
processes, however, inadequate mixing of chemical species or interphase mass
transfer limitations coupled with fast reactions can signicantly aect reactor per-
formance (yield, stability, operability) and product quality (selectivity). The state-of-
the-art computational uid dynamics (CFD) models provide cost-eective tools to
better understand complex reacting ows while designing and operating reliable
industrial reactors.
9.10.1.1 Modeling Challenges
The accurate mathematical formulation of polymerizing ows is a challenging task
for several reasons. For example, turbulent ows require complete resolution of all
length scales in the turbulence physics, such as large-scale transport due to convec-
tion and turbulent diusion (macromixing), mid-scale transport due to dispersion
(mesomixing), and small-scale transport due to molecular diusion (micromixing).
Polymerization mechanisms, on the other hand, often involve a large number of
chemical species representing complex reaction networks. The disparate chemical
time scales result in a sti set of equations, and require enormous computational
eort to integrate the species rate expressions. Since reactions occur on the molec-
ular level, the turbulencechemistry interactions can change the progress of fast,
exothermic reactions [60, 61] and may initiate runaway conditions, or overheat
polymerizing particles, thus aecting the nal polymer properties.
These challenges are further compounded while modeling multiple phases in
heterogeneous polymerization reactors such as bubble column reactors (BCRs)
or uidized bed reactors (FBRs). A range of complexities associated with the dy-
namics of each phase, the interaction between and within phases, sub-grid-scale
heterogeneities (such as size distributions within each phase), and coupling with
reactions at the micro-scale need to be addressed. For example, bubble size distri-
bution is important to correctly model interfacial area and local mass-transfer coef-
cients, which can further aect polymerization reactions. Although phenom-
enological models describing such physical eects have greatly improved over the
years, this area still lacks reliable multiphase turbulence closures, or experimen-
tally validated intraphase and interphase transport models.
As with any other emerging technology, CFD capabilities have been understood
to a certain degree for reacting ows, and applied at the industrial level to model
polymerization reactors. A complete review of the application of CFD for homoge-
neous and heterogeneous reactors would be quite extensive, and the capabilities for
multiphase reacting ows are still evolving. This section, therefore, focuses on the
relatively well-developed CFD models for single-phase reacting ows. We present a
comprehensive CFD algorithm for reactor modeling and a brief review of multi-
phase ow capabilities, followed by illustration of single-phase CFD capabilities us-
ing representative industrial test cases for the two fundamental classes of polymer-
ization (that is, addition and condensation) processes.
9.10.2
Development and Optimization of Modern Polymerization Reactors
Figure 9.26 shows the traditional commercialization process for new polymeriza-
tion technology, involving a number of development stages from discovery to com-
mercial production. Each stage is used to gain a scientic understanding of the
new technology and to make real-world assessments of design decisions required
for commercialization success. This interactive route progresses through expensive
and time-consuming experimental and pilot-plant testing. In recent years, the fo-
cus has shifted to employ CFD as an alternative or a complement to this traditional
route while reducing the process risks and increasing condence in the new tech-
nology. Experience has shown that CFD, when implemented correctly and e-
ciently, can be a cost-eective tool for design and scaleup of new reactors and opti-
mization of existing reactors.
9.10.2.1 Benets of CFD
In the early days of its development, using even simple CFD techniques for reactor
design and analysis was impractical due to limited computational power. With to-
days high-performance computers as well as ecient numerical and chemstry al-
gorithms, the use of CFD is expanding for detailed reacting ow analysis in the
initial stages of design. The sophisticated analysis can be used to investigate reac-
tor conditions that are outside the range of existing experimental facilities, or study
dynamics of reactors for extreme conditions that are dicult to reproduce experi-
mentally due to instabilities. In general, CFD can help process engineers make
well-informed design and operational decisions while meeting stringent environ-
mental and safety laws as well as higher-quality standards for specic end-uses.
9.10.2.2 Limitations of CFD
The validation of a CFD simulation against key experimental and pilot-plant data
remains an integral and essential part of design. For entirely new reactor designs,
it is dicult to estimate the accuracy of a simulation without prior knowledge of
similar ow regimes. Despite the development of easy-to-use commercial CFD
codes, the initial setup for complex polymerization reactors requires signicant in-
vestments of time and expense. This investment increases enormously due to the
computing and meshing limitations when modeling complicated geometric shapes
with rotating parts (for example, CSTRs), with changes in liquid levels (for exam-
ple, in semi-BRs), with changes in ow regimes (for example, dilute to dense, tur-
bulent to laminar in BRs), or with compressibility eects. Commercial codes oer
no direct way of incorporating the possible dependence of kinetic data on physical
properties or the interdependence of physical properties on operating conditions.
New process
Technology
Kinetics data
Commercial
Scale
Plant
Trials
Lab Scale
Tests
Commercial Production
Pilot Plant
Tests
Scale-up
Stage 1 Stage 2 Stage 3 Stage 4 Stage 5
Design/scale-up
new reactors
Optimize/improve
existing reactors
Input
Validate
Implement
Reacting CFD
Technology
Reacting CFD
Technology
Discovery
Fig. 9.26. CFD application strategy for design, scaleup and
optimization of polymerization reactors.
Moreover, the convergence and stability of solution techniques are severely ham-
pered while solving sti chemistry, or changes in physical properties (such as vis-
cosity or density) during ow simulation. The grid size required to resolve all
length scales (for example, the turbulencechemistry interactions) often becomes
prohibitive for reactors involving complex chemistry or complicated geometries.
9.10.3
Integration of CFD with Polymerization Kinetics
Figure 9.27 presents a comprehensive CFD algorithm based on the classical CFD
approach. This algorithm formulates ow characteristics using Eulerian Reynolds-
averaged NavierStokes (RANS) equations for the conservation of mass and mo-
mentum, and energy equations for the convective, conductive, and radiative heat
eects. Homogeneous or heterogeneous reactors can be modeled by increasing
the complexity of physical models according to the ow physics, coupled with
the exact treatment of reactions. The governing model equations result in a set
of coupled, nonlinear, partial dierential equations, which are dicult to solve
analytically in closed form, except for a few special cases. For most engineering
ow problems, the equations can be solved numerically with appropriate boundary
conditions using discretization techniques such as nite dierence, nite volume,
nite element, or boundary element methods.
Commercial CFD codes perform a numerical simulation of the reactor geometry
using a representative axisymmetric two- or three-dimensional mesh with a large
number of computational cells (that is, nite elements used to solve model equa-
CFD Formulation
Continuity equation
Momentum balances
Turbulence model
Mass transfer
Heat transfer
2D/3D geometry
Mesh
Chemistry algorithms
Multi-phase model
Micromixing Model
Population Balances
P
S
D
M
icrom
ixing
Chemistry,
MWD
Full PDF
MEM model
ISAT technique
Chemical look-up tables
Built-in integrators
Kinetic
data
e.g. Multi-fluid model
Increasing
physical details
Moment methods
Discrete-sectional methods
Monte Carlo methods
Properties
Physical
Thermodynamic
Multi-phase
physics
Boundary
Conditions
Fig. 9.27. Generalized CFD algorithm for modeling polymerization reactors.
tions). A typical simulation requires 100,000 to several million cells to accurately
resolve all length scales. The use of a ner mesh adds enormous computational ex-
pense in terms of memory and CPU time. Cells can be distributed selectively so
that denser cells are clustered in a region of interest to resolve sti concentration
gradients or small-scale phenomena. This approach also requires a reasonable ap-
proximation of the turbulent ow characteristics using turbulence models that are
adapted to the NavierStokes equations.
9.10.3.1 Classication and Complexity of CFD Models
Other CFD approaches, namely direct numerical simulation (DNS) and large-eddy
simulation (LES), solve the governing transport equations without any approxima-
tion, but require enormous computational expense for even simple reacting ows.
DNS and LES are limited in their ability to capture the micromixing eect on slow
diusion/fast reaction processes, and are restricted to the fundamental under-
standing of turbulence or verication of mixing closures for use in engineering
models [62]. Another sophisticated approach is to solve joint probability density
function (PDF) transport equations of species and temperature using a stochastic
Monte Carlo algorithm [61, 63]. On the other hand, simplied Lagrangian micro-
mixing models [64] (for example, the interaction-by-exchange-with-the-mean model
[65, 66], or engulfment models using experimentally measured mixing characteris-
tics [67], etc.) have been proposed for investigating the inuence of micromixing
on reactions using residence time distributions. Micromixing models are particu-
larly attractive to the polymerization industry because of their simplicity. Inherent
assumptions regarding the turbulent ow eld, however, make them inadequate to
describe the strong coupling between uid dynamics and complex reaction net-
works or to provide generalized scaleup rules. The complementary capabilities of
the Lagrangian micromixing models and the Eulerian CFD framework can be inte-
grated to describe turbulent micromixing in detail [68].
For heterogeneous polymerization reactors, the ow properties of multiple
phases or mixtures of several components must be included in the CFD simula-
tion. The motion of bubbles (or droplets or catalyst particles) in a ow is modeled
by transport equations for the additional phases as well as interphase and intra-
phase heat and mass transfer. Recent reviews of BCRs and FBRs will provide de-
tailed understanding of various phenomena in multiphase ows and the governing
transport equations [6974]. Commercial CFD codes provide formulations based
on the volume of uid model with multiple uids or phases, the mixture model
with a single uid, or the Eulerian model. Micromixing models are often neces-
sary to account for the sub-grid-scale interfacial and concentration heterogeneities,
whereas the distribution of particle sizes is described by solving population bal-
ances within the CFD framework. Various closure methods are used to model
population balances depending upon the particle dynamics. For example, a re-
cently proposed direct quadrature method of moments (DQMOM) provides an ac-
curate and cost-eective representation of particulate processes (that is, nucleation,
growth, aggregation, and breakage) and predicts the complete particle size distribu-
tion using a small number of transport equations [75]. The technology for multi-
phase reacting ows is still evolving and has yet to realize its full potential for
important applications in the polymerization industry.
9.10.3.2 Treatment of Polymerization Kinetics
The CFD algorithm treats polymerization reactions exactly by integrating the spe-
cies rate expressions, which form a set of highly sti ordinary dierential equa-
tions (ODEs). Although there is no theoretical limitation preventing the use of
detailed polymerization chemistry (with an arbitrary number of species), there is a
practical limit dictated by the high computational expense of direct integration of
the rate expressions involving the exponential functions. Thus, appropriate ODE
solvers along with other simplications must be used. For example, the total num-
ber of species can be reduced by assuming the quasi-steady-state approximation for
free radicals, or by including only reactions that are sensitive to the transport pro-
cesses. Inherent time scale dierences of reaction and transport processes can be
used to handle them separately by employing the fractional time-stepping formula-
tion [63]. Even with these simplications, repeated integrations for all grid points
at each time step present a computationally formidable problem, particularly for
three-dimensional simulations. Alternative ecient chemistry algorithms such
as multilinear interpolation using a chemical look-up table [76, 77] or the in-situ
adaptive tabulation (ISAT) [78] are often explored to reduce computational time.
For example, the ISAT improves the computational eciency by a factor of up to
100 by tabulating the look-up tables only in the accessed composition region for a
given ow simulation. More details of the CFD models and the chemistry algo-
rithms for polymerizing ows (advantages, disadvantages, and implementation in
commercial codes) can be found in Ref. 79.
9.10.3.3 Illustration of Homogeneous Reactor Model Formulation
The application of the CFD algorithm for single-phase turbulent reacting ows
is illustrated in the following case. The multienvironment micromixing (MEM)
model describes concentration uctuations that arise from two poorly mixed reac-
tants in a tubular reactor. The theoretical framework and the parameter selection
for the MEM model are discussed in greater detail by Fox [68]. The formulation of
a three-environment model (Figure 9.28) to quantify the turbulent mixing between
environment 1 (E-1) and environment 2 (E-2) follows.
Formation of a reacting environment (E-3) is governed by the transport equa-
tions for volume fraction of environments ( p
n
):
E-1, p
1
(Pure species I)
E-3, p
3
,
(Reacting)
) 3 (
E-2, p
2
(Pure species M)
r
1
= - (1-p
1
) p
1
r
1
r
2
r
2
r
3
= r
1
+ r
2
Mixing rate = C (/k)
= - (1-p
2
) p
2
Mixing parameter C = 1 for the fully-developed turbulent flow.
Fig. 9.28. Mixing parameter Cf = 1 for the fully-developed turbulent ow.
qp
n
qt
hU
i
i
qp
n
qx
i
=
q
qx
i
G
T
qp
n
qx
i

G
n
(p) n = 1; 2; 3 (187)
The species mixing, heat transfer and reactions in E-3 are governed by the trans-
port equations for the volume-weighted species concentration and temperature in
E-3 (s
(3)
a
= f
(3)
a
p
3
):
qs
(3)
a
qt
hU
i
i
qs
(3)
a
qx
i
=
q
qx
i
G
T
qs
(3)
a
qx
i

M
(3)
a
(p; s
(3)
) p
3
S
a
(f
(3)
) (188)
Repeated roman indices imply summation, and a denotes the species or tempera-
ture in E-3. The NavierStokes equations, the standard ke equations, describe the
turbulence physics, and compute the mean velocity hU
i
i along with the turbulent
parameters (kinetic energy k, dissipation rate e, diusivity G
T
). The micromixing
functions G
n
(p) and M
(3)
a
(p; s
(3)
) are dened in terms of the probability uxes r
n
for environment n, and the chemical source terms S
a
(f
(3)
) are estimated on the
basis of the species rate expressions. This formulation is used to investigate the
turbulencechemistry interactions in the example in Section 9.10.4.1.
9.10.4
Target Applications
Many aspects of reacting ows have been studied for developing CFD models of
polymerization reactors. Table 9.20 documents representative examples of these
studies for various polymerization processes by summarizing reactor type, number
of phases, number of species, CFD techniques, and engineering challenges that
are addressed using CFD. Table 9.21 reports potential CFD applications for other
polymerization processes.
Specic examples of single-phase turbulent reacting ows in a tubular jet reactor
are discussed in Section 9.10.4.1. We select representative industrial problems of
engineering interest for the two fundamental classes of polymerization reactions,
namely addition and condensation polymerization. For each example, we present
a general overview of the problem and detailed reacting ow analyses, followed by
useful process design and operational information.
9.10.4.1 Illustrative Case Studies
Free-radical polymerization [79, 93] Low-density polyethylene (LDPE) accounts for
almost two-fths of the global polyethylene production capacity, reaching about
45 million tons per year in 1996. LDPE is exclusively produced by free-radical poly-
merization in a tubular or autoclave reactor, each of which accounts for about 50%
of the total capacity. In the tubular reactor, a small amount of initiator is injected
into a turbulent monomer ow for initiating the exothermic free-radical chemistry.
Under extreme operating conditions (T @140300
C, p @10003500 atm), these

Tab. 9.20. Target applications in the polymerization (PP) industry.
PP product,
PP process
Reactor, phases,
[a]
species
CFD techniques Design, process
engineering challenges
References
Polyethylene,
Free-radical PP
PFR, S, 6 joint PDF method,
simple chemistry
local hot-spots, MWD 80
PFR, S, 16 joint PDF method,
detailed chemistry
initiator loss, MWD,
local/global decomp.
(reactor stability)
81
autoclave, S, 3 Eulerian CFD,
eddy-dissipation,
[b]
simple chemistry
Initiator consumption,
conversion
83
autoclave, S,
3 to 6
Eulerian CFD,
simple chemistry
conversion, MWD,
temp. distribution,
design changes
8486
Polypropylene,
Free-radical PP
static mixer
reactor, S, 0
Eulerian CFD,
micromixing theory,
[c]
no chemistry
laminar striation
thinning, MWD
57
Polyolen,
Catalyzed PP
FBR, M, 6 multi-uid model,
DQMOM,
simple chemistry
polymer particle
overheating
75
Polyolen,
Catalyzed PP
FBR, S, 0 Eulerian CFD,
heat transfer,
no chemistry
heat removal,
polymer particle
overheating
88
Polystyrene,
PVC, etc.,
Suspension PP
BR, M, 0 Eulerian CFD,
compartment-mixing,
population balance,
no chemistry
PSD control 89, 90
cis-Polyisoprene,
Anionic PP
PFR, S, 6 Eulerian CFD,
representative simple
chemistry
MWD prediction 91
Polyamide, etc.,
Condensation PP
Multijet
reactor, S, 6
Eulerian CFD,
eddy-dissipation,
[b]
simple chemistry
reactor fouling 92
[a]
S: single-phase; M: multiphase.
[b]
Ref. 82.
[c]
Ref. 87.
Tab. 9.21. Potential applications in the polymerization industry.
PP product, PP process Reactor type Design, process engineering challenges
a-Olens, Metallocene PP PFR reactor fouling
Polysulfone, Linear
condensation PP
CSTR sensitivity of chain-length distribution
Ethylenevinyl acetate, Free-
radical PP
PFR initiator loss, MWD, phase separation
Polyamide-6, Hydrolytic PP CSTR/PFR yield, selectivity
Polyisobutylene, Cationic PP PFR reactor stability
Polyester, Polyesterication semi-BR polymer molecular properties
Latex, Emulsion PP CSTR polymer properties, yield
reactors are sensitive to local mixing conditions and serve as an excellent test case
to study the performance and stability of commercial reactors involving single-
phase turbulent reacting ows.
In this example, the mixing between initiator (E-1) and monomer (E-2) is quan-
tied using the MEM model introduced in Section 9.10.3.3. The ISAT algorithm
is customized for a total of 16 species in the LDPE chemistry, including chain ini-
tiation, propagation, termination, chain transfer, and other branching reactions as
well as simplied ethylene decomposition reactions (reported in Table 9.22). More
details of the kinetic scheme, the rate expressions, and the rate constants as well as
the customized ISAT algorithm can be found in Ref. 81. The poorly mixed region
is modeled using a two-dimensional axisymmetric computational domain of length
10 m and radius 1.9 cm. The standard ke model describes the turbulence, as vis-
cosity eects are negligible due to the fully-developed turbulent ow. The MEM
model and the ISAT algorithm (about ten-fold faster than the direct integration)
are solved using an interactive interface via external routines in the Fluent2 v5.3
Tab. 9.22. Comprehensive free-radical polymerization reactions for modeling chemical source
terms [81].
Detailed low-density polyethylene polymerization chemistry:
Organic peroxide initiation I
ni

fni ; kd
I
ni
2A
ni
(ni = 1; 2)
A
ni
M
kI
ni
R
1
Propagation R
i
M
kp
R
i1
Termination by combination R
i
R
j

ktc
P
ij
Termination by disproportionation R
i
R
j

ktd
P
=
i
P
j
(DB)
Chain transfer to monomer R
i
M
ktrm
P
=
i
R
1
(DB)
Chain transfer to transfer-agent R
i
CTA
kCTA
P
i
R
CTA
Chain transfer to polymer R
i
P
j
ktrp
P
i
R
/
j
Backbiting (SCB formation) R
i

kSCB
R
i
(SCB)
LCB formation R
/
i
M
kLCB
R
i1
(LCB)
b-Scission R
/
ij

kb
R
i
P
=
j
(DB)
Simplied ethylene decomposition chemistry:
Initiation 2M
k1
C
2
H
v
3
C
2
H
v
5
Propagation C
2
H
v
5

k2; k
/
2
M H
v
C
2
H
v
5
M
k3
C
2
H
6
C
2
H
v
3
H
v
M
k4
H
2
C
2
H
v
3
C
2
H
v
3

k5
C CH
v
3
CH
v
3
M
k6
CH
4
C
2
H
v
3
Termination CH
v
3
CH
v
3

kt
C
2
H
6
C
2
H
v
3
CH
v
3

kt
C
2
H
2
CH
4
C
2
H
v
3
C
2
H
v
3

kt
C
2
H
2
M
software. An unsteady coupled implicit solver is used to limit the eects of trunca-
tion errors on the solution. The interface also includes the interdependence of the
kinetic, physical, and thermodynamic properties of the reaction mixture.
Figures 9.29(b)(f ) present the detailed reacting ow analysis and the perfor-
mance evaluation using a typical CFD simulation for the feed temperature (T
feed
)
of 250
C. As seen in Figure 9.29(b), center-mode initiator injection causes sharp

radial concentration gradients near the injection point. This phenomenon leads
to the higher termination of initiator free radicals and loss of @64% of the ini-
tiator compared to the plug-ow conditions. Contours of the mean monomer mass-
fraction (Figure 9.29(c)) and the mean temperature (Figure 9.29(d)) show a conver-
sion of @5% and a steady-state temperature rise of @57
C, respectively. The poor

micromixing also aects other reaction rates. For example, the localized release
of the exothermic energy due to higher propagation rates leads to local tempera-
ture uctuations in E-3 (Figure 9.29(e)), whereas non-uniform chain-transfer rates
cause a broader MWD, as indicated by higher polydispersity (Figure 9.29(f )). Thus,
the CFD algorithm is able to capture the eect of the turbulencechemistry inter-
actions on the reactor performance, which cannot be predicted by the traditional
reactor models. Detailed CFD simulations are used to validate and increase the ac-
curacy of a simplied one-dimensional MEM model. The high computational e-
ciency of the simplied approach is extremely useful to evaluate the performance
for a range of operating and mixing conditions. For example, proles in Figure
9.29(g) summarize high-temperature initiator eciency for a range of feed temper-
atures and mixing conditions, whereas the reactor stability map in Figure 9.29(h)
identies unsafe regions of reactor operation. Thus, in this example, CFD oered a
low-cost alternative to replace pilot-plant tests and explore a variety of options for
optimizing initiator consumption while developing oine strategies to control
the reactor safety and product quality in industrial reactors.
Condensation polymerization [92] Several industrially signicant resins poly-
amides (for example, nylon), polyester, polyurethanes, polyacetals, phenol-alde-
hydes, polyurea, and silicones are produced by condensation polymerization.
In this example, a multi-jet tubular reactor is used for the polycondensation be-
tween monomers A and B, each having two reactive groups. Multiple turbulent
jets of B are impinged onto radial ow of A at the inlet of the reactor to achieve
the rapid mixing required for starting the step-growth polymerization. The reaction
forms polymer linkages L and condenses out a small molecule by-product C form-
ing a by-product complex SC (Table 9.23). Solvent S acts as a catalyst and dissolves
all chemical species, thereby maintaining single-phase ow. Subsequent secondary
and branching reactions control the structure and MWD of the nal polymer. The
inlet region (length L @3:5D and residence time t) is sensitive to various uid
dynamic processes and can aect the reactor operability due to deposition of
products.
The continuity and NavierStokes equations, the standard ke turbulence model,
and the transport equations for species concentration and enthalpy are solved us-
ing a three-dimensional computational domain for the inlet region (Figure 9.30(a)).
Outlet
L = 10 m
Co-axial jet, d
jet
= 0.2 mm
Monomer, Q
M
(m
3
/s)
Initiator, Q
I
(m
3
/s)
= 4.52 m/s
p
1
= 0.1
p
2
= 0.9
U
z
= 13.16 m/s
p
1
= 0
p
2
= 1
D = 3.8 cm
For velocity profiles: = 560 kg/m
3
; = 0.0016 kg/m.s
T
feed
= 250 C
Grid size: 400 x 19
M I
I
1,0
Q Q
Q
p

(a) Two-dimensional axisymmetric computational domain

Poorly micromixed region (0 to 0.2 m)
(b) Initiator mass fraction (blue to red: (01.15) 10
3
)
(c) Monomer mass fraction (blue to red: 0.951) (g) Optimization of high-temperature initiator
efficiency
(d) Mean temperature (blue to red: 250307C)
(e)
environment (blue to red: 250329C)
(f ) Polydispersity (blue to red: 07.15)
(h) Reactor stability map for commercial-scale
operation
(Scale-up factor: D ~ 1:85, L ~ 1:40)
Local temperature in the reacting

U
z
=
+
Fig. 9.29. Typical reacting CFD simulation results and
performance evaluation for the coaxial jet tubular LDPE reactor
(scaleup factor for diameter is 1:50).
The chemistry is simplied to include only condensation, solvent regeneration,
and transfer reactions (reported in Table 9.23) that are important in the region of
interest. Finite-rate/eddy-dissipation formulation [82] in the Fluent2 v6.0 software
is used to model the turbulencechemistry interactions. This formulation uses
the minimum of the Arrhenius and eddy-dissipation rates to account for mixing
limitations.
CFD simulations are performed to visualize the velocity, pressure, concentration
(with and without chemical reactions), and temperature distributions for a range of
operating rates. For example, Figure 9.30(b) shows the non-uniform radial distribu-
tion of the reacting species A at the turndown ratio of 0.6 compared to the maxi-
mum operating rate. The presence of a recirculation zone near the inlet results in
a higher mass fraction of the polymer linkage (g
L
). This phenomenon is high-
lighted in the inset of Figure 9.30(c) by clipping the contours to the maximum g
L
in the recirculation zone (g
Lmax; rc
). Visual observations of internals in a fouled reac-
tor conrm the deposition of products in regions of higher polymer linkage mass
fraction (that is, contours at the reactor entrance and the bottom wall of the re-
actor) indicated by CFD simulations. Although nonreacting CFD simulations in-
dicate improved mixing at lower operating rates (Figure 9.30(d)), the reactor opera-
tion is limited due to high values of g
Lmax; rc
. The lower operating limit is predicted
to be a @0.42 turndown ratio corresponding to the experientially estimated g
Lmax; rc
of 7%. The operation at higher rates (turndown ratio > 0:75 in Figure 9.30(d)) is
limited by the maximum available premix pressure for stream B. Thus, the anal-
ysis is helpful in predicting the feasible operating range, and can be used to op-
timize other process conditions as well as design parameters for enhancing the
operating exibility.
9.10.5
Concluding Remarks
CFD is emerging as a powerful tool for the design and optimization of polymeriza-
tion reactors with the rapid growth in high-performance computing resources. Ex-
perimentally validated CFD models can now be used to complement the traditional
design procedure for cost-eective development of new reactors or for the produc-
tivity improvement of existing reactors. While limitations in handling detailed
chemistry in real time still exist, the ability to visualize and quantify the reactor
Tab. 9.23. Primary condensation polymerization reactions for modeling
chemical source terms [92].
Condensation reaction: A B S
k1 =
1:2810
4
t
exp
8:9410
4
Rg
T
DHr =RTA0 =51:3

L SC
Solvent regeneration: A SC
k2 =
4:6910
6
t
exp
8:3310
4
Rg
T
AC S
Transfer reaction: AC S
k3 =
3:8610
6
t
exp
1:5010
5
Rg
T
A SC
3D contours inside the reactor
Clipped between 0 & 0.045

(c) Mass fraction of polymer linkage L; inset contours
highlight formation of high polymer mass at the inle

(d) Reactor performance as a function of the turndown
ratio
3D contours inside the reactor
Clipped between 0 & 0.045

(c) Mass fraction of polymer linkage L; inset contours
highlight formation of high polymer mass at the inlet

Outlet
x / L 0
1.0
D
0.1 0.25 0.35 0.75 0.5
Cross-section locations for post-processing
Injection slot
L / D ~ 3.5
g
T
= T/T
A0
p
r
= p/(p
B
)
max
p
r
= p/(p
B
)
max
Stream B, U
B
Stream A, U
A
g
B
= 1
g
T
= 1.33
p
r
= 1.22
g
A
= 0.1; g
B
= 0.9
g
T
= 1
p
r
= 0.85
d
jet
(a) Schematic diagram of the multi-jet tubular reactor
Symmetry plane
Reactor cross-sectional map
(b) Mass fraction of reactant A
Fig. 9.30. Typical reacting CFD simulation results and
performance evaluation for the multijet tubular condensation
polymerization reactor.
performance without expensive experimentation is accelerating use of these
models in the polymerization industry.
As with other emerging technologies, CFDs capabilities have been understood
to a certain degree for reacting ow modeling. It can predict single-phase turbulent
reacting ows in industrial reactors with sucient detail and increased accuracy.
Multiphase reacting ow modeling, however, lacks experimentally veriable phys-
ical models to describe the complex multiphase uid dynamics (for example,
multiphase turbulence) and its interaction with heterogeneous reactions. Thus, ad-
vanced physical models and ecient numerical algorithms are needed to realize
CFDs full potential for applications involving heterogeneous polymerizations.
Finally, the emerging high-performance supercomputing technology is likely to
have a major impact in polymer reaction engineering for modeling plant-scale re-
actors with an increased level of physical, mechanical, and chemical details.
Steady-state or dynamic CFD calculations can be integrated with a general-purpose
process simulator, using an interface that allows the automatic exchange of critical
variables. This approach will open up new opportunities for real-time design mod-
ications to develop safe, reliable, and ecient polymerization processes and to
control polymer quality by carrying out sophisticated design and analysis at a sub-
stantially reduced cost.
Acknowledgments
N.K. thanks Professor R. O. Fox and his research group at the Iowa State Univer-
sity, Dr. C. LaMarca and colleagues in the DuPont Engineering Research and Tech-
nology department for the review of Sec. 9.10, and DuPont management for the
support.
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10
Scaleup of Polymerization Processes
1
E. Bruce Nauman
10.1
Historic and Economic Perspective
Since the mid-1960s the world has seen remarkable increases in production rates
for commercial polymers. Single-train line rates have increased by factors of 20 to
40 for polymers such as polyethylene, polypropylene, and polystyrene. A rate of
1 t h
1
that would have been economical in 1964 has become 2040 t h
1
. Part of
this improvement is attributable to improved catalysis and innovative processes,
but the greatest increase in productivity is due to classical scaleup. Larger plants
produce more polymer using substantially the same manpower and with reduced
capital investment per ton of annual capacity. The selling prices of the major com-
modity polymers have increased by factors of 3 to 4 since the 1960s, but the US
consumer price index has increased by a factor of 6. The result has been an ongo-
ing decrease in the real cost of polymers that leads to their greater use and a con-
tinuing incentive to build still larger plants.
The success of the petrochemical industry in the 20th century is attributable in
large part to the scalability of typical chemical processes. This chapter discusses
the technical basis for achieving capacity increases without major changes in tech-
nology. These techniques are broadly applicable to the development of new poly-
mers and new polymerization processes. They continue to be applied to existing
processes, although no process is innitely scalable. Eventually, a limit must be
reached.
10.2
The Limits of Scale
Consider the scaleup of a stirred tank reactor. It is common practice to scale using
geometric similarity so that the larger reactor will have the same shape as the small
reactor. Suppose the volume scaleup factor is given by Eq. (1).
ISBN: 3-527-31014-2
533
S =
V
large
V
small
(1)
All linear dimensions such as reactor diameter, impeller diameter, and liquid
height will scale as S
1/3
. Surface areas will scale as S
2/3
while volume itself scales
as S
1
. The total amount of heat transferred to a jacket will increase as S increases,
but heat transfer per unit volume of reactor contents will decrease. Sooner or later,
the reactor will become adiabatic. Similarly, any mass transfer to an external sur-
face will become limiting. These limitations are well known and can be avoided,
for example, by employing processes without external mass transfer and by using
enough inerts so that the adiabatic temperature rise is acceptable. However, there
is still a mixing limit that will ultimately emerge. In very large vessels, it will be-
come impossible to mix the reactive components in a time that is reasonable com-
pared to the reaction half-life. Consider a pilot-scale vessel that has a mixing time
of 30 s using a small electric motor. Suppose it is desired to maintain this mixing
time when the reactor is scaled, using geometric similarity, by a factor of 10 in
linear dimensions and by a factor of 1000 in volume. Standard correlations show
that it is necessary to maintain the same rotational speed of the agitator, say 100
rpm, in both large and small vessels. The agitator power increases by a factor of
S
5/3
= 100 000, so that a 0.5 kW motor scales to 50 000 kW.
The lesson from this is that even a simple phenomenon such blending of two
uids requires longer and longer times as the size of the process increases. Even-
tually, the operation becomes unfeasible.
10.3
Scaleup Goals
The goals of a process scaleup are to obtain acceptable product quality with good
manufacturing economics. Product quality is usually best at the laboratory scale
because mixing and heat transfer are excellent and because the academic training
of chemists puts a high premium on yield and selectivity. The same product qual-
ity can be achieved upon scaleup by employing many bench chemists working in
parallel, but the economics will be poor. The scaleup engineer seeks to design a
single-train process that meets anticipated market demands or else is the largest
capacity unit for which adequate quality can be achieved.
A single-train process may include some equipment in parallel. Shell-and-tube
heat exchangers are a ubiquitous example. They are relatively inexpensive and are
sold as integral units. Another example in the polymer industry is pelletization.
The maximum economic size for extrusion and pelleting has lagged behind the
maximum size for polymerization reactors. Thus it is common for a polymeriza-
tion reactor to feed two or three pelleting lines. These lines are expensive, so the
economics of scaleup are compromised. However, the major cost of a polymeriza-
tion line is in the feed preparation, reaction, and recovery sections, and these are
generally single-train. They have one control system, one operating crew and
534 10 Scaleup of Polymerization Processes
with the possible exception of additives added in the extrusion or pelleting steps
make one product at a time. They are single-train by the practical, working deni-
tion of single train.
Since the ability to mix and transfer heat generally decreases upon scaleup, the
uniformity of a product usually decreases as well. This typically means an increase
in polydispersity of a polymer. It is easy to make polystyrene having a polydisper-
sity of 2 by a laboratory-scale, free-radical process. Industrial processes have di-
culty going below 2.2 and operate best when making products with a polydispersity
of 2.5 and higher. Such products are sellable and are even preferred for injection
molding. However, had the early polystyrene markets required the low polydisper-
sity achievable in the laboratory, the commercial processes would have failed. Re-
sidual volatiles are a similar example. Coagulation and vacuum drying in the labo-
ratory have always been able to produce the low volatilities that are now possible on
a commercial scale after 50 years or so of process development. For a new polymer,
product quality goals and qualication tests must be based on what is possible to
achieve in commercial-scale equipment, not on what is possible in the laboratory.
This may require a change in the laboratory-scale operating conditions so that the
product is economically achievable in a commercial process. The intentional less-
ening of product goals in the laboratory or pilot plant to enable economic scaleup
is called diplomatic scaleup because it may require diplomacy to convince the
bench chemist and management.
10.4
General Approaches
There are many ways of increasing the capacity of a chemical reactor. The simplest
methods are scaling in parallel or scaling in series. When applied to a tubular reac-
tor, the tube diameter is held constant, and capacity is increased by adding tubes in
parallel or in series. There are several scaleup possibilities:
v
Add identical reactors in parallel. The shell-and-tube design used for heat ex-
changers is a common and inexpensive way of increasing capacity. Gas-phase,
heterogeneously catalyzed reactions are usually scaled in this way since temper-
atures and pressures are identical in the small and large scales. The ultimate
scaleup limit is uniform distribution of feed across a large tube bank, but the
limit has not been reached with 10 000 tubes. In the polymer industry, 1000-
tube heat exchanges are used as post-reactors and devolatilization preheaters for
polystyrene. Shell-and-tube designs are also used in solution process loop reac-
tors, but instability or fouling problems arise if the discharge stream has a
much higher viscosity than the feed stream.
v
Make the reactor longer or add reactors in series. Capacity can be increased in
the high-pressure process for LDPE by adding an extra mile to the tubular reac-
tor. Adding stirred-tank or stirred-tube reactors in series is sometimes used to
scale up polystyrene processes. For incompressible uids, scaling in series is lim-
10.4 General Approaches 535
ited by pressure drop. For compressible uids, lengthening a reactor can lead to
a dramatic increase in density so that the ratio of heat transfer area to volume
decreases dramatically.
v
Simultaneously increase two or more characteristic dimensions of the reactor.
Scaling with geometric similarity, so that all linear dimensions increase by a fac-
tor of S
1/3
, is common for stirred-tank reactors but uncommon for tubes. Geo-
metric similarity for a tube means keeping the same length-to-diameter ratio,
L/d
t
, upon scaleup. It is also possible to scale while maintaining a constant pres-
sure drop across the reactor. Turbulent reactors require a reduction in length-to-
diameter ratio to scale at constant pressure drop. Scaling with geometric similar-
ity gives a constant pressure drop in laminar-ow reactors.
Scaling in parallel or series is preferred when heat transfer is a dominant consider-
ation. The third method, scaling with geometric similarity, is cheaper for reactions
that permit adiabatic operation.
Two other methods of scaleup are:
v
Lower product quality expectations to what is readily achievable in a commercial
reactor, ideally an adiabatic reactor with premixed feed. This is the diplomatic
form of scaleup mentioned in Section 10.3.
v
Go from batch to continuous operation. Scaleup is easier, especially for post-
reactor processing techniques that are typically continuous. For a stirred-tank
reactor, the reaction rate will decline because the entire reaction is conducted at
the highest conversion and thus, typically, at the lowest reaction rate. However,
the decline in rate is more than compensated for by the full time utilization
of the reactor compared to occasional utilization in a batch process.
In what follows, we will draw heavily on Ref. 1, in which scaleup is treated in the
general context of reactor design. Another general reference work is by Bisos and
Kabel [2] while McGreavy [3] briey discusses scaleup of polymerization processes.
Many references purport to discuss scaleup but only give modeling equations that
contain scale-dependent parameters, the values of which are left as an exercise to
the reader. Another common approach is to enumerate the various dimensionless
numbers that govern a reaction system. One quickly concludes that scaleup of a
pilot-scale reactor is impossible because it is not feasible to maintain the various
dimensionless numbers at the same values as they had in a pilot plant, except by
scaling in parallel. The secret, of course, is to know when constancy of a dimen-
sionless number can be sacriced without compromising the scaleup. As an obvi-
ous example, the Reynolds number will usually increase upon scaleup, but laminar
ow patterns are largely indierent to Reynolds number until some critical value is
reached. Similarly, the Froude number is unimportant in a baed stirred tank. In
contrast, dimensionless groups involving temperature (for example, T/T
act
where
T
act
is the Arrhenius activation temperature) must be kept nearly constant upon
scaleup of a chemical reaction.
10.5
Scaleup Factors
Equation (1) dened S as the ratio of large and small volumes. A more rigorous
denition bases S on the ratio of holdup (inventory) in the large and small reactors.
This accounts for possible density variations. However, the goal in almost all scale-
ups is to achieve the same reaction environment in the large and small scales and
thus the same density. For this case, S is dened in Eq. (2).
Holdup Scaling Factor =
Holdup in Large System
Holdup in Small System
=
[ ^ rrV[
Large
[ ^ rrV[
Small
A
V
Large
V
Small
= S (2)
The throughput scaling factor, S
T
, is the ratio of production rates for the large and
small reactors [Eq. (3)].
Throughput Scaling Factor =
Throughput for Large System
Throughput for Small System
=
[r
in
Q
in
[
Large
[r
in
Q
in
[
Small
A
Q
Large
Q
Small
= S
T
(3)
The mean residence time, t, is the ratio of holdup to throughput. Reaction systems
are almost always scaled with a constant value for t. This means that S
T
= S is the
almost universal way in which ow reactors are scaled. Batch reactors are usually
scaled using the same batch reaction time.
10.6
Stirred-tank Reactors
The conventional stirred-tank reactor is an agitated vessel, typically a jacketed pres-
sure vessel, and often with provisions for reux of a solvent or monomer. The
continuous-feed version is the CSTR. Continuous operation is typical of high-
volume polymers but large batch and fed-batch stirred-tank reactors are occasion-
ally used. Reactors other than stirred tanks may be functionally equivalent to
stirred tanks. Loop reactors are widely used in the polymer industry, especially for
solution and slurry olen polymerizations; the agitator in the stirred tank is re-
placed with a circulation pump. The loop many consist of jacketed pipe or there
may be heat exchangers and even ash vessels in the loop. The loop may consist
of many legs for space considerations, but the legs are connected in series and
there is only one circulation pump.
Fluidized-bed reactors can also be treated as stirred tanks for many purposes;
so can the stirred-tube reactors used for styrenic polymerizations. A reactor will be-
have like a stirred tank when the contents are approximately uniform in tempera-
ture and composition and when the contents have a nearly exponential distribution
of residence times. If the reaction is rst order or pseudo-rst order, or if the con-
version is low, the yield behavior will be similar to that of an ideal, perfectly mixed
CSTR provided only that the contents are approximately isothermal and have an
exponential distribution of residence times. It is not necessary for the contents to
be well mixed on the molecular level. Mixing on the molecular level, that is, micro-
mixing, is of great academic interest but has so far not been identied as important
in commercial polymerization vessels. Instead, circulation times (mixing times)
are limiting. Typical mixing times in large vessels are a few minutes. In turbulent
vessels, the distance scale over which diusive mixing is limiting is on the order of
the Kolmogorov scale, typically a few tens of microns, and diusive mixing occurs
in a fraction of a second. The Kolmogorov scale varies with power per unit volume
and thus remains constant for a conventional scaleup. Although the underlying
mechanisms are dierent, circulation times are typically much greater than diu-
sion times in laminar ow vessels as well.
The scaling of stirred-tank reactors is usually based on geometric similarity so
that the large vessel looks like the small reactor, and all linear dimensions scale
as S
1/3
. Table 10.1 gives a variety of scaleup factors for this form of scaleup. In the
general case, the agitator rotational speed, N
I
, is independently adjustable. The
throughput scaleup factor, S
T
, is also independently adjustable but has no appre-
ciable eect on the scaleup factors in Table 10.1 because the internal circulation
due to the agitator is normally much higher than the throughput of a CSTR.
Thus, batch stirred tanks and normally designed CSTRs behave in much the
same way with respect to the parameters listed in Table 10.1. The scaleup factors
Tab. 10.1. Scaleup factors for turbulent stirred tanks.
General
scaling
factor
Scaling factor for
constant power per unit
volume
Numerical
scaling factor
for S F512
Vessel diameter S
1/3
S
1/3
8
Impeller diameter S
1/3
S
1/3
8
Vessel cross-section S
2/3
S
2/3
64
Vessel volume S S 512
Reynolds number N
I
S
2/3
S
4/9
8
Froude number N
2
I
S
1/3
S
1/9
0.5
Agitator speed N
I
S
2/9
0.25
Power in turbulent ow N
3
I
S
5/3
S 512
Power in laminar ow N
2
I
S S 512
Power per volume N
3
I
S
2/3
1.0 1
Mixing time N
1
I
S
2/9
4
Circulation rate N
I
S S
7/9
128
Heat transfer area, A
ext
S
2/3
S
2/3
64
Inside coecient, h N
2/3
I
S
1/9
S
1/27
0.79
Coecient area, hA
ext
N
2/3
I
S
7/9
S
17/27
50.8
Driving force, DT N
2/3
I
S
2/9
S
10/27
10.1
for power and heat transfer coecients shown in Table 10.1 are based on generally
accepted correlations for turbulent stirred tanks. Nauman [1] gives details.
As shown in Table 10.1, power in the turbulent regime varies as N
3
I
S
5/3
. As a
practical matter, N
I
must be lowered upon scaleup. Agitation experts have many
criteria for setting N
I
, but scaling with constant power per unit volume is a good
general rule. For fully turbulent vessels, this means that N
I
will vary as S
2/9
. Table
10.1 gives specic scaling factors for scaleups with constant power per unit vol-
ume, and also gives numerical examples for such scaleups with S = 512. In these
examples, the power calculation assumes turbulent ow. Note that for turbine-
agitated vessels, ow is substantially turbulent ow when the impeller Reynolds
number, rN
I
D
2
/m, is above about 100. Power in laminar ow scales as N
2
I
S.
The specialized literature, and especially Paul et al. [4], provide details on close-
clearance impellors (for example, anchors and helical ribbons) and correlations
suitable for deep laminar ow. As a generalization, heat and mass transfer to the
external environment is very low in such devices. However, it is usually possible to
achieve a suciently high circulation rate in the vessel for the tank to be reason-
ably well mixed.
The volumetric scaleup by a factor of 512 anticipates an increase in throughput
by the same factor. Is this possible while maintaining reasonable product quality?
The results in Table 10.1 suggest three possible problems. The rst is mass trans-
fer to the external environment. For geometric similarity, surface areas increase by
a factor of only S
2/3
, or 64, while throughput and volume increase by a factor of
512. A limitation can arise if a condensation product has to be removed across the
free surface at the top of the vessel. A practical example is the removal of byproduct
ethylene glycol in the glycolysis route to PET. Similarly, very high boiling rates in a
reux reactor can cause slugging and liquid entrainment. A potential solution to
such mass transfer problems is the use of an external recycle loop, as shown in
Figure 10.1. The recycled material is ashed into the dome of the stirred tank, cre-
ating extra surface area by foaming (that is, by ash devolatilization).
A second possible limitation is heat transfer. If the vessel contents are cooled
through a jacket or by internal coils, the cooling demand increases by a factor of
512 but the surface area increases by a factor of only 64. Additionally, the heat
transfer coecient decreases when scaling at constant power per unit volume.
The result is that the driving force at the wall must increase by a factor of about
10 when scaling with S = 512 and constant power per unit volume. This may be
acceptable when the pilot unit operates with a DT of 2
C but becomes problematic

when the pilot plant operates with a 20
C DT. There are many solutions. In a

CSTR, use cold feed. Some processes for PMMA use a 40
C feed to control the

reaction exotherm. Diluents and low per-pass conversions can also be used: this
approach is typical of solution polyolen processes. Reux boiling can be used: it
is common in styrenic polymerizations where the reux solvent is normally re-
turned as a liquid. In some polypropylene processes, the returning propylene is
ashed into the rst reaction vessel. Finally, the external loop shown in Figure
10.1 can be used. Indeed, a loop reactor with the elimination of the stirred tank
performs identically to a CSTR provided that the circulation rate is high compared
to the throughput. Heat transfer can be better managed using a shell-and-tube ex-
changer in the loop than by the jacket or internal coils in a stirred tank. A ash can
be built into the loop for mass transfer or to cool the reaction mass. At large scales,
loop reactors are economically superior to stirred vessels and are preferred by so-
phisticated companies for high-volume processes.
The third possible limitation is mixing time. As the scale increases, it becomes
increasingly dicult to mix fresh feed (whether in a CSTR or a fed-batch reactor)
with the contents in the vessel. In the example of S = 512, constant power per unit
volume causes the mixing time to increase by a factor of 4. Does this hurt the prod-
uct? Test for this by decreasing the agitator speed in the pilot plant to give a mixing
time that can reasonably be achieved upon scaleup. Diplomatic scaleup may be
possible. If fast mixing times are really required, multiple injection points can be
used. Loop reactors do not solve the mixing time problem as they are subject to ex-
actly the same limitations of impeller speed, power, and mixing time. However,
they do allow the dilution of feed at a controlled rate. Also, faster mixing times
achieved through the use of multiple injection points are easier to implement in a
loop reactor.
Static Mixer
CSTR Inlet and Fed
Batch Additives
Circulation
Pump
Reactor Outlet
Vapor Condensate
Shell-and-
Tube Heat
Exchanger
Stirred
Tank
Lowers distance
scales for heat transfer
and mixing.
Allows a controlled
dilution rate for
incoming feed.
Can be detuned at the
small scale to simulate
achievable results at the
large scale.
Fig. 10.1. A Generalized Loop Reactor.
The real question in the scaleup of a stirred-tank reactor is simply whether the
contents of the vessel will remain reasonably well mixed upon scaleup. If there is
good compositional homogeneity, then there will be thermal homogeneity as well,
since thermal diusivities are typically two orders of magnitude higher than mo-
lecular diusivities. The absolute value of the temperature in the larger vessel can
be regulated by scalable techniques such as boiling, cold feed, or external heat
transfer if wall cooling is inadequate.
10.7
Design Considerations for Stirred Tanks
Removal of the heat of reaction is the critical factor in vinyl polymerizations. It is
less important for ring-opening polymerizations, such as for Nylon 6, and is unim-
portant for condensation polymerizations, such as for PET and polycarbonate. The
removal of heat through the walls of a stirred tank or by internal cooling coils is
dicult to scale and not recommended. Scaleup of even a moderately exothermic
reaction can lead to a vessel half-full of cooling coils for which the normal correla-
tions for heat transfer are overly optimistic. Scalable techniques include cold feed,
reux (autorefrigeration) of monomer or solvent, use of diluents, low per pass con-
versions, and external heat exchange in shell-and-tube reactors.
Reux reactors remove the heat of polymerization through the heat of vaporiza-
tion of monomer or solvent. Boiling by homogeneous nucleation scales directly
with volume. Vapor bubbles break the free surface of the reactor. The vapor is con-
densed and returned directly to the reactor or is recycled to the feed. Concerns
about boiling reactors include polymerization on the dome of the reactor and foul-
ing of the condensate heat exchanger. The issue is simple. If the polymer is soluble
in the monomer or solvent mixture as it condenses, there is little problem. This
fact seems self-evident, although it took 30-odd years for a company otherwise
noted for its engineering skills to be shamed into recognizing it by a European
subsidiary. If the polymer in insoluble in the condensate, fouling can be expected.
PET nishing reactors (which are more like tubes than stirred tanks) exemplify
this problem, and 30-plus years of research have failed to yield a good solution.
Perhaps the best solution is a hot spare that can be switched into duty as the other
condenser is cleaned.
Another limitation of a boiling reactor is the eect of pressure on boiling point.
A very tall reactor will have higher temperatures at the bottom that will typically
give lower molecular weight polymer and higher polydispersity in the product.
Field erection of stirred tanks is much more expensive than shop erection, and
the maximum size of a stirred-tank reactor may be limited by the size that can be
shipped. Thus plants immediately adjacent to water may be able to have larger re-
actors than plants accessed only by rail or road. Rail and road shipments limit re-
actor sizes to about 100 m
3
. Much larger vessels are eld-erected, but these designs
are usually more suited as low-pressure storage tanks or fermentation reactors
than as polymerization reactors that are typically rated for 1020 atm pressure.
10.7 Design Considerations for Stirred Tanks 541
10.8
Multiphase Stirred Tanks
Polymerization reactors are occasionally multiphase. The boiling reactor is an ex-
ample where scaleup has been easy because homogeneous nucleation depends
on temperature and pressure but is otherwise independent of scale. As discussed
above, potential limits exist for very large vessels, but these have not yet been en-
countered. The precipitation of rubber particles in a HIPS process is another exam-
ple where the phase separation mechanism, that is, spinodal decomposition, is
homogeneous and thus potentially independent of scale. The local concentrations
that drive spinodal decomposition are due to a combination of chemical reaction
and mass transfer between the entering feed and the vessel contents. A scaleup
limitation could occur, for example if the mixing time in the CSTR became too
large, but some compensation is possible by slightly altering conversion in the re-
actor. As a practical matter, vessels diering by more than 25 000-fold in volume
have achieved substantially the same results in HIPS polymerizations.
Sparged reactor vessels present a greater problem for scaleup, although sparging
is not very common in continuous polymerization reactors. The European targeted
research activity on polymer materials (TRA-PM) has addressed the scaleup of mul-
tiphase reactions with the comment: A newer integrated, but still semi-empirical
approach uses experience-based equipment selection, laboratory experiments gen-
erating starting parameters for CFD calculation, numerical calculations using ad-
vanced CFD tools, pilot scale experiments to verify CFD calculations and nal
design and scale-up with CFD.
This approach may become possible as CFD codes become better able to solve
the convective diusion equations for heat and mass transfer in the presence of a
chemical reaction and in addition to their more established but not completely per-
fect role in the prediction of the uid mechanics. At the moment, this procedure
lacks validation even for single-phase stirred-tank reactors.
10.9
Stirred Tanks in Series
One way to double the output of a stirred tank process is to increase each linear
dimension by 2
1/3
= 1:26, but this may lead to heat transfer or mixing limita-
tions. Another way is to add a stirred tank in parallel, but better results and a
more exible process are usually achieved by adding a stirred tank in series. Some
polystyrene processes use ve stirred-tank and stirred-tube reactors in series. Some
polypropylene processes use two or three loop and stirred-tank reactors in series.
Modern uidized-bed processes for polypropylene use two beds in series.
One advantage of using tanks in series is the improvement in residence time
distribution from the exponential distribution of a single stirred tank toward that
of piston (plug) ow. The series arrangement leads to higher conversion and thus
eases the burden of downstream recovery and recycling. The usual case is for two
reactors in series to produce more than two reactors in parallel, although operation
at very high conversions (for example, 70% for styrene) may be an exception be-
cause of the gel eect.
A major advantage of using tanks in series is the ability to have a dierent reac-
tion environment in the various tanks. This advantage is especially useful in poly-
propylene processes where the last reactor adds ethylene for impact modication.
10.10
Tubular Reactors
Scaling tubes in parallel is the standard method for low-viscosity uids when the
reaction exotherm is signicant, and particularly for gas-phase reactions where
the pressure drop is important. Shell-and-tube designs allow tubular polymeriza-
tion reactors to be scaled in parallel, subject to the limitation of distributing the
feed across the tube bundle. Distribution becomes a problem when the viscosity
of the feed is much less than the viscosity of the product. This viscous ngering
problem that arises in secondary oil recovery is also a problem in multitubular
polymerization reactors. The relatively inviscid material entering cannot displace
polymerized or devolatilized material that may form in the tubes. The result can
be many tubes that are completely plugged, with a few tubes gushing unreacted
feed. Static mixers cannot eliminate this problem since they too oer parallel paths
for ow, some of which can plug. The known, practical solution is to limit per pass
conversion so that the outlet viscosity is within about an order of magnitude of the
inlet viscosity. Polystyrene post-reactors and devolatilization preheaters function
satisfactorily when the entering feed is about 70% polymer. Solution HDPE pro-
cesses function satisfactorily when the per pass conversion is limited to about
15%. Multitubular devolatilization preheaters can function with entering polymer
concentrations below 15% by using a motor-controlled, backpressure valve that pre-
vents ashing in the tube bundle.
When scaling in parallel, the number of tubes scales directly with the inventory
scaleup factor, S. Factors for other forms of scaleup for incompressible uids are
given in Table 10.2. This table includes three geometric scaleup factors. They are
for volume, S, radius S
R
, and length, S
L
. They are related by Eq. (4) so that only
two are arbitrarily adjustable.
S = S
L
S
2
R
(4)
Thus the general scaling equation for pressure drop in a single tube in laminar
ow can be given in several equivalent forms [Eqs. (5)].
S
DP
= S
T
S
4
R
S
L
= S
T
S
2
S
L
= S
T
SS
6
R
(5)
The results in Table 10.2 emphasize the constraint of Eq. (4) by eliminating S
L
from the scaleup factors in the column that species S
T
= S.
10.10 Tubular Reactors 543
The general scaleup factor for the Reynolds number is given by Eq. (6).
Re
Large
Re
Small
=
(d
t
u)
Large
(d
t
u)
Small
= S
T
S
1
R
(6)
Scaleup at constant Reynolds number, with S
T
= S, would require SS
1
R
= 1, so
S
R
= S and S
L
= S
1
. The scaled-up reactor would have to be fatter but shorter,
which is a strange form of scaleup. For scaleups other than in parallel, the Rey-
nolds number will increase, although typically not by enough to cause turbulence
or even transitional ow in polymer systems.
Scaling a tube in series is conservative with respect to heat transfer. The neces-
sary wall driving force remains constant in laminar ow and decreases in turbulent
ow. The major diculty is the pressure drop that scales as S
2
for laminar ow
and as S
2:75
in turbulent ow. Polymer solutions are mildly shear thinning, so
these factors somewhat overestimate the pressure drop. Still, the pressure drop in
the pilot-scale reactor had better be small.
Tab. 10.2. Scaleup factors for tubes.
Flow regime General
scaleup
factors
General
factor for
S
T
FS
Series
scaleup
Geometric
similarity
Constant
pressure
scaleup
Laminar
diameter scaling factor S
R
S
R
1 S
1/3
S
1/3
Length scaling factor S
L
SS
2
R
S S
1/3
S
1/3
Reynolds number S
T
S
1
R
SS
1
R
S
L
S
2/3
S
2/3
Length-to-diameter ratio S
L
S
1
R
SS
3
R
S 1 1
Pressure scaling factor, DP S
T
S
4
R
S
L
S
2
S
6
R
S
2
1 1
Laminar with Gz < 75
Inside coecient, h S
1
R
S
1
R
1 S
1/3
S
1/3
Coecient area, hA
ext
S
L
SS
2
R
S S
1/3
S
1/3
Driving force, DT S
T
S
1
L
S
2
R
1 S
2/3
S
2/3
Laminar with Gz > 75
1/3
T
S
1
R
S
1/3
L
S
1/3
R
1 S
1/9
S
1/9
Coecient area, hA
ext
S
1/3
T
S
2/3
L
SS
4/3
R
S S
5/9
S
5/9
Driving force, DT S
2/3
T
S
2/3
L
S
4/3
R
1 S
4/9
S
4/9
Turbulent
Diameter scaling factor S
R
S
R
1 S
1/3
S
11/27
Length scaling factor S
L
SS
2
R
S S
1/3
S
5/27
Length-to-diameter ratio S
L
S
1
R
SS
3
R
S 1 S
2/9
Reynolds number S
T
S
1
R
SS
1
R
S
L
S
2/3
S
0:59
Pressure scaling factor, DP S
1:75
T
S
4:75
R
S
L
S
2:75
S
6:75
R
S
2:75
S
1/2
1
Heat transfer area, A
ext
SS
1
R
SS
1
R
S S
2/3
S
0:59
0:8
T
S
1:8
R
S
0:8
S
1:8
R
S
0:8
S
0:2
S
0:07
Coecient area, hA
ext
S
0:8
T
S
0:8
R
S
L 19
S
1:8
S
2:8
R
S
1:8
S
0:87
S
0:66
Driving force, DT S
0:2
T
S
0:8
R
S
1
L
S
0:8
S
2:8
R
S
0:8
S
0:13
S
0:34
Scaling a laminar-ow, tubular reactor with geometric similarity has the interest-
ing consequence of constant pressure drop. Thus, scaling with geometric similarity
is great for adiabatic reactors. A constant pressure drop is obtained for gases as
well as liquids. However, even though temperature eects may be negligible, the
reactor will have radial concentration gradients due to the laminar velocity prole.
Molecular diusion will alleviate this prole and usually helps the performance of a
laminar-ow reactor. The benecial eects of diusion will diminish upon scaleup.
Geometrically similar scaleup of laminar ow in tubes cannot be recommended
unless radial diusion was negligible in the pilot-scale reactor. Diusion depends
on the dimensionless group Dt/d
2
t
where D is the molecular diusivity. If this
group is less than about 0.001, then diusion has little eect except possibly for
subtle reactions such as crosslinking.
A geometrically similar scaleup in turbulent ow gives a pressure drop that in-
creases as S
1/2
. More energy goes into pumping. The pumping energy increases as
S
T
S
1/2
and the pumping energy per unit throughput increases as S
1/2
. The extra
energy causes more eddy diusion and gives a better environment for reaction.
Unlike molecular diusion in a laminar-ow system, the benet from eddy diu-
sion increases with size, but turbulence is unlikely when the continuous phase
contains a high molecular weight polymer.
For laminar ow of a Newtonian uid, scaleup at constant pressure drop is iden-
tical to scaleup with geometric similarity. For constant pressure drop in turbulent
ow, the reactor diameter increases somewhat faster, S
11/27
, than for scaleup with
geometric similarity. The reactor length increases somewhat more slowly, S
5/27
, so
that the reactor becomes shorter and fatter and heat transfer becomes substantially
more dicult.
Scaleup with constant heat transfer is theoretically possible with any form of
scaleup, provided the wall driving force can be adjusted as shown in Table 10.2.
As a practical matter, the required DT soon becomes excessive if signicant heat-
ing or cooling was needed in the pilot unit.
10.11
Static Mixers
Rather dierent considerations apply when a tube containing a static mixer is
scaled up. If the tube diameter increases upon scaleup, then the number of mixing
elements should also increase, but the increase is minor. For a scaleup based on
geometric similarity, the extra number of elements is given by Eq. (7).
N
extra
=
log(S)
3 log(2)
(7)
This result assumes the static mixer is of the Kenics type that repeatedly divides
the uid into two portions (that is, one that follows the 2
N
model for striation
thickness). See Ref. 5 for details and results for other types of static mixers. Equa-
10.11 Static Mixers 545
tion (7) is a slowly increasing function of S; for example, an increase by a factor of
512 in throughput requires only three extra elements.
10.12
Design Considerations for Tubular Reactors
As discussed above, shell-and-tube reactors and heat exchangers can be employed
in polymerization and recovery trains, provided the inlet and outlet streams have
similar viscosities. Subject to this caveat, scaleup is simple and inexpensive. Static
mixers are sometimes used to enhance heat exchange, but their benet is marginal
compared to the alternative of using open tubes with a somewhat smaller diameter
and greater length to give the same pressure drop. In this connection, there is no
minimum tube diameter. Some companies have used 0.5-inch (12.5-mm) tubes in a
variety of polymer processes since the 1960s. An insistence on large-diameter tubes
can lead product property problems.
Tubular reactors are rarely scaled in series because of pressure limitations. The
great exception to this statement is the high-pressure process for LDPE, where re-
actor lengths are measured in kilometers. The diameter of the tube is strictly lim-
ited to about 5 cm to avoid thermal runaway. A few tubes in parallel, possibly with
separate ethylene compressors, can be used to achieve greater capacity, but conven-
tional shell-and-tube designs present a serious problem of tube-to-tube instability.
Scaleup to large-diameter tubes is generally possible only when the adiabatic
temperature rise is acceptable. A practical example of such scaleup is the adiabatic
post-reactor that is sometimes added to polystyrene reaction trains as an inexpen-
sive way of boosting capacity. Tubular pilot reactors should be run adiabatically; or
if some removal of heat is needed, they should be run at the same value of the ther-
mal diusion group, a
T
t/d
2
t
where a
T
is the thermal diusivity. This means run-
ning the pilot unit at the same value of t and d
t
but with a lower ow rate and a
shorter tube than expected in the scaled-up reactor. It is equivalent to scaling in
series. This approach will also give the same value of the molecular diusion
group, Dt/d
2
t
, where D is the molecular diusivity.
Typical vinyl polymerizations, for example of ethylene, propylene, vinyl chloride,
styrene, and methyl methacrylate, have adiabatic temperature rises between 200
and 1600
C. This leads to the possibility of parametric sensitivity and thermal run-

away. Figure 10.2 demonstrates parametric sensitivity for styrene polymerization
in a tube that is assumed to be well mixed in the radial direction, as might re-
sult from the use of static mixers (that is, the model consists of simultaneous,
ordinary dierential equations for composition and temperature). The dramatic
transition from a controlled reaction to a thermal runaway corresponds to a mere
1 mm dierence in tube diameter. Although inlet and wall temperatures can be
varied, reaction in a large-diameter tube is not feasible for this and similarly ener-
getic reactions absent an excellent control system [6]. A detailed model of this
polymerization in an open tube (the model consists of simultaneous, partial dier-
ential equations for composition, temperature, and velocity) shows that hydrody-
namic instabilities can arise in the absence of static mixers due to large viscosity
dierences between the wall and centerline. For the illustrated case of T
in
= 135
C
and T
wall
= 20
C, a hydrodynamic instability occurs at a smaller tube diameter

than for a thermal runaway. Installation of static mixers merely postpones the
problem until the marginally larger diameters shown in Figure 10.2 are reached.
The overall conclusion is that single-tube polymerization from undiluted styrene
is not feasible if the tube diameter exceeds about 0.06 m or if the conversion ex-
ceeds about 20%. Figure 10.3 illustrates the conversion and stability limits for
open tubes (tubes without a static mixer). Scaling in series using a long tube ap-
pears to be feasible for styrene polymerization, as it is for ethylene polymerization.
However, high pressures are not required for the styrene polymerization, and
stirred-tube reactors or boiling stirred tanks have been preferred.
Scaleup of polycondensation reactions involving multifunctional monomers (for
example, phenol/formaldehyde) in tubular reactors has proven especially dicult.
Even though the overall stoichiometry (for example, formaldehyde at 75 mol% of
the entering phenol concentration) is set to avoid crosslinking, locally crosslinked
regions near the tube walls can result when the diusion group, Dt/d
2
t
, is too
large. The ultimate result is a plugged tube. This empirical observation has been
conrmed in modeling studies. A similar problem may exist in anionically cata-
lyzed polymerizations although modeling studies and some experimental studies
indicate that such polymerizations should be possible in tubular reactors.
0.0
100.0
200.0
300.0
400.0
500.0
0.00 0.60 1.20 1.80 2.40 3.00 3.60
Axial Position, m
T
e
m
p
e
r
a
t
u
r
e
,

C
0.060
0.061
0.062
Fig. 10.2. Temperature proles for the polymerization of
undiluted styrene in a tubular reactor with good radial mixing.
T
in
= 135
C and T
wall
= 20
C. The parameter in the plot is the

tube diameter in meters.
10.12 Design Considerations for Tubular Reactors 547
Fig. 10.3. Polymerization of undiluted styrene in an open tube
with radial mixing only by molecular diusion. The mean
residence time used for conversion calculations is 1 hour.
10.13
Extruder and Extruder-like Reactors
Extruders are sometimes used for polymer modication reactions such as grafting.
As a general rule, scaleup is dicult and expensive. The diculty is primarily due
to the very limited ability of extruders to exchange heat with an external source.
Most production-scale extruders operate almost adiabatically, with energy input
from the motor appearing as enthalpy of the product. This is in addition to any
reaction exotherm. The expense is due to the very high cost of reaction volume in
an extruder. As a practical matter, residence times are limited to a few minutes.
Like stirred tank reactors, extruders are generally scaled using geometric similarity
so that the ability to transfer heat decreases upon scaleup. Similarly, the screw
speed must generally decrease, or at least not decrease, upon scaleup. Extruders
operate in the laminar-ow regime, and the scaleup factor for power, as a func-
tion of screw diameter, is less dramatic than in stirred tanks, particularly for shear-
thinning polymer melts. As a rough approximation, power varies as conveying ca-
pacity, N
I
D
3
, so that the enthalpy input to the polymer is approximately constant.
However, extruders with a screw diameter of less than about 50 mm are generally
considered unscalable because the ratio of external area to volume is too large to
approximate to the nearly adiabatic operation expected upon scaleup.
The nishing reactors used to drive polycondensation reactions (for example, for
PET) to high molecular weights are extruder-like devices that generate surface area
for the removal of the condensation byproduct (such as ethylene glycol). Conven-
tional devolatilization theory suggests they scale as N
1/2
I
D
2
.
10.14
Casting Systems
We consider here two kinds of casting systems, mold casting and casting onto a
moving web. Reliable scaleup of mold casting requires an absence of polymeriza-
tion byproducts, especially gaseous byproducts, and a manageable heat of reaction.
The polyurethane formulations used for RIM (reactive injection molding) have no
byproduct and a negligible heat of polymerization so that the molding process can
be scaled to quite large parts. Similarly, the ring-opening polymerization of capro-
lactam has no byproducts and an adiabatic temperature rise of about 60
C that can
be tolerated in the molding process. Again, quite large parts can be molded. Methyl
methacrylate has a substantial heat of reaction so that a large casting of pure
monomer would boil and ruin the part. Addition of the polymer, PMMA, to the
casting mixture lowers the possible temperature rise. It also increases the viscosity
so that the gel eect is enhanced. In PMMA, the gel eect is pronounced but the
polymerization stops well short of complete conversion because the mixture solidi-
es. The result is that an adiabatic casting of a PMMA/methyl methacrylate mix-
ture never reaches the boiling point of the monomer and a defect-free part is pos-
sible, even a large one.
10.14 Casting Systems 549
Web casting can be used for polymerizations that do have reaction byproducts
and large reaction exotherms. Examples of web-cast products include photographic
lms and coated abrasives. Here, the desired product is obtained directly as a lm
or sheet. Web casting can be used in belt-plus-aker operations where the web acts
a temporary polymerization reactor. Web casting is scaled up at constant web thick-
ness and at constant residence time on the web. Production increases are achieved
by using wider webs or longer, higher-speed webs. The major issues for scaleup are
primarily the mechanical and control systems need to achieve a desired and uni-
form lm thickness.
10.15
Concluding Remarks
The scaleup of polymerization processes is conceptually identical to the scaleup
of ordinary chemical reactions. The principal dierence is that polymer systems
are more likely to be highly viscous and in laminar ow. Although polymer melts
can be markedly non-Newtonian, this is rarely a critical factor in the scaleup of
polymer reaction and recovery systems. Vinyl polymerizations have strong exo-
therms so that parametric sensitivity and thermal runaways can be a problem, but
so do many other chemical reactions. Condensation polymerizations tend to be
equilibrium-limited, but so do many other chemical reactions.
Laminar ow decreases heat and mass transfer both to the environment and
within the uid as molecular and thermal diusion replaces eddy diusion as the
primary mechanism, and their benets diminish upon scaleup. The large viscosity
dierences possible during polymerizations can lead to hydrodynamic instabilities
within a tube or between tubes. These problems are seldom found in ordinary
chemical reactions and prevent the easy application of shell-and-tube designs. The
net result is that scaling in series, either by increasing reactor length or by adding
reactors in series, is more common in the polymer industry than in the ordinary
chemical industry. The complications of laminar ow can also be avoided by sus-
pending the polymer phase in a continuous, low-viscosity phase. Examples include
the gas-phase and slurry processes for polyolens as well as suspension and emul-
sion polymerizations.
Despite the complications that sometimes result from laminar ow, history has
shown that polymer processes can be scaled up with the same technical certainty
and the same good economics as for ordinary chemicals. If anything, the gains in
single-train production rates have been higher in polymers than in their associated
monomers.
Notation
A
ext
external area available for heat transfer
d
t
tube diameter
D impeller or extruder screw diameter
D molecular diusivity
Gz Graetz number, d
2
t
u/(a
T
L)
H inside heat transfer coecient
L tube length
N number of elements in a static mixer
N
I
rotational velocity of impeller (rotations per unit time)
Q volumetric ow rate
Re Reynolds number, rd
t
u/m or rN
I
D
2
/m
S volume or inventory scaling factor
S
L
length scaling factor
S
R
radius scaling factor
S
T
throughput scaling factor
t mean residence time
T temperature
DT temperature driving force
u mean velocity
V volume
Greek
m viscosity
r density
^ rr volume-average density
References
1 Nauman, E. B., Chemical Reactor
Design, Optimization and Scaleup,
McGraw-Hill, NewYork, 2002.
2 Bisio, A., Kabel, R., Editors, Scaleup
in the Chemical Process Industries,
3 McGreavy, C., Editor, Polymer Reac-
tor Engineering, Blackie, London,
1994.
4 Paul, E. L., Atiemo-Obeng, V. A.,
Kresta, S. M., Editors, Handbook of
Industrial Mixing, Wiley, New York,
2004.
5 Thakur, R. K., Vial, Ch., Nigam,
K. D. P., Nauman, E. B., Djelveh, G.,
Static mixers in the process
industries, Chem. Eng. Res. Des., 81,
787826 (2003).
6 Mallikarjun, R., Nauman, E. B.,
Optimal processes for crystal
polystyrene, Polym. Plast. Tech. Eng.,
28, 137149 (1989).
References 551
11
Safety of Polymerization Processes
1
Francis Stoessel
11.1
Introduction
Polymerization that is, polycondensation and polyaddition performed on an in-
dustrial scale presents a number of specic reaction and process engineering as-
pects which dierentiates these processes from reactions of low molecular weight
molecules. This is also true for aspects of the dynamic control of polymerization
reactors. Therefore the concepts developed for low-molecular-weight chemistry
must be adapted to the specic problems of polymerization reactions. The scope
of the present chapter is the assessment of risks linked with the performance of
polymerization reactions on an industrial scale. Moreover, the focus is on the con-
trol of the course of reaction by means of chemical reaction engineering [1]. Risks
linked with handling of raw material or products are not treated in this chapter.
Part of the chapter is based on a comprehensive text by Moritz [2], who is acknowl-
edged for his authorization to use it here.
Barton and Nolan [3] and later Maddison and Rogers [4] analyzed the causes of
chemical runaway incidents based on statistics from the British Health and Safety
Executive. A classication by reaction type (Figure 11.1) reveals how prominent
polymerizations are. From 134 cases where the causes could be identied, 64 were
due to polymerization reactions, including polycondensations and polyadditions.
From these 64 polymerization incidents, 13 (20%) involved phenolformaldehyde
resin production. This led the British Plastics Federation (BPF) to publish a book-
let, Guidance for the Safe Production of Phenolic Resins [5]. A further investigation
among more recent incidents involving polymer reactions showed that most of
the incidents occur in vinyl chloride, vinyl acetate, and polyester resins. Since poly-
merization is the type of reaction where most runaway situations occur, it is worth
devoting special attention to process safety. Understanding how a reaction may
leave its normal course and enter a runaway course is essential for the design
of safe and economic processes. This behavior has its roots in the thermodynamics
ISBN: 3-527-31014-2
553
and chemical engineering aspects of the reactions. This will be explained in the
present chapter.
In Section 11.2, general principles of reactor safety and heat balance of reactors
are presented, with an emphasis on specic aspects of polymerizations. Section
11.3 is devoted to safety-related thermodynamics and reaction engineering aspects
of polymerization reactions. In Section 11.4, cooling of polymerization reactors is
reviewed. The chapter is concluded by a section describing safety aspects of indus-
trial processes, together with technical risk-reducing solutions.
11.2
Principles of Chemical Reactor Safety Applied to Polymerization
Accidents happening in polymerization reactors are practically always due to a lack
of control of the course of reaction caused by a disturbance of the heat balance,
which results in a temperature increase leading to loss of control of the reactor
and a runaway reaction. In this section a systematic procedure based on a failure
scenario with six key questions, allowing assessment of the criticality of a process,
is presented. Since the heat balance is at the center of our concerns in matters of
thermal control of reactors, the dierent terms of the heat balance will be exam-
ined. Finally, aspects of the dynamic stability of reactors and of the thermal stabil-
ity of reaction masses are analyzed.
11.2.1
Cooling Failure Scenario
A common practice in the assessment of risks due to runaway reactions is to use
the cooling failure scenario as developed by Gygax [1, 6]. This is a worst-case as-
0 10 20 30 40 50 60 70
Polymerization
Nitration
Sulpfonation
Hydrolysis
Salt formation
Halogenation
Alklation
Amination
Diazotization
Oxidation
Esterification
Fig. 11.1. Number of runaway incidents, classied by reaction type.
554 11 Safety of Polymerization Processes
sumption that is useful for the risk assessment. It is assumed that, while the reac-
tor is at reaction temperature, a cooling failure occurs. If at this instant uncon-
verted monomer is still present in the reactor, the temperature will increase due
to the completion of the reaction. This temperature increase is proportional to the
amount of nonreacted material. At the temperature reached at the end of this pe-
riod, a secondary decomposition reaction may be triggered and the heat produced
by this reaction may lead to a further increase in temperature. The following ques-
tions help to develop the runaway scenario and to determine the data required for
the risk assessment. This scenario (Figure 11.2) was developed for chemical reac-
tions in general and is well suited to polymerization reactions.
1. Can the process temperature be controlled by the cooling system? This is a typ-
ical question which should be answered during process development. To ensure
thermal control of the reaction, the power of the cooling system must be su-
cient to dissipate the heat produced in the reactor at any time. Special attention
must be devoted to the strong change in the viscosity of the reaction mass dur-
ing polymerization and to possible fouling at the reactor wall (see Section 11.4).
An additional condition, which must be fullled, is that the reactor is operated
in the dynamic stability region as described in Section 11.2.4.
2. What temperature can be attained after runaway of the desired reaction? The
1
Temperature
Time
TMR
ad
Decomposition
Reaction
T
end
Main
Reaction
MTSR
Tp
Cooling Failure
T
ad
2
Normal
Process
4
3
6
5
T
ad
1
Decomposition
Reacti
on
T
end
i
n

l n r
2
4
3
6
5
ad
Fig. 11.2. Cooling failure scenario, presenting the
consequences to the desired reaction of loss of cooling and
triggering of a secondary decomposition reaction. The numbers
represent the key questions used in the assessment of thermal
risks (see text).
answer to this question necessitates a study of the kinetics of the reaction, in
order to determine the degree of accumulation of monomer in the reactor as a
function of time. The concept of MTSR (maximum temperature of the synthe-
sis reaction) was developed for this purpose. In the case of polymerization reac-
tions, the accumulation of monomer is not the only factor which must be
known; the number of living chains must also be considered.
3. What temperature can be attained after runaway by decomposition? The ther-
mal data of the secondary decomposition reactions allow calculation of the adia-
batic temperature rise and determination of the nal temperature, starting from
the level of the MTSR. This temperature gives a direct indication of the pos-
sible consequences of a runaway. In polymerization reactions, the temperature
reached after loss of control of the reaction itself will often determine the con-
sequences. Polymerization reaction masses are often thermally stable, so this
question is often not relevant. Exceptions are polycondensation reactions, espe-
cially hot melts or reactive resins.
4. At which moment does the cooling failure have the worst consequences? Since
the amount of unconverted reactants and the thermal stability of the reaction
mass may vary with time, it is important to know at which instant the accumu-
lation, and therefore the thermal potential, is highest. This will be the worst
case, and obviously the safety measures have to account for it.
5. How fast is the runaway of the desired reaction? Generally, industrial reactors
are operated at temperatures where the desired reaction is fast. Hence, a tem-
perature increase above the normal process temperature will cause a signicant
acceleration of the reaction: therefore, in most cases, this period of time is
short. For polymerization reactions, where decomposition of the reaction mass
is not critical, this time will determine the choice of technical risk reduction
measures. The concept of time to maximum rate under adiabatic conditions
(TMR
ad
) as used for decomposition reactions can be applied to the polymeriza-
tion itself, starting from the process temperature. It allows estimation of the
probability of entering a runaway situation, as explained below for decomposi-
tion reactions.
6. How fast is the runaway of the decomposition starting at the MTSR? The dy-
namics of the decomposition reaction play an important role in the determina-
tion of the probability of an incident. The TMR
ad
concept was developed for that
purpose [7, 8]. The principles of using the time to explosion (TMR
ad
) is that the
longer the time to explosion, the greater is the chance of recovering the situa-
tion. This means that for a longer time to explosion, the probability of triggering
the runaway is lower and, conversely, for a shorter TMR
ad
this probability is
higher.
The questions mentioned in this scenario can be answered using the results of cal-
orimetric experiments which can be directly used in the determination of the char-
acteristic temperature levels: after a cooling failure they will give us rst the tem-
perature due to the runaway of the desired reaction, and then the temperature
reached after the runaway of the decomposition reaction (T
end
).
11.2.2
Criticality Classes Applied to Polymerization Reactors
For reactions presenting a thermal potential we can consider the relative position
of four temperature levels [9]:
The process temperature (T

Process
) is the initial temperature in the cooling failure
scenario. In the case of a non-isothermal process, the initial temperature will
be taken at the instant when the cooling failure has the heaviest consequences
(worst case) according to Question 4 in the scenario, above.
The maximum temperature of synthesis reaction (MTSR) depends essentially

on the degree of accumulation of unconverted monomer and catalytic activity.
Therefore it is strongly dependent on the process design. In polymerization pro-
cesses, this temperature is often high enough to become critical.
The maximum temperature for technical reasons (MTT) represents the technical
limit of the equipment. In an open system, as for solution and emulsion poly-
merizations, it can be the boiling point. For a closed system, it is the temperature
at which the pressure reaches the maximum permissible, that is, the set pressure
of a safety valve or bursting disk. This could be the case for mass polymerization.
This temperature (MTT) is often the critical factor for polymerization reactions.
The temperature at which the TMR

ad
is 24 h (T
D24
): this temperature is dened
by the thermal stability of the reaction mixture. It is the highest temperature at
which the thermal stability of the reaction mass is unproblematic. This is often a
secondary factor since polymerization masses are usually thermally stable.
These four temperature levels allow division of the scenarios into ve dierent
classes, going from the least critical (1) to the most critical (Figure 11.3).
MTT
Temperature
T
P
Class 1 2 3 4 5
T
D24
MTSR MTSR
MTSR MTSR
MTT
MTT
MTT
MTT
Criticality
MTSR
l t
Fig. 11.3. Criticality classes of failure scenarios.
11.2.2.1 Description of the Criticality Classes
Class 1: After loss of control of the synthesis reaction, the MTT cannot be
reached and the decomposition reaction cannot be triggered. Only if the reaction
mass was maintained for a long time under heat accumulation conditions, could
the MTT be reached. Then the evaporative cooling may serve as an additional
safety barrier. The process is thermally safe.
Class 2: After loss of control of the synthesis reaction, the MTT cannot be
reached and the decomposition reaction cannot be triggered. The situation is
very similar to Class 1, but if the reaction mass is maintained for a longer time
under heat accumulation conditions, the decomposition reaction could be trig-
gered and reach the MTT. In this case, reaching this temperature could be a haz-
ard if the heat release rate at the MTT is too high with respect to vaporization or
pressure rise. If the reaction mass is not kept for a longer time under heat accu-
mulation conditions, the process is thermally safe.
Class 3: After loss of control of the synthesis reaction, the MTT will be reached,
but the decomposition reaction cannot be triggered. In this situation, the safety
of the process depends on the heat release rate of the synthesis reaction and on
the pressure, respectively, at the MTT.
Class 4: After loss of control of the synthesis reaction, the MTT will be reached
and the decomposition reaction could theoretically be triggered. In this situation,
the safety of the process depends on the heat release rate of both the synthesis
reaction and the decomposition reaction at the MTT. Evaporative cooling or the
emergency pressure relief may serve as a safety barrier.
Class 5: After loss of control of the synthesis reaction, the decomposition reac-
tion will be triggered and the MTT will be reached during the runaway of the de-
composition reaction. It is very unlikely that the evaporative cooling or the emer-
gency pressure relief can serve as a safety barrier in this case. The heat release
rate of the decomposition at the MTT determines the thermal safety of the pro-
cess. This is the most critical of all the scenarios.
For polymerization reactions the relative positions of the MTSR and the MTT are
dominant: decomposition reactions play a role only in specic cases, such as res-
ins. Thus the most important classes are 1 to 3, whereas the consequences of ex-
ceeding the MTT level may be dramatic.
These criticality classes are very useful in the decision making process of choos-
ing the protection strategy for a reactor. Depending on the criticality class of the
scenario, dierent measures can be applied to avoid, to control, or to stop the
runaway:
Class 1: No special measure is required for this class of scenario. The evaporative
cooling or the emergency pressure relief could serve as a barrier.
Class 2: No special measure is required. The reaction mass should not be held
for longer time under heat accumulation conditions. The evaporative cooling or
the emergency pressure relief could eventually serve as a barrier.
Class 3: The reaction medium temperature exceeds the technical possibilities of

the reactor. Thus technical measures are required. In a rst approach one should
try to avoid conditions in which a runaway situation develops. If this cannot be
ensured, then emergency measures are required.
Class 4: Similar to Class 3. The same measures apply here but the additional
heat release rate due to the secondary reaction has also to be taken into account.
Class 5: In this class the MTT is very unlikely to serve as a safety barrier. There-
fore only emergency measures can be used. Since in most cases the decomposi-
tion reactions release very high energies, particular attention has to be paid to the
design of safety measures. It is worthwhile to consider an alternative design of
the process in order to reduce the severity, or at least the probability, of triggering
a runaway reaction.
11.2.3
Heat Balance of Reactors
The heat balance is important as well for the design of reactors, for their scaleup,
for the risk assessment, and especially for the assessment of the reactor stability.
The heat balance is also at the center of the evaluation of calorimetric experiments
as used for safety studies. Thus understanding the heat balance of a reactor is es-
sential for the design of safe processes. Hereafter the dierent contributions to
the heat balance, such as the heat release rate of the reaction, the heat exchange
at the wall of the reactor, the heat dissipated by the stirrer, the heat accumulation
in the reactor, the eects of the sensible heat of the feed, and the heat losses, will
be discussed in detail. The dierent terms of the heat balance are expressed as heat
release rates or thermal power.
11.2.3.1 Heat Production
The heat production corresponds to the rate of heat release by the reaction. There-
fore it is proportional to the reaction enthalpy and to the reaction rate [Eq. (1)].
q
RX
r
A
DH
R
V 1
This term will be of primary importance with respect to reactor safety: mastering
the heat release by the reaction is the key to reactor safety. For a single reaction of
order n, the reaction rate can be expressed as Equation (2).
r
A
k
0
exp
E
A
RT
!
C
n
A
2
Two features of these expressions are important for safety purposes: the heat re-
lease rate of a reaction is an exponential function of temperature. Secondly the
heat release rate is proportional to the volume of the reaction mass. Therefore it
will vary with the cube of the linear dimension of the vessel (L
3
) containing the
reacting mass. It can also be expressed in a form allowing enhancement of the con-
version rate [Eq. (3)].
q
RX
N
A0
DH
R
dX
dt
3
Consequently, the heat of reaction is obtained by integration, which allows one to
express the conversion as thermal conversion in Equation (4).
X
th

t
0
q
RX
dt
y
0
q
RX
dt
t
0
q
RX
dt
Q
RX
4
The thermal conversion is often used in the kinetic evaluation of calorimetric ex-
periments. It is also very useful for safety assessments, since it gives direct infor-
mation on the accumulation of reactants that could react even after a cooling fail-
ure. The thermal conversion is used for the calculation of the MTSR.
11.2.3.2 Heat Exchange
There are several mechanisms for heat exchange between a reacting medium and a
heat carrier: radiation, conduction, and forced or natural convection. Here we shall
consider convection only.
The heat exchanged with a heat carrier across the reactor wall by forced convec-
tion is proportional to the heat exchange area and to the driving force, that is, the
temperature dierence between the reaction medium and the heat carrier. The pro-
portionality coecient is the overall heat transfer coecient [Eq. (5)]
q
EX
U A T T
C
5
In the case of signicant change in the physical chemical properties of the reaction
mixture, which is quite common with polymerization reactions, the overall heat ex-
change coecient U will also become a function of time. This is essentially due to
the viscosity change during polymerization and to possible fouling at the reactor
wall, which may sometimes become important. With respect to safety, two impor-
tant features must be considered here: the heat removal is a linear function of
temperature and since it is proportional to the heat exchange area, it varies as the
square of the linear dimension of the equipment (L
2
). This means that when the
dimensions of a reactor have to be changed, as for scaleup, the heat removal capac-
ity increases more slowly than the heat production rate. Therefore the heat balance
becomes more critical for larger reactors. The contribution of heat exchange to the
heat balance is examined in more detail in Section 11.4.1.
11.2.3.3 Heat Accumulation
Heat accumulation represents the variation of the energy content of a system with
temperature [Eq. (6)].
q
AC
M
R
c
p

dT
dt
6
This includes all system compounds, the reaction mass as well as the reactor itself,
or at least the parts directly in contact with the reacting system. However, in safety
assessments, and as a worst case assumption, the heat capacity of the reactor itself
is often neglected. Since heat accumulation is the consequence of a dierence be-
tween heat production rate and cooling rate, it results in a variation of the temper-
ature of the reactor contents.
11.2.3.4 Convective Heat Transport due to Feed
If a feed stream to a reactor is at a dierent temperature from the contents of the
reactor, there is convective heat transport to the reactor. The thermal eect of the
feed stream must be accounted for in the heat balance [Eq. (7)].
q
Feed
_ mm
Feed
c
p; Feed
T
Feed
T 7
This eect is also called sensible heat. It can also be used as an additional means
of cooling in semi-batch and in continuous reactors. When the temperature dier-
ence between reactor and feed is important and/or the feed rate is high, this term
may play an important role. In such cases, when the feed is stopped an abrupt in-
crease in the reactor temperature may result. This term is also important in calori-
metric measurements, where the appropriate correction must be performed.
11.2.3.5 Stirrer
The mechanical energy dissipated by the agitator is converted into viscous friction
energy and nally altered into thermal energy. In most cases this term may be
neglected when compared to the heat released by a chemical reaction. But with
viscous reaction masses, as for example with polymerization reactions, this term
must be integrated in the heat balance. It can be estimated from Equation (8).
q
S
Ne r n
3
d
5
S
8
Computation of the thermal energy dissipated by a stirrer requires knowledge
of the Newton number, also called the power number, which depends on the
stirrer type and the ow regime characterized by the Reynolds number. The con-
tribution of the stirrer power to the heat balance is examined in more detail in
Section 4.3.
11.2.3.6 Heat Losses
Industrial reactors are thermally insulated for safety reasons (hot surfaces) and for
economic reasons (heat losses). Nevertheless, at higher temperatures heat losses
may become important. Their calculation may become tedious, since heat losses
are often due to a combination of losses by radiation and by natural convection. If
estimation is required, a simplied expression using a global overall heat transfer
coecient may be useful [Eq. (9)].
q
Loss
h T T
Amb
9
The simplest way of estimating the overall heat transfer coecient (h) is by direct
measurement at plant scale.
11.2.3.7 Simplied Expression of the Heat Balance
An overall heat balance taking all the terms explained above into account can be
established [Eq. (10)].
q
AC
q
RX
q
Feed
q
S
q
EX
q
Loss
10
But in most cases a simplied heat balance, which comprises only the most impor-
tant terms on the right-hand side of Equation (10), is sucient for safety purposes.
Such an expression will be used in Section 11.2.4. The problems linked with the
cooling of polymerization reactors are presented in detail in Section 11.4.
11.2.4
Dynamic Control of Reactors
In fact a chemical reactor is governed simultaneously by its heat balance and its
mass balance. If we consider a single reaction of order n, we obtain a set of equa-
tions [Eqs. (11)].
dT
dt
DT
ad

dX
A
dt

U A T T
C
M
R
c
p
dX
A
dt
k
0
exp
E
A
RT
!
C
n
A0
1 X
A
n
8
>
>
>
<
>
>
>
:
11
In this system of coupled dierential equations, the mass balance corresponds to
the reaction rate and the heat balance is a simplied version showing only the
heat production by the reaction and the heat removal by the cooling system, both
terms resulting in heat accumulation. This system presents the property of para-
metric sensitivity, meaning that a small change in one of the parameters may lead
to dramatic changes in the solution of the system of equations, that is, in the be-
havior of the reactor. This is an old [1012], but always real, problem [13, 14]. This
behavior may be observed for batch reactors and for tubular reactors (plug ow re-
actors) and also for bed reactors [15, 16]. Calorimetric methods make it possible to
determine the data used to assess the dynamic stability of a reactor as a function of
the production scale [1719]. When performing this type of assessment, it is im-
portant to consider also variations in the overall heat transfer coecient and in the
temperature of the cooling system, which may vary with time or even with season.
A further specic aspect of the reactor heat balance is the multiplicity of solu-
tions to the system of equations. This situation may arise with a CSTR in which
an exothermal reaction is performed. The mass balance [Eq. (12)] is coupled with
the heat balance [Eq. (13)], which gives a system of equations [Eq. (14)] that is rep-
resented graphically in Figure 11.4.
F
A0
X
A
r
A
V 12
q
RX
r
A
V DH
R
F
A0
c
p
T
R
T
0
13
X
A

c
p
DH
R
T
R
T
0

1
DT
ad
T
R
T
0
14
In such cases, the temperature of the reactor may jump from the low-temperature
solution to the high-temperature solution, which can be catastrophic if the reactor
is not designed to be operated under these conditions. This problem was exten-
sively studied by Ray and co-workers [20].
11.2.5
Thermal Stability of Polymerization Reaction Masses
Since polymerizations are very exothermal, the potential temperature increase in
the case of loss of control of the reaction itself is often great enough to cause evap-
oration of some components of the reaction mixture or even a partial cracking of
T(C)
0
0.2
0.4
0.6
0.8
1
0 50 100 150 200
X
A
B
C
Fig. 11.4. Multiplicity of solutions for an exothermal reaction
performed in an adiabatic CSTR. The straight line represents
the heat balance and the S-shaped line the mass balance.
A: cold branch operating point. B: instable operating point.
C: hot branch operating point.
the polymer chains. Hence the pressure of the system may increase, and cause the
rupture of the vessel and consequently heavy damage to the plant and/or its envi-
ronment. In most cases the thermal stability of polymerization reaction masses is
not critical by itself: the main risk stems from the intended polymerization reac-
tion. In polyaddition reactions as used for the production of resins, and especially
of hot melts, the reaction mass remains reactive even after the end of the polymer-
ization itself. Often curing is followed by a decomposition of the products that is
accompanied by large gas releases, which means that decomposition may easily re-
sult in the explosion of the vessel containing the resin. This kind of product may
present critical situations in the case of storage or transportation in large amounts.
This problem goes beyond the scope of this handbook, however.
11.3
Specic Safety Aspects of Polymerization Reactions
Polymerization reactions form a well dened and specic class of reactions. They
present some special features linked to the reaction kinetics and also to the ther-
modynamic aspects. These topics are presented in this section together with the
factors that may aect the reaction rate.
11.3.1
Kinetic Aspects
The reactions taking place during the synthesis of a polymer are rather complex
in nature. The description of the chemistry of a polymerization reaction often
involves over 20 dierent elementary reactions. This means that control of the
overall reaction rate that governs the process safety may be rather complicated.
Nevertheless the kinetically determining step in polymerization reactions is the
chain growth reaction.
With respect to chain growth, two main types of reaction may be distinguished
(Table 11.1). One type is the addition of one monomer molecule at a time at the
Tab. 11.1. Polymerization mechanisms.
Type of chain growth
[a]
Reaction steps Terminology for reaction
Monomer addition
P
n
M ! P
n1
initiation
growth
termination
transfer
polymerization
(radical, ionic, coordination)
Polymer addition
P
n
P
m
TP
mn
X
growth polycondensation
polyaddition
[a]
P
n
: active monomer molecule with chain length n; M: monomer; P
n
:
bifunctional polymer molecule with length n; X: low molecular
condensation product.
end of a growing chain until the chain is terminated. This is called a chain growth
polymerization. The active center may be a free radical, an ion, or an available co-
ordination bond on a transition metal complex of the catalyst. Once the active cen-
ter is created, the growth of the chain is very fast, which results in a very short
living time for the active chain in the order of seconds until it is deactivated
by termination. Thus the concentration of active chains is extremely low, at ap-
proximately 10
8
mol L
1
. This renders these polymerizations very sensitive to
impurities. After termination a dead polymer chain remains, but in the case of
free-radical polymerization the dead chain may react again with further radicals.
The other possible growth mechanism involves two molecules carrying reactive
groups, which react together leading to the addition of monomers, oligomers, or
polymers. In this case the growth is achieved by the addition of longer elements
than in chain growth. This type of reaction is called step growth polymerization,
polyaddition, or polycondensation. With this mechanism, the growth of the chain
proceeds more slowly, so the lifetime of the active chain and therefore the polymer-
ization time are longer. These are often equilibrated reactions, so that the low mo-
lecular by-products must be removed from the reaction mass in order to shift the
equilibrium toward the products.
These dierent chain growth mechanisms result also in dierent activation en-
ergies. These are in the order of magnitude of only 20 kJ mol
1
for chain growth
polymerizations. But polycondensations and polyaddition present high activation
energies in the order of 100 kJ mol
1
. Consequently the reaction temperatures are
very dierent: whereas polymerizations are often performed at modest tempera-
ture levels from 50 to 100
C, polycondensations require higher temperatures be-

tween 150 and 250
C. Since the activation energy dictates also the variation of the

reaction rate with temperature, chain growth polymerizations are less sensitive to
temperature excursions than step growth polymerizations are.
11.3.2
Thermochemical Aspects
Polymerizations are generally exothermal reactions with specic energies up to
3600 kJ kg
1
, corresponding to an adiabatic temperature rise of up to 1800 K.
Some typical reaction enthalpies are presented in Table 11.2, together with the spe-
cic heat of reaction and adiabatic temperature rise obtained for mass polymeriza-
tion. Most free-radical and ionic polymerizations have negative standard enthalpies
and standard entropies; thus at higher temperatures these reactions must be con-
sidered reversible [Eq. (15)].
P
n
M P
n1
15
As for every reversible exothermal reaction, there is an equilibrium temperature at
which the chain growth and depolymerization rates are equal. This temperature is
called the ceiling temperature and is related to the equilibrium concentration of
the monomer according to Eq. (16).
T
C

DH
R
DS
0
R ln C
M; C
16
It is important to realize that the ceiling temperature is not a constant, but it is a
function of the monomer concentration. For most monomers, this equilibrium
concentration is lower than the detection limit of common analytical methods. An
exception is a-methylstyrene, with a ceiling temperature of 61
C for 100% mono-

mer and a concentration of 2.2 mol L
1
at 25
C.
In the runaway of a polymerization, if a temperature in the range of the ceiling
temperature may be reached, or in other words the MTSR may be close to the ceil-
ing temperature (MTSRAT
C
), then the safety analysis must account for the con-
tribution of the depolymerization reaction, which produces low molecular species
and may result in a pressure increase. This can easily be realized with the critical-
ity classes presented above, by choosing the temperature T
D24
on the basis of the
depolymerization reaction.
Tab. 11.2. Typical reaction enthalpies and corresponding adiabatic temperature rises.
Monomer Physical
state
[a]
Temperature
[
C]
CDH
R
[ kJ mol
C1
]
CDH
R
[ kJ kg
C1
]
CDT
ad
[
C]
Ethylene g c 25 101.5 3620 1810
Propene l c 25 84 2000 1000
Isobutene l c 25 48 855 428
Butadiene l c 25 73 1350 676
Isoprene l c 25 75 1100 559
Chloroprene l c 61.3 68 768 384
Acrylamide
[b]
s 74.5 81.5 1147 574
Acrylonitrile l c
0
74.5 76.5 1423 721
Acrylic acid l c 74.5 67 930 465
Methyl acrylate l c 76.8 78 1100 435
Methyl methacrylate l c 74.5 55.5 550 277
Vinyl acetate l c 74.5 88 1022 511
Vinyl propionate l c 74.5 86 860 430
Vinyl chloride l c 25 71 1135 542
Vinylidene chloride l c
0
25 75.5 780 390
Styrene l c 25 70 672 336
a-Methylstyrene l c 25 35 296 148
Ethylene oxide l c
0
25 94.5 2145 1073
Propylene oxide g 25 75.5 1300 650
Trioxane
[c]
s c
0
30 19.5 216 108
e-Caprolactam l c 200 15.5 137 68
2-Pyrrolidone l c 75 4.5 53 26
[a]
Physical state: l: liquid; g: gas; s: in solution, c: condensed
amorphous, c
0
: crystalline or part crystalline.
[b]
Solvent is water.
[c]
Solvent is methylene chloride.
The high enthalpy of reaction and the high concentrations often used in indus-
trial polymerization processes lead to very high heat release rates. As an example
[21], the polymerization of vinyl chloride as a 50% (by weight) suspension in water
with a charge of 5000 kg vinyl chloride and 5000 kg water releases an energy of 5.7
GJ and the heat release rate is about 780 kW (Figure 11.5). This high heat ow
presents an engineering challenge in order to ensure a sucient heat transfer
coecient.
The high heat release rates observed in polymerization reactions do not repre-
sent by themselves the only safety engineering problem. A further issue is the
fact that the reaction dynamics leads to fast changes of the heat release rate during
the process. This in turn requires a fast-acting temperature control system, which
may be dicult to achieve for large reactor volumes. In the example given in Fig-
ure 11.5, after about 40 to 50 minutes of reaction time, corresponding to 5 to 10%
conversion, the heat release rate increases from 100 to over 700 kW. This is even
more dicult, in the sense that the reaction temperature should be maintained
constant in order to obtain the required properties of the nal product. The accu-
mulated heat at this stage represents approximately 90%, or 5.4 GJ. This energy
could lead to an adiabatic temperature increase of over 1900 K if not controlled
by the temperature control system. The thermodynamic characteristics of the reac-
tion and the heat transfer capability of the reactor may lead to a parameter combi-
nation giving rise to the parametric sensitivity as explained in Section 11.2.4 and
Eq. (11).
0
0 2 4
0.2
0.4
0.6
0.8
200
400
600
800
q kW X
0
t (h)
Fig. 11.5. Heat release rate (solid line) and monomer
conversion (broken line) during the polymerization of 5000 kg
vinyl chloride and 5000 kg water as a suspension. (after
Hamielec [21]).
11.3.3
Factors Leading to Changing Heat Release Rates
Some polymerization processes present a particular kinetic behavior: after a certain
time the reaction accelerates itself, leading to an increase in the heat release rate.
This can be exemplied with the copolymerization of styrene and methacrylic acid
in emulsion [22]. At the beginning of the polymerization, a fast increase of the
heat release rate is observed (Figure 11.6). This is due to the formation of latex par-
ticles that are essentially nucleated during the initial reaction phase: the reaction
rate is often proportional to the number of latex particles. For higher concentra-
tions of methacrylic acid, a second acceleration of the reaction can be observed:
this self-acceleration is also called gel eect or the Tromsdor eect. It is due to
the fact that the viscosity of the reaction mixture increases and the termination re-
actions of radical chains become diusion controlled. Thus the concentration of
living chains increases and so does the heat release of the reaction. This phenome-
non appears as a self-acceleration, and like other types of self-accelerated reactions,
this is also sensitive to small changes in the process conditions. This is shown in
Figure 11.6 by the changes in the initial concentration of methacrylic acid, which
cause amplied changes in the maximum heat release rate and also in the time
point where this maximum occurs. The maximum heat release rate increases
from 14 W kg
1
with 1.7% methacrylic acid to 30 or 40 W kg
1
when the concen-
tration is increased to 6.3 or 7.7%.
20
30
10
0
1
2 t (h)
q (W)
0
7.7 % MAA
6.3 % MAA
1.7 % MAA

Fig. 11.6. Heat release rate as a function of
time for the copolymerization of methacrylic
acid (MAA) with styrene in emulsion with
dierent mass fractions of methacrylic acid.
The self-accelerating behavior corresponding
to the gel eect is evident after 20 min.
Composition of the reaction mass: 418 g water,
120 g styrene, 10/8/2 g methacrylic acid, 0.505
g K
2
S
2
O
8
, 7 g Na dodecylbenzenesulfonate.
The same copolymerization performed as a seeding process shows a totally dif-
ferent behavior that implies dramatic changes in the heat release rate as a function
of time. In a seeding polymerization, the time required for the formation of the
latex particles disappears because a given amount of latex particles are added at
the beginning of the process [22]. Therefore the particles swell in the presence of
the monomer and only the phases of particle growth and monomer depletion can
be observed (Figure 11.7). This leads to an initial heat release rate, which remains
practically constant during particle growth. The reaction seems to follow a zero-
order rate law. Then after a period of time depending on the initial concentration
of methacrylic acid, the gel eect leads to an increasing reaction rate. Consequently
the heat release rate increases practically exponentially, even under isothermal con-
ditions. The time interval after which this increase occurs and the maximum heat
release rate depend on the concentration of methacrylic acid. Such a behavior may
easily lead to a runaway situation if not anticipated. Additionally the particle size of
the seed aects the dynamic behavior of the reaction.
Therefore it is essential to study the thermal behavior of a polymerization reac-
tion during process development. A safe process may only be designed if these
phenomena are thoroughly understood and if the corresponding engineering
means are used for scaleup. A well suited tool for this kind of study is reaction cal-
orimetry [2326].
0
10
20
q (W)
0 2 4 t (h)
Fig. 11.7. Heat release rate as a function of
time for the copolymerization of methacrylic
acid (MAA) with styrene in emulsion following
a seeding process. The mass fraction of
methacrylic acid was varied: solid line, 10%;
broken line, 4.2%; dotted line, 1.7%.
Composition of the reaction mass: 451 g water,
9 g styrene as seed (d
P
112 nm), 108/115/
118 g styrene, 12/5/2 g methacrylic acid, 0.505
g K
2
S
2
O
8
, 0.26 g Na dodecylbenzenesulfonate.
11.4
Cooling of Polymerization Reactors
Dierent technical means may be used for cooling industrial reactors. Among
them we consider three methods: direct cooling using the sensible heat of a feed
stream, which was treated in Section 11.2.3; indirect cooling using heat exchange
across the reactor wall or with internal cooling systems; and hot cooling using the
latent heat of evaporation. These latter two cooling techniques are discussed in
Sections 11.4.1 and 11.4.2. In Section 11.4.3, the problem of viscosity change is
examined.
11.4.1
Indirect Cooling: Heat Exchange Across the Reactor Wall
The heat transfer across a wall can be expressed by the general equation, Eq. (5). In
practice, the temperature dierence between the reaction medium and the cooling
system must remain within reasonable limits. One limitation is given by the dy-
namic stability in the case of a batch reaction. But another limitation is due to the
fact that too low a wall temperature may cause the buildup of a polymer lm, or
fouling at the inner side of the wall. In a homogeneous reaction mixture, even
without fouling, the resistance of the laminar heat transfer lm increases as the
wall temperature decreases. The result is that too low a cooling medium tempera-
ture may have adverse results, since the reduction of the heat transfer coecient
may overcome the benets of the higher temperature gradient. Increasing the
heat transfer area by using inserts such as cooling coils or other shapes of built-in
heat exchangers is often problematic. These inserts may enhance the formation of
a polymer lm at the wall and they also may have a negative impact on the agita-
tion of the reaction mass. Further, they render the cleaning operations of the reac-
tor more dicult. Another method, which is often used to increase the heat ex-
change area in low molecular reactions, is loop circulation through an external
heat exchanger. This technique may be inadequate if the polymers are sensitive to
the shear forces that will arise in a circulation pump. In certain cases reactors with
an increased height to diameter ratio are used in order to increase the specic cool-
ing area.
The problem of the determination of the overall heat transfer coecient can be
simplied if one considers that the overall resistance to heat transfer consists of
several resistances in series [Eq. (17)].
1
U

1
h
R
d
p
l
p
|{z}
depends on
reaction mass
d
w
l
w
d
f
l
f
1
h
C
|{z}
depends
on reactor
1
h
R
d
p
l
p
1
j
17
The rst two terms, representing the liquid lm at the inner wall of the reactor and
any polymer deposit, only depend on the reactor contents, that is, on the agitation
and on the physical properties of the reaction mass. Here the resistance of the in-
ternal laminar lm and of the polymer deposit at the wall play a key role. Therefore
the reactor should be cleaned regularly with high-pressure cleaner. The last three
terms depend on the reactor itself, especially on its heat exchange system, that is,
on the reactor wall, on fouling in the jacket and on external liquid lm. They are
often grouped into one term: the equipment heat transfer coecient (j). For the
description of the heat transfer coecient of the internal lm, there are several cor-
relations available, the most popular of which is presented in Eq. (18) [27].
Nu C
te
Re
2/3
Pr
1/3
m
m
W

0:14
18
This expression is valid for Newtonian uids; therefore with polymers its validity
must be veried. In this correlation, the dimensionless numbers are dened in
Eq. (19). Here the Reynolds number (Re) is expressed for a stirred tank where the
ow rate corresponds to the tip speed of the agitator.
Nu
h
R
d
R
l
Re
n d
2
S
r
m
Pr
m c
p
l
19
The last term in Eq. (18) represents the ratio of the viscosity of the reaction mass at
reaction (bulk) temperature to its viscosity at wall temperature. It accounts for the
changes of the heat transfer coecient, when switching from heating to cooling.
This produces an inversion of the temperature gradient and therefore aects the
viscosity of the product close to the reactor wall. With reactions performed in sol-
vents it can generally be neglected, but may become important in the case of poly-
mers: the viscosity of the reaction mass is often important and its temperature de-
pendence may give this term a value that cannot be neglected. Equation (18) can be
solved for h
R
, the internal lm heat transfer coecient. By grouping the terms in
an appropriate way, the heat transfer coecient of the reaction mass can be split
into two parts, one (z) representing the technical data of the reactor and the other
(g) grouping the physical properties of the reaction mass [Eq. (20)]. The gravity
constant g is introduced to rend the rst term dimensionless and to give the sec-
ond the dimensions of a heat transfer coecient.
h
R
C
te
n
2/3
d
4/3
S
d
R
g
1/3
|{z}
technical data
of the reactor
r
2
l
2
c
p
g
m
3
s
|{z}
physical--chemical data
of the reaction mass
z:g 20
Thus, for a given reaction mass, the heat transfer coecient of the internal lm
can be inuenced by the revolution speed of the agitator and its diameter. The
value of z, characterizing the internal part of the equipment factor, can be calcu-
lated using the geometric characteristics of the reactor. Some typical values of the
agitator constant are given in Table 11.3. The value of g can either be calculated
from the physical properties of the reactor contents as far as they are known or
measured in a reaction calorimeter by the Wilson plot method [28, 29]. This pa-
rameter is independent of the geometry or size of the reactor. Thus it can be deter-
mined at laboratory scale and used at industrial scale. The Wilson plot consists of
the determination of the overall heat transfer coecient as a function of the agita-
tor revolution speed in a reaction calorimeter. The Wilson plot (Figure 11.8) makes
it possible to verify that the correlation in Eq. (18) is valid: if the measures t on a
straight line, a validation is built into the method. The intercept with the ordinate
represents the reciprocal heat transfer coecient of the equipment, that is, the wall
and the external cooling system of the calorimeter. The slope is the product of z
and g, which allows the determination of either one of these parameters. In a rst
stage, z is determined by a calibration performed using a solvent with known phys-
ical properties. In a second stage g is determined during the actual measurement
with the reaction mixture.
Moreover, the contribution of polymer deposits to the overall resistance to heat
transfer may be important. Since the thermal conductivity of polymers is low, they
Tab. 11.3. Typical agitator constants.
Agitator Constant
Plate stirrer 0.36
Rushton turbine 0.54
Rushton turbine with pitched blades 0.53
Propeller 0.54
Anchor 0.36
Impeller 0.33
Intermig (Ekato) 0.54
1/U
0.006
0.007
0.008
0.009
0.01
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
slope = z. =0.00192
(T)
= 0.00802
(n/n
0
)
-2/3
2 . . .
.

/
1/
Fig. 11.8. Wilson plot measured with toluene
in a reaction calorimeter. The reciprocal heat
transfer coecient is plotted against the
agitator revolution speed to the power 2/3.
The intercept with the ordinate represents the
reciprocal heat transfer coecient of the
equipment and either z or g can be determined
from the slope of the straight line.
act as insulators, and thus even thin deposits may aect strongly the heat transfer
coecient, as shown in Table 11.4.
The resistance of the reactor wall and external lm (h
c
) can be determined in
a cooling experiment realized directly with the production reactor lled with a
known amount of a substance (M) with known physical chemical properties. The
temperature T
R
of the contents of the reactor and the average temperature T
C
of
the cooling system are recorded during this experiment. A heat balance can be
calculated between two instants t
1
and t
2
: the heat removed from the contents of
the reactor is given by Eq. (21), and this is realized with an average cooling power
given by Eq. (22) with the average temperature dierence as expressed in Eq. (23).
Q M c
p
T
R1
T
R2
21
q
EX
U A DT 22
DT
T
R1
T
C2
T
R2
T
C2
lnT
R1
T
C1
lnT
R2
T
C2
23
Tab. 11.4. Factors inuencing the heat transfer with some typical values of heat transfer
coecients in an agitated reactor.
Type Inuencing factors Typical values
[ W m
C2
K
C1
]
Internal lm stirrer: speed and type water 1000
h
R
forced convection reaction mass c
p
; l; r; h toluene 300
physical data, especially
r f T
glycerol 50
h
R
natural convection
(stirrer failure)
water
gases
100
10
Polymer deposit thermal conductivity l With d 1 mm,
thickness of deposit PE 300
PVC, PS 170
Reactor wall l/d construction With d 10 mm,
wall thickness d iron 4800
construction material stainless steel 1600
coating glass 100
glass lined 800
Fouling at external wall thermal conductivity l With d 0:1 mm,
thickness of deposit Gallert 3000
Kesselstein 5000
External lm h
c
jacket water
construction, ow rate with ow 1000
heat carrier, physical
properties, phase
change
no ow
evaporation
100
3000
welded half coil water
construction, ow rate with ow 2000
physical properties no ow 200
The overall heat transfer coecient can then be obtained from the heat balance
equation [Eq. (24)].
U
M c
P
T
R1
T
R2
A DT t
2
t
1
24
This is a simplied method using only two points. A more accurate method is to
use more points by applying the dierential equation of Newtonian cooling, which
expresses the variation with time of the temperature dierence between reactor
contents and cooling system [Eq. (25)].
M c
P

dDT
DT
U A dt 25
By integration, with the initial condition: t 0, DT DT
0
T
0
T
C
, one obtains
Eq. (26) with the thermal time constant t
c
of the reactor given by Eq. (27).
ln
DT
DT
0

t
t
C
or
DT
DT
0

exp
t
t
C

26
t
C

M c
P
U A
27
Thus a plot of the logarithm of the ratio of the instantaneous temperature dier-
ence to the initial temperature dierence, as a function of time, should give a
straight line, as far as cooling is Newtonian. The slope of this line is the thermal
time constant of the reactor, from which the overall heat transfer coecient U
can be calculated.
Then the equipment heat transfer coecient j can be calculated from Eq. (28)
written for a clean reactor. If there was some polymer deposit at the reactor wall
during the cooling experiment, its resistance must be taken into account.
1
j
1
U

1
zg
28
For the calculation of the heat transfer coecient of the external lm some models
are also available. These models describe the hydraulics of the ow in the jacket or
in the half-welded coils. The results depend strongly on the technical design of
these parts of the equipment. Direct measurement is mostly preferred.
11.4.2
Hot Cooling: Cooling by Evaporation
Hot cooling, which uses the latent heat of evaporation of a solvent, is a very e-
cient technique: on one hand it is independent of the heat transfer at the reactor
wall, and on the other hand the condenser can be designed independently of
the reactors geometry. This allows relatively high specic cooling powers to be
reached. In case a reaction cannot be performed at boiling temperature, it is possi-
ble to work under partial vacuum in order to decrease the boiling point and to
work at reux. Hot cooling can be used as the main cooling system for a reactor
working under normal operating conditions; it can also be used as an emergency
cooling system, in cases when the boiling point is reached during the temperature
increase following a failure of the main cooling system. Obviously, this is only pos-
sible provided the condenser is equipped with an independent cooling system and
the equipment has been designed for this purpose.
The boiling rate of the solvent, depending on the instantaneous heat release rate
of the reaction, governs the whole design of the reux system. Some technical as-
pects and limitations must be considered in the design of such cooling systems.
Too high a boiling rate could lead to ooding of the vapor tube, when the conden-
sate ows down in countercurrent to the rising vapor. Further, the presence of
vapor bubbles in the reaction mass increases its apparent volume. The reaction
mass swells, and if its level is high enough to enter the vapor tube, again ooding
will occur. A method was developed for predicting these limitations [30, 31]. If the
boiling point is reached during runaway, like in scenario of criticality classes 3 or 4,
a possible secondary eect of the evaporation is the formation of an explosive vapor
cloud, which in turn can lead to a severe room explosion if ignited. In some cases,
there is enough solvent present in the reaction mixture to compensate for the en-
ergy release, allowing the temperature to be stabilized at the boiling point. This is
only possible if the solvent can be distilled o in a safe way, to a catch pot or a
scrubber. The thermal stability of the concentrated reaction mixture must also be
ensured. In most cases, however, the condensed solvent is reuxed to the reactor.
If the capacity of the reux system is sucient, all of the vapor produced by an
exothermal reaction can be conducted from the reactor to the condenser, where it
is entirely condensed. In such a case, the boiling point may act as a safety barrier.
In the opposite situation, if the ow rate is too high with respect to the capacity of
the system, a pressure increase will result. This may be due to ooding of the
vapor tube or to swelling of the reaction mass. This pressure increase may in turn
lead to the rupture of the weakest element in the distillation system, followed by
the release of a vapor cloud, which could be ignited and cause a vapor cloud explo-
sion. Further, if the condenser capacity is too short, uncondensed vapor will pass to
the ventilation system, where it could cause a secondary incident, if it is not com-
patible with the design. For these reasons, it is essential to know the vapor ow
rate due to an exothermic reaction, which depends on the latent heat of evapora-
tion of the solvent. The capacity of the reux system will be assessed using the
vapor velocity in the dierent parts of the equipment [Eq. (29)].
u
q
RX
DH
V
r
G
S
29
If the diameter of the vapor tube is insucient for a given vapor release rate, the
high vapor velocity results in a pressure increase in the reactor leading to a temper-
ature increase and a further acceleration of the reaction. The consequence will be a
thermal explosion until the rupture of weak parts of the equipment allows pressure
relief. In order to avoid this type of reaction course, it is important to know the
maximum vapor velocity admissible in a given tube and consequently the maxi-
mum admissible heat release rate for the reaction. To predict whether ooding
will occur in existing equipment, an empirical correlation was established experi-
mentally [31]. The experimental study was performed in the laboratory, in the pilot
plant and on an industrial scale with various organic solvents and water for tubes
with an inside diameter between 6 and 141 mm. The maximum allowable heat re-
lease rate is obviously a function of the latent heat of evaporation and of the tube
cross-section. It can be calculated by Eq. (30).
q
max
4:52DH
V
3:37 10
6
S 30
Calculations performed for dierent common solvents show that the limiting ve-
locity remains relatively constant for dierent classes of solvents. Some values are
shown in Table 11.5. This allows the required vapor tube diameter d for a given
heat release rate for dierent solvents to be calculated (Figure 11.9).
The relative volume increase due to swelling of the reaction mass can be esti-
mated using the Wilson correlation (Eqs. (31), (32) with the conditions: if ~ uu < 2
then K 0:68, a 0:62; or if ~ uu b2 then K 0:88, a 0:40) [32, 33]. This corre-
lation was rst established for air in water; it is easy to use and was found to de-
scribe with enough accuracy the swelling of a liquid by bubbles of its vapor.
a K
r
V
r
L
r
V

0:17
~
DD
0:1
H
~ uu
a
31
a
H
B
H
0
H
B
~
DD
H

D
H
s
g r
L
r
V
r ~ uu
u
s
g r
L
r
V
r
s 32
Tab. 11.5. Limiting vapour velocity for dierent solvents.
Solvent
water methanol ethanol acetone dichloro-
methane
chlorobenzene toluene m-xylene
DH
v
[kJ kg
1
] 2260 1100 846 523 329 325 356 343
T
b
[
C] 100 65 78 56 40 132 111 139

M
w
[g mol
1
] 18 32 46 58 85 112 92 106
P [mbar] 1013 1013 1013 1013 1013 1013 1013 1013
r
g
[kg m
3
] 0.59 1.15 1.60 2.15 3.31 3.37 2.92 3.13
u
max
[m s
1
] 10.2 6.6 5.3 5.1 4.5 4.4 4.8 4.6
The correlation allows the maximum admissible heat release rate for given plant
equipment to be calculated, or equipment for the requirements of a given process
to be designed (Figure 11.10). They are both based on easily accessible physical-
chemical properties of the boiling solvent and on geometric data of the reactor.
Such considerations make it possible to adapt the equipment or the process, that
is, the degree of lling of the reactor, to the safety requirements. This kind of mea-
sure often allows processes to be run under safe conditions, whereas a classical as-
sessment would consider them to be critical.
0
1000
2000
3000
4000
5000
0 0.1 0.2 0.3 0.4 0.5 0.6
Water
Methanol
Ethanol
i-Propanol
Acetone
Other solvents
d (m)
q (kW)
Fig. 11.9. Heat release rate at ooding as a function of the
vapor tube (riser) diameter for dierent solvents.
0
1
2
3
4
5
0 0.1 0.2 0.3 0.4 0.5 0.6
u
g
(m/s) Water
Ethanol
Toluene
. . .

Fig. 11.10. Maximum allowed vapor velocity u

g
across the
surface of the reaction mass as a function of its degree of
swelling a.
11.4.3
Importance of the Viscosity
In polymerizations the uid often does not behave in a Newtonian manner. In
such cases Eqs. (18)(20) do not apply as such, and modied equations must be
used. It could be shown experimentally [3436] that the shear forces are propor-
tional to the agitator revolution speed, meaning that an average shear force in the
reactor can be used and the dynamic viscosity can be replaced by an apparent vis-
cosity [37]. Such an example is illustrated in Figure 11.11, where the variation of
the Nusselt number Nu during a polymerization shows the decrease in the overall
heat transfer by a factor of three when the viscosity increases by over one order of
magnitude [38]. In mass polymerization an increase of the viscosity by six or seven
orders of magnitude is common. This means that the viscosity is a key factor for
the control of a polymerization reactor, that is, for its safety.
In fact the viscosity inuences both the heat balance and the mass balance. It
has been shown how the heat transfer coecient is aected by the viscosity. But
the energy dissipation by the stirrer is also strongly dependent on viscosity (see
Section 11.4.4). Furthermore, viscosity aects the molecular diusion, the mass
transport, the mixing time, or the residence time distribution, and therefore the re-
action rate. Since the reaction rates inuence the chain length and particle sizes,
they have a direct eect on the polymer properties. In turn they aect the viscosity
and the shear forces there is a feedback eect. Such complex interactions cannot
be described by analytical equations, so empirical models must be used. Often
Nu
mPas
Fig. 11.11. Nusselt number as a function of
the apparent viscosity during reticulation of
poly(vinyl alcohol) in aqueous solution in a
laboratory reactor with an anchor stirrer.
Geometry V
R
1:3 L, D 0:1 m, d
R
/D 0:95,
H/D 1:9, r 1000 kg m
3
, l 0:65
W m
1
K
1
. After Schmidt and Reichert [38].
these models are very specic for a given reaction system and even for a reactor
geometry. Their use aords deep chemical and engineering knowledge and experi-
ence. To give an example, increasing the stirrer speed in order to improve the heat
transfer may result in an adverse situation: one reason is that the heat dissipation
by the stirrer is increased. But a further eect may arise at the same time: the mix-
ing time is reduced, enhancing the mass transfer and resulting in an increase in
the reaction rate that leads to an eect opposite to the initial intention.
11.5
Chemical Engineering for the Safety of Polymerization Processes
Chemical reaction engineering traditionally addresses the design of processes oper-
ated under nominal operating conditions. But if the same principles are used to
design the process to remain safe even under conditions deviating from the in-
tended conditions, it becomes a strong tool for improving process safety [1]. For
this reason, in this section the dierent reactor types are analyzed with regard to
their safe operation and especially to the design in order to prevent runaway.
Some further risk-reducing techniques for stopping a commencing runaway or
mitigating its consequences are also presented.
11.5.1
Batch Processes
Batch processes are characterized by a closed mass balance. This means that dur-
ing the reaction nothing is added to or withdrawn from the reactor. In fact we con-
sider as batch processes those where the monomer and the solvent, if there is one,
are added at the beginning of the reaction. The initiator or catalyst is also added at
the beginning of an operation. We extend this denition to processes where a vola-
tile compound is evaporated in order to shift the equilibrium to the products, as is
often the case with polyadditions or polycondensations. In these processes the con-
trol of the temperature is the unique way of controlling the reaction course. Dier-
ent strategies of temperature control may be used in this situation.
An isothermal operation requires the cooling capacity to be sucient at any time
to compensate for the heat release rate of the reaction. Moreover, the dynamics of
the cooling system must allow sharp changes in the reaction rate, which are often
observed in polymerization reactions (see Section 3.3), to be followed. Due to the
high energy of reaction, this kind of process is only possible in diluted systems as
emulsion polymerization or polymerization in solution.
In most cases non-isothermal processes are used. A part of the energy of the re-
action is used to heat the reactor to the desired process temperature in the so-called
polytropic reaction mode. A typical temperature control strategy is to use an adia-
batic phase, during which there is no cooling, so that the correct initiation of the
reaction can be checked. Then, in a second stage, after reaching a specied temper-
ature, the cooling system is switched. The correct choice of the initial temperature
11.5 Chemical Engineering for the Safety of Polymerization Processes 579
and of the cooling system switching temperature is critical for the process safety.
This type of strategy is often used in polyaddition or polycondensation reactions,
where high reaction temperatures are desired. Advanced temperature control strat-
egies allowing the optimization of productivity, but taking technical limitations of
the plant equipment into account, are proposed [39]. Great care must be used to
avoid working in the parametrically sensitive eld. Thus a thorough study of the
process by reaction calorimetry is essential for the safe design of such processes.
The aim of process design should be to develop processes that are tolerant to a fail-
ure of the cooling system. This is often a utopian dream, due to the high energy of
polymerization reactions.
In batch operation, the correct charge of the reactor is essential, and requires
great care by the operators, because this is often a manual operation. In every
case a batch process requires emergency measures to be taken in order to recover
control of the reactor when the cooling system fails, or at least to mitigate the con-
sequences of a runaway. The scenario presented in Section 11.2 is a great help for
this purpose.
11.5.2
Semi-batch Processes
In semi-batch operation only a part of the monomer, or no monomer at all, is ini-
tially charged. The main part of the monomer is added to the reactor during the
process, allowing additional control of the reaction course and of the polymer prop-
erties by adjusting the feed rate. In such processes the accumulation of monomer
and therefore of heat is limited to a fraction of the overall heat. Such processes are
often used for emulsion polymerizations. The continuous feed also reduces the in-
stantaneous heat release by the reaction and requires less cooling capacity. A cor-
rect choice of the concentrations and of the temperature even makes it possible to
achieve a so-called feed-controlled process. This means that the monomer entering
the reactor is immediately converted; that is, there is no monomer accumulation.
In such a situation the reaction rate is equal to the feed rate, which can easily be
adapted to the cooling capacity of the reactor (Figure 11.12). In the case of any fail-
ure, stopping the feed immediately stops the reaction and the heat production.
Thus the temperature can be stabilized, making it possible to design fail safe
processes.
The design of a safe semi-batch process requires a strict control of the accumu-
lation of unconverted monomer. In fact the accumulation results from a balance
between monomer addition by the feed, and monomer conversion by the reaction.
Thus it can be inuenced by the feed rate, but also by the reaction rate, which in
turn can be governed by the temperature and the initiator or catalyst concentration.
These parameters must be optimized during process development. Here again, re-
action calorimetry is of great help for the determination of the accumulation [40].
It can be calculated from thermal conversion by means of Eq. (4) obtained directly
from the calorimetric measurement and the actual amount fed. Just by varying the
feed rate and the process temperature, one can verify that the heat release rate of
the reaction never exceeds the cooling capacity of the reactor. A second constraint
is the maximum allowed temperature in the case of a cooling failure, that is, the
accumulation, and therefore the MTSR should remain below a given level (Figure
11.12) [41, 42].
In practice, emulsion polymerizations are often performed according to the
monomer feed process with an initial charge of the monomer, the remaining being
fed over time. Figure 11.13 represents a schematic example of an emulsion poly-
merization according to the monomer feed process [2]. In such processes three
phases may be distinguished: the initiation, the feed and the end of reaction. In
this example, the delay between initiator addition and continuous feed was varied.
11.5.2.1 Initiation
In a rst stage, an initial amount of monomer is added to the reactor. This addition
is immediately followed by the addition of the initiator. During the delay between
initiator addition and monomer feed, inhibition of the polymerization may occur.
This depends on the purity of the reactants and on the oxygen concentration re-
maining in the reactor. Then a fast increase in the thermal power follows: it is
due to formation of the particles. On an industrial scale, such a fast increase of
heat release rates may generally not be compensated by the comparatively slow
cooling system, and results in an accumulation of heat, that is, an increase in the
reactor temperature. But at this stage, the monomer concentration is still low.
Often the total amount of water was charged initially, conferring a high heat capac-
ity on the system. Thus the resulting temperature increase during this stage re-
mains low. In fact the initial charge must be optimized in such a way that the
initiation remains safe. In the case of emulsion feed polymerizations, the initial
contents of the reactor represent an aliquot of the total batch. The situation is sim-
ilar to the monomer feed process, since the initial charge may be designed in such
a way that the temperature increase remains within critical limits. The cooling
capacity, and sometimes also the heat capacity, of the reactor are high enough to
limit the initial temperature excursion.
0
0.1
0.2
0.3
0 2 4 6 8 10 12
t (h)
X
acc
) t (h)
q
RX
(W/kg)
0
10
20
30
40
50
60
0 2 4 6 8 10 2
Fig. 11.12. Heat release rate and accumulation obtained in a
semi-batch reaction for dierent feed rates: 2, 4 and 6 h.
11.5.2.2 Feed
After the particle growth stage of the emulsion polymerization is terminated, the
monomer concentration within the latex particles decreases and so does the heat
production rate. In the meantime, the temperature control system is able to reduce
the temperature of the jacket. When the molar ow rate (mol s
1
) of the monomer
dN/dt
Feed
Initiation
I
n
i
t
i
a
l

m
o
n
o
m
e
r
c
h
a
r
g
e
t
Optimal feed
d
i
l

dN/dt
Feed
Initiation
I
n
i
t
i
a
l

m
o
n
o
m
e
r
c
h
a
r
g
e
t
Feed start too early
i
r

dN/dt
Feed
Initiation
I
n
i
t
i
a
l

m
o
n
o
m
e
r
c
h
a
r
g
e
t
Feed start too late
i

Fig. 11.13. Schematic representations of the
molar ow rates of monomer in a semi-batch
emulsion polymerization. Top graph: the feed
is optimal; it is immediately converted. Middle
graph: the feed was started too early; the
reaction course is no longer controlled by the
feed. Bottom graph: the feed was started too
late; the accumulation results in a quasi
runaway situation.
depletion reaches a value corresponding approximately to the molar ow rate of
the intended feed, the monomer feed should be started (Figure 11.13, top graph).
This allows compensation in order to maintain the concentration constant; that is,
a quasi steady state can be achieved. The reactor is cooled by two methods: heat
exchange across the wall, and via the sensible heat of the cold feed. Here, the emul-
sion feed processes obviously show an advantage due to the higher heat capacity of
the emulsion compared to the monomer.
The right time point for starting the feed is an important safety-relevant param-
eter. If the feed is started too early during the particle formation period (Figure
11.13, central graph), an accumulation of monomer may result. This will cause an
increase in the reaction rate and result in an uncontrollable temperature increase
even a runaway reaction. Matching of feed rate and reaction rate, allowing control
of the course of the polymerization, is only achieved in the very late stages of the
feed time, if ever. If the feed is started too late, the situation may become even
worse (Figure 11.13, bottom graph): the monomer initially present is already con-
verted and the heat release rate is low. But the jacket may still be at a low tempera-
ture due to the previous exotherm, and undercool the reactor. Since the feed is
increasing the monomer concentration at too low a reaction rate, an accumulation
will occur and may lead to a sudden wake up of the reaction, which in turn could
result in a runaway situation.
11.5.2.3 Final Stage
After the end of the feed period, the heat release rate decreases as a consequence of
the monomer depletion. This third stage is very similar to a batch reaction, because
the reaction rate can no longer be inuenced by the feed.
11.5.2.4 Practical Aspects
The diculty concerning the initiation on an industrial scale is that the actual ini-
tiation of the polymerization must be recognized before a great amount of mono-
mer is added to the reactor. This can be realized either by chemical in-line analysis,
or by a heat balance on the industrial reactor [43]. If the initiation fails and the
feed is continued, it may lead to an accumulation of monomer that could react
spontaneously in an uncontrolled way. Thus the process becomes a batch reaction,
for which the reactor is not designed.
In a semi-batch reaction, overcooling, or too low a temperature, may be as criti-
cal as too high a temperature, because the reaction rate is lower and the resulting
accumulation may be important. If the temperature is adjusted to its nominal
value, the accumulated monomer may also react in an uncontrolled way, leading
to a runaway reaction. This may be due to degradation of the initiator which slows
down the reaction. Such eects can be detected by a heat balance on industrial re-
actors.
For polymerization or copolymerization processes performed in semi-batch reac-
tors, the feed rate can also be adjusted to meet quality criteria [4448]. Advanced
techniques are proposed to control the feed rate by taking into account simultane-
ously productivity and safety criteria [49, 50].
Thus not only does a safe process result from sound development, working out
the right process parameters, but on an industrial scale it must be checked that the
polymerization remains on the right path.
11.5.3
Continuous Processes
In continuous polymerizations, the main problem is the dynamic stability of the
reactor. The stability problems have various dierent aspects: the thermal stability
as introduced above (see Section 11.2.4), the concentration stability, the particle
number stability, and the viscosity stability. Even under isothermal conditions these
problems may lead to multiplicity or oscillatory behavior. It is worth emphasizing
the fact that stability and safety are in no case synonymous: a reactor may be un-
safe even if working at a stable working point, or conversely it may be run safely at
an instable working point. But knowledge of stability limits of the reactor is essen-
tial for the design of a safe process.
11.5.3.1 Concentration Stability
In a continuous stirred tank reactor (CSTR) where a homogeneous polymerization
is being performed, the mass balance or the performance equation can be written
in a very simple way [Eq. (33)].
dX
dt

X
t
33
If the reaction follows an autocatalytic kinetic equation, like polymerizations exhib-
iting the Tromsdor eect, then the conversion rate as a function of conversion,
dX/dt f X, shows a typical maximum curve [51]. The operating point is found
at the intercept of the kinetics line and a straight line with the space time recipro-
cal as the slope. This conguration leads to a multiplicity of solutions as repre-
sented in Figure 11.14 for several values of the space time. In a range of space
time between t
1
and t
3
, there are three solutions. The upper and lower solutions
are stable, whereas the intermediate one is instable. In such a situation, the CSTR
should be designed to be operated at the high conversion point (hot branch, or ig-
nited reactor). This allows for a higher productivity and a safer behavior if the high
cooling capacity required can be achieved. If the reactor is operated at the lower
conversion point (cold branch), a small perturbation, for example of a feed pump,
may ignite the reactor, which suddenly jumps to the hot branch, with high con-
version. This could lead to a runaway.
11.5.3.2 Particle Number Stability
The particle size stability is a special form of the dynamic concentration stability
[52]. If the emulsier is present at a concentration above the critical concentration,
new particles will be created. Thus the area growth rate, and therefore the emulsi-
er consumption, are increased. Then the emulsier supply by the feed may be in-
sucient to ensure coverage of the particles surface. This stops the nucleation pro-
cess of new particles. Since the particles are washed out by the reactor outlet, only
fewer, but larger, particles remain in the reactor. The specic interfacial area de-
creases until the emulsier consumption becomes lower than the supply. Then
the concentration increases, and a new cycle starts. These oscillations may occur
especially during start-up of the reactor. They result in oscillations of the conver-
sion that impinge on the quality of the product. They can be avoided by using a
adequate seeding policy for the reactor.
11.5.4
Design Measures for Safety
Safety measures or risk-reducing measures must be considered under the aspect of
inherent safety. Kletz [53], who was the promoter of these ideas for a long time,
formulated some principles for reduction of risks:
intensication, using so little hazardous material that it will not matter if it all
leaks out;
substitution, using a safer material instead;
attenuation, using a hazardous material in a safer form;
limitation of the eects of failures, not by adding on protective equipment but by

equipment design or changing the conditions of use;
simplication, as complex plants provide more opportunities for human error

and contain more equipment that can go wrong;
dX/dt
X
1
2
3
t
Fig. 11.14. Schematic representation of the
conversion rate as a function of conversion
(solid line) in an isothermal CSTR with a
polymerization presenting a gel eect. Three
dierent space times are represented by the
three operating lines (broken lines). Filled
circles represent stable operating points and
the white circle an unstable operating point.
avoiding knock-on or domino eects;
making incorrect assembly dicult or impossible;
making the state of equipment, such as open or shut, clear;
designing equipment that is able to withstand incorrect installation or operation;
making equipment easy to control.

Following these principles in a more specic way for polymerization reactions,
three levels of priority can be dened: in decreasing order, the rst priority is the
reduction of severity by design. As a second priority, technical measures for control
of the reaction to avoid runaway should be considered. The aim is to obtain a fail
safe process by reduction of the probability of occurrence of an incident. As last
resort only, emergency measures should be taken in order to mitigate the conse-
quences of runaway. In any case, the basic principle remains: Avoid runaway
rather than mitigate its consequences.
With reference to this principle, dierent types of risk-reducing measures can be
considered for polymerization reactions (Sections 11.5.4.111.5.4.10).
11.5.4.1 Process Design
Semi-batch processes are preferred to batch processes where possible. This point
was made sbove (see Section 11.4). Continuous processes allow the inventory of re-
action mass to be reduced, and represent an elegant way of reducing the severity of
a process.
11.5.4.2 Reactor Design
Many design elements are in fact preventive measures. Some of them will be men-
tioned here. One may consider building a reactor resistant to the maximum pres-
sure even in the case of loss of control of the polymerization. Often the nal pres-
sure obtained with polymerization reactions is not so high. Another important
element is the agitation. The agitator ensures uniform mixing over a large range
of viscosities, avoids local concentration of reactants that could lead to hot spots,
and ensures heat transfer. The agitation is also required for temperature measure-
ment, that in turn ensures control of the reactor. In this context it is important to
keep heat exchange surfaces (and also the thermometer) clean.
Temperature is often the key parameter for process safety; thus redundant sys-
tems should be used, since failure rates in the order of magnitude of one per year
are reported for them. The temperature probe must be correctly located and the
temperature recorded so that trends can be followed. This is essential for safety as
well as for product quality. The rate of temperature change can also represent very
important information for process control. Utility-independent thermometers are
also very useful. The temperature of the cooling system (if possible at the inlet
and outlet of the jacket) should be monitored.
The process should be designed in order to provide adequate heating proles, es-
pecially to avoid inadvertent fast heating. An interlock may stop heating in the case
of malfunction.
When reux cooling is used, one must avoid deposits inside the condenser
tubes. To do so, the condenser can be pitched to assist drainage, and must be sized
to prevent ooding. The process must be designed to avoid foam-up of the reaction
mixture (swelling; see Section 11.4.2).
Services are very important for the control of the reaction. Redundant systems
should be provided for electrical power, as well as compressed air or inert gases.
The electricity supply must be examined in detail during risk analysis: motors
that is, feeding and cooling pumps, agitators, vacuum, and feed will be stopped
if the electrical power fails. Moreover, instruments dependent on compressed air
become inoperative. For this reason, the fail safe position of valves (open for cool-
ing, closed for heating) should be considered.
Failure of vacuum at reux may lead to the development of a hazardous situa-
tion: the boiling point, and thus the reaction temperature, increase and may end
up in a runaway situation.
11.5.4.3 Control of Feed
In semi-batch or continuous operation, the feed rate allows control of the reaction
course. Hence it plays an important role concerning the safety of the process. With
an exothermal reaction, it is important to be able to limit the feed rate by technical
means. One possibility is feed by portions, a method that is only applicable for
semi-batch reactors. This mode of addition is the traditional way of limiting accu-
mulation. In this case, the addition must be controlled by the conversion: that is,
the next portion is added only if the previous portion has been consumed by the
reaction. Dierent criteria can be used to follow the reaction: the temperature, the
appearance of the reaction mass, chemical analysis, and so on. For a well designed
process, the additions can also be performed on a time basis.
Another possibility is to use a feed tank with a control valve and gravimetric ow.
The valve can be controlled by the weight of the reactor, by the weight of the tank,
by the level in the tank, or by a ow meter. The maximal feed rate can be limited by
the clearance of the valve or by a calibrated orice. If a centrifugal pump is used, it
is necessary to provide also a control valve to limit the ow rate. The ow control
strategies are the same as those described above. With a metering pump, the
through ow rate can be controlled by a stroke adjusting mechanism or a variable
speed drive acting on the stoke frequency. The control can be realized by a xed
adjustment or by through a ow meter.
11.5.4.4 Emergency Cooling
If the cooling system fails, water can be supplied from a hydrant to the cooling
jacket or coil, or an independent emergency cooling system can be provided. With
such a system, it is critical that the temperature does not fall below the solidica-
tion point of the reaction mass, or otherwise a crust would form, resulting in re-
duced heat transfer, which again may favor the runaway situation. The agitation
of the reaction mass is also critical in such a situation: large reaction masses be-
have adiabatically in practice, even if cooled on the outside. Here the injection of
nitrogen into the bottom of the reaction mass has proven to be helpful for an emer-
gency mixing. Such equipment must be tested under practical conditions.
11.5.4.5 Inhibition
This technique may be applied to catalytic reactions where an inhibitor can be
added in small amounts. Mixing is an especially critical factor here, since a small
amount of inhibitor has to be added and mixed into a large volume of reaction mix-
ture [54, 55].
11.5.4.6 Quenching
Some reactions can be stopped by the addition of a suitable component. Dilution
by an inert and cold material may lower the temperature to slow down the reac-
tion. For this type of measure, the critical factors are the amount and rate of addi-
tion and the temperature of the quenching material. The required empty volume
must be also be available in the reactor. Calorimetric methods are of great help in
the design of such measures, because they allow measurement of the heat of mix-
ing, which is often important, and the thermal stability of the resulting mixture.
11.5.4.7 Dumping
This measure is similar to quenching, with the dierence that the reaction mass is
not kept within the reactor, but transferred into a vessel containing the inhibitor or
the diluting compound. This vessel must be prepared to receive the reaction mass
at any instant during the process. The transfer line is critical for the success of this
measure. It must be designed to allow an emergency transfer even in the case of
breakdown of the utilities. This measure is particularly suitable in cases where the
reaction mass must be transferred for workup after a normal operation.
11.5.4.8 Controlled Depressurization
If a runaway is detected in an early stage, where the temperature and the pressure
increase is slow, a controlled depressurization of the reactor can be considered. This
is only suitable for cases where a volatile solvent is present; the reactor is slowly
depressurized until evaporative cooling occurs. Obviously, a scrubber and/or a re-
ux condenser must be installed and designed to work with independent utilities.
11.5.4.9 Pressure Relief
This measure will not be described in detail in this chapter. The design of venting
lines for reactions with thermal potential is a complex matter. There are examples
where pressure release was able to protect reactors from an explosion, but also
cases where a reactor exploded, even with an open manhole. This measure only
applies with reaction systems where the pressure still increases signicantly for
small temperature increases above the normal operating level. In addition, the dis-
charge line must end in a catch tank or in a scrubber to avoid spillage with possibly
toxic or ammable material. The behavior of the reaction mass that is, the tem-
perature and pressure increase under runaway conditions must be known. Criti-
cal factors are foaming and two-phase ow, which require specic design methods
[5659]. Special care must be taken to dene the runaway scenario against which
the reactor has to be protected. Emergency vent systems may also be designed for
liquid discharge (dumping).
11.5.4.10 Time Factor
Time plays a primary role in the eciency of a measure. The following steps must
be taken from the instant a failure occurs up to recovery of the control of the
process (see Figure 11.15): First, when a failure or a malfunction occurs, it must
be detected. The detection time can be inuenced by the choice of appropriate
alarm settings and instrumentation. But the most important is the choice of an
adequate parameter which must be monitored to detect a malfunction. The design
of alarms, interlocks, and control strategies is an important part of process design.
Once the alarm is switched on, some time is required for the measure to be ap-
plied. Quenching or dumping requires some time for the transfer of the mass, an
emergency cooling system must be switched on, and the cooling medium must
ow at the required temperature with the required ow rate. Finally, the measure
must become eective: Some time also elapses from the instant when the measure
was applied until its eects become sensitive to the process. This is especially true
with large reactors such as those used in polymerization processes. This time fac-
tor must be estimated for an eective design of safety measures, and compared
with the dynamics of the runaway of the desired reaction and of decomposition re-
actions. Here the TMR
ad
concept (Section 11.2.1) is of great help.
11.6
Conclusion
Even if polymerization reactions are critical from the point of view of thermal pro-
cess safety, there are means to systematically identify the risks and to design the
Time to discovery
Time to action
Time to effect
Time to Maximum Rate
t
T
Effect
Alarm level
Fig. 11.15. Chronological development of contingency measures.
11.6 Conclusion 589
reactors in order to minimize the risks. The systematic evaluation scheme pre-
sented in this text has proven to be well suited for risk identication. A method
based on the criticality classes and on calorimetric tools for process development
has been presented. Despite the fact that more advanced methods are available,
these nd only few applications in the industrial practice. This is probably not
due to their inherent quality, but may be an eect of long-term traditions in the
polymer industry, which render innovation more dicult.
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Notation
Symbol Name Practical unit SI unit
A heat exchange area m
2
m
2
A; P chemical
compounds
C concentration mol L
1
mol m
3
c
P
specic heat
capacity
J kg
1
K
1
J g
1
K
1
d diameter or
thickness
m m
D diameter m m
E
a
activation energy J mol
1
J mol
1
Notation 591
F molar ow rate mol h
1
mol s
1
g acceleration due to
gravity
m s
2
m s
2
h heat transfer
coecient
W m
2
K
1
W m
2
K
1
H height m m
DH
R
molar enthalpy of
reaction
kJ mol
1
J mol
1
DH
V
specic enthalpy of
vaporization
kJ kg
1
J g
1
k rate constant function of rate law function of rate law
k
0
frequency factor function of rate law function of rate law
_ mm mass ow rate kg h
1
g s
1
M monomer
M
R
mass of reaction
mixture
kg g
n order of reaction
n revolution frequency rpm s
1
N number of moles
q heat release rate W W
Q thermal energy
(heat)
kJ J
r rate of reaction mol m
3
h
1
mol m
3
s
1
R universal gas
constant
J mol
1
K
1
Lmbar mol
1
K
1
J mol
1
K
1
S cross-section m
2
m
2
S entropy J K
1
t time h s
T temperature

C K
u linear velocity m s
1
m s
1
U overall heat transfer
coecient
W m
2
K
1
W m
2
K
1
V volume m
3
m
3
X conversion
z equipment constant
(stirred tank)

Subscripts
Subscript Meaning Example
0 initial value T
0
initial temperature
A; B; P; R; S chemical compounds C
A
concentration of A
AC accumulation X
ac
degree of accumulation
ad adiabatic DT
ad
adiabatic temperature rise
C coolant T
Amb
ambient temperature
ex exchange (heat exchange) T
C
temperature of coolant
f fouling q
ex
heat dissipation rate
Feed feed d
f
thickness of fouling lm
G gas T
Feed
Loss loss r
G
specic weight of gas
M monomer q
Loss
P process C
M
Monomer concentration
P polymer T
P
process temperature
R reactor, reaction mass l
P
thermal conductivity of polymer
RX reaction d
R
diameter of reactor
S stirrer q
RX
heat release rate of reaction
TAmb ambient d
S
stirrer diameter
th thermal X
th
thermal conversion
V vapor m
V
mass ow rate of vapor
W wall d
W
wall thickness
Greek
Symbol Name Practical unit SI unit
a relative volume increase
g material constant for heat
transfer
W m
2
K
1
W m
2
K
1
D dierence (used as prex)
j heat transfer coecient
of equipment
W m
2
K
1
W m
2
K
1
l thermal conductivity W m
1
K
1
W m
1
K
1
m dynamic viscosity cP mPa s Pa s
r specic weight kg m
3
g m
3
s surface tension N m
1
10
3
dyn cm
1
N m
1
( kg s
2
)
t time constant h s
t space time in continuous
reactor
h s
Acronyms
MTSR maximum temperature of synthesis reaction
MTT maximum temperature for technical reasons
TMR
ad
time to maximum rate under adiabatic conditions (time to explosion)
Notation 593
Dimensionless groups
Symbol Name Expression Parameters
Ne Newton (power)
number
Ne
P
r n
3
S
d
5
S
P power of stirrer
r specic weight of uid
n
S
revolution speed
d
S
stirrer diameter
Nu Nusselt number Nu
h d
l
h lm heat transfer
coecient
d characteristic length
l thermal conductivity
Pr Prandtl number Pr
m C
p
l
m dynamic viscosity
C
p
specic heat capacity
l thermal conductivity
Re Reynolds number
(stirred tank)
Re
n d
2
r
m
n stirrer frequency
d diameter of agitator
r specic weight
m dynamic viscosity
12
Measurement and Control of Polymerization
Reactors
1
John R. R. Richards and John P. C. Congalidis
12.1
Introduction
Consistent polymer properties are of paramount importance to end-user manufac-
turers who must produce the polymer in its nal form and shape for the intended
application. These properties are the result of complex polymer architecture and
composition formed in reaction and perhaps further inuenced in isolation and
extrusion processes. Producing consistent, uniform, and in-specication polymer
for the end-user are the tasks of the polymer process measurement and control
systems.
Polymer processes, whether batch or continuous, rarely run under stable equilib-
rium conditions. However, in order to operate such processes safely and in order to
set the characteristics of the products optimally, a set of process manipulated vari-
ables must be kept constant or systematically modied over the duration of the re-
action or in the course of the various reaction steps. The main process variables of
this type are temperature, pressure, concentration, amount, ow, and level. Speeds
(agitator, gear pumps, extruders), power input and viscosity can be of substantial
importance also.
This chapter will discuss various measurement techniques of importance to en-
gineers and scientists designing and operating polymer reactors and associated
equipment. We will then discuss basic control concepts and conclude with more
advanced control strategies. We have attempted to expand and update the ne
chapter from the previous edition of this book [1].
12.1.1
Denitions
The rst step in the objective of obtaining constant or systematically adjusted oper-
ating conditions is the proper measurement of process variables. There are vari-
ISBN: 3-527-31014-2
595
ous organizations developing standards pertaining to measurement and control,
including the US National Institute of Standards and Technology (NIST), the
Deutsches Institut fur Normung (DIN), the International Organization for Stan-
dardization (ISO), and the International Electrotechnical Commission (IEC).
In measurement technology there are a number of standard measurement con-
cepts [28]:
v
A measurement installation translates the measurement quantity to a measured
value.
v
The measured value consists of a numerical value and a unit of measurement.
v
The result of measurement consists of several measured values, which can be re-
produced as a value or a curve of values.
v
The measurement follows certain measurement principles whose application re-
sults in measurement methods.
v
The measuring method is executed with a measuring installation, which consists
of dierent measuring instruments and auxiliary devices.
v
Measuring instruments are situated in the signal ow and are essential to the
measuring installation.
v
Auxiliary devices usually serve to provide the auxiliary energy which is needed to
provide measuring signals.
v
If the measuring signals pass through several measuring devices connected in
series, then a measurement chain is present.
According to Figure 12.1 a measurement installation translates the measurement
quantity to a measured value. Here we follow the connections of the sensor, trans-
mitter, and transducer as described in Ref. 7:
v
The chain consists of a sensing element (sensor), a measuring instrument whose
input consists of the measured quantity and its output consists of the corre-
sponding measurement signal.
v
At the end of the chain lies the output unit, which provides the desired measure-
ment value.
Measured
quantity
(process variable)
Transducer
Sensing
element
Transmitted
signal
(to controller)
Transmitter
(signal generator/
line driver)
Fig. 12.1. A typical process transducer [7]. D. E. Seborg,
T. F. Edgar, D. A. Mellichamp, Process Dynamics and Control,
Copyright 8 2003 John Wiley & Sons, Inc. This material is used
by permission of John Wiley & Sons, Inc.
596 12 Measurement and Control of Polymerization Reactors
v
Between the measured quantity and the measured variable to the output unit lie
transducers (see Figure 12.1), which process (transform and amplify) the signal
from the measurement instruments ahead of them and feed their signal to the
output measurement device.
v
Measurement transmitters are those devices which convert an analog input sig-
nal to an unambiguous standardized analog output signal [4]. The transmitter is
usually required to convert the sensor element output to the standardized form
compatible with, for example, a controller input.
v
Measurement transducers are devices which have input and output signals in
the same or dierent structure (analog/digital or digital/analog). Sometimes the
terms transmitter and transducer are used interchangeably.
v
One calls the measuring device, with its case and accessories, a measuring in-
strument.
v
The instrument gauge or indicator is the part of the measurement device whose
movement allows the reading of the measurement value.
v
To the measurement instrument also belongs a scale. Between the end points of
the scale lies the range, or span, of the measurement device within which indi-
vidual values of the measured quantity are obtained.
v
In order to calibrate and adjust the scale standards are used, which associate a
precisely dened output measurement value to a measured quantity.
12.1.2
Measurement Error
Accuracy of a measurement is the degree of conformity of an indicated value to an
accepted standard or ideal value [4]. Repeatability is the closeness of agreement
among a number of consecutive measurements of the output for the same value
of the input. Each individual measurement x
i
deviates from the correct or ideal
measured value m [2, 8]. This dierence is called the measuring error or deviation
d
i
[Eq. (1)].
d
i
= x
i
m (1)
Measurement errors can be systematic errors, which are found in the measuring
method or in the equipment; with knowledge of the correct measured value these
errors can be compensated by a correction term or a correction factor. Random
errors, which oscillate in sign and amount, cannot be corrected. Averaging elimi-
nates these errors. The simplest mean is the arithmetic average value x, which is
an estimate of the true mean value m [Eq. (2)].
x =
1
n
X
n
i=1
x
i
(2)
The smaller the random errors of the individual measurements and the larger the
number of measurements, n, the smaller the deviation of the arithmetic average
from the true mean. The empirical sample standard deviation, s, is a measure of
the measurement error [Eq. (3)].
s =
X
n
i=1
(x
i
x)
2
n 1
v
u
u
u
t
(3)
With very large n, the discrete measurements x
i
can be thought of as continuous
measurements x and the sample standard deviation s becomes the true standard
deviation s of a Gauss normal dierential distribution function [Eq. (4)].
f (x) =
1
2p
s
exp
1
2
x m
s

2
" #
(4)
A tabulation or histogram of how often the various values of x
i
occur in replication
is approximated by this distribution. From the Gaussian distribution the statistical
condence of the individual values is obtained. From the cumulative values of this
distribution, 68.3% of all measurement values are within the interval x Gs, 95.4%
are within x G2s, and 99.7% are within x G3s. Further statistical concepts can be
found in Refs. 5 and 8.
12.2
Measurement Techniques
The measurement technique to be chosen is principally determined by the mea-
sured quantity and by the accuracy with which the variable must be measured.
The measuring instrument produces a signal, which must be transformed in
such a way that it can be registered by an indicator or recorder and further pro-
cessed. This requirement is fullled directly by some measuring methods; how-
ever, in most cases a measurement transmitter is operated between the sensor
and the measurement device. Pneumatic pressures between 3 and 15 psig, or be-
tween 0.2 and 1.0 bar, or electrical currents between 4 and 20 mA are used [7] as
standard signals. Pneumatic signals are transmitted in plastic tubing and a dis-
tance of approximately 300 m between the sensor and the transducer can be ac-
commodated. Electrical direct current signals can be transferred over a distance of
a few kilometers. Electrical signals are much more commonly used today than
pneumatic signals. To accommodate larger distances the analog signals must be
converted to digital signals; in that case the distance between measurement trans-
ducer and receiver can be expanded practically at will. In the Sections 12.2.1
12.2.11 some particularly common measurement methods from operational prac-
tice will be discussed.
12.2.1
Temperature
In polymer technology temperature is one of the very important variables of state,
probably the most important. Depending on the measurement range, it is mea-
sured with electrical or mechanical contact thermometers or with optical methods.
With contact thermometers one attempts to keep the thermal capacity of the
measuring device and heat transfer as small as possible so that actual temperature
changes can be obtained as soon as possible. Often the sensitive measurement sen-
sors are protectively shielded. Here compromises must be made which are appro-
priate for individual cases.
The most widely used thermometer in polymer technology is the resistance tem-
perature detector (RTD). For higher temperatures or with point measurements, the
thermocouple is often preferred. Mechanical contact thermometers (expansion
thermometers, rod thermometers, or bimetallic thermometers) are nearly always
used only for local measurements. For optical thermometers, radiation pyrometers
are used.
12.2.1.1 Resistance Thermometers
In resistance thermometers (or RTDs) one uses the dependency of electrical resis-
tance on the temperature [2]. The resistance of metals almost always rises with
temperature. In practice one uses platinum thermometers. A light platinum wire
on a ceramic support is covered with a protective layer of glass, enamel, or magne-
sium oxide. This measurement resistance is the end of one so-called measure-
ment element, which ends in connecting terminals. The whole assembly is in a
sleeve, which is solidly connected to the measuring point in the apparatus with
anges or screws (Figure 12.2).
For pure metals, resistance thermometry is governed by Equation (5), where R
t
is the resistance at temperature t, R
0
is the resistance at the reference temperature,
usually 0
C, and a; b; c are coecients based on calibration points [3].

R
t
= R
0
(1 at bt
2
ct
3
) (5)
3 2 5 4 1
Fig. 12.2. Resistance thermometer thermowell assembly.
1: Measuring resistor; 2: terminal block; 3: connection head;
4: protective pipe; 5: screw tap [1].
For example, platinum has a temperature coecient of resistance a = 0:00385 W/
(W
C) in the range 0 to 100
C. The measuring range of commercial-purity plati-

num thermometers is situated between about 200 and 850
C and the accuracy of

these thermometers is G0.15% of span over the full range [4]. Resistance versus
temperature can usually be described by just a quadratic function, which can be
linearized in measurement ampliers. If large temperature ranges are not present,
the linearization can often be omitted. The resistance is usually measured in a
bridge circuit [2].
12.2.1.2 Thermocouples
A thermocouple consists in principle of two wires made of dissimilar metals sol-
dered together in two junctions, which form a closed circuit (Figure 12.3). At the
contact junctions a voltage gradient is produced and a current, which depends on
the temperature, ows around the circuit. So long as both junctions have the same
temperature the voltages compensate and no current ows; if the junctions have
dierent temperatures, then a voltage gradient is produced, which can be mea-
sured in an open circuit and which is approximately proportional to the tempera-
ture (although the relationship is nonlinear over large temperature scales). If one
of the two soldered connections is held at a constant reference temperature, then
the other connection can serve as a temperature probe.
Suitable metal pairs, which supply suciently large thermal voltages to deliver
Copper
Copper
Constantan
Measuring Junction Reference Junction
Fig. 12.3. Thermocouple wiring diagram [1].
reliable measured values, are copper/constantan (type T), iron/constantan (type J),
chromel/alumel (type K) and platinum (70%)rhodium/platinum (94%)rhodium
(type B). Their thermal voltages permit measurements up to 371
C, 760
C,
1149
C, and 1700
C respectively [3]. The standard-grade error limits for the rst

three types areG0.8
C, G2.2
C, andG2.2
C respectively.
Thermocouples oer the benet that one can obtain point measurements and
they are also suitable for measurements of high temperature. The outside shape
resembles a resistance thermometer. The usually inevitable shield tube makes the
benet of the point measurement often invalid. A possibility to prevent this is to
solder together the head of the shield tube with a soldered joint; at the very least,
it is then possible that the components are less sluggish (with time constants of
a few seconds). If that is not possible, one must accept time constants of some
minutes.
12.2.1.3 Expansion Thermometers
The thermal expansion of gases, liquids, and solids is still used to build simple
thermometers, which indicate the temperature in the direct proximity of the mea-
surement location. The most usual measuring media are alcohol and mercury.
However, mercury poses a health hazard and should only be used when necessary.
The measuring range with liquid-lled thermometers (mercury with a glass stem)
is situated between 200 and 370
C, with an accuracy of G1% of full scale, usu-

ally less thanG0.5
C [4].
The principle of the thermal expansion of solids is used in bimetallic thermom-
eters, which consist of two metal strips of dierent materials with dierent coe-
cients of expansion rmly connected together. Temperature dierences bend these
bimetallic springs and they are usually wound in spirals or coils. The useful mea-
suring range is from 73 to 537
C with an accuracy of G1% of full scale [4].

Bimetallic strips are used for temperature compensation in mechanical instrument
movements. They are also used in switching relays to indicate whether a limiting
value is exceeded.
12.2.1.4 Radiation Pyrometers
High temperatures are measured with radiation pyrometers, which capture the
radiation emitted by the object [4, 9]. They are important mostly for high-
temperature, non-contact measurements. According to the StefanBoltzmann law
the intensity of radiation emitted by a black body increases with the fourth power
of the absolute temperature. According to Wiens law the wavelength at maximum
radiation is inversely proportional to the absolute temperature. One can build ther-
mometers based on these two laws, by measuring either the radiation at all wave-
lengths or the radiation at specic wavelengths [4]. In the thermocouple pyrometer
(Figure 12.4) one collects the radiation emitted from the object on a blackened area
whose temperature rise is measured with a thermocouple. In portable devices an
eyepiece lens is behind the measuring area so that one can aim at the object.
Measuring errors result from space losses between object and measuring instru-
ment; for well-known distances compensation can be made for the errors. Addi-
tionally most objects are not black-body radiation emitters; this can be corrected by
using the Planck radiation law to compare the radiation intensities for dierent
wavelengths.
Optical pyrometers can be used for temperature ranges of 7603500
C [4]. In
special cases (narrow-band and total radiation pyrometers) they can be used for
much lower temperatures (between 40 and 4000
C) if a non-contact measure-
ment is desired [4].
Pyrometers are important also for qualitative observations, for example as auto-
matic ame guards, and for protection in the combustion chambers of thermal in-
stallations so that, after the ame is extinguished, fuel oil or heating gas does not
enter the combustion chamber to form an explosive mixture.
12.2.2
Pressure Measurement
Not only is the pressure a signicant thermodynamic process variable, but pres-
sure measurements are also fundamentally important for safety reasons. Besides
the absolute pressure in an apparatus, one is often interested in a pressure dier-
ence, for instance in cases of ow measurements with orices, and level measure-
ments.
Process equipment pressures are usually measured by the elastic deformation of
bellows, a Bourdon tube, a diaphragm, or a capsule [3].
Bellows pressure gauges (Figure 12.5) are very compact and permit linear
pressure/path relationships. They are particularly useful for the measurement of
1 2 3 5 6
4 7 8
Fig. 12.4. Principle of the radiation pyrometer. 1: Radiation
source; 2: radiant heat; 3: collecting lens; 4: black surface;
5: thermocouple; 6: temperature indication; 7: eyepiece;
8: measuring instrument [1].
pneumatic pressure signals and dierential pressure measurement, and have been
used in pneumatic controller feedback elements.
The gauges are available for pressures of 012 mbar (minimum range) and 0
140 bar (maximum range) [3]. For vacuum applications the range is 012 mbar
vacuum. Accuracy is G0.1% toG2% of span [4].
The Bourdon pressure gauge (Figure 12.6) is a versatile instrument. In this in-
strument a tube with an oval cross-section (Bourdon tube) is bent or coiled inside
the instrument. If the internal pressure rises, then the oval cross-section expands
and the tube increases its radius of curvature. At its end a pointer is attached,
which is carried by the movement of the free end. Pressure gauges are available
for pressures of 00.3 bar (minimum range) and 07000 bar (maximum range)
[3]. Above 100 bar the tubes are arranged in several windings. For vacuum applica-
tions the range is 01 bar vacuum.
In a diaphragm pressure gauge the elastic deection of a circularly clamped
metal disk is transferred to a pointer. Such devices are suitable for measuring
ranges of 00.5 mbar and 070 bar [3]. For vacuum applications the range is 0
0.5 mbar and 01 bar vacuum. They are also suitable for dierential pressure mea-
surement if both sides of the diaphragm are connected with the respective measur-
ing points.
Bourdon tube and diaphragm pressure gauge designs are easily calibrated and
have standard designs.
A capsule is formed by joining two or more diaphragms together, with the total
deection of the assembly equal to the sum of the deections of each capsule.
p
1
p
2
Fig. 12.5. Bellows dierential pressure gauge [1].
Pressure sensor selection guidelines can be found in Ref. 3. Pressure sensors
have various transducers connected to them to convert the measurement into a us-
able signal. Strain gauges and piezoresistive and piezoelectric pressure transducers
are commonly used to produce the measured values.
Currently, smart transducers are used; they are characterized by inclusion of mi-
croprocessors and electronics to store ranges, calibrations and diagnostics, and for
other tasks of data handling from the eld instruments to the control room.
12.2.3
Weight
Balances compare unknown weights with one standard weight, or alternatively
with a well-known force. Balances for weight measurement are very reliable and
accurate instruments; their measuring accuracy is often better than G0.1% [4]. It
must be kept in mind that the gravitational attraction on the Earths surface can
vary by as much as 0.5% but this can be compensated by calibration standards
[4]. The hydraulic and electrical strain gauge load cells and the electrical strain
P

Fig. 12.6. Principle of the Bourdon pressure gauge [1].
gauge are now used as primary sensors. The strain gauge type of load cell is capa-
ble of a sensitivity of 1 part in 20 000 [6]. Other more accurate sensors are available,
such as the variable capacitance transducer capable of a sensitivity of 1 part in
1 000 000 [6].
Either bulk weighing of vessels or weighing platforms are generally used in the
polymer industry. Types of balances used include weighing platforms, portable
platform scales, and truck scales. Common methods of weighing include mechan-
ical lever scales, spring-balance scales, and load cell weighing systems. Portable
bench scales have capacities from 10 to 1000 kg. Beam-type weighing platforms
have capacities from 200 to 5000 kg [4].
In electronic balances the force exercised by the load on the base is measured
with a force measurement cell (for example, an electrical strain gauge) and trans-
formed into an electrical signal. This signal is processed within the balance in a
digital or analog fashion and is then displayed. These systems can be calibrated
and used in fully automatic installations. As force measurement cells one can use
pressure sensors with lower requirements for accuracy. These are installations in
which the weight is transformed into pressure pneumatically or hydraulically; one
can determine levels in tanks or reaction vessels by this method, which can also be
used to meter automatically the main ingredients of a batch process, for example
the water and monomer phase in an emulsion or suspension polymerization.
Strain gauges are used widely in force measurement cells. When a strip of con-
ductive metal is stretched or compressed by a mechanical load, without reaching
its elastic limit, its electrical resistance changes. In order to use this principle, one
sticks strain gauges onto elastic cylinders or bending rods, whose deformation is
thus transferred to the strain gauges. An elastic cylinder carries four to eight resis-
tance strain gauges, which are arranged in a bridge circuit. The load on the cell
then detunes the bridge and creates a measuring voltage proportional to the detun-
ing. This conguration also provides compensation for resistance variations due to
temperature. Modern units contain almost exclusively digital balances for signal
indication and analysis. With these units one can meter in weights of ingredients
in a given order.
Belt balances (Figure 12.7) allow simultaneous conveying and weighing, so they
are used frequently as metering devices. In these balances, an endless conveyor
belt is designed to be the load part of a balance [6]. Weight changes are measured
by load cells, and then integrated over short intervals to give the rate of ow. Total-
izers can give the total weight over a given time. The belt is covered continuously
with the material to be weighed. The feed requires a variable metering device, for
example a vibrating hopper or a screw-type feeder.
12.2.4
Liquid Level
Level measurements are used either to control level in vessels or apparatus, or to
measure throughput. Level measurements are important in order to estimate in-
ventories and their movement, or to assure the smooth operation of processes. Fur-
thermore, in batch processes, level measurements are important to limit lling and
emptying steps as well as for alarming. For continuous processes, they serve to
maintain a constant level in the vessels where the ow occurs (for example, the
sump in a rectication column or the contents of a chemical reactor). Flow mea-
surements are indispensable to metering and feeding functions.
A great variety of level measurement techniques are available. These involve
point-contact, visual, buoyancy, oat, and hydrostatic methods, and radio-frequency,
ultrasonic, microwave, nuclear radiation, resistance tape, and thermal level sys-
tems [3].
Point-contact measurements of liquid level are basically length measurements.
For example, one observes the wetting of a dipstick through a sight glass in the
vessel, or the movement of a oat that follows the surface of the liquid in the res-
ervoir. Similarly the point-contact level in a solid hopper can be measured directly
by a mechanical plumb line [4], which is attached at the end of a measuring tape
that is unwound from a barrel so that the plumb line hits the solid surface; mark-
ings on it permit the measurement of the length digitally. Likewise, the length of a
hanging string can monitor the position of a oat on a liquid surface.
In the oat method, a oating gauge is not introduced into the vessel itself but
into a dierent container, such as a side gauge glass, which is arranged in parallel
and communicates with the main vessel. In this way disturbances arising from the
movement of the uid (boiling or circulation) are avoided. Floating gauges can also
be used in order to indicate the position of the separation surface between two im-
miscible liquids.
In the buoyancy method, displacement bodies measure levels in liquid contain-
ers. By measuring the dierence in weight of a partially submerged body at various
degrees of submergence, one may determine the level of the liquid in which it is
M
slidegate valve conveyor
motor balance bridge force receiver data processing
Fig. 12.7. Conveyor belt balance [1].
submerged [3]. The device fails if the weight or the volume of the displacement
body changes during the process, for example because of scaling or if the density
of the medium changes.
In the hydrostatic method, the pressure at the base of the liquid, which is related
to the height of the liquid above the base, is measured. The measured pressure
depends directly on the liquid height according to the Bernoulli equation or me-
chanical energy balance [1012] [Eq. (6), where z
2
is the level at the surface of the
liquid, z
1
is the level at the base, p
2
is the pressure at the surface, p
1
is the pres-
sure at the base, r is the liquid density, and g is the acceleration due to gravity]. In
pressurized reservoirs one measures the pressure dierence p
1
p
2
between the
base and the gas space.
z
2
= z
1

p
1
p
2
rg
(6)
In a variant of this method, an inert gas is bubbled through the liquid with a dip
tube. If the density of the liquid is known, one can also determine the level
through weighing.
It should be noted that in equations such as Eq. (6) a conversion factor may be
necessary in unit systems that are termed inconsistent. In the US Customary Sys-
tem (USCS) the force unit is the lb-force (lb
f
) and in SI units the force unit is the
Newton (N). The conversion factor g
c
= 32:174 lb
m
ft lb
1
f
s
2
is used in USCS
units to resolve expressions involving forces in lb
f
and masses in lb
m
so that New-
tons law [Eq. (7), where F is force, m is the mass, and a is the acceleration] is sat-
ised.
F =
ma
g
c
(7)
In the SI unit system, which is used in this book, g
c
= 1 kg m s
2
N
1
and so this
conversion factor is not necessary.
In polymer reactors one has to deal often with very viscous liquids or melts.
Here oating gauges or displacement methods fail. An alternative is level measure-
ment with radioactive gamma-ray beams (Figure 12.8) that can penetrate metal
walls [4]. The entire reactor is traversed by gamma-radiation; its intensity is given
according to the BeerLambert law [Eq. (8), where I; I
0
are the intensities behind
and in front of the object, e is the absorption coecient, r is the density of the me-
dium and l is the path length.
I = I
0
exp(erl) (8)
Radiation sources include cobalt-60 and cesium-137. Receivers are scintillation
counters. The specimen is usually arranged in a rod-like shape and installed on a
point-shaped detector, particularly if a continuous measurement is concerned. The
benet of the method is that it operates in a non-contact fashion. However, it re-
quires extensive safety measures [4]. The specimen must be shielded with lead
against the environment, so that only the direction toward the detector is free.
Mounting, dismantling, and maintenance may be undertaken by trained personnel
only, and the radiation limiting values are to be checked constantly. For this reason
this method should be used only when other methods fail. The accuracy is 3 mm
to 1% of height span [4].
Other level-measuring methods are also possible [3]. Capacitance measurements
use the change in capacitance of a capacitor, which is built in a probe through the
vessel wall (Figure 12.9). Level can also be measured by the change in resistance of
a resistance tape on the vessel wall.
One can also obtain levels by introducing vibrating sensors into the container at
dierent levels until the vibrations are damped by the liquid (Figure 12.10).
Microwave radar level systems are also possible, which are not aected by den-
sity changes in the beam path as are ultrasonic beam techniques.
12.2.5
Flow
Flow measurements establish the volume or mass of a uid per unit of time
through the measurement device. The methods are similar for both liquids and
gases; nevertheless it must be considered that liquids have a substantially higher
Counter
Screen
Melt entrance
Melt exit
Radioactive
preparation
M
Fig. 12.8. Level measurement using radiation [1].
density than gases. Also, the density dependence on pressure and temperature
must be particularly considered with gases. Because of these considerations, dif-
ferent forms of implementation result [24]. Types of measurement systems in-
clude dierential pressure, magnetic, turbine, oscillatory, mass ow, ultrasonic,
and positive-displacement meters [3].
Direct owmeters are generally counters. They couple the number of self-
repeating periodic processes (for example, circulation) with time measurement.
The most widely used device of this type is the oval gear owmeter (see Figure
12.11). For cold water the ow ranges are 0.85 L min
1
to 4162669 L min
1
a
a
b
b
c
c
A B
Fig. 12.9. Electrical measurement of liquid level. (A) Capacitive
measurement; (B) conductivity measurement; a: electrode;
b: measuring instrument; c: material [1].
A B
Fig. 12.10. Mechanical measurement of liquid level.
(A) Vibration probes; (B) rotary wing probe [1].
and for heavy oil (5300 cP) the ow ranges are 0.27.2 L min
1
to 1673826
L min
1
[3].
In the oval wheel counter, two oval wheels run in gears moving in opposite direc-
tions; the pressure drop along the device drives them. The wheels lock successively
and the volumes V
1
and V
2
convey them and release them again (Figure 12.11).
With each full rotation of the pair of wheels, the volume V = 2(V
1
V
2
) is con-
veyed through the counter [1]. The devices can be calibrated and high accuracies
can be obtained (0.1% [4]); with the smallest types, inaccuracy is highest. The de-
vices are very susceptible to contamination and must therefore be protected by ne
lters of solid particles.
Gases can be measured with the rotating lobe owmeter, which is similar to
the oval gear owmeter (see Figure 12.12). The dierence is that the rotating
lemniscate-like lobed impellers do not run directly on one another and are not
geared together. They are coupled through a gearbox.
The devices are calibrated and can be constructed for ow stream capacities be-
tween 2 and 4800 m
3
h
1
[4]. They have good repeatability (0.015%) at high ow
rates [4]. They can be used for temperatures up to 205
C and pressures up to 83
bar [4]. The temperature and pressure of the gas are captured and processed so
that the volume is indicated in standard conditions of temperature and pressure
(STP). The measured variable is deduced from the speed of the rotors, which is ob-
tained through a magnetic clutch from the pressure chamber.
A B C
V
1
V
2
Fig. 12.11. Oval-shaped gear owmeter [1].
A B C D
Fig. 12.12. Lobed-impeller owmeter [1].
Among the indirect volume owmeters, turbine owmeters are the most impor-
tant. They measure the speed of the owing medium from the speed of an impel-
ler, or rotor. There are devices arranged in an axial or radial direction to the ow.
Turbine owmeters can be used for liquids, gases, and vapors.
The rotating vane meter, which is arranged in the radial direction to the ow, is
the most well known and is used for ows of 14800 m
3
h
1
[4]. The measuring
range is 1:10 with an accuracy of about G0.1% [4].
The turbine owmeter with electrical impulse pick-up, arranged in the axial di-
rection of the ow, is of importance for gas ows. It contains an impeller with
magnetic wings which, with each passage, induce a voltage surge in a solenoid
coil situated outside. The frequency of this alternating current is proportional to
the ow. Reproducible measurements require turbulent ow, because only then
does the slip not depend on the ow velocity. The measuring range also depends
on the viscosity of the owing medium.
There exist gas turbine owmeters for ows up to 4500 m
3
h
1
[4]. Linearity is
G1% over a ow range of 20:1 [4]. Rangeabilities can be as much as 100:1. If one
wants total volumes using owmeters, for example for accounting purposes that
require high accuracy, then the instantaneous measurement must be integrated
with time. This can be accomplished with pneumatic or electrical counters.
Measuring methods which deduce the ow directly from ow characteristics are
very common. There are versatile methods being used, which all depend on the ve-
locity of the owing medium. The most important are measurements with orice
devices, with suspended bodies, and according to a magnetic-inductive method. Be-
yond that there are owmeters which use the pressure drop of a owing liquid in a
capillary, and magnetic-inductive, ultrasonic, and Coriolis owmeters.
Restrictor devices such as venturi tubes, orice plates, and nozzles operate on
the basis of the Bernoulli equation [10, 11]. A venturi tube is depicted in Figure
12.13.
For incompressible uids without friction or pump work at points upstream (1)
and downstream (2) on a streamline in the ow, the Bernoulli equation becomes
Eq. (9), where z
1
; z
2
are the levels at the two points, p
1
; p
2
are the pressures at the
p
1
p
2
d
1
d
2
Fig. 12.13. Venturi nozzle. d
1
: Diameter of the pipe; d
2
: diameter of the throat.
two points, v
1
; v
2
are the average velocities at the two points, a
1
; a
2
are the kinetic
energy correction factors at the two points, r is the liquid density, and g is the ac-
celeration due to gravity.
p
1
r
gz
1

a
1
v
2
1
2
=
p
2
r
gz
2

a
2
v
2
2
2
(9)
The denition of the kinetic energy correction factor is the area average of the
cubed velocity v
3
over the average velocity cubed, v
3
[Eq. (10)] [10].
a =
1
A
v
3
dA
1
A
v dA

3
=
v
3
v
3
(10)
Note that a = 2 for laminar ow and a = 1 for plug ow. For equal heights (hori-
zontal restrictors) the Bernoulli equation becomes Eq. (11).
p
1
r
a
1
v
2
1
2
=
p
2
r
a
2
v
2
2
2
(11)
The continuity equation can be written at two points on a streamline in the ow
[Eq. (12), where A
1
; A
2
are the ow areas at the two points, r
1
; r
2
are the liquid den-
sities at the two points] [10].
r
1
v
1
A
1
= r
2
v
2
A
2
(12)
Since the uid is incompressible, Eq. (13) holds.
r
1
= r
2
= r (13)
Combining Eqs. (11)(13) and eliminating v
1
gives Eq. (14), where b is the ratio of
diameters d
2
=d
1
.
v
2
=
1
a
2
a
1
b
4
p
2(p
1
p
2
)
r
s
(14)
To compensate for the friction loss and kinetic energy factor assumptions, the
velocity equation is modied to Eq. (15), [10] where C
d
is an empirical discharge
coecient.
v
2
=
C
d
1 b
4
p
2(p
1
p
2
)
r
s
(15)
Therefore, for restrictors, the volumetric ow q
v
relationship is Eq. (16) [10].
q
v
= v
2
A
2
=
C
d
A
2
1 b
4
p
2(p
1
p
2
)
r
s
(16)
The mass ow q
m
relationship is Eq. (17) [11].
q
m
= rv
2
A
2
=
C
d
A
2
1 b
4
p
2(p
1
p
2
)r
p
(17)
For compressible ow, similar equations may be used. The mass ow equation is
modied to be Eq. (18) [6, 10, 12]. Y is a dimensionless expansion factor that is a
function of p
2
=p
1
; b, and k, where k = C
p
=C
v
is the ratio of specic heats of the gas
[6, 10].
q
m
=
C
d
YA
2
1 b
4
p
2(p
1
p
2
)r
1
p
(18)
Note that Y = 1 for an incompressible uid.
Both factors C
d
and Y can be determined for dierent tube nominal sizes and
ow velocities with air or water, and can also be obtained from charts in Refs. 6
and 12, or tables in Ref. 2. Typically the data can also be used for other media, if
the Reynolds numbers are kept constant. The most important restrictors are the
venturi tube (Figure 12.13) and the orice plate (Figure 12.14). The discharge coef-
cient C
d
is about 0.940.99 for a venturi tube and about 0.6 for an orice plate [6,
11].
The simplest implementation of a restrictor is the standard orice plate, which
also supplies the most accurate values (Figure 12.14). The orice is a sharp-edged
disk with diameter d
2
in a pipe with diameter d
1
. The pressure tap positions rela-
tive to the plate vary depending on the desired design [6]. For so-called radius taps,
the pressure-measuring drillings are situated inside the anges in each case at a
distance of one pipe diameter upstream and half a pipe diameter downstream of
the orice [6]. The accuracy of the orice plates is G0.25% to G0.5% of actual
ow [4]. The rangeability with a measurement error of less thanG1% of the actual
ow is 3:1, which can be improved with smart transmitters [4].
The orice plate is the restrictor most frequently used in practice. For the mea-
suring accuracy of all standard orices it is essential that the edge sharpness be
maintained in continuous operation. If this is not the case, then the standard noz-
zles have advantages, and their permanent pressure loss is somewhat lower than
in standard orices. They also have advantages for very small throughputs and are
used for very dirty liquids.
In a venturi tube the so-called diuser is attached to the normal nozzle piece
and serves for backpressure gain. This has the smallest permanent pressure loss
among the various restrictors. The accuracy of venturi tubes is G0.75% of the un-
calibrated rate andG0.25% of the rate calibrated in a laboratory.
All measurements with restrictors require turbulent, evenly distributed ow. In
order to smooth out disturbances in the ow stream, orices and nozzles require a
straight and smooth upstream piping length of between six and 40 pipe diameters
[6] depending on the nature of the upstream tting and between two and four pipe
diameters downstream to the nearest tting. Sources of error are clusters of gas
bubbles or dirt particles (in uids) or condensing liquids (for gases) in the dieren-
tial pressure tubes. For gases the pressure ratio p
2
=p
1
at the restriction must not
be less than about 0.53; otherwise sonic velocity is achieved in the restriction [10].
Measuring methods with oating bodies work with vertically arranged, inverted
cone-shaped or slightly tapered tubes, where the uid ows through from bottom
to top. In the rotameter, the ow holds thereby a oating body in equilibrium (see
Figure 12.15), which depends on the ow velocity and the lift of the body against
its weight.
The force balance is written as Eq. (19) [10], where F
W
is the (downward) gravity
force, F
B
is the (upward) buoyancy force, and F
D
is the (upward) drag force.
1
2
p
1
p
2
3 3
d
1
d
2
Fig. 12.14. Orice plate and anges. 1: Orice plate; 2: ange
supports; 3: pressure measurement drill taps [1]. Note that the
pressure tap positions vary, depending on the desired design
[6].
F
W
= F
B
F
D
(19)
If V
f
is the volume of the oat, r
f
is the density of the oat, and r is the density of
the uid, the force balance becomes Eq. (20).
F
D
= V
f
r
f
g V
f
rg (20)
The drag force is given by Eq. (21), where C
D
is the drag coecient, A
f
is the pro-
jected area of the oat, and v
max
is the maximum velocity past the oat.
F
D
= C
D
A
f
rv
2
max
2
(21)
F
B
, F
D
F
W
b
a
Fig. 12.15. Flow measurement with oat (rotameter).
a: Conical ow pipe; b: oat; F
W
: gravity force; F
B
: buoyancy
force; F
D
: drag force [1].
Substituting the drag force into the force balance we get Eq. (22).
C
D
A
f
rv
2
max
2
= V
f
g(r
f
r) (22)
The volumetric ow rate q
v
can be related to the maximum velocity past the oat
by Eq. (23), where A
t
is the tube area at the point of constriction and A
f
is the oat
area.
q
v
= v
max
(A
t
A
f
) (23)
To size the rotameter, v
max
can be eliminated between these two equations and the
expression simplied so that the volumetric ow rate q
v
is obtained as Eq. (24),
where C
d
= 1=
C
D
is a discharge coecient with values between about 0.6 and

0.8 [9].
q
v
= C
d
(A
t
A
f
)
2gV
f
(r
f
r)
rA
f
s
(24)
For a linearly tapered tube with the bottom diameter the same as the oat diame-
ter, the area for ow is a linear function of the height of the oat h [Eq. (25)] [10].
d
2
t
d
2
f
= (d
f
ah)
2
d
2
f
= 2d
f
ah (ah)
2
A2d
f
ah (25)
Substituting this into the mass ow equation gives Eq. (26), from which the ow
rate depends almost linearly on the height of the oating element h and the viscos-
ity of the medium; in each case it is calculated with the help of calibration curves,
which depend on the instrument and the calibration medium (air or water).
q
m
= rq
v
= rv
max
p
4
(d
2
t
d
2
f
) =
2p
4
rv
max
d
f
a

h (26)
The oating elements are available in dierent forms; for simple gas measure-
ments the oating element is a sphere; for uids one mostly nds a cylindrical
oating element (Figure 12.15), which is shaped downward like a cone and at the
upper edge like a at truncated cone-like disk. This disk is sharply grooved in the
side, in order to induce a rotation in the equilibrium position. This movement sta-
bilizes its position in the center of the conical pipe.
The position of the oating element can be observed directly, if the conical guide
tube consists of glass or quartz. If that is not possible, then its position can also
be measured magnetically, if it contains a magnet and the pipe consists of a non-
magnetic material.
Rotameters are useful for ows from 0.01 cm
3
min
1
to 920 m
3
h
1
of liquid, or
0.3 cm
3
min
1
to 2210 m
3
h
1
of gas [4]. The measurement accuracy for industrial
rotameters is approximately G1% toG2% of full scale over a 10:1 range [4].
Magnetic-inductive owmeters consist of one nonmagnetic, insulated pipe,
which is traversed by a magnetic eld. If a conductive uid moves through the
pipe, the ions contained in it are deected crosswise to the ow direction and to
the magnetic eld. Two electrodes, which are attached at the same height inside
the pipe, then indicate a voltage dierence, which is proportional to the ow veloc-
ity. The method is independent of the ow prole, density, viscosity, and contami-
nation. Moreover it does not build up an additional pressure drop in the line. The
measuring accuracy is within G1% [1]. For the time being, there are still dicul-
ties for nominal pressures over 16 bar.
When a uid moves in a tube that is rotated, it experiences a Coriolis force pro-
portional to its mass and velocity and to the angular velocity of the tube. In the
Coriolis owmeter, the tube is not rotated but vibrated. Vibrations in the tube are
set up and a small elastic deformation in the tube results from the Coriolis force.
The deformation magnitude is related to the mass ow rate. These owmeters
have the advantage that the measurement is independent of the temperature, den-
sity, pressure, viscosity, or ow prole [3]. The accuracy is high, G0.15% within the
range of 10:1 of full scale rate [4], but the initial cost is high. The ow range is 0
28300 kg min
1
[4]. The high accuracy can be very useful for ingredients that are
precisely metered to polymerizers, despite the high cost. Because of their operating
principle, Corilis owmeters can simultaneously obtain the density of the uid.
12.2.6
Densitometry, Dilatometery, and Gravimetry
Density is the mass per unit volume of a substance. Specic gravity is the density
of the substance relative to a standard such as liquid water at 4
C. The density of
liquids is monitored by hydrometers, weighing a xed volume (density balance),
the Coriolis method (described in Section 12.2.5), and vibrating methods. Hydro-
static, displacement oat, sonic, and radiometric methods are among others also
used [4].
A hydrometer consists of a tube closed at both ends, with one end enlarged into
a bulb that contains ne lead shot or mercury to cause the instrument to oat up-
right in a liquid. In the glass tube is a scale calibrated so that the reading on it,
level with the surface of the liquid in which the hydrometer is oating, indicates
the number of times the liquid is heavier or lighter than water, that is, the specic
gravity of the liquid. Hydrometers have been connected photometrically or me-
chanically to produce a useable electrical signal [4].
The density balance operates on the principle of weighing a xed volume. In it
the liquid ows through a U-tube, which forms the load part of a balance (Figure
12.16). The deection of the balance can be indicated directly, and usually one uses
electrical or pneumatic transducers so that the measured values can be transferred
and processed further. Density balances must be installed so as to avoid vibrations.
In the tuning fork densitometer one utilizes the dependency of the frequency of
a tuning fork or a vibrating plate, which is excited to produce an under-damped
oscillation, on the density of the surrounding medium. The resonant frequency of
an oscillating system is approximately proportional to the square root of the oscil-
lating mass [4]. A vibrating ow U-tube may also be used for density measurement
[8].
Vibrating and density balance densitometers can also be used for compressed
gases (r > 2 kg m
3
). Gases at standard pressure are measured with gas density
balances, with which one determines the buoyancy of a closed hollow sphere lled
with a comparison gas.
A sonic densitometer consists of a device for measuring the speed of sound in
the liquid [4, 8]. The speed of sound c is given by Eq. (27), where E is the bulk
modulus and r is the mass density [4]. Unfortunately the liquid must be clear of
particles that might scatter the sound waves and limit the received signal.
c =
E
r
s
(27)
The density of liquids can also be measured radiometrically, by the absorption of
gamma-rays in the medium. The intensity of the exiting radiation depends on the
density of the medium and is given according to the BeerLambert law [Eq. (28),
where I; I
0
are the intensities behind and in front of the object, e the absorption
coecient, r the density of the medium and l the path length].
Indicator dial
Balance system
Flow
Flexible tube
U-tube
Fig. 12.16. Density balance [1].
I = I
0
exp(erl) (28)
Unlike level measurements the radiometric measurement of the density requires
high outlet intensity and thus higher safety precautions. However, it has a broad
range of application and is particularly interesting for measurements in polymer
technology; one can measure very viscous melts, emulsions, and suspensions.
Dilatometers measure the volume shrinkage during the course of liquid poly-
merization reactions and are mainly used for laboratory measurement of monomer
conversion. They are based on the principle that polymers are denser than their
monomers. Volume changes are monitored as monomer is converted to polymer
by following the change in height of the solution inside a graduated capillary
tube. Conversion is monitored with a computer-linked photodetector that tracks
the meniscus in the capillary and records the height changes [13].
The percentage of total solids in a polymer sample can be determined by the
gravimetric method through moisture weight loss. The sample is loaded onto a
pan and the weight determined. Then it is put into an oven at high temperature
for a time to remove all volatiles. It is then reweighed and the percentage of solids
is determined.
12.2.7
Viscosity
Viscosities are of interest in polymer technology in order to follow the course of a
polymerization reaction or to monitor continuously the quality of a product. Vis-
cosity m is the constant of proportionality between applied shear stress t and the
resulting shear rate _ gg according to Newtons Law of viscosity [Eq. (29)] [11, 13].
t = m_ gg (29)
Viscosity may be constant (Newtonian), shear thickening (dilatant), or shear thin-
ning (pseudoplastic) with shear rate. For polymer systems, solution or melt, the
viscosity can be related to the molecular weight of the polymer, as discussed in
Refs. 4, 8, and 13.
In most cases viscosity is measured by capillary viscometers or rotating viscome-
ters. In a capillary viscometer one measures the pressure drop by means of con-
stant laminar ow in a capillary; the constant ow can be achieved by a pump
and the pressure drop is obtained by a dierential pressure transmitter whose
plus and minus sides are connected to the capillary. The pressure drop is
then directly proportional to the viscosity according to the HagenPoiseuille law
[4, 11] [Eq. (30), where m is the viscosity, r is the capillary radius, l is the capillary
length, Dp is the pressure drop, and q
m
is the mass ow rate]. The capillary visco-
meter may also be employed in-line for monitoring of molecular weight in poly-
merizations, as described in Ref. 14.
m =
pr
4
Dpr
8q
m
l
(30)
A method to obtain a measure of molecular size that is quick and cheap is the melt
indexer [13]. The melt index is dened as the number of grams of polymer ex-
truded in 10 min through a capillary 2.1 mm in diameter and 8 mm long at a cer-
tain temperature and pressure (ASTM D1238).
Among the dierent possible ways to measure viscosities in rotating viscome-
ters, the coaxial cylinder apparatus is the most commonly used in practice. The
measured liquid intersperses the annular gap between the stationary inner cylin-
der (bob) and the rotating outer cylinder (cup). Therefore a velocity gradient builds
between the inner and outer cylinders (Couette ow). The momentum, which is
transferred by this downward gradient to the inner cylinder, is directly proportional
to the viscosity. Deection is compensated by a torsion bar and the equilibrium de-
ection is measured electrically. The measurement of the angular velocity of the
cup and the angular deection of the bob makes it possible to determine the vis-
cosity [4, 11].
Besides the coaxial device, the cone-and-plate viscometer is also used. In this
device an inverted cone faces a solid plate and the apex of the cone just touches
the plate. The measured liquid is in the free gap. The viscosity of the measured
uid is computed from the torque on the cylinder-driving shaft [4, 11].
The Mooney viscometer, used particularly in the rubber industry, is a variant
of the cone-and-plate viscometer; it restricts the sample to a disk-shaped cavity
(ASTM D1646) [4].
Vibrating-reed viscometers can also be used for continuous in-line polymer vis-
cosity [4]. The amplitude of the probe vibration depends on the viscosity of the
uid. As the viscosity of the uid increases, the resistance to probe vibration in-
creases.
12.2.8
Composition
The composition of raw materials, nished products, and samples of the various
steps of a reaction is normally measured at the laboratory using the appropriate
physical and chemical analytical methods. However, sampling and analysis are
time-consuming and in many cases the result of the analysis is only of current
interest and too late for control decisions to be made. In order to monitor compo-
sitions continuously, one needs automatically functioning analytical instruments
that can continuously obtain and show the composition of a mixture. Some devices
are fast and precise enough to be able to generate signals for control loops. The
controllers would then adjust the desired values of other input variables such as
ow, temperature, or pressure in a cascade control scheme.
Optical methods are common [4, 8, 13]. Infrared (IR) spectrographic analysis
makes it possible in many cases to follow the appearance or the disappearance of
one or more characteristic absorption frequency bands. These frequency bands cor-
respond to frequencies of vibrations of the bonds in the molecules. One must rst
analyze the spectrum of the IR radiation and then measure the corresponding fre-
quencies. More recently the Fourier transform infrared technique (FTIR) has been
used for faster data acquisition and handling than traditional IR spectrographic
analysis. IR and FTIR can be applied to polymer solutions or solid lms for com-
position analysis and are particularly useful for copolymer composition determi-
nation.
Optical analytical devices are also built for measuring radiation in the ultraviolet
(UV) and the visible spectral region, but the spectral absorption bands obtained
here are usually so broad that these devices are used only for special tasks.
The refractive index (RI) of a mixture is a function of the composition of the mix-
ture and the respective refractive indices of the constituents [8]. The mixture re-
fractive index follows mixture laws such as the LorentzLorenz law. Operational
measuring instruments are usually dierential refractometers or critical-angle re-
fractometers [4]. A large disadvantage in the method is that it only provides mean-
ingful results when a two-component system is considered. However, a dierential
refractometer is commonly used as a concentration detector in the euent of a gel
permeation chromatography (GPC) column for molecular weight determination.
Raman spectroscopy is dependent on the collision of incident light quanta with
the molecule, inducing the molecule to undergo a change [13]. It is now being
used to provide a means of studying pure rotational and vibrational transitions in
molecules. Raman scattering of light by molecules may be used to provide their
chemical composition and molecular structure and is currently being applied to
polymers, as shown in Refs. 8, 15, and 16.
Apart from optical methods, one uses magnetic (for paramagnetic materials, for
example oxygen in diamagnetic gases) and electrical methods. Examples of the lat-
ter are conductivity measurements (of ionic liquids, for example purity of boiler
feeding water), ionization methods (for example, the ame ionization detector in
gas chromatographs or the photo-ionization of gases with UV light to measure
tracking of hydrocarbons in air), electro-chemical potential methods (for example,
pH measurements), and occasionally polarographic methods.
Nuclear magnetic resonance (NMR) is based on the principle that when a
hydrogen-containing compound is in a strong magnetic eld and exposed to
radio-frequency signals the compound absorbs energy at discrete frequencies [13].
This technique can be used to measure chain molecular structure, copolymer com-
position, and copolymer sequence lengths. It can also deduce isotactic/atactic ra-
tios and other structure variations, as shown, for example, in Ref. 17. Mass spec-
trometry and NMR are currently not in routine on-line process use, but can be
used to calibrate other on-line methods.
Many methods depend on the separation of a uid mixture. Among these, gas
chromatography (GC) stands out [8]. Suitable devices for on-line control were de-
veloped from laboratory gas chromatographs and operate very reliably. However,
they can be expensive because of the associated program controls. The principle
of gas chromatography is that a carrier gas (helium) is passed over a tubular col-
umn of a ne solid. A sample is injected into the carrier gas stream and the gas
euent from the column is run past a detector such as a ame ionization detector.
Calibration is based on the fact that, all conditions being equal, a given hydrocar-
bon will require the same length of time to pass through the column to the detec-
tor (elution time) [4].
A mass spectrometer source produces ions, and information about a sample may
be obtained by analyzing the dispersion of ions when they interact with the sample
using the mass-to-charge ratio. Sometimes mass spectrometers are used after a
separation step such as gas chromatography or liquid chromatography for fraction
identication.
12.2.9
Surface Tension
In emulsion polymerizations particularly, it may be of some interest to measure
the surface tension of the polymerization. The surface tension can give an indica-
tion of whether or not micelles are present, which is important in particle nuclea-
tion above the critical micelle concentration (CMC) [18, 19].
The on-line method used is usually the bubble pressure method. A dip tube is
inserted below the liquid surface and bubbles are formed by compressed gas. Bub-
bles formed within a liquid are compressed by surface tension. The resulting pres-
sure rises with decreasing bubble radius. This increased pressure, in comparison
to the outside of the bubble, is used to measure surface tension. During the pro-
cess of bubble formation and breakage, the pressure can be measured in the bub-
ble. From the pressure oscillation the surface tension can be calculated.
12.2.10
Molecular Weight Distribution (MWD)
It is widely recognized that a reliable method of monitoring molecular weight dis-
tribution (MWD), and the various molecular weight averages (M
n
; M
w
, and M
z
)
during the polymerization process is of importance to nal polymer quality. The
polydispersity index is dened as the ratio of the weight to the number average
molecular weight [Eq. (31)], which is a measure of the spread of the MWD.
PD =
M
w
M
n
(31)
Monitoring the molecular weight distribution or its averages from a batch or con-
tinuous polymer reactor in real time would be desirable. Monitoring and feedback
control of polymerizations can provide fundamental benets for improved quality.
Traditionally, gel permeation chromatography (GPC) or size-exclusion chroma-
tography (SEC) has been used to determine MWD [8, 13]. In GPC/SEC, polymer
solutions are injected into one or more columns in series, packed with porous par-
ticles. The packing has small pores and during elution the polymer molecules may
or may not, depending on their size, penetrate into the pores. Therefore, smaller
molecules have access to a larger fraction of pores than the larger ones, and the
chains elute in a decreasing order of molecular weights. For each type of polymer
an empirical correlation exists between molecular weights and elution volumes.
This can be used to calibrate the GPC/SEC, which allows the evaluation of average
molecular weights and molecular weight distributions.
Direct column calibration for a given polymer requires the use of narrow MWD
samples of that polymer. The chromatograms of such standards give narrow peaks
and with each standard is associated the retention volume of the peak maxi-
mum. There are a number of polymers for which narrow MWD standards are
commercially available. More recently triple-detector instruments have been de-
signed which include a dierential viscometer, a light-scattering instrument, and
a dierential refractometer that monitors the column euent. A calibration curve
can be obtained from this arrangement as long as all signals are calibrated [13].
For on-line purposes, the viscosity measures previously mentioned (see Section
12.2.7) have been used as a proxy for molecular weight averages in on-line control.
Some vendors are commercializing more rapid GPC/SEC instruments for on-line
control, with certain instruments already available.
12.2.11
Particle Size Distribution (PSD)
The particle size distribution (PSD) can have a fundamental eect on the physical
properties of dispersions that are common polymer products. The measurement of
just the average particle size may not be sucient. For example, the presence of
populations of dierent sizes resulting in a multimodal distribution could have a
strong inuence on nal properties and may need to be controlled.
There are several particle size measurement techniques in use, such as optical
imaging, electron imaging, optical diraction and scattering, electrical resistance
changes, sieving, sedimentation, and ultrasonic attenuation [4].
Optical (larger than 1 mm) and scanning electron microscopy (SEM) techniques
literally give the clearest picture of a PSD. However, analyzing the images may be
tedious without image analyzers. Nevertheless, this method can be used as a check
or calibration on the indirect methods.
The Coulter-counter particle size analyzer (larger than 0.5 mm) is used for mea-
suring volumes of individual particles. Particles are suspended in a conductive
uid, into which electrodes are placed. As a particle passes through an aperture be-
tween the electrodes, it displaces its own volume of electrolyte, and there is a mea-
surable change in the electrical resistance of the system. The change becomes a
precise measure of particle volume. These volumes can then be put into size bins
and the PSD can be constructed.
Today there are two principal light scattering technologies that are commercially
available: light scattering intensity measurement (also known as static, or Rayleigh,
scattering) and dynamic light scattering measurement [also known as quasi-elastic
light scattering (QELS) or photon correlation spectroscopy (PCS)]. It should be
noted that light scattering techniques are applied not only to particle size measure-
ment but also to macromolecule size measurement.
In static light scattering measurements, the light intensity scattered in solution
by a particle, which is small compared with the wavelength of the incident laser
beam, is proportional to the concentration multiplied by the molecular weight.
When the particles are very small compared with the wavelength of the light, the
intensity of the scattered light is uniform in all directions (Rayleigh scattering);
for larger particles (above approximately 250 nm diameter), the intensity is angle-
dependent (Mie scattering). If the concentration of the particles in solution is
known or is measured during the analysis process, the particle size averages and
distributions can be determined.
Dynamic light scattering provides a relatively fast and simple method for submi-
cron particle sizing [8]. When a beam of light passes through a colloidal disper-
sion, the particles or droplets scatter some of the light in all directions. Random
intensity uctuations in scattered laser light arising from the Brownian motion of
colloidal particles are analyzed to give either a simple mean size and polydispersity
index or complete distribution data, even for multimodal distributions.
Turbidimetry has been used traditionally in industry to obtain a measure of aver-
age particle size and even the entire PSD, and is a measure of the attenuation of a
beam of light passing through a suspended particle sample [8].
Acoustic attenuation spectroscopy measurements can be made without the need
for sample dilution and can be used in the particle size range of 10 nm to 100 mm.
As sound travels through a slurry or colloid, it is attenuated. The level of attenua-
tion is related to the particle size distribution as discussed in Refs. 20 and 21.
Acoustic attenuation measurements can be made on high-concentration and/or
opaque samples [8].
Packed column hydrodynamic chromatography (HDC), a technique for separat-
ing particles based on their size by eluting in the order largest to smallest, operates
on a principle similar to that of GPC/SEC [8]. The sample under investigation and
a small-molecule marker solution are introduced so that the euent ow is not
interrupted. HDC has a dynamic operating range from about 20 nm to 1.2 mm.
An ultraviolet (UV) detector response is used to calculate the concentration of
particles of dierent sizes present in the sample. The subsequent computation of
particle size distribution requires a calibration procedure employing a particle size
standard.
Capillary hydrodynamic fractionation (CHDF) is a hydrodynamic method for
measurement of nanometer-sized particles. In this method, slurry containing the
particles is forced through a capillary. Flow rate through the capillary is highest in
the center of the capillary due to the laminar ow velocity prole. Larger particles
extend into the high-ow region while smaller particles travel closer to the wall of
the capillary. Larger particles are swept through the capillary ahead of the smaller
particles, producing particle size fractionation. The particles are detected at the end
of the capillary by a UV detector. The measurable particle size range for CHDF is
about 15 nm to 2 mm.
For on-line control these techniques must be evaluated for speed, reliability, and
sample dead time [4]. As in the MWD techniques, manufacturers are moving
more toward on-line implementation of the more recent methods, but many of
these techniques still remain in the control laboratory.
12.3
Sensor Signal Processing
12.3.1
Sensors and Transmitters
Sensor signal processing involves operations such as amplication, compensation,
ltering, and normalization. As discussed (see Section 12.1), transmitters trans-
form the signals leaving the sensor into a standardized signal, and the sensor
plus the transmitter are considered to be the transducer or measurement instru-
ment [7]. Transmitters should be attached operationally as closely as possible
to the sensor location in order to minimize transmission error. To protect instru-
ments against outside eects from contamination, damage, and corrosion, they
should be placed in sturdy housings. A measurement amplier is connected to
the signal source of an electrical sensor and converts the signal coming from the
sensor into the standardized direct current signal.
The pneumatic or electrical signals depict only the analog measured variable.
The direct measured variable is not always the desired result, however. Thus, for
example, one obtains from ow measurements with diaphragms a dierential
pressure, not the mass ow, q
m
, which for compressible ow in an orice is given
by Eq. (32), where Dp = p
1
p
2
is the pressure drop between the taps upstream
and downstream respectively, r
1
is the upstream density, C
d
is an empirical dis-
charge coecient, A
2
is the area of the orice, Y is a dimensionless expansion
factor, and b = d
2
=d
1
is the ratio of the orice to the upstream pipe diameter (see
Section 12.2.5) [10].
q
m
=
C
d
YA
2
1 b
4
p
2r
1
Dp
p
(32)
As can be seen from Eq. (32), the mass ow is proportional to the product
r
1
Dp
p
.
As density and ow can be subject to variations during the process, the down-
stream pressure will change and so will the density, and the two measured values
are coupled together. Additionally, density is also a function of temperature so this
must also be measured and a correction added. A smart transducer provides func-
tions beyond those necessary for generating a correct representation of a sensed or
controlled quantity. A smart transducer can be used in this situation to correct the
ow for pressure and temperature.
12.3 Sensor Signal Processing 625
12.3.2
Converters
If one wants to use the analog signals for more complicated calculations or in
a process control system, one must digitize them and after processing transform
them back to analog signals, for example to drive the nal control elements or ac-
tuators. Converters are used for this purpose. Measurement converters transform
the analog signal into a digital one (A/D converter) or a digital signal into an ana-
log one (D/A converter). Any decimal number can be converted into the binary sys-
tem by summing the appropriate multiples of the dierent powers of 2. Equation
(33) demonstrates the conversion of binary into decimal numbers as well as that
of decimal into binary numbers; thus 10101101 (binary) is equivalent to 173
(decimal).
(1 2
7
) (0 2
6
) (1 2
5
) (0 2
4
) (1 2
3
) (1 2
2
)
(0 2
1
) (1 2
0
) = 173 (33)
The raw binary sensor data can be encoded according to several binary formats,
such as: pure binary, twos complement binary, signed binary, binary coded deci-
mal (BCD), ASCII, or Gray codes. In order to convert the digits of the decimal sys-
tem to binary digits, which are required for digital technology, one can directly
code these digits. Very frequently BCD is used. Every decimal digit is assigned to
the corresponding binary digit. In the original binary code the number 35 would
be shown as 100011, whereas in the BCD code it would be shown as 0011;0101.
It must be cautioned that during this conversion a quantization error results,
because of round-o errors in the decimal places; for example, 1.354 V (analog)
might become 1:35 = 0001;0011;0101 (BCD). Many process control applications
use A/D and D/A conversions of at least 12-bit unsigned binary representation to
obtain a resolution of 1 part in 2
12
= 0.024% [7].
12.3.3
Indicators
The numerous measurement signals of a process-engineering unit must be indi-
cated so that they can be used and also recorded in some fashion. They are there-
fore combined in a central control room; there they provide a current overview of
the state of the entire plant.
Indicators show the measured value in an analog or digital way. The analog rep-
resentation consists of a pointer before a calibrated scale, and recently also in LED
displays and analog representations on monitors. Digital outputs are indicated as
number displays or on counters. Apart from the measured value, indicator instru-
ment panels also contain alarm functionality (optical and/or acoustical), which in-
dicates if a critical measured value is exceeded in order to automatically shut down
the installation. Once the signal is processed it is sent to the controller, the output
of which, the controlled variable, is then sent to the actuator.
In the past these functions were performed by panel boards consisting of indica-
tors, alarms, strip-chart recorders, and single-loop controllers. Today, distributed
control systems (DCS) and data historians perform these functions (see Section
12.4.6).
12.3.4
Filtering Techniques
As mentioned above (see Section 12.1.2), during a measurement stochastic errors
can be introduced. The eects of process and measurement noise can be mini-
mized by signal conditioning or ltering [7]. Analog lters have been commonly
used for many years. A high-frequency noise (low-pass) lter can be represented
by Eq. (34), where x(t) is the lter input, y(t) is the lter output, and t
F
is the lter
time constant. This equation can be discretized to produce a digital lter with sam-
pling interval Dt [Eq. (35)].
t
F
dy(t)
dt
y(t) = x(t) (34)
t
F
y
n
y
n1
Dt
y
n
= x
n
(35)
When rearranged this gives the exponential smoothing lter in Eq. (36), where the
lter factor, 0 < a a1, is dened by Eq. (37).
y
n
= ax
n
(1 a)y
n1
(36)
a 1
1
1
t
F
Dt
(37)
This lter can be implemented in a digital computer. Other lters, such as a
moving-average lter, are also possible [7].
12.4
Regulatory Control Engineering
12.4.1
General
Measurement instruments supply information on the current operating conditions
of a plant. These form the basis to control the process and to keep conditions con-
stant so that the optimal-quality results are obtained. For this purpose one uses
controllers which determine automatically the sequence of control events. For ex-
ample, a process could be that of the tank shown in Figure 12.17. The tank has a
stream owing into it through a valve and a stream leaving it through a restriction.
A more comprehensive example of a polymer process as shown in Figure 12.33
will be discussed later (see Section 12.5).
In order to be able to keep process or measured variables constant, or to change
them systematically, they must rst be measured continuously and recorded. Flow
rates into and out of the tank (denoted by the ow transducer, or FT) and the level
(denoted by the level transducer, or LT) are measured variables. One therefore ob-
tains information about the instantaneous state of the desired measured variable to
be controlled, the controlled variable, and about its change with time. In the case of
the tank, this variable would be the level in the tank as measured by the level trans-
ducer. The controlled variable value must then be compared with the desired value,
called the set point. Any deviations from the set point, called the error, can
then be corrected through suitable actions. Devices that execute this comparison
and provide output signals, which can be used for the correction sent to the manip-
ulated variable, are called feedback controllers or regulators. In the case of the tank,
the manipulated variable could be the ow into the tank measured by the ow
transducer. If one wants to have a process follow certain time-varying conditions
(as is the case often with batch processes), then one can use controllers to send
the suitable programmed sequence signals. Often measured or unmeasured vari-
ables that aect the process and cause deviations from the set point are called dis-
turbance variables. In the case of the tank, this variable could be an uncontrolled
leak from the tank or a secondary ow into the tank.
LT
h
q
v1
FT
q
v0
FT
R
Fig. 12.17. Tank with liquid level height h, inlet valve with
volumetric ow q
v0
, and outlet volumetric ow q
v1
through
a restrictor with resistance R.
The signals leaving the controller are used to aect temperatures, pressures, and
ow rates by means of actuators. Actuators are usually valves whose ow area
changes with the signal coming from the controller. Metering machines, or posi-
tive displacement pumps, can also be used as actuators.
Measurement, comparison, and adjustment constitute an entity called a control
loop. Very schematically one may describe the control loop in terms of sensors,
controllers, actuators, and the process to be controlled. Shown in Figure 12.18 is a
level control system for a tank. Broken lines denote control signals. The controller
(denoted by LC) receives the level signal from the level transducer (LT) that sends a
signal to the current-to-pressure transducer (I/P) that then applies a pneumatic
pressure to the valve diaphragm.
Shown in Figure 12.19 is the control loop pictured as a block diagram. In the
control loop the controlled variable y is continuously measured and compared
with the set point y
sp
; it is desirable to have the deviation or error e = y
sp
y
made as small as possible. The controller then decides what control action to
make on the manipulated variable u. Disturbances in the process denoted by d
inuence the controlled variable y and are compensated for by the manipulated
variable u.
In contrast to the controlled system, the tank in Figure 12.17 is not under feed-
back control. It could be operated in a manual semi-batch mode, where the inlet
LT
LC
h
q
v1
FT
I/P
q
v0
FT
R
Fig. 12.18. Feedback level control on a tank.
valve is used to ll the tank to a certain level. The control consists of a sequence of
operating conditions, which must be carried out under a well-dened plan. It is
used around well-dened processes, for example to automate the loading step of a
batch emulsion.
By analogy with the control loop hierarchy, one can split the control chain into
the process to be controlled and the control system, as shown (for example) in Fig-
ure 12.18. In the given example, the process consists of the tank, which can be
lled, the control valve with the appropriate piping, the restrictor, the level and
ow transducers and perhaps a recorder; the control system covers the program-
mable controller, the signal transmission, and the I/P converter.
Expenditure for measurement, control, and actuator systems in the process in-
dustries is substantial. The proportional cost is higher the smaller the process is,
because the absolute expenditure depends only on the number of measurement
points and control loops, not on the size of the installation.
12.4.2
Process Dynamics
It is the task of the control system of a plant to drive the controlled variable (tem-
perature, pressure, ow, and so on) to the desired values, by either constant or
prescribed trajectories. In order to accomplish this, the controlled variable must
be continuously measured and the dynamics of the process must be known. In
control technology one distinguishes processes with self-regulation and without
self-regulation. In the rst case the output variable y assumes a new equilibrium
state after the input variable u is changed; an example is the ow through a pipe
after a change at the control valve. Another example is the tank mentioned above:
when the inlet ow is changed a new level is reached, as long as the outlet ow has
a restrictor whose ow depends on the height of liquid in the tank. One calls such
systems self-regulating, because the output reaches a new steady state when sub-
Controller Valve Tank
Level
Transducer
Controlled
Variable
y
Setpoint
y
sp
Manipulated
Variable
u
Error
e
+
-
Disturbance
Variable
d
Fig. 12.19. Block diagram of the tank level control loop.
jected to step-changes in the input. In the second case a change in the input does
not produce a new steady state. For instance, in a tank that is continuously fed and
drained by manipulation of an outlet valve, the level remains constant only if the
dierence between output ow and input ow is zero. One calls such systems
non-self-regulating, because the output does not reach a new steady state when
subjected to step-changes in the input.
12.4.2.1 First-order System
In many cases the relationships between plant inputs and outputs may be derived
in the form of a mathematical model, which can then be used to understand and
control the plant. For the tank example in Figure 12.17 the dynamic mass balance
becomes Eq. (38), where r is the liquid density, A is the cross-sectional area of the
tank, h is the height of liquid in the tank, and q
v0
; q
v1
are the inlet and outlet volu-
metric ow rates [7, 22]. If we assume constant density this becomes Eq. (39).
d
dt
(rAh) = rq
v0
rq
v1
(38)
A
dh
dt
= q
v0
q
v1
(39)
The ow restrictor may be modeled, to a rst approximation, as a linear relation-
ship between ow and height of liquid in the tank [Eq. (40), where R is the valve
resistance]. The material balance becomes Eq. (41).
q
v1
=
h
R
(40)
RA
dh
dt
= Rq
v0
h (41)
Since this is a self-regulating process, a steady state exists, governed by Eq. (42),
where the subscript s denotes the steady-state value. Subtracting Eq. (42) from Eq.
(41) yields Eq. (43).
0 = Rq
v0s
h
s
(42)
RA
dh
dt
= R(q
v0
q
v0s
) (h h
s
) (43)
Since we are mainly only interested in deviations from the steady state, in this case
we may dene deviation variables by Eqs. (43), where u is the manipulated ow de-
viation variable and y is the controlled level deviation variable.
u = q
v0
q
v0s
y = h h
s
(44)
In terms of the deviation variables, our mass balance becomes Eqs. (45). This is in
the form of a rst-order system [Eq. (46), where the time constant is given by Eq.
(47) and the process gain by Eq. (48).
RA
dy
dt
= Ru y (45)
t
dy
dt
= K
p
u y (46)
t = RA (47)
K
p
= R (48)
The dynamic behavior of a dynamic system can be well represented through the
so-called step response. The dynamic evolution of the output variable can be
monitored in response to a step-change of the input. We may ask how this system
responds to a step-change of magnitude M in the input ow rate. The rst-order
system becomes that described by Eqs. (49), where H(t) is the Heaviside step func-
tion dened by Eq. (50).
t
dy
dt
= K
p
MH(t) y
y(0) = 0
(49)
H(t) =
0 if t < 0
1 if t b0
&
(50)
The solution to this dierential equation, which may be found with the assistance
of Laplace transforms [7, 22] is Eq. (51).
y(t) = K
p
M(1 e
t=t
) (51)
This result is plotted in Figure 12.20 (denoted by one tank) for the case of M = 1
m
3
min
1
, K
p
= 1 min m
2
, t = 1 min. Note that the output is over-damped and
approaches a steady value after long times.
12.4.2.2 Second-order System
In a similar fashion one may analyze the system of two non-interacting tanks in
series, as shown in Figure 12.21.
The system mass balances are Eqs. (52), where the subscripts 1 and 2 denote
tanks 1 and 2 respectively [22].
A
1
dh
1
dt
= q
v0
q
v1
A
2
dh
2
dt
= q
v1
q
v2
(52)
The outlet restrictors may again be considered linear as a rst approximation [Eqs.
(53)].
q
v1
=
h
1
R
1
q
v2
=
h
2
R
2
(53)
The material balances become those given by Eqs. (54), and at steady state they are
given by Eqs. (55).
R
1
A
1
dh
1
dt
= R
1
q
v0
h
1
R
2
A
2
dh
2
dt
=
R
2
R
1

h
1
h
2
(54)
0
0.2
0.4
0.6
0.8
1
1.2
-1 0 1 2 3 4 5
t, min
y
,

m
0
0.2
0.4
0.6
0.8
1
1.2
u
,

m
3

m
i
n
-
1
u
1 tank (first order)
2 tanks (second order)
5 tanks
10 tanks
Infinite tanks
Fig. 12.20. Step responses of n = 1; 2; 5; 10, and an innite number of tanks in series.
0 = R
1
q
v0s
h
1s
0 =
R
2
R
1

h
1s
h
2s
(55)
Subtracting Eqs. (55) from (54) yields Eqs. (56).
R
1
A
1
dh
1
dt
= R
1
(q
v0
q
v0s
) (h
1
h
1s
)
R
2
A
2
dh
2
dt
=
R
2
R
1

(h
1
h
1s
) (h
2
h
2s
)
(56)
LT
h
1
q
v1
FT
q
v0
FT

LT
h
2
q
v2
FT
R
1
R
2
Fig. 12.21. Two tanks in series without feedback control.
Introducing deviation variables given by Eqs. (57), the mass balances become Eqs.
(58), which are in the form of two rst-order systems [Eqs. (59)] where the time
constants and process gains are given by Eqs. (60).
u
0
= q
v0
q
v0s
y
1
= h
1
h
1s
y
2
= h
2
h
2s
(57)
R
1
A
1
dy
1
dt
= R
1
u
0
y
1
R
2
A
2
dy
2
dt
=
R
2
R
1

y
1
y
2
(58)
t
1
dy
1
dt
= K
p1
u
0
y
1
t
2
dy
2
dt
= K
p2
y
1
y
2
(59)
t
1
= R
1
A
1
; K
p1
= R
1
t
2
= R
2
A
2
; K
p2
=
R
2
R
1
(60)
These mass balances [Eqs. (58)] may be combined into one equation in y
2
by dif-
ferentiating the second and then eliminating y
1
by successive substitutions [22] to
aord Eq. (61).
t
1
t
2
d
2
y
2
dt
2
(t
1
t
2
)
dy
2
dt
y
2
= K
p1
K
p2
u
0
(61)
This is the equation of a second-order system. Again we may ask how this system
responds to a step-change of magnitude M in the input ow rate. The second-order
system becomes that described by Eqs. (62).
t
1
t
2
d
2
y
2
dt
2
(t
1
t
2
)
dy
2
dt
y
2
= K
p1
K
p2
MH(t)
y
2
(0) = 0
(62)
The solution to this dierential equation, which again may be found with the assis-
tance of Laplace transforms, is Eq. (63) [22].
y
2
(t) = K
p1
K
p2
M 1
t
1
t
1
t
2
e
t=t1
t
2
t
2
t
1
e
t=t2

(63)
For the special case of equal time constants (t
1
= t
2
= t=2), the solution is Eq. (64).
y
2
(t) = K
p1
K
p2
M 1 e
2t=t
2t
t
te
2t=t

(64)
This result is plotted in Figure 12.20 (denoted by two tanks) for the case of M = 1
m
3
min
1
, K
p1
K
p2
= 1 min m
2
, t = 1 min. Note that the response of the two-tank
process is over-damped and slightly lagged compared with the single tank, produc-
ing an S-shaped curve.
12.4.2.3 High-order and Dead Time Systems
One may proceed in a similar fashion to obtain solutions for more and more tanks
in series with equal time constants, with the constraint that the total time con-
stant is equal to the sum of the identical individual time constants so that t
1
=
t
2
= = t
n
= t=n, creating systems of higher and higher order. These results
are plotted in Figure 12.20 for the cases with the numbers of tanks in series
n = 1; 2; 5; 10; y with M = 1 m
3
min
1
, K
p1
K
p2
. . . K
pn
= 1 min m
2
, t = 1 min.
As the number of tanks increases, the response approaches that of a pure delay or
dead time, y, equal to the total time constant of the innite tanks, y = t.
12.4.2.4 First-order Plus Dead Time System
Since dead time is a frequently occurring phenomenon, many systems can be rep-
resented by a combination of a rst-order system plus dead time (FOPDT) system.
In the time domain the FOPDT system equation is Eq. (65).
t
dy(t)
dt
= K
p
u(t y) y(t) (65)
For a step-change in input ow rate of magnitude M the system becomes Eqs. (66),
the solution to which is Eq. (67).
t
dy(t)
dt
= K
p
MH(t y) y(t)
y(0) = 0
(66)
y(t) = K
p
(1 e
(ty)=t
)MH(t y) (67)
This result is plotted in Figure 12.22 in original height h = y h
s
variable for the
case of the FOPDT tank with parameters M = 1 m
3
min
1
, K
p
= 10 min m
2
,
t = 20 min, y = 2 min, h
s
= 4 m and t
0
= 10 min is the initial time of the step-
change in ow rate.
If at time t
0
in a system the input variable q
v0
is increased by the amount Dq
v0
and the output variable instantaneously changes by Dh, then we are dealing with a
self-regulating system without time delay. If the output variable follows with de-
lays, then delay elements are present such as storage/accumulation or ow lags. If
the response of the output variable begins also after a certain time y, then there
exists a system with dead time.
Figure 12.22 suggests a method to determine these parameters from a step test
experiment [6, 7, 22]. The parameters can be geometrically obtained from Figure
12.22 and this forms the basis for model identication. At time t
0
the steady-state
input to the process is stepped by an amount Dq
v0
and the steady-state output
change Dh measured. Then the process gain is given by Eq. (68).
K
p
=
Dh
Dq
v0
(68)
The dead time y is the delay in the response after the input step at time t
0
. The
time constant t is the time after the output has risen 0.63Dh above its original
steady value h
s
after the input step at time t
0
.
Dead time is always to be expected if there are transport processes in the system.
A pure dead time is observed during the metering of compounds with a weigh belt,
0
2
4
6
8
10
12
14
16
0 20 40 60 80 100
t, min
h
,

m
0
2
4
6
8
10
12
14
16
q
v
0
,

m
3

m
i
n
-
1
h
0.63 h
q
v0
h
K
p
= h / q
v0
h
s
q
v0

Fig. 12.22. Step response of a rst-order plus dead time process.
because for every adjustment at the entrance slide, the new quantity is only ob-
served at the output after the residence time on the belt (Figure 12.7). Dead time
and time lags are to be expected in mixing control in a pipe, because in addition
to the transport time longitudinal mixing also plays a role. Higher-order lags are
often hard to distinguish from dead time, as shown in Section 12.4.2.3.
12.4.2.5 Integrating System
Suppose the situation of the tank in Figure 12.17 is that the euent ow restrictor
is replaced by a xed ow rate. This is a non-self-regulating or integrating process.
The mass balance is Eq. (69), as before [22].
A
dh
dt
= q
v0
q
v1
(69)
However, this time the euent ow is ow controlled by a valve or pump, not the
height of liquid in the tank. At steady state for a xed value of q
v1
Eq. (70) applies;
that is, at steady state, the inlet and outlet ows are exactly matched.
0 = q
v0s
q
v1
(70)
Subtracting Eq. (70) from Eq. (69) gives Eq. (71).
A
dh
dt
= q
v0
q
v0s
(71)
Introducing deviation variables [Eqs. (72)], the mass balance becomes Eq. (73),
where the process gain is given by Eq. (74).
u = q
v0
q
v0s
y = h h
s
(72)
dy
dt
= K
p
u (73)
K
p
=
1
A
(74)
For a step-change in input ow rate of magnitude M the system becomes that de-
scribed by Eqs. (75), the solution to which is Eq. (76), which is a ramp function
with slope K
p
.
dy
dt
= K
p
MH(t)
y(0) = 0
(75)
y(t) = K
p
Mt (76)
Thus the tank will overow or run dry if the inlet and outlet ows are not exactly
matched.
12.4.2.6 Integrator plus Dead Time System
With dynamic systems that are non-self-regulating one nds, likewise, step re-
sponses with and without dead time. An integrator plus dead time process would
be modeled like Eq. (77).
dy(t)
dt
= K
p
u(t y) (77)
For a step-change in input ow rate of magnitude M the system becomes as in
Eqs. (78), the solution to which is Eq. (79).
dy(t)
dt
= K
p
MH(t y)
y(0) = 0
(78)
y(t) = K
p
M(t y)H(t y) (79)
This result is plotted in Figure 12.23 in original height variable h = y h
s
with pa-
rameters M = 1 m
3
min
1
, K
p
= 2 m
2
, y = 2 min, h
s
= 4 m and t
0
= 10 min.
The parameters for this process may be obtained from a step test. At time t
0
the
steady-state input to the process is stepped by an amount Dq
v0
and the gain K
p
is
found from the measured slope [Eq. (80)].
Slope =
Dh
Dt
= K
p
Dq
v0
(80)
The dead time y is the delay in the response after the input step at time t
0
.
12.4.3
Controllers
Controllers are devices that are meant to keep a specic controlled variable con-
stant despite outside disturbances. One dierentiates between continuous, digital,
and OnO controllers, depending on whether the output is continuous, discrete,
or ono. The great majority of controllers have been continuous, but the digital
controller is now commonplace due to the widespread use of computers and dis-
tributed control systems.
Referring again to Figure 12.19, the controller compares the measured value of
the controlled variable with the desired value, the set point, computes the manipu-
lated variable, and inuences the actuator so that the set point and the controlled
variable can be as close to each other as possible. Independently of design and ap-
plication, one nds three basic functions, which can be simply represented mathe-
matically: namely the proportional, integral, and derivative functions.
12.4.3.1 Proportional Control
The proportional controller (P controller) assigns to each value of the deviation a
specic value of the manipulated variable. For our tank example, the P controller
mode takes the form of Eq. (81), where q
v0
; q
vs
are the new output and the steady-
state values of the ow rate respectively, K
c
is the controller gain, and h
sp
; h are the
current level input height set point and measured value respectively.
q
v0
(t) = q
vs
K
c
[h
sp
h(t)[ (81)
The steady-state value of the ow rate q
vs
, or bias, is the ow rate when the devia-
tion from the set point is zero. The sign on the gain term, or controller action, is
adjusted to be either positive or negative to create negative feedback control in
which the controlled variable approaches a stable steady state. We may write this
controller in terms of deviation variables, according to Eqs. (82), where e is called
the error and u is the controller output, to obtain the deviation form [Eq. (83)].
0
5
10
15
20
25
0 5 10 15 20
t, min
h
,

m
0
5
10
15
20
25
q
v
0
,

m
3

m
i
n
-
1
h
t
q
v0
h
K
p
q
v0
= h / t
h
s
q
v0
Fig. 12.23. Step response of an integrator plus dead time process.

e = h
sp
h(t)
u(t) = q
v0
(t) q
vs
(82)
u(t) = K
c
e(t) (83)
Pure proportional controllers have the disadvantage that in order to change the
actuator, the controller needs a certain deviation; therefore this deviation can never
be entirely eliminated and is termed oset.
As given here the controller gain has units of ow/height or m
2
min
1
. In com-
mercial controllers the manipulated and controlled variables are often made di-
mensionless with the range and standard signal of the transmitter and actuator so
that the units of the gain would be, for example, %/% or mA/mA. Also, in older
controllers the term proportional band (PB) is used instead of controller gain
and is dened by Eq. (84).
PB =
100%
K
c
(84)
12.4.3.2 Integral Control
The integral controller (I controller) assigns the integral over time of the error to a
specic change in the output variable. In the case of large errors over time, the
action is large; in the case of small errors over time, the action is small.
The I controller obeys Eq. (85), where t
I
is the reset time, in deviation variables.
u(t) =
1
t
I
t
0
e(t) dt (85)
The output changes until the error has disappeared. Pure integral-only controllers
have the disadvantage that they are sluggish for large t
I
and that they may be
prone to oscillation for small t
I
.
A disadvantage of integral control is reset windup. This results from the situa-
tion where, if the controller output saturates and the error remains large for an ex-
tended period of time, the integral gets large and does not recover immediately
even if the error then goes to zero or reverses sign. The integral has to be manually
reset in this situation in actual implementation.
12.4.3.3 Derivative Control
Derivative controllers (D controllers) are practical only in combination with other
controller modes. They provide a fast engagement at the beginning of the control
action. Here the derivative controller output is proportional to the rate of change of
the error [Eq. (86), where t
D
is the derivative time].
u(t) = t
D
de(t)
dt
(86)
The derivative mode of a D controller causes theoretically a large change in output
of extremely short duration for a step-change in error. In practice, the eect of a
derivative controller is to cause a short increase in the output variable, which then
returns to the previous value.
12.4.3.4 PI, PD, and PID Control
These basic controllers are used in combinations; P, PI, PID, and also PD control-
lers are common. The appropriate equations are linear combinations of the se-
lected components. The PI controller obeys the relationship of Eq. (87). It reacts
to a deviation with fast correcting action, and corrects the rest of the deviation
slowly. It kicks in immediately and operates very accurately in the long term.
u(t) = K
c
e
1
t
I
t
0
e(t) dt

(87)
The PD controller obeys Eq. (88). It kicks in rst very strongly; the output then re-
verts back to a value that corresponds to the output of a P controller.
u(t) = K
c
e t
D
de(t)
dt

(88)
If one combines all three controller actions, then a PID controller results. It obeys
Eq. (89). This is the universal type of controller, which acts fast and avoids lasting
oset.
u(t) = K
c
e
1
t
I
t
0
e(t) dt t
D
de(t)
dt

(89)
The PID form implemented usually includes a derivative mode lter such as a
rst-order lter to eliminate noise, which would be written in the time domain as
Eqs. (90), where e
F
(t) is the ltered error and 0:05 < a < 0:2 is the dimensionless
lter constant [7].
at
D
de
F
(t)
dt
= e
F
(t) e(t)
u(t) = K
c
e
1
t
I
t
0
e(t) dt t
D
de
F
(t)
dt

(90)
The PID controller may also use the rate of change of the measured variable (for
example, h(t)) instead of the error e(t) to eliminate set point change derivative kick.
Derivative kick is mitigated if a derivative mode lter is used.
12.4.3.5 Digital Controllers
Modern implementations of controllers are not analog but digital due to the wide-
spread use of computers and digital control systems. Digital control algorithms can
be derived from the continuous versions using standard numerical approximations
of the analog controllers. Digital signals are discrete in nature and arise from sam-
pling continuous measurements at equal time intervals of width Dt, or they may
arise from naturally discrete signals such as, for example, from analyzers.
We may illustrate the nature of digital PID algorithms by starting with the ideal
PID controller [7, 22, 23] according to Eq. (91), where q
v
(t); q
vs
are the new output
and the steady-state bias values of the ow rate respectively, and e(t) = h
sp
h(t) is
the current error in the level height set point and measured value.
q
v
(t) = q
vs
K
c
e(t)
1
t
I
t
0
e(t) dt t
D
de(t)
dt

(91)
A simple digital form of this equation may be written for the nth time interval
using the rectangular rule of integration approximation to the integral and a rst-
order backward nite dierence approximation of the derivative to yield the posi-
tional form, Eq. (92), where e
n
; q
v; n
are the error and controller output respectively
at the nth sampling instant, and Dt is the sampling period.
q
v; n
= q
vs
K
c
e
n

1
t
I
X
n
i=1
e
i
Dt t
D
e
n
e
n1
Dt

" #
(92)
We may write this equation for the (n 1)st sampling instant [Eq. (93)].
q
v; n1
= q
vs
K
c
e
n1

1
t
I
X
n1
i=1
e
i
Dt t
D
e
n1
e
n2
Dt

" #
(93)
If we subtract this Eq. (93) from Eq. (92), we obtain the velocity form [Eq. (94)],
since it calculates the change in output.
q
v; n
q
v; n1
= K
c
(e
n
e
n1
)
1
t
I
e
n
Dt t
D
e
n
2e
n1
e
n2
Dt
!
(94)
Solving for the output at the nth instant, we have a form [Eq. (95)] that calculates
the output directly.
q
v; n
= q
v; n1
K
c
(e
n
e
n1
)
1
t
I
e
n
Dt t
D
e
n
2e
n1
e
n2
Dt
!
(95)
One major advantage of the velocity form Eq. (95) over the positional form Eq. (92)
is that, as the summation is lacking, it has inherent anti-reset windup. Also, an ini-
tial value of the output bias is not required [7].
If the sampling period is small compared with the process time constant
(Dt ft) these integral and derivative approximations are accurate and the conven-
tional tuning techniques used for continuous controllers discussed in Section
12.4.3.6 may also be used for digital controllers [7].
12.4.3.6 Controller Tuning
Controller parameters are tuned to provide both performance and stability and
there are many dierent rules for the tuning parameters of a control loop [6, 7,
22]. After deciding on the controller structure, one decides on the desired closed-
loop response criteria. Then one must distinguish between processes where there
is at least an approximate model with known parameters and the case when the
process model is unknown.
Process model is known An approximate model of the process may be obtained by
the step response test noted earlier (see Section 12.4.2.4) (or from rst principles).
When an approximate model of the process is known we may obtain the tuning
parameters directly. We use here the example of the rst-order plus dead time pro-
cess, since its dynamics are so representative of the polymer equipment dynamics.
Here we have chosen for the tuning criteria to minimize the integral of the time-
weighted absolute error (ITAE) [Eq. (96)] [7].
ITAE =
y
0
t[e(t)[ dt (96)
Tab. 12.1. Minimum ITAE model controller tuning rules based on a FOPDT process [22].
[a]
Controller type Type of response K
c
t
I
t
D
P disturbance
0:49
K
p
t
y

1:084

PI set point
0:586
K
p
t
y

0:916
t
1:03 0:165
y
t
!
PI disturbance
0:859
K
p
t
y

0:977
t
0:674
y
t

0:680
PID set point

0:965
K
p
t
y

0:855
t
0:796 0:147
y
t
! 0.308t
y
t

0:929
PID disturbance
1:357
K
p
t
y

0:947
t
0:842
y
t

0:738
0:381t
y
t

0:995
[a]
Tunings should only be applied in the range 0:1 < y=t < 1:0.
B. A. Ogunnaike, W. H. Ray, Process Dynamics, Modeling, and Control,
Copyright (1994 Oxford University Press. This material is used by
permission of Oxford University Press.
The minimum ITAE tuning rules based on a FOPDT process are given in Table
12.1 [22]. Note that the tunings in Table 12.1 should only be applied in the range
0:1 <
y
t
< 1:0.
Figure 12.24 shows the dynamic response of P, PI, and PID controller types to a
step-change in the input of the rst-order plus dead time (FOPDT) process of Fig-
ure 12.22 with parameters K
p
= 10 min m
2
, t = 20 min, y = 2 min. For the
FOPDT example the tuning for the P controller is K
c
= 0:595 min m
2
, for the PI
controller it is K
c
= 10 min m
2
, t
I
= 19:7 min, and for the PID controller it is
K
p
= 0:691 min m
2
, t
I
= 25:6 min, t
D
= 0:725 min. The derivative mode lter
was used for the PID controller with a lter constant of a = 0:1. The control loop
was simulated numerically for Figure 12.24. It can be seen that the P controller
produces a long-term oset, which the PI controller eliminates, but with some
overshoot of the set point. The addition of the derivative action for the PID control-
ler eliminates the overshoot and produces the best controller performance.
Process model is unknown If the process model is unknown, the continuous cy-
cling method may be used [7]. The rules of Ziegler and Nichols [24] have proven
0
0.2
0.4
0.6
0.8
1
1.2
0 5 10 15 20 25
t, min
y
,

m
y
sp
P
PI
PID
Offset
Fig. 12.24. Responses for step-change in set point with ITAE
tuned P, PI, and PID controllers on a rst-order plus dead time
process.
themselves useful in practice. For this test the controller is rst brought into auto-
matic as a pure P controller with small gain, the reset time t
I
is set to the largest
value, and the derivative time t
D
is set to the lowest value. Then the gain K
c
is
slowly increased. When the controlled variable has an oscillatory response, the ulti-
mate gain K
cu
has been reached and the oscillation has the ultimate period P
u
. The
rules of Ziegler and Nichols then give the controller settings in Table 12.2. From
these starting values one can then nd the optimal tunings very quickly by small
systematic modications.
Figure 12.25 shows responses for a step-change in set point with P and PID con-
trollers on the rst-order plus dead time process with parameters. The ultimate
gain for the P-only controller, found by trial and error, is K
cu
= 1:68 m
2
min
1
,
and the ultimate period from Figure 12.25 is found to be P
u
= 7:4 min. The PID
controller is tuned with ZieglerNichols parameters from Table 12.2 of K
c
= 1:008
m
2
min
1
, t
I
= 3:7 min, t
D
= 0:925 min. Note that the PID response in Figure
12.25 has a much greater overshoot and much longer settling time than the ITAE
response given in Figure 12.24. Other alternative tuning rules have been developed
since the ZieglerNichols rules [7].
12.4.3.7 OnO Controllers
OnO controllers output the manipulated variable in discrete values (on/o, in/
out) at discrete time intervals. The ideal OnO controller is given by Eqs. (97),
where u
max
and u
min
are the on and o values of the output and e(t) is the error
[7].
u(t) =
u
max
if e(t) b0
u
min
if e(t) < 0
&
(97)
Figure 12.26 illustrates an OnO controller applied to the FOPDT process with
parameters K
p
= 10 min m
2
, t = 20 min, y = 2 min. Controller outputs O and
On are u
min
= 0 m
3
min
1
and u
max
= 0:2 m
3
min
1
respectively. Although the
controller is very simple and there are no tuning parameters other than the on
and o values, it can be seen that continuous cycling results, which may or may
not be desirable.
Tab. 12.2. ZeiglerNichols controller tuning parameters based on the continuous cycling
method [7, 22, 24].
Controller type K
c
t
I
t
D
P 0.5K
cu

PI 0.45K
cu
P
u
1:2

PID 0.6K
cu
P
u
2
P
u
8
A modication of the ideal OnO controller is the two-point controller, which
switches the output when an upper or lower limit value is exceeded, the dierence
between these two points being the deadband [6]. Limit signal transducers can be
used as two-point controllers (such as contact thermometers).
The benets of the two-point controller as compared with the continuous con-
troller are that it is simple, durable, reliable, and cheap, requires no auxiliary
power, and does not lead to instability in the control loop. The disadvantages are
the wear on the actuator working parts, the cyclical oset, and the fact that large
power circuits must be switched. Two-point controllers are therefore hardly ever
used in an industrial environment.
12.4.3.8 Self-operated Regulators
Controllers which acquire sucient force from the measurement to move the actu-
ator do not require auxiliary power. Such controllers have a simple and durable
construction, and many combine measuring instrument, controller, and actuator
-0.5
0
0.5
1
1.5
2
0 5 10 15 20 25
t, min
y
,

m
y
sp
P control
K
c
= K
cu
PID control
y
sp
P
u
Fig. 12.25. Responses for a step-change in set point with P
and PID controllers on a rst-order plus dead time process.
The gain for the P controller is the ultimate gain K
cu
and cycles
at the ultimate period P
u
. The PID controller is tuned with
ZieglerNichols tunings.
functions. They have the advantage that they keep functioning if the auxiliary
power fails. Therefore simple pressure control valves of this type are suitable as
safety valves, in which a spring holds the plug of a valve in the seat, until an adjust-
able overpressure overcomes the force of the spring (Figure 12.27).
Here the exit pressure aects a diaphragm and holds a valve in an equilibrium
position against the force of a spring. If the pressure rises, this closes the cross-
section of the plug against the seat, and if the pressure lowers it opens again. This
is also the method of operation of the pressure controllers in pneumatic transmis-
sion lines. Supply pressure-reducing valves are controllers without auxiliary power.
Simple ow controllers use the dierential pressure at an adjustable restrictor:
the plus and minus sides are on the two sides of a spring-supported diaphragm.
These controllers are used as backow (check) valves or as isolation valves, which
shut o if the ow is reversed or too high. Level controllers with oats are in con-
densate separators often coupled with simple temperature controllers as in Figure
12.28. These devices contain an electrical jump switch and operate therefore as
two-point OnO controllers. Controllers without auxiliary energy are used, where
it is not essential to have high control accuracy and when one must do without the
auxiliary power for safety reasons.
0
0.2
0.4
0.6
0.8
1
1.2
0 10 20 30 40 50
t, min
y
,

m
0
0.2
0.4
0.6
0.8
1
1.2
u
,

m
3

m
i
n
-
1
y
sp
y
u
Fig. 12.26. Responses for step-change in set point with an
OnO controller on a rst order plus dead time process.
Single-loop controllers with auxiliary power use compressed air or, more com-
monly now, electrical power to receive and transmit signals. These devices are
much more accurate than those without the auxiliary power; also they are not inte-
grated in the measurement apparatus or the actuator. Distributed control systems
are rapidly replacing the single-loop controller panel boards unless only a small
number of control loops are involved.
inlet pressure
spring
(reference)
diaphragm
exit pressure
(controlled variable)
intake valve
(control member)
Fig. 12.27. Pressure controller with no auxiliary power [1].
Setpoint adjuster
lever
jump
switch
feeler
(staff of stretch-
thermometer)
Fig. 12.28. Electrical discrete temperature controller [1].
12.4.4
Valve Position Controllers
The output signal of a controller is sent electrically or pneumatically to a valve po-
sitioner that modulates the supply pressure to the control valve actuator and must
make the stem position proportional to the input signal from the controller despite
loads on the valve [6, 25]. There the electrical signal must be converted to a pneu-
matic positioning pressure or the pneumatic signal must be brought to a higher
pressure in order to move the stem of the actuator reliably and to adjust the posi-
tion of the valve accurately.
In the pneumatic position controller, which is attached directly to the valve actu-
ator, the pneumatic adjusting signal output from the controller works on a mem-
brane and summing beam [6]. If the pressure signal rises, then a connection to the
plant compressed-air network is opened to a pneumatic spool valve then to the
actuator that moves the valve stem downward until a compensating spring on
the summing beam holds the signal line pressure in equilibrium. Then the valve
stem lifts until a new equilibrium position that is sensed by a cam lever is
achieved. Thus a complete feedback loop exists where in this case the actuator is
the process, the stem position is the controlled variable, the input signal is the set
point, and the pneumatic amplier network is the controller.
Electro-pneumatic valve positioners are used with diaphragm-actuated, sliding-
stem control valves. The electro-pneumatic valve positioner receives an electronic
input signal from a control device and modulates the supply pressure to the con-
trol valve actuator, providing an accurate valve stem position [25].
12.4.5
Single-loop Controllers
Single-loop controllers, which used to be more prevalent, are still used in some ap-
plications, such as laboratory or pilot plant. They are a rectangular package that has
a faceplate for displaying the set point of a controller, to compare the set point with
the actual value, and to enable the switch from manual control to automatic control
or to cascade control. Single-loop controllers can be combined in a compact unit,
which is built directly into a panel board. The faceplates of pneumatic and electri-
cal control devices are very similar to each other. The transition to process control
systems with newer display technologies is resulting in the disappearance of
single-loop controllers.
12.4.6
Digital Control Systems
Since the 1970s the hardware used in the implementation of process controls has
evolved from pneumatic analog technology to electronic analog technology to
microprocessor-based controls. Although pneumatic and electronic analog process
controls may still be in service in older facilities, almost all of the newer plants now
utilize microprocessor technology in implementing process control. Because of
rapid advances in computer technology and the increasing computation power
available on a single microprocessor, the hardware is becoming more powerful in
terms of available functionality. Excellent descriptions of control system hardware
is available in Refs. 4, 6, and 7 as well as in the technical literature provided by the
major vendors such as Honeywell, ABBBailey, Fisher Controls, and Siemens and
also in the specialized trade shows, publications, and books sponsored by the In-
strument Society of America. From the perspective of polymer reaction engineer-
ing, there are four types of digital control hardware, which are listed in order of
increasing functionality, complexity, and cost:
1. Single-loop controllers are a stand-alone microprocessor-based version of the older
analog single-loop controller (see Section 12.4.5). They can operate independ-
ently or be part of a distributed control system and can execute the standard
PID algorithm but also increasingly cascade control and gain scheduling.
2. Programmable logic controllers (PLCs) were the rst digital technology to success-
fully compete with conventional technology in industrial control applications.
They were originally developed to replace hard-wired relay logic. PLCs are ex-
tremely important in batch control applications, because they are ideally suited
to program large and complex batch sequencing cycles using ladder diagrams
and a higher-level programming language. Because of their logic handling capa-
bility PLCs can also be used to implement process interlocks, which are de-
signed to prevent process conditions that would unduly stress equipment (per-
haps resulting in minor damage) or lead to o-specication product.
3. Personal computer (PC) controllers are appropriate for the control of a laboratory
or small- to medium-size pilot plant installations. The typical PC is augmented
by the appropriate input/output (I/O) interface software. Software tools are
available for the implementation of the previously discussed PID controllers us-
ing the PC. Advanced control algorithms can also be executed at the PC level.
The PC also provides graphic capability for the monitoring of the performance
of the control loop and can also provide data historian capability, which can be
very important for polymer process development.
4. The distributed control system, the process control architecture referred to as a
DCS, was introduced in the mid-1970s and has since become the standard for
large installations. The main concept behind the DCS is that microprocessor-
based nodes are interconnected by a digital communications network often re-
ferred to as the data highway. A typical DCS installation handles seamlessly
process I/O from the eld, including interfaces with process analyzers (that is,
gas chromatographs), which are important in advanced control applications.
The DCS can be interfaced with PLCs, with operator stations for process moni-
toring and control including alarm management, with engineering workstations
for the system conguration activities, and also with a set of host computers
which can provide product quality information, data compression, reporting,
and archival capabilities, as well as advanced control calculations.
12.4.7
Actuators
Actuators govern the ow of energy and mass streams in the process [25]. Through
the actuators the controller output results in changes to the controlled variable
(temperature, pressure, ow, level, and so on) and thus the control loop is closed.
Actuators consist of the control positioner (for example, a valve positioner) and the
actuator element. The control positioner transfers the signal output of the control-
ler in a controlled movement to bring the actuator element into a new position.
Examples of actuators are rheostats to set and control electrical current, valves,
aps, and metering pumps for liquids. The actuator, which is most frequently en-
countered in chemical process engineering, is the diaphragm valve (Figure 12.29).
The input actuating pressure lies on one side of a diaphragm and exercises a
force on it; the spring works against this force. The actuating pressure shifts the
position of the diaphragm so as to create equilibrium of forces with the spring.
The diaphragm is connected with the valve stem; the stem (and the plug) therefore
make a stroke proportional to the actuating pressure. Between the plug and the
valve seat a variable annular gap opens or closes, thus resulting in variable ow.
The seat and the plug are in a housing, which is solidly anchored and also holds
the stem. For high-temperature service the housing is cooled with ns in order to
protect the bushing packing. With dangerous material one uses valves with sealed
bellows and therefore no bushing is needed. Additional equipment, for example
position controllers or limit switches, can be attached to the valve as necessary.
In the pressure-free state the valve stem goes naturally to a terminal position. In
Figure 12.30(a), as the pneumatic controller output signal increases, increased
pressure on the diaphragm compresses the spring, thus pushing the stem in and
closing the valve further. Such a valve is termed air-to-close (AC). By reversing
either the plug/seat or the spring/air inlet orientation, the valve becomes air-to-
open (AO) as in Figure 12.30(b). Normally the choice of AC or AO valve is
based on safety considerations. One chooses the way the valve should operate (full
ow or no ow) safely in case of a transmitter failure.
Standard diaphragm valves have a diaphragm area from 200 to 1000 cm
2
and a
stroke of 1530 mm [1]. Very large valves are equipped with diaphragms of up to
3000 cm
2
and have a 100 mm stroke. These large valves have large power require-
ments and operate with 3 bar pressure. In addition a valve positioner is needed. To
achieve higher strokes, specialized cylinders are used.
The valve stem, plug, and seat (called the trim) have dierent forms: ball, plug,
disk, or gate valves [7, 25]. Plugs are normally fabricated as rotationally symmetric
parabolic cones. There are numerous other plug shapes, which can be selected for
each individual case. The ow rate as a function of stem position, or lift, l, is called
the valve characteristic, f (l). A valve characteristic may be linear, quick opening,
or equal percentage. The plug shape, seat, and cage primarily determine the valve
characteristic, the sensitivity to contamination, and utter avoidance.
To size a valve for liquids we may return to a modied form [Eq. (98)] of the
equation given for restrictors [7, 12, 25].
q
v
= C
V
f (l)
Dp
d
r
(98)
Here q
v
is the volumetric ow rate, C
V
is the valve coecient, Dp = p
1
p
2
is the
pressure drop across the valve, and d is the relative liquid density (specic gravity)
[Eq. (99), where r is the uid density at operating temperature and r
w0
is the water
density at a standard temperature and pressure (usually 4
C and 1 bar)].
d =
r
r
w0
(99)
The valve characteristic 0 a f (l) a1 is given by Eq. (100), where 0 al a1 is the
lift and 20 aRa50 is a valve design parameter [7].
Diaphragm
with disk
St
Pl
Di
Actuator
springs
Control
air
Di
Yoke
uffing
box
ug
Seat
rection
of flow
Valve
body
Valve
stem
aphragm
casing
Fig. 12.29. Diaphragm valve [1].
f (l) =
l; for a linear valve
; for a quick opening valve

R
l1
; for an equal percentage valve
8
>
<
>
:
(100)
In USCS units the valve coecient, C
V
, is the full open ow rate in gal min
1
of
water at 60
F (15.6
C) that will ow through the valve with a 1 psi (6.89 kPa) pres-
sure drop. In SI units the valve coecient (called K
V
) is the full open ow rate in
m
3
h
1
of water at 20
C that will ow through the valve with a 1 bar pressure drop.

International control valve standards are listed in Ref. 25.
For gases the pressure ratio p
2
=p
1
at the valve must not be less than about 0.53;
otherwise sonic velocity, c, is achieved in the restriction [10]. At the sonic velocity
the throughput cannot be increased as the valve cross-section continues to open
[10]. The pressure inside the valve must be lower than the liquid vapor pressure;
otherwise ashing or cavitation occurs.
Besides diaphragm valves, one frequently uses buttery valves (particularly for
gases in lines with large diameter), which are constructed with a stop (Figure
12.31) or without (Figure 12.32). Buttery valves without a stop (so-called regulat-
ing aps; see Figure 12.32) do not seal completely; their leakage ow is within 5
10% of the expected value when the valve is fully open.
Diaphragm
chamber
Spring
Seat (a) Air-to-close valve
Plug
Valve stem
(b) Air-to-open valve
Control air
Diaphragm
chamber
Control
air
Fig. 12.30. Diaphragm valves with dierent rest states: (a) air-to-close; (b) air-to-open [1].
Fig. 12.31. Buttery valve with a stop [1].
Fig. 12.32. Buttery valve without a stop [1].
With large nominal sizes and higher pressure, gate valves are used. It is advan-
tageous that they have only a low-pressure drop and are insensitive against con-
tamination. Gate valves have one large stroke; one cannot equip them with a dia-
phragm control drive, but the stem moves with gear racks, piston drive units, or
electric motors.
12.5
Advanced Control Engineering
The polymerization reactor is usually at the heart of the manufacturing process,
impacting both downstream processing and nal customer-related polymer proper-
ties. The following factors have contributed to the industrial signicance of poly-
mer reactor control:
v
the need to improve xed-asset productivity by optimizing reactor yield and
uptime;
v
the trend toward shorter manufacturing campaigns for the dierent polymer
grades manufactured in the same reactor, or toward more frequent on-line prod-
uct transitions to reduce product inventories and hence working capital;
v
global competition, which imposes tough requirements for polymer grade uni-
formity;
v
safety and environmental considerations regarding the stable operation of a po-
tentially thermally unstable reaction.
The measurement and control techniques discussed in the previous sections,
many of which are generic in nature, are not always adequate to meet the following
practical considerations specic to a polymerization reactor, which pose additional
challenges to the successful application of a control strategy:
v
Polymerization reactors are well known both theoretically and experimentally
to exhibit multiple steady states [26, 27] and in some cases they may also exhibit
oscillations in terms of monomer conversion and polymer particle diameter [28].
In other cases it may be necessary to choose an open-loop unstable state as the
reactor operating point. Furthermore, polymerization reactors can be highly exo-
thermic and result in reactor thermal runaway.
v
On-line measurements of polymer architecture such as composition, molecular
weight, and degree of branching which were discussed in Sections 12.2.8 and
12.2.10, are not always available and for some polymer systems may be simply
unavailable. In many cases the control engineer may have to rely on polymer
properties inferred from infrequent laboratory analysis of reactor samples or
from laboratory analysis of the nal polymer after it has experienced signicant
post-reactor processing, thus introducing large dead times in the control loop.
v
The relationship between reactor operating conditions, such as monomer conver-
sion, temperature, residence time, polymer composition, and viscosity, and the
customer-related nal properties, such as tensile strength, elongation at break,
and processability in an injection molding machine, may not always be well de-
ned. Variability in the polymer isolation process and long-term polymer struc-
ture changes such as aging may result in the fact that, although in some cases
the reactor may be operating on-aim within well-dened manufacturing speci-
cations, the nal polymer may not process satisfactorily when delivered to the
customer.
v
The control system for a polymerization reactor must be suciently robust
to handle unmeasured disturbances, which impact polymer reactor operation.
These disturbances typically result either from trace amounts of polymerization
inhibitors left over after monomer purication before the polymerization reac-
tion or from trace amounts of other compounds which may be present in a typi-
cal polymerization recipe and which may be aecting the reaction.
v
A polymerization reactor often produces several grades (in terms of composition
and viscosity) of the same polymer and therefore the control strategy must be
easily adapted to a multi-product plant and in some cases to on-line grade transi-
tions. In the case of a multi-product plant it may be necessary to operate the
reactor in terms of rather short campaigns in order to minimize the nished-
product inventory and thus the working capital. In these cases the reactor control
system must be designed in such a way as to achieve fast startups while mini-
mizing o-specication polymer formation.
The purpose of this section is to highlight several control engineering techniques,
some of which are known in the literature as advanced control, which can be
deployed to meet some of the challenging aspects of polymer reactor control.
These techniques have been extensively discussed in literature reviews such as
Refs. 2932 and in books [18, 19].
The discussion will be facilitated by focusing on the polymerization process
shown in Figure 12.33 [33]. Although the process is generic, the owsheet cap-
tures many of the elements of actual free-radical polymerization reactor installa-
tions. Monomers A and B are continuously added with initiator, solvent, and chain-
transfer agent. In addition, an inhibitor may enter with the fresh feeds as an
impurity. These feed streams are combined (stream 1) with the recycle stream
(stream 2) and ow to the reactor (stream 3), which is assumed to be a jacketed
well-mixed tank. A coolant ows through the jacket to remove the heat of polymer-
ization. Polymer, solvent, unreacted monomers, initiator, and chain-transfer agent
ow out of the reactor to the separator (stream 4), where polymer, residual initiator,
and chain-transfer agent are removed. Unreacted monomers and solvent (stream
7) then continue on to a purge point (stream 8), which represents venting and
other losses and is required to prevent accumulation of inerts in the system. After
the purge, the monomers and solvent (stream 9) are stored in the recycle hold
tank, which acts as a surge capacity to smooth out variations in the recycle ow
and composition. The euent (stream 2) recycle is then added to the fresh feeds.
It has been found that the hierarchical approach summarized in Figure 12.34 is
very useful in the successful application of process control in a complex industrial
environment. Process knowledge, which is usually captured in an experimentally
validated mathematical model, is the cornerstone of a successful control strategy.
This is particularly true for polymerization reactors, where the in-depth knowledge
of process operation in terms of the eect of operating variables on polymer prop-
erties can be used to great advantage in the design of the control system and can
result in a much more straightforward (and therefore easy to maintain) strategy
than would have been possible otherwise (see, for example, the control strategy
discussed in Ref. 30). Process knowledge together with the appropriate sensors,
transmitters, and analyzers are the prerequisites for the design of the basic control
system to regulate pressure, temperature, level, and ow (PTLF). Only when the
elements of the regulatory control system are in place and are properly designed
and maintained can the control engineer attempt, in increasing order of com-
plexity, the implementation of more advanced regulatory control strategies, multi-
variable model-based control algorithms, and on-line scheduling and optimization
strategies to compute set points for the regulatory controls. In many instances ad-
vanced control applications have failed in an industrial environment not because
Reactor
Hold Tank
Separator
4
6
Polymer, Initiator, Transfer Agent
1
2
3
Coolant Coolant
9 8
Purge Valve
7
Monomer
(A)
Monomer
(B)
Initiator
(I)
Solvent
(S)
Transfer
Agent
(T)
Inhibitor
(Z)
Fig. 12.33. Copolymerization with recycle loop [33].
the algorithms were necessarily faulty but because the basic regulatory control sys-
tem performed poorly, either because of inadequate design or because one of the
critical measurements (that is, a process analyzer) was poorly maintained.
12.5.1
Feedforward Control
The traditional PID feedback controller, which was discussed previously (see Sec-
tion 12.4.3.4), is very widely used, because it requires minimal process knowledge
for its design. In particular, a mathematical model of the process is not required
although it can be quite useful for appropriate tuning. Furthermore, if process con-
ditions change, the PID controller can be retuned to maintain satisfactory perfor-
mance. A properly tuned PID controller can be quite robust in maintaining good
steady-state operation in the face of unmeasured disturbances.
However, since control action can only occur if a deviation occurs between the
set point and the measured variable, perfect control is not possible. Therefore feed-
back control fails to provide predictive control action to compensate for the eects
of known disturbances. A more serious limitation, which is particularly important
for polymer reactor control, is that the controlled variable cannot always be mea-
sured on-line.
Feedforward control was developed to counter some of these limitations. Its
basic premise is to measure the important disturbance variables and then take
corrective compensatory action based on a process model. The quality of control is
directly related to the delity and accuracy of the process model. Two implementa-
tions of feedforward control which are widely used in polymer reactor control will
be discussed, namely feedforward control design based on steady-state models, and
SCHEDULING
AND
OPTIMIZATION
MODEL BASED CONTROL
ADVANCED REGULATORY
CONTROL
REGULATORY CONTROL (P,T,L,F)
SENSORS, TRANSMITTERS, ANALYZERS
PROCESS
Fig. 12.34. The process control hierarchy.
ratio control. Furthermore, the powerful combination of feedforward and feedback
control will be considered, because it utilizes the best of both approaches: feedfor-
ward control works by reducing the eects of measured disturbances, and feedback
control provides the necessary trim to compensate for the eect of model and
measurement inaccuracies as well as measurement error.
12.5.1.1 Steady-state Model Feedforward Control
To illustrate this approach the polymerization process previously described in Fig-
ure 12.33 is considered. The presence of the recycle stream introduces distur-
bances in the reactor feed which perturb the polymer properties. The objective of
the feedforward control is to compensate for these disturbances by manipulating
the fresh feeds in order to maintain constant feed composition and ow to the re-
actor. Feedforward control of the recycle allows the designer to separate the control
of the reactor from the rest of the process.
As shown in Ref. 33, the feedforward control equations were obtained by writing
component material balances around the recycle addition point. For example, for
monomer A this balance is given by Eq. (101).
q
n3
= q
na1
y
a2
q
n2
(101)
This equation is then solved in Eq. (102) for the fresh feed of monomer A since it
is desired to keep the goal ow of monomer A to the reactor (q
na3
) constant.
q
na1
= q
na3
y
a2
q
n2
(102)
The recycle composition ( y
a2
) is typically measured by online gas chromatographs,
which may have signicant time delays. If a faster response time of the analyzer is
required, an infrared or Raman spectroscopy probe may be used. As discussed in
Section 12.2.8 ow q
n2
is typically measured and controlled by manipulating the
recycle valve to maintain the desired inventory in the feed tank. Any disturbances
in the recycle composition or ow will cause variations in the fresh feed in order to
keep the reactor feed constant. Similar feedforward controllers are implemented
for monomer B and solvent, which are also present in the recycle stream.
As shown in Refs. 22 and 33, the performance of the feedforward control allows
perfect compensation of disturbances that can arise, for example, from a step-
change in the purge ratio, so that the reactor polymer characteristics (composition,
molecular weight) are unaected. Without the presence of the feedforward control-
lers the reactor dynamics and hence its control can be aected directly by the pres-
ence of three lags in series (reactor, separator, hold tank) and thus become unnec-
essarily more complex.
12.5.1.2 Ratio Control
Ratio control is a form of feedforward control which is widely used in the chemical
industry and has proven very useful in polymerization reactor control. As is evi-
dent from its name, its purpose is to keep the ratio of two process variables at a
given value; hence it can be deployed when the objective is to maintain a certain
proportion (or stoichiometry) of reactants in the reactor.
The implementation of ratio control can be described by referring back to the
polymerization process in Figure 12.33 and to the discussion in Ref. 7.
Typically, ow controllers are designed for each of the reactor feed streams (for
example, monomer, initiator, chain transfer) and each one of these controllers has
a set point, which is dependent on the particular polymer being made. However,
when ratio control is implemented as shown in Figure 12.35, one of the reactor
feed streams (monomer A in this case) is chosen as the reference stream. The
measured ow rate of monomer A is then transmitted to the ratio station RC,
which multiplies the signal by the desired ratio K
R
(typically determined by the
polymer chemist) to calculate the set point y
sp
for the ow controller of monomer
B. Dynamic simulations for the polymerization reactor shown in Figure 12.33 and
reported in Ref. 33 showed that the selection of ow ratios as manipulated vari-
ables reduced the interactions among the output variables such as composition
and molecular weight. It is important that the ow controller for monomer B be
tightly tuned with short settling times so that when there are disturbances in the
ow of monomer A, any transient mismatches between monomer A and B ows
are minimized.
12.5.2
Cascade Control
Cascade control is also widely used in the chemical process industries and espe-
cially in cases where there may be nonlinear behavior in the dynamics of the con-
FT
FT
FC
RC Monomer B/A
Ratio Setpoint
Monomer (B)
Monomer (A)
Fig. 12.35. Ratio control.
trol loop. It also addresses the main drawback of conventional feedback control,
namely the fact that control action only occurs where the controlled variable devi-
ates from the set point. Unlike feedforward control, which requires that distur-
bances be explicitly measured and a model be available to calculate controller
output, cascade control introduces an additional measurement and an additional
feedback controller. The secondary measurement is typically located so that it rec-
ognizes the upset conditions sooner than the controlled variable.
The concept of cascade control has been traditionally very much used for eec-
tive reactor temperature control. An example of the implementation of cascade
control is shown in Figures 12.36 and 12.37.
In many instances polymerization reactors are operated adiabatically. In the case
shown in Figure 12.36, in which only traditional feedback control is used, mea-
surement of the reactor temperature is used to manipulate the heat exchanger
ow to cool the reactor feed so that the reactor adiabatic temperature rise is ade-
quate to remove the heat of polymerization. This conventional scheme may regu-
late reactor temperature satisfactorily but disturbances that occur in the feed line
may result in a rather sluggish response of the temperature controller. Polymer
properties are very sensitive to temperature excursions and in many cases this
sluggish response of the temperature control loop may not be acceptable. Cascade
control as shown in Figure 12.37 resolves the problem by introducing an additional
measurement, namely the temperature of the reactor feed, and an additional con-
troller. The cascade control structure has the following characteristics:
v
The output signal of the primary (frequently referred to as the master) reactor
temperature control loop serves as the set point of the secondary (frequently re-
ferred to as the slave) reactor feed temperature control loop.
Polymerizer
TT
TC
Coolant
Polymerizer Feed
Feed Heat
Exchanger
Fig. 12.36. Conventional temperature control of an adiabatic polymerizer.
v
The two feedback controllers are nested with the secondary control loop located
inside the primary control loop.
v
There is one manipulated variable but two sensors and two controlled variables.
The secondary controller responds rapidly to any temperature disturbances in the
reactor feed line and provides improved reactor temperature control. As discussed
in Ref. 7, a similar cascade control scheme can be implemented in the case where
the reactor is jacketed and the reactor temperature is controlled by manipulating
the cooling medium (typically water) inlet stream. In this case the additional mea-
surement is the temperature of the jacket, which is compared with a set point pro-
vided by the master reactor temperature controller. The resulting error signal is the
input to the controller for the cooling water makeup.
It is obvious from the preceding discussion that for a cascade control system to
function eectively, the secondary control loop must be selected and tuned so as to
have a faster response than the primary controller. According to Ref. 7, the second-
ary controller is normally a P or PI controller with derivative action hardly used.
The primary controller is typically a PI or PID controller.
12.5.3
FeedforwardFeedback Control
The combination of feedforward and feedback control provides a very powerful
practical strategy for the control of polymer properties such as composition and
molecular weight. Typically it is still fairly dicult to have on-line direct measure-
ments of polymer composition, so the control design has to incorporate the avail-
Polymerizer
TC
TT
TT
TC
Coolant
Master
Slave
Polymerizer Feed
Feed Heat
Exchanger
Fig. 12.37. Cascade temperature control of an adiabatic polymerizer.
able o-line reactor sample composition measurements obtained at the laboratory,
typically using IR or NMR techniques. Similarly, despite advances in size exclusion
chromatography/gel permeation chromatography technology (SEC/GPC), on-line
SEC/GPC is not routinely available for most industrial polymer reactor control
applications. In many cases the control engineer has therefore to rely on o-line
measurements of molecular weight. Typically measures of molecular weight used
in control applications are the inherent viscosity and/or the melt index. The latter
is very common in polyolen production and recent advances in capillary rheome-
try, as reported in the vendor literature, provide the capability of continuous mea-
surement of melt index and viscosity during polymer production using on-line or
at-line instrumentation. It is also very important to establish appropriate set points
and specications for the inherent viscosity and melt index by relating them to the
underlying molecular weight distribution, as shown for example in Ref. 34.
Returning to the polymerization process shown in Figure 12.33 and following
the discussion in Ref. 30 (which dealt with an emulsion polymerization reactor)
as well as the previously discussed concept of the process control hierarchy, it is
very important to use process understanding (typically captured in dynamic simu-
lations using experimentally validated models) in the design of the control system
for polymer composition and molecular weight. For example, it was shown for a
specic case, which is however typical of a wide class of continuous polymer reac-
tors in industrial practice, that the reactor temperature control is crucial because
inherent viscosity is extremely sensitive to temperature variations. As discussed
above (see Section 12.5.2), cascade control can be eectively deployed to control
reactor temperature within very tight specication limits. Achieving good reactor
temperature control can become particularly challenging in multi-product semi-
batch polymerization reactors, because physical properties of the reactor contents
vary from run to run and within a run and the standard PID controllers used in a
cascade design may not be able to perform satisfactorily over the entire range of
operation required. In these cases more advanced temperature control strategies
based on adaptive control [7] or model-based control can be eectively used, as
shown, for example, in Ref. 35 for an industrial reactor and in Ref. 36 for a
laboratory-scale one. Moreover, adaptive cascade control strategies can provide
better performance without the need for retuning than a traditional PI cascade
control system in the case of jacketed stirred tank reactors in which multiple prod-
ucts are produced and the overall heat-transfer coecient is unknown and can vary
signicantly as a result of fouling, as shown, for example, in Ref. 37.
An additional diculty in the control of polymer properties is that in some cases
the control problem is multivariable, in the sense that there are interactions be-
tween the molecular weight and composition loops and therefore when a manipu-
lated variable is chosen to control molecular weight it may also aect composition.
It is important to use process knowledge to validate the selection of manipulated
variables. For example, for the polymerization reactor shown in Figure 12.33, pro-
cess simulations showed that one way to decouple polymer quality control is to
take advantage of the fact that polymer composition is naturally very sensitive to
changes in reactor feed composition but inherent viscosity is relatively insensitive
to reactor feed composition changes. As discussed in Ref. 33, there exists a much
more formal way for feedback controller design. It consists in creating an approxi-
mate linear multivariable model from the nonlinear polymer reactor model using
step test data and then using the techniques of relative gain array (RGA) and sin-
gular value decomposition analysis (SVD) (as described, for example, in Ref. 7) to
determine the best pairings of controlled and manipulated variables for robust
multi-loop control.
A typical control strategy for polymer composition, which can be implemented
for the reactor shown in Figure 12.33, is illustrated in Figure 12.38. The measure-
ments used are the ows of the fresh monomer feeds, the recycle ow, the mono-
mer composition of the recycle feed and the total monomer reactor feed provided
by two on-line gas chromatographs, and the polymer composition provided by lab-
oratory analysis of reactor samples. The supervisory control consists of three levels
implemented in a cascade fashion:
Monomer
(A)
Monomer
(B)
Initiator
(I)
Solvent
(S)
Transfer
Agent
(T)
Inhibitor
(Z)
Reactor
Hold
Tank
Separator
4
6
Polymer
1
2
3
9 8
Purge Valve
7
FT
XT
Polymer
Composition
Feedback
Gas
Chromatograph
Feedback
Feed
Forward
XT
XT
Lab
FT FC
FT FC
FT FC
FT FC
FT FC
Fig. 12.38. Copolymer composition control strategy.
1. Feedforward controller, previously discussed, which maintains the total monomer
feed rate and monomer A feed composition at the appropriate set points for the
specic polymer grade being produced. The feedforward controller can be easily
extended to n monomers by specifying the total monomer reactor feed rate and
the feed composition for n 1 monomers.
2. Gas chromatograph feedback controller, which uses the velocity algorithm for digi-
tal PID control, discussed in Section 12.4.3.4 to calculate ow correction factors
for the monomers from the gas chromatograph measurement of the actual
monomer feed composition. This controller provides the necessary integral
action so that the oset between the actual reactor monomer feed composi-
tion and its set point, which may be caused by owmeter inaccuracies or other
unmeasured disturbances, is minimized.
3. Polymer composition feedback controller, which updates the set points for the reac-
tor monomer feed composition based on the laboratory analysis of a reactor
sample. This controller thus provides the necessary integral action so that the
oset between the measured composition of the reactor sample and the poly-
mer grade composition is minimized.
It is important to note that these feedforward and feedback controllers have been
designed hierarchically, in the sense that each level in the structure will not activate
unless the levels below it are functioning properly. Furthermore, in practice exten-
sive data validation checks must be incorporated so that robust performance can be
assured even when the gas chromatograph or laboratory analysis measurements
may be unavailable or faulty.
The control of inherent viscosity shown in Figure 12.39 uses the same approach
as the composition control. Depending on the polymer grade being manufactured,
the initiator or the chain-transfer agent may be used to control emulsion viscosity.
An inherent viscosity feedback controller adjusts automatically the set point of the
monomer to transfer agent ratio controller based on the measured viscosity value,
(Section 12.2.7) and provides the necessary integral action so that the dierence be-
tween the reactor inherent viscosity and the polymer grade inherent viscosity spec-
ication is minimized. As in the case of composition control, extensive data and
controller output checks must be incorporated in any practical implementation to
provide robust performance.
12.5.4
State Estimation Techniques
In the design of the composition and viscosity feedback controllers it is very impor-
tant to establish whether the polymer reactor dynamics need to be taken explicitly
into account. The choice of sampling frequency balances the requirements for
good quality control versus the need to minimize analytical costs. Usually, when
the reactor residence time is much shorter than the sampling frequency, integral
control is appropriate, because the time between measurements is usually su-
cient for the eect of an adjustment to a process variable set point to be com-
plete within this interval. In other cases the sampling dead time introduced by
the periodic analysis of polymer concentration, polymer composition, and molecu-
lar weight may necessitate the incorporation of on-line state estimators of polymer
properties.
Reaction calorimetry aims to measure heat released from a polymerization in
order to infer monomer conversion and polymerization rate (as reviewed, for ex-
ample, in Refs. 8, 38, and 39). Careful measurement and balancing of mass and
energy ows are necessary for success of this technique. For example, the commer-
cial MettlerToledo RC1 jacketed reactor acts as a calorimeter supplying mass bal-
ance, polymerization heat generation, and transport data.
On-line estimation may also be accomplished using rst-principles polymeriza-
tion kinetic models implemented on-line in the form of an extended Kalman lter
(EKF) (as illustrated for example in Refs. 8 and 4042). It should be pointed out
that the choice of techniques for on-line estimation of polymer properties is still
an active area of research and is very much dependent on the specics of the poly-
mer chemistry and available on-line instrumentation.
Monomer
(A)
Monomer
(B)
Initiator
(I)
Solvent
(S)
Transfer
Agent
(T)
Inhibitor
(Z)
Reactor
Hold
Tank
Separator
4
6
Polymer
1
2
3
9 8
Purge Valve
7
Monomer to
Transfer Agent
Ratio Controller
XT
Lab
FT FC
FT FC
FT FC
FT FC
FT FC
Polymer Inherent
Viscosity Feedback
Controller
Fig. 12.39. Inherent viscosity control strategy.
12.5.5
Model Predictive Control
The previously discussed single-loop and appropriately chosen multi-loop feedfor-
ward and PID feedback control strategies may not be adequate for the eective
control of polymer properties, particularly in the case when the polymerization
reactor exhibits strongly nonlinear dynamic behavior, or when there are strong in-
teractions between the controlled variables, or when there are constraints on the
manipulated variables. From the advanced process control techniques such as in-
ternal model control (IMC), inferential control, and adaptive control that have
been developed by the academic process control community for these tough multi-
variable control problems, model predictive control (MPC) has reached the stage
where it is having a signicant impact on industrial practice. MPC algorithms are
rapidly becoming imbedded in the distributed control system (DCS) software li-
braries, which facilitates their use. As reported in a 2003 survey [43], by the end
of 1999 there were at least 4500 industrial MPC applications worldwide, mainly in
oil reneries and petrochemical plants.
The structure of MPC is shown in the block diagram of Figure 12.40 [7]. A math-
ematical model of the process is used to predict the current values of the output
(controlled) variables. The model is usually implemented in the form of a multi-
variable linear or nonlinear dierence equation. It is typically developed from data
collected during special plant tests consisting of changing an input variable or a
disturbance variable from one value to another using a series of step-changes with
dierent durations, or more advanced protocols such as the pseudo random-binary
sequence described in Ref. 7. The residuals (that is, the dierence between the pre-
Set points
(targets)
Inputs
Process
Control
calculations
Prediction
Model -
+
Set-point
calculations
Predicted
Outputs
Process
outputs
Model
outputs
Inputs
Residuals
Fig. 12.40. Block diagram for model predictive control [7]. D. E.
Seborg, T. F. Edgar, and D. A. Mellichamp, Process Dynamics
and Control, Copyright 8 2003 John Wiley & Sons, Inc. This
material is used by permission of John Wiley & Sons, Inc.
dicted and actual output variables) serve as a feedback signal to the prediction
block and are used in two types of control calculations that are performed at each
sampling instant, namely set point calculations and control calculations.
A unique feature of MPC is that inequality constraints can be incorporated in
both the set point and control calculations. In practice inequality constraints arise
as a result of physical limitations on plant equipment such as pumps, control
valves, and heat exchangers. The set points for the control calculations are typically
calculated from an economic optimization of the process based on a steady-state
model. Typical optimization objectives can include maximizing a process function,
minimizing a cost function, or maximizing a production rate. The objective of the
control calculations in the control block is to determine a sequence of control
moves (changes in the manipulated variables) so that the predicted response
moves to the set point in an optimal manner, for example by following a reference
trajectory. The calculated control actions are implemented as set points to regula-
tory control loops. A detailed explanation of the dierent design choices that are
necessary for the eective implementation of design of the MPC controller is avail-
able in Refs. 7 and 22. It is also essential to point out that the quality of MPC is
very strongly dependent on the availability of a reasonably accurate process model
that can capture the interactions between input, output, and disturbance variables.
Although MPC control has become an established technology for tough control
problems in petrochemical plants, its application in polymer reactor control is cur-
rently transitioning from purely academic studies using simulated examples to ap-
plications in industrial reactors. Referring to the polymerization process previously
described in Figure 12.33 [33], several academic researchers (for example, in Refs.
4446) have designed and implemented MPC controllers. These controllers were
used successfully for plant startup, minimization of o-grade product during
grade transitions, and regulation around a set point. Recently reported industrial
applications of MPC in polymer reactors, for example in Refs. 47 and 48, have fo-
cused on the transition control requirements, which typically consist in completing
the transition in either a minimum time period or with minimum amount of o-
specication product. MPC is well suited to the grade transition problem [49],
which often translates into aggressive manipulated variable moves, often against
manipulated variable limits or plant constraints. Depending on the specic process
reported, benets have also been achieved in product consistency or increased pro-
duction rate.
12.5.6
Batch and Semi-batch Control
12.5.6.1 Operation and Variability
Batch reactors are the most common reactor used in polymerization engineering.
They may vary in size from a ve-gallon pilot unit to a 30 000-gallon (or greater)
production size [19]. Removal of the heat of polymerization is accomplished by cir-
culating coolant through a jacket or by reuxing monomer and solvent. The main
advantage of batch reactors is the exibility to accommodate multiple products.
They are well suited for low-volume products and for products for which there
are numerous grades (as in specialty polymers), because each batch can be made
according to its own recipe and operating conditions without the costs incurred
when a continuous reactor is shut down and restarted. Process control of batch
reactors must address the main disadvantage of batch reactors versus continuous
ones, namely variability within a batch and/or variability from batch to batch. This
variability is particularly important in free-radical batch polymerization, where the
time of formation of a single chain is only a very small fraction of the batch time
and therefore inhomogeneity results from the fact that polymer chains are formed
under very dierent conditions during the course of the batch. This is especially
signicant for composition control in a free-radical batch copolymerization reactor
where, unless special control strategies are deployed, polymer chains formed early
in the reaction may contain a higher fraction of the more reactive monomer than
the chains formed later in the reaction (compositional drift). On the contrary, in
step growth polymerization (polyamides, polyesters), where the growth time of an
individual chain is approximately the batch time, the eects of the changing reac-
tion environment, and hence within-batch inhomogeneities, are much less of an
issue, since all chains will see the same changing environment [19].
Operation in semi-batch reactor mode is very common in polymer reaction engi-
neering practice. Typically, one way to address the issue of compositional drift in
free-radical batch copolymerization is to operate the reactor under the so-called
starved feed policy. In this case the monomer feed rate is automatically adjusted
to maintain a constant rate of reaction, as inferred for example by reactor pressure
(Section 12.2.2). In this starved feed operation the reaction environment is main-
tained constant during the batch and therefore the monomer composition in the
reactor feed is equal to the desired polymer composition. It is also possible to im-
plement more sophisticated control strategies during the batch by establishing op-
erating trajectories for initiator addition, monomer addition, and/or reactor tem-
perature to achieve desired polymer properties in minimum time, to maximize
productivity, or to tailor the polymer molecular weight distribution. This is typically
accomplished by solving o-line an optimization problem using a kinetic model of
the process as shown, for example, in Refs. 5054. These essentially open-loop tra-
jectories constitute a form of feedforward control and are then implemented as
part of the batch sequential logic and recipe management system using ladder
logic and binary logic diagrams as shown in Ref. 7.
If monomer conversion and molecular weight information is available during
the batch (for example, through on-line densitometry, energy balance estimation,
or on-line gel permeation chromatography) it can be incorporated as part of a feed-
back adaptive predictive control strategy, as for example in Ref. 55, to maintain
the molecular weight at a desired value, while bringing the reaction to a specied
monomer conversion in minimum time by manipulating initiator feed rate and
coolant jacket temperature. In addition, if a fundamental model of the process is
available including reaction kinetics and an energy balance, control moves during
the batch can be calculated by solving a nonlinear dynamic optimization problem
within the context of the previously discussed model predictive control to account
for the wide variety of constraints typically encountered in batch systems. This
approach has been described [56] and applied recently [57] to a set of commercial
polymerization reactors exhibiting challenging dynamic behavior that prevented
conventional control from delivering optimum manufacturing performance.
12.5.6.2 Statistical Process Control
In many cases of batch and semi-batch polymerization control there are no on-line
measurements of polymer quality (for example, polymer composition, molecular
weight) during the batch and these measures of end-use properties are only avail-
able at the end of the batch. In this case recipe modications from one run to the
next are common. The minimal information needed to carry out this type of run-
to-run control is a static model relating the manipulated variable to the quality
variables at the end of the batch. As pointed out in Ref. 7, this model can be as
simple as a steady-state (constant) gain relationship or a nonlinear model that in-
cludes the eects of dierent initial conditions and the batch time. The philosophy
of statistical process control can be very useful in this case, since the polymer qual-
ity variable (for example the Mooney viscosity in elastomer manufacture) can be
plotted for each successive batch on a Shewhart (x-bar) chart with the upper and
lower control limits placed at three standard deviations above and below the target.
A point outside the control limits means that the batch is out of control and the
batch recipe and possibly the sequence logic must be adjusted for the next batch.
If the quality variable for the batch is within the control limits, no control action is
taken to prevent manipulations of the batch process based on stochastic variations
within it.
Very often in DCS-operated batch polymer reactors the primary process variables
such as pressure, temperature, level, and ow (Section 12.2.112.2.4) are recorded
during the batch as well as the quality variables at the end of the batch. However, it
may be very dicult to obtain a kinetic model of the polymerization process due to
the complexity of the reaction mechanism, which is frequently encountered in the
batch manufacture of specialty polymers. In this case it is possible to use advanced
statistical techniques such as multi-way principal component analysis (PCA) and
multi-way partial least squares (PLS), along with an historical database of past suc-
cessful batches to construct an empirical model of the batch [8, 58, 59]. This em-
pirical model is used to monitor the evolution of future batch runs. Subsequent
unusual events in the future can be detected during the course of the batch by
referencing the measured process behavior against this in-control model and its
statistical properties. It may therefore be possible to detect a potentially bad batch
before the run is over and to take corrective action during the batch in order to
bring it on aim.
12.5.7
Future Trends
Trends in industry, which reinforce the importance of measurement of polymer re-
actor process control, include the increasing emphasis by customers on receiving
a more uniform product with desired property specications from their polymer
suppliers; the increasing computing power provided by DCS manufacturers; and
the availability inside the DCS of advanced control modules such as the MPC so
that the implementation of nonlinear multivariable control is easier and faster. As
new polymer reactors are designed (for example, to manufacture polymers with
tailor-made properties using novel metallocene catalysts or living radical polymer-
ization technology), it would be benecial to incorporate process control consider-
ations in the process design phase, so that the controllability of the plant can be
established before it is actually constructed. Furthermore, it is expected that the
on-line control not only of average polymer properties but also of polymer distribu-
tions such as the particle size distribution, as shown for example in Ref. 60, and
the branching distribution will become important, together with recipe manage-
ment, production scheduling, and production optimization. The instrumentation
and control methodologies that will be needed to be deployed to meet these needs
are a challenging and vibrant area of investigation for academic researchers and in-
dustrial practitioners alike.
Notation [61, 62]
Symbols
Symbol Units
A area m
2
a acceleration m s
2
a resistance coecient based on calibration

C
1
b resistance coecient based on calibration

C
2
c resistance coecient based on calibration

C
3
c speed of sound m s
1
C
D
drag coecient
C
p
heat capacity at constant pressure J mol
1
K
1
C
v
heat capacity at constant volume J mol
1
K
1
C
d
discharge coecient
C
V
valve coecient in USCS units gal min
1
psi
1=2
d diameter m
d disturbance variable various
d relative liquid density (specic gravity)
d dierential operator
d
i
discrete deviation or error various
E modulus of elasticity Pa (= N m
2
)
e controller error, y
sp
y various
e
F
ltered error various
f valve characteristic
F force N (= kg m s
2
)
g gravitational acceleration m s
2
g
c
gravitational conversion factor in SI units 1 (= kg m s
2
N
1
)
g
c
gravitational conversion factor in USCS units lb
m
ft s
2
lb
f
h height m
H(t) Heaviside step function
I radiant intensity W m
2
K
c
controller gain various
K
cu
ultimate controller gain various
K
p
process gain various
K
V
valve coecient in SI units m
3
h
1
bar
1=2
l length m
l valve lift
m mass kg
M magnitude of step-change in input variable various
M
n
number average molecular weight kg mol
1
M
w
weight average molecular weight kg mol
1
M
z
z-average molecular weight kg mol
1
n number of measurements
p pressure Pa (= N m
2
)
P
u
ultimate period s
PB proportional band %
PD polydispersity index
q
m
mass ow rate kg s
1
q
n
molar ow rate mol s
1
q
v
volume ow rate m
3
s
1
r radius m
R resistance W
R valve resistance coecient s m
2
R equal percentage valve parameter
s sample standard deviation various
t Celsius temperature

C
T thermodynamic temperature K
t time s
u manipulated deviation variable various
v velocity m s
1
v velocity average m s
1
V volume m
3
x input deviation variable various
x(t) continuous input variable various
x
i
discrete measured value various
x
n
discrete input variable various
x sample mean various
y controlled deviation variable various
y(t) continuous output variable various
y mole fraction
Notation 673
Y expansion factor
y
n
discrete output variable various
y
sp
set point various
z space coordinate m
Greek
Symbol SI unit
a lter factor
a kinetic energy correction factor
b diameter ratio, d
2
=d
1

_ gg shear rate or rate of deformation s
1
Dp pressure drop Pa (= N m
2
)
Dt time interval s
Du change in input deviation variable various
Dy change in output deviation variable various
e absorption coecient m
2
kg
1
y dead time s
k ratio of specic heats, C
p
=C
v

m viscosity Pa s
m population mean various
r mass density kg m
3
r
w0
mass density of water at reference temperature kg m
3
s population standard deviation various
s surface tension N m
1
X
summation operator
t
D
controller derivative time s
t
F
lter time constant s
t
I
controller reset time s
t shear stress Pa (= N m
2
)
t time constant s
Indices
0 refers to inlet, reference, standard, or in front of
1 refers to datum, upstream, or outlet of tank 1
2 refers to surface, downstream, in throat, or outlet of tank 2
B refers to buoyancy
c refers to conversion factor or controller
D refers to drag or derivative control
F refers to lter
f refers to oat
I refers to integral control
i refers to ith sample
m refers to mass
max refers to maximum
min refers to minimum
n refers to nth sample, tank number, or moles
p refers to pressure or process
s refers to steady state value
sp refers to set point
t refers to temperature or tube
u refers to ultimate
v refers to volume
w refers to water
W refers to weight
x bar above symbol refers to average
_ gg dot above symbol refers to time rate of change
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Crowley, Hybrid model based
approach to batch-to-batch control of
particle size distribution in emulsion
polymerization, Computers Chem.
Eng., 2003, 27, 1153.
61 I. Mills, T. Cvitas, K. Homann, N.
Kallay, K. Kuchitsu, Quantities, Units
and Symbols in Physical Chemistry (The
Green Book), Blackwell Science, 1993.
62 J. Inczedy, T. Lengyel, A. M. Ure,
Compendium of Analytical Nomencla-
ture (denitive rules 1997), 3rd ed.,
Blackwell Science, 1998.
13
Polymer Properties through Structure
1
Uday Shankar Agarwal
Since polymers display an incredible range of properties, their potential for appli-
cations is ever increasing. The link between polymer structure and the resulting
properties has long been realized, and emerged as the concept of tailor making of
polymers. In earlier times, developments were largely targeted on achieving the
desired properties through new monomers, copolymer and blend compositions,
physical and chemical additives, and control of polymer molecular weights, as
well as through structural changes derived from processing. In recent years, the
increased expertise in anionic polymerization and the emergence of controlled rad-
ical polymerization techniques have led to relatively easy access to several precisely
controlled topologies such as those of telechelic, block, graft, star-shaped, and sev-
eral other branched homoploymers and copolymers with controlled molecular
weights. For example, phenomenal growth has been recorded in the area of synthe-
sis of block copolymers, as well as in examination of their self-assembling character-
istics leading to unique control of nanoscale morphology. This is providing tools for
development of properties suitable for applications extending from those requiring
mechanical toughness to electronic and biological uses. Another rapidly developing
area is nanocomposites, where the attainable range of properties is further expanded
by incorporating inorganic and organic nanoparticles in polymeric matrices.
In this chapter we aim to demonstrate the relationship of the structure of poly-
mers with their thermal, solution, and rheological behavior. Besides providing a
general review of such behavior, we will emphasize some of the recent develop-
ments in these areas.
13.1
Thermal Properties of Polymers
The thermal behavior of polymers is dierent from that of simple compounds in
that, on heating, the transition of polymers from solids to liquids occurs not at
ISBN: 3-527-31014-2
679
a sharp temperature, but over a range of temperatures. Such behavior is at least
partly attributable to the mixture of chain lengths of molecules that make up a
polymeric material. In addition to a crystalline solid phase that gains liquid-like
mobility at the corresponding crystalline melting point, polymeric materials dis-
play an amorphous phase that undergoes a gradual transformation to a liquid-like
state over a temperature range called the glass transition temperature.
13.1.1
Crystalline and Amorphous Polymers
Crystallization of polymers is important because it imparts several highly useful
properties such as strength, toughness, stiness, and solvent and chemical resis-
tance. A polymer can crystallize when it is cooled from a melt, or concentrated
from a diluted solution. This is because the approaching chains may fold and
pack into a regular, long-range, three-dimensional, positional and orientational
order characterized by a certain unit cell of that polymer. Figure 13.1 shows the
Fig. 13.1. Arrangement of polyethylene molecules in the
orthorhombic unit cell of dimensions a 7:41 A
, b 4:94 A
,
c 2:55 A
(from C. W. Bunn, in Fibers from Synthetic Polymers,

ed. R. Hill, Elsevier, Amsterdam, 1953).
680 13 Polymer Properties through Structure
unit cell in a crystal of a commercially important crystalline polymer: polyethylene.
Here, the chains are extended in planar zigzag (trans) conformation, which corre-
sponds to low energy. However, steric hindrances can lead to other chain confor-
mations in crystals. For example, in the presence of bulky substituents, the vinyl
polymer chains rotate to take up a rotated helical conformation (Figure 13.2).
If a given polymer lacks a tendency to get ordered, the chains stay randomly
coiled and entangled during solidication (Figure 13.3). Such polymers (for exam-
ple, poly(methyl methacrylate)) are called amorphous. Crystallinity is best detected
by wide-angle X-ray diraction (WAXD, Figure 13.4), where the peak positions
provide information about the repeat distances in the crystal lattice. Unlike small
molecules that display sharp peaks during WAXD, even crystallizable polymers
display broad WAXD peaks (Figure 13.4). This is because polymers are never
Fig. 13.2. Helical conformation of an isotactic vinyl polymer
crystalline chain (from F. Rodriguez, Principles of Polymer
Systems, 2nd Ed., McGraw Hill Intl., Auckland, 1982).
~10 nm
Fig. 13.3. Lack of long-range order in an amorphous polymer.
100% crystalline due to entanglements between chains, and are therefore called
semicrystalline. The extent of crystallization (x
c
) can vary from nearly 100% for
polytetrauoroethylene or linear polyethylene to nearly zero for noncrystallizable
polymers such poly(methyl methacrylate). The extent of crystallization is deter-
mined by considering the variation of properties (r, such as density, specic heat,
and electrical resistivity) between amorphous phase polymer and crystalline phase
polymer to be linearly additive [Eq. (1)].
r 1 x
c
r
a
x
c
r
c
1
13.1.2
Inuence of Polymer Structure on Crystallizability of Polymers
Since crystallization requires that the participating chains to come close together,
the spatial regularity and the packing possibilities of the polymers are the most
important factors in determining their crystallizability. For example, isotactic and
syndiotactic polypropylene are stereoregular, and show a higher tendency to crys-
tallize than atactic polypropylene (Figure 13.5). Randomly arranged or bulky pen-
dent groups reduce this tendency because they hinder the close alignment of the
polymer molecules that is necessary for intermolecular interactions. For example,
diffraction
intensity
diffraction angle (deg)
10
fully
crystalline
material
amorphous
material
semicrystalline
polymer
32
Fig. 13.4. WAXD patterns of fully crystalline solids, amorphous
solid/melts, and semicrystalline polymers.
poly(vinyl acetate) with large pendent groups (aOaCOaCH
3
) is amorphous, but
crystallizes easily when hydrolyzed to poly(vinyl alcohol), which has small pendent
groups (aOH). Crystallizability is also induced by existence of functional groups ca-
pable of intermolecular hydrogen bonding (such as amides, urethanes, urea, and
so on) or functional groups capable of polar interactions (such as aCl and aCN).
Block copolymers have large segments of regular structure capable of participating
in crystallization, and hence show a higher tendency to crystallize than random
copolymers.
13.1.3
The Glass Transition Temperature
An amorphous polymer can exist in the glassy (hard, brittle, and sti ) or the rub-
bery (soft) state, depending on the temperature being lower or higher than the so-
called glass transition temperature (T
g
). The glass-to-rubber transition at T
g
is
associated with an increase in free volume resulting in an increase in cooperative
rotational and translational motion of the chain segments (2050 atoms), as the
thermal energy overcomes the intermolecular restraints imposed by secondary
bonding forces between polymer chains. This results in marked changes, such as
an increase in the number of possible chain conformations and an increase in the
free volume. This is manifested as jumps in the thermal expansion coecient (Fig-
ure 13.6) and specic heat (Figure 13.7), and a drop of a few orders of magnitude
in the mechanical modulus (Figure 13.8). Even as the chain segments gain mobil-
ity above T
g
, the chain entanglements persist, imparting rubberlike elasticity (Fig-
ure 13.8). With further increases in temperature and the associated energy and
motion of the molecules, translation/slip of the entire molecules becomes possible.
A consequence of Eq. (1) is that the changes at T
g
are less drastic in semicrystalline
polymers as the crystallites impart rigidity, even at temperatures higher than T
g
.
isotactic
syndiotactic
atactic
Fig. 13.5. The regularity of a polypropylene chain structure
decides its crystallizability. The isotactic and syndiotactic
polypropylene crystallize, but atactic polypropylene does not.
13.1.4
Inuence of Polymer Structure on T
g
of Polymers
The T
g
of a polymer is important as it denes the maximum temperature at which
an amorphous solid polymer still displays structural rigidity. For a given polymer
structure, the T
g
increases with an increase in molecular weight (M) [Eq. (2),
where T
g; y
is the T
g
of a polymer with innite molecular weight, and K is a con-
stant]. T
g
is aected by structural features of the polymer chains, such as chain
stiness and intermolecular forces.
T
g
T
m
Specific
volume
amorphous
solid
melt
crystalline
solid
Temperature
Fig. 13.6. Volume expansion (dilatometry) in amorphous and
crystalline polymers with increasing temperature.
50 100 150 200 250 300
Temperature (C)
Heat
flow
(W/g)
T
g
T
c
T
m

Fig. 13.7. Heat ux during heating of poly(ethylene
terephthalate) (PET) at a constant rate in a dierential
scanning calorimeter (DSC), showing changes in specic heat
at T
g
, crystallization exotherm at T
c
, and melting endotherm at
T
m
.
T
g
T
g; y
K
M
2
For example, while low T
g
values are exhibited by exible chains such as polyethyl-
ene with easy rotation about the backbone, a higher T
g
results from chain stiness
such as that resulting from cyclic structures in the backbone (as in BPA polycar-
bonate). This concept is used in enhancing the T
g
of PET by partial replacement
of the aliphatic glycol in it with an alicyclic glycol, thereby making the polymer
more suitable for high-temperature applications [1]. While bulky side groups (for
example, in poly(a-methylstyrene)) enhance the T
g
because of the resulting steric
hindrance, long and exible side groups decrease the T
g
as they enhance the sepa-
ration between polymer backbones and introduce additional chain-ends. Secondary
attractive forces (for example, polarity) enhance the T
g
. The extent of syndiotactic-
ity in polymers such as PMMA can be inuenced by the method of polymerization,
and in-turn inuence the T
g
[2, 3].
When a random or alternating copolymer is made up of non-interacting mono-
mers, its T
g
can be calculated from the weight fractions (w
i
) and glass transition
temperatures (T
gi
) of its components, by means of Eq. (3).
1
T
g
w
1
T
g1
w
2
T
g2
3
When a polymer is desired to be exible at the temperature of use, this eect
(Eq. 3) can be used to plasticize a polymer internally (that is, reduce its T
g
) by
incorporating comonomers such as vinyl acetate and vinyl chloride. In the case
of block or graft copolymers, microphase separation of the blocks often leads to
separate glass transitions of the corresponding blocks [4, 5]. The case is similar
for immiscible blends. Plasticization can be achieved externally by addition of low
molecular weight, high-boiling organic compounds (plasticizers) that can enhance
T
g

T
m
Temperature (C)
Log G
(MPa)
glass
+ crystals
rubber
+ crystals
rubber
(entanglements)
liquid
Fig. 13.8. Inuence of temperature on mechanical modulus of
a semicrystalline polymer. The broken line indicates the
corresponding curve at higher crystallinity.
inter-backbone distance and drastically reduce T
g
. For example, dioctyl phthalate is
often added to turn the otherwise rigid plastic poly(vinyl chloride) into a exible
material [6].
13.1.5
The Crystallization Temperature and the Melting Point
When heated beyond its T
g
, a crystallizable polymer undergoes crystallization that
is detected calorimetrically as an exotherm (Figure 13.7). The rate of crystallization
rst increases with temperature, reaching a maximum at the so-called crystalliza-
tion temperature, T
c
. With a further increase in temperature, the solid undergoes
a rst-order transition into a melt at T
m
(Figures 13.7, 13.8), corresponding to zero
free energy change on melting [Eq. (4)].
T
m

DH
m
DS
m
4
The T
m
is high for polymers with a lower DS
m
; this is due, for example, to chain
stiness in PEEK (poly(ether ether ketone), T
m
395
C) or to specic interactions
that persist into melts (nylon-6, T
m
228
C). T
m
can also be high for polymers ex-
hibiting high DH
m
values, for example through regular and frequent polar interac-
tions. Random addition of a comonomer leads to reductions in both the T
m
and
the extent of crystallization, while long homopolymer segments in block and graft
copolymers or in immiscible blends may crystallize into their respective crystalline
forms and display two melting points.
Heating a polymer above T
m
to a melt allows its fabrication into the desired
shape in processing operations such as injection molding, extrusion, ber spin-
ning and blow-molding. During cooling from melt, a semicrystalline polymer
undergoes crystallization at temperatures below T
m
but above T
g
. Since crystalliza-
tion involves translation from a highly disordered melt to a highly ordered state
under viscous conditions, the extent, size, and perfection of crystallization depends
on crystallization conditions such as the rate of cooling and the temperature of
crystallization. For example, rapid cooling often results in a large number of crys-
tals, as well as reductions in the extent and perfection of crystallization. On the
other hand, crystallization at temperatures just below T
m
for long periods results
in larger and more perfect crystals.
13.1.6
Tuning Polymer Crystallization for Properties
Crystallization plays a major role in determining the thermal and mechanical be-
havior of polymers as it permits polymers to retain rigidity at temperatures ex-
ceeding the T
g
. Crystallization also enhances the barrier properties and solvent
resistance, as small molecules cannot diuse through crystalline domains. Crystal-
lization of polymers can be tuned, and thus can provide very useful control over
the subsequent processing and nal properties. For example, crystallization from
dilute solutions can lead to disentanglement and high drawability in polyethylene,
producing bers with a very high modulus and strength [7]. Crystallization and
morphology development in polyethylene during its formation on heterogeneous
catalysts leads to a nascent state with special characteristics such as a high T
m
compared to molded polyethylene. One hypothesis attributes this to the inuence
of strain resulting from the temperature gradient at the polymerization site, in a
manner somewhat similar to strain-induced extended chain crystallization from
stirred solutions [8, 9]. Polymer molecules being formed at the heterogeneous
catalyst fragment surface experience strong elongational ow, which could inu-
ence the nascent crystallization process [10, 11] Innovations in polyethylene reactor
technology are directed toward controlling the morphology and properties of the
polymerization product [12]. One expectation is that polyethylene as a nascent re-
actor product can be directly drawn into high-modulus, high-strength bers similar
to those produced via the solution route [13].
Crystallization in step-growth polymers such as polyesters and nylons is known
to assist their subsequent solid-state polymerization because exclusion of reactive
end-groups from crystalline domains enhances their eective concentration in the
amorphous domains [14, 15]. However, the condensation reaction between the last
fraction of end-groups may be hindered by crystallization [16, 17]. The possibility
and rate of crystallization can also be enhanced by processes that enhance orienta-
tion, such as shearing and ber drawing [18]. For example, partial replacement of
terephthalic units with isophthalic units in PET reduces crystallinity, so that no
crystallization in seen in 70:30 random poly(ethylene terephthalate-co-ethylene iso-
phthalate) under quiescent conditions. However, heating its amorphous ber above
its T
g
under a moderate tensile force results in rapid stress-induced crystallization
[19]. The reduction in crystallization by copolymerization has been employed to en-
hance drawability of melt-spun polyester and polyamide bers [20].
On the other hand, a high rate of crystallization during cooling from melts is
desired, as it determines the cycle time and thus the suitability of a polymer for
very important shape-forming processes such as injection molding. The crystalliza-
tion rate is easily enhanced by reducing the molecular weight of polymers, but that
is also detrimental to the mechanical properties. Therefore, nucleating agents are
often used to enhance the crystallization rate. The activity of several heterogeneous
nucleating agents is related to oriented deposition of polymer chains on the sur-
faces of inorganic particles [21]. Nucleating agents such as talc, by virtue of their
highly oriented crystalline surfaces, induce epitaxial crystallization of polymers
such as PE and PET [22]. The activity of organic compounds (salts) such as sodium
benzoate for PET crystallization is related to formation of ionic chain-ends that ag-
gregate in polymer melts to form nucleating clusters [23]. The crystallization en-
hancement that occurs on replacing a small fraction (< 1%) of the ester segments
in PET with amide segments was attributed to self-assembly of the amide seg-
ments [24]. These homogenous nucleators may oer an advantage in impact prop-
erties. Their incorporation in PETcan be carried out by simple solid-state modica-
tion reactions, thus avoiding the degradation reactions accompanying melt-mixing
methods [25]. Figure 13.9 shows the enhanced tendency to crystallize of the thus-
modied PET during cooling from melt.
The optical clarity of polymers generally decreases with the appearance of crys-
tallinity. Semicrystalline polymers are generally opaque because of the scattering
due to the dierence in the refractive indices of the crystalline and the amorphous
domains. However, enhancement of the nucleation density with suitable nucleat-
ing agents can lead to reduction of spherulite sizes (below the wavelength of light)
and hence to transparent semicrystalline polymers. For example, the recently de-
veloped derivatives based on d-sorbitol dissolve in a polypropylene melt and are
thus easily dispersed. On cooling, these additive molecules aggregate, and provide
nucleation sites for ne PP spherulites [26]. More recently, nanoparticles (such as
clay) and carbon nanotubes are being explored as potential nucleating agents [27].
13.1.7
Morphology of Crystalline Polymers
Early X-ray diraction work in the 1920s indicated the polymers to be semicrystal-
line, with crystallites dispersed in an amorphous matrix. The longest dimension of
the crystallites in polymers is 550 nm, which is a fraction of the length of the ex-
tended polymers (up to 5 mm). Based on this, the crystalline morphology was
conceived to be of the fringed micelle type, where the long polymer chains pass
successively through the lengths of several crystalline and amorphous domains
(Figure 13.10).
Later work showed that crystalline domains are most often made up of at rib-
Fig. 13.9. DSC cooling scans of (i) PET
homopolymer (h 0:62 dL g
1
); (ii) PET
chemically modied in the solid-state with
ethylene diamine (EDA) vapor to replace
2.2 mol% of ester functionality with amide
functionality (nitrogen content 0.31%,
PETEDA-1: h 0:5 dL g
1
, PETEDA-3:
h 0:61 dL g
1
); and (iii) PET melt mixed
with 0.3% talc. The modied samples undergo
crystallization at a higher temperature (that is,
sooner during the cooling process). (Reprinted
from Polymer, Volume 43, page 5709, Copyright
2002, U. S. Agarwal, G. de Wit, P. J. Lemstra,
with permission from Elsevier).
bons like lamellae, within which the chains are largely folded (insets a and b
of Figure 13.11) and oriented along the smaller-thickness direction (@10 nm). The
lamellae grow to dimensions of approximately 1 mm by addition of segments to a
fast-growing direction (inset a of Figure 13.11). The growth in the thickness di-
rection is by a not-so-regular stacking of multiple lamellae, with some interlamellar
links (inset b of Figure 13.11). The crystal thickness increases with the temperature
of crystallization, or with subsequent annealing at a higher temperature.
During cooling from melt or concentration from solution, polymers form spher-
ulites which are spherical aggregates of lamellae (Figure 13.11). These spherulites
Fig. 13.10. Fringed micelle model of semicrystallinity in
polymers. (Reprinted from Paul J. Flory, Principles of Polymer
Chemistry. Copyright 1953, Cornell University and Copyright
1981 Paul J. Flory. Used by permission from the publisher,
Cornell University Press).
Fig. 13.11. Growth of a spherulite with
lamellar growth. (a) Lamellae grow as chain
segments (parallel to lamellar thickness
direction) are added successively in the fast
growth direction. (b) Lamellae are stacked
somewhat irregularly, with some interlamellar
links (adapted from G. Strobl, The Physics of
Polymers, Springer, Berlin, 1996 and J. M.
Schultz, Makromol Chem. Makromol Symp.
1988, 15, 339).
grow radially from a central nucleus, to dimensions ranging from about 0.1 mm to
a few millimeters, until they meet the neighboring spherulites. Polymer chains are
oriented tangentially around each nucleus. On deformation of such material under
stress (for example, during ber drawing), the spherulitic structure is destroyed
and crystalline rearrangements lead to polymer chain orientation coinciding with
the stress direction (Figure 13.12). This imparts a high modulus and strength to
the bers in the axial direction.
13.1.8
Tailoring Polymer Properties through Modication, Additives, and Reinforcement
The properties of polymers are determined by the nature and composition of the
structural units, as well as the molecular architecture. Polymers are most often
made from the corresponding monomers. In comparison with developing new
monomers and polymerization methods, a less expensive route to tailor-making of
polymers is through blending, copolymerization, architecture control during poly-
merization, post-polymerization chemical modication, and additives. Detailed dis-
cussions on such possibilities are available in several reviews [3742]. Here we will
briey highlight two recent developments in the areas of block copolymers and
polymeric nanocomposites.
Increasing deformation of single crystals
(a)
Phase
changes,
twinning
(b)
Tilt, slip &
twist
(c)
Cracks formed,
some chains pulled
out of crystals,
more tilt, slip, twist
(d)
Fibrils formed Undeformed
crystals
L
L
11
L
1
Fig. 13.12. Mechanical deformation (drawing)
of spherulitic structures breaks the constituent
lamellae into blocks and tie molecules. The
blocks tilt, with the chains aligning along the
load axis, and make up highly oriented micro-
brils. (From A. Peterlin, in Macromolecular
Reviews, Volume 1 (ISBN 0470-68245-0).
Copyright 1967, John Wiley. Used by permis-
sion from the publisher, John Wiley & Sons,
Inc.).
13.1.8.1 New Morphologies through Block Copolymers
Traditionally, well controlled block copolymers were prepared by living anionic po-
lymerization. However, the advent of controlled radical polymerization techniques
[28, 29] has led to more facile synthesis of block copolymers in large quantities.
The sizes of the blocks are controlled by the ratio of monomer to initiator, which
thus also provides control over their relative sizes. Since the blocks are covalently
bonded, their phase separation on the macroscopic scale is prevented. However, a
repulsive interaction between the constituent blocks can lead to chain segregation,
and thus self-organization into a variety of periodicities in the range of 1020 nm
[4, 5] (Figure 13.13). Self-assembling behavior of polymers leads to interesting
characteristics that can be gainfully employed in improvement of mechanical prop-
erties [30]. Shell long ago commercialized PIPSPI triblock copolymers in which
the glassy PS domains provided physical crosslinks, and thus elastomeric behavior,
even in the absence of chemical crosslinks [31]. Other morphologies may nd
applications in catalysis, membranes, electro-optics, production of nanoparticles,
absorption/release of drugs, and so on. For example, selective removal of one block
from a bicontinuous morphology (gyroid, Figure 13.13) leads to a nanoporous
micelle
cylindrical micelle
resicle gyroid ( )
PCC FCC
HEX
F surface ( )
P surface ( )
LAM
PLAM
NLAM
Fig. 13.13. Self-organization of block copolymers into various
possible morphologies (from S. Forster, T. Plantenberg, Angew.
Chem. Int. Ed. 2002, 41, 688).
structure with a network of interconnected nanochannels (diameter 2030 nm).
Metal plating of these channels can provide a very high internal surface area for
catalytic activity [32]. Homopolymers and block copolymers have also been used
to design novel materials through their capacity to organize organic and inorganic
nanomaterials [33, 36].
13.1.8.2 Polymeric Nanocomposites
Conventionally, high-modulus, high-strength bers are used as reinforcing materi-
als in polymer composites, and llers such as CaCO
3
, talc, silica, glass and carbon
black are used to reduce resin cost or modify electrical conductivity, dimensional
stability, abrasion resistance and other properties. In recent years, enhancement
of polymer properties by composite formation with nanoparticles has developed
as an area of intensive research. Nanostructured materials such as nanoclay, graph-
ite nanosheets, carbon nanotubes, and polyhedral silsesquioxane (POSS) are being
explored as potential nanoscale reinforcing agents in polymeric matrices [43, 44].
In particular, single-wall carbon nanotubes (SWNTs) are unique among nanopar-
ticles due to their large aspect ratio and their mechanical as well as electronic and
conductive properties. For example, the modulus and strength of nanocomposites
with 1 wt.% SWNT compare with those of conventional ber composites with 10
wt.% carbon bers [45]. Incorporation of 1 wt.% SWNT in PMMA is shown to re-
sult in a seven-fold increase in the strain to fracture [46]. In addition, several elec-
trical, thermal, barrier, and crystallization properties are enhanced. For example,
threshold concentrations for electrical conductivity of SWNTs in polymers have
been reported to be as low as 0.1% [47]. Crystallization in PP, nylon-66, and PPT,
and thermal stability in PET, PPT, PBT, and nylon-66 have been shown to be en-
hanced by incorporation of nanoparticles. One critical issue is how to achieve a
good dispersion of the nanoparticles in the polymeric matrix. This is often dicult
by melt-mixing in the high-viscosity polymers. Better dispersion of nanoparticles
often requires either solvent processing, or mixing with monomers followed by
in-situ polymerization [4850].
13.2
Polymer Conformation and Related Properties
A large variety of polymer properties are attributable directly not to their chemical
nature, but to their macromolecular constitution that is, the long chains. In par-
ticular, several properties of polymers are related to, and can thus be estimated
from, the conformational characteristics of the long chains.
13.2.1
The Chain Conformation
Polymer molecules mostly exist as random coils in solutions and melts. Their larg-
est dimension is much smaller than the fully extended chains, but several times
larger than the dimensions based on polymer density. The size of a polymer mole-
cule is often described by its characteristic dimension: the root mean square end-
to-end distance, r
2
1=2
. Representing a polymer molecule as a chain made up of
n bonds of length l (Figure 13.14), it can be shown that Eq. (5) applies, where
f y
1 cos y
1 cos y

and gj
1 cos j
1 cos j

are 1 for a hypothetical freely jointed
chain, and are greater than 1 for real chains where the bond angle is xed at y and
rotation about the bonds is restricted unequally at some value of j between 0 and
2p (Figure 13.15).
r
2
hR Ri f ygja
0
nl
2
5
The factor a
0
is 1 for the unperturbed coil dened in this way, and is larger (or
smaller) when a polymer molecule is expanded (or compressed) due to polymer
solvent interactions. Thus, for an idealized freely jointed chain in theta solvent,
we have r
2
nl
2
, and the corresponding mean square radius of gyration S
2
nl
2
=6. When one accounts for the steric eects that prevent distant chain segments
from overlapping (excluded volume eect), the dependence of r
2
1=2
is predicted
to be n
3=5
(closer to experimental observation), rather than n
1=2
[Eq. (5)]. This
polymer coil size is much larger than that based on polymer density, and hence
markedly inuences the viscosity behavior of polymers.
R
1
2

3
n
l
Fig. 13.14. End-to-end distance of a polymer coil made up of n segments, each of length l.
Fig. 13.15. Possible restriction on bond angles (y) and on

rotation about the bonds at some values of f between 0 and
2p.
13.2.2
Solubility of Polymers
Flory [51] and Huggins [52] were the rst to examine the case of overlapping
chains in solutions. They represented the chains of n segments by placing n beads
on the interconnected cells of a lattice (Figure 13.16), and the other cells were
occupied by solvent molecules. Statistical analysis of the possible conformations
allows calculation of the entropy, while the enthalpic interactions between the poly-
mer segments and solvent molecules are represented by the so-called w parameter,
which is temperature-dependent: w < 0 represents good solvents, and w
1
2
repre-
sents the so-called y-condition where Gaussian statistics prevails. The correspond-
ing free energy change for mixing per site is given by Eq. (6), where f is the frac-
tion of polymers made up of n segments each.
DG
m
k
B
T

f
n
ln f 1 f ln1 f wf1 f 6
This allows the calculation of osmotic pressure by Eq. (7), where c is the mass con-
centration of the polymer of molecular weight M.
p
cR
g
T
M
ln1 f 1
1
n

f wf
2
!
7
Equating the derivative of the mixing free energy [Eq. (6)] with respect to f allows
Fig. 13.16. Segments of a polymer chain in a liquid lattice.
(Reprinted from Paul J. Flory, Principles of Polymer Chemistry.
Copyright 1953 Cornell University and Copyright 1981 Paul J.
Flory. Used by permission from the publisher, Cornell University
Press).
the calculation of two f values (for w values larger than a critical value w
c
) corre-
sponding to minimum energy, and thus the coexistence curve (Figure 13.17) that
describes separation of polymer solutions into two phases at low temperatures
(w A B=T > w
c
) [53]. The molecular weight dependence of w
c
0:5 n
1=2
yields a downward shift of the curve in Figure 13.17, indicating an increasing ten-
dency toward phase separation with increasing molecular weight of the polymers.
Extension of the calculations to the case of polymerpolymer blends [51, 52] sug-
gests incompatibility at w values greater than w
c
2=n for two polymers with an
equal number of segments. This strong tendency for phase separation of polymers
when no specic polymerpolymer enthalpic interactions (for example, favorable
hydrogen bonding) are present is attributed to the only small increase in entropy
on mixing of high molecular weight polymers. A detailed discussion on blending
of polymers and the resulting morphologies and properties is beyond the scope of
this review; the interested reader is referred to more specialized texts [5456].
13.2.3
Dilute Solution Zero-shear Viscosity
Rheology is the science of deformation and ow. Viscosity (h) is a measure of the
stress (t) required to make a uid deform (ow) at a desired strain rate [Eq. (8),
where _ gg dv
x
=dy; Figure 13.18].
t
yx
h_ gg
yx
8
n
2
n
1
1/2
-line
T
n
1
< n
2
C
c
Fig. 13.17. Phase separation in polymersolvent systems

predicted by FloryHuggins theory. The system exhibits UCST
behavior: that is, phase separation at temperatures below a
critical point C. Coexistence curves for two dierent molecular
weights are shown.
A unique characteristic of polymers is that even a small concentration (c) of a high
molecular weight polymer can signicantly enhance the viscosity of a solution (h)
as compared to the viscosity of the solvent (h
s
). This is because the expanded poly-
mer coils in slowly deforming dilute solutions behave as rigid spheres with a ra-
dius of the order of r
2
1=2
, resulting in a large polymer volume fraction f [Eq. (9)]
with the corresponding solution viscosity (Einstein, for f f1) given by Eq. (10).
f
4
3
pr
2
3=2
cN
A
=M 9
h h
s
1 2:5f 10
A polymers capacity to enhance solution viscosity is described in terms of its in-
trinsic viscosity ([h]):
h lim
c!0
h h
s
ch
s
11
Combining Eqs. (9)(11) with Eq. 2.1, and realizing that n @M, one nds that
[h] has an M
1=2
dependence on polymer molecular weight. In reality, the factor a
0
[Eq. (5)] depends to a small extent on M, resulting in the MarkHouwink relation
[Eq. (12)].
h KM
a
12
The constants K and a are obtained by tting experimental data for a given
polymersolvent system. The intrinsic viscosity [h] is conveniently measured by
observing the time for ow of a certain volume of solution (and solvent) through
a capillary, and thus provides an easy indication of the molecular weight from the
tabulated MarkHouwink constants [57].
13.2.3.1 Polymers as Dumbbells
More details of the rheological behavior of polymer solutions can be evaluated
by representing a polymer molecule as a dumbbell: that is, two beads connected
by spring (connecting vector Q, Figure 13.19). Their contribution to the uid
y

V
v
x
Fig. 13.18. Simple shear ow between two parallel plates
separated by a distance y, and moving with relative velocity
V y_ gg
yx
.
stress [Eq. (10)] on any plane comes from the tensile or compressive spring force
(F
c
HQ, H being the spring constant) transmitted through the springs [58]
[Eq. (13), where n is the number concentration of the springs].
t h
s
_ gg nk
B
Td nhQF
c
i 13
For example, a linearly elastic dumbbell model representation (Figure 13.19) of
polymer molecules predicts Eq. (14) to apply, where l x=4H is a time constant
and x is the bead friction factor.
h h
s
nk
B
Tl 14
When it is desired to represent a real polymer as a dumbbell, l can be estimated
from the intrinsic viscosity measurement by means of Eq. (15).
l
hh
s
M
N
A
k
B
T
15
13.2.3.2 Polymers as Chains of Beads and Springs
A more realistic representation of polymer chains is the Rouse model [59], which
considers a polymer molecule to be a linear chain of N free-draining beads inter-
connected by springs (each of time constant l
H
x=4H), and predicts Eq. (16) to
apply.
h
N
A
k
B
Tl
H
h
s
M
N
2
1
3
16
Q
F
(c)
v
1
v
2
Fig. 13.19. Microscopic denition of polymer contribution to
stress on a plane, as the stress exerted by the dumbbell bead
above the plane on the bead below the plane.
This implies that [h] has a linear dependence on molecular weight. This is not con-
sistent with the experimental observations [Eq. (12)]. When hydrodynamic interac-
tion and excluded volume eects between chain segments are considered, the cor-
responding Zimm model [60] correctly predicts the @M
1=2
dependence [Eq. (17)].
h @
N
A
M
N
3=2
l
3
17
13.2.4
Viscosity of Concentrated Solutions and Melts
The models discussed in Section 13.2.3 for dilute polymer solutions all predict
[h] to be independent of concentration; that is, they predict linear dependence
of viscosity on concentration. When the concentration of polymer in solution is
higher than the overlap concentration (c
@1=h @M
1=2
), the random coils get
entangled with each other (f b1). This is responsible for a faster than linear in-
crease in viscosity with concentration (Figure 13.20), which often follows the scal-
ing relation of Eq. (18) [61]. That is, if h=h
s
is plotted against c=c
or hc, then the

curves of various molecular weights can be superimposed.
h
h
s
F
c
c

Ghc 18
While accounting for the concentration eects by analyzing a single chain placed
in an eective medium made up of the other chains, the dependence expressed
semi-
dilute
dilute

C*
viscosity
(cP)
0 20 40 60 80 100 120
concentration (mg/mL)
0
12
8

6

10
2

4

140
Fig. 13.20. Concentration dependence of viscosity of synapse
(molecular weight 18.55 kDa) solution is linear at c < c
,
c
@50 mg mL
1
. Redrawn from Malvern application note no.
MRK511-01 (http://www.particular.ie/
m%20wt%20protein%20nano%20zs.pdf ).
in Eq. (19) was obtained [62], indicating Rouse-like [Eq. (16)] linear dependence on
N at intermediate concentrations (Figure 13.20).
h @h
s
1
c
2
l
6
24
N

19
The transition from the Zimm regime [Eq. (17), h @N
1=2
] at dilute concentra-
tions to Rouse-like behavior [Eq. (16), h @N] at the intermediate concentrations
is related to the hydrodynamic screening at high concentrations: the hydrodynamic
interactions between segments become negligible because the local velocity around
the beads falls quickly.
At even higher molecular weights and concentrations, the viscosity in concen-
trated solutions and melts goes from a linear to a 3.4 power dependence on M
[Eq. (20); Figure 13.21].
h @c
4--5
M
3:4
20
This behavior is described by connement of a polymer molecule to its own tube
whose walls are dened by the network of surrounding entangled chains (Figure
13.22) [63, 65]. Hence, chain motion (including stretching and relaxation) is per-
mitted only curvilinearly to the tube (reptation), while motion of the chain perpen-
dicular to the tube is hindered. During ow, the relaxation of chain stretching
along the tube axis is instantaneous, while a nonrandom orientation of tube seg-
ments contributes to the stress.
13.2.5
Nonlinear Polymers
Modern synthesis methods have allowed preparation of polymers with a great vari-
ety of branching architectures, such as random, comb, uniform and nonuniform
star, brush, and dendritic [66, 67]. It is understandable that the conformations
and hence several properties of these structures can vary remarkably among linear
polymers of similar compositions and molecular weights. The compression of the
branched molecule compared to linear molecules of same molecular weight can be
quantied in terms of the factors dened in Eqs. (21) and (22), where the sub-
scripts b and l represent the branched and the linear polymers.
g S
2
b
=S
2
l
21
g
0
h
b
=h
l
22
The factors g and g
0
can often be related, depending on the branching architecture.
For example, for star polymers with p equal arms [68, 69], the relationship is given
by Eq. (23).
g
3
p

2
p
2
0:2624 1 0:2624g
0
1:088
g
0
0:6087
23
Such characteristics of several other branched architectures have been examined
[70]. The molecular compression behavior by branching allows high loading of
the polymeric additives without the excessive viscosity enhancement associated
with polymers. As we shall discuss in Section 13.3.6, the rheological eects of
Fig. 13.21. Variation of polymer melt viscosity with molecular
weight. (from C. W. Macosko, Rheology: Principles,
Measurements and Applications, Copyright 1994 VCH. Used by
permission from the publisher, John Wiley & Sons, Inc.).
branching are more substantial and are put to use in strongly owing polymer
melt systems.
13.2.6
Rigid Rod-like Polymers
Some polypeptides and para-linked synthetic aromatic polymers take up elongated
forms, forming rodlike structures (rather than exible coils). Their solution viscos-
ity displays a strong dependence on the polymer molecular weight according to Eq.
(24), where L and R are the length (@M) and the radius, and r
b
is the bulk density
of the rodlike molecules [64].
h
2L=R
2
45r
b
lnL=2R 0:8
24
At higher concentrations (number concentration > 1=L
3
), the motion of rodlike
polymers is highly hindered in the directions perpendicular to the rod axis, and
the viscosity increases spectacularly with mass concentration (r) and molecular
weight [Eq. (25)] [64].
h zr
3
M
6
=lnN 25
Fig. 13.22. Connement of a polymer chains
motion in its own tube dened by a xed
network of surrounding chains. Back and forth
motion in the tube leads to tube renewal and
thus to the loss of the original tube orientation
and stress (adapted from M. Doi, S. F.
Edwards, The Theory of Polymer Dynamics,
Clarendon, Oxford, 1986).
Due to this eect, the increase in molecular weight during their step-growth poly-
merization leads to a reduction in the reaction rate of such polymers [71], and pro-
vides the possibility of controlling the kinetics and molecular weight distribution
by orienting ow [72]. Spontaneous liquid-crystalline ordering of these polymers
at still higher concentrations allows their processing into very strong bers [73].
13.3
Polymer Rheology
In Section 13.2 we discussed the equilibrium conformations of polymers and their
inuence on the polymeric behavior. We shall now discuss the rheological proper-
ties of polymers associated with their very special characteristic that their confor-
mation changes under imposed ows.
13.3.1
The Viscous Response: Shear Thinning
One important characteristic of polymers is their shear thinning behavior: the vis-
cosity decreases with increasing rate of deformation (Figure 13.23). This behavior
at _ gg @l
1
is attributed to the partial disentanglement of the chains as they get ex-
tended in the ow direction. Since the relaxation time increases with molecular
weight [for example, l @M
1:5
at low concentrations; Eqs. (12), (15)] and with poly-
mer concentration, shear thinning begins at lower shear rates for polymers with
Fig. 13.23. Shear thinning behavior of an ABS
polymer melt at three dierent temperatures.
Broken lines are power law ts and solid lines
represent the Cross model. (from C. W.
Macosko, Rheology: Principles, Measurements
and Applications, Copyright 1994 VCH. Used by
permission from the publisher, John Wiley &
Sons, Inc.).
higher molecular weights and at higher concentrations. The shear thinning behav-
ior is responsible for the processibility of many polymer melts. For example, high
strain rates of extrusion are employed lest they should undergo stress and thermal
degradation, and the circumferential shear (due to screw rotation) during extrusion
reduces the viscosity suciently to enable axial ow (due to the pressure devel-
oped) [74].
Empirically, the shear thinning behavior is most conveniently represented by the
power law relationship expressed by Eq. (26) [75] (Figure 13.23) or, more appropri-
ately by a four parameter Cross model [Eq. (27), where h
o
and h
y
correspond to the
low (zero) and the high shear plateaus, and l and n < 1 correspond to the loca-
tion of transition and the slope on a loglog plot (Figure 13.23)] [76].
h K_ gg
n1
26
h h
y
h
o
h
y
1 l_ gg
2
n1=2
27
It is interesting to examine the ability of the simple molecular models (Section
13.2.2) to represent the shear thinning phenomena. The linearly elastic dumbbell
and the Rouse models represent chain extension (unlimited at increasing _ gg), yet
these predict the viscosity to be independent of shear rate. The nitely extensible
nonlinear elastic (FENE) dumbbell model considers the connecting spring to
stien innitely as the extension approaches the maximum possible value Q
o
.
This permits prediction of the shear thinning behavior starting at (l_ gg @1) [58].
Similarly, when one accounts for hydrodynamic interaction, the linearly elastic
dumbbell model also predicts shear thinning according to Eq. (28).
h h
s

nk
B
Tl1 x
1 2x1 x=2l_ gg
2
28
13.3.2
Normal Stresses during Shear Flow
In contrast to simple uids under shear that generate stresses parallel to the direc-
tion of shear, polymeric uids also generate normal stresses perpendicular to the
ow direction [Eqs. (29), (30), where N
1
and N
2
are called the rst and the second
normal stress dierence, respectively, and are dependent on the shear rate].
N
1
is positive, corresponding to a tendency of the polymeric uid to push apart
the two plates between which the uid is sheared (Figure 13.24). Such a tendency
of polymeric uids is manifested in interesting phenomena such as die-swell and
rod-climbing (Figure 13.25).
t
xx
t
yy
N
1
29
t
xx
t
zz
N
2
30
fluid

rotating
flat plate
stationary
cone
manometers
at various
radial positions
Fig. 13.24. When a polymeric uid is sheared between a cone
and a plate, stresses are generated that are also normal to the
ow direction, as is evident from the monomeric uid levels.
Fig. 13.25. Normal stresses in shearing polymeric uids are
responsible for their swelling on exit from a die.
13.3.3
Extensional Thickening
A ow that converges or diverges is called extensional or compressional (Figure
13.26). For example, stretching of a lament creates extensional ow with the cor-
responding velocity gradient ( _ gg
xx
dv
x
=dx) resulting in tensile stress [Eq. (31),
where h
e
is called the extensional viscosity].
t
xx
t
yy
h
e
_ gg
xx
31
With an increase in ow time or strain at low _ gg
xx
, h
e
increases to its asymptotic
steady-state value given by Eq. (32).
h
e
3h 32
However, many polymers show strain hardening, that is, an increase in h
e
beyond
this asymptotic value at high strain rates (Figure 13.27). Such behavior of high mo-
lecular weight polymers is responsible for stabilizing stretching processes involved
in the production of lms and bers.
v
Fig. 13.26. Uniaxial extensional ow generated between a xed
plate and a plate moving at desired velocity (v), while the entire
geometry is held in a constant-temperature bath. Measurement
of the sample dimension and the required tension force allows
calculation of the elongational viscosity.
13.3.4
The Elastic Response
13.3.4.1 Ideal Elastic Response
Polymeric materials often tend to behave as springs (that is, they have a tendency
to retract on stretching), thus displaying some degree of elasticity. An ideal elastic
material responds instantaneously to application or removal of stress, with the
strain (g) being proportional to the stress (Hookean), independently of the strain
rate [Eq. (33)]. Here, the constant G is the modulus of the elastic material.
t Gg 33
13.3.4.2 Rubberlike Elasticity
Elastic polymers contain a crosslinked network to restrain the gross mobility of
their chains. When the chain segments between crosslinks are deformed anely
in a macroscopic sample due to application of an external force, the resulting de-
crease in chain entropy brings in a springlike retractive force (with spring constant
3k
B
T=r
2
) [77]. Generalization to a three-dimensional deformation to account for
cross-sectional area changes corresponding to an axial strain of a 1 results in
Fig. 13.27. Uniextensional extensional
viscosity (h
u
, open symbols) and shear
viscosity (h
, closed or half-lled symbols) of

low-density polyethylene (LDPE) as functions
of ow time after inception of the steady
extensional rate (_ ee) or shear rate ( _ gg),
respectively. (from C. W. Macosko, Rheology:
Principles, Measurements and Applications,
Copyright 1994 VCH. Used by permission from
the publisher, John Wiley & Sons, Inc.).
the retractive force per unit deformed cross-sectional area according to Eq. (34),
where G N
e
k
B
T, and N
e
is the number of crosslinked chains per unit volume.
t
xx
G a
2
1
a

34
The a
2
dependence indicates that the chains become progressively harder to
stretch. As seen in Figure 13.28, this simple model based on (innitely extensible)
Gaussian chains fails to explain the extreme stiening behavior at very high strains
near the maximum possible chain extension.
13.3.5
The Viscoelastic Response
Elastic behavior in polymers is rubberlike and thus not Hookean, and viscous be-
havior is shear thinning and thus not Newtonian. Further, real polymers display
characteristics that are a combination of such elastic and viscous responses. This
is best illustrated by the Maxwell model [75, 78], which considers the viscoelastic
Fig. 13.28. Stressextension curve for a
sample of natural rubber compared with the
ideal rubber prediction [Eq. (35)] (Reprinted
from Paul J. Flory, Principles of Polymer
Chemistry. Copyright 1953 Cornell University
and Copyright 1981 Paul J. Flory. Used by
permission from the publisher, Cornell
University Press).
behavior to be a series combination of the Hookean elasticity as represented by a
linear spring and the Newtonian viscous behavior as represented by a dashpot (Fig-
ure 13.29). The stress (t) being the same for the spring and the dashpot, and the
total strain (g) being the sum of the strains of the spring and the dashpot, one ob-
tains Eq. (35) or, substituting l h=G, Eq. (36).
dg
dt

dg
1
dt

dg
2
dt

1
G
dt
dt

t
h
35
t l
dt
dt
h
dg
dt
36
In Figure 13.30, we compare the creep and stress relaxation responses of such a
material with the responses of an ideal elastic solid and a viscous Newtonian uid.
It is easily realized from the creep behavior that a small value of h and large value
of G (and thus a small value of l) correspond to the viscoelastic response approxi-
mating to the viscous response. Further, the creep response of the viscoelastic
material at short times (for example, instantaneously) closely approximates to the
elastic behavior, because viscous ow occurs only over time. At long times, the ac-
cumulated viscous response represents the overall deformation. Similarly, the
stress relaxation behavior of the viscoelastic material suggests that l is a measure
of time taken for stress to relax to 1/e of the original stress, and hence this is called
the relaxation time of the material. The eect of material characteristics l and pro-
cess time (t) are thus easily put together in the dimensionless parameter called the
Deborah number De, as in Eq. (37).
G

,
1

,
2

,
Fig. 13.29. The Maxwell model for a viscoelastic material

considers an elastic spring and a viscous dashpot connected in
series.
De l=t 37
De > 1 and De < 1 correspond to predominantly elastic and viscous responses re-
spectively. De determines the level of shear stress that can relax during the melt
processing, and hence the residual chain orientation, morphology, and properties
in the solid-state article fabricated by melt processing.
The Maxwell model [Eq. (36)] can also be expressed in the integral form of Eq.
(38) [75]. That is, the stress can be looked upon as the sum of every incremental
strain _ ggt
0
Dt
0
multiplied by the corresponding exponentially decreasing modulus
Ge
tt
0
=l
.
t
t
y
Ge
tt
0
=l
_ ggt
0
dt
0
38
13.3.5.1 Linear Viscoelasticity in Dynamic Oscillatory Flow
When a sinusoidally varying strain (Figure 13.31) of frequency o and a small am-
plitude g
max
is imposed on a uid according to Eqs. (39) and (40), the correspond-
ing stress also oscillates [Eq. (41)], albeit with a phase delay (d, Figure 13.31) after
the imposed strain rate that can be decomposed into two strain-dependent terms
[Eq. (42)], of which the rst is the elastic contribution in phase with the strain
[Eq. (39)], and the second is the viscous contribution in phase with the strain
rate [Eq. (40)].
g
yx
g
max
sinot 39
_ gg
yx
_ gg
max
cosot 40
t
yx
t
max
cosot d 41
t
yx
G
0
g
max
sinot G
00
g
max
cosot 42
(a) (b)
time
0
/
o
1

1/e

time
0
/G
/

Fig. 13.30. (a) Creep behavior (strain

response to an applied step-stress t
o
) and (b)
stress relaxation behavior (stress response to
step-strain g
o
). The behavior of an elastic solid
(broken lines with long dashes), a viscous
liquid (broken line with short dashes, and
dotted line), and a Maxwell viscoelastic
material (solid line) are compared.
G
0
t
max
cos d=g
max
and G
00
t
max
sin d=g
max
are called the storage modulus and
the loss modulus, corresponding to the elastic and viscous contributions, re-
spectively. For the Maxwell model [Eq. (36)], their dependence on frequency is
given by G
0
G
ol
2
1 ol
2
and G
00
G
ol
1 ol
2
. With an increase in frequency,
a polymer behaves increasingly like a solid (storage/elastic), G
0
! G: that is, the
storage modulus equates to the elastic modulus. This single-mode Maxwell model
correctly represents the observed G
0
@o
2
and G
00
@o dependence in the terminal
zone (long time, small o), and a crossover at o 1=l (Figure 13.32). However, real
polymers display not a single time constant and a single modulus, but a spectrum
0 2 4 6 8 10
max
ma x
,

t

Fig. 13.31. Imposed sinusoidal strain (solid line), and the
corresponding sinusoidal stress (broken line) response of a
viscoelastic material.
crossover
defines (1/ )
G', G''
log ()
Fig. 13.32. Frequency response of a viscoelastic material.
Storage modulus (G
0
, solid line) and loss modulus (G
00
, broken
line) are shown.
of relaxation times (l
i
) and modulus parameters (G
i
) corresponding to dierent
modes of relaxation. The Maxwell model can then be generalized by considering
the stress to be a sum (superposition) of the contributions of each mode of relax-
ation, as represented by Eq. (43), where G
i
and l
i
can be found by carrying out a
multiparameter t of the stress response to step-strain or dynamic strain.
t
t
y
X
i
G
i
e
tt
0
=l
i
_ ggt
0
dt
0
43
These values of G
i
and l
i
constitute the relaxation spectrum of a polymer, and are
useful in correlating the viscoelastic behavior of polymers with their molecular
characteristics, such as long-chain branching in polyethylene (Figure 13.33) [79].
13.3.6
Inuence of Polymer Branching Architecture in Bulk Polymers
Polymer chemistry has played a very important role in providing polymeric mate-
rial with pre-designed molecular architectures. In particular, the branching archi-
tecture has been seen to greatly inuence the rheological behavior of polymer
melts as the reptation of the arms is severely suppressed. Relaxation of the arms
can take place only by arm withdrawal, which is exponentially slowed with increas-
ing arm length [63]. It is only after sucient movement of the arms that the mo-
tion of branching points (otherwise hindered by the network around them) can
branched
linear
10
-3
10
-1
10
1
10
3
10
1
10
3
10
5
G
i
(Pa)
i
(S)
Fig. 13.33. Relaxation spectra for linear and
branched polyethylene (PE). The spectrum of
the branched PE includes a relaxation time that
is 10 times longer than the longest relaxation
time of linear PE. This is consistent with the
long relaxation times predicted for branched
PE. (redrawn from S. H. Wasserman in
Metallocene Catalyzed Polymers, Eds. G. M.
Benedikt, B. L. Goodall, BF Goodrich,
Brecksville, 1998).
slowly take place (Figure 13.34) [80]. Some spectacular eects of these entangle-
ments in long-chain branched industrial polyethylene (LDPE) are the following:
very long relaxation times (Figure 13.33), greater extensional thickening (Figure
13.27), and greater shear thinning (Figure 13.35) [81, 82]. The extensional thicken-
ing is critical for imparting the characteristics necessary for lm blowing, blow-
molding and foaming applications of polyolens, and the increased shear thinning
allows easier extrusion at high shear rates. Eorts have been made to enhance
processibility of polyesters by introducing branching, and lower melt and solution
viscosities are obtained. However, the solid-state properties were found to be poor
[83].
Hyperbranched polymers are compact, highly branched, three-dimensional mac-
romolecules with a high density of end-groups [84]. Their compact structure re-
sults in inherently low viscosity, as evidenced by the value of the MarkHouwink
constant a being less than 0.5. Hyperbranched aliphatic polyesters have been ap-
plied as toughners for epoxy thermosets without a signicant increase in viscosity
[85]. Hyperbranched polymers can be used as rheology control agents during the
processing of polymers, for example to obtain a dramatic decrease in viscosity
[86], as lubricants [87], or for sharkskin elimination [88].
Dendrimers are a relatively new class of highly and regularly branched polymers
with well dened numbers of branching layers and a low molecular weight be-
tween branches. Dendritically branched polymers may have somewhat higher
molecular weights, yet lower intrinsic viscosity, than corresponding regular star-
shaped polymers, due to their dense internal structure [89]. They can display high
elasticity [90], and this makes them potentially interesting rheology modiers. The
large number of peripheral terminal groups contribute to their solubilities, and
oer potential for loading high functionalities when utilized as additives, for exam-
ple for solubility enhancement, ber dyeability, crystallization suppression, and
suchlike [91, 92].
Dense grafting of side chains onto linear backbones, and homopolymerization of
macromonomers, are both used to synthesize macromolecular brushes. Steric re-
pulsion of the side chains forces the main chain into an extended wormlike confor-
mation, resulting in liquid-crystalline phases, and lower dynamic shear moduli
than linear exible coils in concentrated solutions [93, 94]. Densely grafted poly-
meric brushes on sliding surfaces have been found to reduce friction, and there-
fore have potential for providing biolubrication for articial implants [95].
13.3.7
Polymers as Rheology Modiers
Due to their large coil size and hence their great inuence on the shear and elon-
gational behavior of solvents, polymers are used as rheology-modifying additives in
applications ranging from fuels, lubricants, coatings, and sprays to enhanced oil
recovery and turbulent drag reduction [96]. For example, macromolecular coils
of poly(alkyl methacrylate) and ethylenepropylene copolymers that expand with
temperature are used to oset the solvent viscosity decrease upon heating (Figure
Fig. 13.34. Relaxation in a branched H-polymer melt involves
retraction of arms by uctuations, followed by crossbar
reptation as branch points move along the dilated tube
(Reprinted with permission from T. C. B. McLeish et al.,
Macromolecules, Volume 32, Page 6734. Copyright 1999).
frequency
(rad/s)
complex
viscosity
(Pa-s)
Fig. 13.35. Complex viscosity of linear (broken curve) and
long-chain branched (solid curve) polymers. Long-chain
branching results in stronger shear thinning properties.
13.36), resulting in atter viscositytemperature curves [97]. This kind of applica-
tion in automotive lubricating oils is termed viscosity index improvement [96]. Ex-
tensional thickening by polymers is responsible for the use of polymeric additives
as anti-misting agents to resist uid breakup into minute droplets [98, 99]. An-
other application of polymers is as drag-reducing agents where a few parts per mil-
lion of polymeric additives can locally enhance the elongational viscosity in order
to dampen turbulence, thereby enhancing uid ow by as much as 100%. At the
high deformation rates during such applications, polymers can undergo chain scis-
sion and thus lose their eciency in rheology modication [100]. Enhancement of
shear stability against such chain scission by way of control of chain architecture is
of much interest [101]. Once again, developments in living polymerization tech-
niques in recent decades have provided access to new polymeric topologies. Some
of these have now been optimized suciently to yield polymers of high enough
molecular weight to be of interest for rheology modication [102].
13.3.8
Rheological Control with Block Copolymers
Nanophase separation of block copolymer melts introduces interesting rheological
behavior. For example, the transient elongational viscosity behavior of a triblock co-
polymer of styrene and olens was found to be strongly dependent on the initial
orientation of the cylindrical domains [103].
While conventional processing of polymers involves melting, block copolymers
such as PSbPnBA display melt-like behavior simply on application of pressure
at room temperature; this is due to pressure-induced miscibility of the blocks
(baroplastics [104]).
Precipitation and gelation of long-chain parans in waxy crude oils hinders
their ow and hence their recovery and processing. Flow characteristics can be im-
Fig. 13.36. Temperature eect on intrinsic
viscosity of ethylenepropylene copolymers in
toluene. The calculated hydrodynamic volume
of EP-5 (M
w
322 000, ethylene 80 mol%)
increases from 5:6 10
18
to 43:7 10
18
cm
3
/molecule as the temperature increases
from 10
C to 50
C. (Reprinted with
permission from A. Sen, I. D. Rubin,
Macromolecules, Volume 23, Page 2519.
Copyright 1990, American Chemical Society).
proved with addition of a diblock copolymer with a crystalline polyethylene block
and an amorphous poly(ethylenepropylene) block which self-assembles in the
oil. The former block provides nucleation sites for crystallization of the parans,
and the latter provides steric stabilization for the wax crystals [105].
13.3.9
Polymer-like Structures through Noncovalent Associations
As compared with the all-covalently linked monomers forming polymeric
structures, weak noncovalent associating interactions between macromolecules/
oligomers also provide a possibility of forming chainlike structures. Examples of
such interactions are van der Waals and Coulomb interactions, hydrophobic inter-
actions, hydrogen bonds, and ionic bonds. Use of reversible associations like these
have been successful in tailoring rheological behavior. For example, polymers with
ionically associating groups have been described as useful drag-reducing agents, as
their shear stability is enhanced due to sacricial breaking of the reversible associ-
ations at high shear, and reassociation in appropriate low-shear conditions [106,
107]. Hydrophobically associating polymers (HEURs) are used for controlling the
rheological behavior of industrial coatings, since they provide sucient shear vis-
cosity through network formation [108]. As compared to solutions of high molecu-
lar weight polymers that show divergent trends with solvent evaporation, linear
polymers and networks can be built by strongly associating 2u-ureido-4-pyrimidone
end-groups [109]. High sensitivity of the associating behavior to temperature pro-
vides opportunities for on-line tuning of rheological behavior.
Introduction of ionic groups or proteins into polymers (forming ionomers) leads
to physical associations at the temperature of use [110, 111]. For example, Surlyn
(DuPont) is a copolymer of ethylene and methacrylic acid that shows enhanced
zero-shear viscosity and elastomeric green strength. Viscoelastic characteristics are
also enhanced due to loss of associations at the appropriate dissociation tempera-
ture. Ion pair associations are exploited to obtain miscibility in otherwise immisci-
ble polymers [112].
Molecules that are capable of spatial complementarity and weak reversible non-
covalent interactions with each other can self-assemble from a less ordered state
(such as a solution) to an ordered structure (such as a solid crystal) without human
intervention [113]. In this manner, precise tuning of oligopeptide associating struc-
tures provides an completely new route to a hierarchy of structures such as tapes,
ribbons, brils, bers, and ber networks, which can be useful as materials [114
116].
13.4
Summary
In this chapter, we have discussed the interrelationships of the molecular struc-
tures of polymers with their thermal, solution, and rheological behavior. The ther-
13.4 Summary 715
mal response is largely determined by interactions at short distances, such as
symmetry and steric eects. On the other hand, the solution and rheological be-
havior is dominated by topological considerations such as the long-chain struc-
ture and branching. Thus, a large variety of polymer properties can be tuned
by characteristics such as (co)polymer composition, average molecular weight,
molecular weight distribution, branching architectures, reversible associations,
and (nano)additives. In the context of the present handbook, it seems appropriate
to emphasize once again the role of the emerging polymerization techniques in
achieving these characteristics in polymers.
Notation
a MarkHouwink constant
c mass concentration of the polymer [kg m
3
]
c
critical overlap concentration of the polymer [kg m

3
]
De Deborah number
f y factor for coiled chain dimension corresponding to bond angle
F
c
spring force in the connector of a beadspring model [N]
g; g
0
factors describing compression of branched polymer versus linear poly-
mer
gj factor for coiled chain dimension corresponding to rotation about bonds
G elastic modulus [Pa]
G
0
; G
00
the storage modulus and the loss modulus [Pa]
DG
m
free energy change on mixing [J]
H spring constant in a beadspring model
DH
m
heat of melting [J]
k
B
Boltzmanns constant [J K
1
]
K MarkHouwink constant
l length of bonds (segments) in polymer chain [m]
L length of the rodlike molecules [m]
M molecular weight [kg kmol
1
]
n number of bonds (segments) in the polymer chain
n number concentration of the springs
N number of beads in the beadspring model
N
A
Avogadros number
N
e
number of crosslinked chains per unit volume [m
3
]
N
1
; N
2
rst and second normal stress dierence [Pa]
p number of arms in a star polymer
Q connector (spring) vector in a beadspring model
R polymer chains end-to-end distance vector [m]
R
g
universal gas constant [J K
1
kmol
1
]
S
2
mean square radius of gyration [m
2
]
DS
m
entropy of melting [J K
1
]
t time [s]
T temperature [K]
T
g
T
g; y
glass transition of a polymer with innite molecular weight [K]
T
m
melting temperature [K]
v
x
x component of velocity [m s
1
]
w
i
weight fraction of species i
x
c
extent of crystallization
Greek
a extension ratio of an elastic material
a
0
factor for polymer coil expansion due to polymersolvent interactions
_ gg shear rate [s
1
]
g strain
d phase delay in dynamic analysis
h viscosity of a polymer solution [Pa s]
h
s
shear viscosity of the solvent [Pa s]
h
e
extensional viscosity [Pa s]
[h] intrinsic viscosity of a polymer in solution [m
3
kg
1
]
y angle between consecutive bonds in a polymer chain [rad]
l time constant of a polymer [s]
l
H
time constant of a polymer segment [s]
x bead friction factor
p osmotic pressure [Pa]
r polymer property such as mass concentration, density, specic heat
r
b
bulk density of a polymer
t
ij
stress tensor [Pa]
f polymer volume fraction in solution
j angle describing rotation of bonds at xed y [rad]
w Florys interaction parameter for mixing
w
c
critical value of w for phase separation
o angular frequency [s
1
]
Acronyms
BPA bisphenol-A
EDA ethylene diamine
HEUR hydrophobically associating polymer (hydrophobically modied, ethoxy-
lated urethane resin)
PBT poly(butene terephthalate)
PE polyethylene
PEEK poly(ether ether ketone)
PI polyimide
Notation 717
PnBA poly(n-butyl acrylate)
POSS polyhedral silsesquioxane
PP polypropylene
PPT poly(propylene terephthalate)
PS polystyrene
SWNT single-wall carbon nanotube
WAXD wide-angle X-ray diraction
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14
Polymer Mechanical Properties
1
Christopher J. G. Plummer
14.1
Introduction
14.1.1
Long-chain Molecules
A polymer is made up of macromolecules, that is, long chains of covalently linked
chemical units, called monomer units. In many synthetic macromolecules, these
units are identical, and the term polymer implies their number per chain ex-
ceeds about 10
2
, although it may reach over 10
5
in many instances. Branched and
highly crosslinked architectures are also important in practice, but it is above all
the presence of long linear monomer sequences that leads to the unique properties
of polymers. For conciseness, therefore, the emphasis in the present overview of
mechanical properties will be on isotropic, chemically homogeneous polymers
composed of exible linear or lightly crosslinked macromolecules.
Long chains of atoms or molecules linked by single covalent bonds are usually
exible in that rotation about the bonds is relatively unhindered, so that they
have many internal degrees of freedom. The forces that oppose any attempt to
constrain the macromolecule, such as maintaining its ends at xed positions, are
therefore essentially entropic in origin. This entropic contribution to their mechan-
ical properties is one of the key features of polymers; it gives rise to the phenome-
non of rubber elasticity, for example, as will be discussed in Section 14.2. Another
characteristic of polymers is the important role of their glass transition tempera-
ture, T
g
. Polymers with regular congurations, such as polyethylene (PE), may
crystallize, but generally remain partly amorphous, even at temperatures, T, well
below their melting point, T
m
. Moreover, polymers with random congurations,
such as atactic polystyrene (aPS), often show little crystallinity at any T and are
consequently referred to as amorphous. In either case, a signicant proportion
of a polymer becomes glassy at T < T
g
. The glass transition therefore has a pro-
ISBN: 3-527-31014-2
721
found eect on polymer properties, whereas in many low molar mass materials
it only has observable physical consequences if solidication is associated with ex-
tremely rapid cooling rates.
Figure 14.1 shows schematically the eect of T on the low strain mechanical be-
havior of various types of polymer, along with the principal regimes of behavior.
Below T
g
, unoriented polymers are rigid solids with a Youngs modulus, E, of be-
tween about 1 and 4 GPa, whose low strain response is conditioned by the cohesive
forces between nonbonded atoms. In organic polymers, these are mainly due to
weak Van der Waals interactions so that, even below T
g
, the moduli are much lower
than in ionic and metallic crystals as well as in three-dimensional covalently
bonded structures such as diamond. As T is increased above T
g
, E drops by a factor
of more than 10
3
in amorphous polymers such as aPS, although the decrease is
less marked in semicrystalline polymers, whose T
m
is typically very much greater
than T
g
, and the reinforcing eect of the relatively rigid crystalline regions persists.
Remarkably, even in uncrosslinked amorphous polymers, the modulus remains
nearly constant as T is increased further. This gives rise to a rubbery plateau,
whose extent depends strongly on the molar mass, M, as indicated by Figure 14.1.
Thus, the plateau becomes eectively innite for an innite, crosslinked network
of chains, but disappears altogether when M is less than some critical molar
mass, M
c
. Beyond the plateau there is a transition to viscous liquid behavior, a
transition that is dened by T
m
in semicrystalline polymers.
14.1.2
Simple Statistical Descriptions of Long-chain Molecules
A real macromolecule contains bonds with xed valence angles, as shown in Fig-
ure 14.2(a) for PE. However, as one moves along an instantaneous snapshot of a
Fig. 14.1. Sketch of the low strain mechanical response of various types of polymer.
722 14 Polymer Mechanical Properties
typical macromolecular chain, taking any bond as a starting point, the correlation
between the direction of the skeletal bonds and that of the starting bond decreases
rapidly. Thus, taken as a whole, a linear molecule resembles a long, exible piece
of string, as shown in Figure 14.2(b). It may therefore be modeled as a sequence of
N freely jointed bonds of length b, in which there is no correlation between the
vector corresponding to the nth bond, r
n
, and r
n1
. The end-to-end vector R that
links one extremity of the chain to the other is then given by Eq. (1).
R
X
N
n1
r
n
1
The magnitude of R in an unconstrained chain is uncorrelated with its direction,
so that its value averaged over a large number of arbitrarily chosen conformations
must be zero. Because thermal motion causes a real chain to change its local con-
formation every few picoseconds, for more familiar time scales it would therefore
be perceived as a fuzzy ball with hRi 0 and a time-averaged mean square end-
to-end distance given by Eq. (2) (r
n
and r
m
are uncorrelated so that hr
n
r
m
i must
vanish for n 0m).
hR
2
i
X
N
n1
X
N
m1
hr
n
r
m
i
X
N
n1
hr
2
n
i Nb
2
2
For a real macromolecule, the value of b characteristic of the equivalent freely
jointed chain is greater than the mean length of the skeletal bonds, l
o
, owing not
only to xed valence angles but also to the presence of rigid units and steric hin-
drance to rotation about single bonds. If N
l
is the number of skeletal bonds in the
chain, hR
2
i C
y
N
l
l
2
o
, where the constant C
y
is the Flory characteristic ratio,
also called the chain stiness [1, 2]. It is of the order of 10 in exible polymers
(7.3 in PE and 9.6 in aPS, for example [3]), but may be much higher for more rigid
architectures such as para-linked benzene rings. C
y
provides the link between
Fig. 14.2. Schematic representations of an isolated polyethylene chain at two length scales.
molecular architecture and general models for macroscopic physical properties
governed by chain statistics, often expressed in terms of b C
y
N
l
l
2
o
/R
max
, where
R
max
is the maximum end-to-end distance of the chain (which depends on both l
o
and the bond angles).
In the limit of large N, the freely jointed chain model implies the probability
density PR; N for a given R to be a Gaussian distribution [Eq. (3)], whence
the frequent use of the term Gaussian chain to refer to idealized exible linear
macromolecules [4].
PR; N
3
2pNb
2

3/2
exp
3R
2
2Nb
2

3
This result is a simplication in that it does not take into account long-range inter-
actions and solvent eects, for example. It nevertheless provides a working descrip-
tion of conformations in solid and molten polymers, and hence forms the basis for
a wide range of theoretical models in polymer physics and mechanics, some of
which will be discussed in what follows.
14.2
Elasticity
14.2.1
Deformation of an Elastic Solid
The stress state associated with an elemental cube may be dened in terms of the
six independent quantities in Eq. (4), where the rst subscript refers to the direc-
tion of the normal to the plane on which the stress acts and the second subscript
refers to the direction of the stress (at equilibrium the net torque is zero so that
s
ij
s
ji
).
s
ij

s
xx
s
xy
s
xz
s
xy
s
yy
s
yz
s
xz
s
yz
s
zz
2
6
4
3
7
5 4
The deformation may likewise be dened in terms of the components of engineer-
ing strain [Eq. (5)].
e
ij

e
xx
e
xy
e
xz
e
xy
e
yy
e
yz
e
xz
e
yz
e
zz
2
6
4
3
7
5 5
The generalized form of Hookes law, which proposes a linear relationship between
stress and strain at vanishingly small strains, is then given by Eq. (6).
e
ij
E
ijkl
s
kl
6
In an isotropic solid, there is no coupling between tensile and shear stresses, and
Hookes law takes the familiar form of Eq. (7), where n is Poissons ratio and G is
the shear modulus.
e
xx

1
E
s
xx

n
E
s
yy
s
zz
; 2e
xy
1g
1
G
s
xy
7
Moreover, it is easily shown that Eq. (8) holds, so that a complete description of the
small strain response requires only two independent parameters.
G
E
21 n
8
Similarly, the bulk (compression) modulus, K, is given by Eq. (9).
K
E
31 2n
9
It is implicit in such descriptions of small-strain elasticity that the stress is un-
aected by the deformation, which justies the assumption of linearity. For the
large deformations associated with rubber elasticity and shear yielding in glassy
and semicrystalline polymers, however, this is no longer valid, and it is more usual
to express deformations in terms of the deformation ratios, l, such that the point
x; y; z is transformed to l
1
x; l
2
y; l
3
z. If the coordinate system is dened with
respect to the deformed system, it is always possible to choose the axes so that
they are not rotated by the deformation. The shear components of the deformation
are then equal to zero, which permits considerable simplication. For example, the
incremental work per unit volume of undeformed material is given by Eq. (10),
where the f
i
are the applied forces along the axes of a unit cube of undeformed
material [5].
dw f
1
dl
1
f
2
dl
2
f
3
dl
3
10
14.2.2
Thermodynamics of Rubber Elasticity
Perhaps the most striking dierence between rubbers and other materials is their
capacity for large reversible or nearly reversible deformations at their service tem-
perature, and it is this aspect of their behavior that will be described here. The
commercial exploitation of natural rubber developed rapidly with the discovery
that crosslinking greatly improves its mechanical properties, giving the rst of
what is now a broad class of materials often referred to as elastomers. Elasto-
14.2 Elasticity 725
mers are characterized by exible chains, T
g
well below room temperature, little or
no crystallinity in the undeformed state, and light chemical or physical crosslink-
ing (through the presence of rigid glassy or crystalline microdomains, for exam-
ple).
Although E drops signicantly as T is raised above T
g
, K changes relatively little,
so that K gE and, from Eq. (9), nA0:5. Volume changes may hence be considered
negligible compared with other types of deformation. This justies the use of the
Helmholtz free energy in the thermodynamic analysis of rubber elasticity, dened
by Eq. (11).
A U TS 11
where U is the internal energy and S is the entropy. For a reversible change of
state, the rst law of thermodynamics gives Eq. (12), where dW is the work carried
out on the system and dQ is the heat transfer into the system, leading to Eq. (13).
dU dQ dW TdS dW 12
dA dU TdS SdT dW SdT 13
The work done when a specimen subject to a force f undergoes an incremental
elongation dl is dW fdl. The corresponding change in free energy is given by
Eq. (14), from which Eq. (15) follow.
dA fdl SdT 14
f
qA
ql

T
; S
qA
qT

l
15
From the identity of Eq. (16), one obtains Eq. (17), and hence Eq. (18).
q
qT
qA
ql

T
q
ql
qA
qT

l
16
qf
qT

l

qS
ql

T
17
f
qA
ql

T
qU
ql

T
T
qS
ql

T
qU
ql

T
T
qf
qT

l
18
Measurements of f T at large xed deformations, such as shown in Figure 14.3,
indicate that f TACT for T > T
g
, where C is a constant. The second term in Eq.
(18) therefore dominates under these conditions and the response is almost en-
tirely entropic [4, 6]. (The increase in f with decreasing T below T
g
is due to ther-
mal contraction.)
Another characteristic of elastomers is that their temperature increases during
rapid deformation, for which dQA0. In this case, one can show that Eq. (19) ap-
plies, where C
l
is the specic heat at xed l.
qT
ql

S
T
C
l
qf
qT

l
19
Given that qf /qT
l
> 0 (Figure 14.3), T must indeed increase with l. It may also
be shown that the length of an elastomer subject to a constant force should decrease
as T is increased, which is again consistent with observation, albeit somewhat
counterintuitive, given that crystalline and glassy solids tend to become less rigid
on heating [4].
14.2.3
Statistical Mechanical Approach to Rubber Elasticity
The entropy changes that give rise to rubber elasticity may be modeled in terms of
the chain statistics introduced in Section 14.1.2. For a chain whose end-to-end vec-
tor is xed and equal to R, the number of conformations, WR, that the chain can
adopt is proportional to PR; N. From Eq. (3), one thus obtains Eq. (20), where k is
Boltzmanns constant and S
o
is a constant.
Fig. 14.3. Tensile stress at constant extension (350%) as a
function of T in a crosslinked rubber (after Ref. 2).
14.2 Elasticity 727
S S
o
k ln W S
o

3kR
2
2Nb
2
20
Hence, for constant U, the free energy is obtained from Eq. (21).
A TS A
o
Tk ln W A
o

3kTR
2
2Nb
2
21
The magnitude of the restoring force on a chain with end-to-end vector R is there-
fore given by Eq. (22).
f
qA
qR

3kTR
Nb
2
22
The total free energy change when a large deformation is applied to the chain, so
that R x; y; z changes to RO l
1
x; l
2
y; l
3
z, is given by Eq. (23).
DA TDS
3kTRO
2
R
2
2Nb
2

3kTl
2
1
1x
2
l
2
2
1y
2
l
2
3
1z
2
2Nb
2
23
In an elastomer the forces are transferred to individual chains through the cross-
links, which constitute the nodes of a continuous network. If the chains linking
these nodes are assumed to be freely jointed chains composed of N links of length
b, Eq. (2) implies the spatial separation of the nodes, R, to be given by Eq. (24) in
the undeformed state.
hR
2
i hx
2
i hy
2
i hz
2
i Nb
2
24
Because R has no preferred direction, Eq. (25) holds.
hx
2
i hy
2
i hz
2
i
Nb
2
3
: 25
If there are n
x
chains per unit volume, then assuming ane deformation of the
nodes (so that they move as if xed to a uniform elastic background), it follows
from Eq. (23) that the total change in the free energy per unit volume, a, for a de-
formation l
1
; l
2
; l
3
Da
n
x
kTl
2
1
l
2
2
l
2
3
3
2
26
From the incompressibility criterion, l
1
l
2
l
3
1. Hence, for a uniaxial extension
along x, that is l
1
l, l
2
l
3
l
1/2
, Eq. (27) applies and, from Eq. (10), the
force f
1
acting on a unit cube of undeformed material (equivalent to the nominal
or engineering stress) is given by Eq. (28).
Da
n
x
kT
2
l
2
2
l
3

27
f
1

qw
ql
qDa
ql
n
x
kT l
1
l
2

28
This remarkable result implies that the deformation behavior depends only on the
number of network chains per unit volume and on T. The detailed chemistry of
the chain is therefore unimportant, with the proviso that the chains must be
much longer than the statistical segment length b. For very small deformations,
l 1 e
xx
, and s
xx
s
xx
Af
1
A3n
x
kTe
xx
29
Given that nA0:5 and hence that E 3G [Eq. (9)], Eq. (30) follows.
G n
x
kT 30
There are many shortcomings with this simple treatment, and, as illustrated
in Figure 14.4, the behavior of real elastomers deviates markedly from Eq. (28),
particularly at large l. A particular diculty with Eq. (3) is that it predicts nite
probabilities for jRj > R
max
, which is clearly unphysical. To account for the nite
extensibility of the chains, and hence for the observed work hardening, it is neces-
sary to chose more realistic expressions for PR; N, such as the inverse Langevin
function or the associated analytical approximations [4]. Moreover, in the case of
relatively sti chains such as DNA or certain polypeptides, the worm-like chain
model of Porod and Krattky may be more appropriate than the Gaussian chain.
Even if the chain statistics are correctly described, non-ane deformation of the
network junctions, long-range inter- and intra-chain interactions (entanglement),
specic interactions such as hydrogen bonding, strain-induced crystallization (ob-
served in natural rubber, for example), the presence of llers, and so forth may
need to be taken into account in real rubbers and elastomers [79].
14.3
Viscoelasticity
14.3.1
Linear Viscoelasticity
The discussion has so far implicitly been limited to behavior in the rubbery plateau
regime in Figure 14.1, where the conditions for rubber elasticity in amorphous
polymers are met, namely long exible chains, weak intermolecular forces
T > T
g
and anchoring of the chains to form a network (the nature of this anchor-
ing in uncrosslinked polymers will be discussed in Section 14.3.3). The corre-
sponding constitutive expressions [Eq. (28), for example] predict the response to
deformation to depend weakly on T and to be independent of the deformation
rate. Although this is reasonably consistent with experiment, the situation changes
drastically near T
g
, for example, where time, t, becomes a very important factor,
and the mechanical behavior is said to be strongly viscoelastic.
In a linear viscoelastic material, the moduli and compliances Et; Gt; Dt, and
Jt (tensile and shear modulus and tensile and shear compliance respectively) are
functions of t, although they remain independent of stress or strain. Development
of constitutive equations for such materials is generally based on the idea that the
eects of small increases in stress or strain are additive, which is known as the
Boltzmann superposition principle [4, 10, 11]. A strain et may be considered to
result from a sum of step strains applied at time u and maintained for a time
t u [Eq. (31)].
deu
deu
du
du 31
Fig. 14.4. Experimental stressextension ratio curve for natural
rubber along with a best t of the predicted behavior for
network described by the inverse Langevin function, and of
Gaussian network [Eq. (28)] with the same network parameters
(after Ref. 7).
In uniaxial tension, the Boltzmann superposition principle implies Eq. (32).
st
t
y
Et u
de
du
du 32
Similarly, for a given stress history, Eq. (33) results.
et
t
y
Dt u
ds
du
du 33
Linear viscoelastic materials thus retain a memory of their entire mechanical his-
tory although, conveniently for the experimentalist, the memory fades with t u,
and for practical purposes the lower limit of integration in Eqs. (32) and (33) is
often set to zero. Equations (32) and (33) may be used to calculate the response to
an arbitrary deformation using Et or Dt determined from simple static experi-
ments (creep or relaxation).
Another important class of experiments involves periodic tensile or shear strains
of the type et e
o
cos ot Ree
o
e
iot
. In a linear elastic solid deformed in ten-
sion, s oscillates in phase with e with amplitude Ee
o
. In a linear viscous liquid,
s hde/dt and hence varies as he
o
o sin ot he
o
o cosot p/2. In a linear vis-
coelastic material, however, intermediate behavior is observed [Eqs. (34), where
0 < d < p/2].
et e
o
cos ot
st s
o
cosot d
34
It is hence possible to dene two dynamic moduli, the storage modulus, E
0
(or G
0
,
in the case of a shear experiment), which gives the stress component in phase with
the strain, and the loss modulus, E
00
(or G
00
), which gives the stress component out
of phase with the strain. Thus, in tension, Eqs. (35) is obtained, where E
0
; E
00
, and
tan d are given by Eq. (36).
st s
o
cosot d E
0
e
o
cos ot E
00
e
o
sin ot 35
E
0

s
o
e
o
cos d; E
00

s
o
e
o
sin d; tan d
E
00
E
0
36
Equation (35) is sometimes more conveniently expressed in complex notation as
Eq. (37), where the complex modulus E
is dened by Eq. (38).

st Res
o
e
iotd
ReE
e
o
e
iot
37
E

s
o
e
o
cos d i sin d 38
Viscoelastic materials are often modeled using linear combinations of xed
Hookean and Newtonian elements (springs and dashpots). Although such models
may not fully account for the complexity of real materials, generalizations of this
approach have been extensively developed and methods and approximations for
transforming between the dierent viscoelastic functions are widely available in
the literature [10, 11]. For the sake of illustration, one simple example will be con-
sidered here, namely the Zener element, a possible representation of which is
shown in Figure 14.5. At very high frequencies most of the deformation in a Zener
element is taken up by spring 1 and the limiting modulus E
o
is equal to E
1
. At very
low frequencies, where the stress in the dashpot becomes negligible, the deforma-
tion is taken up by spring 1 and spring 2 in series, and the limiting modulus
E
y
E
1
E
2
/E
1
E
2
. However, at intermediate frequencies, the behavior becomes
strongly inuenced by h [Eqs. (39), where DE E
o
E
y
and the relaxation time is
given by Eq. (40)].
E
E
o
DE
1 iot
1 o
2
t
2
; tan d
DEot
E
y
E
o
o
2
t
2
39
t h
DE
E
2
o
40
The behavior predicted by Eqs. (39) for values of E
1
and E
2
appropriate to the glass
transition in an amorphous polymer (compare Figure 14.1) is shown in Figure
14.6. The model accounts for the qualitative features of experimentally observed
transitions, namely a step-like drop in modulus as o decreases below t
1
, and
a characteristic peak in tan d. However, more complex models involving many
relaxation times, that is, a discrete or continuous relaxation time spectrum, are
necessary if more quantitative agreement with experiment is to be obtained (for
an example of a discrete relaxation time spectrum derived from a molecular model,
see Section 14.3.3) [10, 11].
Fig. 14.5. The Zener model (or standard linear solid).
Similar behavior to that in Figure 14.6 is observed if the viscoelastic functions
are measured as a function of T at xed o, because the viscous response, which
tends to dominate the relaxation times, is a strongly decreasing function of increas-
ing T, particularly close to T
g
. The eect of increasing T is therefore equivalent to
that of decreasing o (or increasing t in a static experiment). Thus, in dynamic tor-
sion temperature sweeps on poly(methyl methacrylate) (PMMA), the glass transi-
tion at about 120
C is associated with a clear peak in tan dT. As shown in Figure

14.7, other transitions may also be observed at T well below T
g
in this type of ex-
periment. These secondary relaxations are important features of both glassy and
semicrystalline polymers because they show that molecular motions are not en-
tirely suppressed at T < T
g
. Indeed, such motions play an important role in plas-
ticity (see Section 14.4.1). Conventionally, the rst relaxation encountered as T de-
creases is labeled a, and may correspond to either the melting/crystallization
transition (for semicrystalline polymers) or the glass transition. The secondary re-
laxations are designated b; g, and so on, in order of their appearance as T decreases
further (see Figure 14.7). They may often be assigned to specic types of molecular
motion, such as side-group motions or cooperative motion of several main-chain
units, and often show an Arrhenius T dependence. Activation of side-group mo-
tions typically requires more energy than main-chain motions. Thus the main-
chain relaxation in bisphenol-A polycarbonate (PC) occurs at about 80
C, which
is about 230 K below T
g
(150
C), whereas relaxation of the aromatic side groups in

aPS is observed at 50
C, which is only 50 K below T

g
(100
C) [5].
Fig. 14.6. Predictions of the Zener model for the dynamic
behavior in the vicinity of a transition (E
1
2 10
9
Pa,
E
2
10
6
Pa, t 0:05 s).
14.3.2
TimeTemperature Superposition
The idea of timetemperature equivalence introduced in Section 14.3.1 is of con-
siderable practical importance because one would often like to predict the long-
term response of materials on the basis of experiments carried out on a laboratory
time scale. This is to some extent possible in polymers, for which it has been
widely veried that viscoelastic functions determined at dierent T over a xed
range of o or t, slightly adjusted to take into account the eect of T and density r
on the elastic response [through Eq. (30)], superpose if the o or t scale is multi-
plied by a shift factor, a
T
T; T
r
, where T
r
is some convenient reference tempera-
ture. A typical master curve obtained in this way is shown in Figure 14.8 for stress
relaxation data from polyisobutene, taking T
r
66:5
C. The eect is to expand

the t or o scale of the measurement carried out at T
r
, revealing the whole of the a
transition in this case.
Williams, Landel, and Ferry (WLF) observed that if T
r
is set to T
g
, the variation of
log a
T
with T T
r
is similar for a wide variety of polymers [10]. They rationalized
this in terms of the molecular response, starting with Doolittles equation [Eq. (41)]
for the viscosity, where A and B are constants. f
v
is the fractional free volume,
equivalent to the unoccupied volume divided by the total volume of the polymer
(the occupied volume includes that necessary to accommodate thermal vibra-
tions).
ln h ln A
B
f
v
41
Fig. 14.7. Dynamic behavior as a function of T of poly(methyl
methacrylate) (PMMA) tested in torsion at 10 Hz.
Equation (41) is based on the idea that the greater f
v
, the greater the molecular mo-
bility (owing to reduced crowding), and the lower h. For T > T
g
, f
v
is given by Eq.
(42), where a
f
is the coecient of thermal expansion of the fractional free volume
and f
g
is the fractional free volume associated with the glass transition.
f
v
Af
g
a
f
T T
g
42
If the T dependence of all the relaxation times is assumed to be that of h in Eq.
(41), the shift factor for the scaled viscoelastic functions is given by Eq. (43), and
hence Eq. (44) follows.
a
T

hT
hT
g
43
log a
T

B
2:303f
g
T T
g
f
g
a
f
T T
g
1
C
g
1
T T
g
C
g
2
T T
g
44
Fig. 14.8. Stress relaxation data for polyisobutene at dierent
temperatures T, as indicated and superposed onto the data for
66.5
C by shifting along the logt axis (after Ref. 7).

Equation (44) is the well-known WLF equation. Universal values of the various
physical parameters in Eq. (44) lead to C
g
1
17:44 and C
g
2
51:26 K [10]. These
are of the same order of magnitude as C
g
1
and C
g
2
obtained empirically (34 and
80 K for PMMA, for example), and indeed, timetemperature superposition has
been found to work well for a wide range of single-phase polymers, with the pro-
viso that it begins to break down for the relatively fast vibrational modes charac-
teristic of the glassy state [12]. Moreover, although superposition may work for
T gT
g
, at temperatures above about T
g
50 K the shift factors tend to show an
Arrhenius dependence rather than following the WLF equation.
14.3.3
Molecular Models for Polymer Dynamics
The starting point for molecular models for polymer dynamics based on the ideas
introduced in Section 14.2.3 is the Rouse model for an isolated chain in a viscous
medium, in which the chain is taken to behave as a sequence of m beads linked
by Gaussian springs [Figure 14.9(a)] [1316]. The chain interacts with the solvent
via the beads, and the solvent is assumed to drain freely as the chain moves.
Hence, Eq. (22) leads to Eqs. (45), where N
0
is the number of links between adja-
cent beads, z is a friction coecient per bead and r
i
is the position of the ith bead.
z
dr
i
dt

3kT
N
0
b
2
2r
i
r
ix
r
i1
0 45
Rouse solved the m 1 simultaneous equations [Eqs. (45)] by transforming them
into a set of uncoupled equations for the normal modes of motion of the chain.
Fig. 14.9. (a) The beadspring model for the dynamics of an
isolated chain in solution; (b) sketch of the second to fourth
normal modes of motion (the circles represent xed nodes and
the arrows indicate coherent motion of the sub-chains dened
by the nodes).
The moduli of a dilute solution containing n chains per unit volume may then be
expressed in terms of a discrete relaxation time spectrum, where each relaxation
time corresponds to one of the normal modes of motion [Figure 14.9(b)]. For sim-
ple shear, this leads to Eqs. (46) and (47), with t
p
given by Eq. (48) [1316].
Gt nkT
X
m
p1
e
t/tp
46
G
o nkT
X
m
p1
o
2
t
2
p
1 o
2
t
2
p
inkT
X
m
p1
ot
p
1 o
2
t
2
p
47
t
p
N
0
b
2
z 24kT sin
2
pp
2m 1
& ' !
1
; p 1; 2 . . . ; m 48
Because the length of chain corresponding to each Gaussian spring is the shortest
unit that can relax in the model, these expressions are only physically meaningful
for mg1. In this limit, Eq. (48) may be replaced by Eq. (49), where z
o
z/N
0
is a
monomeric friction coecient and N mN
0
is the total number of statistical
segments per chain.
t
p
A
N
02
m
2
b
2
z
o
6p
2
p
2
kT

N
2
b
2
z
o
6p
2
p
2
kT
49
Hence, the longest Rouse relaxation time, t
R
, is proportional to N
2
. For t > t
R
,
the motion of the chain becomes essentially diusive, and the diusion constant of
the center of gravity of the chains is given by the Einstein relation, Eq. (50).
D
R

kT
Nz
o
50
Rouse-like behavior is not in fact observed in dilute solutions, for which it is neces-
sary to take into account the inuence of the chain on the motion of the solvent,
and deviations from Gaussian statistics arising from polymersolvent interactions
[17, 18]. These factors are incorporated in the Zimm model, which predicts the dif-
fusion constant to be proportional to N
n
, for example, where n depends on the sol-
vent quality, in better agreement with experimental data [4, 14]. Indeed, although it
was rst proposed for isolated chains, the Rouse model turns out to be more ap-
propriate to polymer melts, where exible linear chain conformations are approxi-
mately Gaussian and hydrodynamic interactions are relatively unimportant [4, 14
16].
The Rouse model is nevertheless inadequate to describe the high-frequency re-
sponse associated with bond rotations and local cooperative motions, important
for the glassy state (see, for example, Ref. 4). Moreover, as the chain length in-
creases (or the concentration increases in a solution of long chains), the fact that
chains cannot cross one another leads to additional constraints on chain motion,
known as entanglement, which remain eective at T > T
g
. Figure 14.10(a) shows
the origin of these constraints schematically for an arbitrary chain in a polymer
melt. The dots correspond to the nearest neighbors of the chain, which are as-
sumed for the sake of illustration to intersect the plane of the drawing. Because
the chain cannot cross its neighbors, it cannot move very far in directions perpen-
dicular to its local trajectory. Diusion is therefore limited to snake-like motion of
the chain along its own contour, called reptation [14, 18]. A convenient way of
representing this eect in three dimensions is to assume the chain to be trapped
in a tube with a primitive path length L, as shown in Figure 14.10(b), so that only
motion within or along the tube is possible. For an undeformed Gaussian chain,
the tube is also Gaussian, with an end-to-end vector R. The primitive path may
thus be represented by N
L
statistical segments of length a, such that L N
L
a and
hR
2
i N
L
a
2
La. Because hR
2
i must also equal Nb
2
, Eq. (51) follows.
L Nb
2
/a 51
The tube model forms the basis for detailed theoretical approaches to the dynamics
of an entangled polymer melt pioneered by Doi and Edwards [13, 14]. The present
discussion will be restricted to a simple description of some of its basic features.
Consider, for example, the relaxation behavior of a chain subjected to a step shear
strain at t 0. As shown in Figure 14.11, the applied strain results in a deforma-
tion of the tube, and hence of the chain trapped inside it. The rst relaxation oc-
curs within the tube at times t < t
e
, where t
e
is the Rouse relaxation time for a
chain with N
e
a/b
2
statistical segments, and hence a mean square end-to-end
distance equal to a
2
. At t > t
e
, the constraints due to the tube begin to dominate
and the only way the stress can relax further relax is for the chain to escape
the deformed tube and re-establish a random (unperturbed) conformation. As
sketched in Figure 14.11, it achieves this through Brownian motion backward and
Fig. 14.10. (a) Schematic representation of entanglement constraints; (b) the tube model.
forward along the tube. The time necessary for the chain to diuse a distance L
and hence relax fully is t
D
L
2
/D
R
, where D
R
is given by Eq. (50). Hence, Eq.
(52) is obtained from Eq. (51).
t
D

N
3
b
4
z
o
a
2
kT

6p
2
N
3
N
3
e
t
e
52
Because t
D
, which is known as the reptation time, is signicantly longer than
t
e
for large N, in Figure 14.11 there is an intermediate regime of roughly time-
independent behavior, which is identied with the rubbery plateau. Thus, entan-
glement may be considered to play an equivalent role in this regime to the chemi-
cal crosslinks in an elastomer. The greater N, that is, the higher M, the greater the
extent of the rubbery plateau (compare Figure 14.1).
By analogy with an elastomer [Eq. (30)], the small strain rubbery plateau modu-
lus may be set equal to G
e
n
e
kT, where n
e
is the entanglement density, as-
sumed to play an equivalent role to n
x
in an elastomer. G
e
may therefore be
expressed in terms of an entanglement molar mass, M
e
, according to Eq. (53),
where N
A
is Avogadros number.
G
e

rN
A
kT
M
e
53
In terms of the tube model, M
e
is interpreted as the mass that corresponds to N
e
statistical segments. Values of n
e
and M
e
deduced from G
e
are found to vary widely
Fig. 14.11. Relaxation according to the tube model (small
strain limit): (a) Rouse relaxation; (b) rubbery plateau; (c) to
(d) reptation.
according to chemical structure; n
e
A4 10
25
m
3
in aPS, which has relatively
bulky chains, but is nearly an order of magnitude higher in PC, which has com-
pact, relatively rigid chains [19].
The network and tube models both imply entanglement to be ineective for
M < 2M
e
, so that M
c
, the critical mass introduced in Section 14.1.1, may be taken
to equal 2M
e
. As well as dening the threshold of rubber-like behavior above T
g
,
M
c
marks the transition from a regime in which the melt viscosity h mM (Rouse
dynamics), to a regime in which h mM
3:4
, characteristic of an entangled melt. The
original theory of Doi and Edwards predicts h mM
3
, but better agreement with ex-
periment has since been obtained by incorporating the eects of primitive path
uctuations and constraint release (if all the chains reptate simultaneously, the
constraints in Figure 14.10(a) cannot be considered strictly permanent for times
of the order of t
D
) [4, 5, 14]. Even so, in the limit of very long monodisperse
chains, for which the tube eectively remains xed, or free chains trapped in a
crosslinked network, the M
3
dependence is recovered. A strong dependence of the
viscosity on M is a general feature of entangled polymers and is of great practical
importance, because the choice of M in applications is often dictated by the need to
reach a compromise between fracture resistance, which tends to improve with M
(see Section 14.4.4) and melt processing, which is facilitated by low viscosities.
14.3.4
Nonlinear Viscoelasticity
Although it is a powerful means of investigating molecular structure and of basic
characterization, and provides a general indication of the inuence of M on ow
behavior, the restrictions imposed by linear viscoelasticity make it inapplicable to
a wide variety of practical problems. Nonlinearity is often associated with the phe-
nomenon of shear thinning, that is, a reduction of the viscosity with shear rate in
steady ow, characteristic of many polymer melts at intermediate shear rates [15].
This contrasts with the Newtonian behavior implied by the Boltzman superposi-
tion principle for steady ow [Eq. (54), in a liquid, Gs must vanish as s !y].
st
t
y
Gt u_ gg du _ gg
y
0
Gs ds _ ggh 54
Newtonian regimes are nevertheless widely observed in polymer melts in the high
and low shear rate limits, where the viscosities are designated by h
y
and h
o
respec-
tively. This is reected by the empirical expressions widely used in engineering
practice to describe the response to steady shear ow, an example being the Cross
model [Eq. (55)], which reduces to the well known power law of Eq. (56) when
h
y
gh gh
o
, with n 1/m 1 between 10 and 20 for most polymer melts.
h
o
h
h h
y
K_ gg
m
55
s
s
o
_ gg
_ gg
o

1/n
56
However, these simple empirical expressions are far from universal, and fail to ac-
count for eects specic to nonlinear behavior, such as the appearance of nite
rst and second normal stress dierences s
xx
s
yy
N
1
_ gg and s
yy
s
zz
N
2
_ gg
in steady shear ow. (For a linear viscoelastic material in shear, s
xx
; s
yy
and s
zz
are
equal to the applied pressure, usually atmospheric pressure.) These may be linked
to the development of molecular anisotropy in polymer melts subject to ow, and
are responsible for the Weissenberg eect, which refers to the tendency for a non-
linear viscoelastic uid to climb a rotating rod inserted into it, as well as practi-
cally important phenomena such as die swell [20].
There has been considerable eort to develop phenomenological models for non-
linear viscoelasticity that provide a comprehensive description of such phenomena
by extending the formalism of linear viscoelasticity to include situations where the
viscoelastic functions can no longer be considered independent of stress or strain
[21]. These are exemplied by the K-BKZ (Kaye-Bernstein, Kearsley, and Zapas)
formalism, which includes a damping function in order to account for the accel-
eration of the relaxation rate at large deformations. The popularity of the K-BLZ
approach is partly linked to the fact that the DoiEdwards tube model, with the
so-called independent alignment approximation, leads to expressions of the
same form when generalized to large deformations, providing a molecular basis
for its interpretation (in terms of the tube model, a large deformation will signi-
cantly increase L, giving rise to a supplementary relaxation process called chain
retraction on a time scale t
R
, during which L returns to its equilibrium value
[13, 14]). Phenomenological models, as well as expressions derived from the gener-
alized DoiEdwards approach are able to account for many of the observed features
of polymer melts, and, although they are cumbersome, numerical techniques are
now powerful enough to permit their incorporation into complex ow simulations
of direct relevance to industrial practice.
14.4
Yield and Fracture
14.4.1
Yield in Polymers
The stresses and strains of practical importance for polymers at T < T
g
or T
m
are
often relatively large, and, unlike the small strains referred to in the preliminary
discussion of the glassy state in Section 14.1.1, they may result in signicant plas-
tic deformation, in that the associated changes in specimen morphology are not
recovered after stress release over laboratory time scales. A plastically deformed
polymer with suciently high M is nevertheless able to return to its initial shape
when heated above T
g
or T
m
, so that such deformation cannot strictly be consid-
ered irreversible.
As the extent of plastic deformation increases with the overall deformation, pro-
nounced softening occurs, even when adiabatic heating eects are negligible (as
will be assumed here). If fracture does not intervene, the force, f , on a specimen
tested at constant speed in tension typically reaches a local maximum at a strain of
a few percent, which is taken to correspond to a plastic yield stress, s
y
(typically
between 20 and 100 MPa in unoriented polymers). The subsequent yield drop is
at least partly geometric in origin, although many glassy polymers also show an in-
trinsic yield drop [5]. The true stress on the polymer is given by s A
1
o
lf , where
A
o
is the initial cross-sectional area of the specimen, so that Eq. (57) holds.
df
dl
A
o
1
l
ds
dl
s
l
2

57
Given that ds/dl is a decreasing function of l in the initial stages of deformation,
as shown schematically in Figure 14.12, A
1
o
f s/l > ds/dl beyond a certain
value of l, and df /dl becomes negative. The resulting instability leads to localized
necking in a tensile test, but if deformation continues beyond the yield point, the
neck is stabilized by work hardening (df /dl becomes positive again) and propa-
gates to the rest of the specimen at roughly constant f . Global work hardening
then takes place, followed by rupture.
Fig. 14.12. Schematic of (a) the intrinsic stress-deformation
curve of a polymer and (b) the force per unit area of an
undeformed specimen observed as a function of total
deformation in a tensile test.
In an amorphous glassy polymer, work hardening is considered to correspond to
stretching of the entanglement network invoked to account for the rubbery plateau
above T
g
(see Section 14.3.3). This explains the recoverability of the deformation
above T
g
(in the absence of an applied force, the network retracts to its equilibrium
conformation) and it is borne out by the observed correlation between the value of
l in the neck and the maximum extensibility of the network, l
max
AN
1/2
e
. In semi-
crystalline polymers, the evolution of the crystalline texture may also contribute to
work hardening, because the resolved shear stress on activated slip systems tends
to decrease as deformation proceeds at constant stress, as will be discussed further
(see Section 14.4.3).
The large strain response in the glassy or semicrystalline state is that of a non-
linear viscoelastic solid. However, both engineering and theoretical approaches to
plasticity in polymers have largely developed as an independent discipline, in
which s
y
plays a central role, in spite of its somewhat arbitrary denition (indeed
it is not always possible to associate s
y
with a maximum in the forcedeformation
curve [5]). This is because in practice the yield point, rather than the ultimate
strength, is usually considered to be the failure criterion for ductile materials.
For yield to occur at all, the global stress state must contain a deviatory compo-
nent, so that pure hydrostatic stress states do not result in plasticity in a uniform
specimen. Indeed, in many types of material, including metals, yield is usually
well described by the Von Mises criterion, in which it is considered to be inde-
pendent of the hydrostatic pressure, p s
xx
s
yy
s
zz
/3. With an appropriate
frame of reference, any multiaxial stress state may be expressed as Eq. (58), where
s
1
; s
2
, and s
3
are the principal stresses (compare Section 14.2.1).
s
s
1
0 0
0 s
2
0
0 0 s
3
2
6
4
3
7
5 58
The von Mises criterion is then Eq. (59).
s
1
s
2
2
s
2
s
3
2
s
3
s
1
2
b2s
2
y
59
It may be veried that s
y
is equal to the tensile yield stress by setting any two of the
principle stresses to zero. For comparison, in pure shear, s
1
s
2
and s
3
0, and
the yield stress is t
y
s
y
/
3
p
. Moreover, it is easily seen that Eq. (59) is indepen-
dent of p. In fact, most polymers do show a pressure-dependent yield stress, an ob-
servation that is attributed to their relative compressibility, so that a negative value
of p signicantly reduces the space available for the molecules and hence reduces
their mobility. However, this can usually be accounted for by replacing Eq. (59)
with Eq. (60), where S and m are materials constants [5].
s
1
s
2
2
s
2
s
3
2
s
3
s
1
2
S mp 60
14.4.2
Models for Yield
The yield stress in disordered solids is strongly dependent on T and the deforma-
tion rate, and eorts have consequently been made to describe it in terms of a
ReeEyring activated rate process, in which a rheological element jumps from
place to place by overcoming local energy barriers [5, 22]. For an activation energy
Q, and an attempt frequency n
0
, the jump rate n n
0
expQ/kT. In the absence
of an applied stress, the jumps are in arbitrary directions, and there is no net de-
formation. However, an applied stress, s, alters the eective energy barrier height
for forward () and backward () jumps with respect to the stress axis, so that Eqs.
(61) apply, where x is the displacement associated with each jump and A is the ef-
fective area of the rheological element.
n

n
o
2
exp
Q sAx
kT

n
2
exp
sAx
kT

n

n
2
exp
sAx
kT

61
The strain rate in the stress direction is proportional to the net jump rate n
,
leading to Eq. (62), where V xA typically corresponds to a few repeat units and is
interpreted as an activation volume.
_ ee m
v
2
sinh
sV
kT

A_ ee
O
exp
Q
kT

exp
sV
kT

62
s is then taken to equal s
y
when Eq. (62) is satised for a given strain rate _ ee,
which implies s
y
mlog _ ee. This simple approach, which may easily be modied
to include a pressure-dependent contribution to the activation energy, is often re-
markably successful in predicting the strain rate dependence of s
y
, as shown in
Figure 14.13(a) for PC. However, as shown in Figure 14.13(b), the agreement
is more limited in polymers such as poly(vinyl chloride) (PVC). Because the Ree
Eyring model includes no assumptions regarding the nature of the rheological ele-
ment, changes in the slope of s
y
versus log _ ee, such as those in Figure 14.13(b),
have been attributed to secondary relaxations in the corresponding range of T and
_ ee. As pointed out in Section 14.3.1, the main secondary relaxation in PC occurs at
80
C, but in PVC it is at about 50
C. This suggests that a complete description of

yield may need to involve multiple activated rate processes [23].
Among the better-known eorts to provide a more microscopic description of
yield within the general ReeEyring framework is the approach of Argon, based
on metallurgical models, in which the energy barrier is associated with the elastic
displacements necessary to accommodate the elementary shear processes [24].
Another well known, but somewhat dierent, approach is that of Robertson, who
postulated that yield takes place when the average polymer conformation is equiv-
alent to that at the glass transition [25]. He adopted a simplied model for a poly-
mer chain such that skeletal bonds adopt either a high- or a low-energy state with
an energy dierence DE. At equilibrium, the proportion of bonds in the high-
energy state is given by the Boltzmann factor, so that for a polymer below its T
g
.
Eq. (63) holds, assuming the conformations at T
g
to be substantially frozen in on
vitrication.
w
expDE=kT
g
1 expDE/kT
g
63
Fig. 14.13. s
y
/T versu log_ ee in (a) polycarbonate; (b) poly(vinyl chloride) (after Ref. 23).
The value of w in the presence of an applied stress, w
def
, is estimated by assuming
the stress to modify the energy barrier to DE sv cos a, where a is the local orien-
tation of the bond with respect to the stress axis and v is the volume swept out dur-
ing the transition from the low to high energy state. From the expression for w
def
,
obtained by averaging the eective energy barrier over all possible orientations, a
stress-dependent structure temperature, Y, may be dened through Eq. (64).
w
def

expDE/kY
1 expDE/kY
64
The WLF equation [Eq. (44)] may be used to calculate the viscosity as in Eq. (65),
where h
g
is viscosity at T
g
.
hy; T h
g
exp 2:303
C
g
1
C
g
2
Y T
g
C
g
2
Y
T
C
g
1
" # !
65
The strain rate is then given by Eq. (66).
_ ee
s
hy; T
66
Robinsons model has met with some success in regimes of T close to T
g
where
the role of intramolecular barriers is relatively important. However, for T well
below T
g
, intermolecular barriers are expected to dominate, so that phenome-
nological or semi-phenomenological approaches of the ReeEyring type are ar-
guably more appropriate to the observed T dependence, as borne out by Figure
14.13.
14.4.3
Semicrystalline Polymers
In amorphous polymers, plasticity is associated with deformation at T < T
g
.
In semicrystalline polymers, however, there is a further regime T
g
< T < T
m
,
in which the amorphous regions are in the rubbery state and hence no longer con-
tribute directly to yield. Plasticity is therefore dominated by the intermolecular bar-
riers that oppose chain slip in the crystalline regions. This is of considerable prac-
tical importance, given that commodity semicrystalline polymers such as PE and
isotactic polypropylene (iPP) are typically employed at T > T
g
. Considerable eort
has therefore been made to describe yield in semicrystalline polymers in terms of
crystal plasticity theory. In isotropic polycrystalline materials, ve independent
crystal slip systems are generally necessary for global plasticity, but this require-
ment is relaxed in polymers owing to the presence of the amorphous phase. In-
deed, yield in polymers is thought to involve a relatively limited number of slip sys-
tems with slip planes parallel to the chain axes (slip in planes perpendicular to the
chain axes would require rupture of covalent bonds).
The classical approach of Young to yield in lamellar semicrystalline polymers is
based on the nucleation of dislocations by thermal uctuations [26]. The activation
energy is calculated from the shear strain energy for a screw dislocation of width u
[Eq. (67), where b is the magnitude of the Burgers vector (usually the repeat dis-
tance along the chain), r
o
is the size of the dislocation core (about 4b according to
computer simulations), G is the shear modulus, l
c
is the length of the dislocation
in the direction of the Burgers vector (taken to equal the lamellar thickness) and s
is the shear stress].
DU
Gb
2
l
c
2p
ln
u
r
o

sbul 67
The activation energy for the formation of the dislocation, DU
, corresponds to the
maximum of DUu, which leads to Eqs. (68) and (69).
u

Gb
2ps
68
DU

Gb
2
l
c
2p
ln
u
r
o

1

69
Given DU
, one can estimate the critical stress for the formation of a dislocation
s
c
. Usually, it is assumed that DU
A50kT, which gives a s

c
comparable with ex-
perimentally determined values of the shear yield stress, t
y
. The main objection to
the dislocation model is that the predicted temperature dependence of the yield
stress is much weaker than that observed experimentally, particularly at higher T,
and more recent eorts to describe yield have been based on thermally activated
helical motions of polymer chains within their crystals, believed to be associated
with the a relaxation, but which may occur below T
m
[27].
In an isotropic polycrystalline polymer whose microstructure consists of stacked
lamellae arranged in the form of spherolites, the slip systems activated depend on
the local orientation of the lamellae with respect to the applied stress and, as defor-
mation proceeds, these orientations are modied. To calculate the evolution of the
crystalline texture, one can consider the polymer to behave as a crystalline aggre-
gate. Although the entropic contribution of chain orientation in the amorphous re-
gions may also need to be considered, the major contribution to work hardening in
tension is rotation of the slip planes toward the tensile axis, so that the resolved
shear stress in the slip direction diminishes. This results in a ber texture in the
limit of large deformations, such that the crystallites are oriented with their c axis
(the chain axis) parallel to the stretch direction. Despite the relative success of such
models, they do not explicitly address the micro-mechanisms involved in the trans-
formation of the spherulitic texture into a ber texture. One possibility is that the
repeated shearing of lamellar fragments renders them thermodynamically unsta-
ble because of their small size. Models for the development of crystalline textures
during drawing, based on this idea, thus explain the establishment of a new lamel-
lar long period in highly deformed regions, which depends only on the deforma-
tion T and not on the initial lamellar thickness [27].
14.4.4
Crazing and Fracture
Rather than undergo homogeneous (non-cavitational) ductile necking, glassy
amorphous polymers often show brittle behavior in tension, in that they fail
abruptly prior to yielding and hence at a relatively low strain. In uncrosslinked or
lightly crosslinked polymers, this phenomenon is usually associated with crazing
[28, 29]. As shown in Figure 14.14, crazes are crack-like defects spanned by highly
drawn brils with lateral spacings of the order of 10 nm and a constant draw ratio,
close to l
max
, which implies that bril extension takes place by ductile drawing at
the crazebulk interface. The presence of the brils means that crazes are capable
of bearing loads normal to their faces. Indeed, the stress normal to the faces of an
isolated growing craze, s
c
(the bril drawing stress), is approximately equal to the
global applied stress along most of the craze length. Hence, isotropic bulk samples
deformed in uniaxial tension may contain a high density of crazes whose planes
are parallel and perpendicular to the tensile axis. Even so, plastic deformation asso-
ciated with crazing remains highly localized and contributes relatively little to the
overall deformation. Given that crazes may act as preferential sites for crack initia-
Fig. 14.14. Craze microstructure in a thin lm of amorphous
polycarbonate deformed in tension at 100
C.
tion, this accounts for their association with brittle macroscopic behavior as de-
ned above. Crazing and ductile necking may nevertheless co-exist, depending on
the relative stability of the crazes with respect to crack initiation.
Empirical criteria for the formation of crazes in multiaxial stress states, analo-
gous to the von Mises criterion for yield [Eq. (59)], are based on the observation
that crazing is absent in both compression and simple shear, which is reasonable
given that one would expect cavitation to be favored by large values of p. A critical
strain to craze, e
c
A B/p, is generally found to provide a reasonable description
of craze nucleation, so that in terms of the principal stresses the criterion is given
by Eq. (70), where A; B; C, and D are constants.
s
1
ns
2
ns
3
C
D
s
1
s
2
s
3
70
Given that highly triaxial stress states are unfavorable to yielding [compare Eq.
(59)], crazing tends to dominate in highly constrained geometries, such as notch
tips, or in the vicinity of local stress concentrations in bulk specimens. This is not
inconsistent with brillation by ductile drawing, because the void formation associ-
ated with crazing releases constraints on plastic deformation at the microscopic
level.
The very small size of craze brils means that their surface energy is expected to
play an important role in craze formation. Hence, although the large hydrostatic
stress gradients associated with closely separated voids favor bril drawing, they
are oset by stress gradients arising from the surface tension at the void tips, G.
In kinetic models for bril formation, the brils are therefore argued to adopt the
characteristic spacing D
o
that maximizes the overall stress gradient and hence the
rate of bril extension. It has been shown on this basis that the craze stress
s
c
mG
1/2
, for a xed deformation rate [28].
There is evidence that polymers with high entanglement densities, n
e
, craze less
readily than polymers with low n
e
. One possible explanation for this is in terms of
the creation of surface associated with brillation. For a xed entanglement net-
work, the creation of free surface must involve chain scission, as shown in Figure
14.15. The higher n
e
, the more entanglements are lost during brillation, the
higher the energy cost in creating the brils and hence the higher s
c
. This may ac-
count for the ductility of amorphous, high n
e
engineering thermoplastics such as
PC, in which crazing tends to be suppressed in favor of homogeneous deformation
(s
y
is not directly dependent on n
e
). It follows that highly crosslinked polymers, in
which the inuence of n
e
and n
x
may be considered additive, do not show crazing,
although their ductility, and hence their toughness, is limited by the limit extensi-
bility of the network [28]. The competition between homogeneous deformation
and crazing is also likely to be strongly inuenced by secondary relaxations, so
that the relatively low b relaxation temperature of PC (see Section 14.4.2) may also
contribute to its ductility. Indeed, shifting the secondary relaxation to higher T by
chemical modication at constant n
e
has been found to lead to embrittlement in
PC [30]. Similarly, polymers that craze easily, such as aPS and PMMA, typically
have relatively high secondary relaxation temperatures.
The macroscopic property of immediate practical concern is often not so much
craze formation as fracture resistance. In a cracked specimen, stress is concen-
trated at the crack tip, and the local stress state depends on the crack length. For
small global deformations, it may be expressed in terms of a stress intensity factor,
K, given by Eq. (71), where a is the crack length and F is a dimensionless function
of the specimen geometry [31, 32].
K F

pa
p
s 71
In many fracture mechanics-based approaches, crack advance is taken to occur
when K reaches some critical value K
c
(equivalent energy-based criteria are also
widely used). K
c
may then be measured using a pre-cracked specimen, in which a
and hence K are well dened. In some cases (PMMA, for example) crack advance
is observed to proceed via breakdown of a single craze at the crack tip. By modeling
a craze as an orthotropic linear elastic body it has been shown that K
c
is given by
Eq. (72), where n is Poissons ratio, a is related to the craze anisotropy, s
c
is the
draw stress normal to the craze-bulk interface, v
f
is the bril volume fraction in
the craze, and s
f
is the stress to break a craze bril [33].
K
c
Aa
1/4
1 v
f
1 n
2
E
s
c

1/2
pD
o
p
s
f
72
This approach incorporates the stress-concentrating eect of cross-tie brils, widely
observed in crazes in glassy polymers (compare Figure 14.14). In the absence of
any stress-concentrating eect, that is, for a ! 0, a time-independent bril failure
criterion s
f
implies crack advance can never occur, because the stress in a given
bril can never exceed s
c
. This result has been conrmed by more detailed micro-
mechanical modeling, and is important in that it provides a direct link between the
Fig. 14.15. Schematic of craze widening at the crazebulk
interface, illustrating the geometrically necessary entanglement
loss.
macroscopic fracture behavior and microscopic quantities, which can be estimated
by direct observation of craze microstructures. Although Eq. (72) is not strictly ap-
plicable to the more usual case of multiple crazing, or mixed crazing and shear at
the crack tip, the guiding principle remains valid and serves to underline the
importance of entanglement, not only for craze formation but also for ultimate
failure.
Bulk semicrystalline polymers deformed in tension also show considerable lo-
calized micro-necking at T between T
g
and T
m
, in the form of either crazes or
craze-like deformation zones, such as that shown in Figure 14.16. As with amor-
phous polymers, these are thought to have a strong inuence on the ultimate fail-
ure properties. Although the details of the lamellar structure may vary widely, qual-
itative models for micro-necking in melt-crystallized semicrystalline polymers
above T
g
show many features in common. Deformation is usually assumed to ini-
tiate in interlamellar amorphous regions, which stretch and cavitate, so that cavity
sizes are commensurate with the lamellar separation. The intervening material
is then drawn down to form the mature brillar structure. Again, a high degree of
entanglement and strong anchoring of the chains by the lamellae (that is, high M)
are expected to promote toughness in semicrystalline polymers [5, 34, 35].
To improve the fracture resistance of polymers that craze readily, but which may
have other advantages, such as cheapness in the case of aPS, a common strategy is
to increase the density and extent of localized damage (crazing, for example) by
creating local stress concentrations [36]. The greater the extent of local damage,
the greater the energy dissipation during crack advance, and hence the greater the
crack resistance. The presence of rubber inclusions in a glassy or semicrystalline
matrix results in considerable local mismatch in stiness. This increases their
stress-concentrating eect and provides local concentrations in the von Mises
stress or the hydrostatic stress, which will favor shear and craze yielding respec-
tively. Cavitation of the modier particles is also thought to be important in tough-
Fig. 14.16. Fibrillar deformation zone at a crack tip in a bulk
specimen of semicrystalline high-density polyethylene deformed
at room temperature (thin section stained with RuO
4
).
ening and may in some cases change the local stress state suciently to promote a
change in mechanism (for example, shear to craze transitions in glassy polymers).
14.5
Conclusion
The aim of this contribution has been to link the basic macroscopic phenomena
associated with polymers with the unique features of their structure, the most ob-
vious being the presence of long, exible molecular chains. The important role of
the conformational entropy of exible chains, not only for rubber elasticity but for
polymer dynamics in general, has been demonstrated. Moreover, the concept of an
entanglement network, which underpins much of the theory of polymer dynamics
in the melt, has also been shown to have important repercussions for the high
strain behavior of solid polymers, namely plastic deformation, crazing, and frac-
ture.
Notation
A Helmholtz free energy [J]
A
o
cross-sectional area of a tensile specimen [m
2
]
a Helmholtz free energy per unit volume [J m
3
]
a statistical segment length of the primitive path (tube model) [m]
a
T
WLF shift factor
b equivalent bond length (Kuhn length) [m]
b magnitude of Burgers vector [m]
C
l
specic heat at xed specimen length [J kg
1
]
C
g
1
WLF constant
C
g
2
WLF constant [K]
C
y
characteristic ratio
D tensile compliance [Pa
1
]
D
o
craze bril spacing [m]
D
R
Rouse self-diusion coecient [m
2
s
1
]
E Youngs (tensile) modulus [Pa]
E
0
tensile storage modulus [Pa]
E
00
tensile loss modulus [Pa]
E
complex tensile modulus [Pa]

E
ijkl
stiness tensor [Pa]
f force [N]
f
g
fractional free volume at T
g
(dimensionless)
f
v
fractional free volume (dimensionless)
G shear modulus [Pa]
G
0
shear storage modulus [Pa]
G
00
shear loss modulus [Pa]
G
complex shear modulus [Pa]

G
e
plateau modulus [Pa]
J shear compliance [Pa
1
]
K bulk modulus [Pa]
K stress intensity factor [Pa m
1/2
]
K
c
critical stress intensity for crack advance [Pa m
1/2
]
k Boltzmann constant 1:38066 10
23
J K
1
L tube contour length (tube model) [m]
l length [m]
l
c
lamellar thickness [m]
l
o
mean length of skeletal bonds in a real macromolecular chain [m]
M molar mass [g mol
1
]
M
b
molar mass per statistical segment [g mol
1
]
M
c
critical molar mass [g mol
1
]
M
e
entanglement molar mass [kg mol
1
]
m number of beads in Rouse model (dimensionless)
N number of statistical segments in a freely jointed chain (dimensionless)
N
0
number of statistical segments between beads (Rouse model) (dimen-
sionless)
N
l
number of skeletal bonds in a real macromolecular chain (dimension-
less)
N
1
rst normal stress dierence (dimensionless)
N
A
Avogadros number 6:022 10
23
N
e
number of statistical segments in a chain of molar mass M
e
(dimension-
less)
N
L
number of statistical segments in the primitive path (tube model) (di-
mensionless)
n number of chains per unit volume [m
3
]
n
e
entanglement density [m
3
]
n
x
number of crosslinks per unit volume [m
3
]
PR; N probability distribution of R in a chain with N links
p hydrostatic pressure [Pa]
Q activation energy [J]
Q heat transfer (into a thermodynamic system) [J]
R end-to-end vector of a linear chain [m]
R
max
maximum end-to-end distance of a real macromolecule
r
n
vector corresponding to the nth bond in a chain [m]
r
o
dislocation core radius [m]
S entropy [J K
1
]
T temperature [K,

C]
T
g
glass transition temperature [K,

C]
T
m
melting point [K,

C]
U internal energy [J]
u width of screw dislocation [m]
Notation 753
u
critical screw dislocation width [m]

V activation volume (Eyring model) [m
3
]
v
f
craze bril volume fraction (dimensionless)
W work (done on a thermodynamic system) [J]
Greek
a craze anisotropy factor
a
f
coecient of thermal expansion of fractional free volume [K
1
]
G surface tension at craze void tips [N m
1
]
g shear strain
DE energy dierence (Robertson model) [J]
DU shear strain energy of screw dislocation [J]
DU
activation energy for screw dislocation [J]

d phase angle
d
c
critical crack opening displacement [m]
e
c
strain to craze
e
ij
engineering strain
e
ij
components of the engineering strain
z friction coecient [N s m
1
]
z
o
monomeric friction coecient [N s m
1
]
h viscosity [N s]
h
o
zero shear viscosity [N s]
h
g
viscosity at T
g
[N s]
h
y
limiting high shear rate viscosity [N s]
Y structure temperature (Robertson model) [K]
l deformation ratio (dimensionless)
m pressure coecient (stress-dependent von Mises criterion) (dimension-
less)
n jump rate (Eyring model) (dimensionless)
n Poissons ratio (dimensionless)
n scaling exponent (Zimm model) (dimensionless)
n
0
attempt frequency (Eyring model) (dimensionless)
r density [kg m
3
]
s
c
craze bril draw stress [Pa]
s
f
stress to break a craze bril [Pa]
s
ij
components of the engineering stress [Pa]
s
ij
engineering stress [Pa]
s
y
tensile yield stress [Pa]
t relaxation time [s]
t
c
critical stress for the formation of a screw dislocation [Pa]
t
D
reptation time [s]
t
R
Rouse relaxation time [s]
t
y
shear yield stress [Pa]
WR number of conformations at xed R (dimensionless)
o angular frequency (dimensionless)
w proportion of high energy states (Robertson model)
Acronyms
aPS atactic polystyrene
iPP isotactic polypropylene
K-BKZ Kaye-BernsteinKearsleyZapas
PC bisphenol A polycarbonate
PE polyethylene
PVC poly(vinyl chloride)
WLF WilliamsLandelFerry
References
1 P. J. Flory, Statistical Mechanics of
Chain Molecules, John Wiley, New
York, 1969.
2 W. L. Mattice, U. W. Suter,
Conformational Theory of Long Chain
Molecules, John Wiley, New York, 1994.
3 L. J. Fetters, D. J. Lohse, W. W.
Graessley, J. Polym. Sci., Part B:
Polym. Phys., 1999, 37, 1023.
4 M. Rubenstein, R. H. Colby, Polymer
Physics, Oxford University Press,
Oxford, 2003.
5 I. M. Ward, D. W. Hadley, An Intro-
duction to the Mechanical Properties of
Solid Polymers, John Wiley, New York,
1993.
6 U. W. Gedde, Polymer Physics,
Chapman and Hall, London, 1995.
7 L. R. G. Treolar, The Physics of
Rubber Elasticity, Clarendon Press,
Oxford, 1958.
8 J. E. Mark, B. Erman, Rubber-Like
Elasticity, a Molecular Primer, John
9 B. Erman, J. E. Mark, Structures and
Properties of Rubberlike Networks,
Oxford University Press, Oxford, 1997.
10 J. D. Ferry, Viscoelastic Properties of
Polymers, 3rd ed., John Wiley, New
York, 1980.
11 N. W. Tschoegl, The Phenomenological
Theory of Linear Viscoelastic Behaviour,
12 K. L. Ngai, D. J. Plazek, in Physical
Properties of Polymers Handbook (J. E.
Mark, editor) AIP Press, Woodbury,
NY, 1996.
13 M. Doi, Introduction to Polymer
Physics, Oxford University Press,
Oxford, 1996.
14 M. Doi, S. F. Edwards, The Theory of
Polymer Dynamics, Oxford University
15 R. G. Larsen, The Structure and
Rheology of Complex Fluids, Oxford
University Press, New York, 1998.
16 R. B. Bird, C. F. Curtiss, R. C.
Armstrong, O. Hassager, Dynamics
of Polymeric Liquids, Vol. 2, Kinetic
Theory, 2nd ed., John Wiley, New York,
1987.
17 J. des Cloizeaux, G. Jannink,
Polymers in Solution: Their Modelling
and Structure, Clarendon Press,
Oxford, 1990.
18 P. G. DeGennes, Scaling in Polymer
Physics, Cornell University Press,
Ithaca, 1979.
19 L. J. Fetters, D. J. Lohse, R. H.
Colby, in Physical Properties of Poly-
mers Handbook (J. E. Mark, editor)
AIP Press, Woodbury, NY, 1996.
20 H. A. Barnes, J. F. Hutton, K.
Walters, An Introduction to Rheology,
Elsevier, Amsterdam, 1989.
21 R. G. Larson, Constitutive Equations
References 755
for Polymer Melts and Solutions,
Butterworths, Boston, MA, 1988.
22 B. Crist, in Materials Science and
Technology, Vol. 12 (E. L. Thomas,
editor), VCH, New York, 1993.
23 J. C. Bauwens, C. Bauwens-Crowet,
G. Home` s, J. Polym. Sci. A2, 1969, 7,
735.
24 A. S. Argon, Phil. Mag., 1973, 28, 839.
25 R. E. Robertson, J. Chem. Phys., 1966,
44, 3950.
26 R. J. Young, Introduction to Poly-
mers, Chapman and Hall, London,
1981.
27 A. Galeski, Prog. Polym. Sci., 2003, 28,
1643.
28 E. J. Kramer, Adv. Polym. Sci., 1983,
52, 1.
29 E. J. Kramer, L. L. Berger, Adv.
Polym. Sci., 1990, 91/92, 1.
30 L. P. Chen, A. F. Yee, E. J. Moskala,
31 J. G. Williams, Fracture Mechanics of
Polymers, Ellis Horwood, Chichister,
1984.
32 H.-H. Kausch, Polymer Fracture,
33 H. R. Brown, Macromolecules, 1991,
24, 2752.
34 C. J. G. Plummer, H.-H. Kausch, J.
Macromol. Sci. Phys., 1996, B35, 637.
35 J. J. Benkoski, P. Flores, E. J.
Kramer, Macromolecules, 2003, 36,
3289.
36 C. B. Bucknall, Toughened Plastics,
Applied Science, London, 1977.
15
Polymer Degradation and Stabilization
1
Tuan Quoc Nguyen
15.1
Introduction
Most synthetic plastics and natural polymers are principally constituted of the ele-
ments C, H, N, and O, all of which are primary components of organic molecules.
As with smaller organic molecules, these atoms are attached by relatively weak co-
valent bonds that are susceptible to chemical attack, particularly to oxidative degra-
dation. During their potential lifetime, engineering plastics are exposed to diverse
environmental factors which can act alone or in combination to adversely aect the
initial material properties. These changes generally occur over several years, but
can be accelerated or retarded in the presence of internal and external elements
temperature, and temperature variations. Environmental factors that contribute to
degradation include mechanical stresses, temperature variations, humidity, sun-
light, oxygen, atmospheric pollutants, and microbial enzymes. Depending on the
structural level at which material changes occur, it is usual to distinguish between
physical, physicochemical, and chemical degradation.
v
Physical degradation, commonly known as physical aging, results from changes
in the thermodynamic state of the system (temperature, pressure, molar volume)
during the daily use of the material. During processing, chains may be oriented
and the sample inhomogeneously cooled, resulting in internal stress. With time,
the chains have the opportunity to relax from their nonequilibrium conforma-
tions to a state of lower free energy. Partly immiscible blends, for instance, can
remain in a homogeneous metastable state for an extended period of time. The
presence of stress or heat can accelerate the phase separation process. The resul-
tant changes in orientation, free volume, internal stress, crystalline content, and
ISBN: 3-527-31014-2
757
phase transitions are known globally as physical aging. In principle, physically
aged samples do not aect chemical structure and can be rejuvenated by proper
thermal treatment.
v
Physicochemical degradation involves diusion of small to medium size mole-
cules either from the polymer (plastier or other additives) or into the polymer
(water absorption, solvent, surface-active liquids), resulting in changes in poly-
mer properties. Exudation of plastier and surface migration of additives fol-
lowed by washing are among the common problems encountered in natural
weathering. In the presence of surface-active agents, environmental stress crack-
ing can also develop. Although preserving the structural integrity of the polymer,
physicochemical degradation is in general irreversible as a result of local changes
in chemical composition, and can result in severe alterations of material prop-
erties.
v
Chemical degradation concerns irreversible changes in the chemical structure of
the polymer initiated by a number of activation agents frequently encountered in
outdoor weathering:
oxygen (causing oxidation), reactive pollutants (ozone, nitric oxides), enzymes
(causing biodegradation);
heat (causing thermal degradation);
photons (from UV or g-radiation), electrons and high energy particles (causing
photodegradation and radiative degradation);
mechanical stress (causing mechanochemical degradation).
In this review, we will focus exclusively on chemical degradation, with particular
emphasis on environmental degradation. It should be kept in mind, however, that
under practical weathering conditions, physical, physicochemical and chemical
degradation may happen simultaneously and in a synergetic way, in some cases
resulting in premature material failure.
Although the term degradation usually has a negative connotation, some poly-
mer applications require degradability as an asset or even a prerequisite as, for in-
stance, in biodegradable detergents in some biomaterials, and in the manufacture
of microelectronic circuitry. In fact, the growing importance of degradation and
stability assessment in plastic materials is largely motivated by two apparent con-
tradictary interests:
v
on one hand, there is an increased consumer demand for quality and durability
to avoid the expensive labor costs of replacing deteriorated components;
v
on the other hand, for some applications, the plastic should be able to de-
grade spontaneously and safely when disposed of, to reduce the solid waste
burden.
Obviously, this degradability-on-demand can be realized only with an adequate
understanding of the degradation and stabilization mechanisms.
758 15 Polymer Degradation and Stabilization
15.2
General Features of Polymer Degradation
Over 95 wt.% of polymers are synthesized from eight vinyl monomers, and most of
the remainder are from another couple of dozen monomers with diverse chemical
structures. Despite this relative simple chemistry, the problem of degradation and
stabilization of synthetic polymers is exceedingly complex. This complexity stems
from the structural organization of plastic materials, which occurs at dierent
levels:
v
At the molecular level, most commercial plastics are mixtures of macromole-
cules with diverse substances, which can be traces of solvent or catalyst residues,
pigments, llers, and a variety of additives.
v
The macromolecules themselves can be blends of homopolymers or copolymers.
v
As to the dierences in small organic molecules, even a simple homopolymer
presents a diversity in chain length and conguration. The presence of chain
branching, tacticity, monomer linking, or chain defects may all have important
consequences for the materials stability.
v
Molecular chains can arrange themselves into amorphous, oriented, and crystal-
line domains of dierent sizes, shapes, and distributions. This intricate morphol-
ogy is globally known as supramolecular organization.
Studying degradation requires not only identication of the diverse chemical reac-
tions which induce structural changes in the polymer, but also the interactions be-
tween the numerous chemical species initially present in the sample or formed in
the course of degradation. Interdependence of the change in material morphology
that occurs upon aging, and its inuence on the rate of degradation, should be con-
sidered additionally.
15.2.1
Degradative Reactions
From the complexity of chemical processes, and the intricate relationship between
chemical, morphological, and environmental factors which control degradation,
it is safe to state that there are as many degradation mechanisms as commercial
plastic formulations. Obviously, examining in detail all the eects mentioned for a
given polymer system requires considerable eort. Fortunately, a large group of
polymer degradation problems share a number of common features. Most degra-
dative reactions of polyolens, for instance, can be envisioned as the reverse pro-
cess of vinyl polymerization, with four steps: radical initiation, depropagation (the
reverse of propagation), chain branching under oxidative conditions (produced by
intermolecular and intramolecular hydrogen transfer followed by b-scission), and
radical termination. Except for the mode of initiation, the thermal, photolysis, and
radiolytic degradation processes are similar in many respects and can be described
by the same reaction scheme, a simplied version of which, based on polyolen
degradation but applicable to other types of polymers with a carbon backbone, is
given as Eqs. (1)(9) in Scheme 15.1 [1].
15.2.1.1 Initiation
Covalent bond scission, with formation of free radicals or charged species, is the
starting process in any type of chemical degradation. This primary event requires
energy, which can be supplied by heat (thermal degradation), UV photons (photo-
degradation), high-energy photons or particles (radiolysis), mechanical forces (me-
chanochemical degradation), or reactive chemicals (solvolysis, enzymatic degrada-
tion). Heterolytic bond scission is restricted to degradation by reactive chemicals
and by enzymes in biodegradation. For the other modes of degradation, bond scis-
sion is mainly homolytic, except in some particular situations described in Section
15.2.2. Apart from its free-radical nature, homolytic initiation is generally a com-
plex and less well-known process (radical X
v
of reaction (1)). The exact mechanisms
of initiation depend on the polymer structure, the presence of internal and external
impurities, and the degradation conditions. Also, the mode of initiation may
change during the course of reaction. Under oxidative conditions, for instance, for-
mation of hydroperoxides followed by their decomposition rapidly becomes the
prevalent mode of initiation.
15.2.1.2 Propagation
Once initiated, the alkyl macroradical can proceed through a number of possible
reaction pathways. In the absence of oxygen, some macroradicals can depolymerize
by unzipping, or they can abstract a hydrogen atom from a nearby molecule or
from another group inside the same molecule. In oxidative environment, the free
Initiation PH X
v
P
v
XH (1)
Radical conversion P
v
O
2
PO
2
v
(2)
Propagation PO
2
v
PH POOH P
v
(3)
Chain branching POOH PO
v

v
OH (4)
PO
v
PH POH P
v
(5)
HO
v
PH H
2
O P
v
(6)
PO
v
various chain-scission reactions (7)
Termination P
v
P
v
inactive products (8)
PO
2
v
PO
2
v
inactive products (9)
Scheme 15.1. General oxidative degradation mechanism for
polyolens (PH designates the polymer, P
v
a macroradical, and
X
v
a radical of unspecied nature).
radical combines readily with molecular oxygen to produce peroxy radicals, which
can subsequently abstract H atoms to re-form an alkyl radical. Radical conversion
reaction is extremely rapid and is diusion-controlled, owing to the diradical na-
ture of molecular oxygen, with k
2
@10
8
10
9
L mol
1
s
1
. Hydrogen abstraction
reactions, on the other hand, require a high activation energy and are the rate-
determining step with k
2
/k
3
> 10
6
. The activation energy for k
3
depends on the en-
thalpy of reaction DH = D
e
(PaH) D
e
(POOaH), where D
e
is the bond dissocia-
tion energy. With D
e
(POOaH) A360 kJ mol
1
, peroxide abstraction reactions
are endothermic with a rate constant decreasing rapidly with increasing CaH
bond dissociation energy, according to the sequence: tertiary CaH (D
e
= 385
kJ mol
1
) > secondary CaH (400 kJ mol
1
) > primary CaH (410 kJ mol
1
). This
behavior has been veried in the case of polyolens, for which it is found that
HDPE is more resistant to oxidative degradation than LDPE, which is itself more
resistant than isotactic polypropylene (iPP), owing to the increasing presence of
tertiary CaH bonds in the polymer [2].
15.2.1.3 Chain Branching
Hydroperoxide decomposition is the key step in polymer oxidative degradation and
has been extensively studied in a number of systems, using low MW analogs of the
polymers. Corresponding rate constants and activation energies can be found in
Ref. 2, p. 383. The fate of the hydroperoxides formed is diverse. The OaO bond en-
ergy is only approximately 170195 kJ mol
1
and is easily cleaved by heat or UV
light below 340 nm according to Eq. (10).
POaOH
D; hn<340 nm
PO
v

v
OH (10)
Cations of transition metals (Cu, Fe, Mn, Co, Ti) which may exist in the polymer as
contaminants or as catalyst residues can induce the decomposition of hydroperox-
ides and contribute to an increase in the oxidation rate at low temperature (Haber
Weiss reaction, Eqs. (11) and (12)).
POaOH M
n
PO
v

OH M
(n1)
(11)
POaOH M
n1
PO
2
v

H M
n
(12)
At high hydroperoxide concentrations, a bimolecular dissociation mechanism [Eq.
(13)] between hydrogen-bonded molecules (for instance, between adjacent peroxide
groups formed by an intramolecular abstraction reaction in PP) can also occur.
2POaOH PO
2
v
PO
v
H
2
O (13)
Apart from homolytic cleavage, the hydroperoxides can undergo a number of other
reactions such as addition to double bonds that may have been initially present in
the polymer or formed in the course of degradation [Eq. (14)] and radical-induced
decomposition [Eqs. (15) and (16)].
POaOH aHCbCHa PO
v
aHCaCHa (14)
a
v
OH
P
v
POaOH PO
v
POH (15)
HO
v
POaOH PO
2
v
H
2
O (16)
The decomposition of hydroperoxides creates more radicals than are initially
formed by initiation, resulting in an autoacceleration of the degradation process
(chain branching). Additionally, initiation by hydroperoxides is autoregenerated in
the sense that, overall, the same quantity of peroxides is recovered at the end of the
decomposition cycle.
Polyalkoxy and polyperoxy radicals formed from hydroperoxide decomposition
are unstable intermediates, owing to the presence of an unpaired electron which
weakens the dissociation energy for bonds in the b-position by some 100 kJ mol
1
.
Monomolecular b-scission is the main mechanism for a decrease in MW and ac-
counts for the variety of oxygenated products observed during oxidative degrada-
tion (see Section 15.4.4.6).
15.2.1.4 Termination
Under anaerobic conditions, the alkyl macroradicals can recombine by combina-
tion and dismutation [Eq. (17)].
P
v
P
v
PaP or PaH P(aH) (17)
In the presence of oxygen, hydroperoxy radicals are the most abundant; this is a
result of their relative low reactivity in solid polymers. Recombination of peroxy
radicals can proceed through a tetroxide intermediate, giving peroxides, polymer
alkoxy radicals, and oxygen [Eqs. (18a) and (18b)], or it can take place through a
six-membered transition state which would lead to an alcohol, singlet oxygen, and
triplet excited carbonyl, which, upon de-excitation, produces the chemilumines-
cence observed in many oxidative degradations (compare the Russell mechanism,
Section 15.3.6).
POaOP O
2
(18a)
2PO
2
v
PaOaOaOaOaP PO
v
O
2

v
OP
cage
2PO
v
O
2
(18b)
As with smaller radicals, the reactivity of a macroradical much depends on the
electron density of the atom bearing the unpaired electron. If reactivity is low,
the chance of a radical being trapped before abstraction can occur increases with
decreasing reactivity. For radicals formed by degradation, the lifetimes follow the
order P
v
< PO
v
< PO
2
v
. Free isolated PO
2
v
in polypropylene may have a half-life-
time as long as 500 s at ambient temperature. To account for this exceptional sta-
bility, and in analogy to the post-gel eect in free-radical polymerization, it may be
appropriate to include a monomolecular mechanism for radical recombination, in
addition to the classical bimolecular scheme [Eq. (19)] [3].
(P
v
; PO
v
; PO
2
v
) trapped radicals (19)
The various steps described by the general auto-oxidative degradation of Scheme
15.1 will be illustrated by the oxidative degradation of polypropylene (Section
15.4.4).
15.2.2
Some Nonradical Degradation Mechanisms
Although the majority of polymers degrade thermally or photochemically by a free-
radical process, there are a few examples where covalent bond scission occurs by
electron transfer around a six-membered transition state. Thermal degradation of
poly(ethylene terephthalate) [Eq. (20)] and side group cleavage in poly(methyl acry-
late) and poly(tert-butyl methacrylate) are some examples where b-scission of the
alkyloxygen bond takes place from a cyclic transition state without free-radical for-
mation [4].
H
O
O
O
H2C
C O
O
O
O
O
CH2
CH
H
O
O
O
O
+
(20)
Cyclization of side chains may also occur without bond scission as in polyacryloni-
trile (see Section 15.4.6.3).
15.2.3
Physical Factors
Polymer degradation is highly dependent on chemical and physical factors. The
chemical factors will be examined in relation to thermal degradation (see Section
15.4.2). This section will be focused exclusively on the inuence of physical factors
on polymer degradation.
Polymer degradation can be observed in solution, in melt or in the solid state.
Degradation in solution is principally used with model compounds for kinetics
studies, whereas degradation in melt is frequently associated with processing con-
ditions. Obviously, solid-state experiments are the most relevant to normal polymer
weathering conditions. It is also in this state that degradation kinetics reveals its
highest degree of complexity, as a result of interplay between physical, physico-
chemical, and chemical variables. From the chemical viewpoint, elementary reac-
tions should depend on temperature and not specically on the state of aggrega-
tion. Chemical reactions in the solid do dier, however, from those in the gas or
in the liquid phase by the rate of transport of reacting species, a factor which is
further exacerbated by the heterogeneity of the reacting medium. Some prevalent
factors which may aect chemical reactions in solid polymers are summarized in
Table 15.1.
15.2.3.1 Glass Transition Temperature
In contrast to small organic molecules, long-chain polymers are characterized not
only by the center of mass diusion, but also by small-scale diusion of a few
monomer units. It is generally observed that even monomolecular reactions could
happen only if these motions are unfrozen. In the wider sense, the dependence of
reaction eciency on polymer morphological structures can be described in terms
of the free volume concept, and of diusion constants [6]. These molecular charac-
teristics are themselves dependent on the thermal transitions in polymers, the
most important of which being the glass transition temperature.
The glass transition corresponds to the onset of large-scale motions of long seg-
Tab. 15.1. Factors relevant to chemical reactions in solid polymers [5].
Principal factor Inuences
Mobility of reactants translational and rotational diusion of reacting groups
as function of
v temperature and macromolecular motions
(T
g
; T
b
; T
g
; . . .)
v size and shape of reacting groups
v free volume and conformation
v interactions between reacting groups and matrix
cage eect
Heterogeneity of the system macroheterogeneity (gradients of absorbed light,
oxygen concentration, . . .)
morphological heterogeneity (crystalline and
amorphous domains, phase separation in block
copolymers and blends)
microheterogeneity (distribution of reactive sites, free
volume)
Change in matrix structure during
reaction
selective depletion of reactive sites
crosslinking, chain scission, change in absorbance
change in crystallinity
Factors other than mass transfer excited energy transfer and migration
electron transfer
transfer of active sites due to chain reaction
ments of the macromolecules (1020 monomer units). These liquidlike motions
require more free volume, resulting in a larger volumic thermal expansion coe-
cient above the glass transition temperature (T
g
). Below T
g
, intra- and intermolec-
ular rearrangements are strongly hindered. This restricted mobility also limits the
diusion of oxygen, which is a controlling factor in oxidative degradation. Reac-
tions which require a notable change in activation volume should depend much
on the T
g
. This is the case for the Norrish II process, in which the transition state
involves a six-membered ring conformation (Section 15.5.5.2). In the photolysis
of vinyl ketone polymers and ethylenecarbon monoxide copolymers, it was ob-
served that the quantum yield in solid lm above the T
g
was identical to that in
solution, but decreased with temperature below T
g
, to become negligible below
the b-transition temperature. Reactions which involve free radicals generally re-
quire little change in activation volume and should proceed equally well below or
above T
g
, as is the case for the photo-Fries rearrangement (Section 15.5.5.3) [7].
Chain mobility has important implications for bimolecular reaction eciency.
Bimolecular reactions depend on (i) the frequency of encounter and (ii) the con-
centrations of the reactive species. Upon bond cleavage, macroradicals are formed
in pairs and can initiate degradative reactions only if they are suciently exible to
move apart. If the macroradicals are held rigid, as in thermosets or below the T
g
,
they may recombine by the cage eect without any detectable molecular change.
Mass transfer limitations are a function of the diusion coecient for each
species. Two situations can be encountered [6]:
v
At least one reactant is a small molecule (or radical). Diusion of small species,
such as oxygen or methyl radicals, in solid glassy polymer can be much more
rapid than predicted from the bulk viscosity of the medium. The internal viscos-
ity of solid polymers can be very low and bimolecular reactions in the solid state,
even below the T
g
, can be almost as ecient as in solution.
v
Both reactants are polymeric species. In this case, the eective encounter rate
is highly limited by mass transfer and shows a marked increase above the T
g
. Be-
low the T
g
, all the large-scale motions are suppressed although motion of short
segments or of side groups of the main polymer may persist and have an inu-
ence on the rate of degradation. It is observed, for instance, that recombination
of macroradicals in PMMA, PS, and PVC can occur well below the T
g
. A valency
migration mechanism [Eq. (21)], in which the unpaired electron is transferred
between neighboring polymers until another macroradical is encountered, has
been proposed [6].
a
v
CHa aCH
2
a aCH
2
a a
v
CHa (21)
The rate constant for this radical relay transfer reaction has the same activa-
tion energy as that of the b-relaxation in the corresponding polymer. This result
again suggests that the kinetics of macroradical reactions in solid polymers is
sensitive to small-scale molecular dynamics characterized by the secondary
(b; g; . . .) transitions.
15.2.3.2 Polymer Morphology
Structural organization of a solid polymer can be characterized by three principal
supramolecular parameters: the content of the amorphous phase, the degree of
chain orientation in this phase, and the degree of crystallinity in semicrystalline
polymers. These parameters depend to a large extent on its processing history,
and on the glass transition (T
g
) and melting temperature (T
m
).
Crystallinity It is generally considered that only the amorphous regions in semi-
crystalline polymers can participate in the degradation reactions. The chemical in-
ertness of the crystalline phase originates from the close packing of the polymer
chains (minimum free volume), from the rigidity of the crystal lattice, and from
the lack of oxygen to initiate oxidative degradation. Only small species such as hy-
drogen atoms can penetrate the crystal lattice. Any macroradical which may be cre-
ated is virtually trapped in the crystallites as an inert species. From the eects men-
tioned, it is obvious that degradation stability parallels the degree of crystallinity. In
some infrequent circumstances, it has been observed that increasing the degree of
crystallinity in a polymer sample may increase the rate of photodegradation. Closer
scrutiny of the results has indicated that multiple light scattering by the crystalli-
tes, which increases the eective optical length, and hence the number of absorbed
photons for degradation, is the proper explanation for this unusual behavior. In
addition to the degree of crystallinity, the size of the crystallites can also inuence
the polymer stability through the dual action of chain orientation and presence of
tie molecules. A quenched LDPE, for instance, has a higher resistance to photo-
oxidation than an annealed sample of the same degree of crystallinity, as a result of
smaller crystallite sizes and a greater number of tie molecules [8]. In iPP, a reverse
trend has been observed when the rate of oxygen diusion becomes the control
step (Section 15.4.4). It has been suggested that oxygen diusion may depend on
the type of amorphous phase, which is distinguished in PE as intralamellar, inter-
lamellar, and interspherulitic (Ref. 6, p. 292).
Although it is well established that oxidative degradation of semicrystalline
polymers initiates and spreads in the amorphous interphase without aecting the
crystalline domains, it does change the density and crystalline content through a
process known as chemicrystallization. The best documented account of this phe-
nomenon is found in isotactic polypropylene. At the beginning of degradation,
chain shortening from bond scission facilitates molecular rearrangement, leading
to an increase in crystallinity. For long degradation times the crystallinity de-
creases, sometimes with a shift toward lower T
m
, even if the degradation tempera-
ture is too low to allow for a change in molecular conformation [9].
Chain orientation Drawing orients the polymer chains, changes the sample mor-
phology and can inuence the rate of degradation in two ways:
v
Orienting chains increases the intermolecular interactions, while at the same
time decreasing the free volume and segmental mobility. Most of the orientation
experiments have been performed with semicrystalline polymers (iPP or HDPE).
In many respects, the behavior of oriented amorphous phases shows qualitative
similarity to that of the crystalline phase. The reduction of molecular mobility
results in a decrease in the rate constant for chain propagation reactions. A de-
crease in free volume results in a reduction in the rate of oxygen diusion.
v
Even at the same concentration of absorbed oxygen, an oriented sample retains
its mechanical strength better than an isotropic polymer and can survive a longer
period of degradation.
Hydrogen bonding Polar polymers such as the polyamides, aliphatic or aromatic,
are strongly hydrogen-bonded in the solid state. Polymers devoid of polar groups
can nevertheless develop hydrogen bonding during the course of degradation as a
result of formation of oxidation products (hydroperoxy, hydroxy, carbonyl, and car-
boxyl groups) which can then interact through the acidic hydrogen and the basic
oxygen groups. The eect is similar to crosslinking, with a reduction in segment
mobility and a decrease in gas permeability. In addition, hydrogen bonding
changes the activation energy for some chemical reactions, such as hydroperoxide
decomposition (Section 15.4.4).
Externally applied stress Most polymers in practical use are subjected to some
type of deformation process. Depending on the amplitude, the duration, and the
geometry of these deformations, the polymer morphology may change in a num-
ber of complex (although generally predictable) ways, such as chain orientation,
shear banding, and crazing. How these stress-induced morphologies interact with
environmental degradation factors is, however, less well documented.
In photo-oxidation, it is found that the rate of decomposition increased with ap-
plied stress. The main factors which aect the rate of decomposition following ap-
plication of tensile stress are an increase in oxygen diusion and an acceleration of
chain scission. It is believed that the latter eect may result from a decrease in rad-
ical recombination rate, following the pulling apart of the formed radicals by the
applied stress before they can recombine again. Several investigations in the
1970s tended to favor a molecular interpretation for stress-activated chemical deg-
radation (Section 15.7.1). However, recent investigations of polyolens tend to indi-
cate that chemical evolution does not depend on mechanical stresses, which mod-
ify only the consequences of the chemical evolution and not the kinetics of the
chemical reactions [10].
15.3
Degradation Detection Methods
A few eects of outdoor weathering, such as discoloration and embrittlement,
are readily detectable by visual or manual inspection. Quantitative investigations
nevertheless require modern analytical techniques capable of probing material
changes at dierent levels, from determining macroscopic bulk properties to un-
derstanding molecular mechanisms. The hierarchy of methodologies which has
been applied to degradation investigation is summarized in Table 15.2.
Many analytical techniques used to inspect the cited properties are common
to the eld of polymer characterization: vibrational spectroscopy (FTIR, Raman),
magnetic resonance spectroscopy (NMR, ESR) and liquid chromatography (GPC,
HPLC). A few methods, such as oxygen consumption and chemiluminescence,
are more specic to oxidative degradation. Mechanical tests are frequently used in
combination with other analytical tools to asset the eects of degradation on me-
chanical properties.
15.3.1
Mechanical Tests
Many plastic materials are used for their load-bearing properties, and mechanical
testing occupies a dominant position among the dierent criteria for degradation.
Typical molecular consequences of degradation processes are chain scission and
crosslinking. These eects have a profound inuence on the mechanical properties
of the material. In general, a predominance of crosslinking over chain scission in-
creases the tensile strength while decreasing the elongation at break and the visco-
elastic ow of the material. The reverse eects are observed for chain scission. The
loss of toughness in semicrystalline polymers arises from oxidatve chain scission
in the amorphous region, which involves:
v
scission of tie molecules
v
recrystallization of lower MW polymer fraction following scission
v
densication from increasing polarity.
In thermal aging of polypropylene, for instance, a rapid transition from ductile to
brittle behavior was observed before the appearance of carbonyl groups in the FTIR
spectra. Recent data nevertheless indicate that some of the delay in
a
a
CbO buildup
Tab. 15.2. Hierarchy of degradation investigative methodologies.
Scale Aspect investigated Methodology
Macroscopic decrease in mechanical
properties with time
tensile test, fracture energy
measurements
Microscopic development of surface
microcracks
optical and electronic microscopy
Supramolecular change in morphology DSC, TEM
Macromolecular change in molecular weight
distribution
GPC
Chemical stable degradation products oxygen uptake, FTIR, Raman,
NMR, impedance spectroscopy
Reactive intermediates free-radical formation ESR, chemiluminescence
may result from the loss, during the initial degradation stage, of volatile ketones
and carboxylic acids which hence elude detection by FTIR. Gel permeation chro-
matography reveals the presence during the induction period of chain scission,
most likely b-scission of alkoxy radicals, which accompanies loss in mechanical
strength when the weight-average molecular weight M
w
drops below some value
of the order of 10
5
g mol
1
(Figure 15.1) [11].
Degradation, particularly photodegradation, is a surface phenomenon which
aects essentially only the outer few hundred microns from the surface. Scanning
electron microscopy invariably reveals the appearance of multiple cracks and mi-
crocracks at the surface of degraded polymers, as in Figure 15.2.
The morphology of these cracks depends on the type of polymer and the degra-
dation conditions. Crack formation normally occurs on unstrained material accord-
ing to the following sequence:
Oxidation of the supercial layer change in material density
volume contraction dierential deformation crack formation
Oxidized polymers show an increase in density owing to the presence of polar
functions. Densication of the degraded material creates internal stresses between
the outer layer and the intact interior. Ultimately, cracks will appear when the me-
chanical strength of the degraded layer falls below the dierentiial tensile stresses.
Water absorption from ambient humidity or from rain, followed by surface evapo-
Fig. 15.1. Change in elongation at break, weight-average MW
(M
w
), and carbonyl content as a function of degradation time,
in the thermo-oxidative degradation of unstabilized iPP.
F
i
g
.
1
5
.
2
.
T
h
e
r
m
a
l
l
y
d
e
g
r
a
d
e
d
p
o
l
y
p
r
o
p
y
l
e
n
e
s
a
m
p
l
e
s
.
L
e
f
t
:
m
a
c
r
o
s
c
o
p
i
c
a
s
p
e
c
t
,
s
h
o
w
i
n
g
t
h
e
i
n
t
e
r
i
o
r
o
f
a
w
a
t
e
r
p
i
p
e
d
e
g
r
a
d
e
d
i
n
h
o
t
w
a
t
e
r
(
s
i
x
m
o
n
t
h
s
,
9
0
C
)
.
R
i
g
h
t
:
m
i
c
r
o
s
c
o
p
i
c
(
S
E
M
)
v
i
e
w
o
f
a
n
H
A
S
-
s
t
a
b
i
l
i
z
e
d
s
a
m
p
l
e
t
h
e
r
m
a
l
l
y
a
g
e
d
i
n
a
n
o
v
e
n
(
5
4
d
a
y
s
a
t
1
3
5
C
[
1
1
]
)
.
ration, is another source of cyclic mechanical stresses which can favor crack forma-
tion in certain polymers. The spatial irregularities in oxidation are another source
of dierential stresses between degraded and undegraded domains.
Fracture usually occurs from surface cracks. Starting from the degraded layer,
these surface microcracks can easily propagate into the internal intact layer by
stress concentration at the crack tip. Some mechanical tests are more sensitive to
the outer layers than to the bulk properties, and this peculiarity should not be over-
looked when interpreting experimental results. Tensile strength of degraded elasto-
mers, for instance, shows a dierent behavior when compared with tensile elonga-
tion, because the former depends on the entire cross-section of the material,
whereas ultimate elongation is correlated with surface modulus because cracks ini-
tiated at the hardened surface immediately propagate through the sample (Ref. 10,
p. 557).
15.3.2
Gel Permeation Chromatography
Polymer degradation involves cleavage of bonds, resulting in a decrease in MW,
branching, cyclization, and crosslinking. These changes in the MW and MWD,
and their evolution with the extent of degradation, can give valuable insights into
the degradation mechanism. Before the advent of GPC, dierent MW averages
such as M
n
; M
v
or M
w
, were used routinely in evaluation of polymer degradation
processes. Determination of the number-average MW (M
n
) has the major advan-
tage that it is directly related to the inverse of the number of molecular chains per
unit polymer mass [Eq. (22), where n
i
is the polymer molar fraction of molecular
mass M
i
].
M
n
=
X
n
i
M
i

(22)
In polymer degradation experiments, it is convenient to dene the scission index s
as the number of broken bonds per initial macromolecule. Because each main-
chain scission produces an additional molecule, the indice s is directly given by
the change in number-average MW regardless of the initial MWD and degradation
mechanism [Eq. (23), with n representing the number of polymer chains per gram
of polymer, and the superscript
referring to the initial conditions].

s = [n n
[/n
= [M
n
/M
n
[
1
(23)
Pure chain scission seldom occurs without other competitive radical reactions,
except perhaps during the early stage of oxidative degradation. When chain scis-
sion and crosslinking happen simultaneously, the polymer molecular weight may
increase or decrease depending on the relative importance of each process. For
random scission and crosslinking, Flory and Charlesby have shown that a three-
dimensional network begins to occur at the gel point, when the crosslink density
reaches one unit per weight average molecule. The soluble fraction (s) after the gel
point can be used to determine the relative yield of chain scission to crosslinking
during degradation (see Section 15.6.2).
Gel permeation chromatography (GPC), particularly in its multidetection ver-
sion, is now a mature and well-accepted technique for MW characterization. The
capability of GPC to determine changes throughout the MWD, in addition to the
dierent MW averages, opens new possibilities for polymer degradation studies.
The scission probability as a function of position along the molecular chain, for in-
stance, could be inferred from the MWD of degraded polymer [12].
In a given polymer where most of the covalent bonds have on the average the
same bond energy, it is expected that the rate of bond scission may not depend on
its position along the chain (random scission). Although this is generally true for
the thermal and photodegradation of several polymers, other bond scission statis-
tics can also be observed, as shown in Figure 15.3 [12].
The Gaussian scission probability distribution function, with a preference for
mid-chain scission, is frequently encountered in shear-induced mechanochemical
degradation. The parabolic distribution, on the contrary, indicates a preference for
chain-end degradation. This phenomenon has been reported in the hydrolysis of
dextran, as a result of chain branching.
A fourth situation, not depicted in Figure 15.3, is encountered in some polymers
which have weak links at a chain end or a low ceiling temperature. In the former
situation, initiation starts at the chain end bearing the weak bond with volatiliza-
tion of a monomer out of the reaction medium. In the second case, exemplied
by polyacetals, initiation also occurs at a terminal position, but the process contin-
random scission
Gaussian scission
parabolic scission
k(i,j)
j=0 j=i/2 j=i
Fig. 15.3. Some commonly encountered scission probability distribution functions.
ues and the monomers keep being evolved until complete volatilization of the poly-
mer (unzipping).
15.3.3
Fourier Transform Infrared Spectroscopy
Identication of the degradation mechanism, and its evolution with time, are
mainly based on analysis of the intermediate and nal chemical products. FTIR
proves to be particularly suited to that purpose. The infrared absorption intensity
A
s
is related to the square of the change in dipole moment (m) during molecular
vibration according to Eq. (24), where n is the frequency of the band center, and
Q, the normal coordinate of the vibration.
A
s
mn (qm/qQ)
2
(24)
The dynamic dipole moments of oxidized compounds are high, owing to the polar
nature of the oxidation products, and FTIR provides a sensitive and quantitative
technique for the investigation of oxidative degradation.
Oxidized polymers show changes in the IR absorption spectrum over the whole
range of measuring wavelengths. Most noticeable are the appearance of complex
overlapping bands in the carbonyl (16001800 cm
1
) and hydroxyl (32003600
0
0.2
0.4
0.6
0.8
1
500 1000 1500 2000 2500 3000 3500 4000
a
b
s
o
r
b
a
n
c
e
cm-1
degraded
undegraded
Fig. 15.4. Evolution of the ATR-FTIR spectra of an unstabilized
commercial iPP, before () and after (- - --) 3 h of thermal
treatment at 120
C.
cm
1
) regions (Figure 15.4). The content of carbonyl groups is an indirect indicator
of the number of scission events. The average ratio of the absorption coecient
of hydroxyl (aOaH) to carbonyl (
a
a
CbO) functions is approximately 3.4:1, and this
value can be used to estimate the relative proportion of hydroperoxides to other oxi-
dation products of degradation.
IR absorption bands in amorphous solids are rather broad, with extensive over-
lap. Direct identication and quantication of the numerous oxidation products,
most often of similar chemical structures, in a degraded polymer are dicult.
More precise conclusions about the nature of absorbing species can be obtained
by selective chemical derivatization. Selective modication of functional groups
with reactive gases, such as SF
4
, NH
3
, SO
2
, or NO, results in a shift in absorption
band positions, which can then be compared with model compounds to allow for a
better chemical assignment of the absorbing species (Table 15.3) [13].
Chemical derivatization can also be used for structure elucidation in complex
mixtures. For instance, dimethyl sulde has been used to dierentiate peracids
from other peroxy compounds. The rate of conversion of dimethyl sulde into di-
methyl sulfoxide is almost instantaneous with peracids [Eq. (25)], whereas it is
slow with sec- and tert-hydroperoxides [Eq. (26)].
+ CH
3
SCH
3

O
OOH
R
R
O
C + CH
3
SCH
3

OH
R
R
O
C
(25)
CHOOH + CH
3
SCH
3

R
R
CHOH + CH3SCH3
R
R
O
(26)
Tab. 15.3. Some common derivatization techniques for identication by FTIR.
Functional group Derivatization reaction IR frequency [cm
C1
]
Carboxylic acid O
b
RaCaOH NH
3
RaCOO
1564
Carboxylic acid O O
b b
RaCaOH SF
4
RaCaF
1848
1841 (a-branching)
Hydroperoxides RaOaOH NO RaONO
2
1276 1290
the sharp and intense absorption bands of nitrates and nitrites can be
used to dierentiate primary from secondary and tertiary
compounds
Alcohols RaOH NO RaNO
2
778
Aldehydes RaCHbO 2Ag(NH
3
)
2
OH RCOO
NH
4
2Ag| 3NH
3
H
2
O
(Tollens reagent does not react with ketones)
15501555
The carboxyl group, in the presence of hydroxyls, may be dierentiated by reaction
with silver triuoracetate [Eq. (27); Ref. 7, p. 76] or with triuoroanhydride [Eqs.
(28) and (29)].
aCOOH CF
3
COOAg aCOOAg CF
3
COOH (27)
aOH (CF
3
CO)
2
O aOaCOaCF
3
(28)
aCOOH (CF
3
CO)
2
O aCOOaCOaCF
3
(29)
15.3.4
Magnetic Resonance Spectroscopy
15.3.4.1 Nuclear Magnetic Resonance (NMR)
NMR is an absolute and unique method of resolving the microstructure of polymer
species. This technique has been instrumental in the elucidation of degradation
mechanisms in several polymer systems, including poly(vinyl chloride) (PVC).
At around its glass transition temperature (81
C), unstabilized commercial PVC

starts to discolor with release of hydrochloric acid, according to the global reaction
of Eq. (30).
a(H
2
CaCHCl)
n
a a(HCbCH)
n
a nHCl (30)
Because the thermal stability of PVC is substantially lower than one may expect
from its nominal structure, numerous studies have been initiated to identify the
defect sites responsible for this anomaly. After considerable controversy concern-
ing the role, nature, and importance of possible irregular structures, the most
active sites for initiating PVC degradation were nally identied by
1
H- and
13
C-
NMR as internal allylic (Figure 15.5, I, II) and tertiary chlorine structures (III, IV)
[14].
It was believed for a long time that head-to-head radical addition to monomers is
a major route for formation of labile structures. Kinetic studies, in association with
NMR measurements, reveal that formation of internal allylic and tertiary chlorine
structures actually proceeds through an intramolecular or intermolecular chain-
transfer reaction to polymer [Eqs. (31), (32); VC = vinyl chloride].
CH
2
CHCl CH
2
CH
2
Cl (III)
|
CH
2
CC1 CH
2
CH
2
CHCl CH
2
CHCl (IV)
|
CH
2
CC1 CH
2
HC=CH CH
2
Cl (I) HC=CH CHCl (II)
Fig. 15.5. Major labile structural defects in emulsion PVC.
CH
2
aCHClaCH
2
aCH
2
Cl
a
P
v
aCH
2
a C
v
ClaCH
2
aCHClaCH
2
aCHCl aCH
2
aCClaCH
2
a
(31)
CH
2
aCHCla
a
P
v
aCH
2
aCHClaCH
2
a aCH
2
aC
v
ClaCH
2
a
VC
VC
aCH
2
aCClaCH
2
a
(32)
15.3.4.2 Electron Spin Resonance (ESR)
Most mechanisms for the degradation of polymers during processing, storage, and
long-term use include free radicals. The technique of ESR is therefore a logical
choice for the study of polymer degradation. Two kinds of free radicals are of key
importance in determining degradation kinetics: (i) the carbon-centered macro-
alkyl CaC
v
aC; and (ii) the oxygen-centered alkylperoxyl ROO
v
, alkoxyl RO
v
, and
acylperoxyl R(CO)OO
v
radicals. Most of these species have unique ESR spectra
which allow their unambiguous identication under favorable conditions. In addi-
tion to structure identication, the decay signal of the radicals with time provides
information about termination rates and reaction order.
At room temperature and in solutions, free radicals are too reactive, and their
concentrations too low, to be conveniently detected by ESR spectroscopy. To ob-
serve and quantify transient radicals, it is customary to transform the unstable spe-
cies into stable nitroxide radicals with the spin-trapping technique. Spin-trapping
of a macroalkyl radical with pentamethylnitrosobenzene, for instance, can be rep-
resented schematically by Eq. (33). The structure of the parent radical could be de-
duced from the ESR spectrum of the spin adducts, using standard rules of spin
coupling and experimental coupling constants.
CH3
CH3
H3C
H3C
H3C
N=O +
.
R
CH3
CH3
H3C
H3C
H3C
NR
O
.
(33)
15.3.5
Oxygen Uptake
Oxygen uptake provides a simple, yet highly sensitive means to monitor oxidative
degradation. A weighed amount of polymer is hermetically enclosed with a xed
amount of oxygen under controlled pressure. Oxygen consumption can be moni-
tored by measuring volumetric change, or the decrease in oxygen content by gas
chromatography. The rst method cannot discriminate oxygen consumption from
the release of volatile gases (CO, CO
2
, H
2
O, and so on) and tends to underestimate
the amount of oxygen consumed. The second technique benets from the high
sensitivity and separation capability of gas chromatography which, with proper
care, allows determination of oxygen consumption rates down to 10
13
mol g
1
s
1
. The gas chromatography approach has been used to determine the instanta-
neous oxidation rate of elastomers even at room temperature, and reliable lifetime
can be predicted under ambient conditions without having recourse to extrapola-
tion from accelerated testing [15].
Measurement of oxygen consumption is the starting point for several analyses of
polymer oxidation kinetics. The oxygen uptake curve for most polyolens shows an
induction period with a very slow oxidation rate, before reaching a steady state
with constant slope. The value of this slope has been often interpreted as the limit-
ing oxidation rate of the polymer. The induction period is generally much shorter
in photodegradation than in thermal degradation (Figure 15.6). The main dier-
ence stems from the dierent modes of initiation. The activation energy of primary
photochemical processes, 840 kJ mol
1
, is generally much less than the energy
required for thermal activation (120200 kJ mol
1
). Because photodegradation
generally occurs at low temperature, photodecomposition of peroxides is slow and
this class of products tends to accumulate rather than being decomposed to initiate
chain branching reactions as in thermal degradation.
During oxygen uptake, part of the absorbed oxygen is transformed into hy-
droperoxides, while the remaining fractions are found in hydroxyl- and carbonyl-
containing compounds formed by competitive reactions of P
v
and POO
v
radicals.
The relative importance of each process depends on the oxygen partial pressure,
and various kinetic equations have been derived to relate the rate of oxygen absorp-
tion (d[O
2
]/dt) to the formation of oxidation products, under low and high oxygen
oxidation rate
induction period
o
x
y
g
e
n

u
p
t
a
k
e
degradation time
thermal oxidation
photooxidation
Fig. 15.6. Oxygen uptake curves during photo-oxidation and
thermal oxidation of unstabilized polymers.
pressure conditions. Kinetic information, and rate coecients for propagation and
termination, have frequently been obtained from the t of the oxygen consumption
curve at relatively low conversions. This procedure, however, is complicated by the
facts that intermediate oxidation products may be orders of magnitude more sus-
ceptible to oxidation than the starting material, and that degradation in solid poly-
mers is fundamentally heterogeneous. Therefore, any obtained value can yield only
average information about the degradation process.
15.3.6
Chemiluminescence
As with oxygen micro-uptake, chemiluminescence is an ultrasensitive technique
for determining the rate of oxidation at the earliest stage of degradation. Oxidative
degradation of polymers is generally accompanied by weak photon emission, with
a very low quantum yield (approximately 10
9
). The light-emitting reaction which
accompanies free-radical oxidation is generally attributed to an exoenergetic termi-
nation reaction of peroxy radicals according to the Russell mechanism [Eq. (34)].
H
R
O
C
O
.
R
R
O
O
.
H
R
O*
C
O
R
R
O
O
C=O* +
1
O2 + ROH
H = -460 kJ
.
mol
-1
R
R
(34)
The Russell mechanism requires one of the terminating radicals to be either pri-
mary or secondary so that a six-membered transition state can be formed. Such
a mechanism may be prevalent in PE and PA, but not in PP, where the chain-
carrying radical is tertiary. For this polymer, more complex alternative routes for
chemiluminescence-producing reactions have been proposed [Ref. 10, p. 175].
15.4
Thermal Degradation
Industrial plastics are frequently exposed to elevated temperatures during melt
processing and in many engineering applications, some of which will be described
in Section 15.4.6. The glass transition temperature (T
g
) and the melting point (T
m
)
of semicrystalline polymers are the most important thermal characteristics of poly-
mers. These two parameters alone are generally not sucient to predict the mate-
rials service temperature, if thermal stabilization is not properly controlled. Several
polymer systems produce toxic low molecular weight compounds when subjected
to heat, which can create hazardous conditions if they come into contact with a hu-
man body, either by ingestion or by breathing. Flammability of polymers used in
construction is another concern when the polymers are exposed to high tempera-
tures. All these factors combined make thermal stability appraisal a necessity in
most application developments.
15.4.1
Thermal Stability
The notion of thermal stability is a vague concept, since it depends primarily on
the time scale of observation. A PMMA sample, for instance, can be stable at
300
C for a few seconds, but can withstand only a temperature of 150
C if the
heating time spans several hours.
To be able to compare thermal stability between polymers of dierent structures,
it is necessary to rely on some standardized system, such as the temperature of
half-decomposition (T
1/2
). The temperature of half-decomposition is dened as
the temperature at which the polymer loses half of its weight when heated in vacuo
for 30 min. Experimentally, T
1/2
can be conveniently determined by thermal grav-
imetry (TG). From the TG curves obtained at dierent scan speeds, an Arrhenius
plot at constant weight-loss ratio is derived. The pre-exponential factor and activa-
tion energy determined are then used to calculate T
1/2
.
15.4.2
Polymer Structure and Thermal Stability
Intrinsic chemical factors which inuence heat resistance include primary bond
strength, secondary or van der Waals interactions, hydrogen bonding, resonance
stabilization, the mechanism of bond cleavage, structure regularity, intrachain ri-
gidity, crosslinking, and branching. Owing to the presence of multiple secondary
reactions, the eect of chemical structure on degradation kinetics is not easily ra-
tionalized from chemical rst principles. The actual degradation kinetics is highly
variable and depends not only on the polymer structure, but also on the reaction
conditions: sample size, internal or external unstable structures, and additives.
More specically, it is experimentally observed that the degradation temperature
and the product distribution can be controlled by changing the heating rate of the
polymer, as a result of competitive pathways for degradation. Apart from the pri-
mary eects cited, dierences in thermo-oxidative resistance can be discerned be-
tween dierent stereoisomers of the same compound (PMMA, PVC, and PP).
Notwithstanding this complexity, some semiempirical rules could be identied
by analogy with small organic model molecules, and by considering that thermal
degradation is a homolytic bond scission process initiated by thermally activated
molecular vibrations:
v
The rate of thermal degradation is related to the number of pendent groups pres-
ent on the polymer chain. Thus polyisobutylene (PIB) degrades faster than iso-
tactic PP, which itself decomposes faster than HDPE.
v
A rigid polymer backbone has less possibility of rearrangement and fragmenta-
tion and can withstand higher thermal energy.
v
The heat resistance increases with the number of covalent bonds per repeat unit:
a crosslinked or ladder polymer can be broken only after scission of two or more
covalent bonds.
v
The bond of lowest energy is the rst bond to be cleaved. Conversely, polymers
with multiple bonds and aromatic structures are less prone to thermal degrada-
tion.
Poly(para-phenylene), with its rodlike structure composed of highly delocalized p-
electron orbitals, satises most of the requirements for high thermal stability. Pos-
sessing T
1/2
> 400
C and an estimated melting point of 1400
C, PPP constitutes a
reference for heat-resistant polymer. Poly(para-phenylene) can be synthesized by a
number of routes, with the best heat-resistant material obtained by polymerization
of 1,3-cyclohexadiene, followed by dehydrogenation of the polymer formed accord-
ing to Eq. (35) [16].
n
n n
- H
(35)
Moldable polymers can be obtained by increasing chain exibility with substitution
of lateral groups, at the expense of decreasing thermal stability. Polyimides and
polyetherimides (V), with a semi-rigid structure and electronically stabilized aro-
matic rings, form an important class of melt-processible polymers with outstand-
ing heat resistance (Table 15.4).
Apart from the decomposition temperature, the propensity for char formation is
another polymer thermal characteristic of practical importance. The char-forming
tendency generally shows a negative correlation with ammability: a sample with
the greatest char residue is also the least ammable polymer and the presence of
ame retardant additives also increases char formation. In the case of re, the
amorphous crust of char material that forms on the uid surface reduces the heat
ux to the burning uid, which in turn reduces the combustion rate.
15.4.3
Computer Simulation
Thermal degradation involves scission of covalent bonds which can be formally
written as Eq. (36).
A
k
B C (36)
According to Eyrings transition-state theory, the rate constant k is given by Eq.
(37), with k
B
= Boltzmanns constant, h = Plancks constant, DE
0
= molecular en-
ergy dierence at absolute zero between the activated complex and the reactant,
and q
t
and q
A
the molecular partition functions of the transition state and reactant,
respectively. The transition state is distinguished by a single negative vibration, a
characteristic which has been used to identify true transition states in computer
modeling.
k(T) = (k
B
T/h)(q
t
/q
A
) exp(DE
0
/k
B
T) (37)
With the increasing capabilities of computers and development of new numerical
methods, it is now possible to predict polymer properties computationally. In addi-
tion to saving time, computer-aided chemistry can sometimes provide new insights
into some decomposition mechanisms which are dicult to obtain by experimen-
tal techniques. Computer modeling has been used in an increasing number of
ways to simulate thermal degradation. A few representative examples are described
below.
v
Ab-initio calculations were performed on a series of model structures to predict
the eect of lateral alkyl substituents on the thermal stability of degradable poly-
carbonate. The optimized transition structures revealed that the C
a
aO bond
dissociates rst, followed by abstraction of the b-hydrogen atom, developing a
carbocation character in the transition state on the C
a
atom. Substituents which
stabilize the transition state will also accelerate the degradation rate [17].
Tab. 15.4. Chemical structure and thermal stability by thermogravimetry of some representative
polyetherimides
Ar
O
N
O
O O
O
O
N
n
(V)
xAr x Thermal stability [
C]
T
g
[
C] 1 wt.%
loss (air)
1 wt.%
loss (N
2
)
5 wt.%
loss (air)
5 wt.%
loss (N
2
)
4,4
/
-biphenyl 247 500 515 530 543
4,4
/
-benzophenone 239 490 485 530 523
4,4
/
-diphenyl ether 227 480 480 513 523
4,4
/
-diphenyl sulde 209 470 470 504 505
v
Molecular dynamics simulation has been conducted to understand the signi-
cant reduction in ammability of polymer nanocomposites. Using graphite as a
model compound, it was found that polymer in an intercalated structure loses
fewer fragments generated by the degradation and retains its shape longer as a
result of repulsive nonbonding interactions between the polymer and the graph-
ite layers. The fragments generated by thermal activation collide with the graph-
ite and bounce back into the central unit cell, where they undergo recombination
reactions with other free radicals. The decrease in polymer fragments which can
escape as combustible fuel accounts for the observed improvement in re resis-
tance [18].
v
Force eld calculations with the MOPAC PM3 package [19] allow the prediction
of thermal degradation mechanisms. First, the smallest representative section of
the polymer to be investigated was selected. The program then calculated the
heat of formation and Gibbs free energies at dierent temperatures of the poly-
mer and for dierent radical fragments. The kinetic barrier for bond dissociation
was estimated by stretching each individual bond to its breaking point, and plot-
ting the heat of formation (enthalpy) as a function of bond extension. Calcula-
tions on the PA-6,6 structure identify the
a
a
COaCH
2
a bond as the one having
the lowest transition state energy, and the carbonyl carbon as the most suscepti-
ble site for radical attack. Upon dissociation, the methyl radical created folds
back and attacks the
a
a
CbO bond, forming cyclopentanone, in accord with exper-
imental ndings [20].
15.4.4
Thermal Oxidative Degradation of Polypropylene
Isotactic polypropylene (iPP) is a major commodity plastic material which cannot
be utilized without thermal stabilizers. With a moderately complex structure, iPP
is frequently used as a model system to test the dierent theoretical and experi-
mental approaches to macromolecular degradation.
15.4.4.1 Initiation
The homogeneous oxidation of PP follows the free-radical auto-oxidation mecha-
nism depicted in Scheme 15.1. Under isothermal conditions, the oxygen uptake
curves display a pseudo-induction period during which oxidation is autoacceler-
ated. The duration for the induction period t
i
depends on the sample purity and
preoxidation history. For clean samples, t
i
is reasonably reproducible and is of the
same order of magnitude as the POOH lifetime, determined by iodometric titra-
tion. The temperature dependence of the induction time obeys an Arrhenius law
with an apparent activation energy of 105 G15 kJ mol
1
, which is the same as for
the decomposition of hydroperoxides. The corresponding rate constants are much
lower than for the other degradation processes and account for the induction pe-
riod during which hydroperoxides accumulate before reaching a maximum. It has
long been recognized that residual ZieglerNatta polymerization catalysts, gener-
ally at the 120 ppm level, accelerate the solid-state degradation of PP. The nega-
tive inuence of polymerization catalyst residues depends not only on the type of
catalyst, but also on its concentration. The induction period stage is complicated by
the morphology of the sample. In iPP, for instance, a sample with small spherulite
sizes (< 100 mm), obtained by rapid quenching, has a short induction time (Figure
15.7). A large spherulite sample (350500 mm), obtained by prolonged annealing,
results in a signicant increase in the induction period. The dierence was ex-
plained by a dierence in the oxygen diusion rate in the oriented amorphous re-
gions, which are more strained in large spherulite structures [21].
It was shown from decomposition kinetics and by treatment with dimethyl
sulde that peroxides consist of two types: a fast-decomposing one composed of
peracids, and a slowly decomposing one consisting of hydroperoxides and hydro-
peresters. During the induction period, the slowly decomposing hydroperoxides ac-
cumulate and the oxidation rate is controlled by the rate of decomposition, which
may be nally catalyzed by metal ion residues. The autoacceleration stage is con-
trolled by the fast-decomposing peracids [22].
Regardless of the exact mechanism of bond scission, the mechanistic step for
initiation in PP can be described schematically by Eq. (38).
0
0.1
0.2
0.3
0
0.2
0.4
0.6
0.8
1
1.2
0 10 20 30 40 50
degradation time [min]
oxygen uptake
(left scale)
peroxide content
(right scale)
m
o
l
e

O
2
/
k
g
m
o
l
e

P
O
O
H
/
k
g
Fig. 15.7. Oxygen uptake (left-hand scale) and hydroperoxide
formation (right-hand scale) in the thermo-oxidative
degradation of iPP lms at 130
C, with small () and large

(- -- -) spherulites.
CH CH
2
CH
3
CH
2
+ X
.
CH CH
2
CH
3
CH
C CH
2
CH
3
CH
2
.
.
(38)
15.4.4.2 Propagation
For PP, the radical conversion step with oxygen is given by Eq. (39).
+ O
2
C CH
2
CH
3
CH
2
O
O
.
C
CH
3
H
C CH
2
CH
3
CH
2
C
CH
3
H
.
(39)
Hydrogen abstraction from tertiary carbon has an activation energy lower by ap-
proximately 15 kJ mol
1
than an abstraction reaction on secondary carbon (Ref. 2,
p. 386), and is the predominant mode of formation of hydroperoxides in PP. In ad-
dition to energy considerations, the hydrogen abstraction rate constant is depen-
dent on steric factors and polymer conformation. It is found, for instance, that k
3
(Scheme 15.1) in solution is lower in a theta solvent than in a good solvent, owing
to increased steric repulsion in a contracted molecular coil [7].
Abstraction reaction in polymers can occur intramolecularly or intermolecularly.
The former possibility is important in polymers which possess lateral groups (PP
and PS), whereas it is nonexistent in linear polymers (HDPE). The possibility of
intramolecular H abstraction has been advanced as one of the reasons for the
high sensitivity of PP (in comparison to HDPE) toward oxidative degradation.
Infrared studies have revealed that more than 90% of hydroperoxides in PP are
hydrogen-bonded in sequences of two or more. This result supports an intramolec-
ular hydrogen abstraction reaction, facilitated by a six-membered ring stereochem-
ical arrangement [Eq. (40)].
C CH
2
CH
3
CH
2
O
OH
C
CH
3
+ O
2
C CH
2
CH
3
CH
2
O
OH
C
CH
3
O
O
.
CH
2
C
CH
3
H
C CH
2
CH
3
CH
2
O
O
.
C
CH
3
H
.
(40)
15.4.4.3 Chain Branching
Chain branching by homolytic decomposition of polymer hydroperoxides results
in formation of highly reactive polymer alkoxy (PO
v
) and hydroxyl (
v
OH) radicals.
The small and mobile
v
OH can readily abstract hydrogen from a nearby polymer
chain, creating a secondary or tertiary macroalkyl radical. The tertiary alkoxy radi-
cal can abstract hydrogen intramolecularly, forming a primary alkyl radical as in
Eq. (41).
CH3
C
O
CH
2
CH
CH
2
H
CH
3
C
O
CH
2
CH
CH
2
H
(41)
The polyalkoxy radicals can decompose further by b-scission, yielding ketones, al-
dehydes, and alkyl radicals, depending on the initial position of the radical [Eqs.
(42a), (42b), and (43)].
-scission
C CH
2
CH
O
CH
3 CH
3
CH
2
C CH
2
CH
O
CH
3
CH
3
CH
2 +
C
O
CH
3
CH
2
CH
CH
3
+
CH
2
(42a)
(42b)
CH CH CH
CH
3
O
CH
3
O
CH
CH
3
CH
CH
3 H
+
-scission
C (43)
Similarly, the cleavage of peroxy radicals results in the formation of double bonds
along with aldehydes and ketones [Eqs. (44) and (45)].
CH CH CH
CH
3
O
CH
3
O
CH
CH
3
H
+
-scission
C
O
HC
CH
3
CH + OH
(44)
C
O
CH
3
CH
2
CH
CH
3
+
CH
2
-scission
C CH
2
CH
O
CH
3 CH
3
CH
2
O
+ OH
(45)
15.4.4.4 Termination
In an oxygen-decient atmosphere, vinylidene and vinyl compounds may be
formed from the disproportionation of polypropylene radicals [Eqs. (46) and (47)].
2PaCHaCH
2
v
PaCbCH
2
PaCHaCH
3
(46)
a a a
CH
3
CH
3
CH
3
2PaCH
2
aCH
v
PaCH
2
aCHbCH
2
PaCH
2
aCH
2
aCH
3
(47)
In the presence of oxygen, the majority of recombinations occur between tertiary
peroxy radicals, to give dialkyl peroxides and oxygen [Eq. (48)].
CH
2
C
CH3
O
CH
2
O
CH
2
C
CH3
O
CH
2
O
+
CH
2
C
CH3
O
O
C
CH3
O
CH
2
O
CH
2
C
CH3
O
C
CH3
O
CH
2
+ O2
H = -300 kJ
.
mol
-1
(48)
15.4.4.5 Secondary Reactions
In oxidative degradation, it is convenient to make a distinction between primary
chemicals formed by reactions of the polymer peroxy radicals, and secondary prod-
ucts created in subsequent reactions of these primary compounds. Ketones and al-
dehydes formed by b-scissions may react further with hydroperoxides to form a va-
riety of oxidation products. The formation of peracids, for example, proceeds via a
multistep oxidation of aldehydes [Eq. (49)].
POO
.
POOH
O
CH
CH
3
C
.
CH2
O
CH
CH
3
H
C CH2
+ O2, PH
O
CH
CH
3
C CH2
OOH
(49)
It should be emphasized that the reaction scheme of Eq. (49) is unlikely if hydro-
peroxides are distributed homogeneously over the whole sample. Owing to re-
stricted mobility below T
m
, the oxidation products cannot diuse away. Locally, hy-
droperoxides can reach suciently high concentrations for secondary reactions to
occur at a signicant rate. In a similar fashion, the formation of carboxylic acids,
esters and g-lactones proceeds through a complex series of oxidation reactions of
alcohols and ketones.
The aldehydes and ketones formed by b-scission can undergo Norrish type I
[Eq. (50a)] and Norrish type II reactions [Eq. (50b)] during photodegradation (see
Section 15.5.3).
C
O
CH3
CH
2
CH
2
CH
CH
3
+ CH3CO N
o
r
r
is
h
I
N
o
r
r
i
s
h
I
I
CH CH
CH
3
CH CH
3
+ CH3COCH3
(50a)
(50b)
For a long time, the similarity between thermal and photolytic products was a mys-
tery because Norrish photoprocesses are absent in the former situation. By using
low MW model compounds, chemical derivatization, and
13
C-NMR techniques, it
has been assessed that a large fraction of the carbonyl-containing compounds
formed during oxidative degradation of PP are a-methylated acids. Such a car-
boxylic structure can only originate from the oxidation of macroalkyl radicals
[Eq. (51)], which can be formed either by a Norrish I photoprocess or by b-scission
of alkoxy radicals (Ref. 10, p. 583).
+ O
2
, PH
HOOCH2 CH
CH
3
C CH
CH
3
O
HO
or hv
CH
2
CH
CH
3
(51)
Once the structure of the carboxylic acids had been elucidated, the IR absorption
band which appears as a shoulder at 1740 cm
1
in thermal or photo-oxidation of
PP, and was initially attributed to ester functions, was reassigned to an acidic
group hydrogen-bonded to a vicinal hydroperoxide (VI).
CH2 CH
CH
3
O
OH
C
OH
CH
CH
3
O
(VI)
15.4.4.6 Formation of Volatile Compounds
At least 40 dierent volatile compounds have been identied during the oxidative
degradation of iPP, some of which are important for spreading the degradation ac-
cording to the infection mechanism (Section 15.4.5). The mode of formation of
the principal volatile products is indicated in Eqs. (52)(55) [23]. It is proposed that
CO and CO
2
are formed by the decomposition of carbonyl and carboxyl radicals
following hydrogen abstraction from the parent compounds [Eqs. (52) and (53)].
Peracids formed by oxidation of formaldehyde can decompose into formic acid,
water, carbon dioxide, and triplet oxygen according to Eqs. (54) and (55).
POO
.
POOH
O
CH
CH
3
C
.
CH
2
O
CH
CH
3
H
C CH
2
C
.
CH
3
CH
2
H
+ CO
(52)
O
CH
CH
3
OH
C CH
2
POO
.
POOH
O
CH
CH
3
O
C
.
CH
2
CO
2 C
.
CH
3
CH
2
H
+
(53)
O
H
O
C
OH
CO
2
+ H
2
O
(54)
O
2 H
O
C
OH
O
2 H
OH
C + O
2

(55)
15.4.5
Homogeneous versus Heterogeneous Kinetics
Degradation reactions in the solid state are spatially heterogeneous, not only across
the sample but also within the sample. At least two factors can account for the het-
erogeneity of the degradation:
v
Nonuniform distribution of the reactants (oxygen, additives, impurities): uptake
of oxygen and formation of reactive chemicals are the highest near the surface.
Additives distribution can also be inhomogeneous as a result of inadequate
blending or migration.
v
Heterogeneous structure of the sample: oxygen (or any other chemical reactant)
can diuse more readily into amorphous than into crystalline domains, thus fa-
voring oxidative degradation of the former regions.
Superimposed on this macroheterogeneity, which occurs on a micron scale, is mi-
croheterogeneity resulting from the low diusivity of macromolecular species. In
solid polymer, it is expected that most macromolecular constituents formed from
radical reactions are localized in microdomains of size not exceeding 1030 nm.
The preceding considerations indicate that degradation kinetics of solid poly-
mers cannot be studied solely within the framework of homogeneous free-radical
kinetics. In spite of these complications, it has been found in many instances that
the homogeneous kinetics treatment of thermal oxidation gives a surprisingly good
t with experimental data [24]. It has been argued that the homogeneous kinetic
model may be applied to an inhomogeneous system by considering the parameters
as average values. It should be kept in mind, however, that the real concentrations
of degraded species may be much higher locally than the mean values averaged
over the bulk sample, and that extrapolating microscopic kinetics from macro-
scopic average data is a nontrivial problem.
The evidence for heterogeneous oxidation of solid polypropylene was revealed
by chemiluminescence measurements. Chemiluminescence from single polymer
powder particles revealed a large spread in the induction periods. The oxidation be-
havior changed with particle separation, and the result was interpreted as a result
of physical infection from a particle with the shortest induction period to its
nearest neighbors, causing rapid oxidation of the complete sample. The origin of
this infection was traced back to the formation of volatile compounds, more specif-
ically acetic acid and formaldehyde, which have the propensity to accelerate oxida-
tive degradation [25]. Highly mobile radicals, such as
v
OH, can also diuse far and
spread the degradation.
Devising a chemical kinetics model which encompasses all sources of heteroge-
neity present in a solid polymer is a challenge. The starting point in most hetero-
geneous kinetics models is to consider that oxidation is initiated nonuniformly at a
few sites, presumably around catalyst residues or other impurity centers in the
amorphous region of the polymer. One approach to heterogeneous modeling was
by Monte Carlo simulation, based on the random-walk diusion of low MW reac-
tive radicals. Another concept, called the epidemic model, utilizes the analogy be-
tween the spreading of oxidation through the amorphous region of solid polymer,
and the infectious contamination of a disease through a population. In this model,
three distinct polymer populations are assigned: the infectious oxidizing fraction
p
i
, the remaining unoxidized fraction p
r
, and the dead or oxidized fraction p
d
.
These populations may be described by a series of coupled dierential equations,
Eqs. (56)(58), which are developed by noting that oxidation can spread only if
there is unoxidized material within contact distance of the infected one.
dp
r
/dt = bp
r
p
i
(56)
dp
d
/dt = ap
i
(57)
dp
i
/dt = dp
r
/dt dp
d
/dt (58)
Integration of the above system of dierential equations using experimental b and
a parameters give an excellent t with the chemiluminescence curve when dealing
with single particles, but the quality of the t deteriorated with groups of particles,
as a result of multiple-spreading processes [26].
By considering only the oxidized and the unoxidized fractions, a simplied
spreading model was developed to explain the time dependence of hydroperoxide
concentration during oxidative degradation of LDPE [27], expressed as Eq. (59),
where n is the number of oxidized domains, N the total number of amorphous do-
mains, and r the rate coecient for spreading.
dn/dt = r n r (n
2
/N) (59)
15.4.6
Applications of Thermal Degradation
Although the word degradation usually has a pejorative connotation, a number
of important industrial applications depend on this class of reactions to develop
new products or processes.
15.4.6.1 Analytical Pyrolysis
Pyrolysis of a polymer means thermal degradation in the complete absence of any
external reactant. Analytical pyrolysis, dened as pyrolysis conducted in combina-
tion with some physicochemical separation technique (pyrolysisGCMS, for in-
stance), has found a wide range of applications in biopolymers and synthetic poly-
mers. Polymers pyrolyze by dierent combinations of three general mechanisms:
random scission (PE), depolymerization (POM, PMMA), or elimination of small
molecules other than monomer (for instance, HCl in PVC). Each polymer under
strictly controlled pyrolytic conditions provides a typical pattern of degradation
products, which can be used for ngerprint identication, composition analysis,
structure determination, or mechanistic studies [28].
15.4.6.2 Introduction of New Chemical Functionalities
Controlled thermal degradation of polyolens in the presence of peroxides has
been carried out in extruders or in continuous mixers, to reduce polymer MW and
sample polydispersity. The resulting material has more processing advantages than
the undegraded one. Based on the same principle, random chemical functionaliza-
tion of polyolens with polar groups has been achieved by extruding the polymer
in the presence of peroxy ketals or peroxy esters [29].
15.4.6.3 Chemical Modication of Polymer Structure
Carbon ber is used in a variety of structural and electrical applications, and is
probably the most well-known example of high-performance material produced by
thermal degradation. Although carbon ber can be produced in several ways, in-
cluding alignment of molecules of pitch in its mesophase state, the most econom-
ical way consists of hot-stretching high MW polyacrylonitrile (PAN) bers and
while heating under controlled conditions. The laments are rst oxidized under
tension at around 260
C in air, to convert the PAN precursor to a thermally stable

structure by an exothermic reaction (E
a
= 3:5 kJ g
1
, DH = 2:5 kJ g
1
), accord-
ing to Eq. (60) [30].
C
N
C
N
C
N
C
N
C
N
C
N
260 C, air
N N N N N N
O
H
O
H
C
N
O
C
OH
O
C
NH2
stabilized PAN
(60)
The carbonization step is carried out in an inert atmosphere (high-purity N
2
) above
1000
C to yield carbon bers containing 9395% carbon [Eq. (61)] and a tensile
modulus (E) of 140200 GPa. This grade is mostly used in sporting goods and in
composites.
N N N N
N
N
N N N N N N
N N N N
N N
N N N N N N
1000 C, N2
(61)
To achieve bers in which the carbon crystals are further stretched and aligned,
graphitization takes place around 20003000
C. These graphite bers have a car-

bon content greater than 99% and a tensile modulus of 4001000 GPa. For com-
parison, the tensile modulus of carbon nanotubes is 1000 GPa, and of diamond
1200 GPa.
15.4.6.4 Metal Injection Molding (MIM)
Polyacetals have a low ceiling temperature, and are readily depolymerized by un-
zipping at low temperature (0.40.8% min
1
at 222
C for POM). Owing to this

low thermal stability, polyacetals can be used only if end-capped with stable groups
(acetate or ether). This inherent thermal instability is exploited in an industrial
method known as metal injection molding, which allows ne metal powder
mixed with a polymer binder to be processed by injection molding, in much the
same way as thermoplastic materials [31]. In a procedure based on POM, the
binder is removed by thermal devolatilization according to Eq. (62)
Ra(CH
2
aOa)
n
H
HNO3/150
C
RaCH
2
OH (n 1)H
2
CbO (62)
15.4.6.5 Recycling
Polymer can be recycled by reuse of existing material (primary recycling), by regra-
nulating the waste by mechanical means so that it can be melted and formed again
(secondary recycling), or by transforming the waste into new chemical compounds
(tertiary recycling) through chemical reactions. The last of these methods presents
several economic advantages in comparison to primary or secondary recycling,
since revalorizing steps can be avoided. Recently, thermolysis has been viewed as
a viable alternative to recovery for polymer recycling and numerous studies have
been directed toward this objective [32].
The term feedstock recycling has been used to describe this new class of plas-
tics recycling technology, which breaks down solid polymers into a spectrum of ba-
sic chemical compounds that can be reused as raw materials for the chemical in-
dustry. Vinyl polymers, when pyrolyzed at temperatures from 200 to 500
C in the
total absence of air, usually degrade to yield monomers (poly(methyl methacrylate),
poly(a-methylstyrene), polystyrene, polyisobutylene) or a wide distribution of mo-
lecular fragments (polyethylene and polypropylene). In order to reduce the process
temperature and to limit the range of products, particularly in the case of polyeth-
ylene, several catalyst cracking systems based on zeolites or clays have been devel-
oped. A newly developed technique in the recycling eld is thermolysis coupled
with reactive distillation.
15.5
Photodegradation
15.5.1
Absorption of UV Radiation by Polymers
Photo-oxidation is the most common mode of weathering for industrial polymers,
and diers from thermal degradation principally in the mode of chemical activa-
tion. In place of vibrational energy, the energy of the photon provides the driving
mechanism for free-radical generation. Photochemical processes are based on two
fundamental principles: the GrotthusDraper law, which states that only radiant
energy that is eectively absorbed can activate molecules, and the StarkEinstein
law, which asserts that one absorbed photon can induce photochemical reaction of
only a single molecule [33]. The rst law implies the presence of an appropriate
chromophore in the polymer, whereas the second law indicates that the formation
of photoproducts is linearly dependent on the light intensity, and that a photoreac-
tion can occur only if the energy of the photon is sucient to overcome the corre-
sponding activation energy.
For most organic molecules, absorption in the near-UV (190400 nm) involves
electronic transition from the highest occupied molecular orbital (HOMO) to
the lowest unoccupied molecular orbital (LUMO). Commercial polymers can be
broadly divided into two categories, depending on whether or not they contain de-
localized p-electrons, sometimes combined with heteroatoms with nonbonding
valence shell electron pairs (O, N, S) in their chemical structure. Polymers
which contain carbonyls (
a
a
CbO), conjugated polyenes (
a
a
CbCaCbC
a
a
), ketenes
(
a
a
CbCaCbO), and sulfones (aFaSO
2
aFa) belong to the rst group of chromo-
phores and are capable of absorbing light in the near UV (190 nm < l
max
< 400
nm); see Table 15.5. Those from the second group possess only single covalent
bonds, such as CaC, CaH, CaO, CaCl, and CaF, and can in principle absorb light
only in the far UV (l
max
< 190 nm).
Owing to vibrational and electronic couplings, UV absorption bands of poly-
atomic molecules in the condensed state are generally quite broad, with width at
half-maximum commonly exceeding 6080 nm. Even with this broadness, poly-
mers such as polyolens, polyacetals, poly(vinyl chloride), or polyacrylonitrile
should neither absorb nor degrade when exposed to light with wavelength above
@230 nm. In practice, however, the UV absorption spectra of commercial samples
of all the cited polymers show a broad absorbance band which extends well above
the expected limits (Figure 15.8). Generally, these extraneous absorbances are weak
and can be determined only after proper signal processing. This situation is illus-
trated in Figure 15.9 for commercial additive-free lms of HDPE and iPP.
Tab. 15.5. Principal chromophore groups in synthetic polymers
[a]
.
Polymer Chromophore l
max
[nm] e
max
[L mol
C1
cm
C1
]
Polyesters
a
a
CbO 188 (279) 900 (15)
Polyaromatics aFa 200 (256) 4 400 (226)
Poly(aryl ketone)s aFaCOaFa 250 (350) 18 000 (120)
Polydienes
a
a
CbCa
a
185 (230) 8 000 (2)
Conjugated polyenes
a
a
CbCaCbCa
a
a(CbC)
3
a
a(CbC)
10
a
217
263
432
20 900
@5 10
4
@2 10
5
Ketenes
a
a
CbCaCbO 220 (350) 2 10
4
(30)
Sulfones aFaSO
2
aFa
[a]
Values in brackets refer to the secondary absorption band.
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
200 250 300 350
PSU, 1m
PET, 2m
PC, 2m
PS, 5m
PMMA, 20m
PVC, 100m
a
b
s
o
r
b
a
n
c
e
wavelength [nm]
Fig. 15.8. UV absorption spectra of some common industrial
polymer lms, at the thickness indicated.
Far-UV spectroscopy indicates that the absorption edge of long-chain alkanes
starts at about 155 nm. Absorption at much longer wavelengths observed in com-
mercial polyolens could be explained only by the presence of chromophore im-
purities and chemical defects formed during the synthesis, storage, and processing
of the polymer. The absorption peak at 180 nm recorded in HDPE, for instance,
has been attributed to vinylidene end groups, as revealed by independent FTIR
measurements (Figure 15.9).
Impurities in polymers can be classied as internal or external [7].
Internal impurities These are part of the molecular structure, situated either along
the chain or at chain end(s), and may consist of:
v
Anomalous structural units, which result from the kinetics of polymerization.
v
In-chain peroxides, formed during polymer synthesis. Free-radical polymeriza-
tion is generally accomplished without strict exclusion of air and small amounts
of oxygen dissolved in the monomer will be scavenged by the macroradicals and
included in the polymer chain as peroxide linkages. Photolysis of these peroxide
groups gives alkoxy radicals, leading ultimately to hydroperoxides. Alternatively,
if polymerization has been carried at elevated temperatures, the peroxides incor-
porated will undergo thermal fragmentation and disproportionation to form phe-
nyl alkyl ketone end-group chromophores.
v
Carbonyl containing groups formed during material transformation. Processing,
with elevated temperature and high shearing stresses, provides ample opportuni-
ties for thermal oxidation. Even at ambient temperature, some polymers such
0.0
1.0
2.0
3.0
160 180 200 220 240 260 280 300 320 340
wavelength [nm]
HDPE
iPP
a
b
s
o
r
b
a
n
c
e
Fig. 15.9. UV absorption spectra of 50 mm-thick lms of
additive-free commercial HDPE () and iPP (-- -).
as isotactic polypropylene or cis-polybutadiene, can be readily oxidized if un-
stabilized.
External impurities Such impurities are contained in the sample but not incorpo-
rated in the polymer structure.
During synthesis, processing and storage, the polymer can be contaminated
or blended with a variety of external chemical species which may contain chromo-
phore and photoreactive groups. Some typical external impurities found in com-
mercial plastics are:
v
residual catalysts and initiators,
v
traces of solvents (aromatic solvents, in minute amounts, can act as photosensi-
tizers (Ref. 26, p. 125),
v
pigments, dyes, and additives,
v
traces of metal, metal oxides, or metal salts from the reactor, processing equip-
ment, and containers.
15.5.2
The Solar Spectrum
The majority of polymer bond dissociation energies are within the 290420
kJ mol
1
bracket (allylic CaC being the lowest, and aCH
2
aH the highest). The acti-
vation energy of photochemical reactions in the gas phase usually lies just a few
percent above the corresponding bond dissociation energy, while it can reach 40
kJ mol
1
for diusion-controlled reactions in the condensed state. Therefore, de-
pending on the type of bond to be broken, any absorbed photons with wavelength
shorter than approximately 420 nm for the weakest bonds, to 290 nm for the stron-
gest ones, could promote chain scission.
The importance of photodegradation in outdoor weathering depends much on
the sunlight spectrum. The solar spectral irradiance at the top of the atmosphere
is well-approximated by black-body radiation with a temperature of 5770 K. The
Earths atmosphere, on the other hand, is practically opaque to any wavelength
shorter than about 290 nm as a result of ozone absorption. The UV range of solar
irradiation is commonly divided into three spectral regions of decreasing wave-
lengths denoted by UV-A, UV-B and UV-C. Although UV-B light is the most e-
cient at initiating photodegradation, its intensity at the Earths surface is fortu-
nately very limited, owing to the screening eect of ozone, and accounts for
<0.5% of the total radiant energy of @1300 W m
2
at noon in the southern regions
(Figure 15.10).
15.5.3
Photo-oxidation Prole
It has long been recognized that photochemical damage is more severe at the sur-
face than in the sample interior. The reasons for this inhomogeneity are twofold:
Penetration distance of light For transparent systems, the light intensity I(x) de-
creases with penetration distance x according to the LambertBeer law according
to Eq. (63), where I
0
is the incident light intensity, and a the absorption coecient,
which is proportional to the molar absorption coecient e.
I(x) = I
0
exp(ax) (63)
Because most radiation is polychromatic, the range of available a is broad. For
many materials, the propensity for degradation increases in parallel with the
absorption coecient when the light wavelength decreases. As a consequence,
the depth of penetration decreases for the wavelengths which are most eective
in promoting photodegradation. As the extent of degradation increases, more UV-
absorbing substances are formed, which act as surface screeners and further in-
crease the fall-o of the depth of the degraded layer.
For materials which scatter light, such as semicrystalline polymers, and for poly-
mers which contain charges or pigments, the LambertBeer law should be re-
placed by the KubelkaMunk equation [Eq. (64), with K = absorption coecient,
S = scattering coecient and R = reectance of the material].
(K/S) = (1 R)
2
/2R (64)
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
250 300 350 400
nm
ozone absorption spectrum
W
.
m
-
2
.
n
m
-
1
UV-C UV-B UV-A
top of the atmosphere
bottom of the atmosphere
Fig. 15.10. Spectral irradiance of sunlight at the top () and
bottom ( ) of the atmosphere, in the summer at latitude
41
N. The dierence results from ozone absorption.

Penetration distance of oxygen Oxidative degradation is a reaction between oxygen
and the polymer. The solubility and diusion coecient of oxygen in solid poly-
mers are typically one order and two orders of magnitude less, respectively, than
in organic liquids. Because of this slow diusion of oxygen, the oxidative rate de-
creases rapidly with depth from the surfaces. The eect of oxygen diusion can be
modeled by Ficks second law, modied by the rate of oxygen consumption (k). It is
frequently assumed that the rate of oxygen consumption exactly matches the oxy-
gen supply by diusion, that is, d[O
2
]/dt = 0. In this steady-state situation, the
oxygen concentration prole does not change with time, resulting in a dierential
equation [Eq. (65)].
D(q
2
[O
2
[/qx) k[O
2
[ = 0 (65)
The oxygen diusion constant, D, depends on the state of aging process, the reac-
tant concentrations, and the sample morphology (orientation, crystallinity). It fol-
lows approximately an Arrhenius-type temperature dependence as in Eq. (66),
where D
0
is a proportionality constant, and R the molar gas constant.
D = D
0
exp(E
a
/RT) (66)
In the case of iPP lm, for instance, the values given by Eqs. (67)(69) have been
determined (Ref. 6, p. 169).
Small-spherulite iPP: D = 26:0 exp[43 900/RT) cm
2
s
1
(67)
Large-spherulite iPP: D = 3:5 exp[38 500/RT) cm
2
s
1
(68)
Oriented iPP: D = 2:0 exp[38 500/RT) cm
2
s
1
(69)
Free radicals react with oxygen according to reactions (2) and (3) of the simplied
degradation (Scheme 15.1). A simple approximation for k[O
2
[ is given by Eq. (70),
where C
1
and C
2
are constants [34].
k[O
2
[ = C
1
[O
2
[/C
2
[O
2
[ 1 (70)
By combining Eqs. (65) and (70), the oxidation distribution can be calculated by
numerical methods and compared with experiments using some depth-proling
technique (microFTIR on microtome slices, ATR-FTIR, photoacoustic FTIR). The
frequently encountered U-shaped curve indicates a diusional regime, in which
the rate of chemical reactions is limited by oxygen diusion (Figure 15.11). The
temperature coecient of the oxidation rate, 105125 kJ mol
1
, is much higher
than the activation energy for oxygen diusion (@40 kJ mol
1
). Thus, by lowering
the temperature, one can reach the kinetic oxidation regime, characterized by an
oxidation rate independent of sample size.
15.5.4
Inuence of Wavelength: the Activation and Action Spectrum
The actinic eects of UV and visible radiation on material are wavelength-
dependent, owing to the spectral selectivity in the absorption of the incident radia-
tion, and the quantum eciency of degradation. The absorption of a photon by a
chromophore promotes an electronic transition between two molecular orbitals of
dierent energies. Starting from the ground state, a transition to a dierent elec-
tronic state can be eected by changing the energy of the photon. It is therefore
logical to expect that the irradiation wavelength may have a profound inuence
not only on the rate, but also on the mechanism of photodegradation. The concept
of quantum yield, dened as the number of degraded molecules per absorbed pho-
ton, is widely applied in the photochemistry of small organic molecules. It is di-
cult to apply to industrial plastics, which are complex mixtures of species with vari-
able photon absorption and dierent photophysical and photochemical properties.
Early investigations relied on the notion of an activation spectrum to characterize
the eect of the photon wavelength on the extent of degradation. The activation
spectrum of a material is dened by (i) the spectral absorption properties of the
material; (ii) the emission properties of the light source; (iii) the quantum e-
ciency of the photoinitiated processes; and (iv) the type of degradation being mea-
sured.
Although simple to measure, the activation spectrum does not consider the
amount of incident radiant energy present at each wavelength, and is hence depen-
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0 50 100 150 200
distance from exposed surface (m)
A
b
s
o
r
b
a
n
c
e

(
1
7
1
8

c
m
-
1
)
Fig. 15.11. Typical photodegradation prole for a weakly
UV-absorbing, 200 mm-thick polymer lm.
dent on the specic light source involved. The action spectrum is introduced to cor-
rect for this weakness by explicitly taking into account the eciency of light-induced
damage per incident photon, as a function of irradiation wavelength. Relatively
few investigations have been performed on polymer action spectra until recently,
as a result of the lack of suitable high-intensity, tunable, monochromatic source
for irradiation. The use of sharp-cut lters in pairs with half-height bandwidths of
approximately 20 nm does not usually provide sucient wavelength resolution.
The availability of large spectrographs now allows the recording of continuous acti-
vation and action spectra across the whole wavelength range of interest [34].
An action spectrum is a graph of the reciprocal of the radiant exposure required
to produce a given eect (for instance, yellowing index or increase in absorbance
at a standard wavelength) at each wavelength (Figure 15.12). All the data in such
curves are normalized to the datum at the most ecient wavelength. This kind of
plot gives crucial information on the spectral sensitivity of the material. Its knowl-
edge is particularly important for proper comparison between outdoor weathering
and accelerated articial aging, for which the light source spectrum may dier sig-
nicantly from solar irradiance.
In most instances, the action spectrum decreases empirically with increasing
irradiation wavelength according to a logarithmic relationship (Figure 15.13B), as
given in Eq. (71), with l = irradiation wavelength, and S(l) = relative spectral
damage [33].
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
280 290 300 310 320 330 340 350 360 370 380 390 400
wavelength [nm]
0.5
1.0
1.5
2.0
2.5
3.0
3.5
0.0
a
b
s
o
r
b
a
n
c
e
sample absorbance
(right scale)
lamp irradiance
(W
.
m
-2.
nm
-1,
left scale)
increase in absorbance
(left scale)
Fig. 15.12. Activation spectrum of a 700 mm
lm of unstabilized bisphenol-A polycarbonate,
based on the increase in absorbance at 310 nm
after accelerated aging with a borosilicate-glass
ltered xenon lamp. Superimposed are the
spectral irradiance of the irradiation source
and the UV-absorption spectrum of the
polymer (redrawn from data in Ref. [35]).
0
5
10
15
20
25
30
290 300 310 320 330 340 350
irradiation wavelength [nm]
10C 50C
r
a
d
i
a
n
t

e
n
e
r
g
y

[
J
.
c
m
-
2
]
(A)
-3
-2
-1
0
1
2
3
4
290 300 310 320 330 340 350
10C
50C
l
n
(
r
a
d
i
a
n
t

e
n
e
r
g
y

/
J
.
c
m
-
2
)
(B)
Fig. 15.13. Action spectrum of a 700 mm lm of bisphenol-A
polycarbonate, based on the radiant energy required for a 10%
decrease in transmittance at 360 nm: (A) linear plot; (B)
semilogarithmic plot.
ln S(l) = ln(a) bl (71)
Based on absorption and energetic considerations, photochemistry has long relied
on the existence of a critical wavelength below which no reaction should occur
(Section 15.5.1). The question then arises of the limit of applicability of the loga-
rithmic relationship when the irradiation wavelength is much greater than the ab-
sorption maximum.
15.5.5
Photodegradation Mechanisms
Photodegradation diers from thermal degradation mainly in the mode of initia-
tion. All the other mechanistic steps bond scission, propagation, chain branch-
ing, and termination are similar to thermal degradation. Indirect dierences
may exist, however, between thermal and photodegradation as a result of variations
in experimental conditions, such as a higher temperature for the former mode of
aging which may result in a lower concentration of dissolved oxygen, a lower rate
of peroxide decomposition, or a change in material morphology.
15.5.5.1 Photoinitiation
It is practical to distinguish two types of initiation: primary, when the radiation is
directly absorbed by the functional group of the polymer; and secondary, when the
radiation is absorbed by certain of the oxidation products (peroxides, carbonyls).
For saturated polymers, such as polyolens, secondary initiation is the predomi-
nant mode of initiation, particularly in the latter stages of deterioration.
Formation of excited states following photon absorption constitutes the rst step
in any photochemical reaction. When light is absorbed by a chromophore, either
in-chain or external, the energy is used to promote an electron from the
ground state to an excited state. The excited state can relax back to the ground state
with release of extra energy in the form of a photon or heat. Photochemistry begins
if the energy stored in the excited state is used to drive a chemical reaction. The
rate at which this reaction occurs depends on the energy content (the exciting
wavelength), the chemical nature of the absorbing chromophore, and its environ-
ment. The chemistry of the excited state in polymers has been studied with model
compounds. In a real environment, however, the presence of additives, impurities,
residual catalysts, and so on can exert a decisive inuence not only on the degrada-
tion rates but also on the degradation mechanisms. The reactions are further com-
plicated by the occurrence of additional chromophores which are formed during
photodegradation. Following the diversity of impurities which can be encountered,
and the complexity of ensuing reactions, there has been much controversy in the
literature about the true photoinitiation mechanisms. This debate, however, is es-
sentially academic, since the initiation mechanism does not inuence the global
rate of photo-oxidation.
Although acting as an external agent, oxygen deserves a special situation, owing
to its presence in any practical weathering situation. Oxygen can be easily con-
verted to the singlet state (
1
D
g
or
1
S
g
) by absorption of a photon, or it can be
formed during decomposition of secondary compounds. An important mode of
photoinitiation occurs via a charge-transfer complex between oxygen and the poly-
mer (for instance, a polyolen), with formation of hydroperoxides [Eq. (72)].
C
R
3
R
2
R
1
H + O
2
C
R
3
R
2
R
1 H
.....
O
2
C
R
3
R
2
R
1
H
+

-
O
2
C
. .
O
2
H
R
3
R
2
R
1
C
R
3
R
2
R
1 OOH
(72)
In spite of the diversity in photoinitiation mechanisms, two principal modes of re-
action can be identied in most commercial polymers: the Norrish photoprocesses
and the photo-Fries rearrangement.
15.5.5.2 The Norrish Photoprocesses
One common chromophore frequently encountered in a number of polymers is
the carbonyl ketone which shows a weak pp
+
transition band centered at 280 nm
but extending into the UV-B region. Polymers containing this chromophore un-
dergo two types of photochemical reaction (Scheme 15.2):
v
the Norrish type I reaction, resulting in an a-cleavage with formation of two end-
polymeric radicals and carbon monoxide;
v
the Norrish type II reaction, which involves an intramolecular H-abstraction via a
cyclic six-membered transition state. The photoscission proceeds by means of a
short-lived triplet state and a biradical intermediate.
15.5.5.3 Photo-Fries Rearrangement
A second large class of polymers contains phenyl moieties, either in the backbone
(PPO, PC, PET, PSU) or as a side group (PS). Another common phenyl group
photoreaction, when subjected to UV radiation, is the photo-Fries rearrangement
(Scheme 15.3). Upon absorption of a photon, the n- or p-orbital of the chromo-
phore is promoted to a singlet p
+
excited state. Bond scission occurs primarily at
aromatic ether CaO bonds, and causes rearrangement or degradation of the poly-
mer backbone. Because the photo-Fries rearrangement proceeds in a caged envi-
ronment, it is independent of free volume and is almost independent of T
g
.
The photo-Fries mechanism can be promoted with light in the region above 300
nm (Figure 15.14), and accounts for the yellowing of the polymer observed at long
wavelengths. Chain scission, on the other hand, is promoted by light at shorter
wavelengths. Because photo-Fries products are easily photodegraded, only small
CH
2
CHCH
2
CHCH
2
R
O
C
R
O
C
CH
2
CHCH
2
CHCH
2
+ C
R
O
C
O
R
CH
2
CH
2
+ CH
2
=CCH
2
R
O
C
R
O
C
N
o
r
r
i
s
h

I
N
o
r
r
i
s
h
I
I
Carboxyl in pendent groups
N
o
r
r
i
s
h

I
N
o
r
r
i
s
h
I
I
CH
2
CH
2
CCH
2
CH
2
CH
2
O
CH
2
CH
2
C + CH
2
CH
2
CH
2
O
CH
2
CH
2
CCH
3
+ CH
2
=CH
2
O
Carboxyl in backbone
CH
C
CH
2
C
H
O
R
CH
C
CH
2
C
H
O
*
R
RC
O
CH
hv
Six-membered transition state
.
.
. .
Scheme 15.2. Norrish photoprocesses in carbonyl-containing polymers.
O
. .
CO C
CH
3
CH
3 O
C
CH
3
CH
3
OCO
O
C
CH
3
CH
3
C
CH
3
CH
3
hv
OH
C
CH
3
CH
3
C
CH
3
CH
3
CO
O
OH
C
CH
3
CH
3
C
CH
3
CH
3
C
O
OH
hv
Scheme 15.3. Photo-Fries rearrangement in bisphenol-A polycarbonate.
amounts of them remain in aged material, which shows a predominance of side-
chain oxidation products.
Once photoradicals are formed, they can either recombine in the cage or diuse
to the outside for further reactions. The radicals formed can undergo a variety of
abstraction and decomposition reactions, resulting in a multitude of chemical
products. The propagation and recombination steps are similar to those encoun-
tered in thermal degradation, and will not be discussed further here. In the pres-
ence of UV > 240 nm and oxygen, the phenyl groups in PS, PPO, and PC can un-
dergo ring-opening oxidation with formation of mucondialdehyde (Scheme 15.4)
[36].
15.6
Radiolytic Degradation
15.6.1
Interaction of High-energy Radiation with Matter
Understanding the eects of ionizing radiation on the properties of plastics mate-
rials is important in nuclear engineering, space research, radiation processing, and
radiation sterilization.
Radiation composed of photons or particles with energy much higher than those
encountered in electron bonding orbitals is referred as high-energy radiation (X- or
g-rays, high-energy electrons, protons, and charged particles). Owing to this excess
0.E+0
1.E-4
2.E-4
3.E-4
4.E-4
5.E-4
6.E-4
7.E-4
8.E-4
9.E-4
250 260 270 280 290 300 310 320
q
u
a
n
t
u
m

y
i
e
l
d
Fig. 15.14. Quantum yield for chain scission (o), eciency
of photo-Fries rearrangement (k), and absorption spectrum
(- -D- -) of bisphenol-A polycarbonate [34].
energy, high-energy radiation can penetrate much deeper into material to create
ions, superexcited states, and hot radicals. The degradative eects are also much
more extensive than with UV. The principal sources of high-energy radiation are
electron beam accelerators, which account for 90% of commercial radiation capac-
ity; the remainder consist of
60
Co installations.
60
Co is unstable and decays to the
stable
60
Ni according to Eq. (73).
60
Co(t
1/2
= 5:27 y) =
60
Ni
+
b
(73)
The nuclei of Ni atoms that result from this decay are in an excited state and im-
mediately emit two g-rays of energies 1.332 and 1.173 MeV. The low-energy b
are
absorbed by the
60
Co housing and all the radiolytic eects result from the g-ray
emission.
Electron accelerators can deliver higher dose rates, whereas
60
Co sources are
characterized by a greater depth of penetration.
A fast electron loses most of its kinetic energy by inelastic collisions with elec-
trons from the medium, producing energetic secondary electrons. Depending on
the energy of the radiation, many secondary electrons of decreasing energy will be
P
.
PH
CH
2
O C
O
CH
3
O
.
C
CCH
3
O
O
COH
O
O
OH O
hv/O
2
+ HCOOH + CH
3
COOH
O C
O
C
CH
3
CH
3
O
OC
O
C
CH
3
.
CH
2
O
(A)
C O
.
OH
+
1
O
2
C O
O O
acids, esters
(B)

Scheme 15.4. Chain scission (A) and ring-opening (B) reactions in bisphenol-A polycarbonate.
created (d-rays). Owing to the augmentation of linear energy transfer (LET) with
decreasing kinetic energy, the fast electrons lost most of their kinetic energy near
the end of the track, resulting in local regions of highly reactive species called
short tracks, blobs, and spurs (Figure 15.15).
In
60
Co irradiation, the primary interaction is Compton scattering between the
high-energy photon and an atomic electron. Only part of the photon energy is
transferred to the electron and the resultant photon of lower energy is scattered.
The process will continue with creation of more scattered electrons and secondary
electrons (Figure 15.16). Except for the primary event, the eects of g-rays and ac-
celerated electron irradiation are similar. From a single incoming g-photon or high-
energy electron, a shower of secondary electrons is generated which is responsible
for most of the ensuing chemical reactions.
15.6.2
Radiation Chemistry
Radiation chemistry is now a well-established area of science that deals with chem-
ical and physicochemical changes produced by the absorption of high-energy radi-
ation (HER) by matter. The subject covers events that occur from the passage of the
ionizing particle to the completion of chemical reactions. To encompass the enor-
spurs <100 eV
blobs 100-500 eV
short tracks <5000 eV branch tracks >5000 eV
delta rays
primary
Fig. 15.15. Schematic representation of a fast electron track.
hv
0
hv
1
hv
2
hv
3
e
-
e
-
e
-
Fig. 15.16. Compton scattering and fate of the secondary electrons.
mous time span for the various processes, it is usual to distinguish between the
physical stage (10
17
10
11
s) when energy from the incident particle is depos-
ited into localized regions of space (spurr), the physicochemical stage (10
12
10
3
s) during which reactive species (ions, quasi-free electrons, excited molecules,
hot radicals) are formed and react within the spurs, and the chemical stage
(10
9
10
3
s in solution, several days in solid polymers) where stable species (rad-
icals, trapped electrons, cations) diuse and react outside the clusters. The stan-
dard unit of absorbed dose is the Gray (Gy), dened as the energy imparted by the
high-energy radiation to a mass of matter equivalent to 1 J kg
1
(1 Gray = 100
rad). Molecular changes are characterized by a G factor, in units of mmol J
1
, de-
ned as the event yield per 100 eV of absorbed energy.
Although much discussion has occurred in the past on the relative importance of
radical and ionic reactions, it is now established that the major chemical changes
in irradiated polymers are accounted for by free-radical reactions [37]. In the early
stage of the reactions, the reactive species are concentrated in spurs and particle
tracks in a manner similar to their parent ionized or excited molecules. The ki-
netics at this point must take into account the inhomogeneous distribution of the
radicals, before they can diuse away. Ionizing radiation is unique in the sense
that reactions can be initiated randomly at any temperature. Cryogenic tempera-
tures, at 4 K and below for instance, have been used extensively to prolong the
macroradicals lifetime for ESR measurements. Apart from the mode of initiation,
all other material changes brought about by high-energy radiation are governed by
radical reactions, in perfect analogy to those generated by other means, such as
photochemical, thermal, or mechanochemical degradation. As a matter of fact, de-
spite the enormous dierence in HER energy (10
6
eV) and molecular binding en-
ergy (@5 eV), the chemical eects of HER can best be compared with those of UV
light with energy in the 520 eV range.
The eects of ionizing radiation depend greatly on the structure of the polymer,
the temperature, and the nature of environment. A 50% loss in ultimate elonga-
tion (a common measure of the eect of irradiation), for instance, can vary from
doses as low as 3.5 kGy for PTFE, to more than 4000 kGy for PS, polyimide, or
PEEK (Table 15.6). The unusual radiation sensitivity of PTFE is attributed to the
unique stability of peruoro macroradicals which favors chain scission over cross-
linking. In the presence of air, these uorine-containing radicals are converted into
peroxy radicals which degrade readily into low MW fragments. PTFE can be cross-
linked by HER when irradiated in an inert atmosphere above its melting point
(330340
C). Polymers containing phenyl groups owe much of their radiation re-
sistance to excited-state energy transfer to the benzene rings, which act as excited-
state quenchers (see Section 15.6.3). Although energy transfer is the widely ac-
cepted protection mechanism in the HER degradation of aromatic compounds, it
does not explain why styrene does not show the same protective eect as polysty-
rene. One alternative suggestion is that H atoms resulting from the primary eect
of radiation are added to the aromatic rings, and are no longer able to produce sec-
ondary macroradicals by abstraction.
The two fundamental processes that result from radiochemical reactions
are chain scission and crosslinking, characterized by G
s
and G
x
, respectively. If
G
s
< 4G
x
, branched polymers can be formed and may eventually evolve into a
three-dimensional network structure. Based on the assumptions that:
v
the initial polymer MWD follows a random distribution,
v
cross-linking occurs by H-linking, and
v
crosslinking and scission occur with random spatial distribution (without cluster-
ing),
Charlesby and Pinner have shown that the sol fraction(s) should follow Eq. (74),
where R [kGy] is the absorbed dose [37].
s s
0:5
= 0:96 10
5
/(R M
w
G
x
) (G
s
/2G
x
) (74)
The CharlesbyPinner plot of (s s
0:5
) as a function of 1/R gives a straight line,
with slope m1/G
x
, and an intercept on the ordinate equal to G
s
/2G
x
. Departure
of the plot from a straight line may originate from deviation from a random distri-
bution, or from chemical heterogeneities in copolymers. Regardless of the shape of
the curve, the incipient dose for gelation is determined, by denition, from the sol
curve at s s
0:5
= 2 (Figure 15.17).
Tab. 15.6. Relative radiation stability in air of major
commercial polymers (based on a 50% decrease in ultimate
elongation).
Polymer Dose [kGy]
Polytetrauoroethylene 10
Polytriuorocholorethylene 30
Poly(methyl methacrylate) 300
Polycaprolactam 600
Isotactic polypropylene 1000
High-density polyethylene 1000
Poly(vinyl chloride) 1500
Poly(ethylene terephthalate) 2000
Poly(triethylene glycol dimethacrylate) 2000
Low-density polyethylene 3000
Polyurethanes 3000
Melaminoformaldehyde resin 4000
Polycarbonates 5000
Polystyrene 5000
Epoxy resin ED-10 15000
Epoxy resin ETZ-10 30000
Polyimides 100000
15.6.3
Radiolysis Stabilization
It has been known since the early days of radiation chemistry that some simple
organic compounds, such as benzene, halogenated hydrocarbons, nitriles, amines,
and alcohols, can protect the polymer from the deleterious eects of high-energy
radiation. Many of these antirad substances interfere at some stage with the ra-
diolytic degradation scheme, as depicted in Table 15.7, to reduce damage to the
plastics. The most ecient present-day antirad agents are antioxidants which
act essentially in the chemical stage by scavenging free radicals in a similar way
to that in the other types of degradation. Aromatic compounds are highly ecient
at quenching excess energy of excited states formed by geminal recombination. Be-
cause most commercial antioxidants have aromatic rings in their structures, they
can also act as primary absorbers by diverting the radiation energy into harmless
vibrational energy, as in Eqs. (75) and (76).
P
g; e
spur
P
+
2R
v
(75)
P
+
Q P Q
+
(76)
Aromatic polymers owe much of their radiation resistance to this internal protec-
tion eect [40]. An ecient method of radiation protection would be to blend the
0
1
2
0
10
-3
2
.
10
-3 (kGy/R)
1980 kGy 870 kGy 38 kGy
1.0
0.72
G
s
/2G
x
= 0.36
1000 500 (R/kGy) 2000 400

s

+

s
50% 70% 100% SAN
Fig. 15.17. CharlesbyPinner plot of irradiated
compatible PMMASAN blends. The sol and
gel fractions refer solely to the SAN
component in the mixture and are corrected
for grafting to PMMA. Large curvatures of the
plot for blends are interpreted as a result of
chemical interactions between the two
components (redrawn from Ref. [38]).
degradative polymer with a radiation-resistant one. Energy transfer (Forster type) is
ecient only at short range and the eect is most noticeable with compatible
blends, such as PMMA and SAN (Figure 15.17).
15.6.4
Applications
High-energy radiation can penetrate deeply into organic materials, and can initiate
reactions at low temperature without added chemicals or catalyst. These unique
features are exploited in an increasing number of industrial applications, particu-
larly in the biomedical eld, in which chemical contamination or thermal degrada-
tion should be avoided [41]. Radiation sterilization of medical commodities, one of
the early achievements of radiation engineering, continues to increase its market
share to the detriment of standard methods such as chemical sterilization with di-
Tab. 15.7. Polymer protection scheme during radiolysis.
Radiolysis stage Physical or chemical event Protection means Protection mechanism
Physical energy absorption sheets of lead or concrete decrease in radiation intensity
Physicochemical molecular ionization positive ion scavengers transfer of one electron to
polymer cation without
subsequent excitation
geminate recombination electron scavengers acceptance of ejected electron
and lower probability of
dissociative recombination
dissociative states electronic excited-state
quenchers
divergence of excitation
energy into heat or longer-
wavelength electromagnetic
radiation
cleavage of CaH bonds H atom donors transfer of H atom to
macroradicals (reparation
mechanism)
Chemical diusion and abstraction
reactions of mobile H
atoms
H atom acceptors acceptance of H atoms,
preventing formation of
more radicals
reactions of macroradicals radical scavengers reaction with macroradicals,
formation of stable species
surface coatings decrease in oxygen diusion
reactions of macroradicals
with oxygen
oxygen absorbers React with molecular oxygen
under irradiation
benzophenone derivatives Antioxidants Disrupt oxidation chain
reaction by converting
peroxy radicals into stable
products
chain reaction of peroxy
radicals (radio-oxidation)
peroxide decomposers catalytic destruction of peroxy
radicals
ethyl ether, or heat treatment. In the examples mentioned, the value of the nished
products is generally high and the cost of radiation processing does not enter into
consideration. In other applications, where the product is inexpensive radiation
processing can still be economically viable if the quantity of radiation energy re-
quired is low. Radiation treatment of food and radiation-induced grafting or cross-
linking of certain plastics belong to the latter category. Food is commonly irradi-
ated at low doses in the 0.110 kGy range, in ordinary boxes or containers. Food
preservation by irradiation is gaining acceptance for an ever-increasing number of
agrochemical products such as spices, vegetables, and processed meat. This tech-
nique is currently viewed as the most eective of the available alternatives (cold
storage, heat treatment, fumigants).
15.6.4.1 Radiation Sterilization
Disposable medical products are required by legislation to be sterilized prior to
use. Among the four basic methods of sterilization heat, ethylene oxide, gamma
irradiation (
60
Co), and electron beam techniques the last has steadily increased
its market share, largely at the expense of the diethyl ether method as a result of
regulatory concerns about the quantity of chemical residuals. The Federal Drug
Administration (FDA) in the US allows a device to be labeled as sterile if less
than one device out of a batch of one million can show biological contamination.
The standard dose to achieve this level is 25 kGy. Medical plastics that need to be
sterilized must withstand at least this dose. The data given in Table 15.6 can be
used as an initial estimate in material selection. Materials which are likely to de-
grade, such as PTFE or POM, should be avoided. Polymers containing aromatic
groups have much greater radiation resistance than those with an aliphatic struc-
ture. Similar improvements can be obtained with crosslinks, and most thermo-
sets and elastomers can withstand at least one radiation sterilization. The use of
antioxidant additives can signicantly oset the eects of radiation, and even a
radiation-sensitive polymer such as polypropylene can withstand several radiation
sterilization cycles when properly stabilized.
15.6.4.2 Controlled Degradation and Crosslinking
The reactions of chain scission, crosslinking, and grafting initiated by ionizing ra-
diation have found many important applications in the plastics and rubber indus-
tries. Although high-energy radiation is destructive for most materials, this propen-
sity can be usefully exploited in the controlled degradation of several polymers,
such as PTFE, PEO, PP and cellulose. The most well-known example of degrada-
tion application is the manufacture of PTFE powders. Undegraded PTFE is too
tough and slippery to grind. After submitting the polymer to a high dose range
(5001000 kGy), the degraded PTFE becomes brittle and can be converted to ne
particles while conserving its low surface energy. The PTFE powder is used as a
solid lubricant, or formulated as grease for high-temperature applications.
Radiation crosslinking is another way to tailor properties to specic applications.
High-energy radiation provides a clean and cost-eective method to achieve this
means. The technique has been applied in the crosslinking of high-purity medical
products, such as gloves and condoms, orthopedic ultra-high MW PE hip joints,
and biocompatible hydrogels. Other important industrial applications of radiation
crosslinking include the production of heat-shrinkable products, wires, cables, and
tubing.
15.7
Mechanochemical Degradation [42]
15.7.1
Initiation by Mechanical Stresses
15.7.1.1 Eect of Tensile Stress on Chemical Reactivity
The input of external energy, of either thermal or electromagnetic origin, is well
known to the organic chemist as an ecient way to promote chemical reactions.
Mechanical energy, although ubiquitous in everyday life, is rarely considered as a
bona-de source of chemical activation. The main reason probably stems from the
ineciency of this mode of excitation for small molecules where most of the ap-
plied mechanical energy is readily dissipated into heat and the work of bulk defor-
mation, leaving little available as chemical potential. In polymer systems, on the
contrary, mechanochemical reactions are ubiquitous as a result of the unique pro-
pensity of macromolecules to store free energy upon deformation and to sustain a
high level of stress for a suciently long time for chemical reactions to occur. Me-
chanochemical degradation is ubiquitous in macromolecular systems and can be
encountered in practically any eld involving high MW polymers. The formation
of free radicals by mechanical stress has been detected during polymer processing,
analysis, weathering, and gel swelling. Chain scission has also been observed in
applications as diverse as drag reduction, rubber mastication, and mechanochemi-
cal synthesis. It was known for centuries that the application of stress under cer-
tain conditions, such as the combing of wool, the mastication of rubber, or the
kneading of dough, can improve the physical properties of a few materials which
were later recognized as being polymeric.
Following the application of stress, a molecular system will attempt to minimize
its total free energy by a series of congurational rearrangements, such as kink
annihilation, chain disentanglement, and orientation. According to molecular me-
chanics, the excess energy of stress (E
s
) in a chemical system comes from several
sources, namely nonvalence and coulombic interactions, torsional deformation,
and angular and valence-bond strain energies. Among the dierent modes of mo-
lecular deformation, bond-angle distortion and valence-bond stretching have the
most profound inuence on the electronic density distribution, and hence on the
chemical reactivity. In the region of stresses of around 80 GPa, the valence angles
for CaC bonds will become deformed from their equilibrium positions whereas
bond stretching and rupture occur at some still-higher values in the vicinity of
740 GPa. Although stress-induced chemical reactivity can be explained only by
quantum mechanical calculations, as was done for the acceleration eect of water
during crack propagation of silica glasses, a qualitative picture can be gained based
on mechanical arguments. In carbocyclic compounds, E
s
originates principally
from valence-angle deformation and it is well known that ring strain could aect
the rate of some chemical reactions in a drastic way. For example, if the transition
state necessitates distortion of the valence-bond angle from y
0
to y
+
, the valence
bond-angle contribution to the activation energy is given by Eq. (77), where k
y
is
the elastic constant for bond-angle deformation.
E
ang
=
1
2
k
y
(y
0
y
+
)
2
(77)
If, however, the same bond angle is already distorted from y
0
to y under mechani-
cal stress, the activation energy will be given by Eq. (78), resulting in a dierence of
DE
ang
[Eq. (79)].
E
ang
=
1
2
k
y
(y y
+
)
2
(78)
DE
ang
=
1
2
k
y
[(y
0
y
+
)
2
(y y
+
)
2
[ (79)
In solid polymers, rate enhancement under stress has frequently observed, for
example in UV-photo-oxidation of natural silk, polycaprolactam, and poly(ethylene
terephthalate). However, quantitative interpretation is dicult in these systems
due to interdependence of several stress-dependent factors such as the rate of oxy-
gen diusion or changes in polymer morphology which supersede the elementary
molecular steps. Similar experiments in the uid state showed unequivocally that
ow-induced stresses can accelerate several types of reaction, the best studied
being the hydrolysis of DNA and polyacrylamide. In these examples, hydrolysis
involves breaking of the ester OaPO and the amide NaCO bonds. The tensile
stress stretches the chain, and therefore facilitates the formation of a transition
state in which the bond length is increased for hydrolysis, thus enhancing the
rate constant for the process. Other documented examples of stress-induced chem-
ical reactions are the acylation of cellulose and the addition of 4-hydroxy-2,2,6,6-
tetramethylpiperidine-1-oxy to rubber during mastication.
15.7.1.2 Breaking Strength of a Covalent Bond
Initiation in mechanochemical degradation involves homolytic scission, so one
basic question would be what level of stress is necessary to separate two chemical
moieties which have been attached by a covalent bond. The earliest account for this
problem was reported by de Boer in 1936 [42]. The potential of a bond under equi-
librium is normally approximated by the Morse potential, given by Eq. (80) where l
is the length of the bond, l
0
is the equilibrium separation distance of the atoms, D
is the bond dissociation energy, a = (k
f
/2D)
0:5
is a parameter which denes the
width of the potential minimum, and k
f
is the bond force constant in the neighbor-
hood of the equilibrium separation.
V(l) = D(1 exp[a(l l
0
)[
2
) (80)
If the bond is under tension with a constant force f
ext
pulling on either end, the
potential energy V
/
(l) will be decreased by an amount equivalent to the work per-
formed by the mechanical force over the stretching distance from the equilibrium
position [Eq. (81); Figure 15.18].
V
/
(l) = V(l) (l l
e
); where C is a proportional factor (81)
The potential function V
/
(l) has a minimum at l
/
0
> l
0
, in accord with the intuitive
expectation that the bond separation should increase in the presence of a tensile
stress. The new activation energy (D
/
) required to break the stressed bond could
be calculated from the principle of virtual work performed on the bond in going
from l
/
0
to l
b
(Figure 15.19).
15.7.1.3 Rate of Stress-activated Chain Scission
From a chemical viewpoint, bond scission under stress is a particular case of a un-
imolecular dissociation reaction whose rate is enhanced by mechanical stress. As
such, it could be treated with Eyrings transition-state theory [Eq. (37)], which per-
mits one to bring the treatment of rate processes within the scope of thermo-
dynamic arguments. By combining de Boers thermodynamic formulation and the
transition-state theory, Tobolsky and Eyring in 1943 developed the rate theory for
thermally activated fracture of polymeric threads. When put into an Arrhenius-
-0.2
0.0
0.2
0.4
0.6
0.8
1.0
-2 -1 0 1 2 3 4 5
l-l
0
Morse potential
Morse potential for a stressed bond
mechanical potential
D'
V
(
l
)
/
D
Fig. 15.18. The Morse potential of a bond under equilibrium
(- -- -) and in the presence of an applied force equal to 0.6 f
b
(- -- -).
like form, Eq. (82) was obtained, where k
c
is the rate constant for bond scission,
U
0
, the thermal energy for bond rupture, and c the molecular stress.
k
c
= A exp[U
0
f (c)/k
B
T[ (82)
Several attempts to relate the rate for bond scission (k
c
) to the molecular stress
have been reported over the years. The simplest and still the most popular is a lin-
ear relationship [Eq. (83)] between the decrease in activation energy and molecular
stress [42].
f (c) = bs (83)
The factor b has the dimension of volume and is identied as the activation vol-
ume for the reaction.
15.7.2
Extrusion Degradation
To achieve useful properties, polymers are generally compounded with a variety of
additives, transformed into granulates, before being processed into the nal shape
for commercial exploitation. During each step, the material is exposed to a high
shear-rate and temperature. The two major sources of chemical degradation during
processing are therefore mechanical stresses, which tend to decrease with in-
creased temperature as with the melt viscosity, and thermal reactions. As a result
of excessive pressure within the equipment in the course of processing, oxygen
-0.4
-0.2
0.0
0.2
0.4
1 2 3 4 5
l-l
0
f
(
l
)
/
D
a
l
b
l
f
l
0
'
0
Fig. 15.19. Derivative of the Morse potential. The hatched area
corresponds to the bond energy under stress.
from the air generally has no access to the polymer melt. Except during the initial
stage, when dissolved air can be used up at high rate, most of the degradation oc-
curs under oxygen-decient conditions. This feature has been veried during mul-
tiple extrusion of polypropylene [44]. In this experiment, as in other similar experi-
ments, the concentrations of oxidation products detected by FTIR were very low.
On the other hand, changes in the MW and MWD were always observed during
extrusion. Because the MWD is of the utmost importance for the rheological prop-
erties, it is important to know the molecular parameters which may inuence the
rates of chain scission and crosslinking. Oxidative b-scission of alkoxy radicals is
relatively unimportant in extrusion, as a result of lack of oxygen and low activation
energy (59 kJ mol
1
). The majority of chain scissions are caused by the b-cleavage
of alkyl radicals, with activation energies of 84117 kJ mol
1
. Cleavage of a second-
ary alkyl radical or a tertiary radical produces a vinyl (H
2
CbCHR) or vinylidene
group (H
2
CbCRR
/
), respectively. A kinetic model for PE crosslinking and scission
involving alkyl radicals under processing conditions has been developed, based on
and activation energy of 146 kJ mol
1
for chain scission, and 96 kJ mol
1
for cross-
linking. As a result of the dierence in activation energies, crosslinking tends to
dominate at low temperatures and scission at high temperatures. Crosslinking re-
actions are attributed to the addition of alkyl radicals to vinyl groups, either initially
present during synthesis or formed by thermal scission.
15.7.3
Applications
One of the earliest industrial applications of mechanochemical degradation was in
the mastication of rubber, to reduce the MW of the latex to a level which could be
processed. Rubbers vulcanized with a conventional high sulfur/accelerator system
are known to be more resistant to fatigue than peroxide-cured rubbers and rubbers
cured by sulfur-free or low-sulfur systems. This behavior was associated with the
presence of polysuldic (aCaS
n
aCa) crosslinks in the conventional vulcanizate
[45]. Because the SaS bonds are more labile than the CaC bonds (see Figure
15.18), it is postulated that they can be easily broken under fatigue, resulting in
the release of local stresses during bond rearrangement.
Mechanochemical degradation creates free macroradicals in pairs, practically
without any side reactions, and most potential applications of this technique are
centered around the formation and subsequent reactions of these reactive species.
Elongational ow-induced degradation breaks polymer chains exactly at their cen-
ter [42, 46]. This remarkable propensity is being explored in the authors laboratory
as a simple means of obtaining well-dened block copolymers. Polymerization and
CC CSC CSSC C(S)nC
410 kJmol
-1
350 kJmol
-1
300 kJmol
-1
260 kJmol
-1
Fig. 15.20. Bond dissociation energies in vulcanized rubber.
synthesis of block or graft copolymers by mechanical forces have been the subjects
of several reviews and books [47]. Although mechanochemical synthesis of inor-
ganic materials has enjoyed wide industrial application, no similar development
has yet been witnessed with plastic materials.
15.8
Control and Prevention of Aging of Plastic Materials
It has been shown in the preceding sections that raw polymers are highly suscepti-
ble to degradative oxidation. The success of plastic materials, which nd applica-
tions in practically any aspect of life, relies heavily on the performance of polymer
stabilizers, 70% of which are used for polyolens. According to their principal pro-
tection activity, common polymer stabilizers are conventionally classied as antiox-
idants, photoantioxidants, photostabilizers, metal deactivators, antiozonants, and
heat stabilizers for PVC.
15.8.1
Antioxidants
Antioxidants prolong the useful lifetime of the polymer by trapping free radicals
(primary antioxidants) and by decomposing hydroperoxides (secondary anti-
oxidants) formed during the course of degradation.
15.8.1.1 Radical Antioxidants
Since polymer degradation is initiated by free radicals, the most eective approach
in both heat and light stabilization would be to reduce the number of reactive rad-
ical species by scavenging. Secondary aromatic amines and substituted phenol de-
rivatives are among the most popular radical-scavenging stabilizers. The stabiliza-
tion action of these compounds is based on the formation of aminoxy and phenoxy
radicals, respectively, which can scavenge propagating radicals formed during deg-
radation. Amine additives are converted into conjugated secondary products which
absorb visible light. For this reason, hindered phenols are preferred in applications
where discoloration is undesirable. Typical phenolic antioxidants are shielded with
bulky alkyl substituents in the 2-, 4- and 6-positions to reduce the reactivity of phe-
noxy radicals toward hydrogen atom abstraction reactions on polymer and mutual
coupling. The principal mode of action of hindered phenols is the transfer of a hy-
drogen atom to a propagating alkyl (R
v
) or alkylperoxy (ROO
v
) radical [Eq. (84)].
R' HO R' O ROO ROOH + +
(84)
The phenoxy radicals are relatively long-lived and can undergo self-disproportiona-
tion, recombination with alkylperoxy radicals, or isomeric rearrangement followed
by recombination. The resulting compounds may have some stabilization activity.
Propionate-type hindered phenols constitute a special class in this category: during
reaction, the phenol is transformed into phenolic cinnamates, which are known to
be ecient chain-breaking antioxidants [Eq. (85)].
+
O
O
CHCH
2
COR
OH
O
CH
2
CH
2
COR
OH
O
CH=CHCOR
2
O
O
CH
2
CH
2
COR
(85)
15.8.1.2 Hindered Amine Stabilizers (HAS)
With a few exceptions, such as hydroxybenzoate derivatives, most conventional
phenolic antioxidants suer from low photostabiliy and could not be used for pho-
tostabilization. This problem was solved with the introduction and development of
hindered amine light stabilizers (HAS) [49]. Because this class of compounds was
originally developed for photostabilization, they are frequently referred as hin-
dered amine light stabilizers or HALS. HAS are commercialized under a variety
of structures, most of which contain one or several 2,2,6,6-tetramethylpiperidine
moieties linked together to form polynuclear species. The structure of a typical
commercial HAS, Chimassorb2 944, is shown in Figure 15.21.
The protection mechanisms of HAS are based on a complex series of chemical
transformations, with many unresolved details. The primary step includes oxida-
tion in situ of secondary or tertiary HAS into nitroxides
a
a
NO
v
by the various
oxidants present during oxidative degradation [Eq. (86)]. The substituent can be
H, CH
3
, OR, or COCH
3
, and the oxidative species
3
O
2
,
1
O
2
, O
3
, POO
v
, POOH,
PC(O)OO
v
, or PC(O)OOH.
a
a
NaR oxidative species
a
a
NO
v
products (86)
Stable nitroxide radicals are traditionally considered as the principal species which
account for the free-radical scavenging activity of HAS. Nitroxide radicals can trap
alkyl, alkylperoxy and acylperoxy radicals. The probability of direct radical scaveng-
ing, such as in Eq. (87), is nevertheless limited as a result of the higher rate for
competitive reactions of R
v
with dissolved oxygen and by self-recombination.
a
a
NO
v

v
R
a
a
NOR (87)
As with the formation of peracids, it is suggested that scavenging occurs inhomo-
geneously and is enhanced in regions of accumulated hydrogen-bonded com-
plexes, owing to the formation in situ of R
v
[Eq. (88)].
a
a
NO
v
HOOR
a
a
NO
v
; HO
v
; RO
v

a
a
NO
v
; R
/
v
(88)
The formation of hydrogen-bonded associates with hydroperoxides or phenolic ad-
ditives is favored by the resonance-stabilized dipolar structure of nitroxides repre-
sented by Eq. (89).
N O N O
+
(89)
The transformed hydroxylamines and dialkylhydroxylamine ethers are assumed to
play a key role in the mechanism of stabilization of HAS, through a regenerative
inhibition cycle known as the Denisov cycle [Eqs. (90a)(90c)] [50].
NOCHCH
2
ROO
NO + CH=CH + ROOH
NO + C=O + ROH
NO + RO
OCCH
2
+
(90a)
(90b)
(90c)
Tertiary hydroxylamine ethers, the main constituent in degraded polypropylene,
lead preferentially to the formation of alkyl peroxides [Eq. (90c)].
N
N N
N
CH
3
CH
2 CH
3
CH
3
N (CH
2
)
6 N
N
H
n
Fig. 15.21. Structure of a typical commercial hindered amine stabilizer (HAS).
There is increasing evidence that other regeneration mechanisms are involved,
such as scavenging of alkylperoxy or peracyl radicals by hydroxylamines and alkyl-
hydroxylamines according to Eq. (91).
NO
CHR
1
R
2
+ (RCOO
.
)
O OCHR
1
R
2
RO
.
O
.
N
+
NO
.
+ O=CR
1
R
2
+ ROH (RCOH)
O
....
ROO
.
(91)
Another proposed mechanism of action involves long-range energy transfer from
polymeroxygen exciplexes to HAS or HASoxygen complexes [49]. This process
is particularly ecient in inhibiting photoinitiation which takes place essentially
at the crystalline/amorphous interface, where the HAS is concentrated.
Basicity of HAS Secondary and tertiary HAS are relatively basic and may catalyze
hydrolysis of some polycondensation polymers, such as polycarbonate. HAS lose
their activity if they come into contact with strong acids, and hence cannot be
used to stabilize PVC or in formulations which contain halogenated ame retard-
ants. HAS with an acylated amino group (
a
a
NCOCH
3
) has a lower pK
a
and can
better resist an acidic environment.
Thermal stabilization with HAS As a result of its protection mechanism, HAS are
particularly eective in photodegradation. Recently, it has been assessed that HAS
can also be used for thermal degradation. In this case, however, HAS should be
used in combination with hindered phenols because many degradation products
of HAS, which are ecient antioxidants, can be formed only with light.
15.8.1.3 Peroxide Decomposers
Peroxides are responsible for the autoacceleration stage during oxidative degrada-
tion of polymers. Hydroperoxide decomposers, which cause the reduction of hy-
droperoxides to alcohols, comprise two main chemical classes: organic sulfur and
trivalent phosphorus compounds, generally used in combination with phenolic
antioxidants. The decomposition mechanism is complex and involves radical and
nonradical processes. During the course of decomposition, a mixture of oxidation
products, generally endowed with additional peroxidolytic properties, are formed.
For instance, the decomposition of a thioether in the presence of alkyl hydroperox-
ides can be represented schematically by a series of reactions [Eq. (92)] which in-
volve thiyl RS
v
, sulnyl RS
v
(O), sulfonyl RS
v
(O)
2
, and perthiyl RSS
v
radicals.
[RaOaCa(CH
2
)
2
a[
2
S [RaOaCa(CH
2
)
2
a[
2
SO
RaOaCa(CH
2
)
2
aSOOH H
2
CbCaCaOaR SO
2
; H
2
SO
4
; . . . (92)
Sulfur dioxide and sulfuric acid, both of which are also active hydroperoxide de-
composers, are formed at the ultimate stage of transformation.
Organic phosphites are very eective hydroperoxide decomposers. Their peroxi-
dolytic activity results from a sacricial transformation of phosphite (trivalent) to
phosphate (pentavalent), according to the general reaction scheme in Eq. (93).
RaOOH P(OR
/
)
3
ROH ObP(OR
/
)
3
(93)
15.8.2
Photostabilizers
Outdoor weathering is the most common source of polymer degradation. The most
direct and ecient way to avoid photodegradation would be to prevent the photons
from reaching the polymer either by applying a paint or coating to the surface, or
by blending the polymer with strong light-absorbing particles such as carbon black.
This procedure, however, is inapplicable for situations where aesthetic appearance
or transparency of the material is essential.
UV absorbers The use of organic compounds with a high absorption coecient in
the UV but transparent to the visible, known as UV absorbers, should act in a sim-
ilar fashion to paints, by protecting the polymer while conserving the optical clarity
of the material. Paints and coatings themselves are not stable to solar radiation and
are often compounded with UV absorbers to prolong their protection eciency. To
be useful, UV absorbers must strongly absorb at wavelengths harmful to the poly-
mer, must harmlessly dissipate the energy that they absorb, and must persist in
the matrix for the expected lifetime of the article. Most commercial UV absorbers
are derivatives of benzophenone, benzotriazole, triazine, oxanilide, or cyanoacrylate
with aromatic substituents. All have a highly delocalized p-electron structure with a
high extinction coecient (e = 10 00040 000 L mol
1
cm
1
) in the near-UV re-
gion (290350 nm). The photostability of benzophenone-based UV absorbers is
conferred by intramolecular proton transfer in the excited state, and most likely
by a charge-separation mechanism in the case of a cyanoacrylate structure.
hv
heat
H
O
O
O
R
H
O
O
O
R
CN
COOR
hv
heat
CN
COOR
+ -
Scheme 15.5. Energy dissipation mechanism for a protic (left)

and a cyanoacrylate (right) UV absorber.
Quenchers Quenchers are used to capture the excess energy of excited chromo-
phores [Eqs. (94) and (95)], which is then dissipated as vibrational energy, before
they can initiate harmful reactions.
P P
+
radicals (94)
P
+
Q P Q
+
(95)
Eective quenchers are based on nickel complexes (phenolate, dithiocarbamate, di-
thiophosphate) and are used almost exclusively in polyolens at a concentration of
0.20.5%. Nickel complexes impart a green coloration to plastic articles and their
importance was signicantly reduced with the introduction of hindered amine
light stabilizers (HALS).
15.8.3
PVC Heat Stabilizers
In spite of its inherent thermal instability (see Section 15.3.4), PVC possesses sev-
eral attractive properties, such as economy of production and processing, and the
ease of variation of its properties, with appropriate blending with other polymers
or additives, from hard and tough materials to elastomeric ones. Currently, PVC
ranks second only to polyolens in terms of worldwide production among indus-
trial polymers. This technical success is the result of considerable research in the
eld of degradation and stabilization of this polymer since its introduction as a
commodity plastic in the middle of the 20th century.
The low thermal stability of PVC originates from the presence of labile struc-
tures and of the autocatalytic deleterious eect of the hydrochloric acid evolved.
Thermal stabilizers for PVC consist principally of metal carboxylates and organotin
compounds (primary stabilizers), used in combination for preventive and curative
functions. As with degradation, uncertainties continue to exist in the exact stabiliz-
ing mechanisms of these additives. There is evidence that organotin derivatives sta-
bilize PVC by substituting the labile allylic chorine with a more thermally stable
thioether group [Eq. (96)].
(C
4
H
9
)
2
Sn(SCH
2
COOaC
8
H
17
)
2
aCH
2
aCHbCHaCHClaCH
2
a
aCH
2
aCHbCHaCH(SCH
2
COOaC
8
H
17
)aCH
2
a
ClaSn(C
4
H
9
)
2
(SCH
2
COOaC
8
H
17
) (96)
Hydrogen chloride is bound with metallic (Zn, Ca, Ba) organic acid salts with for-
mation of the metal chloride and the corresponding free fatty acids. The formation
of polyene sequences can be prevented by combination reactions with thiol or mal-
eate derivatives. Although ecient in blocking the degradation, most of the inor-
ganic stabilizers leave toxic residues and current research is focused on the devel-
opment of new, less polluting, organic stabilizers.
15.8.4
Other Classes of Stabilizers
15.8.4.1 Metal Deactivators
Very often, thermoplastics contain minute amounts of metallic compounds which
originate from polymerization catalysts, contaminated llers, polymerization or
processing equipment, or metal contact (wire and cable insulators) during the use
of the polymer. The interactions between the polymer and metallic substances are
complex, but generally result in the accelerated aging of the material. Most metal
deactivators are bifunctional stabilizers with phenolic and nitrogen, or phenolic
sulde and phosphite, moieties in their structure, and act by a chelating action
which reduces the harmful eects of the metal ions.
15.8.4.2 Antiozonants
Diene-type rubbers are particularly sensitive to ozone attack and should be pro-
tected by antiozonants. Common antiozonants are aromatic diamines capable of
direct ozone scavenging by adduct formation.
15.9
Lifetime Prediction
Most of the additives used to protect the polymer from degradation are eventually
consumed during the stabilization processes. In addition to chemical loss, the sta-
bilizers can also be depleted by precipitation, migration to the surface, and extrac-
tion. For all these reasons, the concentration of additives diminishes with time up
to a point where no protection eect could be observed. In general, the stabiliza-
tion lifetime increases with the amount of added stabilizer, up to an optimum de-
termined by the nite solubility of the additives in bulk polymers, or by secondary
reactions which may have adverse eects on the stabilization mechanisms (Figure
15.22).
Excluding disposable devices, most plastic materials are expected to perform re-
liability for many decades. In general, outdoor weathering of stabilized samples is
too slow to be useful for quality control or for formulation development. As a rem-
edy for this aw, a number of accelerated weathering tests have been devised. De-
pending on the type of degradation, accelerated tests can be obtained by increasing
the temperature (thermal degradation), or increasing the light intensity (photo-
degradation) and/or the partial oxygen pressure (oxidative degradation). Owing to
its economic relevance, photoaccelerated aging is enjoying the most dramatic de-
velopment, with numerous commercial systems based on a UV source or mirrors
designed to mimic the action of the Sun, with a several-fold increase in irradiation
intensity. Most of the time, results of accelerated aging show poor correlation not
only with outdoor weathering, but also between dierent devices, or for identical
devices between dierent laboratories. This lack of correlation is not entirely un-
expected, in view of the wide variability inherent in weathering conditions: biologi-
cal disturbances, pollution, climate (temperature, humidity, wet periods); and
changes in the spectrum and intensity of the source with aging, and in the test du-
ration. In addition to the external factors, more fundamental reasons for deviations
could be traced back to the bimolecular reactions between intermediate species,
whose concentrations in real conditions are too low to interact, or to diusional
processes of the reactants (oxygen, water, stabilizers) that become limiting factors
in accelerated conditions. By using conditions which mimic exact weathering con-
ditions in terms of spectral distribution, temperature, and oxygen uptake, but with
a dierent photon intensity, it has been assessed that accelerated aging in polyole-
ns is not mechanistically dierent from natural weathering. Therefore, an extrap-
olation procedure between these two modes of degradation is possible, providing
all the dynamics (diusion) factors could be kept under control. Identifying and
controlling all the dynamics factors in a real system is nevertheless a challenging
task.
To account for the poor reproducibility in accelerated aging, statistical ap-
proaches have been proposed, such as the nonparametric statistics which relies
on performance comparison with a control material. The control material should
be as similar as possible to the tested polymer in terms of structures, size, and
shape, and its weathering durability should be well established in the specied ex-
posure test. One useful approach to reduce error analysis was to compare a test
property, not as a function of time or absorbed radiation, but relative to another
0
0.05
0.1
0.15
0.2
0 100 200 300 400 500 600
irradiation time [h]
0% 0.01% 0.1%
0.5%
c
a
r
b
o
n
y
l

i
n
d
e
x
Fig. 15.22. Photo-oxidation of commercial polypropylene, in
the absence and in the presence of the indicated
concentrations of hindered amine stabilizer.
15.9 Lifetime Prediction 825
process going on in the aging material. The objective sought is to have the rates of
the two processes occur in the same relationship relative to one another under a
wide range of experimental conditions, from natural to accelerated test conditions.
The process of interest should be easy to determine and sensitive to low levels of
degradation, to minimize the extrapolation range. In thermal aging of nitrile rub-
ber, for instance, it has been found that the ultimate tensile elongation shows good
correlation with the rate of oxygen consumption over the experimentally accessible
temperature range for mechanical measurements, which was 9671.5
C. At lower
temperatures, the time to failure was inconveniently long for measurement. Oxy-
gen consumption, on the other hand, could be determined by gas chromatography
all the way down to room temperature. Based on indirect evidence that the chem-
istry underlying oxygen consumption is responsible for changes in modulus and
elongation values, a lifetime of 100 years was predicted for the elastomer in ambi-
ent conditions. It should be noted that an Arrhenius plot extrapolation, based
solely on the mechanical properties at elevated temperatures, predicted a lifetime
of 50 000 years, which is some 500 times longer than the correctly estimated value
[15].
15.10
Conclusions
This chapter has given a general description of some recent advances in the eld of
polymer degradation and stabilization. Despite a considerable volume of work and
equally impressive progress in the comprehension of the molecular mechanisms
which underlie polymer degradation, many challenging problems are still open to
further investigation. The ever-increasing complexity of commercial plastics, which
includes the use of copolymers, polymer blends, and dierent combinations of ad-
ditives in their formulations, adds another degree of diculty to the already com-
plex problem of polymer degradation. Each type of interaction between the dier-
ent components in the formulation, both polymeric and nonpolymeric, may
inuence dierently the degradation process. In particular, the antagonistic and
synergistic eects between stabilizers in additive blends need better mechanistic
comprehension.
Two main areas where major advances can be expected in the future include in-
tegral characterization of the degraded polymer, and realistic modeling of degrada-
tion kinetics.
Most degradation and stabilization mechanisms reported in the literature are in-
ferred from the observation of a few end products (generally carbonyl and hydroxyl
compounds, which can be easily monitored by FTIR). A comprehensive character-
ization of the starting material, and of the degradation products at dierent stages
of aging, is still lacking in most investigations. Such a complete chemical identi-
cation, which appears to be feasible with the modern analytical techniques avail-
able, is a prerequisite to establish a correlation between eects of specic struc-
tures on the behavior of signicant degradation intermediates.
The inhomogeneity of reaction sites, inherent in solid-state reactions, may lead
to distributions of reactivity and to time-dependent rate constants. These eects
should be recognized and taken into account when performing kinetics analysis.
This is consequential to the problem of stabilization, since additives need to diuse
toward degradation centers for the stabilization process to be operative. Some het-
erogeneous reaction models aimed toward a better description of radical chain pro-
cesses in solid polymers have appeared in the literature. One of these models, the
infectious spreading reaction, has been examined in Section 15.4.5. Among other
advances in solid polymer degradation, one can cite:
v
the concept of polychronal kinetics which was introduced to explain the step-
wise conversion of reactive species under isothermal conditions [6]; and
v
the spongy micelle microreactor model in which the amorphous phase in a
semicrystalline polymer is depicted as formed by granule-core zones, sur-
rounded by oriented domains close to the crystallites [51]. By applying dier-
ent chemical kinetics scheme to each zone, with allowance for interzone radi-
cal migration, the autooxidation curve of polyolens can be faithfully reproduced.
It is found that the induction period for oxygen consumption corresponds to the
homogeneous oxidation stage, whereas the (exponential) autoaccelerated stage
may be interpreted as a result of heterogeneous oxidation spreading of low MW
peroxides. This model refutes the interpretation of chain branching as a source
of oxidation autoacceleration.
All these theories need to be conrmed by experimental verication and tested for
their general applicability to dierent polymer systems.
Notation
A
s
infrared absorption intensity [cmmmol
1
]
a constant of the Morse potential [m
1
]
D oxygen diusion constant [cm
2
s
1
]
D
e
bond dissociation energy [kJmol
1
]
E tensile modulus [GNm
2
]
E
a
energy of activation [kJmol
1
]
E
s
excess energy of stress [kJmol
1
]
E
ang
valence-bond angle contribution to the activation energy [kJmol
1
]
DE
0
molecular energy dierence at absolute zero between the activated
complex and the reactant [J]
DH enthalpy of reaction [kJmol
1
]
h Plancks constant 6.625610
34
[Js]
I
0
incident light intensity [Wm
2
]
I(x) light intensity [Wm
2
]
K KubelkMunk absorption coecient [cm
1
]
k rate of reaction [s
1
] (rst-order), [Lmol
1
s
1
] (second order)
Notation 827
k
f
bond force constant in the neighborhood of the equilibrium sepa-
ration of two chemical moieties [Nm
1
]
k
B
Boltzmanns constant 1.38010
23
[JK
1
]
k
c
rate constant for bond scission [s
1
]
k
y
elastic constant for bond-angle deformation [Nrad
1
]
l length of a covalent bond [nm]
l
0
equilibrium separation distance of the atoms in a bond [nm]
M
i
molecular weight of ith polymer [gmol
1
]
M
n
number-average molecular weight [gmol
1
]
M
v
viscosity-average molecular weight [gmol
1
]
M
w
weight-average molecular weight [gmol
1
]
N total number of amorphous domains
n number of polymer chains per gram of polymer [g
1
]
n number of oxidized domains
n
i
polymer molar fraction
p
d
dead or oxidized fraction of polymer
p
i
infectious oxidizing fraction of polymer
p
r
remaining unoxidized fraction of polymer
Q normal coordinate of vibration [nm]
q
t
molecular partition function of the transition state
q
A
molecular partition function of the reactant
R reectance
R molar gas constant 8.314 [Jmol
1
K
1
]
R absorbed dose of radiation [Gy or Jkg
1
]
r rate coecient for spreading [s
1
]
S KubelkaMunk scattering coecient [m
1
]
S(l) relative spectral damage
s scission indice
T temperature [
C]
T
1/2
temperature of half-decomposition [
C]
T
g
glass transition temperature [
C]
T
m
melting point [
C]
t
i
induction period [
C]
t
1/2
half-life [s]
U
0
thermal energy for bond rupture [kJmol
1
]
V(l) Morse potential [J]
x penetration distance [m]
Greek
a absorption coecient [cm
1
]
b activation volume for a reaction [m
3
mol
1
]
l irradiation wavelength [nm]
l
max
wavelength of light absorption peak [nm]
e extinction coecient [Lmol
1
cm
1
]
m dipole moment [Cm]
n frequency of band center [cm
1
]
y angle [rad]
c molecular stress [GNm
2
]
Acronyms
ATR-FTIR attenuated total reection FTIR
ESR electron spin resonance
FDA Federal Drug Administration
FTIR Fourier Transform infrared spectroscopy
iPP isotactic polypropylene
GPC gel permeation chromatogaphy
HAS hindered amine stabilizer
HDPE high-density polyethylene
HER high-energy radiation
LET linear energy transfer
HAS hindered amine light stabilizer
HOMO highest occupied molecular orbital
LUMO lowest unoccupied molecular orbital
MIM metal injection molding
MW molecular weight
NMR nuclear magnetic resonance spectroscopy
PA polyacrylamide
PAN polyacrylonitrile
PC polycarbonate
PET, PETP poly(ethylene terephthalate)
PIB polyisobutylene
PMMASAN PMMApoly(styrene-co-acrylonitrile)
POM polyoxymethylene
PP polypropylene
PPO poly(phenylene oxide)
PPP poly(para-phenylene)
PS polystyrene
PSU poly(ethersulfone)
PTFE polytetrauoroethylene
PVC poly(vinyl chloride)
SEM scanning electron microscopy
TG thermal gravimetry
VC vinyl chloride
Notation 829
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12 T. Q. Nguyen, Polym. Degr. Stab.,
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13 L. Lacoste, D. J. Carlsson, J. Polym.
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14 W. H. Starnes Jr., Progr. Polym. Sci.,
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15 K. T. Gillen, M. Celina, R. L.
Clough, J. Wise, Trends Polym. Sci.,
1997, 5, 250.
16 J. P. Critchley, G. J. Knight, W. W.
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17 V. van Speybroeck, Y. Martele, M.
Waroquier, E. Schacht, J. Am.
Chem. Soc., 2001, 123, 10650.
18 M. R. Nyden, J. Gilman, Comp. Theor.
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19 J. J. P. Stewart, J. Comp. Chem., 1989,
10, 221.
20 D. A. Gallagher, Scientic Computing
& Automation, June 1996.
21 T. A. Bogaevskaya, T. V. Mona-
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Vysokomol. Soyed., 1972, 14A, 1552.
22 P. Gijsman, J. Hennekens. Polym.
Degr. Stab., 1993, 42, 95.
23 S. Commereuc, D. Vaillant, J. L.
Philippart, L. Lacoste, J. Lemaire,
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24 S. Verdu, J. Verdu, Macromolecules,
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25 P. Eriksson, T. Reitberger, B.
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26 M. Celina, G. A. George, N. C.
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Degradation, S. Halim Hamid, ed.,
Marcel Dekker, New York, 2000,
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27 F. Gugumus, Polym. Degr. Stab., 1996,
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30 J. P. Riggs, in High Performance
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31 B. A. Mathew, R. Mastromatteo,
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32 W. C. McCaffrey, D. G. Cooper,
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35 A. L. Andrady, N. D. Searle, L. F. E.
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36 H. Zweifel, Chimia, 1993, 47, 390.
37 T. Q. Nguyen, Ph.D. thesis, No. 243,
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40 V. S. Ivanov, Radiation Chemistry of
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References 831
16
Thermosets
1
Rolf A. T. M. van Benthem, Lars J. Evers, Jo Mattheij, Ad Hoand,
Leendert J. Molhoek, Ad J. de Koning, Johan F. G. A. Jansen, and
Martin van Duin
16.1
Introduction
16.1.1
Thermoset Materials
The world of thermoset materials is characterized by a high degree of both diver-
sity and complexity, often dicult for non-experts to oversee [1]. Let us rst ask
ourselves what thermoset materials have in common. Polymeric materials are di-
vided into two classes, thermoplastic and thermosetting materials. The term ther-
moplastic refers to the ability of these polymers to become plastic, that is, to melt
and ow upon heating. In terms of viscoelasticity, a thermoplastic material can be
hard and elastic at room temperature, but it behaves like a liquid when heated to
a certain higher temperature. The expression thermoset or thermosetting is
sometimes erroneously understood to be exclusively a material which sets (be-
comes hard and elastic) upon heating, but there are many examples of thermoset
materials which have set without a temperature trigger, for example through ir-
radiation (see Section 16.8.5). For the discussions in this chapter, the term ther-
moset will merely refer to the inability of this class of polymeric materials to be-
have like a liquid when heated. A thermosetting material can be hard and elastic at
room temperature and be heated above its glass transition temperature to become
softer, and deformable. The deformation, however, will be transient rather than
permanent: the softened material is still fully elastic and behaves like a rubbery
material.
ISBN: 3-527-31014-2
833
16.1.2
Networks
The molecular origin of thermoset behavior lies in the formation of a polymeric
network. Unlike thermoplastic materials, which consist of individual macromole-
cules that can move relative to each other over innite distances in the melt, the
polymeric chains in a thermosetting material are attached to each other and
can therefore not move any more relative to each other over greater distances.
They are bound together through so-called crosslinks and form an innite, three-
dimensional structure. A consequence of the presence of junctions between the
polymeric chains, other than the inability to behave like a liquid and ow, is the
inability of this material to dissolve in another medium such as a solvent. Solvent
or plasticizer molecules can migrate into the network structure, to swell it, but this
is limited to a maximum determined by the crosslink density.
The ideal network structure can be envisaged as a three-dimensional array of
crosslink points, each crosslink point being connected to at least three other cross-
link points via linear polymer segments, which are called elastically active network
chains. In practice non-ideal network elements are also present, such as loops or
dangling ends (Figure 16.1). Network density, or crosslink density, is expressed as
the concentration of either the crosslink joints or the elastically active network
chains (those chains that are part of the innite structure and attached to crosslink
junctions at both ends) per unity of volume of the unswollen material.
EAN
Cross-link
Loop
Dangling end

Fig. 16.1. Network nomenclature: crosslinks, elastically active
network chains (EAN), dangling ends, and loops.
834 16 Thermosets
16.1.3
Advantages
There are two obvious advantages in the material property of a thermoset compared
to a thermoplastic material: the network structure will ensure a higher resistance
toward unwanted penetration of chemicals (solvents, dyes, water, acids, bases, and
electrolytes) in use, and secondly, a thermoset has a high-temperature stability as it
retains its shape and (some of ) the properties at elevated temperatures. These are
not the main advantages of a thermoset material, however. The wide processing
window of thermosets has given them the present position in the performance ma-
terials market. A thermoset can be processed easily (shaped, cast, molded, poured)
as a liquid; the liquid is transformed into the nal thermoset material after the
processing, through a series of chemical reactions. The nal properties of the ma-
terial are thus determined by the network formation reactions performed in situ.
As a consequence, the chosen molecular weight of the starting material can be ar-
bitrarily low. The viscosity, in relation to the molecular weight of the (short) poly-
meric chains, is decreased strongly as well. In contrast, a thermoplastic material
derives its properties from the high molecular weight of its polymer chains which
allows the chains to entangle with each other. This high molecular weight in most
cases results in rather high melt viscosities for these polymers. A high processing
viscosity is a disadvantage with respect to both processing speed (lling the mold,
owing out) and wetting phenomena: dispersion of pigments and llers and even
ow-out over the walls of the mold or the substrate.
16.1.4
Curing Resins
In thermoset nomenclature the low molecular weight polymers (oligomers) are
referred to as resins. Apart from their relatively low molecular weight, typically be-
tween a few hundred and a few thousand grams per mole, resins are characterized
by the presence of reactive groups in the chains, ideally at least two per molecule.
These reactive groups form the chemical handles to connect the polymer chains
together through covalent crosslink bonds, via a chemical reaction. The process of
crosslinking is mostly referred to as cure or hardening. When the reaction pro-
ceeds, the gel point is dened as the moment in time when the rst molecule of
innite dimensions is formed in the polymer mixture. The viscosity of the mixture
then approaches innity and in this state the material is referred to as gel. The cur-
ing reaction can still proceed beyond this point to increase the crosslink density.
16.1.5
Functionality
The number of reactive groups present in one molecule is referred to as function-
ality. This term can reect both on a monomer and on a polymer. For example,
ethylene glycol is a two-functional monomer for a polyester (see Section 16.6),
and a linear epoxy resin with two glycidyl groups on each end is a two-functional
polymer (Section 16.4). An unsaturated polyester (Section 16.7) or EPDM rubber
(Section 16.9) can have much higher functionalities, that is, unsaturations along
the polymer chain. Functionality is an important concept to understand the role
of a polymer chain in the nal network. For example, a two-functional polymer of
a certain molecular weight can only be built in as an elastically active network
chain of that same length (at maximum, provided that it reacts at both groups). A
three-functional polymer chain of similar molecular weight, containing a branch in
the chain, can give a higher crosslink density because it has an internal network
junction as well. The junctions in the network can originate from a branching
point already present in the polymer, or from chemical reaction between polymer
strands.
16.1.6
Formulation
The mixture of the dierent constituents of a formulation for a thermosetting ma-
terial is always rather complex and referred to as a system. Systems can be clas-
sied as either 1K (one component) or 2K (two components). In the rst case, all
the (co)reactive ingredients of the formulation are already mixed, but the network
formation is only started when it is triggered chemically or physically, for example
by a raise in temperature, by electromagnetic radiation, or by exposure to air (oxy-
gen) or moisture. In the latter case the two components will immediately start
their chemical reaction once they are mixed with each other, with or without an
additional inuence from outside (such as a rise in temperature to speed up the
crosslinking reaction).
Independently of the systems reactivity (1K/2K), the combination of reactive
groups required to form the network can range from very simple to highly com-
plex. Reactions can be between co-reactive groups of dierent chains of one resin
type, or between the reactive groups on one resin type with corresponding reactive
groups of another compound, that compound either being a chemical (monomer)
or another resin (polymer) that is added to the rst resin. In some resins only
one kind of reactive group A is present which is reactive with itself (A A !AA);
in most resins, however, A is not reactive with itself and requires the presence
of an additional compound (B) of complementary reactivity to give a chemical
bonding reaction (A B !AB). Dual-cure reactions also exist (A B C D !
AB CD) between mixtures of resins of dierent reactivities. In the next sections
the most important resin classes will be presented. Systems can be formulated
from just one one of them but also from a wide, almost innite, variety of combi-
nations of these resins.
The systems are made more complex with the addition of additives to control the
chemical reaction, either to enhance it (catalysts, accelerators, initiators) or to slow
it down or inhibit it (stabilizers, inhibitors). Besides additives that control the net-
work formation, other additives can also be used to inuence the nal properties:
llers, pigments, plasticizers). Formulation of thermosetting systems is a technol-
836 16 Thermosets
ogy of its own and requires a deep insight into both the complex chemical reac-
tions and the nal network structure in order to steer toward the desired material
properties.
16.1.7
Production
It is highly important to note, however, that the production of the resins them-
selves is in most cases far from as straightforward as would be expected for a sim-
ple low molecular weight polymer. Unlike the (linear) thermoplastic polymers, res-
ins are designed to react to form networks; they contain several reactive groups
and often are branched polymers. Either by uncontrolled reaction or uncontrolled
branching, polymer molecules with a much higher molecular weight than in-
tended, or even polymer networks, could already be formed during the production
stage (gelation). This should be avoided at all times, as the production facility
could be plugged and highly damaged in such a case. In each of the following sec-
tion on the resin types a short description is given of the (mostly batchwise) pro-
duction technology associated with them, and the measures for controlling un-
wanted, premature, reactions.
16.1.8
General Areas of Application
The areas of application of thermosetting materials are in coatings, rubbers, inks,
adhesives, laminates, press moldings, composite (glass-lled) moldings, mineral
wool, and electronic materials. A general overview of the main application areas
of the resins discussed in the following sections is given in Table 16.1 [1]. They
are found in a wide variety of markets (household, automotive, building and con-
struction, electronics, paper and press) and have a collected industrial volume of
several tens of millions of tons.
Tab. 16.1. General overview of thermoset applications.
Resin Coating Structural
parts
Wood
and paper
composites
Adhesives Inks Elastic
rubbers
Phenolic
Amino
Epoxy
Alkyd
Saturated polyester
Unsaturated polyester
Acrylate
Rubber
16.2
Phenolic Resins
16.2.1
Introduction
Historically, phenolformaldehyde resins (phenolic resins, phenoplasts) are the
oldest synthetic thermoset materials: as early as in 1910 the rst ones (bakelite
to their inventor Baekeland) were introduced. Who does not remember the black
telephones and light switches that were popular in the 1930s and 1940s? Phenolic
resins are based on hydroxy-aromatic compounds (phenol and phenol derivatives)
and aldehydes [2]. Furfural is occasionally used as aldehyde; but by far the most
widely used aldehyde is formaldehyde. Formaldehyde can be administered as an
aqueous solution (formalin), polymeric solid (paraformaldehyde) or solid adduct
with ammonia (hexamethylenetetramine, HMTA). The resins are formed by a
step-growth mechanism in aqueous solution.
Thermoset materials can be made from phenolic resins themselves, requiring
an acid or base catalyst or additional formaldehyde source, or in combination with
various other resins. An exhaustive list is not given here, but examples of com-
binations with all the resin types in the next sections are known (especially amino
resins, Section 16.3; epoxy resins, Section 16.4; alkyd resins, Section 16.5; and sa-
turated polyester resins, Section 16.6).
16.2.2
Chemistry
The reactive group involved on the hydroxy-aromatic compound is not the hydroxy
group itself but the carbon atoms on the ortho (2,6) and para (4) positions relative
to the hydroxy group (attached to carbon atom 1). Unsubstituted phenol can there-
fore react with formaldehyde from three dierent positions independently, so
should be regarded as a three-functional monomer. If the phenol derivatives have
substituents on the ortho and/or para positions, their functionality is decreased ac-
cordingly. For example (see Scheme 16.1), cresol (methylphenol) is two-functional
when the methyl group is in the 2 or 4 position relative to OH (o-cresol and p-
cresol, respectively) but three-functional when in the 3 position (m-cresol). Further,
commonly used two-functional substituted phenol derivatives are p-tert-butylphenol
and p-tert-nonylphenol. The aliphatic groups on these monomers decrease the solu-
bility of the resins in water but increase the solubility (compatibility) of these resins
with more hydrophobic solvents (hydrocarbons) and resins.
The aldehyde group of formaldehyde can react twice with an aromatic carbon
atom of a phenolic monomer and should therefore be regarded as a two-functional
monomer. After the rst reaction, the carbonyl group has been changed into a
hydroxy group. After the second reaction, the hydroxy group is either etheried
or substituted for a carboncarbon bond. The reaction pathways are displayed
838 16 Thermosets
in Scheme 16.2 Starting from three-functional phenol and formaldehyde, a
branched structure is obtained in which the phenol moieties are linked together
by formaldehyde-derived bridges. These bridges can comprise either one methyl-
ene group (methylene bridge) or two methylene groups connected by an ether
oxygen atom (ether bridge). One formaldehyde molecule is needed to form
a methylene bridge; two are needed to form an ether bridge. The relative amounts
OH OH OH OH
Phenol o-Cresol
p-Cresol m-Cresol
2
4
6
OH
HO
Resorcinol
OH
OH
Nonylphenol
p-tert-Butylphenol
Scheme 16.1. Some phenolic monomers.
OH
OH
OH
OH
HO
OH
OH
OH
OH
OH HO
OH
OH
OH HO
OH OH OH OH
O
OH
O
OH
Novolac resin
ether bridges methylene bridges
Resol resin
Scheme 16.2. Phenolic resin formation.
of these bridges are determined during the resin synthesis by the reaction
parameters.
Two reaction parameters are of specic importance: pH and molar ratio. When
phenol and formaldehyde are dissolved together in water, a pH of about 34 is
reached (phenol is slightly acidic). After prolonged heating, hardly any reaction is
noticeable. The reaction requires a catalyst, either an acid or a base, to reach a suf-
cient speed. Depending on the ratio between phenolic monomers and aldehyde,
the phenolic resins are classied as either resol or novolac types.
16.2.2.1 Resols
In a resol synthesis reaction, formaldehyde is used in excess over the phenolic
monomer. In the case of phenol (P), typical P/F (formaldehyde) ratios are between
1:1 and 1:3. Therefore the ready resin will still contain reactive groups derived from
single-sided reacted formaldehyde: hydromethylene groups (methylol groups).
Care must be taken not to let the reaction run too far, because the mixture can
form a gel. Acid catalysis, for example, is therefore not applicable, because the re-
action will be out of control (proceed spontaneously toward the gel point). With
weak-base catalysis, however, it is possible to reach a more or less stable situation
(at fairly low temperature, below 60
C) in which most formaldehyde molecules

have reacted with phenols to form methylols, but hardly to form bridges. Catalysts
often used are alkali and alkaline earth oxides and hydroxides (such as potas-
sium hydroxide, calcium oxide). ortho-Methylols are slightly preferred over para-
methylols. The higher the pH, the higher the para content and the more ether
bridges are transformed into methylene bridges. If a higher molecular weight is
desired, the reaction can be allowed to proceed further in a slow and controlled
manner at 60
C, until the right viscosity is reached. A higher molecular weight

can be obtained more easily without risk of gelation by using two-functional phe-
nol monomers, partly (together with phenol) or exclusively. Resols can be cured to
thermoset materials themselves by adding an acidic catalyst and/or increasing the
temperature.
16.2.2.2 Novolacs
Novolac resins are obtained by reacting formaldehyde with an excess of the pheno-
lic monomer (P/F > 1:1). Either strong acids or strong bases can be used as cata-
lysts. Acids are most widely used, but with bases a higher content of orthoortho
linkages can be obtained if desired for mechanical properties. Unlike resols, which
are mostly methylolated monomer species with some occasional polymeric species,
novolacs immediately form true polymer chains of predictable molecular weight.
In principle methylene bridges, being more thermodynamically stable than ether
bridges, predominate in the polymer chains. So the P/F ratio (P being in excess)
determines ideally the (number-averaged) molecular mass M
n
. Novolacs cannot
form extensive networks by themselves because of the formaldehyde deciency. A
gel could possibly be formed, however, because of branches in the polymer chains
when a P/F ratio close to 1:1 is chosen with a three-functional phenolic monomer.
840 16 Thermosets
The higher the M
n
of the resin and the higher the functionality of the phenolic
monomers, the higher the risk of gelation during production. This can be calcu-
lated with the FloryStockmayer and related mathematical theories. One easy
way out is not to use phenol (three-functional) but, for example, p-cresol (two-
functional) as the monomer: only linear polymeric chains can then be formed.
Curing of novolacs requires addition of extra formaldehyde; mostly HMTA, typi-
cally 815%, is used as a solid formaldehyde source.
16.2.2.3 Epoxy-novolacs
Without extra formaldehyde, novolac resins are hardly reactive with other resins, as
the aromatic hydroxyl groups are relatively inert. They can be used to introduce
other reactive functionalities, however. The most important example of a function-
alized novolac resin is in the reaction with epichlorohydrin (Scheme 16.3). The re-
sulting resins contain glycidyl groups and can be used as epoxy resins (see Section
16.4). The advantage of these epoxy resins over classical bisphenol-A glycidyl resins
is that they contain more epoxy groups per unit of weight and have a higher func-
tionality as a resin (one glycidyl group per phenolic unit). Both phenol- and cresol
based novolacs are used as epoxy resin precursors. Besides reaction with epichlor-
ohydrin, phenolic resins are sometimes also reacted with alkyl chlorides or alco-
hols to etherify the aromatic hydroxy groups. In this way, their compatibility/
solubility in combination with other resins (or solvents) is enhanced.
16.2.2.4 Discoloration
The major disadvantage of phenolic resins, both resols and novolacs, is the strong
yellow to black color of the resins, or the cured materials. The discoloration (the
monomers and sometimes the resins are colorless in principle) takes place when
the material comes into contact with oxygen, which is virtually impossible to
prevent. By oxidation of methylene bridges, for example, p-quinone puered struc-
tures are formed which have a high extinction coecient for visible light (Scheme
16.4 top). Azomethine structures also can be formed when oxidation takes place in
a resin which was cured in the presence of ammonia (for example, from hexa);
see Scheme 16.4 bottom.
OH OH OH
n
O
Cl
(n+2)
n
O O
O O O
O
Scheme 16.3. Epoxy-novolac resins formed with epichlorohydrin (ECH).
16.2.3
Production
Phenol resins, both resols and novolacs, are exclusively made in batch processes.
In the production of novolacs, molten phenol is charged into the heated and stirred
reaction tank together with the weak acidic catalyst (for example, oxalic acid). At
95
C, the aqueous formalin solution is slowly added, while the reaction heat is re-
moved through distillation of water at slightly diminished pressure. When all the
formaldehyde has reacted, the water is distilled o and the reaction with the excess
phenol is continued at higher temperature (140160
C). When the desired viscos-

ity is reached, the excess of unreacted phenol is removed by distillation as well. The
molten resin is let down onto a cooling belt, and broken into small glassy lumps.
Resol resins are made at temperatures from room temperature to a maximum of
60
C. As in novolacs, molten phenol is charged rst into the reactor together with
the basic catalyst (for example, calcium oxide), after which the formalin solution is
slowly added with cooling of the mixture through water distillation. A higher vac-
uum (4050 mbar) must be used than with resol resins because of the lower reac-
tion temperature. When the desired viscosity has been reached, the reaction can be
quenched by addition of a small amount of acid (to a pH of approximately 45).
Then water is removed through distillation, either to dryness or to a concentrated
aqueous solution. If the resol resin has sucient molecular weight to be a stable
solid at room temperature, the dry resin melt is processed to glassy lumps over a
cooling belt, like a novolac resin. Very low molecular weight resol resins (M
n
< 200
g mol
1
) are dispensed as aqueous solutions; resins having higher molecular
weight (500800 g mol
1
) are often diluted with alcohol solvents (for better sol-
ubility).
16.2.4
Properties and Applications
Phenol resins have found their ways to numerous applications in varying markets:
wood glues, bonding agents for mineral and glass bers, laminates, molded parts,
coatings, inks, rubbers, matrix materials for grinding and brake composites. Their
HO O
1/2 O
2
-H
2
O
CH O
OH
NH
OH
-H
2
O
1/2 O
2
OH
N
OH
O
Scheme 16.4. Oxidation of phenolic resins leading to discoloration.
842 16 Thermosets
success is explained by their relatively low price and high degree of chemical and
thermal inertness. Thermal decomposition sets in only between 220 and 250
C,
depending on the composition. Phenol resins are quite stable to hydrolysis, even
at high pH, and are therefore suitable for making particle board for contact with
concrete castings. Once cured, phenolic materials are hard but brittle. To overcome
their brittleness, they can be combined with other resins in thermoset formula-
tions. Their compatibility with other resins can be tuned through the choice
of phenolic monomer (resins based on nonylphenol can be dissolved even in
hydrocarbons), their molecular weight, and the degree of etherication. Due to
their discoloration they are mostly used in non-surface applications. For exam-
ple, coatings based on phenol/epoxy systems are used as primers but not as top-
coats. High-pressure laminates are composed of a pile of papers impregnated
with resol resin, on top of which a decor paper impregnated with a colorless
melamineformaldehyde resin (next paragraph) is placed, the stack being cured
together in a press.
Resols can also be used in combination with unsaturated rubbers such as EPDM
(see Section 16.9) which are cured cationically.
16.3
Amino Resins
16.3.1
Introduction
Amino resins are based on reactions of compounds containing amino, imino, or
amide groups with aldehydes [3]. As in phenolic resins, the most widely used
aldehyde is formaldehyde. In an aqueous environment a condensation reaction
between formalin and the amino, imino, or amide compound leads to highly
branched, low molecular weight polymers. Introducing an acid catalyst is usually
necessary to initiate further condensation reactions that lead to curing.
The commercial history of amino resins goes back to 1924 with the use of urea as
the amino source. In 1935 melamine (2,4,6-triamino-1,3,5-triazine)formaldehyde
(MF) resins were introduced, as more expensive but higher quality resins than the
ureaformaldehyde (UF) resins. These two resins are still the main amino resins
used to date. Applications exist of pure UF or MF, but also of physical or chemical
mixtures of melamine and urea resins, leading to melamineureaformaldehyde
(MUF) resins.
16.3.2
Chemistry
In principle the condensation reaction between formalin and the amino group,
referred to as methylolation and somewhat similar to the reaction of phenol and
formaldehyde (see Section 16.2.2), can take place at four positions on a urea mole-

)
2
( OH
N
N
N
NH
2
2
HN N
)
2
( OH
N
N
N
N(
)N N
OH)
2
2
(HO
)
2
( OH
N
N
N
N(
2
HN N
OH)
2
H
OH)
2
N
N
N
N
2
HN N(
OH
OH)
2
N
N
N
N(
N N(
OH)
2
HO
H
OH
N
N
N
NH
2
2
HN N
H
Monomethylomelamine
N,N'-Dimethylolmelamine
N',N'-Dimethylolmelamine
N,N',N"-Trimethylolmelamine
N,N',N'-Trimethylolmelamine
N,N,N',N"-Tetramethylolmelamine N,N,N',N'-Tetramethylolmelamine
Pentamethylomelamine
Hexamethylolmelamine
(Mono)
(Di)
(Tri)
(Tetra)
(Penta)
(Hexa)
OH)
2
N
N
N
N
N N(
OH
HO
H
H
OH
N
N
N
N
N N
OH
H
HO
H
H
OH
N
N
N
N
2
HN N
OH
H
H
Scheme 16.5. The nine possible methylol adducts of melamine and formaldehyde.
844 16 Thermosets
cule and at six positions on a melamine molecule. The methylolation reactions of
melamine and urea are fast and reversible at temperatures over 70
C. Melamine
actually dissolves in the reaction mixture due to this methylolation reaction. For
melamine nine dierent methylolated melamine molecules have been identied
(Scheme 16.5), each with its own molecular equilibrium constant. Both primary
(HOCH
2
NH) and secondary methylols (HOCH
2
NCH
2
OH) are formed. In particu-
lar the tri- (primary) and hexa- (secondary) methylolated species are the most sta-
ble. In the polymerization reactions, depending on the molar ratio of melamine to
formaldehyde, any substitution state of melamine can be found. Therefore, MF
resins are usually highly branched. For urea four dierent methylolated ureas
have been identied (Scheme 16.6). The existence of a fth, tetramethylolurea, is
uncertain. The primary dimethylolated species is the most stable one and in poly-
merization reactions urea tends to react primarily as a two-functional monomer.
In accordance, UF resins with a low urea/formaldehyde ratio are only slightly
branched.
16.3.2.1 Polymerization Chemistry
In MF resins, melamine methylol groups condense with melamine amino groups
into methylene bridges linking two triazine moieties. Two melamine methylol
groups condense to a methylene ether, in short ether bridges (see Scheme 16.7).
The main reaction parameters are pH and the molar ratio of formaldehyde to mel-
amine (F/M) and/or urea. Typical evolution of the chemical composition of a mel-
amine formaldehyde resin during synthesis is shown in Figure 16.2.
In UF resins urea homocondensation results in methylene and ether bridges as
well, as shown in Scheme 16.8. In MUF resins, next to the homocondensations of
melamine and urea species, co-condensations can also take place, again via both
ether and methylene bridges (see Scheme 16.9) [4]. The critical parameters inu-
Monomethyllurea
N,N'-Dimethylolurea
N,N-Dimethylolurea
Trimethylolurea
)N NH
2
O
2
(HO
N NH
2
O
H
HO
)N N
O
2
(HO OH
H
N N
O
H
HO
OH
H
Scheme 16.6. The four possible methylol adducts of urea and formaldehyde.
N
N
N
NH
2
NH
2
H
2
N
+ N
N
N
NH
2
N
H
H
2
N
N
N
N
NH
2
N NH
2
HO
H
N
N
N
NH
2
NH
2
N
H
2
N
N
N
NH
2
NH
2
N
H
OH
N
N
N
NH
2
2
HN N
H
N
N
N
NH
2
N
H
H
2
N O
"Methylene bridge"
"Ether bridge"
Scheme 16.7. Condensation reactions of amino resins: homocondensation of melamine.
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 140
Time (min.)
m
o
l
/
k
g

r
e
s
i
n
Di
Mono
Tri
Tetra
Penta
Hexa
Methylene
Ether
120 100 80 60 20 40
Fig. 16.2. The concentration of the methylol groups (solid
lines) and the methylene and ether bridges (broken lines) as a
function of synthesis time. (F/M 1:65, 95
C, pH 9.5). For the

labels on the methylol lines, see Scheme 16.5.
846 16 Thermosets
encing homo- and co-condensation, as well as homo- and co-condensation, are the
molar amounts of M, U, and F during each phase of the resin synthesis, tempera-
ture, and pH. Changes in the pH have a direct and substantial inuence on the
condensation reaction kinetics and, thus, on the number of methylene and ether
linkages formed. Changes in the pH of 0.3 can double the rate of an individual
reaction. In moderately alkaline media (pH 79) methylene bridges are formed
predominantly, while in stronger alkaline conditions (pH 910) primarily ether
bridges are produced. Unlike methylene bridges, ether bridges are susceptible to
hydrolysis. Equilibrium is reached after short reaction times. Therefore, a fairly
constant concentration of ether bridges is often observed, caused by similar rates
of formation and hydrolysis. Methylene bridges do not undergo this hydrolysis
and thereby increase in concentration during synthesis; see also Figure 16.2.
H
2
N NH
2
O
H
2
N N
H
O
N
H
NH
2
O
N NH
2
O
HO N
H
H
2
N
O
N
H
NH
2
O
O
+
2
H
N NH
2
O
HO
H
"Methylene bridge"
"Ether bridge"
Scheme 16.8. Condensation reactions of amino resins: homocondensation of urea.
H
2
N NH
2
O
N
N
N
NH
2
NH
2
H
2
N
OH
N
N
N
NH
2
2
HN N
H
N NH
2
O
HO OH
N
N
N
NH
2
2
HN N
H
N
H
NH
2
O
N
N
N
NH
2
H
2
N N
H
O
+
+
+
N
N
N
NH
2
H
2
N N
H
NH
2
O
N
H
H
N NH
2
O
HO
H
"Methylene bridge"
"Ether bridge"
Scheme 16.9. Condensation reactions of amino resins: co-condensation of melamine and urea.
16.3.3
Production
Amino resins are produced in batch processes at temperatures of around 90
C in
aqueous solution under alkaline conditions. The solid content (amount of dry sub-
stance: melamine, urea, and formaldehyde) in the reactor is around 5070% by
weight. For MF resins the pH during production is around 99.5 at the beginning
of the process when all the raw materials are added to the reactor, and will stay
around that value during resin preparation. For UF resins the rst phase of the re-
action is similar, alkaline methylolation, but after some hours the pH is brought
down to around 5 to promote the bridge formation reactions.
When producing a MUF resin, dierent scenarios for adding the raw materials
to the reactor are possible regarding the moment of dosing. One should choose
dierent pH settings accordingly. Numerous recipes are described for synthesizing
a MUF resin. It is possible to simply use a mixture of ureaformaldehyde and
melamineformaldehyde resins, but usually melamine and urea are introduced
into the reactor at dierent times. Two major concepts have found general indus-
trial acceptance. One starts with the synthesis of a UF resin, followed by a co-
condensation step of melamine (UFM); the other starts with a MF resin and
co-condenses urea in the second stage (MFU). Mostly, in each case a nal urea
dosage is used to lower the molar ratio. The UFM concept is characterized by a
backbone of UF chains and a lower branching eciency of the melamine mole-
cule. In the MFU concept the branching degree of the melamine molecule is in-
creased and the melamine is more eciently incorporated into the polymeric
structure, resulting in a reduction of the dominant character of the urea backbone.
Both methods of production have their own merits in resin stability and in the per-
formance in the dierent elds of application.
The desired degree of condensation of the resins is determined in the case of UF
and MUF by the viscosity of the reaction mixture. Typically resins have viscosities
in the range of 50400 mPa s. UF resins are milky white due to small crystallites of
linear UF segments; MUF resins can be milky white as well, but also clear. In MF
resins the degree of condensation is determined via the so-called water tolerance.
This value is expressed as the relative amount of water that can be added to the
resin while remaining clear, that is, not turning turbid because of phase separation
of water-insoluble higher oligomers. Increasing condensation times give rise to in-
creasing molecular weight and, hence, lower water tolerance.
Because of their reactivity and intrinsic gelating potential, amino resins are char-
acterized by a limited storage stability. In general an aged resin (more than one to
three months old) has a very high viscosity or is gelled and cannot be applied any
more. Typically acceptable storage times are one month, depending on storage con-
ditions but also on initial viscosity, and/or water tolerance, and/or the chemical
structure of the resin. For some applications the resins are spray-dried and applied
as dry solid or redispersed solutions. Solid amino resins do not show this fast
ageing behavior because the polymerization reactions are halted by the strong de-
crease in molecular mobility (vitrication) of the polymeric system.
848 16 Thermosets
16.3.4
Curing of amino resins proceeds readily in an acidic environment; an acidic cata-
lyst is usually added to the amino resin just prior to use. As catalysts, ammonium
sulfate for UF and MUF and p-toluenesulfonic acid for MF are typical examples.
A cured amino resin is hard and brittle. Some degree of exibilization can be
achieved by adding glycols or polymers containing hydroxyl groups to the resin.
UF resins are much more sensitive to moisture than melamine resins. Applica-
tions which require a certain moisture resistance, either in swelling or hydrolysis,
necessitate the use of melamine (MUF or MF).
The majority of amino resins are used in combination with wood or paper. The
interaction with these materials is very good; amino resins are used as wood glues
in wood composites like particle board, plywood, and engineered lumber products.
Amino resins can also be the binder material in paper. Most money papers are
reinforced by melamine resins. A larger application in combination with paper,
especially for melamineformaldehyde, is as impregnation resins. Paper is im-
pregnated with resin and hot-pressed, giving decorative lms for products like
worktops and laminate ooring with a very durable surface (hard, scratch- and
chemical-resistant).
Laminate ooring provides a very good illustrative example of the application of
melamine in combination with mainly paper and wood bers. This product has
acquired its own place among other oor coverings such as carpets, tiles and par-
quet. Going from the bottom to the surface of a laminate oor, one nds: a backing
paper impregnated with melamine resin; a substrate such as particle board where
the wood particles are glued together with MUF resin; a wood decor printed paper
impregnated with melamine resin, and a transparent overlay paper impregnated
with melamine resins. This pile of materials is then hot-pressed (typically at 150
200
C and 4060 bar) for between 30 s and 2 min. After sawing into pieces and
sanding, the laminate decorative ooring is ready for application in homes and
commercial remises, being very durable, scratch- and liquid-resistant, and easy to
clean.
Other applications include binders for molding materials such as electrical plugs
or dinnerware, binders for mineral and glass wool insulation and roong, ame-
retarding agents, and leather auxiliaries.
16.4
Epoxy Resins
16.4.1
Introduction
Epoxy resins also can look back at a long history of development, as the rst ones
became commercial in the early 1940s after their invention in 1938. The term
epoxy refers to the presence of an epoxide group in the compound (monomer or
resin). This group is a three-membered cyclic ether (two carbon atoms and one ox-
ygen atom in a ring) and is called an oxirane in ocial IUPAC nomenclature. Ep-
oxy compounds can, for example, be made though oxidation of a carboncarbon
double bond. By far the largest industrial source of epoxy groups is epichlorohy-
drin (ECH). This compound contains a highly reactive, highly toxic, epoxy group
that can easily be attached to other molecules, including polymers, by a substitu-
tion reaction at the carbonchloride bond. Epoxy groups originating from reaction
with ECH are called glycidyl groups; examples are given in Scheme 16.10. The ep-
oxy novolac resins, polymeric and polyfunctional glycidyl ethers, have already been
discussed (see Section 16.2.2). The most dominant class of expoxy resins com-
prises glycidyl ethers of bisphenol-A.
16.4.2
Chemistry
The synthesis of epoxy resins from bisphenol-A and epichlorohydrin (ECH) is, in
simplied form, a net substitution reaction of the chlorine group of ECH by the
aromatic hydroxy groups of bisphenol-A to give a diglycidyl ether with evolution
of hydrochloric acid; 1 mol of base is required per hydroxy group to neutralize
this acid. In more chemical detail, the aromatic hydroxy group is rst deprotonated
by the base and then reacts with the epoxy group of ECH. Then the chloride group
is eliminated by an internal rearrangement by which a new glycidyl group is
formed. The idealized reaction product is the diglycidyl ether of bisphenol-A
(DGEBPA), a crystalline solid, as shown in Scheme 16.11. In industrial practice
the compound is a liquid which contains a small amount of higher oligomers
(n 0:13), and is called standard liquid. These higher oligomers are formed
by reaction of aromatic hydroxy groups with the glycidyl group of DGEBPA. It is
also possible to purposely synthesize higher oligomers (n 220) by catalyzing
this reaction with, for example, quaternary ammonium salts or triethanolamine as
nucleophilic catalysts. The dierent ways of making higher molecular weight
polymers is described below (see Section 16.4.3). The closer the molar ratio of
ECH/bisphenol-A in the resin to 1:1, the higher the molecular weight. A higher
molecular weight results in a higher glass transition temperature of the polymer
and a lower number of epoxy groups per unit weight (see Table 16.2). In contrast
to epoxy-novolac resins, an epoxy resin of this kind is always two-functional, with
O
Cl
O
O
O
O
O
ECH Glycidyl ether Glycidyl ester
Scheme 16.10. Epichlorohydrin (ECH) and glycidyl compounds.
850 16 Thermosets
glycidyl groups on both ends only. Some slightly higher functionalities can be the
result of side reactions (branching as a result of the aliphatic hydroxyl groups react-
ing with glycidyl groups during the polymer synthesis). This branching can be
minimized by using a selective catalyst such as triethanolamine.
16.4.2.1 Cure
For the chemistry of curing epoxy resins both the glycidyl groups and the aliphatic
hydroxyl groups are of importance. The higher the molecular weight of the resin,
O
Cl HO OH
O
Cl
2 NaOH - 2 NaCl
O O
O O
DGEBPA
Higher oligomers
O
O O
OH
O O
O
n
Scheme 16.11. Synthesis of the diglycidyl ether of bisphenol-A
(DGEBPA), and higher oligomers.
Tab. 16.2. Epoxy resin overview.
Resin n ECH/BPA
[a]
DGE-BPA/BPA
[b]
M
n
T
g
[
C]
Standard liquid 0.16 360 <10 (liquid)
1001 type 2 1.33 2 900 6575
1004 type 5.5 1.15 1.4 1900 95105
1007 type 14 1.07 1.14 4300 125135
1009 type 16 1.05 1.12 5000 145155
[a]
Molar ratio of building blocks in product. Applicable to Tay process
for the 1001 type.
[b]
Molar ratio of monomers in Advancement process.
the more hydroxyl groups are present in relation to the glycidyl groups. Epoxy res-
ins can be cured themselves by addition of a (Lewis) acidic or basic catalyst. Ter-
tiary amines and imidazolines are especially eective catalysts. They serve as a nu-
cleophilic ring-opening initiator for a cascade of epoxyepoxy reactions, resulting
in ether linkages between the polymer chains. The glycidyl groups can also un-
dergo ring-opening reactions with a wide variety of active hydrogen-containing
compounds, in close analogy to the synthesis reaction where the aromatic hydroxyl
groups acted as active hydrogen donors (see Scheme 16.12). Depending on the re-
activity of the active hydrogen donor, a catalyst may be needed to eect a su-
ciently fast cure reaction.
Amines generally do not need a catalyst, as the reaction with epoxy resins occurs
spontaneously at room temperature. Therefore, amine curing agents can be used
O
R
HNu
Nu
OH
R
O
O
R
O
OH
O
OH
O
O
R
Scheme 16.12. Reactions of glycidyl groups with compounds
containing active hydrogen groups, such as carboxylic acids.
Primary amine Secondary amine
Tertiary amine
R
1
N
OH
O
R
2
OH
O
R2
O
O
R
2
R
1
N
H OH
O
R
2
O
O
R
2
R
1
N
H
H
Scheme 16.13. Reaction of amine groups with glycidyl groups, formation of tertiary amines.
852 16 Thermosets
for epoxy resins only in two-component (2K) formulations. Low molecular weight
polyamines such as diethylenetriamine and triethylenetetramine are frequently
used as such. Because of their toxicity, they are also modied with amide groups
to lower their volatility. To their advantage, the functionality of these amines is
quite high. Not only do they contain several nitrogen groups in a small molecule,
but each NH counts as an active hydrogen donor in the reaction with epoxy
groups. A primary amine group, NH
2
, is two-functional: after one reaction with a
glycidyl group a secondary amine group, NH, remains which can undergo an addi-
tional reaction with a glycidyl group, as shown in Scheme 16.13.
Phenolic resins can react in two ways with epoxy resins. Using the right catalyst,
the aromatic hydrogen groups can react with glycidyl groups, in analogy to the syn-
thesis of higher epoxy resin oligomers. This applies to both resol and novolac type
resins (see Section 16.2.2). Methylol groups, as present in resol resins, can also re-
act with the aliphatic hydroxyl groups of bisphenol-A based epoxy resins, with for-
mation of ether linkages.
Carboxylic acids and anhydrides also can be used for curing epoxy resins. Car-
boxylic anhydrides can react spontaneously at room temperature with the aliphatic
hydroxyl groups of bisphenol-A based epoxy resins, with formation of carboxylic
acid groups. The carboxylic acid groups can then react further with the glycidyl
groups (see Scheme 16.12), at higher temperatures and using the right catalyst
such as a quaternary ammonium or phosphonium halide. Polyester resins (see
Section 16.6) can be used as a source of carboxylic acid functional polymers to
cure the epoxy resins.
16.4.3
Production
Three variations on the synthesis of epoxy resins from bisphenol-A and ECH exist
to date, diering in the ratio between these monomers and the viscosity of the
product resins, as determined by the removal of the sodium chloride formed.
16.4.3.1 Standard Liquid
The diglycidyl ether of bisphenol-A (DGEBPA) is made with a large excess of ECH
(6 equiv.) to minimize formation of higher oligomers. Bisphenol-A and ECH are
charged together into the reactor. Powdered base (NaOH) is added slowly to this
mixture at 60
C to make the reaction proceed, while salt (NaCl) is formed as a by-

product. After the exothermic reaction is nished the temperature is raised to
100
C while water (also a by-product of the reaction) is distilled o under reduced

pressure, and then the temperature is raised further to 120
C to drive the reaction

to completion. The salt formed and residual base are removed from the product
through washing with water. Finally all remaining volatile components, including
the excess ECH, are removed under vacuum (30 mbar). This technical grade (aver-
age n 0:16) contains approximately 90% DGEBPA (n 0), 9% dimer (n 1),
and 1% trimer (n 2).
16.4.3.2 Tay Process
With a much lower excess of ECH, and in the presence of a catalyst, it is possible
to make higher oligomers directly in a procedure similar to that for the standard
liquid, called the Tay process. Bisphenol-A and a stoichiometric amount of
NaOH (10% aqueous solution) are charged into the reactor, and ECH is added
with vigorous stirring at 45
C. The reaction mixture is heated to 95
C and is kept
at this temperature for another 12 h. The product, a viscous liquid at this temper-
ature, is washed with water to remove the salt and catalyst, dried, let down over a
cooling belt and aked. Because the viscosity of the product is a limiting factor in
the water washing step, this process is applicable to lower oligomers only, maxi-
mum n 4, for example the 1001 type.
16.4.3.3 Advancement Process
When even higher oligomers are desired, it is important to remove the salts from
the reaction before the nal molecular weight is obtained. This is achieved in the
Advancement process (see Scheme 16.14). In this process the reactor is charged
with standard liquid resin, free of salts. Fresh bisphenol-A, in a specic molar ratio
to the DGEBPA for the desired M
n
, and an appropriate catalyst are added. The po-
lymerization is eected exclusively by consecutive reactions of the hydroxyl groups
of the bisphenol-A with the glycidyl groups of the DGEBPA. It is carried out at
higher temperatures than the Tay process, well above the glass transition temper-
atures of the targeted polymer; see Table 16.2. After the desired viscosity has been
reached, the product is let down over a cooling belt and aked to glassy pellets.
Unlike the Tay process, in which oligomers with every value of n are formed
(n 0; 1; 2; 3; 4; 5 . . .), the Advancement process yields polymers with predomi-
nantly (> 90%) even numbers of repeating units (n 0; 2; 4; 6; 8; 10 . . .) as a result
of the consecutive reactions between DGEBPA and bisphenol-A. The presence of
about 10% n 1 dimer in the standard liquid resin causes 10% of the Advance-
ment product to have odd numbers of n.
O O
O O HO OH
n
O
O O
OH
O O
O
(n + 1) (n)
Scheme 16.14. Epoxy resin synthesis via the Advancement process.
854 16 Thermosets
16.4.4
Epoxy thermosets have excellent mechanical properties: they are characterized by
a high hardness but relatively low brittleness (in comparison with phenolic and
amino resins). This is caused by the b-transitions in the bisphenol-A moieties
along the polymer chain. The higher the molecular weight, the higher the exibil-
ity of the network (the longer the elastically active network (EAN) chain) and the
lower the crosslink density when the cure reaction involves only the glycidyl
groups. If a high exibility is desired with a higher crosslink density, rubbery
resins can be used to modify the lower molecular weight resins. During cure they
separate as small rubber domains inside the thermoset matrix.
The lower molecular weight epoxy resins, when cured with, for example, amines
or anhydrides, are used as 2K adhesives and in liquid coatings. When cured with
phenolic resins, excellent hydrolysis resistance is obtained. Beverage and food
packaging cans are coated on the inside with such systems for good sterilization
performance. Epoxy resins are popular for their properties in many other coating
applications also, but predominantly in primers and coatings for indoor use. The
high T
g
of the higher oligomers makes them very suitable for powder coatings
(see Section 16.6.5), especially when cured with dicyanodiamide or acidic polyester
resins. The presence of many aliphatic hydroxyl groups along the chain provides
good chemical interaction with, for example, metal surfaces. This results in excel-
lent adhesion to metal substrates, and a high resistance to corrosion. The disadvan-
tage of epoxy resins based on bisphenol-A or novolac is that they are very prone
to photooxidation at the aromatic ether bonds and are, thus, poorly resistant to
UV light during outdoor weathering.
An example of epoxy resins that cure when a strong acid is liberated is given
in Scheme 16.35 (see Section 16.8.5, on UV curing). Press moldings from epoxy
resins, catalyzed by tertiary amines for cure, are used in automotive and electronic
components. As they only react with their glycidyl end groups, they are relatively
insensitive to over-cure. They are furthermore dimension-stable, and are very resis-
tant to heat and chemical inuences.
16.5
Alkyd Resins
16.5.1
Introduction
Alkyd resins can be described as polyesters containing unsaturated fatty acids.
Many of the chemical and technological aspects coincide with those of saturated
polyesters (see Secion 16.6). We discuss them here rst because the alkyd technol-
ogy, itself originating from early in the 20th century, stemmed from the use of veg-
etable oils in the painting and graphic arts industry. In comparison with simple
vegetable drying oils, alkyds provide harder lms and much faster drying. As vege-
table oils, they are crosslinked through an autoxidative drying mechanism by am-
bient oxygen from the air. They are compatible with a wide range of solvents and
other resins. They currently constitute a versatile and economic group of binders
for the paint industry, with a world annual volume of approximately 1.5 Mt.
16.5.2
Chemistry
Alkyd resins are essentially built up of three groups of components: polyhydric
alcohols, polyacids and (vegetable) monoacids. The polymerization process is by
esterication (see Section 16.6.2). Examples of typical alkyd monomers are pen-
taerythritol (tetramethylolmethane), trimethylolpropane, and glycerol as polyhydric
alcohols (Scheme 16.21, below), and mainly phthalic anhydride but occasionally
isophthalic acid, maleic anhydride, and adipic acid as polyacids (Scheme 16.22, be-
low). The most commonly used monoacids are polyunsaturated fatty acids (the
main chemical species of which are oleic, linoleic, and linolenic acids; Scheme
16.15) that impart to the alkyd its drying properties, and benzoic acid which is
sometimes used to raise the T
g
. The main vegetable oils of industrial relevance
are linseed oil, soybean oil, saower oil, and sunower oil. They all contain dier-
OH
O
OH
O
OH
O
OH
O
OH
O OH
OH
O
OH
O
Stearic acid
Palmitic acid
Oleic acid
Linoleic acid
Linolenic acid
Ricinic acid
-eleostearic acid
Scheme 16.15. Some vegetable fatty acids used in alkyd resins.
856 16 Thermosets
ent amounts of fatty acids (Table 16.3). The numbers given are merely indications,
as seasonal inuences aect the relative fatty acid contents. The concentration of
unsaturated groups in the oil is expressed by the iodine number (g I
2
per 100 g
oil), based on the known addition reaction of iodine to unsaturated carbon bonds.
The fatty acids can be incorporated, along with the other polyester monomers,
into the resin as such. This is called the fatty acid process, but, if glycerol also is
desired to be present in the resin, it can be more economical for the vegetable oil,
that is, a triester (triglyceride) composed of glycerol and fatty acids, to react directly
with the polyester ingredients. In that case the oil cannot be introduced in the
polyesterication stage, as the oil itself is not compatible with the growing poly-
ester. A kind of dispersion of oil-free polyester particles would then be formed in
the oil. These undesired systems are called glyptals. To avoid the formation of glyp-
tals, the fatty acids in the oil have to be randomly distributed over the glycerol of
the oil and the polyhydric alcohols present in the formulation in a rst transester-
ication step. The resulting hydroxyesters can intermix in a second step with the
acids and then result in a homogeneous product. This alcoholysis process is de-
picted in Scheme 16.16.
In a similar process, called acidolysis (Scheme 16.17), the glycerol from the oil is
distributed over the fatty acids and isophthalic acid. This procedure is not possible
Tab. 16.3. Unsaturated fatty acid content of vegetable oils.
Fatty acid Linseed oil Soy oil Saower oil Sunower oil Tung oil Castor oil
Palmitic 6 11 8 11 4
Stearic 4 4 3 6 2
Oleic 22 25 13 29 4 9
Linoleic 16 51 75 52 8 83
Linolenic 52 9 1 2
Ricinoleic 8
Eleostearic 82
Iodine number 180 130 145 130 175 155
O
O
O
O
C
17
H
31
O
C
17
H
31
O
C
17
H
31
+2
HO OH
HO OH
O
C
17
H
31
OH HO
O HO O
OH
OH
O
C
17
H
31
+
2
Scheme 16.16. The alcoholysis process for alkyd resins.
with phthalic anhydride, since free carboxylic acid groups are required for this
transesterication reaction. Orthophthalic acid is not stable at the acidolysis tem-
peratures (260
C) and will form mainly the more stable cyclic anhydride. The pro-
cess is therefore primarily used in the production of printing ink resins, where iso-
phthalic acid is the diacid of choice.
If a higher T
g
of the resin is desired, for example to obtain harder coatings, the
chemistry of the alkyd resin can be modied after the polycondensation process by
incorporation of phenolic (see Section 16.2) and/or colophonium resins.
16.5.2.1 The Alkyd Constant
In contrast to radical-type polymerization, in the making of branched polyconden-
sates like alkyds the build-up of molecular weight can be controlled to a large de-
gree. The starting point in these calculations is the understanding that an innite
molecular weight (gelation) can in principle only be obtained if the average func-
tionality F of the monomers is equal to or higher than 2.
This average functionality is dened as: F E
alcohol
E
acid
/M
0
, in which
E
alcohol
denotes the number of equivalents of alcohol groups, and E
acid
the number
of equivalents of acid groups, while M
0
denotes the total number of moles of
monomers in the system. In practice, alkyd resins are cooked with a surplus of
hydroxyl groups. This means that not all the hydroxyl groups will esterify and con-
sequently the number of eective alcohol equivalents is equal to the number of
acid equivalents; in other words, E
alcohol
E
acid
2E
acid
. Thus, F 2E
acid
/M
0
. The
alkyd constant K is dened as 2/F, equalling M
0
/E
acid
, and should not be lower
than 1. In practice, an alkyd constant of 1.021.06 is recommended to avoid gelat-
ion regimes at all times.
16.5.2.2 Autoxidative Drying
A basic reaction scheme of the autoxidative drying process is depicted in Scheme
16.18. A catalyst is needed to give this reaction sucient speed; usually a cobalt(II)
salt is used. The diene moieties of the linolenic acids, especially, are involved in
this process. After formation of a conjugated hydroperoxide with molecular oxygen
from the ambient air, the hydroperoxide decomposes into oxy-radicals that can fur-
O
O
O
O
C
17
H
31
O
C
17
H
31
O
C
17
H
31
+2
O
O
O
C
17
H
31
O
O
O
CO
2
H
CO
2
H
+
2 HO
2
CC
17
H
31
CO
2
H
CO
2
H
Scheme 16.17. The acidolysis process for alkyd resins.
858 16 Thermosets
ther react with unsaturations of other fatty acids. Mainly by addition and recombi-
nation reactions of these radicals the nal network structure is formed. Side reac-
tions during the autoxidation process can lead to yellowing.
16.5.3
Production
The alcoholysis process has lower raw material costs than the fatty acid process but
higher production costs, since it is a two-step process. The decision whether to pro-
duce from oil or from fatty acids is thus largely based on the amount of oil/fatty
acids in the formulation (see short oil/long oil resins, discussed in Section 16.5.4).
Regardless of the way fatty acids are incorporated, the main step of alkyd synthe-
sis is the polyesterication. This process is quite similar to the process for satu-
rated polyester resin production, and actually more or less the same equipment
can be used (Figure 16.3). The polyesterication of the alkyd raw materials nor-
mally proceeds at 240
C with the aid of xylene as a mode of transportation of the

water, by forming a binary azeotrope with it. The xylene and water vapors rise
through the column on top of the reactor and are condensed on top of a separator.
The xylene is pumped back into the reactor and the water is removed. Because of
O
O
Oxygen, Cobalt (II)
O
O O
OH
Cobalt (II)
O
O O
O
O O
O
O
OH
Polyester
Polyester
Polyester
Polyester
Polyester
.
Scheme 16.18. Autoxidative drying of alkyds and oils.
undesirable volatile by-products that often form ternary azeotropes with water, the
reaction water cannot be disposed of in the sewage system without incineration.
Variables measured at regular intervals to control and, if necessary, adjust the
process are:
Acid value: a measure for the amount of acid groups still present in the reaction
mixture, expressed in mg potassium hydroxide needed to neutralize 1 g of solid
resin. This value drops throughout the process as the esterication proceeds.
Viscosity: an indication of the weight-averaged molecular weight, usually mea-

sured by the torque of the reactor stirring motor or that of a separate rotor/stator
measuring device. The viscosity increases with time as a result of increasing mo-
lecular weight of the resin. If desired, a graph can be drawn plotting log viscosity
against acid value. This is a more or less straight line and enables the operator to
judge whether the resin will be within the specications, which show up on the
graph as a rectangle.
After reaching these specications, potential modications can be made, for exam-
ple with silicones for better outdoor durability, or polyamides to impart thixotropy.
Finally the resin is cooled, diluted in solvent and/or emulsied, and if necessary
ltered.
FC
vacuum
vent
oil in
oil out
conden-
sate tank
inert gas
TC
T
distillation
column
T
Fig. 16.3. Reactor design for production of polyester and alkyd
resins. FC, ow control; T, temperature measurement; TC,
temperature control.
860 16 Thermosets
16.5.4
16.5.4.1 Short Oil Alkyds
Short oil alkyds contain less than 35% oil by weight, calculated as triglyceride.
These resins have a relatively high T
g
and therefore will feel dry as soon as the
solvent has evaporated from the paint. Chemical drying through the unsaturated
fatty acids will be relatively modest and other crosslinking reactions will have to
be considered. Examples are etherication of the OH groups with resol (see Sec-
tion 16.2) or amino resins (Section 16.3), either thermally (stoving) or by acid catal-
ysis. Applications are in non-yellowing wood varnishes and protective coatings, for
example for steel constructions.
16.5.4.2 Long Oil Alkyds
Long oil alkyds can contain from 55% oil, even up to 80%. Long oil alkyds are
typically used for trade (professional painting) and DIY (do-it-yourself ) applica-
tions. Application is mostly by brush and roller and the paints are supplied in
white spirit.
Their T
g
is low and resins will feel sticky several hours after the solvent has
evaporated. Chemical drying is intensive and as a result of this the molecular
weight builds up gradually in time. For a typical long oil alkyd resin, full chemical
drying is obtained in a period of weeks, and can be accompanied by some yellow-
ing. Typical oils/fatty acids that are used are linseed and soybean. Since linseed
contains triply unsaturated fatty acids, it has more crosslinking potential but will
also smell and yellow more. For this reason linseed oil based alkyds are mainly
used for primers. For topcoats the oil of choice is soybean but saower and sun-
ower are also used, the latter being superior to soybean with regard to yellowing
and smell. Other oils with very high unsaturation that are often used in primers
for semi-industrial applications, applied on-site, are sh oil (marine applications)
and tung oil (marine and industrial construction maintenance).
16.5.4.3 Medium Oil Alkyds
Medium oil alkyds contain, as the name already suggests, 3555% oil by weight
and are used in the higher-quality trade and DIY paints. In quick-drying properties
and yellowing they outperform the long oil alkyds and they are mostly dissolved in
white spirit.
16.5.5
Alkyd Emulsions
Alkyd paints dominated the architectural coating market for a long period until the
appearance of polymer dispersions or the so-called latex paints. Specically for wall
application waterborne paints based on poly(vinyl acetate) homo- and copolymers,
styreneacrylics and pure acrylic latexes almost completely took over the market
from the alkyd resins for both interior and exterior application. However, for
wood and metal application alkyd paints still enjoy the majority of the market
share, thanks to better overall paint performance. For the same application elds,
alternatives to the conventional alkyd paints were desired for environmental rea-
sons: namely, to avoid the use of (neurotoxic) solvents and solvent emissions to
the air. From about 1980, aqueous alkyd emulsions have been developed and are
now breaking through in the market as environmentally friendly systems. Alkyd
emulsions can best be described as a dispersion of solventless alkyd resin droplets
in water (o/w). When the paint dries, the water evaporates and the emulsion
changes from oil-in-water (o/w) to water-in-oil (w/o). The paint properties of the
dried and autoxidatively crosslinked lm are largely comparable to those derived
from solvent-borne alkyd paints [5].
16.5.5.1 The Inversion Process
In order to keep this emulsion stable in time during storage, the particle size of the
droplets must be small enough (typically <2 mm) and surfactants must be used.
Alternatively to the use of additional surfactants, incorporation of surface-active
groups, such as polyethylene glycol derivatives, in the alkyd resin is also possible;
it is sometimes even more desirable not to have free surfactant molecules in the
resin from a paint quality point of view. The production of an alkyd emulsion
with built-in surfactants starts with a conventional alkyd polyesterication process,
in which acid- or hydroxy-functional surfactants are added along with the other
monomers. Care must be taken to keep the viscosity as low as possible to facilitate
the next step. After the polycondensation reaction is nished, the resin is cooled to
<100
C and water is slowly added to the hot resin to form a w/o emulsion. With
increasing water content, an inversion to an o/w emulsion will take place. The in-
version is accompanied by a large increase in viscosity. After the inversion more
water can be added to reach the right viscosity at room temperature.
16.6
Saturated Polyester Resins
16.6.1
Introduction
Thermosetting polyester resins are almost as old as alkyd resins. The rst attempts
to make polyesters derive from the second half of the 19th century. In the begin-
ning of the 20th century more and better-dened polyesters were made by Vor-
lander and later by Smith. Most of the polyester resins were based on glycerin
and aliphatic diacids as fumaric and adipic acids. From these times the rst appli-
cation of polyester resins in paints and coatings was developed. Besides the modi-
cation with fatty acids (alkyd resins), which are cured by air, thermosetting resins
were developed which are cured by crosslinkers or other resin types. The choice
of monomers, more specically the ratio of polyacids to polyalcohols, deter-
mines the type of end groups, for a polyester these being either acid aCOOH
862 16 Thermosets
or hydroxy aOH. These functional end groups can react with epoxy resins (see Sec-
tion 16.4), isocyanates, phenolic resins (Section 16.2), and melamine resins (Sec-
tion 16.3).
16.6.2
Chemistry
Polyester resins consist of polyfunctional acids and polyalcohols [6]. These com-
pounds esterify at higher temperatures with evolution of water (Scheme 16.19).
The chemical equilibrium for this polycondensation reaction is unfavorable. It is
important that water is removed from the reaction mixture continuously, shifting
the equilibrium to the right (see Chapter 4). The temperature for this reaction lies
normally between 200 and 260
C and the choice is dependent on the stability of

the raw materials used. This direct esterication reaction is far the most used
chemistry for saturated polyester resins. Polycondensation via transesterication,
as in Scheme 16.20 and primarily used in the synthesis of thermoplastic poly-
esters, is only occasionally used for resins. By varying the type and the molecular
ratio of the reactants, the molecular weight and structure of the polymer, and the
type and number of functional end groups, can be varied. Excess of acid functional
raw materials gives an acid functional polymer. Excess of polyfunctional alcohols
gives a polymer with hydroxyl end groups. If branching is desired, polyfunctional
raw materials are used. Mostly three- or four-functional polyhydroxyl compounds
are used. In practice a large variety of raw materials are available for the formulator
HO R1 OH HO
O
R2
O
OH
(n+1) n
HO R1 O
O
R2
O
O OH R1
n
+ 2n H
2
O
Scheme 16.19. General esterication scheme for OH-polyester resins.
HO R1 OH CH
3
O
O
R2
O
OCH
3
(n+1) n
HO R1 O
O
R2
O
O OH R1
n
+ 2n CH
3
OH
Scheme 16.20. General transesterication scheme for OH-polyester resins.
to design the polymer molecule. Schemes 16.21 and 16.22 give an overview of the
most frequently used polyol and polyacid monomers, respectively. In principle, the
molecular weight distribution can be calculated, but for the more complicated for-
mulations computer aid is needed.
The choice of diols depends on which properties the resin would get. Rigid and
HO OH
neopentylglycol
HO OH
HO OH
2-methyl-1,3-propanediol 1,3-propanediol
HO
OH
HO
OH
1,2-propanediol ethyleneglycol
HO
OH
buteneglycol
OH
HO
1,4-cyclohexanedimethylol
HO O
O
OH
2,2-dimethyl-1,3-propanediol hydroxypivalic ester
OH HO
OH
trimethylolpropane
OH
OH HO
OH
pentaerythritol
Scheme 16.21. Some polyol monomers used in polyester resins.
CO
2
H
CO
2
H
CO
2
H
CO
2
H
O
O
O
terephthalic acid isophthalic acid phthalic anhydride
HO
2
C
CO
2
H
adipic acid
O
O
O
CO
2
H
trimellitic anhydride
CO
2
H
CO
2
H
cyclohexane-1,4-dicarboxylic acid
HO
2
C
CO
2
H
sebacic acid
O
O
O
hexahydrophthalic anhydrid
Scheme 16.22. Some polyacid monomers used in polyester resins.
864 16 Thermosets
cyclic diols will increase the T
g
, melting point, and hardness of the polyester resin.
Long and exible diols will decrease the T
g
and melting point, and improve the
exibility. Diols which are substituted on the b-position toward the hydroxyl
groups, such as neopentyl glycol, are normally more resistant against hydrolysis
and photooxidation. Besides a wide variety of diacids, several cyclic anhydrides are
available as well. Anhydrides react faster than the corresponding acids and require
less water to be distilled o. Aliphatic diacids will lower the T
g
and melting point,
but give more exibility. Aromatic diacids give a higher T
g
and hardness to the
coating lm and are more resistant toward hydrolysis. Aliphatic diacids impart
less UV absorbance to the resin and therefore enhance the UV resistance of coat-
ings made from these resins. From aliphatic diacids, crystalline or semicrystalline
polyester resins can also be made.
16.6.3
Production
Most saturated polyester resins are produced in the melt phase. At temperatures
of about 200260
C and in the presence of a catalyst the diacids and the diols are
esteried by removal of water. The high temperature during the synthesis is nor-
mally sucient to remove the water eciently from the reactor by distillation,
under reduced or normal pressure. To remove the last percentages of water and to
complete the reaction, a stronger vacuum is applied at the end of the reaction.
In cases where the resins are to be supplied in a solvent anyway, azeotropic
distillation can be used to remove the water more eciently and at lower temper-
atures. Figure 16.3 describes the reactor design for polyester resin production,
which can also be applied to alkyd resin production (see Section 16.5). The product
resin can be either cooled and discharged via a cooling belt in case a solid delivery
form is required, or thinned with solvents.
16.6.3.1 Monitoring the Reaction
The conversion and progress of the esterication reaction are controlled by analyz-
ing samples that are taken from the mixture. For the application of thermosetting
resins the amount of end groups is very important and has to be measured during
production. The concentration of end groups (aCOOH and aOH) is measured by
titration; several titration methods have been developed. The concentration is ex-
pressed as the acid value or hydroxyl value in mg KOH per gram resin (by
back-titration in the case of aOH). The removal of water by distillation is not
100% ecient and some diols, diacids, small oligomers, and side products of the
reaction at high temperature can be removed from the reactor with the water. In
order to reach the right specications, small amounts of either diols or diacids
can be added (corrections), as even in the early stages of the reaction a mis-
balance of the OH/COOH groups can be detected. Another important specica-
tion is the viscosity of the melt or of the solution, as an indication for the molecu-
lar weight. Both parameters are plotted for a typical polyester resin in Figure 16.4.
16.6.4
The ratio of hard to soft monomers determines the T
g
of the polymer. The re-
activity during the curing reaction and network formation is determined by the
overall amount of end groups and the overall functionality.
The main application of these types of polyester resins is in thermosetting coat-
ings. Thermosetting paints are formulated by mixing polyester resins (in solid
form, melt, or solution) with a crosslinker, pigments, and additives. These paints
will be cured to a coating lm, generally with stoving. Surface coatings based on
saturated polyester resins distinguish themselves from other resins by good adhe-
sion on metals, good exibility (ability to be deformed together with the substrate
after painting), and hardness. Their resistance to hydrolysis is rather poor; their
outdoor durability is modest in comparison to acrylic binders but superior to epoxy
resins. Saturated polyester resins can be applied in all kinds of paint types. The
major application elds today include coatings for beverage and food cans, and
coated steel coils. Saturated polyester resins further play a dominant role in the
binders for thermosetting powder coatings, described in the next paragraph.
16.6.5
Powder Coatings
Powder coatings are, as the name suggests, paints in solid, powdery form [7]. All
the ingredients are solid materials, which are mixed in a hot-melt compounding
Fig. 16.4. Evolution of acid number and viscosity with time during polyester resin synthesis.
866 16 Thermosets
process (extrusion). Figure 16.5 depicts the powder coating preparation process.
Powder paints consist of a binder (polymer, crosslinker and curing catalyst), pig-
ments, and additives. All these solid ingredients are mixed thoroughly in a pre-
mixer and fed into an extruder. The mixture is molten and homogenized in a short
period of time, typically in half a minute, to prevent premature crosslinking reac-
tions. After the extrudate is cooled down, it is crushed and milled to the required
particle size, which is dependent of the application but is normally in the range of
about 50100 mm.
16.6.5.1 Application
Powder paints are commonly applied by electrostatic spraying on metal substrates.
The powder particles are charged inside the spray gun (Corona or Tribo) and ad-
here to the earthed metal object. Powder coating is ideal for coating complicated
three-dimensional objects because the powder particles can easily reach recessed
surfaces or even the backside of surfaces, following the electrical eld lines from
the gun to the substrate. Powder paint which does not reach the object or disasso-
ciates from the surface (overspray) can easily be gathered, recycled, and re-used
without loss of quality (Figure 16.6). The substrate, covered with a layer of powder
paint, is subsequently heated in a hot-air oven. The powder particles melt, coalesce,
and ow out into a lm.
In some special cases the powder paints can be applied by dipping. The object is
preheated and dipped into a uid bed of powder paint particles. The powder par-
ticles adhere to the preheated surface of the object and melt into a lm. Further
Fig. 16.5. Powder coating production.
heating causes the crosslinking reactions in the lm to give the required thermoset
properties. The processes of melting, owing, and curing take place in the same
cycle and this makes it dicult to obtain a completely at lm before the cure pro-
hibits further ow. Powder coatings are therefore characterized by a certain visual
orange peel eect.
16.6.5.2 Crosslinking
Although many examples exist of thermosetting powder coatings (using mainly
polyamide, polyethylene, and polypropylene), most powder paints are thermoset-
ting systems, which are cured at much higher temperatures (typically 180200
C)
than the extrusion temperature (90110
C). Because of these high curing temper-

atures, powder coatings nd their application mainly on metal surfaces.
The rst thermosetting powder coating systems were based on bisphenol-A
epoxy resins, which were cured by either amide/amine or carboxylic anhydride
crosslinkers (for the chemistry, see Section 16.4.2). The epoxy-based powder coat-
ings show excellent application properties, such as ow, mechanical strength, and
chemical resistance. However, they have limited exterior durability and they show a
severe tendency toward yellowing. These disadvantages have greatly stimulated the
development of powder coatings based on saturated polyesters with carboxylic end
groups.
When cured with bisphenol-A resins, these polyester resins result in coatings
with much improved exterior durability with less yellowing. When cured with tri-
glycidyl isocyanurate (TGIC) excellent outdoor durability is obtained and polyester
resin coatings are used, for example, in the building industry (facades). The muta-
genic properties of TGIC have stimulated the search for safer crosslinkers, such as
b-hydroxyalkylamides, which are now taking over the market.
Hydroxyl-functional polyester resins are also used; these polyesters are cured
with aliphatic (for outdoor use) or aromatic (indoor use) polyisocyanates.
Fig. 16.6. Powder coating spraying and recycling system.
868 16 Thermosets
16.6.5.3 Advantages
The advantages of powder coating compared to the more classic type of coatings in
solution are clear: they are 100% solvent-free and thick layers up to 500 mm can be
applied in one step. Moreover, they are very cost-ecient owing to a very high ap-
plication eciency, close to 100%, as over-sprayed powder can be easily recycled.
Last but not least, their mechanical properties are usually equal or superior to
those of their solvent-borne counterparts.
Powder coating can also be favorably combined with UV curing (see Section
16.8.5.2). In that case, the powder coating can also be applied to heat-sensitive sub-
strates such as wood, paper, and plastics because the powder can melt and ow
from about 100
C. In addition, the melt/ow-out phase is easily separated (hot air

or infrared radiation) from the cure phase (irradiation with UV light) resulting in a
good ow. Binders for UV-curable powder coatings are either based on acrylated
saturated polyester resins (see Section 16.8.3.2) or on unsaturated polyesters (Sec-
tion 16.7) in combination with vinyl ether crosslinkers (Secheme 16.34).
16.7
Unsaturated Polyester Resins and Composites
16.7.1
Introduction
Unsaturated polyester resins (UP resins) cover a broad range of products serving a
wide variety of market segments. They can be considered the most versatile of the
thermoset resins. By varying the resin composition, one can produce an amazing
range of properties in polyesters. Additionally, polyesters are capable of being pro-
cessed by a number of dierent methods, varying from simple hand-lay-up contact
molding to highly automated compression molding. Glass ber reinforced UP res-
ins are extensively used in building and construction; and in the transportation,
electrical, and electronic industries; and for sanitary and domestic applications.
The biggest use of these resins is in the construction industry, followed by trans-
portation. The worldwide consumption of UP resins in 2002 was approximately
2.5 million metric tons.
16.7.2
Chemistry
The unsaturated polyester is a macromolecule with an M
n
value between roughly
1000 and 3000 g mol
1
, obtained from a polycondensation reaction (that is, a poly-
merization with the formation and elimination of water) between unsaturated- and
saturated dicarboxylic acids (or their corresponding anhydrides) and diols [8]. This
reaction and the most commonly used raw materials are represented schematically
in Figure 16.7. Mono- or trifunctional acids or alcohols or other monomers may be
incorporated optionally into the polyester backbone to tailor properties.

POLYCONDENSATION

Unsaturated
dicarboxylic acids

Maleic anhydride
Fumaric acid
Saturated
dicarboxylic acids

Phthalic anhydride
Isophthalic acid
Terephthalic acid
Adipic acid
Glycols

Propylene glycol
Dipropylene glycol
Ethylene glycol
Diethylene glycol
Neopentyl glycol
Propoxylated
bisphenol A
Other

Benzoic acid
Ethylhexyl alcohol
Trimethylol propane

Dicyclopentadiene
Unsaturated Polyester
Macromolecule
Reactive Monomers

Styrene
Methyl styrene
Methyl methacrylate
Vinyl toluene
Diallylphthalate
Triallylcyanurate

UP resin
Cured UP-based
composite
Radical initiator

Methyl ethyl ketone peroxide
Benzoyl peroxide
Cumene hydroperoxide
tert Butyl perbenzoate
Glass fiber reinforcement
Chopped rovings
Chopped strand mat
Woven rovings

Fillers
Calcium carbonate
Aluminum trihydrate

Pigments / colorants
Titanium dioxide
Zinc sulfide
RADICAL POLYMERIZATION
Finishing ingredients

Inhibitors hydroquinone / benzoquinone
tert. butyl catechol
Stabilizer copper (I) naphthenate
Accelerator cobalt- octoate or naphthenate
Thixotropic agent fumed silica
UV absorber benzophenone derivatives
LSE agent paraffin or wax
OH + HOOC
+ water
-
Fig. 16.7. Unsaturated polyester resins: from raw materials to cured composites.
870 16 Thermosets
The preferred unsaturation in the polyester backbone is the fumaric double
bond, which results from using either fumaric acid or maleic anhydride as the un-
saturated dicarboxylic acid. Under the reaction conditions normally applied to syn-
thesize the polyester, most of the maleic (cis) double bonds isomerize to fumaric
(trans) double bonds. The unsaturated polyester macromolecule itself is either a
very viscous liquid or a solid. Usually this polyester is dissolved in a reactive mono-
mer containing a double bond capable of copolymerizing through a radical poly-
merization with the (fumaric) unsaturations in the polyester backbone. The work-
horse of the reactive solvents is styrene. The low-viscosity polyester solution (UP
resin) thus obtained is formulated with a number of ingredients that provide criti-
cal properties, such as storage stability, reactivity, thixotropy, UV resistance, and
color, before being sold by the polyester producer.
16.7.2.1 Crosslinking
The processor converts the liquid polyester by means of a radical polymerization,
in the presence of glass ber reinforcement and/or llers, into a three-dimensional
composite network as displayed in Figure 16.7. This so-called crosslinking or cur-
ing reaction takes place between the fumaric unsaturations in the polyester back-
bone and the unsaturation in the styrene monomer. The reaction is typically initi-
ated by free radicals generated by the decomposition of peroxides. Depending upon
the type of peroxide (and optionally the accelerator used) the crosslinking reaction
may take place at temperatures as low as 10
C or as high as 160
C.
The rate at which these radicals are generated is one of the factors determining
how fast a resin gels and cures. The temperature development of a mass of resin
against time from the moment of (accelerator and) peroxide addition is an impor-
tant characteristic of a polyester resin. This is illustrated for a typical curing pro-
cess at ambient temperature in Figure 16.8. The portion AB is the induction period
during which free radicals produced by decomposition of the peroxide are being
absorbed by the inhibitor present in the resin. This is the so-called pot life of the
resin, during which processing of the part can take place. This time may vary from
a few minutes up to 20 h. At point B the inhibitor concentration has become low
enough for an appreciable proportion of the free radicals produced to initiate resin
polymerization. Due to heat of polymerization, the temperature rises. The exother-
mic peak D does not necessarily correspond to completion of the curing process.
As the resin solidies during the latter part of the curing process, the rate of reac-
tion is greatly reduced (diusion-controlled). A post-cure at elevated temperatures
may be needed to reach full cure.
16.7.2.2 Styrene Emission
Actually more than 50% of UP resin consumption still involves open-mold techni-
ques, hand lay-up and spray-up being the most important. During processing and
curing, styrene emission is considerable. Styrene (boiling point 145
C) is classied
as a dangerous substance according to EC Directive 67/548/EEC and is labeled
with the following R (Risk) and S (Safety) phrases: R10 (ammable), R20 (harmful
by inhalation), R36/38 (irritating to eyes, skin, and respiratory tract), S2 (keep out
of reach of children), S23 (do not breathe gas/fumes/vapor/spray). In 1992 the Eu-
ropean Center for Ecotoxicology and Toxicity of Chemicals concluded in a study,
Styrene Toxicology, that the carcinogenic potential of styrene is so low that occupa-
tional or environmental exposure to styrene is unlikely to present any genotoxic or
carcinogenic hazard in humans. Styrene has, however, a proven neurotoxic eect.
Occupational exposure to high styrene concentrations may lead to symptoms like
drowsiness, headache, and tiredness. As a consequence the threshold limit value
(TLV) has been lowered signicantly since the 1980s in virtually all countries.
The UP industry reacted by developing so-called LSE (low styrene emission)- and
LSC (low styrene content) resins. An LSE resin contains paran or wax in such a
concentration that upon only a little styrene evaporation it forms a thin barrier lm
on top of the laminate, curtailing styrene emission. However, one aspect that war-
rants attention is the interlaminar adhesion of parts built up from several laminate
layers. Note that these LSE resins are only active in the static state when the sur-
face of the laminate is at rest. During processing, when the surface is regularly dis-
turbed, the eect of the lm-forming additive is far less.
LSC resins have a styrene concentration between 2535% versus the 4050% of
classical UP resins. Because of the lower styrene content, the evaporation during
processing and cure is considerably less. As the processing technique is deter-
mining the viscosity range of the resin that can be used, this property cannot be
changed. So, keeping the same resin viscosity at lower styrene content implies
that the viscosity of the unsaturated polyester must be reduced. This can be
achieved by reducing the molecular weight of the unsaturated polyester but, un-
fortunately, this leads to a strong deterioration of mechanical and chemical proper-
80 50
A B
D
C
Peak temperature
Peak time
Temp (C)
Time (min)
25
35
150
Fig. 16.8. A typical curing prole of unsaturated polyester resins at ambient temperature.
872 16 Thermosets
ties. Another way is to replace the polar end groups of the polyester by apolar end
groups, which show good solubility in styrene. Dicyclopentadiene (DCPD) end-
capped polyesters (see Scheme 16.23) are therefore the resins of choice to reach
the required properties. Of course, addition of paran to these resins will further
reduce the styrene emission.
The most obvious way to reduce styrene emission is to use another monomer.
However, there appears to be no real alternative that fullls all the technical and
economical requirements as well as being less toxic, and consequently styrene is
at most partially replaced in some cases.
Other elements which alone, or in combination, will contribute to less styrene
emission/exposure in the workplace are:
use of specially designed spray guns (for example, ow coaters), which reduce
the surface area of the resin that is sprayed, and consequently reduce emission;
a change from open mold techniques to closed or semi-closed mold techniques;

in particular, the vacuum-assisted resin infusion technique, whereby a exible
lm is used as a counter-mold, is gaining popularity;
proper and adequate ventilation;
use of robots.
16.7.2.3 Vinyl Ester Resins
A special class of unsaturated polyesters, developed for composite applications in
corrosive environments, is the so-called vinyl esters and vinyl ester urethane resins.
The best-known vinyl ester is made by reacting the diglycidyl ether of bisphenol-
A (DGEBA; see Section 16.4.2) with a monocarboxylic unsaturated acid such as
methacrylic or acrylic acid; see Scheme 16.24. This addition reaction occurs at a
temperature of 120140
C. The vinyl ester urethanes, on the other hand, are syn-

thesized from a low molecular weight (unsaturated) polyester diol, mostly based on
bisphenol-A, a diisocyanate, and a hydroxyalkyl (meth)acrylate (see also Schemes
16.30 and 16.31, Section 16.8.3.3). As for standard UP resins, the most commonly
used reactive solvent is styrene. Both types of products have only a few ester link-
ages (which are the points of greatest vulnerability to chemical attack) in the mole-
Glycols,
(un)saturated
dicarboxylic acids
Polycondensation
Unsaturated Polyester with DCPD end groups
100-150C
O
O
O
OH
O
OH
O
OH
80-100C
H
2
O
O
O
O
Scheme 16.23. Synthesis of DCPD end-capped unsaturated polyester resins.
cule and hence show improved chemical resistance, whilst the network built up
from the terminal (meth)acrylate double bonds results in a tougher, more resilient
resin structure.
In Table 16.4, the UP, vinyl ester, and vinyl ester urethane resins are classied in
order of chemical resistance.
16.7.3
Production
Unsaturated polyesters are produced batchwise in agitated stainless steel reactors
of up to 50-ton capacities (see Figure 16.3). The reactors are equipped with heating
jackets and internal heating coils to bring the raw materials to the required reac-
tion temperature (190230
C).
The production starts by charging the raw materials into the reactor by the use of
pumps and meters for liquids such as most of the glycols, molten maleic anhy-
dride, and molten phthalic anhydride. Solid raw materials, such as isophthalic
acid, are added manually by emptying big bags or automatically by pneumatic
transport from silos. All the reactants may be charged in one go except for a few
dicarboxylic acids which are somewhat more dicult to esterify. In the latter case
a two-stage method is applied in which the rst step is the reaction of such a dicar-
boxylic acid (for example, isophthalic or terephthalic acid) with a large excess of
glycol until a clear solution with a low acid number is obtained, followed by addi-
tion and reaction of the other raw materials. When the reactor is brought up to its
reaction temperature the contents are periodically sampled to determine the acid
number (a measure of the acid groups that have not yet reacted) and viscosity;
this may be done either o-line or in-line. The synthesis is continued until the
specied acid number and viscosity values are achieved. The distillation column
performs the separation of water from unreacted (low-boiling) glycols. During syn-
thesis, inert gas (usually nitrogen) ows continuously through the reactor to pre-
vent gelation due to oxidation and to aid removal of water. An alternative method
used to remove the water formed from the reaction mixture is to apply vacuum.
O O
O O
O
OH
O
HO
O O
OH
O
OH
O
O O
Scheme 16.24. Synthesis of vinyl esters from methacrylic acid and DGEBPA.
874 16 Thermosets
Reaction times vary from 8 to 30 h, depending on the raw materials used, the
degree of condensation or molecular weight desired, and the reaction temperature
employed.
After cooling, the unsaturated polyester is discharged from the reactor into the
so-called thinning tank, which has a preweighed styrene charge in it. The resin is
then nished with additives, tested for quality control, and pumped to storage.
16.7.4
Reinforcement
The majority of the UP resins are used in glass ber reinforced (GRP) applications.
Because E-glass oers sucient strength at low cost it accounts for more than 90%
of all glass ber reinforcements. It also provides good electrical resistance (hence
its name). Sizing is applied to the laments immediately after their formation to
ease processing, to protect the bers from breakage during processing, and to cre-
ate better bonding between the ber and the resin matrix. Although it comprises
only 0.255% of the total ber weight, sizing is a dynamic force behind the perfor-
mance of any berglass product. Sizing chemistry distinguishes each manufac-
turers product and determines the grade of berglass for dierent processing
techniques. Sizing can improve the wettability of the ber during resin impregna-
tion, thereby reducing part-manufacturing time. Coupling chemistry to enhance
bonding between the glass ber and the matrix resin can also improve the overall
strength of the nal composite.
Glass laments are supplied in bundles called strands, rovings, or yarns. A
strand is a collection of more than one continuous glass lament. A roving gener-
ally refers to a bundle of untwisted strands wound in parallel to form a cylindrical,
at-ended package, similar to thread on a spool. Single-end roving contains only
one continuous strand of multiple glass laments. Multiple-end roving contains
numerous wound strands. Yarns are collections of laments or strands that are
twisted together.
Rovings, the most common form of glass ber, can be chopped or woven to cre-
ate secondary ber forms used in composite manufacturing.
Mats are non-woven fabrics that provide equal strength in all directions.
Chopped mats contain randomly distributed bers cut to lengths typically ranging
from 4 to 6 cm and held together with a chemical binder. These mats provide low-
cost polymer reinforcement primarily in hand lay-up, continuous laminating, and
some closed-mold applications. Continuous-strand mat is formed by swirling ber
onto a moving belt nished with a chemical binder that holds the ber in place.
Continuous-strand mat is primarily used in compression molding, resin transfer
molding, and pultrusion applications.
Woven rovings are made by weaving the untwisted rovings into cloth. Bidirec-
tional woven fabrics provide good strength in the 0
/90
directions and allow fast

composite fabrication. To prevent laminates failing by interlaminar shear between
layers of woven rovings, these are generally interspersed with layers of chopped-
strand mat.
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876 16 Thermosets
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Surfacing mat, or veil, is used in conjunction with reinforcing mats and fabrics
to provide good surface nish. It is eective in blocking out the ber pattern of the
underlying mat or fabric. Surfacing mats are also used as the inside layers of cor-
rosion resistant composites, providing a smooth, resin-rich surface.
Fibers can also be produced from carbon, boron, and aramid materials. Gener-
ally these bers exhibit higher tensile strength and stiness than do their glass
counterparts, as can be seen in Table 16.5. However, these specialty bers are
more expensive. Therefore they are typically reserved for applications demanding
exceptional ber properties, for which the customer is willing to pay a premium.
16.7.5
Fillers
Fillers not only reduce the costs of composites, but also frequently impart perfor-
mance improvements which might not otherwise be achieved by the reinforcement
and resin ingredients alone. Fillers can improve re and smoke resistance by re-
ducing organic content in composite laminates. Other important properties that
can be improved through the proper use of llers include water resistance, weath-
ering, surface smoothness, stiness, dimensional stability, and temperature resis-
tance. Calcium carbonate is the most widely used inorganic ller. It is available at
low cost in a variety of particle sizes and surface treatments.
Aluminum trihydrate is used as a ller when improved re/smoke performance
is required. When exposed to high temperatures this ller gives o water in a
Tab. 16.5. A comparison of reinforcing bers.
Reinforcing ber Tensile
strength
[MPa]
Tensile
modulus
[GPa]
Specic
gravity
[g cm
C3
]
Properties
Aramide 28003000 85130 1.44 low density, good specic
properties, moderate cost
Boron 3500 400 2.55 high modulus, high cost
Carbon 25003200 210700 1.751.96 high modulus, electrical
conductivity, high cost
Glass: E-glass
S-glass
2400
4500
72
85
2.54
2.49
good strength and
processability, low cost
high strength and good
processability
Polyester 1050 10 1.38 good impact resistance and
chemical properties
Polyamide 1000 5 1.16 good impact resistance,
alkali resistant
Ultra high molecular
weight polyethylene
3400 110 0.975 low density, good impact
878 16 Thermosets
highly endothermic reaction, thereby reducing the ame spread and development
of smoke.
16.7.6
Processing
Fabricators of unsaturated polyester resins use either open-mold or closed-mold
processes. The main open-mold processes are hand lay-up, spray-up, continuous
lamination, lament winding, and centrifugal casting. The most used closed-mold
techniques are hot-press molding and resin-transfer molding. Pultrusion and cold-
press molding may be considered as semi-open or semi-closed processes. An over-
view of the processing techniques for UP resins, their possibilities and limitations,
is given in Table 16.6.
Irrespective of the process used to produce glass-reinforced composites there are
three basic principles in selecting materials for a particular end use [9]:
mechanical strength;
chemical, electrical, and thermal properties;
cost/performance.
Mechanical strength The type of ber, the amount in the composite, and the way
in which the individual strands are positioned determine the direction and level of
strength that is achieved. There are three generic types of ber orientation:
unidirectional oriented bers, providing the greatest strength in the direction of

the bers;
bidirectional oriented bers, with some bers positioned at an angle to the rest,
as with woven fabric: this provides dierent strength levels in each direction of
ber orientation;
multidirectional or randomly oriented bers: this arrangement provides essen-

tially equal strength in all directions of the nished part.
Chemical, electrical, and thermal properties The chemical building blocks of the
polyester, the molar ratio of maleic anhydride to saturated dicarboxylic acid, and
the choice and content of the monomer dictate to a large extent the mechanical
properties (rigid or exible), the glass transition temperature (T
g
) or HDT (heat de-
ection temperature), and the thermal and chemical resistance of the cured prod-
ucts. Additives are available for use with many resin systems to provide properties
such as color, high surface nish, UV resistance, and low shrinkage.
Cost/performance If a large number of parts are to be made from one set of
molds, the lowest unit production cost is likely to be obtained by using compres-
sion or injection molding. In these processes, presses, tooling, and automated han-
dling equipment can be applied to speed production cycles and reduce direct labor
T
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costs. Conversely, if only a limited number of parts are required, the simpler pro-
cesses such as hand lay-up or spray-up may be the cost-eective methods, since
they usually involve low-cost tooling and minimal fabrication equipment. Occa-
sionally, the shape of the part dictates that a particular process is used. For in-
stance, cylindrical objects can often best be made by centrifugal casting or la-
ment winding, and components having constant cross-sections that require high
strength by pultrusion.
The main conversion techniques for UP resins are explained in Sections
16.7.6.116.7.6.10.
16.7.6.1 Hand Lay-up and Spray-up
Both hand lay-up and spray-up processes essentially involve placing reinforcement
and liquid resin onto the surface of an open mold. As the two names suggest, hand
lay-up involves applying the resin and reinforcement (for example, glass ber
chopped-strand mats) by hand, while spray-up uses spray equipment to deposit
resin and reinforcement (for example, chopped glass bers) onto the mold. These
relatively cheap techniques are often used to produce large, complicated, strong
composite parts such as boat hulls.
16.7.6.2 Continuous Lamination
Continuous lamination is another open-mold process. In this method resin is doc-
tored onto a lm of cellophane or poly(vinyl alcohol) and glass mat or chopped rov-
ings placed on top of the resin. A second lm is then placed on top of this, and the
sandwich obtained is passed through rollers, which compact and remove air. They
can also shape, as with corrugated type laminates. The sandwich is then passed
through a heat source for curing.
16.7.6.3 Filament Winding
Filament winding is a technique used for the manufacture of pipes, tubes, cylin-
ders, and spheres and is frequently used for the construction of large tanks and
pipe work for the chemical industry. In the process glass bers are drawn through
a resin bath to impregnate them with resin. The impregnated rovings are then
wound under tension round a rotating mandrel. Generally the feed head supplying
the rovings to the mandrel traverses backward and forward along the mandrel.
By suitable design, the structures obtained, having a glass content of up to 80%,
can withstand very high pressures.
The lament winding process may be combined with spray-up. This hybrid pro-
cess is called chop hoop. The reinforcement of the resulting laminate than con-
sists of a blend of continuous and randomly chopped bers.
16.7.6.4 Centrifugal Casting
In centrifugal casting, resin, llers, and reinforcement are deposited against the in-
side surface of a rotating mold. Centrifugal force holds the material in place until
the part is cured. The interior surface of the centrifugally cast parts can be given an
882 16 Thermosets
additional layer of pure resin to improve their surface appearance and to provide
additional chemical resistance. Large-diameter composite pipes are produced by
this technique.
16.7.6.5 Pultrusion
Pultrusion is a technique used for producing continuous-ber reinforced sections
in which the orientation of the bers is kept constant during cure. The composites
are made by pulling reinforcement through a resin-impregnating bath and then
through a heated die, the interior of which has the desired shape. Pultruded com-
posites, due to their generally high reinforcement levels (6075%), have exception-
ally high mechanical properties parallel to the direction of pultrusion. Examples
of pultruded products are ladder rails, electrical equipment, insulator rods, light
poles, window proles, and gratings.
16.7.6.6 Cold-press Molding
Reinforcing material, which may be glass mat or woven fabric, is cut to shape and
placed in the GRP or light metal mold. Then the resin is poured in and the press
closed with a strong deceleration toward the end of the stroke. The resin displaces
air and impregnates the reinforcement. The heat of polymerization generated ac-
celerates the cure of the resin, giving a relatively short cycle time.
16.7.6.7 Resin Infusion
In this process one GRP mold is used and a plastic bag or lm mounted along the
mold ange. Resin is pulled through the reinforcement that is placed between the
rigid and exible molds, using vacuum. Applications include large parts, which are
normally produced using contact molding. Resin infusion is a closed process and
thus limits the evaporation of styrene into the atmosphere.
16.7.6.8 Resin-transfer Molding
This method employs a male and a female GRP or metal mold, which are designed
to t tightly together with a rubber gasket seal. The reinforcement is placed be-
tween the molds. After the molds have been clamped together, catalyzed resin is
forced into the mold by pressure (or vacuum) until resin leaves the mold through
a vent hole. An overspill area is built into the mold to ensure that after trimming a
good-quality molded edge is left. Low-viscosity resins are necessary to keep the
pressure requirements moderate and to facilitate wetting-out of the reinforcement.
16.7.6.9 Hot-press Molding
With hot-press molding the most convenient method is to use a preformed mold-
ing compound to which all the necessary ingredients have been added. Two com-
monly used molding compounds are SMC (sheet molding compound) and BMC
(bulk molding compound).
SMC is composed basically of ve principal ingredients: unsaturated polyester
resin, shrink-reducing thermoplastic, reinforcement, llers, and additives (see
Table 16.7). SMC technology comprises two distinct manufacturing steps: com-
pounding and molding. In the compounding operation all the ingredients, except
the bers, are mixed together to form a highly viscous paste. The paste is then ap-
plied to two carrier lms (usually polyethylene) to form a sandwich layer with the
glass bers in the middle (see Figure 16.9).
The compounded sheets are then stored to mature in a controlled environment;
in a period of three to seven days the viscosity of the compound increases from
about 25 Pa s to 25 000 Pa s or higher. This thousand-fold increase in viscosity is
obtained through a so-called thickening reaction. In chemical terms the added
magnesium oxide reacts with the carboxylic end groups of the unsaturated polyes-
ter to obtain longer polyester chains through complex salt formation. Moreover, the
obtained magnesium carboxylate salts cluster in an ionic lattice, giving rise to a fur-
Tab. 16.7. Typical compositions of SMC and BMC.
Ingredient Function Formulation [parts by weight]
SMC BMC
Unsat. polyester styrene resin 100 100
t-Butyl peroxybenzoate radical initiator 23 12
Zinc stearate mold release 34 34
Magnesium oxide thickening 23 03
Pigment dispersion color 08 015
Calcium carbonate ller 150200 200250
Thermoplastic additive shrink reduction 520 520
Chopped rovings reinforcement 50100 4575
Carrier film
Resin / filler
paste
Continuous strand roving
Paste
Chopper
Carrier film
Compaction rollers
Take-up roll
Fig. 16.9. Schematic representation of the SMC machine.
884 16 Thermosets
ther viscosity increase. The rst part of the reaction, the salt formation, is irrevers-
ible, while the ionic forces break down within the lattice again upon heating in the
molding process and allow the compound to ow.
When the compound is ready for molding it is cut into pieces of predetermined
dimensions. The pieces are then stacked in a specic arrangement (charge pattern)
in the mold so that the ow of the material is optimal. The ow is achieved by the
compression action of the mold, which is normally a matched set of steel dies
heated to a temperature of about 150
C. During the molding cycle (at a pressure

of about 7.5 GPa), which is about 13 min long, the resin cures completely. When
the mold opens, the part is removed and trimmed before it is sent to secondary
operations, which may include cutting holes and openings using a water jet,
router, punch, or drill. Very often, dierent SMC parts are glued together to im-
prove structural integrity as well as to provide space for hardware assembly.
In the past, molding compound growth into many high volume applications was
excluded because of high polymerization shrinkage resulting in surface defects,
warpage, internal cracks, and notable depression (sink) on the surface opposite
reinforcing ribs and bosses. The ultimate solution to the problem has been the
addition of certain thermoplastics to the formulation of the composite. These ther-
moplastics, also called low-shrink- or low-prole additives, are usually present at
only 25 wt% of the nal molded part or 720 wt% of the organic portion of the
formulation.
In all eective formulations two phases are formed in the cured composite: a
crosslinked thermosetting phase and a separated thermoplastic phase well dis-
persed throughout the resin matrix. Upon heating of the composite during the
molding process the thermoplastic is far above its glass transition temperature
and the thermal expansion counteracts the volume shrinkage of the crosslinking
unsaturated polyester. Upon cooling, micro-voids are created in the composite due
to a higher thermal shrinkage of the thermoplastic phase than the crosslinked ther-
moset. The best shrinkage control systems (low-prole and class A systems), those
with the most phase separation and micro-voiding, do not provide uniform pig-
mentation, particularly in darker colors. Shrinkage control systems that are less ef-
fective (low-shrinkage systems) provide reasonable pigment acceptance but at the
cost of reduced dimensional stability and surface smoothness.
A parallel technology to SMC is bulk molding compound (BMC). BMC consists
basically of the same ingredients as SMC (see Table 16.7). However, its production
method, appearance, and properties dier.
BMC is commonly manufactured by using high-speed plowshare mixers. The
dierent components of the paste are fed into the mixer and mixed until the com-
pound is fully homogeneous. The chopped-glass bers are introduced at the end of
the process to prevent too much ber degradation.
BMC may be used in compression as well as in injection molding. In the latter
process the compound is conveyed from the hopper to the nozzle of the barrel by
screw rotation or plunger displacement. The metered charge is fed into the heated
mold by fast translation of the screw or plunger. Similarly to SMC-based compo-
sites, BMC products are characterized by stiness, temperature resistance, and di-
mensional stability. Due to the shorter glass bers, however, strength and impact
are lower.
16.7.6.10 Casting, Encapsulation, and Coating (Non-reinforced Applications)
Although the majority of UP resins nd their way to reinforced composites, there
are also some non-reinforced applications, such as the polyester resins widely used
for button manufacture. Here the resin needs to be colorless and color-stable after
cure. Furthermore, when cured the resin should exhibit good hot water resistance,
hardness, and impact resistance. Such resins are also used for encapsulation pur-
poses. In most non-reinforced applications, however, use is made of resins with
high ller loadings of up to 85 wt%. Cultured marble, polyester concrete, and
auto-repair putties are examples of such applications. Yet another non-reinforced
application is that of coatings: gel coat and topcoat are typical coatings used for
polyester-based laminates, while special UV-curable unsaturated polyester resins
are used in high-gloss coatings for furniture.
16.7.7
Design Considerations: Mechanical Properties of Composites
Composite designers choose from a variety of ber reinforcement and resin sys-
tems (both thermoset and thermoplastic) to develop a part. Basically, the reinforce-
ment provides mechanical properties such as stiness and tensile and impact
strength. The matrix material transfers the loads to the bers, and also protects
the bers from abrasion and chemical attack.
Thermoset matrices have E-moduli between 3000 and 4000 MPa while those of
E-glass reinforcements are about 70 000 MPa. The tensile strength of glass bers is
around 2400 MPa and that of an UP resin about 5060 MPa. The glass ber con-
tent of the composite is usually between 25 and 75%.
The bers may be oriented randomly within the resin, but it is also possible to
arrange for them to be oriented preferentially in the direction expected to have the
highest stress. Such a material is said to be anisotropic (having dierent properties
in dierent directions), and control of the anisotropy is an important means of op-
timizing the material for specic applications.
Consider a typical region of composite of unit dimensions constructed from
parallel and continuous arrangements. This region can be idealized as shown in
Figure 16.10 on the left-hand side, by gathering all the bers together, leaving the
matrix to occupy the remaining volume.
The total load applied in the direction of the bers to the composite (F
//
) is
carried partly by the reinforcing bers and partly by the matrix according to the
generic Eq. (1).
F
//
F
f
F
m
1
The ber and matrix phases act in parallel to support the load. In terms of stress
886 16 Thermosets
(s) equation (1) can be rewritten as Eq. (2), where s
//
; s
f
, and s
m
are respectively
the average stress in the tensile bar, the stress in the ber, and the stress in the
matrix. A is the cross-section of the test bar, A
f
the total cross-section of the bers,
and A
m
the remaining cross-section of the matrix.
s
//
A s
f
A
f
s
m
A
m
2
To what extent the stress is carried by the bers depends on the grip the matrix
has on the reinforcement. In the worst case, due to a total lack of adhesion be-
tween the ber and the matrix, there is no grip at all. The matrix solely then gov-
erns the properties, and consequently the composite shows a poor mechanical per-
formance. The perfect grip, on the other hand, results from innitely long bers
with an excellent adhesion to the matrix. In this ideal case the strain (e) in the
bers is equal to that of the matrix (iso-strain conditions). Knowing that for a ma-
terial with a linear elastic behavior s Ee, wherein E is the stiness or Youngs
modulus, we can derive Eq. (3) from Eq. (2).
E
//
e A E
f
e A
f
E
m
e A
m
3
For innitely long bers the volume fraction is directly represented by the respec-
tive cross-sections. Bearing in mind that the strain is the same in all cases, we re-
write Eq. (3) to get Eq. (4), where E
//
; E
f
, and E
m
are the moduli of the composite,
ber and matrix, and j
f
and j
m
are the volume fractions of the ber and matrix
(j
f
j
m
1).
m

f

F
m

f
F
//
Fig. 16.10. Loading of the composite parallel (left) and
perpendicular (right) to the direction of the bers.
E E
f
j
f
E
m
j
m
4
This relationship is known as the rule of mixtures, predicting the overall modu-
lus in terms of the moduli of the constituent phases and their volume fractions.
Using essentially the same approach, but for iso-stress conditions, it is possible
to calculate the corresponding relationship for the modulus perpendicular to the
ber direction. In that case the total grip of the matrix is not sucient to deform
the reinforcement, which usually has a much higher modulus than the matrix.
Here, as a rst approximation, the transverse modulus, E
?
, is determined by con-
sidering the matrix and reinforcement acting in series (see Figure 16.12, right-
hand side). In this situation it is not the strains of the reinforcement and the ma-
trix that are equal, but the stresses (an idealization), as Eq. (5) states.
s
?
s
f
s
m
5
The deection of the bers and the matrix add to give the overall transverse deec-
tion [Eq. (6)].
e
?
e
f
e
m
6
Since s E e for small deformations, the Eq. (7) for the transverse modulus can
be derived.
1/E
?
j
f
/E
f
1 j
f
/E
m
7
Inspection of these simple equations reveals that at the usual levels of ber addi-
tion the longitudinal modulus is dominated by the ber modulus but the trans-
verse modulus is more inuenced by the matrix modulus. The prediction of trans-
verse modulus is considered less reliable, in spite of its occasional agreement with
experiment.
In more complicated composites, for instance those with bers in more than one
direction or those having particulate or other non-brous reinforcements, Eq. (4)
provides an upper bound to the composite modulus, while Eq. (7) is a lower
bound.
The formulas above are related to continuous bers but in practice the bers
have a nite length. There is a critical length, equal to the shortest length which
will allow the stress in the ber to reach the tensile fracture stress. This length de-
pends upon the ratio of the moduli of the two phases, the strength of the interfa-
cial bond, and the shear strength of the polymer. Typical values for glass and car-
bon bers are about 12 mm; in fact it is not the ber length by itself but, more
precisely, the aspect ratio, that is, the ratio of length to diameter of the ber, that
governs the properties.
More detailed calculations of the mechanical properties of composites can be
found in Ref. 10.
888 16 Thermosets
16.8
Acrylate Resins and UV Curing
16.8.1
Introduction
The term acrylate resins refers to acrylate-functional polymers. This means that
the reactive group, which can be either an acrylate or a methacrylate functionality
(Scheme 16.25), is still present in the polymer. (This is also the distinction from
acrylics, which are polymers prepared from acrylate monomers and in which the
acrylate functionality is no longer present.) These polymers are generally dissolved
in a reactive diluent or in a diluent mixture. Depending upon the application these
resins are cured with a peroxide initiator or with the combination of light and a
photoinitiator, the so-called UV curing [11]; see Section 16.8.5. When curing oc-
curs with a peroxide, the peroxide is mixed with the resin and the mixture is then
cast into on a mold.
The reactive diluent is required for tuning the resin formulation to the applica-
tion viscosity. The nature of the diluent is partly dependent on the structure of the
resin. In the case of methacrylate-functional resins, methacrylate-functional di-
luents are mostly used, whereas in the case of acrylate-functional resins, acrylate-
functional diluents are commonly applied.
Between acrylates and methacrylates there is a great dierence in the homopoly-
merization rates. As a rule of thumb, it can be said that acrylates are ten times
more reactive than their methacrylate analogs. Mixtures of acrylates and methacry-
lates are not often used, as acrylates are not able to increase the rate of a methacry-
late resin. In that specic case, considering the reactivity ratios of this copolymer-
ization, the methacrylate will dominate both the rate and the composition of the
polymer formed.
The composite resin industry is the main exception with respect to the selective
choice of reactive diluents. Within this industry, styrene is used as well as reactive
diluent (known in combination with unsaturated polyesters). Methacrylates are
then often referred to as chemically erroneously vinyl esters.
O
O
H
R
O
O
CH
3
R
Acrylate Methacrylate
Scheme 16.25. Chemical structures of acrylate and methacrylate functionality.
16.8.2
Chemistry
The basic chemistry upon curing is the homopolymerization of a (meth)acrylate
functionality as is depicted in Scheme 16.26. This polymerization is a radical chain
polymerization. The propagating radical is carbon-centered, and therefore this
polymerization is sensitive to oxygen inhibition as oxygen can quench carbon-
centered radicals very eectively. As a result of this oxygen inhibition the top layer
is generally not as thoroughly cured as the bulk of the material.
The three-dimensional crosslinked network which is formed upon curing
(Scheme 16.27) consists of two main segments: the polyacrylate chain and the
polymer, to which some acrylate groups are attached. This schematic picture
clearly illustrates the methods by which the properties of the network can be
adjusted: the polyacrylate chain, the side groups, the number of crosslinks, and
the acrylate-functional polymer.
O O
R
O O
P
O O
R
O O
R
O O
R
O O
P
O O
R
O O
R
Radical
Scheme 16.26. Chain polymerization of acrylate groups.
Polymer
Polymer
Polymer
Polymer
Polymer
Polymer
Scheme 16.27. A network formed by polymerization on an acrylate resin.
890 16 Thermosets
16.8.3
Production
Within the acrylate-functional resins many distinctions can be made, for instance
for functionality, polymerization speed, polarity, and so on. However, these distinc-
tions generally do not result in dierent methods of production. The production
can be divided into three main classes, from each of which a characteristic example
will be given.
16.8.3.1 Epoxy Acrylates
The easiest acrylates to produce industrially are the epoxy acrylates; their prepa-
ration (see Scheme 16.28) starts with an epoxide-functional resin (see Section
16.4.2). In principle any epoxide-functional material can be chosen. In this reac-
tion (meth)acrylic resin is added to the epoxide at elevated temperatures. (around
90130
C). The (meth)acrylic acid adds to the epoxide in a ring-opening reaction

resulting in an ester alcohol group. Basically this reaction is similar to the reac-
tions used in the preparation of epoxy resins (see Section 16.4). The reactions can
be either acid- or base-catalyzed; base catalysis is the more frequently used, since it
limits the number of possible side reactions (for instance, transesterications).
Although these reactions can be carried out in solvent, industrially they are most
frequently performed in bulk. Generally these preparations are performed in a
batch-type process.
Acrylated oils are a special type of epoxy acrylates. They are formed from epoxi-
dized oils such as linseed oil, and (meth)acrylic acid.
16.8.3.2 Polyester Acrylates
The synthesis of polyester acrylates (Scheme 16.29) is a batch process as well. In
contrast to the preparation of epoxy acrylates this reaction is performed in a sol-
vent, and generally acid-catalyzed. The preparations dier from the synthesis of
unsaturated polyesters (see Section 16.7), mainly because (meth)acrylates have
very reactive double bonds, which can easily homopolymerize. Consequently high
reaction temperatures cannot be used. Generally the maximum temperature that
+
O
O
polymer
O
O
Diepoxide
Epoxy acrylate
O
polymer
O
OH HO
O
O
O
O
O
OH
Acrylic acid
Scheme 16.28. Preparation of epoxy acrylates.
can be applied in these reactions is 130
C. In order to remove the water which is

formed in this condensation reaction in an ecient manner at these low temper-
atures, a solvent is selected which forms an azeotropic mixture with water. In most
cases toluene is the preferred solvent.
After the preparation of the polyester acrylates, the mixture is washed with water
and/or dilute base in order to remove the catalyst and excess acrylic acid. Next the
toluene is evaporated and the resin is obtained.
Silicone acrylates also are usually prepared via an esterication reaction between
a silicone diol and (meth)acrylic acid.
16.8.3.3 Urethane Acrylates
Urethane acrylates are produced in a batch-type fashion as well. Two procedures
can be followed:
Inside-out (Scheme 16.30), or

HO Polyester OH
O
OH
+
O Polyester
O
O
O
Polyester acrylate
Scheme 16.29. Synthesis of polyester acrylates.
O Polymer O N R N
O
N
O
R N
O
O
O
O
O
O
O
OH
O
O
Hydroxyethyl acrylate (HEA)
+
urethane acrylate
HO Polymer OH
Diol
OCN R NCO
Diisocyanate
O Polymer O N R NCO
O
N
O
R OCN
Isocyanate functional polymer
O
Scheme 16.30. Inside-out synthesis of a urethane acrylate.
892 16 Thermosets
Outside-in (Scheme 16.31).

Each procedure has its own advantages and disadvantages, which will be briey
discussed after a description of both methodologies.
For both procedures the reaction temperatures normally never exceed 90
C.
Many diisocyanates can be used in these reactions. In those cases in which more
than just statistical control is needed, isophorone diisocyanate (IPDI) is generally
employed which has two dierent isocyanate groups (primary/secondary). The
alcoholisocyanate reactions are generally catalyzed with Lewis acids such as
dibutyltin dilaurate (DBTDL). Tertiary amines can be used as well.
With respect to IPDI, it should be noted that with DBTDL as catalyst the second-
ary isocyanate is approximately 1020 times more reactive than the primary iso-
cyanate. With a tertiary amine as catalyst, however, the primary isocyanate is about
ve times more reactive than the secondary isocyanate.
16.8.3.4 Inside-out
The preparation of a urethane acrylate according to the inside-out technology starts
with the polymeric diol. The reactor is charged with the diisocyanate, catalyst, and
stabilizer. Now the diol is added slowly and a strong exothermic reaction starts. The
rate of isocyanate addition is generally used to control the reaction exotherm in
such a way that the temperature does not exceed 45
C. The control of this exo-

therm is especially important when IPDI is used as diisocyanate. For a higher se-
+
O Polymer O N R N
O
N
O
R N
O
O
O
O
O
O
O
urethane acrylate
HO Polymer OH
Diol
Isocyanate functional acrylate
O
O
O
N R NCO
O
OCN R NCO
Diisocyanate
OH
O
O
Hydroxyethyl acrylate (HEA)
O
Scheme 16.31. Outside-in synthesis of a urethane acrylate.
lectivity, then sometimes even a maximum temperature of 35
C is chosen. After
complete addition of the isocyanate, the intermediate isocyanate-functional poly-
mer can be isolated, although normally the subsequent reaction step is performed
in the same reactor. Next 2-hydroxyethyl acrylate (HEA) is added at such a rate that
the temperature rises to 6070
C. After addition of the HEA the reaction is nor-

mally stirred at 80
C until all the isocyanate has been converted.

16.8.3.5 Outside-in
The basic reactions are similar to the Inside-out methodology. However, the reac-
tion sequence starts with reaction of HEA (the outside of the polymer) with the
diisocyanate instead of the polyol (the inside). The reaction vessel is charged with
diisocyanate, catalyst, and stabilizer to which the HEA is added, resulting in an
acrylate-functional isocyanate. Next the polyol is added, and a urethane acrylate
can be obtained.
16.8.3.6 Comparing Inside-out with Outside-in
The main advantages and disadvantages are summarized below.
The Inside-out advantages are: higher reactor lling; and the reactive group is
introduced in the last reaction step, thereby reducing the risk of gelation. The dis-
advantages are: high viscosities in the reactor from the start so that temperature
control becomes dicult; and oligomerization of diols via reaction of two diols
with a diisocyanate can occur, resulting in higher viscosities and a broader M
w
dis-
tribution.
The Outside-in advantages are: reduced viscosity, and therefore improved cooling
and stirring; and consequently higher addition rates (shorter batch times) and a
higher selectivity. The main disadvantage is the higher risk of gelation as the reac-
tive acrylate is in the reactor from the start.
For many urethane acrylates both methods can be used without any problems,
and in practice they are both used. Some disadvantages of the Inside out technol-
ogy related to the viscosity can be overcome by performing the reaction in a reac-
tive diluent. However, in that case, there is a higher risk of gelation.
In special cases only one method is available, namely in those cases in which the
higher selectivity of the Outside-in method is required. For instance, in the case of
a triol the Inside-out method will result in a gel, whereas such a three-functional
urethane acrylate can be made by the Outside-in method. An extreme example is
that the Outside-in technology makes it possible to use hydroxy-functional acrylics
(polymers with at least ten OH groups per chain) as the polymers in the prepara-
tion of urethane acrylates.
16.8.3.7 Stabilization
All the acrylate resins suer a severe risk of homopolymerization. One can even
safely state that without correct stabilization these resins cannot be made. The
most often applied stabilization package consists of a phenolic stabilizer such as
2,6-di-t-butyl-4-methylphenol in combination with air; it is especially the oxygen
in air that is required. Oxygen is a very ecient acrylate polymerization inhibitor
894 16 Thermosets
and this is one aspect in which the preparation of acrylate resins diers from most
other resin synthesis.
Many resin syntheses are performed under nitrogen (no discoloration, and so
on) while here, without oxygen, the synthesis would almost be impossible. A direct
consequence is that the evaporation of the toluene in the production of polyester
acrylates is the critical step due to the reduced amount of oxygen and not the syn-
thesis. For those cases an anaerobic inhibitor like phenothiazine can be used.
16.8.3.8 Dilution
The viscosity of the acrylate resins is generally not so high that dilution is required
for the synthesis or for discharging the reactor at ambient temperatures. Conse-
quently most acrylate resins can be obtained without reactive diluent, leading to a
larger formulating freedom for the end formulator.
The selection of the reactive diluent is generally based on factors such as dilution
power, reactivity, tensile properties, surface tension (wettability), shrinkage, volatil-
ity, odor, color, and stability.
16.8.3.9 Safety
Almost all acrylates and many methacrylates are sensitizers. This means that an
allergic reaction can occur due to improper handling; over the years many exam-
ples have been reported where workers have become allergic due to repeated skin
contact. In order to minimize skin contact, gloves should be worn at all times and
all (meth)acrylates should be treated carefully, unless the producer has proven by
testing that a specic (meth)acrylate is not a sensitizer.
16.8.4
Properties
The properties of the cured resin can be varied to a large extent. However, as these
resins are regarded as expensive compared to the unsaturated polyester resins, they
are generally used in areas in which a higher demand or control on the properties
is required. An example of such an application is the chemical anchoring in which
methacrylate resins are used to attach steel for balconies, bridges and suchlike to a
concrete wall, oor or even ceiling.
In tuning the properties the reactive diluent plays an important role as well. For
instance, when the side chain of the acrylate diluent is changed from linear ali-
phatic to cycloaliphatic, the hardness of the network will increase without aecting
the exibility of the network. The hardness increases as well when the overall func-
tionality of the diluents is increased; so going from a monofunctional to a difunc-
tional diluent results in a large increase in hardness. However, in this case the net-
work becomes harder and more brittle.
When cure speed (or polymerization time) is irrelevant, the choice between an
acrylate and a methacrylate gives another parameter for adjusting the hardness.
In general the hardness of a polymethacrylate is 100
C higher than that of the cor-

responding polyacrylate.
The polarity of the network also can be varied by manipulation of the side chains
of the reactive diluent. Both apolar rubbers and polar hydrogels can be obtained
through the correct choice of side chain substituent.
In the above-mentioned examples, it appears that most of the mechanical prop-
erties can be achieved by correct choice of side chain. This is, however, not correct.
Many of the basic mechanical properties, such as elasticity, elongation at break,
and modulus, originate from the polymer in the acrylate resin and not from the
side chain functionality.
Generally, epoxy acrylates yield hard, tough materials, while urethane acrylates
give elastic networks and polyester acrylates possess properties which lie between
urethane and epoxy acrylates.
16.8.5
Introduction to UV Curing
16.8.5.1 General Introduction to UV-initiated Radical Polymerization
A special area of application in which the (meth)acrylate resins described above are
used predominantly is UV curing. A UV curing resin formulation comprises a pho-
toinitiator, that is, an organic compound that generates radicals upon UV irradia-
tion [12]. The basic reaction scheme is depicted in Scheme 16.32.
This cure on demand, combined with exibility with respect to the properties of
the network, makes this system the most ecient process for the rapid production
of polymeric crosslinked materials with well-dened properties. This very e-
ciency is the reason why photoinitiated radical polymerization is widely employed
in high-performance applications where emphasis is put on the mechanical as
well as the optical properties. For instance, modern dental restorative llers are
UV-curable materials. The aspherical lenses in CD applications are prepared via a
UV curing process. Contact lenses are nowadays prepared in the same way. The
Internet could not exist without UV curing, as the optical bres used for data
transport are protected by two UV-curable coatings. In stereolithography, three-
dimensional objects are prepared via UV curing, which makes this type of curing a
valuable aid in modern medicine. UV curing is not limited to apparently high-tech
applications, however. Most common glossy magazines have a UV-cured coating.
It should be noted that, due to the time control of curing, these resin systems are
ideally suited for fundamental kinetic investigations, especially combined with an-
alytical techniques like real-time infrared spectroscopy. These investigations have
PI R
.
hv
O
O
Polymer
R
.
+
Scheme 16.32. A UV-initiated radical polymerization.
896 16 Thermosets
led to the conclusion that the radical polymerization is dominated by a reactive
diusion-controlled process and that bimolecular termination is the main termina-
tion mode.
A standard UV-curable acrylate resin formulation consists of at least three ingre-
dients: a photoinitiator, an acrylate resin, and a reactive diluent.
The UVcuring process is strongly dependent on the photoinitiator. In fact, by the
choice of photoinitiator the chemistry can be altered completely. There are funda-
mentally dierent photoinitiators that can be used for three dierent chemistries:
radical curing, employing a radical photoinitiator;
cationic curing, employing a cationic photoinitiator; and
base-mediated curing, employing a photolabile base.

Around 9095% of all UV curing processes are radical initiated polymerizations.
Consequently, radical UV curing will be discussed in more detail below, while cati-
onic and base-mediated curing will be discussed briey in separate sections.
16.8.5.2 Photoinitiators for Radical Polymerization
The photoinitiator makes the resin formulation UV-curable. Only the development
of thermally stable but photolabile compounds enabled the development of UV
curing. For an ecient UV curing, the absorption of the photoinitiator should
match, at least partly, the emission spectrum of the light source used. Two main
types of photoinitiators are used: photoinitiators based on an a-cleavage process
(Norrish type I), and photoinitiators based on an electron transfer followed by a hy-
drogen abstraction process (Norrish type II). a-Cleavage photoinitiators are mono-
molecular initiators, of which a-hydroxy or a-alkoxy ketones and benzoyl phosphine
oxides are well known examples shown in Scheme 16.33.
Norrish type II photoinitiators are bimolecular initiators. Generally an aromatic
ketone is used in combination with a tertiary amine. Both aliphatic and aromatic
tertiary amines can be used. A well-known example of such an initiating system is
benzophenone with dimethylaminoethanol.
Irrespective of the initiating system, type I or type II, it is clear that at least two
dierent radicals are formed. Initiation proceeds in the case of type I via both rad-
icals although at dierent rates. However, in the case of a type II initiating system
only the amine radical initiates and the ketyl radical can be considered inert with
respect to initiation. Consequently type I initiations are preferred when speed is an
issue. The advantage of a type II system is that it is less sensitive to oxygen inhibi-
tion than a type I, as the ketyl radical can react with oxygen thereby reducing the
active amount of oxygen.
16.8.5.3 Resin
All the acrylate resins described above in Section 16.8.3 can be employed in UV
curing. Low molecular weight materials are mostly used since they possess a lower
viscosity. In many UV applications thin layers are employed, which makes the
resin viscosity an important processing parameter.
However, the urethane acrylates, which generally possess higher viscosities, also
have higher polymerization rates.
Unsaturated polyesters (see Section 16.7) can be used in UV curing as well, but
only in combination with a special reactive diluent system, which is based on vinyl
ethers. Kinetic analysis has revealed that in that specic case the fumarate forms a
charge transfer complex with the vinyl ether and a homopolymerization of this
charge-transfer complex takes place as depicted in Scheme 16.34. An advantage of
a charge-transfer complex radical polymerization is that it is less susceptible to-
ward oxygen inhibition than methacrylate systems. This is illustrated by the fact
that the rst commercial UV powder system, in which the powder is sprayed
(much oxygen), melted, and then UV-cured, was based on a fumaratevinyl ether
system.
16.8.5.4 Reactive Diluent
In liquid UV curing systems there is even more emphasis on the judicious choice
of the reactive diluents, due to the applications viscosity requirements. The reac-
tive diluent also has a large impact on the cure speed. An example concerns polar-
ity: apolar reactive diluents polymerize more slowly than more polar analogs. Hy-
drogen bonds play a role as well, which is illustrated by the fact that monomers
which possess hydrogen bonds react faster than their analogs without hydrogen
bonding. However, monomers with hydrogen bonds generally possess a higher
+
O
O
OH
hv
OH
.
O
.
+
T
hv
N
OH
OH
.
.
N
OH
O
S
+
Type I Photoinitiators
Type II Photoinitiators
Scheme 16.33. Dierent types of radical photoinitiators. S, singlet state; T, triplet state.
898 16 Thermosets
viscosity. The functionality is another important factor, as higher-functional materi-
als polymerize faster than lower-functional materials. The hardness or T
g
of the re-
sulting polymer is also important, as reactive diluents which give rise to high-T
g
polymers polymerize faster than monomers which result in low-T
g
materials (as-
suming the same functionality). Obviously the basic functionality is important;
methacrylates react approximately ten times more slowly than acrylates.
N-Vinyl amides such as N-vinyl caprolactam are sometimes used as reactive
diluents as well, especially in those cases in which a high demand is put on the
polymerization speed. An example of this is the ber optic industry, in which the
cure process is performed at draw speeds around 30 m s
1
(irradiation times are in
the order of milliseconds).
When an unsaturated polyester is used as resin, only reactive diluents containing
vinyl ether can be applied. Moreover, the molar ratio of fumarate bonds to vinyl
ether bonds should be around 1:1 because the crosslinking reaction is a strictly al-
ternating copolymerization.
16.8.5.5 Curing Process
The cure process of a sheet covered with a UV-curable resin is depicted schemati-
cally in Figure 16.11. The basic process is very simple: a sheet is put on the con-
veyor belt and the resin is cured under the UV lamp. After irradiation the resin is
O
O
O
O
O
+
R
.
+
O
O
O
O
O
[
]
O
O O
O
O O
O O
Scheme 16.34. Copolymerization of fumarate with vinyl ether via a charge-transfer complex.
Conveyor belt
UV lamp
Fig. 16.11. Representation of a basic UV curing process.
fully cured. When very thin layers or high speeds are employed, curing in air be-
comes more dicult due to the inhibiting eect of oxygen. In these cases nitrogen
inerting, that is, ushing the area under the UV lamp with nitrogen, can be used
to overcome this problem. Other gases such as carbon dioxide can be used as well.
A main disadvantage of acrylate polymerization is shrinkage. However, this
shrinkage process is well dened since it is directly related to the number of dou-
ble bonds converted. In the lens applications the quartz molds are adjusted for this
shrinkage.
16.8.5.6 Cationic Curing
Besides photoinitiators which generate radicals, photoinitiators also exist which
generate a strong acid. These initiators enable the on-demand curing of epoxide
and hydroxy/epoxide mixtures. The initiators are sulfonium or iodonium based. A
cationic curing of an epoxy/alcohol system is depicted in Scheme 16.35.
The acid strength of the resulting acid is strongly dependent on the counter ion.
The acid strength of the system can be directly related to the polymerization rate
(stronger acid results in faster polymerization). Consequently water can reduce or
even inhibit these polymerizations. However, minimal amounts of alcohols or even
O
R
1
+
H
+
+
R OH
O
R
1
H
+
R
1
O
OH
R
H
+
R
1
O
OH
R
+
H
+
BF
4
-
S
+
Sulfonium salt
hv
Strong acid
PF
5
-
I
+
Iodonium salt
PF
5
-
H
+
+
Scheme 16.35. Cationic photoinitiators and cationically
photoinitiated polymerization of epoxide resins.
900 16 Thermosets
water can enhance the cure speed. The highest rates are generally obtained in
those cases in which the molar ratio of alcohol to epoxide is 1:51:10.
Besides an epoxide system, vinyl ether systems also exist. The cationic vinyl
ether polymerization is among the fastest polymerizations known in the UV cur-
ing industry, especially since termination is almost absent.
16.8.5.7 Base-mediated Curing
Base-mediated UV curing is a recent development, since UV-labile bases have only
recently become commercially available. Depending on the base liberated and its
base strength, various kinds of organic chemistry can be used for the network
formation.
Weak UV-labile bases are commonly used in lithographic processes, in which
their main function is as an acid scavenger. In these processes the photochemically
liberated base scavenges a thermally formed acid and no polymerization will occur
on the irradiated areas.
16.9
Rubber
16.9.1
Introduction
In this nal section a class of thermoset materials will be introduced, elastomers or
rubbers, which has some distinct dierences from the thermoset resins presented
in the preceding sections [13]. First, most elastomers are characterized by very ex-
ible polymer chains and, as a result, the glass transition temperature of elastomers,
indicating the transition between a hard, rigid, glassy phase and a soft, mobile,
rubbery phase, is well below room temperature. Crosslinked elastomers are rela-
tively soft materials in their actual application (typically with a modulus of 110
MPa; that is, in the Sh A (Shore A) hardness range), whereas most crosslinked
thermoset resins are hard materials (1 00010 000 MPa). Secondly, elastomers are
high molecular weight polymers (typically with a weight-averaged molecular
weight M
w
ranging from 50 000 to 500 000 g mol
1
), resulting in a high melt vis-
cosity. Therefore, the processing temperature is higher than for thermoset resins
and the processing equipment is much heavier. Thirdly, most elastomers have
a large number of sites per chain available for crosslinking (typically a functionality
of 1010 000 sites per chain). Consequently, the gel point is already reached at a
low crosslinking conversion and any crosslinking must be avoided during mixing,
processing, and shaping. Many rubber properties are directly related to the cross-
link density; for example, the modulus, the elastic recovery, and the swelling resis-
tance all increase upon increasing the crosslink density. However, these properties
are not determined only by the number of chemical crosslinks, but are also af-
fected signicantly by the number of physical entanglements which are trapped
upon crosslinking.
16.9 Rubber 901
Despite these dierences in chain exibility, molecular weight, and functionality,
elastomers have the formation of a three-dimensional network in the nal process-
ing step in common with the thermoset resins such as the phenolic, epoxy, and ac-
rylate resins. Crosslinking of a rubber renders it insoluble and, in addition, yields a
material which has strongly enhanced physical properties, such as tensile proper-
ties (modulus, tensile strength, and elongation at break) and elastic recovery (un-
der both compression and tension).
16.9.1.1 Types of Rubber
The most important rubber is natural rubber (NR), with an average volume of
roughly 50% of the total world rubber production (approximately 15 500 kton y
1
)
over the decade 19902000. NR is a relatively low-cost rubber collected as a latex
from Hevea brasiliensis, and yields excellent physical and dynamic properties, ex-
plaining applications ranging from tires (low heat buildup) to thin-walled, soft
products like gloves and balloons. Of the synthetic rubbers polybutadiene (BR)
and styrenebutadiene copolymers (SBR) have also found major applications in the
tire industry, while the latter is also used in foams and footwear. Acrylonitrile
butadiene copolymers, that is, nitrile rubber (NBR), have a high swelling resistance
because of their high polarity, making them suitable for applications with oil and
solvent contact. These so-called polydiene rubbers have unsaturation in the poly-
mer backbone, making them relatively sensitive to oxidation, ozonolysis, and ther-
mal degradation. Ethylenepropenediene terpolymers (EPDM) are much more
stable in this respect. Some other rubbers worth mentioning are butyl rubber,
which has a low air permeability used in inner-tire tubes, and silicone rubbers
and uor rubbers, which are high-performance rubbers (high heat and solvent
resistance).
In summary, the range of commercial rubbers is quite large, with each rubber
type being available in a large number of dierent grades. Because it is beyond
the scope of this overview to discuss all these rubbers in detail, we will zoom in
on one rubber only. EPDM (Scheme 16.36) was chosen for that purpose for two
reasons. First, EPDM has a very wide structural variation in
molecular weight (distribution),
long-chain branching (LCB) (distribution),
chemical composition (including ethylene and propene levels, type and level of
diene, but also monomer sequence distribution),
yielding an almost countless number of combinations, many of which have spe-
cic application advantages, and making EPDM a good representative for rubbers
in general. Secondly, EPDM has a very good balance between processability, prop-
erties, and price, and has evolved since the early 1990s from a high-performance
rubber into a mature commodity-plus rubber. With its annual world usage of ap-
proximately 900 kton y
1
, EPDM is today the fourth rubber volume-wise after NR,
SBR, and BR, and its usage is actually the largest for a non-tire rubber.
902 16 Thermosets
16.9.2
Polymerization
EP(D)M is produced via insertion polymerization of ethylene, propene, and a diene
[14] (Scheme 16.36). Traditionally, ZieglerNatta-type vanadium-based catalysts are
used in combination with metal alkyl cocatalysts and sometimes promoters in or-
der to obtain an ecient, well-controlled polymerization. The EPM copolymer
cannot be crosslinked with sulfur due to the absence of unsaturation, and the e-
ciency for peroxide cure is not that high (Section 16.9.3). This explains why up to
10 wt% dienes are incorporated in the EPM chain; it is to allow sulfur vulcaniza-
tion and to enhance the peroxide curing eciency. The diene should have two un-
saturated bonds which have quite dierent anities for polymerization, in order to
prevent gelation during polymerization. 5-Ethylidene-2-norbornene (ENB) and di-
cyclopentadiene (DCPD) fulll this requirement, with the endocyclic norbornene
unsaturation being the most reactive for polymerization (ring tension!), and upon
incorporation they yield EPDM with pendent, unsaturated bonds that are suscepti-
ble to sulfur and peroxide crosslinking. 5-Vinylidene-2-norbornene (VNB) is some-
times used because the exocyclic vinyl unsaturation participates to some extent in
polymerization, yielding LCB EPDM with enhanced processability. Recently, metal-
locene catalysts have been developed and are applied commercially, which have a
much higher activity than the traditional catalysts and also have enhanced anity
for polymerization of higher a-olens like 1-butene, 1-hexene and 1-octene. The
ethene/a-olen copolymers thus produced are a new class of materials, namely
plastomers, bridging the gap between rigid polyethylene and elastic EP(D)M.
Traditionally, ZieglerNatta EP(D)M polymerization is performed in a solution
process using a volatile hydrocarbon as the solvent. The ethylene and propene
monomers are cooled prior to the exothermic polymerization, to avoid heating to
temperatures that are so high that the catalyst activity is signicantly reduced. All
the monomers and the solvent have to be puried: polar moieties especially have to
be removed, since they kill the catalyst. After polymerization the unreacted mono-
mers are recycled and the polymer is recovered, a process which includes removal
EPDM
CH
2 CH
2
CH
CH
3
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
2
CH
CH
3
CH
2
CH
2
+ +
ENB propene ethene
CH
2
=CH-CH
3
CH
2
=CH
2
Scheme 16.36. Polymerization and structure of ethylene/
propene/diene terpolymer (EPDM), with 5-ethylidene-2-
norbornene (ENB) given as an example for the diene.
16.9 Rubber 903
of traces of unreacted monomers and residual solvent, deactivation and washing of
the catalysts, and rubber crumb formation. The activity of the metallocene catalysts
is so high that catalyst removal is not necessary. Finally, gas-phase technology has
been developed, and has recently been applied commercially, by which the poly-
merization is performed in a uidized-bed reactor with carbon black as uidizing
agent.
16.9.3
Crosslinking
Most EPDM applications involve some sort of crosslinking [15], about 80% via sul-
fur vulcanization. Sulfur vulcanizates have a relatively low thermal stability, which
explains the slow transition to peroxide cure in critical applications. The tensile
and dynamic properties of sulfur-vulcanized EPDM are superior, whereas the elas-
tic recovery of peroxide-cured EPDM is superior.
16.9.3.1 Sulfur Vulcanization
Sulfur vulcanization is the traditional crosslinking method for unsaturated elasto-
mers. It was developed by Charles Goodyear and Thomas Hancock in the 1840s.
Since then the sulfur vulcanization recipes have been further developed and
optimized and today sulfur is always used in a cocktail with accelerators (mainly
sulfur- and nitrogen-containing chemicals) and activators (zinc oxide, stearic acid).
EPDM is an apolar rubber with relatively little unsaturation in comparison to the
polydiene rubbers, and it has low solubility for the polar accelerators. As a result,
the vulcanization mixture may consist of up to ten ingredients, which allows for
ne-tuning of the crosslinking rate, the crosslink density, and the type of sulfur
crosslink. The last two determine the physical properties of sulfur-vulcanized
EPDM. In Scheme 16.37 a generally accepted mechanism for sulfur vulcanization
of EPDM is presented. First, sulfur reacts with the accelerators and the activators,
yielding a so-called active sulfurating species (its precise structure has still to be
elucidated). Next, the crosslink precursor is formed by substitution of one of the
allylic hydrogen atoms, yielding an alkenyl sulde. Note that the unsaturation of
EPDM is essential for activating the allylic position, but is not consumed during
vulcanization. Next, the crosslink precursor reacts with a second EPDM chain,
yielding the initial crosslink with a relatively high number of sulfur atoms in the
crosslink, which upon further heating converts into shorter crosslinks. In the case
of ENB as the diene, about 50 crosslink structures can be formed, because of the
variation in the length of the sulfur bridge (typically one to ve sulfur atoms), the
three dierent allylic sites (C3(exo), C3(endo) and C9) and the isomerism at C8/C9
(Entgegen versus Zusammen). For normal recipes about 2575% of the ENB units
are involved in crosslink formation. Zinc salts act as catalysts for all three reac-
tion steps. There is still a debate on the exact nature of the sulfur vulcanization
reactions (ionic versus concerted). Oxidation may occur as a side reaction. Side re-
actions that are frequently observed during sulfur vulcanization of polydiene rub-
bers, such as cistrans isomerization, allylic rearrangement, and/or the formation
904 16 Thermosets
of conjugated dienes/trienes, do not occur for ENBEPDM, because of the stability
of the tris-substituted unsaturation in ENB and its isolation from other ENB units.
16.9.3.2 Peroxide Curing
The mechanism of peroxide crosslinking is shown in Scheme 16.38. Upon heat-
ing, the peroxide decomposes into the primary alkoxy radicals, which may further
react to secondary radicals. These radicals abstract hydrogen atoms from the EPM
chain. In the case of EPM, crosslinks are formed by combination of two macro-
radicals, whereas in the case of EPDM crosslinks are formed via combination, but
also via addition of the macro-radical to the pendent unsaturation of a second
EPDM chain. The formation of CaC bonds explains the higher thermal stability
of peroxide-cured EPDM in comparison with sulfur-vulcanized EPDM with its
labile SaS crosslinks. The reactivity for peroxide cure increases in the series
ENB@DCPD < VNB, because of the decreased steric hindrance at the unsatura-
tion. The eciency of peroxide curing is enhanced by the addition of co-agents,
that is, chemicals with two or more unsaturated bonds, which are actually built
DT
EPDM
thiophene
DT, diaryldisulfide DT
oxidation
products
pendent sulfur
(cross-link precursor)
devulcanization desulfuration
matured cross-link
( p < n )
+
S S
p
oxidation
initial cross-link
x 2 disproportionation
allylic
substitution
S
m
X
soluble sulfurated
zinc complex
S
8
+ accelerator(s) + ZnO + stearic acid
S
n
Scheme 16.37. Products and generally accepted mechanism
for accelerated sulfur vulcanization of EPDM (X accelerator
residue; sulfur substitution at C3(exo) and C9 of ENB is just
given as an example).
16.9 Rubber 905
into the elastic network, whereas the peroxide only initiates the crosslinking re-
action. Note that in contrast to sulfur vulcanization, the EPDM unsaturation is con-
sumed during peroxide cure.
16.9.3.3 Processing
EPDM is rst mixed with llers and oil on two-roll mills or batch kneaders, and
next the crosslinking chemicals are added at moderate temperatures. Then the
EPDM compound may be shaped and crosslinked in a hot (> 160
C) press or cal-
endered into a foil, and cured in a steam autoclave. EPDM strips and proles may
be continuously extruded and subsequently crosslinked in a hot-air oven, a salt
bath, or an ultrahigh-frequency radiation unit.
ROH RO
1/2
EPDM
EPDM
cross-link
cross-link
H-transfer
combination
+ EPDM
addition
+ EPDM
EPDM macro-radical (EPDM )

H-abstraction
EPDM
DT
peroxide
decomposition
RO-OR
Scheme 16.38. Products and mechanism for peroxide cure of
EP(D)M (DCPD is just used as an example; the formation of
tertiary free radicals is chosen arbitrarily).
906 16 Thermosets
16.9.4
In Section 16.9.1 it was explained that EPDM is a very versatile polymer, because of
the large number of structural combinations. A broad molecular weight distribu-
tion (MWD) at a given viscosity is benecial for processability, but detrimental for
network properties (a large number of dangling ends). LCB has been introduced to
enhance processability. The combination of a narrow MWD with LCB yields supe-
rior materials. At ethylene levels above 55 wt%, the average length of the ethylene
sequences is suciently large to give rise to diuse crystalline regions, which give
higher hardness, modulus, and tensile strength to EPDM. At lower ethylene levels,
EPDM is a fully amorphous rubber. The type and level of diene determines the
crosslinking rate and density (Section 16.9.3). The latter in its turn determines the
tensile, elastic, and dynamic properties. It should be noted that EPDM, like most
rubbers, is hardly used as such, but always in compounds with llers and extender
oil, because of performance improvement and cost reduction. The addition of large
amounts (up to 150 phr) of reinforcing ller, mainly carbon black, results in greatly
improved physical properties and UV stability at the cost of increased compound
viscosity. To maintain good processability large amounts (up to 150 phr) of ex-
tender oil are added in addition to the ller.
16.9.4.1 Advantages and Disadvantages
The main advantage of EPDM over the polydiene rubbers, such as NR, BR, SBR,
and NBR, is the saturated character of the main chain. As a result, EPDM has a
relatively high resistance against oxidation, ozonolysis, heat, and UV light. This
makes EPDM especially suitable for outdoor and high-heat applications, such as
roof sheeting, window proles, automotive seals (for both doors and windows), ra-
diator hoses, cable and wire insulation, and all sorts of technical items like seals
and tubes. The main disadvantages of EPDM are also related to the structure of
the main chain: actually being a hydrocarbon results in a relatively low oil resis-
tance and poor adhesion to polar substrates (metal, glass, and polar polymers).
Most EPDM applications require elasticity and thus crosslinking. However, EPM
is also used without crosslinking, as an impact modier for crystalline thermoplas-
tics such as polypropylene (PP) and polyamides, and as an oil additive.
16.9.4.2 Thermoplastic Vulcanizates
We started this chapter with a description of the fundamental dierences between
thermoplastic and thermoset materials; we will end it with an example of a subtle
blend of their respective properties. A disadvantage of the three-dimensional
network of EPDM, but actually of all thermoset materials, is the lack of recyclabil-
ity. Crosslinked EPDM, both the waste from production and after use, cannot
be processed in the melt again like thermoplastics. Reclaiming technologies have
been developed for vulcanized rubber, degrading part of the network via high-
temperature and shear treatment, but these technologies are less eective for
EPDM vulcanizates, probably because the EPDM chains are so stable. A break-
16.9 Rubber 907
through in this respect has been the development of thermoplastic vulcanizates
(TPVs), which combine the elastic properties of thermoset crosslinked rubbers
with the melt processability of thermoplastics. The most important TPVs from a
commercial perspective are based on blends of EPDM and PP. Dynamic vulcaniza-
tion of EPDM/PP blends results in a crosslinked EPDM phase, which is nely dis-
persed in a PP matrix. PP being the matrix in TPVs makes them melt-processable.
At high EPDM loadings the thin PP layers, surrounding the crosslinked EPDM
particles, act as a sort of glue and transfer the macroscopic stress to the rubber par-
ticles. Resol resins, that is, p-alkylphenolformaldehyde condensates produced at
high formaldehyde/phenol ratios and at high pH (Section 16.2.2) are used as the
main crosslinking agent activated by acids for the production of TPVs. In addition
to being melt-processable, TPVs have other advantages over thermoset crosslinked
EPDM, such as higher oil resistance, colorability (no carbon black reinforcement),
and co-extrusion with polyolen thermoplastic parts. The volume of TPVs is grow-
ing above the average for the rubber market, and they are partly replacing thermo-
set EPDM in technical goods and sealing systems.
Notation
M
n
(number-averaged) molecular weight
M
w
weight-averaged molecular weight
T
g
glass transition temperature
Acronyms and Abbreviations
1K one-component
2K two-component
BR polybutadiene butadiene rubber
BMC bulk molding compound
DCPD dicyclopentadiene
DBTDL dibutyltin dilaurate
DGEBPA bisphenol-A diglycidyl ether
EAN elastically active network chain
ECH epichlorohydrin
ENB 5-ethylidene-2-norbornene
EPDM Ethenepropenediene terpolymer
EPM ethene/propene co-polymer
HEA 2-hydroxyethyl acrylate
HDT heat deection temperature
HMTA hexamethylene tetramine
IPDI isophorone diisocyanate
LCB long-chain branching
LSC low-styrene content
LSE low-styrene emission
908 16 Thermosets
MF melamineformaldehyde
MPa 10
6
Pascal
MWD molecular weight distribution ( M
w
/M
n
)
NBR acrylonitrilebutadiene copolymer nitrile rubber
NR natural rubber
PF phenolformaldehyde
phr parts per hundred
PP polypropylene
Sh Shore (hardness degree classes)
SBR styrenebutadiene copolymer
SMC sheet molding compound
TGIC triglycidyl isocyanurate
TPV thermoplastic vulcanizate
UF ureaformaldehyde
UP unsaturated polyester
UV ultraviolet light
VNB 5-vinylidene-2-norbornene
References
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Hanser Verlag, Munich, 1973.
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strom, Manufacturing of
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D. R. Clarke, S. Suresh, I. M. Ward,
An Introduction to Composite Mate-
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Cambridge, UK, 1996.
10 a] A. K. Kaw, Mechanics of Composite
Materials, CRC Press, Boca Raton, FL,
1997. b] F. L. Matthews and R. D.
Rawlings, Composite Materials:
Engineering and Science, CRC Press,
1999.
11 a] Sita Technology Ltd., Chemistry &
Technology of UV and EB Formulations
for Coatings, Inks and Paints, Ed. P. K. T.
Oldring, 8 volumes, Wiley, London,
1998. b] J. P. Fouassier, J. F. Rabek,
Radiation Curing in Polymer Science
and Technology, 4 volumes, Elsevier,
London, 1993.
12 a] J. P. Fouassier, Photoinitiation,
Photopolymerization and Photocuring,
Hanser, Munich, 1995. b] K. D.
Beleld, J. V. Crivello, Photo-
initiated Polymerization, ACS
Symposium Series Vol. 847, ACS,
Washington DC, 2003.
13 W. Hofmann, Rubber Technology
Handbook, Hanser Publishers,
Munich, 1989.
14 a] J. W. M. Noordermeer, Ethylene-
propylene polymers, in Kirk-Othmer
Wiley InterScience, New York, 5th ed.
2004. b] F. P. Baldwin, G. Ver
Strate, Polyolen elastomers based
on ethylene and propylene, Rubber
Chemistry and Technology 1972, 45,
709.
15 M. van Duin, Chemistry of EPDM
crosslinking, Kautschuk und Gummi
Kunststoe, 2002, 55, 150.
910 16 Thermosets
17
Fibers
1
J. A. Juijn
17.1
Introduction
17.1.1
A Fiber World
Look around and see the ber world! Clothes in a wide variety of shapes and colors,
carpets and curtains in your house, sheets and blankets on your bed. Step in your
car and see the safety belts, and hopefully never see the airbags. Rely on the strong
cords reinforcing your tires, timing belt, V-belts. Enjoy many ber-reinforced com-
posites in your leisure activities: tennis rackets, golf clubs, skis, the frame of your
racing bike. Go sailing and use those novel lightweight sails and strong ropes. Or
maybe youre a military man and wear a helmet and bulletproof vest based on new
advanced bers.
Fiber production is a large-volume business: around 60 million metric tons per
year. About 40% of this is natural ber: cotton and wool; the remaining part is
man-made, synthetic ber: polyester, polyamide, cellulose, acrylics, and so forth.
More than 90% is applied in textiles or carpets. Only about 5% is used in industrial
applications. And the new, advanced, high-modulus bers? Technically and
commercially very interesting, but we are talking of no more than about 0.2% of
the ber capacity!
You may become curious and study some yarns with a magnifying glass and dis-
cover that single bers are as thin as 1030 mm. With a pair of tweezers you un-
ravel the structure and pull out bers a few centimeters in length or discover that
in some cases the bers have innite length. You may test yarns by pulling them
between your hands and cut your ngers when it is an aramid yarn!
Gradually, you start realizing that bers are a completely dierent class of poly-
mer materials: dierent in shape, molecular structure, and physical and mechani-
cal properties.
ISBN: 3-527-31014-2
911
17.1.2
Scope of this Chapter
This chapter has been written for polymer engineers, not for ber specialists. A
comprehensive impression of ber technology can be obtained from relevant sec-
tions in an encyclopedia [1] or more specic textbooks [25], but this would involve
reading hundreds of pages of fairly detailed text. This chapter had to be much
shorter but should nevertheless give a broad survey of the ber eld. Therefore,
clear choices had to be made. Natural bers will almost completely be neglected.
Man-made bers are still in part based on natural polymer (cellulose), but fully
synthetic bers have become more important. The choice was easy: we will pay
more attention to fully synthetic bers. Many of those are spun from solution but
melt-spun bers are growing more rapidly, especially polyester. Therefore, more
attention will be given here to melt spinning than to dry and wet spinning.
The advantage of this approach is that most polymer engineers are already familiar
with melt processing and will more easily recognize the details of a melt spinning
process.
The novel high-modulus, high-strength bers, especially aramid and gel-spun
polyethylene, deserve a special status. These yarns are spun from solution again,
and we will discuss the specic modications of the old wet spinning process that
were required to produce yarns stronger than steel.
This approach has led to the following arrangement of this chapter. It starts in
Section 17.2 with an introduction to ber terminology, because this will be new
for most polymer engineers. In Section 17.3 we see which properties are required
to make a polymer suitable as a ber material, and how simple the selection of a
spinning process seems to be. Melt spinning is discussed in some detail in Section
17.4, with attention to typical machine parts, rheology, and orientation during spin-
ning and drawing. Examples of simple process calculations are given. The section
includes the large melt-spun ber materials polyester, polyamide, and polypropy-
lene. Section 17.5, which is much shorter, and inevitably more supercial, contains
accounts of cellulose (rayon), cellulose acetate, acrylics, and poly(vinyl alcohol), the
large dry- or wet-spun bers. Then in Section 17.6 we discuss the typical dieren-
ces in process limitations between melt spinning and spinning from solution. The
chapter concludes with Section 17.7 on high-modulus, high-strength bers: aramid
and gel-spun polyethylene, but including carbon bers.
Finally, for those who have read this chapter as an appetizer, a full menu is pro-
vided in the References.
17.2
Fiber Terminology
17.2.1
Denitions: Fibers, Filaments, Spinning
Until the end of the 19th century all yarns were based on natural bers, such
as cotton and wool; all these bers are thin (10100 mm) and short (230 cm).
912 17 Fibers
For continuity in a yarn the bers must be twisted. This is the process we call
spinning producing yarn from bers, for example on a spinning wheel but
industrial equipment has been developed for spinning on a larger scale. More than
50% of the worlds yarn production is based on bers. Cotton is still ber material
number one, being used in pure cotton yarns but also in blends with synthetic
bers.
One natural ber has a much greater length: silk. About 1000 m of ber quality
can be unwound from one cocoon, and such laments are combined into a yarn.
This introduces the word lament a ber of (almost) innite length. And we
have met the rst spinning machine, the silkworm. Please note that spinning
has a second meaning here: the production of continuous laments; all synthetic
bers are spun as continuous laments.
A yarn spun from bers is called a ber yarn (Figure 17.1a), whereas a yarn
containing endless laments is called a lament yarn (Figure 17.1b). It seems
logical that all synthetic yarns would be lament yarns, but this is not the case. Fil-
aments are often cut into (short) staple bers at the end of their spinning process,
and then spun again into a ber yarn, either as a blend with cotton or wool, or in a
fully synthetic product. The reason is that the brous character of a yarn is pre-
ferred in many textile applications, and that it is dicult to imitate these tactile
properties by treatment of lament yarns.
Finally, we must introduce the term cord a construction of two or more
twisted yarn ends (Figure 17.1c). For example, staple bers are rst twisted into a
thin yarn and two or three yarn ends are then twisted in the opposite direction
to form a corded yarn. This is a common construction for textile knitware or fab-
rics, and carpet yarns. Cords are also used in industrial applications. Filament
yarns are then twisted to high levels (several hundred turns per meter) and twisted
yarns are combined in a second twisting step again in the opposite direction to
form twofold or threefold cords. A well-known example is tire cord.
Strictly speaking, one should distinguish between ber and lament: a ber
has a limited length and a lament is essentially endless. To avoid misunderstand-
ing, synthetic bers with a limited length are in most cases called staple bers. It
a

b

c

Fig. 17.1. (a) Fiber yarn (the construction shown is in fact a
loosely twisted cord); (b) lament yarn; (c) industrial cord.
is common practice, however, to use ber also as a general term for ber, la-
ment, yarn, and cord materials.
17.2.2
Synthetic Yarns
Synthetic cellulose yarns were developed between 1880 and 1910, rst from a nitro-
cellulose solution, and later as copper rayon and viscose rayon. The cellulosics
are often called half-synthetic because the raw material is a natural polymer.
The most important fully synthetic yarns were developed between 1935 and 1942
polyamides (PA66, PA6), polyester (PET), and acrylic yarns (PAN copolymers).
Another half-century later, many high-performance bers were introduced, for ex-
ample aramid (PPTA), gel-spun polyethylene, and carbon ber.
All synthetic yarn processes are continuous, so endless laments are formed. For
lament yarns, the spinneret contains as many holes as the number of laments
required for that particular type of yarn. For synthetic staple ber production, the
spinneret contains thousands of holes and the laments are cut into bers at the
end of the process.
17.2.3
Titer: Tex and Denier
It is fairly dicult and inaccurate to measure the diameter of bers or laments. It
is much easier to weigh a certain length of lament or yarn. We thus determine a
linear density, or titer. The tex unit is ocially included in the SI system, and has
become the standard in Europe. The older unit denier stems from the silk industry
and is still common in the USA and in many Asian countries. The denitions are:
tex grams per 1000 meter (lament or yarn).
denier grams per 9000 meter (lament or yarn).
It is fairly common practice to use decitex (dtex) instead of tex (dtex grams per
10,000 meter). Numbers in dtex and denier dier by about 10%; for accurate rela-
tionships, see Table 17.1.
The diameter of a lament can be calculated from the lament titer if the density
Tab. 17.1. Conversion factors for denier, tex, and dtex.
Multiply ; to obtain m denier tex dtex
denier 1 1/9 10/9
tex 9 1 10
dtex 0.9 0.1 1
914 17 Fibers
is known. Using the denition of dtex (g 10 000 m
1
) and expressing density in
g cm
3
, we can calculate the diameter D in mm from Eq. (1).
D 10
4 dtex
pr
s
1
For example, a polyester lament (r 1:38 g cm
3
) of 10 dtex has a diameter of
30.4 mm, and a lament of 1 dtex has a diameter of 9.6 mm.
For yarn titers it is useful to specify the number of laments. For example, an
aramid yarn type could be indicated as 1500 denier f 1000, which means that the
yarn contains 1000 laments, each of 1.5 denier. In dtex, this yarn type would be
1670 dtex f 1000, a lament titer of 1.67 dtex.
17.2.4
Tenacity and Modulus: g denier
C1
, N tex
C1
, or GPa
After having introduced the denier and tex units the next logical step is to express
breaking strength (tenacity) and modulus in g denier
1
or N tex
1
instead of in
Pascals (1 Pa 1 N m
2
), MPa, or GPa. Fiber engineers often deviate from using
the basic SI units and convert N tex
1
to cN tex
1
or mN tex
1
, or even cN dtex
1
:
1 N tex
1
100 cN tex
1
1000 mN tex
1
10 cN dtex
1
.
The unit g denier
1
(g den
1
, g d
1
, gpd) stands for gram-force per denier.
In conversion factors to Newtons, the gravity constant therefore appears: 1
gf 9.806 650 10
3
N. In combination with the conversion factor from denier
to tex, this results in:
1 g denier
1
8:826 10
2
N tex
1
; or 1 N tex
1
11:33 g denier
1
For conversion of g denier
1
or N tex
1
to Pa or GPa one needs to know the den-
sity r of the yarn. The main conversion factors are given in Table 17.2.
Dierences in densities can be large, especially when we compare organic bers
(11.5 g cm
3
) with glass bers (2.5 g cm
3
) or steel cord (7.8 g cm
3
). Therefore,
aramid producers may argue that their product is ve times stronger than steel (in
g denier
1
or N tex
1
), while steel cord producers can rightfully respond that steel
has the same strength (in GPa).
Tab. 17.2. Conversion factors for g denier
1
, N tex
1
and GPa (express r in g cm
3
).
Multiply ; to obtainm g denier
C1
N tex
C1
GPa
g denier
1
1 8:826 10
2
8:826 10
2
r
N tex
1
11.33 1 r
GPa 11.33=r 1=r 1
17.2.5
Yarn Appearance
Most natural bers have a non-round cross-section and low luster (Figure 17.2);
silk is the exception. Moreover, yarns spun from these bers have a high volume
(bulk) and ber ends make them hairy. All these factors are appreciated for appli-
cations in textiles and carpets. Synthetic yarn is most easily spun from round spin-
ning holes, the lament yarns have a high luster, they are at (not textured), and
hairiness is absent. This may be perfect for industrial yarn applications, but it is
not desirable for most textile and all carpet yarns.
The cross section can be adapted by using proled spinning holes, for example
trilobes, triangles or hexagonal stars. Delustering can be achieved by the addition
of ne titanium dioxide or another dulling agent, thus producing semi-dull, dull,
or deep-dull yarns, as desired.
To give the yarns a voluminous appearance (bulk), a texturing process is re-
quired. For low-titer textile lament yarns this is often a false-twist operation: twist-
ing by torsion, heat setting, and subsequently detwisting, in a continuous opera-
tion. For higher yarn titers the yarn may be stued into a hot chamber and then
pulled out with simultaneous cooling: this is called stuer box texturing, and is
the common process for staple ber and carpet yarns. An example of a textured
carpet yarn is shown in Figure 17.3(a).
Blowing with air can be used as a texturing process, but also to give the yarn
coherence. The yarn is led through a narrow channel or slit and air is blown per-
pendicularly onto it. At low yarn tension, air blowing creates lament loops. These
loops give volume to the yarn and air blowing can therefore be regarded as a textur-
ing process. The eect of air impingement on a yarn under tension is an intermin-
gling of the laments. This is called interlacing for improvement of the weav-
ability of textile yarns. For industrial yarns the air impingement may be quite
Fig. 17.2. Examples of cross-sections of bers and laments.
a

b

Fig. 17.3. Textured and tangled yarns: (a) textured lament
carpet yarn; (b) a knot appears when a needle is moved
through a tangled yarn.
916 17 Fibers
vigorous, in a so-called tangling jet. If a needle is pulled through a tangled yarn a
knot is formed, typically after a pull-through length of about 10 cm. The eect is
shown in Figure 17.3(b). Tangled yarn packages can be easily unwound, and the
yarns are weavable; the tangling operation replaces a more expensive twisting after-
treatment.
17.2.6
Textile, Carpet, and Industrial Yarns
Further aspects of yarn appearance are the yarn titer and the number of laments:
there may be thin or thick yarn bundles. This will obviously depend on the appli-
cation.
Textiles and carpets are often based on ber yarns cotton, wool, or blends, for
example cotton/polyester and wool/polyamide but 100% synthetic ber yarns
also nd wide application. Fiber yarns are hardly ever found in industrial applica-
tions.
Textile lament yarns have low tex values and a low number of laments, al-
though there is a trend toward lower lament titers, as in microlaments (a1 dtex
per lament). Textile yarns with higher titers are found in home furnishing. Textile
yarns often have non-round laments and are often textured. Carpets can be pro-
duced from ber yarns as well as from lament yarns. The laments or bers are
proled and very thick, typically 1030 dtex. Carpet yarns are always textured. In-
dustrial yarns, including high-performance yarns such as aramid and polyethylene,
are always synthetic lament yarns. They have high dtex values and a lament
thickness depending on the spinning process. Wet-spun yarns usually have thinner
laments than melt-spun yarns (this is also valid for textile yarns). Industrial yarns
are at (without texture) and have round laments, with only a few exceptions. A
survey is given in Table 17.3.
The mechanical properties of textile and industrial yarns dier considerably,
even if we neglect the inuence of texturing; see Figure 17.4. A textile yarn has a
high elongation (2050%) and a low tenacity (200400 mN tex
1
). Industrial yarns
(always at) have an elongation below 20% and a tenacity of 600900 mN tex
1
.
High-modulus, high-strength bers (HMHS), like aromatic polyamide yarns and
Tab. 17.3. Yarn composition in synthetic lament yarns.
Yarn titer [dtex] Number of laments Filament titer [dtex]
Textile yarns
melt-spun 20200 3200 15
wet-spun 50200 50200 12
Carpet yarns ca. 1500 ca. 50 1030
Industrial yarns
melt-spun 5002000 100400 310
wet-spun 5002000 2502000 12
gel-spun polyethylene, have an even lower elongation (24%) and a much higher
tenacity (20004000 mN tex
1
). The initial moduli are accordingly low for textile
yarns, medium to high for industrial yarns, and very high for HMHS bers. The
stressstrain curve of a typical textile yarn shows an intermediate at section, indi-
cating that the orientation could have been improved further still. The curves of
polyamide or polyester industrial yarns have the remnant of this intermediate
section although the yarns have been drawn almost to the limit. The aramid
and gel-spun polyethylene processes enable complete orientation. As a result, the
stressstrain curves have become almost straight lines.
17.2.7
Physical Structure
Most bers are semicrystalline. A few of them aramid and gel-spun polyethylene
approach 100% crystallinity. Examples of the ber structure of PETand PPTA are
shown in Figure 17.5. All bers have a uniaxial organization: properties in the
direction of the axis are completely dierent from those in the cross-direction.
This is an essential dierence from other polymer materials.
The crystallization of polymers in a spinning or drawing process diers from the
crystallization in quiescent melts, for example in extrusion or injection molding
processes. The conditions in ber production are highly anisotropic, and nuclea-
tion and growth rates are orders of magnitude higher. Therefore Avrami equations
from the literature and values from DSC studies cannot be used to describe ber
crystallization.
A direct result of the anisotropic crystallization conditions is that the crystalline
0
500
1000
1500
2000
2500
0 10 20 30 40 50
Elongation, %
HMHS yarn
Industrial yarn
Textile yarn
Tenacity, mN tex
1
Fig. 17.4. Typical stressstrain curves of textile, industrial and
high-modulus, high-strength yarns.
918 17 Fibers
part will become almost perfectly oriented in the axis direction. The remaining
amorphous regions are more disordered, and will determine the ber properties
to a large extent. Fibers drawn to a high ratio will also have a high orientation in
the amorphous regions between the crystallites. It is understandable that amor-
phous orientation will be moderate for most textile yarns and high for industrial
yarns.
The total result of crystallization and orientation is a measurable overall orienta-
tion in the ber direction, uniaxially. Fibers are always birefringent: the index of
refraction in the axis direction (n
==
) is larger than the index crosswise (n
?
). The dif-
ference is the birefringence: Dn n
==
n
?
, and is a measure of ber orientation.
Orientation factors can be calculated from birefringence measurements ( f 0 for
random orientation, f 1 for complete orientation), and are often split into crys-
talline orientation ( f
c
A1) and amorphous orientation (0 < f
a
< 1).
An understanding of the physical structure is important to explain ber proper-
ties. For example, diusion of molecules is rapid through large amorphous regions
and extremely slow in crystallites. Fibers with low crystallinity and a coarse struc-
ture will therefore dye fast and deep, but their chemical stability may be low be-
cause small molecules (oxygen, ozone, water, and suchlike) can rapidly diuse
into the laments.
For industrial bers the relationship between mechanical properties and physical
structure is important. With almost perfectly oriented crystals, the orientation of

a b
Fig. 17.5. Physical structure of bers: (a) semicrystalline
structure of poly(ethylene terephthalate), PET; the broken lines
are the borders of a bril; (b) paracrystalline structure of
poly( p-phenylene terephthalamide), PPTA.
the amorphous regions largely determines the ber modulus and its tendency to
shrink. A high crystallinity, implying a low amorphous content, will contribute to
modulus and will reduce shrinkage. These factors combined give the ber engi-
neer the possibility of developing yarns with high modulus and yet low shrinkage.
A typical aspect of a ber structure is bril formation. Fibrils are an arrangement
of many crystallites and amorphous regions in series, and are common in both
natural and synthetic bers (see Figure 17.5). Chains travel through many crystals
within a bril, but rarely transfer to neighboring brils. An eect of this structure
is the tendency of many synthetic bers, especially those with a high orientation,
toward brillation. This axial splitting of bers can be a disadvantage, but it can
be applied advantageously, for example to produce the aramid pulp used as a re-
placement for ne asbestos bers.
The word paracrystalline is used for aramid and gel-spun polyethylene. Amor-
phous regions are no longer present; rather, the discussion is about defects in the
crystal regions. Fiber moduli approach theoretical crystal moduli and shrinkage is
virtually absent. Indeed, this is a completely dierent class of materials.
17.3
Fiber Polymers: Choice of Spinning Process
17.3.1
Polymer Requirements
Fibers must have a reasonable thermal stability. This means that the melting and/
or decomposition temperature must be high, preferably above 200
C. This will al-

low easy ironing of textiles, curing of reinforced rubber at 190
C, coating of fabrics
with PVC around 190
C, and so on. All the large-volume bers are semicrystalline,

with crystalline contents of 30% or more. One can argue about the proper value of
the crystallinity, which depends on the way it is measured. Sometimes there is
discussion of whether a structure is really crystalline: for example, acrylics (PAN
copolymers) would rather have a kind of organized amorphous or defective
crystalline character.
Table 17.4 shows the well-known ber polymers, and a few which seem unsuit-
able as ber material, namely polystyrene and poly(vinyl chloride). The latter nds
limited ber application, but a special syndiotactic grade with some crystallinity is
then used. Polypropylene has a fairly low melting point but is nevertheless a large
ber product, because the material is cheap and versatile. Polyethylene is even
lower melting and is used only as a superstrong ber at ambient temperature.
17.3.2
Selection of Spinning Process
On paper, the selection of a spinning process seems simple. If the polymer melt
is thermally stable a melt-spinning process will be preferred, because this pro-
920 17 Fibers
cess is relatively simple and cheap. If a polymer is not melt-spinnable, a solvent
must be found which can be used in a solution-spinning process. If the solvent
can be easily evaporated, dry spinning can be applied. In many cases it will be
necessary to spin into a bath containing a nonsolvent, which results in coagulation
of the polymer solution. This is called wet spinning. In a single case viscose
rayon a chemical reaction taking place in the spinning bath is a further compli-
cation.
The preference for melt spinning is very strong. Attempts have therefore
been made to make solution-spun polymers melt-spinnable. For example, small
amounts of solvent/plasticizer can make acrylics melt-processable. Cellulose triace-
tate can be melt-spun if the residence time is held very short. These attempts have
not led to commercial processes, however.
If a choice can be made between dry and wet spinning, the trend is to favor wet
spinning. This may seem surprising because wet spinning is technically compli-
cated. Organic solvents used in dry spinning are often highly ammable, however,
which considerably increases the processing costs.
New, advanced ber types are often spun from solution. Aramid, for example,
has to be spun from solution because the polymer does not melt, but the developed
process strongly deviates from standard wet spinning. The new process is called
air-gap spinning, or dry-jet wet spinning. In the case of polyethylene the choice
was made to spin ultra-high molecular weight polymer from a dilute solution.
This sounds economically unattractive, but the resulting ber is much stronger
than a melt-spun product. A new name, gel spinning, was introduced for this
process.
A survey of the most important ber polymers and the spinning processes ap-
plied is given in Table 17.5.
Tab. 17.4. Properties of ber polymers.
[a]
Polymer T
g
[
C] T
m
or T
d
[
C] Crystallinity [ %]
Polyethylene 100 130140 >50
>80, gel-spun
Polypropylene 20 170 >50
Poly(vinyl chloride) 85 200 (d) <10
Polystyrene 100 275 (d) 0
Polyacrylonitrile 85 ca. 250 (d) ca. 30
Poly(vinyl alcohol) 70/85 ca. 250 (d) 4060
Cellulose 230 200250 (d) 4050
Polyamide 6 a50 225 4050
Polyamide 66 a50 260 4050
Poly(ethylene terephthalate) 75 255 3040
Poly( p-phenylene terephthalamide) ca. 400 (d) ca. 100
[a]
T
g
glass transition temperature, T
m
melting temperature,
T
d
decomposition temperature.
17.3 Fiber Polymers: Choice of Spinning Process 921
17.3.3
Spinnability
What makes a polymer melt- or solution-spinnable? A theoretical prediction is
hardly possible [6]. Laboratory tests are in fact small spinning trials. This is the
way most ber producers will test newly developed polymers, or modications
and new grades of known polymers: on a small spinning machine, which may be
a one-hole laboratory machine. The reason is that in the initial stage of develop-
ment often only small amounts of material are available.
The rst aspect of the test is whether the extrusion through the spinning holes
proceeds smoothly, without excessive die swell, and without extrudate distortion.
Modest problems may be solved by increasing the temperature in melt spinning
or reducing the polymer concentration in solution spinning. In more severe cases
one must probably conclude that the molecular weight is too high or the molecular
weight distribution too broad. Elastic behavior is more problematic in spinning
than in most other polymer shaping processes.
The second aspect of spinnability is whether the laments will break under their
own weight or if the spin-line stress is increased by imposing higher spinning
speeds. Filament breaks during spinning indicate too low a melt strength. This
problem can only be solved by increasing the molecular weight of the polymer
and/or the concentration of the spinning solution.
Obviously, the use of a high molecular weight polymer grade will be preferred. It
gives increased melt strength, and will usually give better yarn properties. Prob-
lems with die swell and melt fracture can make a compromise necessary, however.
For wet spinning there is an additional factor inuencing spinnability. The
thread formation process is complicated: it involves diusion of solvents out of
Tab. 17.5. The most important polymer ber processes.
Polymer Spinning process
Polyethylene gel spinning (dilute solutions of UHMW polymer)
Polypropylene melt spinning (or brillation of melt-extruded lm)
Acrylic copolymers dry spinning (e.g., DMF solvent)
wet spinning (e.g., NaSCN/water solvent)
Poly(vinyl alcohol) wet spinning or dry spinning (solvent: water)
Cellulose wet spinning
rayon: polymer is derivatized during dissolution in NaOH
lyocell: direct dissolution in NMMO
Cellulose acetate dry spinning
acetate in acetone/water
triacetate in DCM/methanol
Polyamide 6 melt spinning
Polyamide 66 melt spinning
Poly(ethylene terephthalate) melt spinning
Poly( p-phenylene terephthalamide) air-gap spinning (solvent H
2
SO
4
)
922 17 Fibers
the lament and nonsolvent from the spinning bath into the lament, followed by
gelation and/or coagulation. Unstable coagulation can make the spinning la-
ments weak. A polymer solution may therefore appear unspinnable until the
proper composition of the spinning bath has been discovered. With tongue in
cheek, one could say that melt spinning is for engineers while wet spinning is a
technique for artists.
17.4
Melt Spinning
The most important melt-spun polymers are polyester (PET), polyamide (PA6 and
PA66) and polypropylene (PP). A scheme for a melt-spinning machine is given in
Figure 17.6. We will follow the process scheme, from extruder to winder.
17.4.1
Extrusion
Some large-scale processes (for polyester and polyamide 66) use direct spinning,
which means that polymerization and spinning are integrated. In most cases poly-
Fig. 17.6. Scheme for a melt spinning
machine (reproduced from Ref. 5): a, extruder;
b, central lter; c, manifold (polymer lines);
d, spin-box with pumps and spinnerets;
e, cooling; h, interoor tube. In section I
as-spun yarns are wound separately (i).
Section II is a typical arrangement for staple
ber production: f, deection of bundles;
g, combination of bundles, which are laid
down in containers.
mer chips are extruded, however. For melt spinning single-screw extruders are
used, no dierent from those applied in other elds of polymer melt processing.
Screw designs may vary considerably, and certainly depend on polymer type and
grade, but there are no typical melt-spinning screws.
Twin-screw extruders are necessary for blending, compounding, or reactive ex-
trusion, but these operations are not usually applied in melt spinning. Moreover,
twin-screw extruders may not easily build up the high pressure necessary to
pump the melt through a long distribution system (see Section 17.4.2). And, of
course, twin-screw extruders are more expensive than single-screw extruders.
Complete de-aeration of the melt is an absolute requirement. Remnant undis-
solved gas will give small bubbles in the extruded laments and cause breaks in
the spin-line. Vacuum in the hopper would solve this problem but is technically
complicated. Spinning under nitrogen is more common. A proper screw design,
especially of the feed zone, and temperature control should ensure sucient de-
aeration.
The size of the extruders for commercial production varies between 90 and 150
mm screw diameter, with outputs of about 100600 kg h
1
. This mass ow should
feed many spinning positions. For textile yarns with a low titer, the output per
spinneret can be as low as 1 kg h
1
and consequently an extruder then should
feed at least about 100 spinning positions. For industrial yarns the output per bun-
dle can easily go up to 50 kg h
1
, and one would see about ten spinning positions
per extruder.
17.4.2
Polymer Lines and Spin-box
Each spinning position should receive polymer with the same time and tempera-
ture history because yarn processing and properties depend on molecular weight
in particular. Residence times of a few minutes between head extruder and spin-
ning plate are common, and some degradation will always occur. Therefore, poly-
mer line systems (manifolds) have simple splits (into two or three) and the same
length between the head of the extruder and all positions. An example is given in
Figure 17.7.
It is obvious now that the examples in Section 17.4.1 were inaccurate. The textile
machine would have 96 positions (3 2
5
) rather than about 100, and the indus-
trial yarn machine eight positions (2
3
).
Many producers insert static mixers in their polymer lines, for example before

Fig. 17.7. A polymer line system for eight spinning positions.
924 17 Fibers
each split in the system. The disadvantages are an additional pressure drop and
fouling of the elements. There are special redistribution elements however, guid-
ing the stagnant wall layer to the center of the line again, with only a modest pres-
sure drop.
Fouling has already been mentioned: it is a very critical issue for spinning ma-
chines. Small particles of degraded polymer (gels) will cause lament breaks. Dead
pockets must be prevented and bends in polymer lines are therefore as smooth as
possible. A careful cleaning operation must be performed before a spinning ma-
chine is started. Not surprisingly, this is often carried out with high molecular
weight polyolens, which are highly viscous, very elastic, not spinnable, but eec-
tive as cleaning compounds. In some occasions (PA66) the distribution system can
even be completely dismantled in order to be cleaned by burning in an oven at
500
C or higher.
Polymer lines can be heated electrically, but temperature control is more accu-
rate when a thermal vapor uid is used. The standard uid is a mixture of di-
phenyl and diphenyl oxide, with a boiling point around 260
C. Double-walled lines
are therefore almost standard.
The spin-box is a vapor-heated enclosure containing the spinning pumps and
the spinning assemblies. Each spinning position has its own metering pump. The
pump and spinning assembly are installed close to each other. The spinning as-
sembly is inserted in a hole in the spin-box. Both top loading and bottom loading
are possible.
17.4.3
Spinning Pumps
Each spinneret of a spinning machine should be fed with a constant volume ow
of polymer melt because otherwise the titer of the resulting yarn bundle would
vary. This is done with positive displacement pumps: that is, gear pumps with low
tolerances. Their output should be independent of the pressure dierence over the
pump. A melt-spinning pump must ensure a constant output up to 400 or 500 bar.
Most pumps have one driven gearwheel and one co-rotating wheel, but two, three
or more co-rotating wheels are also possible. Having a combination of two (or
more) spinning pumps on one driving axis is also a fairly common practice. All
spinning pumps on a machine run at the same speed, and thus the linear density
of all yarn bundles is the same.
The capacity of spinning pumps is indicated by their volume per revolution, usu-
ally in cm
3
; values of 0.550 cm
3
are common. They are operated at 1050 rpm.
For example, for a low yarn titer the required volume ow could be 50 cm
3
min
1
,
which would be delivered by a 2 cm
3
spinning pump running at 25 rpm; or a
heavy industrial yarn titer could require a 20 cm
3
pump at 3040 rpm. Note that
volume ows are adjusted while mass ows are prescribed. A recalculation is easy
when the density of the melt is known, but in practice a mass ow check is always
made.
Melt-spinning pumps can be constructed from normal steel. Tolerances are not
too critical when melt viscosities are suciently high. Pumps are cleaned in hot
ovens at b500
C.
17.4.4
Spinning Assembly
The spinning assembly can be round or rectangular. It contains a lter package on
top of a supporting/distribution plate. The spinning plate is the bottom of the
spinning assembly.
17.4.4.1 Filtration
For production of bers, usually having diameters of 1030 mm, very ne ltration
is necessary. The rule of thumb is that particles of more than one-third of the even-
tual ber diameter will cause interruptions of the spinning or drawing process and
should therefore be removed. The particles that must be removed can be solid (cat-
alyst remnants, dust) or gel-like (not fully melted or crosslinked polymer). Solid
particles can more easily be removed than gel particles. Pigments or delustrants
may be added to the spinning melt. Note that these must almost be submicronic
and should easily pass any lter.
Filtration can be applied in all stages of the process: in a central lter in the poly-
mer melt line, or at the end of the line, in the spinning assembly. Central lters are
common in large-scale melt-spinning processes, for example, staple ber produc-
tion. Two parallel lters may be used to enable lter cleaning without interruption
of the process. Rotating lters with continuous cleaning are also used.
Spinning assemblies always contain lters. In many cases it is the only place
where ltration takes place, but there may also be a combination of preltration
in a central lter and a last, and nest, ltration just above the spinning plate.
Filter packages are usually a stack of screens, going from coarse to ne in the
streamline direction, on top of a support plate with holes for further distribution
of the ow. Screens are plain-weave, or sometimes twill-weave, steel wire fabrics.
Their neness is indicated in mesh (threads per inch), openings per cm
2
, or pore
size in microns. For example, 325 mesh 16 800 opening s cm
2
A40 mm. 500
mesh (25 mm) ltration is common in melt spinning. For even ner ltration, steel
nonwoven materials are used, with a lter neness going down to 5 mm.
An alternative ltration method is a sand lter 15 cm thick, on top of sup-
porting screens. Rather than sand, a sharp-edged stainless steel powder would
nowadays be used. The alleged advantage of a sand lter is the breakdown of gel
particles, which would pass through a relatively thin screen package.
17.4.4.2 Spinning Plate
The bottom of the assembly is the spinning plate: 530 mm thick. The number of
holes varies enormously. A hosiery yarn may have one or three laments, a carpet
yarn 60 laments, an industrial yarn 350 laments. For low lament numbers per
926 17 Fibers
yarn bundle, two or more bundles can be spun from one plate. The number of
holes can go up to 100010 000 for staple ber production. The size of the spin-
ning plates is chosen accordingly, and the plates can range, for example, from
round 60 mm textile plates to rectangular plates 1 m wide for staple ber pro-
duction.
The spinning holes are relatively large: 200500 mm round is common, <200 mm
may be used for textile microtiter yarns, and >500 mm for some industrial yarns.
The holes are large in comparison with the eventual diameter of the laments.
This implies that a considerable draft (see Section 17.4.13.3) is applied in the
spin-line, reducing the lament diameter without however inducing much orien-
tation.
It is impossible to manufacture 200500 mm holes in a melt-spinning plate,
which must be 530 mm thick to withstand the high spinning pressure. Moreover,
such a long narrow hole would give too high a pressure drop. In practice there is
always a backhole (pre-channel, counterbore), with a diameter of 23 mm. The
actual spinning capillary is usually short, with an L=D ratio of only 12.
If possible, spinning holes are made by drilling or punching, because these
are cheap operations. Very small and non-round holes, however, must be made by
spark erosion, making use of an electrode in the form of the hole. The simplest
shape of a hole backhole spinning capillary (see Figure 17.8a) is rarely ap-
plied. At the least there is some smoothening of the entrance and especially of the
transition region to avoid turbulence ow (Figure 17.8b). Holes may have a tapered
section or even a trumpet form (Figure 17.8c). The backhole is always round, but
the spinning capillary may be proled. One can imagine how complicated it then
is to make a smooth transition zone.
The holes are positioned 510 mm from each other. This spacing is necessary
for the air-cooling process. Cold air must penetrate easily into the bundle, and
some mobility of the laments should be allowed without laments immediately
sticking as a result.

a, backhole
and spinning hole
b, as a, but
smoothened
c, trumpet form,
tapering
Fig. 17.8. Examples of spinning holes.
17.4.5
Quenching
The standard quenching or cooling system is crossow, in which cold air (at 15
70
C) ows from one side, perpendicular to the yarn bundle (see Figure 17.9).
The disadvantage of this system is that laments close to the blow-box cool faster
than those in the front of the yarn bundle (see Figure 17.10a). This can be mini-
mized by adapting the drilling pattern and limiting the number of rows of
holes in the cross-direction (Figure 17.10b). An alternative is radial cooling (Figure
17.10c), usually outside to inside, with the disadvantage, however, that a column of
hot air will be enclosed in the bundle, again resulting in dierences in cooling
across the bundle.
Enforced cooling only takes place in the rst 0.51.5 m, whereas the total height
of the spin-line is 1.56.0 m. Cooling air speeds are in the order of 0.11 m s
1
.
A standard spinning machine with a cooling height of 6 m requires at least a
four-story building, with chips handling on the fourth oor and extruders, spin-
boxes, and cooling on the third oor (the spinning oor). On the second oor one
would only see interoor tubes, or chimneys, through which the bundles
travel downward and cool further. The rst oor is the winding oor.
At high spinning speeds the yarn bundle attracts its own cooling air, by self-
suction. With only a few measures to avoid turbulence and ensure symmetric sta-
bility, this can be sucient for textile yarns. For industrial yarns the initial cooling
Fig. 17.9. Principle of a crossow quenching system
(reproduced from Ref. 5): a, spin-box; b, spinneret; c, lament
bundle; d, lter; e, air supply.
928 17 Fibers
is always enforced, but the remaining necessary cooling air is attracted automati-
cally by the bundle.
For highly viscous polyester and polyamide 66 yarns there may be no cooling
in the rst 0.10.5 m. On the contrary, an electrically heated ring or box, which
keeps the laments at the spinning temperature, would be positioned around the
bundle. The technique is called retarded cooling, and the device is a quench col-
lar. In this way the spinning plate is kept at an even temperature and the orienta-
tion level is reduced as well as the variation in orientation between laments. This
results in applicability of higher draw ratios, and in higher tenacities of the yarns.
The cooling speed depends on the mass ow per hole and the temperature dif-
ference between the lament and the air. Of course, large bundles spun at high
speeds require much cooling air; this is a simple energy balance calculation. The
limiting step in the cooling process is the formation of a sublayer around the la-
ments. Removing or refreshing this sublayer is the key for a fast and even cooling
process.
The laments in a bundle should not touch each other before they are solid, be-
low the glass transition temperature or below the crystallization temperature. Poly-
propylene and polyamide 66 always crystallize in the spin-line, polyamide 6 and
polyester crystallize in the spin-line only at high speeds.
17.4.6
Finish
A yarn without spin nish cannot be processed; yarnmetal friction is too high,
and static charge would build up. A nish is therefore applied before the yarn rst
touches guides, rolls, and so on. Finishes can have sophisticated compositions, but
two components are always present: lubricants and antistatics. In water-based n-
ishes emulsiers are a third essential component. Finishes are specic for certain
a, crossflow
circular drilling
pattern
b, crossflow
optimal cooling
of all filaments
c, radial cooling

Fig. 17.10. Yarn cooling.
yarn types: a polyamide nish cannot be used on polyester or polypropylene; a n-
ish for polyester textile cannot be used on a polyester tire yarn.
Finishes must be adapted to the polarity of the ber polymer. They must spread
over the surface within a very short time. Another criterion is that the nish
should not interfere with later applications. For example, components which are
necessary in a textile nish could ruin the rubber adhesion of a tire cord.
Knowledge of nishes used to be proprietary, with most ber producers using
their own nishes and keeping the compositions secret. Commercial producers
have developed good general-purpose nishes, however, which have found wide
application. Only a few larger ber producers still develop their own nishes, espe-
cially for critical processes. One feature has remained: still, ber producers do not
reveal which nish is used or how it is applied.
Spin nishes often used to be solutions in white spirit, but for environmental
reasons this is no longer the case. Emulsions in water, or nishes without a diluent
so-called neat oils, with components of a suciently low viscosity are used
instead.
Application of nish requires special applicators. Fairly old-fashioned is a nish
roll, a porous ceramic roll which constantly takes up nish from a bath, which is
then transferred to the yarn that just touches the surface of the roll (see Figure
17.11a). More modern applicators accurately supply the required amount of nish
via a small gear pump, to stift or block applicators, through a hole or slit. The
yarn is spread as a ribbon over the applicator and takes up the nish (Figure
17.11b,c). At higher yarn speeds the even distribution of nish becomes increas-
ingly dicult. An applicator with multiple slits or a nish wheel (a roll with small
holes under the yarn path) may then be applied.
Finishes of a dierent nature, so-called after-oils, may be applied at the end of
the spinning and drawing process to improve the yarn for a specic application,
for example to produce a wrinkle-free textile fabric, to make carpet yarns antistatic
a, finish roll b, stift applicator c, block applicator
Fig. 17.11. Application of nish.
930 17 Fibers
and/or non-soiling, or to enhance PVC or rubber adhesion for industrial yarns.
There is a distinct overlap with other nish-like aftertreatments such as sizes for
weaving and dips for tire cords.
17.4.7
Spinning Speed
Falling under its own weight a spinning bundle would reach a speed of 300
400 m min
1
. In practice, spinning speeds of at least 500 m min
1
are required
to obtain a suciently high tension in the spin-line. Much higher speeds can be
enforced, as long as the laments do not break under the constantly increasing
tension. Speeds of 40008000 m min
1
have become common practice, especially
for polyester. This is called high-speed spinning (HSS), in contrast to LSS
(< 1000 m min
1
). The air friction can only build up modest forces in the la-
ments. Even at high speeds the molecular orientation level remains limited, and
further drawing is always possible, or even necessary. For further information on
HSS see Ref. 7 and Section 17.4.14.
17.4.8
Winding
An old-fashioned winder, operating at 500 m min
1
, was still a simple piece of
equipment. Modern high-speed winders, operating at 6000 m min
1
or more, are
high-tech devices, the area of specialists. In order to make packages with a good
cylindrical shape, the traverse system of the yarn must be very rapid and smooth,
especially at the reversal points. A second problem is how to handle the very great
weights of the packages, for example, four packages of 30 kg each, wound on one
spindle, at >5000 rpm! A third problem is that threading in and transfer to a
new package must be fully automated; winders therefore have revolver systems
which simultaneously end the winding of one package and start the next one.
For textile production the capacity of winders has been increased by winding
eight or even 12 packages on one winder. For industrial yarns the standard number
of packages is two to four.
Winders are used at the end of the spinning process, LSS or HSS, or at the end
of an integrated process (spindraw winding; see Section 17.4.9), always at high
speed. Winders for separate drawing processes (see Section 17.4.9) usually operate
at a1000 m min
1
. At these low speeds it is possible to wind and twist the yarn
simultaneously. This is done for textile yarns. For industrial yarns twist is often ap-
plied as a separate aftertreatment.
17.4.9
Drawing
A yarn spun at low speed (< 1000 m min
1
) still requires additional drawing. The
elongation is still a few hundred percent and the tenacity is too low. A yarn spun at
high speed (> 4000 m min
1
) may already have sucient strength for textile or
nonwoven applications, but is never strong enough for industrial use. If additional
orientation is required, this can be enforced in the spin-line, in a narrow hot tube
where drawing takes place. This is called hot-tube spinning (HTS) and is applied
only for textile yarns. In most cases drawing is a separate operation. This can be
on a separate machine, or combined with the spinning operation, but then in a
separate step.
The drawing process is usually carried out in two steps: cold and hot drawing.
Cold drawing is the so-called neck-drawing step. For a stable process the position
of the neck should be xed, by tension and/or temperature. Hot drawing is distrib-
uted over a longer distance, in a more homogeneous deformation process.
The simplest setup of a drawing machine is a drawing pin (with one yarn wrap
around it) and a hotplate (the yarn loosely touches the surface) between two rolls
(see Figure 17.12a). The pin is heated to about the glass transition temperature,
while the hotplate is held at a temperature safely below the melting temperature.
The speed ratio of the two rolls is the adjusted draw ratio (for example, 5.4). The
yarn necks on the pin and completes a natural draw (for example 3). The re-
maining factor (1.8) is the draw ratio over the hotplate. One lets the as-spun
yarn decide how and where it wants to draw, which is not necessarily the optimum
situation.
More control is possible if the two steps are separated. As an example, drawing
in hot gas (steam or air, Figure 17.12b) is depicted, with a set of pins for the cold
drawing step and an oven for the hot drawing step. The scheme in Figure 17.12(c)
shows that drawing is also possible on rolls only, provided that these are heated to
a, pin-plate drawing
cold drawing on a static pin;
hot drawing on the plate
c, roll-roll drawing
a steamjet fixes the neck in the
cold drawing step
b, hot gas drawing
three-roller sets determine the initial, intermediate and end speed
cold drawing on 5 static pins; hot drawing in a oven, with hot steam or air
Fig. 17.12. Drawing processes.
932 17 Fibers
approximately the previously applied pin and plate temperatures, respectively. An
alternative is to insert a steam jet between the rolls, which xes the neck position.
Traditionally, spinning and drawing were two separate processes. A spinning
spool was made and then unwound again to feed a drawing machine. Later, the
two steps were combined. This technique is called spindraw winding (SDW).
The winding speeds on spindraw winders are always high. For example, a mini-
mum spinning speed of 500 m min
1
should be multiplied with a draw ratio (DR)
of 56, resulting in speeds of 25003000 m min
1
. For better economics, speeds
of b4000 m min
1
are preferred, which are achieved at spinning speeds of
b700 m min
1
. Figure 17.12(c) shows a typical set of drawing rolls (godets) for an
SDW machine.
Textile yarns are drawn to moderate tenacity and still high elongation. A
(super)high-speed spinning process may fulll the demands; the term fully ori-
ented yarn (FOY) is used for the product. If a drawing process is still necessary it
is often very simple, in one step, for example combined with a texturizing process.
High-tenacity industrial yarns always require extensive drawing, in most cases in
two steps, even if the spun yarn is already highly preoriented.
When higher draw ratios are applied the stressstrain curves become steeper: te-
nacity is increased and elongation is reduced (see Figure 17.13). We nd the end-
points of a series of curves on an envelope, often described with empirical relation-
ships. A popular one for polyester and nylons is TE
0:5
constant (T tenacity;
E elongation). A demand to raise this factor, which implies a higher breaking
energy, cannot be fullled by adapting the draw ratio, but only by adapting a qual-
ity factor. In the example given this is an increase of the polymer molecular
0
100
200
300
400
500
600
700
800
900
1000
0 10
Elongation, %
Increasing Molecular Weight
Increasing Draw Ratio
Tenacity, mN tex
1
20 30 40 50
Fig. 17.13. Stressstrain curves of polyester yarns: inuence of
draw ratio and molecular weight.
weight. Figure 17.13 shows realistic values of T and E for polyester textile and in-
dustrial yarns, the latter being produced from a 50% higher molecular weight.
17.4.10
Relaxation and Stabilization
High orientation of the amorphous phase results in yarn shrinkage, for example in
boiling water or in hot air. The shrinkage can be partly relieved in a stabilization
step: a heat treatment at (almost) constant length (DR 1). If the heat treatment
is carried out at low tension the term relaxation is used (DR < 1). Almost zero-
shrinkage yarns (pre-shrunk) can thus be produced. The equipment is the same
as for drawing: hotplates, hot ovens, or rolls, often installed as an additional step in
the drawing process.
17.4.11
Process Integration
It is expensive to let operators handle intermediate products and it is therefore nec-
essary to reduce the number of process steps or to integrate process steps, in order
to remain competitive. The rst trend has been to increase spinning speeds and
get so much orientation that the drawing step can be omitted. This is the case for
textile yarns spun at high speed, fully oriented and spun-bonded polyester or
polypropylene nonwovens. A second trend is to combine spinning and drawing
(SDW) and, if possible, to include stabilization and texturing. An example of the
latter integration is spindraw bulk winding (SDBW) of carpet yarns. A third pos-
sibility is to couple polymerization with yarn production, by direct spinning for
example, in a continuous polyester polymerization unit coupled with staple-ber
spinning or a series of spindraw winders. This is the ultimate wish: for mono-
mers going in and full yarn spools coming out.
17.4.12
Rheology
For the design of polymer lines, lter packs and spinning plates, rheological data
are required to make the proper calculations. Fiber polymer melts have a fairly
common rheological behavior: they are viscoelastic and shear thinning.
17.4.12.1 Shear Viscosity
Most rheological processes during spinning are determined by shear. It is impor-
tant to understand the typical shear rates in spinning machines. We will use Eq.
(2), for the apparent shear rate, to work out a few examples.
_ gg
app

32F
v
pD
3
2
934 17 Fibers
For a polymer line with a diameter of 4 cm through which a mass ow of 360
kg h
1
(r
melt
1 g cm
3
) is pumped, we calculate _ gg 16 s
1
, a low-shear condi-
tion. For a ow of 5 g min
1
through a 500 mm spinning hole, however, we calcu-
late _ gg 6790 s
1
, a high-shear condition. In the lter package the pores can be
small, but the total ow is divided over as large a surface as possible, in order to
prevent a high pressure buildup. As a result, shear rates will be in the order of
1002000 s
1
. Finally, in the metering pumps the shear rates between gearwheel
and housing may be in the order of 10
5
s
1
. For melts with pronounced shear thin-
ning, narrow tolerances may thus be required for a proper metering.
For appropriate calculations of the ow in spinning machines one thus needs a
rheological curve over about four decades of shear rate, such as Figure 17.14. A
zero-shear viscosity (h
0
) or a melt ow index (MFI) gives insucient insight.
The polymer molecular weight is the most important factor determining the
viscosity of melts. The scaling rule is h @M
3:4
w
. In many cases a solution viscosity
(for example, intrinsic viscosity, [h]) is used as a measure for polymer molecular
weight. Since for many exible polymers h @M
0:7
w
we can derive another scaling
rule, of melt viscosity as a function of solution viscosity: h @h
5:0
. It is evident that
a higher melt temperature will reduce melt viscosity, but only small variations in
molecular weight can be compensated for by temperature adjustment.
100
1000
10000
1 10 100 1000 10000
Shear rate, 1 s
1
polymer lines
filters
spinning holes
M
e
l
t

v
i
s
c
o
s
i
t
y
,

P
a
.
s
Fig. 17.14. Melt viscosity of polyester as a function of shear
rate. h 0:9, at 300
C and 100 bar. An indication of the shear

rate domains in a spinning machine has been added.
17.4.12.2 Elasticity
Elastic behavior is the background of melt fracture just below the spinning plate,
which in practice means the immediate interruption of a running process. Elas-
ticity can be controlled by avoiding the use of high molecular weight polymer. For
example, the common grades of polypropylene have a broad molecular weight
distribution and it may be required to remove the high molecular weight tail by
degradation, for example with a peroxide. The resulting ber grade is indicated
as controlled rheology.
17.4.12.3 Elongational Viscosity
Elongational behavior is induced in the entrance of the spinning hole and in the
transition region from backhole to actual capillary. In practice hardly any perma-
nent orientation is built up in this way, however, because molecular relaxation is
rapid. Spinning hole proles are smoothened only to prevent the formation of
vortices which would lead to extrudate distortion. Promoting orientation already
in the spinning holes is not common for melt spinning. It could be benecial for
the orientation of melt-spun liquid-crystalline polymers, however, for example in
the production of carbon ber from pitch.
More important is the elongation in the spin-line, where uniaxial deformation of
the material obviously takes place. Measurement of elongational viscosity on labo-
ratory equipment is very complicated. Fiber engineers may include it in developing
spinning models, thereby using the spinning machine itself as a rheometer, but
will usually keep the information they gather proprietary.
In situations of low elongational rate one can simply apply Troutons ratio [Eq.
(3), where h
E
is the elongational viscosity and h
S
is shear viscosity; the subscript S
is often omitted].
h
E
3h
S
3
At higher rates, and in contrast to shear thinning, strain hardening (increasing h
E
)
may occur, resulting in rapid orientation. In practice this is often induced or ac-
companied by cooling, solidication, and crystallization of the melt, making the
analysis of elongational behavior even more complicated.
Catastrophic strain hardening, resulting in breaking laments, is rare for melt-
spun polymers. Buildup of fairly high orientation in the spin-line has become
common, however, in modern high-speed spinning processes.
17.4.13
Process Calculations
Fiber engineers are notorious users of non-SI units: feet or yards instead of meters,
minutes or hours instead of seconds, grams instead of kilograms, and denier or
dtex instead of tex. Nevertheless, most process calculations are quite simple, with-
out dicult conversions being necessary.
936 17 Fibers
A few examples for a polyester spindraw winding process will show this, and
hopefully give an impression of how melt-spinning machines are designed.
The process concerns the production of an industrial yarn with a titer of 1670
dtex f 325. We assume that spinning holes are used with a diameter of 500 mm
and an L=D ratio of 1.5; there are 325 holes per spinning plate. There are eight
spinning bundles per extruder. The spinning speed is 800 m min
1
and the spun
yarn is immediately drawn ve times on the same machine (an integrated process)
and then wound with a speed of 4000 m min
1
.
17.4.13.1 Mass Flow
By denition 1 dtex 1 gram per 10,000 m. The output per bundle is then calcu-
lated from Eq. (4).
fyarn titer in dtex 10;000
1
g spinning speed in m min
1
1670/10;000 4000 668 g min

1
4
Note that the mass ow is constant in the process, from spinning pump to winder.
No mass is lost, in contrast to dry or wet spinning. For example, at the end of the
spin-line the speed is 800 m min
1
, ve times lower than after drawing, but the
undrawn yarn still has a ve times higher titer. Also note that the volume ow is
not completely constant, because the density increases (by about 20%) when the
melt cools down, solidies, and crystallizes.
Eight yarn bundles make 8 668 5344 g min
1
320.6 kg h
1
, which
would require a 120 mm, maybe 150 mm, extruder. The unit produces about 7.6
ton day
1
, or about 2700 ton y
1
.
17.4.13.2 Volume Flow
The density of a polyester melt is approximately 1.18 g cm
3
. The volume ow per
yarn bundle and spinning pump thus is 668=1:18 566 cm
3
min
1
. This ow can
be achieved with a 20 cm
3
pump at 28.3 rpm.
17.4.13.3 Extrusion Speed and Elongation in the Spin-line
A volume ow of 566 cm
3
min
1
is extruded through 325 holes, which is
566=325 1:74 cm
3
min
1
per hole. The holes have a diameter of 500 mm
(0.05 cm) and their cross-section is p=4 0:05
2
0:001964 cm
2
. The extrusion
speed through the holes is (1.74 cm
3
min
1
)/(0.001964 cm
2
) 887 cm min
1
8.87 m min
1
.
The spinning speed is 800 m min
1
, and the laments are thus accelerated in
the spin-line by a factor of 800=8:87 90. In practice this is viscous ow rather
than molecular orientation. Calling this a draw ratio is misleading; draft, draw-
down or spin stretch factor are better notions.
17.4.13.4 Pressure Drop over the Spinning Holes
For the calculation of shear rate it is essential to convert accurately to meters and
seconds in order to obtain shear rate in reciprocal seconds (s
1
). The formula is
given by Eq. (5), with F
v
1:74 cm
3
min
1
and D 500 mm.
_ gg
app

32F
v
pD
3
5
The shear rate in the spinning holes in this case is _ gg 2363 s
1
. In the rheology
graph (Figure 17.14) we see that h 220 Pa s at this shear rate.
We can now calculate the pressure drop over the spinning hole with Poiseuilles
law [Eq. (6)].
DP
128
p
F
v
h
L
D
4
6
The result is 3119335 Pa 31 bar. The pressure drop over the much wider back-
hole would add only a few bars.
This is a reasonable pressure drop: not too high, but also not too low, because
this would lead to an uneven distribution of the ow over the holes, which would
result in lament titer dierences within a yarn bundle. For a lower melt viscos-
ity (for example, 100 Pa s), narrower spinning holes (350 mm) would have been
necessary.
The pressure drop over the lter package would add 3050 bar, resulting in an
initial pressure drop over the spinning assembly of 6085 bar. The pressure drop
over the lter does increase during the lifetime of the spinning assembly. The as-
sembly would be taken out of the machine at 200250 bar.
17.4.14
Polyester (Poly(ethylene terephthalate), PET)
Polyester and PET are almost synonyms. Other polyesters, such as poly(butylene
terephthalate) (PBT), poly(trimethylene terephthalate) (PTT), and poly(ethylene
naphthalate) (PEN), have hardly any signicance as ber materials.
17.4.14.1 PET Polymer
Textile-grade polyester has an intrinsic viscosity around 0.6 (degree of polymeriza-
tion 100) and is spun at about 285
C, which is 30
C above the melting point.

Grades for industrial yarns have an intrinsic viscosity of 0.80.9 (degree of poly-
merization 140160) and must be spun at 300310
C. The main degradation prob-

lem for PET is hydrolysis: each water molecule gives one chain break in the PET.
There is no hydrolysis problem when a polymerization unit directly feeds the spin-
ning machine. Handling of polymer chips requires closed systems, ultra-dry air or
nitrogen, among similar precautions. Thermal degradation is unproblematic for
textile yarn polyester, but becomes severe for industrial yarn polyester grades
938 17 Fibers
spun above 300
C. Even at a short residence time in the machine (below 10 min) a

total drop of 0.1 in the intrinsic viscosity must often be accepted.
17.4.14.2 Spinning of PET
PET is a slowly crystallizing polymer. It remains amorphous in the spin-line at
speeds below 3000 m min
1
. At higher speeds nucleation takes place high in the
spin-line, at high temperature, and these nuclei grow rapidly on their way down.
The air drag forces deform the crystalline network in a neck-like fashion in the
spin-line (see Figure 17.15). This necking is more pronounced for higher speeds,
ner laments, and higher molecular weights. These as-spun yarns have a low
shrinkage even when the crystallinity is still low. The remaining draw ratio of
such yarns is below 2.
17.4.14.3 PET Staple Fiber
The majority of polyester ber production is for textile application, and most of
this is staple ber. Staple ber is produced by direct spinning from continuous
polymerization units based on pure terephthalic acid. The spinning plates have
20005000 holes, and the spinning speed is around 2000 m min
1
. The bundles
are not wound but are laid down loosely in a container. Drawing (more than three
times) and texturing is a second, separate step: spinning bundles are combined
into a tow of several hundred thousand dtex and drawn, crimped, and heat-set col-
lectively. Cotton-type ber is the standard: 0.52 dtex, drawn to 20% elongation, cut
to 3240 mm in length. Wool-type bers have a titer of 27 dtex; they are drawn to
40% elongation and cut to 40120 mm in length. Staple ber is delivered to the
customer in large bales.
6000
4000
2000
0
0 0.5 1.0 1.5
Distance from spinning plate, m
yarn speed,
m min
1
1000
3000
2000
4000
5000
6000
Fig. 17.15. Yarn speed curves for LSS and HSS of polyester.
17.4.14.4 PET Textile Filament Yarns
Most textile lament yarns are also direct-spun. The output per bundle is small,
and therefore hundreds of spinning positions must be fed from one polymeriza-
tion unit, making the polymer melt-line system very complicated. Winders make
four, six, eight, or even 12 packages simultaneously, and spinnerets and spinning
pumps are clustered accordingly.
Partly oriented yarn (POY) is a large product; spun at about 3500 m min
1
, with
a round cross-section, and draw-textured (DR@1:8, at about 1000 m min
1
) in a
separate step. Fully oriented yarn (FOY) can be spun at b6000 m min
1
, or drawn
in the spin-line (hot-tube spinning, HTS), or spin-drawn. Typical yarn titers are 30,
50, 76, 110, and 176 dtex, and the lament titers 23 dtex, although there is a trend
toward values of 1 dtex or lower.
17.4.14.5 PET Industrial Yarns
Direct spinning is not very common for industrial yarns because there are only
a few yarn types that would match the large capacity of polymerization units
(b25 000 ton y
1
). A further complication is that the polymer must be condensed
to a high molecular weight, but this can be achieved in deep-vacuum, thin-lm
nishers. In most cases chips with a textile viscosity are solid-state postcon-
densed, at a relatively low temperature (about 230
C), which takes many hours

but has the advantage that thermal degradation is minimized.
There is a limited eld of application for low yarn titers, 200550 dtex, in sewing
yarns and ne fabrics. Most industrial yarns have titers of 11002200 dtex. The l-
ament titer is usually around 5 dtex, but yarns for safety belts have coarser la-
ments (1015 dtex) and modern tire yarns may have ner laments (around 3
dtex).
Large spinning holes (350800 mm) are used to handle the high melt viscosities.
The standard process for PET is spindraw winding (SDW) at speeds of 4000
5000 m min
1
. This is the cheapest process, especially when two, three, or four
bundles are combined on one set of spinning and drawing godets and one winder.
The yarns are strong (700850 mN tex
1
), but may have a fairly high shrinkage.
For applications such as nets, ropes, cables, and most fabrics (safety belts, conveyor
belts) this is an ideal combination. For some applications almost zero shrinkage
can be required (PVC-coated fabrics) and a separate, slow, drawing and stabiliza-
tion process may still be applied.
Tire cord is a dierent case. Polyester is the most important reinforcing material
for radial tires. The cords run radially, from rim to rim, and their high modulus
reduces the deformation of the rolling tire, and thus fuel consumption. The prop-
erties of the reinforcement in the tire depend on how well the modulus is retained
during the dipping and curing processes. Therefore, tire yarns are always spun at
high speeds (> 3000 m min
1
), which gives lower shrinkage and somewhat lower
tenacity in the yarn. After dipping of the cords and curing of the rubber, these
yarns oer the best strength/modulus combination. To reduce costs, even these
940 17 Fibers
yarns are spin-drawn, which implies winding speeds of at least 6000 m min
1
(high-speed spin-draw winding, HSSDW).
The most important applications of polyester industrial yarns have been men-
tioned above: tires, other rubber reinforcement, narrow and wide fabrics, nets,
ropes and cables, and sewing yarns. It is not unusual for a company to list 20 dif-
ferent types of polyester yarn, each type being further divided into various yarn
titers and twist levels.
17.4.15
Polyamide (PA6 and PA66)
The former dierence in usage between the USA (PA66) and Europe (PA6) is still
evident. PA66 seems to be the larger-volume product but PA6 is still large in South
American countries, eastern Europe, and India. High-melting PA46 is gradually
nding application in airbag fabrics. Other polyamides (PA11, PA12) are not im-
portant as ber materials.
17.4.15.1 PA Polymer
Polyamide 6, melting point 225
C, is spun at 260280
C (290
C); polyamide 66,

melting point 265
C, is spun at 290300
C (310
C). Thermal degradation is rela-

tively unproblematic for polyamide 6, but is more severe for polyamide 66 because
of the higher spinning temperature and the tendency of polyamide 66 to crosslink.
Filtration of gel particles is an issue for PA66, not for PA6. PA66 polymer melt-
lines must be burned out once a year because a crosslinked, charred polymer layer
is built up at the hot walls. High-shear conditions in narrower polymer lines can
help to remove the gel layer from the walls and prolongs the cleaning cycle.
Both polyamides evolve oligomer vapor upon extrusion from the spinning holes,
and snow-like deposits are formed on cold spots in the top of the spinning ma-
chine. Measures such as steam injection, suction, and regular manual cleaning
must be taken to keep these under control.
Polyamides are prone to oxidative degradation, resulting in yellowing. The nitro-
gen gas in the chips hoppers must therefore be completely free of oxygen.
The reaction of polyamide with water is an equilibrium. When the chips are too
dry, the polymer will postcondense in the spinning machine. When they are too
wet hydrolysis will take place. The equilibrium water content depends on the
molecular weight: for a higher molecular weight, the water content must be lower.
There is always some loss of molecular weight by thermal degradation. This can
be compensated for by postcondensation when the water content is adjusted to
slightly below the equilibrium level.
17.4.15.2 PA Spinning
Polyamides crystallize faster than polyester. At low spinning speeds polyamide 6
does not crystallize in the spin-line but fairly rapidly on the spinning spool, thereby
also attracting water. As a result, the packages increase in volume (grow) and can
be unwound only with diculty when the storage conditions are not kept very con-
stant. At speeds of 10004000 m min
1
no proper spinning spools can be made.
Above 4000 m min
1
the yarns crystallize suciently in the spin-line and stable
packages are built. Polyamide 66 crystallizes faster than PA6. As-spun yarns are al-
ways crystalline, even at low spinning speeds. Complete melting of the crystalline
chips is essential because remnant crystal nuclei can even cause spherulitic crys-
tallization.
17.4.15.3 PA Staple Fiber
Staple ber is a large product, especially for applications in carpets. The production
resembles that for polyester staple. The spinning speed is about 2000 m min
1
,
which is not problematic because the as-spun yarn is not wound but laid down in
containers. The lament titer may be low (4 dtex, for velour carpet) but is usually
around 20 dtex. The cross-section is proled: it may be trilobal or a square with
holes.
17.4.15.4 PA Textile Filament Yarns
The yarn counts are lower than for polyester because the main applications are as
hosiery yarn (for example 20 denier: 22 dtex f 1 or 22 dtex f 5) or in ladies un-
derwear (typical yarn titers 44 dtex f 10, 78 dtex f 28, or 78 dtex f 60). The processes
are, for POY, spinning at >4000 m min
1
followed by a draw-texturing treatment
(at approximately 1000 m min
1
), or SDW at >5000 m min
1
. The elongation of
nylon textile yarns is 4550%.
17.4.15.5 PA Industrial Yarns
Polyamide industrial grades have much lower melt viscosities than polyester, and
are therefore spun through smaller spinning holes (250400 mm). Polyamide yarns
can be drawn to elongations slightly below 20%, but subsequent stabilization to re-
duce shrinkage may add a few percent elongation. Tenacities are at least as good as
for polyester, but the modulus is much lower.
Polyamide is applied in fabrics, especially in airbags, where PA66 has an impor-
tant advantage over other ber materials. Airbags are blown up with hot gas and
PA66 does not melt because it has a high specic heat and a high melting point.
In this respect, PA46 is even better. The high tenacity and breaking energy of poly-
amide yarns make them suitable for application in shing nets, ropes, and cables,
but the competition with cheaper polyester is erce. For rubber reinforcement PA6
has the disadvantage of its low melting point. Nevertheless it is still widely applied
in India and South America. PA66 is used on a large scale: in conveyor belts, rub-
ber hoses, and tires. In radial tires PA66 cannot be used in the tire walls because
its modulus is too low, but it is present as a cap ply around the steel belt. In old-
fashioned bias-belted tires, for bumpy roads, polyamide is the perfect reinforce-
ment. Aircraft tires also have a diagonal construction, and usually contain many
layers of nylon cords.
Spindraw winding (SDW) is the standard process for the polyamides: spinning
speeds are 5001000 m min
1
, winding speeds 30005000 m min
1
. Drawing
942 17 Fibers
usually takes place in two steps, cold and hot drawing, but one-step drawing is
possible for low yarn counts. For better economics it is essential to process two,
three, or four bundles on one set of drawing godets, and to wind them on one
winder.
Yarn titers are 200600 dtex for airbags and other ne fabrics, and 11002200
dtex for most other applications. Filament titers are around 5 dtex. Tenacities are
between 750 and 850 mN tex
1
, and elongations between 18 and 25%.
17.4.16
Polypropylene (PP)
17.4.16.1 PP Polymer
Polypropylene is an addition polymer with a fairly broad molecular weight distribu-
tion. The strong viscoelastic eects make spinning through small holes, or slits in
proled holes, dicult. PP ber grades are therefore made by cracking the high
molecular weight tail by oxidative degradation, for example by the addition of per-
oxide in a twin-screw extruder.
Polypropylene is full of tertiary carbon atoms which give oxidative and light sta-
bility problems. Stabilizer packages are therefore always included in bers, with
their small diameters and high specic surface. The polymer is hydrophobic. Spe-
cial treatments or additions are required to make polypropylene dyeable.
Polypropylene melts at about 175
C but is spun relatively hot, b75
C above its
melting point. Polypropylene is often spun from large and long spinning holes
(8001500 mm, L=D 35). It is evident that the low melting point is a limit for
industrial applications. A further disadvantage of polypropylene is its low creep
resistance.
17.4.16.2 PP Spinning
Polypropylene crystallizes fast, always in the spin-line, even at low speeds.
17.4.16.3 PP Staple Fiber
This is probably the largest-volume spun product, for application in carpets. The
usual machines resemble those for polyester and polyamide, with the spinning
speed around 1000 m min
1
, collection of as-spun yarn in a container, and draw-
texturing a tow of several hundred thousand dtex. Short spinning is an alterna-
tive: it involves a one-oor machine, holes at a very short distance from each other,
cooling over a short distance, and the spinning speed so low (@100 m min
1
) that
drawing and texturing can be included on the same machine.
17.4.16.4 PP Split Fiber
Much polypropylene ber is not spun, but produced from lm. A lm is blown, or
cast on a chill roll, drawn 610 times and then brillated. There are numerous
ways of slitting, brillating, and cutting. Split ber nds applications in twines
and ropes (as a replacement for sisal), cheap fabrics for bags and tarpaulins, and
carpet backing (replacing jute).
17.4.16.5 PP Filament Yarns
The production machines can be normal spindraw winders, as for the other melt-
spun bers. But here also, compact machines have been developed, for example
for bulked continuous lament yarn (BCF, for carpet) with all the process steps on
one machine, at an end speed of a1000 m min
1
.
Polypropylene is small in textile applications (in sportswear) but it has a reason-
able position in high-tenacity yarns, in low-temperature applications such as ropes,
cables, and geotextiles. It should be added that polypropylene can be drawn to high
ratios (see Section 17.7.2). This results in very good tenacities, but the helix cong-
uration of the isotactic chain in the crystals severely limits the modulus.
17.5
Solution Spinning
17.5.1
Preparation of Spinning Dope
If a polymer cannot be melt-spun, a solution must be made which can be spun.
Chemical ractions may be involved, for example the xanthogenation or acetylation
of cellulose. In general, the spinning dope is prepared in large vessels, not in ex-
truders. Filter presses for very ne ltration are included in the equipment setup
and de-aeration is carried out in a storage tank just before pumping the solution to
the spinnerets.
Solution spinning implies the handling of large quantities of solvent. At a poly-
mer concentration of 20% the total mass ow for dry spinning is ve times higher
than the polymer mass ow. For wet spinning there is a very large additional ow
of nonsolvent from the spinning bath.
17.5.2
Dry Spinning
The principle of dry spinning is shown in Figure 17.16. Dry spinning is not widely
applied; cellulose acetate bers are dry-spun, and whereas acrylics and polyvinyl al-
cohol can be dry spun, wet spinning is preferred.
The gas in the column is preferably hot nitrogen when ammable organic sol-
vents are used. If the solvent is water (for poly(vinyl alcohol)), hot air can be used.
The column height is limited to about 5 m and the residence time of the running
laments in the column is about 1 s, during which most of the solvent must be
removed from the laments. Complete removal is not necessary because at a high
polymer concentration the laments solidify by gelation and can then be handled.
Removal of solvent can be completed in later process steps, for example during
additional drawing.
Control of gas ows in the column, avoiding turbulence or sticking of laments,
is important. Therefore, the hot gas ow would often be downward rather than in
944 17 Fibers
countercurrent, and spinning holes must be a few millimeters apart, as in melt
spinning.
Evaporation of solvent is a relatively slow process, slower than cooling in melt
spinning. It is therefore essential that the spinning laments are thin. The com-
mon approach is to use small spinning holes (50100 mm) and apply a low draft
in the spin-line. For example, both the extrusion speed from the holes and the
exit speed from the dry-spinning column would be around 300 m min
1
. Even a
draft below 1 is possible, which means that the die swell eect is not completely
undone.
Another approach is a high-draft process, spinning from large holes (500 mm)
and taking up the yarn at relatively high speeds. For example, the extrusion speed
through the holes could be 2050 m min
1
and the exit speed around 500
m min
1
, which implies a draft of 1025. The draft in the spin-line is viscous
ow and only limited orientation is built up, a situation completely comparable
with melt spinning.
17.5.2.1 Cellulose Acetate
There are two types of cellulose acetate bers. When all three hydroxyl groups per
cellulose unit (see Section 17.5.3.1) are acetalized, cellulose triacetate is obtained.
Cellulose triacetate is spun from dichloromethane (DCM) plus 515% methanol
Fig. 17.16. Scheme for dry spinning (reproduced from Ref. 6):
1, metering pump; 2, spinneret; 3, spinning bundle; 4, drying
column; 5, 6, 7, take-up system; 8, 9, inlet and outlet of drying
gas.
or ethanol. Triacetate is a small product, mainly in the form of yarns with low titers
for textile applications.
Cellulose acetate contains approximately 2.5 acetate groups per cellulose unit,
and is actually produced by partially hydrolyzing the triacetate. The polymer is
spun from a solution in acetone/water (approximately 95:5). With a large excess
of drying air it is possible to remain below explosion limits. Nevertheless, all oper-
ations are carried out in closed equipment.
Secondary acetate has a remarkably poor crystallinity, in fact too low to survive
in a strong interber competition for textile applications. The main application of
cellulose acetate is as tow in cigarette lters.
17.5.2.2 Acrylics
Most acrylic bers are wet-spun, but dry spinning is also applied. The most com-
mon solvent is dimethylformamide, DMF. The polymerization of acrylics can also
be carried out in DMF and the polymerization solution can then be directly spun.
The boiling point of DMF is 153
C, making complete removal of solvent in the

spinning column almost impossible. Most dry-spun acrylic production is staple
ber, and the remaining solvent is then removed during tow processing.
Further information on acrylic bers is given in Section 17.5.3.2.
17.5.2.3 Poly(vinyl alcohol)
The preferred process for polyvinyl alcohol is wet spinning, but dry spinning is
also possible. The solvent is water and the polymer concentration is so high (25
50%) that solid chips can be produced at room temperature. These can be pro-
cessed in a single-screw extruder, as for melt spinning. PVA dry spinning can
be a low-draft or high-draft process. The low-draft as-spun yarn has a better draw-
ability. Very high draw ratios are possible for PVA, resulting in high tenacity and
modulus.
For more information see Section 17.5.3.3.
17.5.3
Wet Spinning
The principle of wet spinning is shown in Figure 17.17. Wet spinning is applied
for two large-scale ber products viscose rayon and acrylics and one smaller
product poly(vinyl alcohol).
The critical factor for each wet spinning process is how the coagulation process
in the laments proceeds. In the ternary diagram shown in Figure 17.18 the three
corners represent polymer (P), solvent (S), and non-solvent (N, from the spinning
bath). SD is the spinning dope composition on the line PS. The hatched area is
where phase separation takes place.
The route from SD into the separation region will determine how the coagula-
tion will proceed. (Note that a path on the line SP represents dry spinning: solvent
is removed from the ber and the polymer concentration is increased; there is no
coagulation but there is gelation of the system.) If the amount of nonsolvent enter-
946 17 Fibers
ing the ber is relatively small in comparison with the ow of solvent out of the
ber (path 1), phase separation will occur at high polymer concentrations. A homo-
geneous, dense structure will be formed; the continuous phase is polymer-rich.
This takes a long time, however, because diusion of solvent will become slower
at higher polymer concentrations. The opposite occurs along path 2: nonsolvent
enters relatively rapidly into the ber and coagulation occurs at low polymer con-
centrations. A heterogeneous, porous structure is formed; the continuous phase
has a low polymer concentration and the ber will be very weak. Path 1 is pre-
ferred, but ber formation is relatively slow then.
Fig. 17.17. Scheme for wet spinning (reproduced from Ref. 6):
1, metering pump for spinning dope; 2, spinneret; 3, spinning
bundle; 4, spinning or coagulation bath; 5, godet; 6, 7, inlet
and outlet of spinning bath; 8, drawing bath; 9, 10, take-up
system.
S
P N
SD
1
1 2
Fig. 17.18. Ternary diagram for wet spinning: P polymer,
S solvent, N nonsolvent, SD spinning dope. 1, 2,
coagulation paths (see text).
It is noteworthy that coagulation is the general term for the solidication pro-
cess in wet spinning, regardless of whether the solidication process is heteroge-
neous (coagulation) or homogeneous (gelation). Even aramid spinners use the
word coagulation (see Section 17.7.1.1).
In any case, solvent diusion and coagulation will be more rapid in the skin
than in the core of laments. Skin formation is an inherent problem for wet spin-
ning (and also for dry spinning). The main eect is that the laments collapse: the
original round cross-section is transferred into a dog bone shape. Further informa-
tion is available in Ref. 6, Chapter 4.
17.5.3.1 Viscose Rayon
O
H
H
O
H
OH H
OH
H
O
CH
2
OH
n
(1) Cellulose
It is amazing to see how complicated the technology is for this rst large-scale
man-made ber. The complications are caused by the insolubility of cellulose (1).
Chemical modication was necessary to make the polymer spinnable. The rst
attempt was nitration of the hydroxyl groups, but cellulose nitrate proved more
useful as gunpowder than as a basis for ber manufacure. Xanthogenation proved
more successful, although the rst attempts were aiming at producing carbon la-
ments for electric lamps, rather than textile bers.
In the modern process (Figure 17.19), sheets of wood pulp cellulose are swollen
in concentrated alkali and alkali cellulose is formed [Eq. (7), writing CellOH for a
cellulose hydroxyl group].
CellOH NaOH ! CellONa H
2
O 7
The sheets are shredded and the white crumbs are aged, which implies depoly-
merization to a molecular weight which is suitable for textile applications or tire
cord. The material is then treated in closed equipment (batchwise or continuous)
with carbon disulde in order to xanthate the cellulose [Eq. (8)].
CellONa CS
2
! CellOCS
2
Na 8
Byproducts give an orange-yellow color: yellow crumbs are formed. The degree
of xanthation (of cellulose) is low: fewer than 0.5 hydroxyl groups need be derivat-
ized to accomplish dissolution in dilute alkali. The polymer concentration for a tex-
tile yarn would be around 9% and the alkali concentration 56%. For a tire cord
the polymer/alkali ratio is lower, both concentrations being 7%, for example. The
948 17 Fibers
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o
r
d
p
r
o
c
e
s
s
)
.
spinning solution is then ripened, which implies a redistribution and slight reduc-
tion of xanthate groups. The eventual degree of xanthation would be below 0.3 for
a textile yarn and close to 0.4 for a tire cord. After ne ltration and de-aeration the
viscose spinning dope is spun into an acid bath, where the cellulose is regenerated
[Eq. (9)].
2 CellOCS
2
Na H
2
SO
4
! 2 CellOH 2 CS
2
Na
2
SO
4
9
The spinning bath for viscose contains sulfuric acid (at about 10% concentration)
for the decomposition of the xanthate and neutralization of the alkali. Sodium sul-
fate is formed anyway, but is also dissolved in large quantities (about 20%) in the
spinning bath to control the coagulation process. A further addition is zinc sulfate
(< 3%), again to control coagulation.
The spinning solutions caustic plus acid are highly corrosive. The spinnerets
are made of gold/platinum, round, with diameters of a few centimeters only. The
capillaries are small (5075 mm) and close to each other (< 1 mm). The number of
holes must be large because the standard lament titer of rayon yarns is around
1.7 dtex. The freshly spun laments are very weak and a tube is often placed
around the spinning bundle.
Drawing is always carried out in a combined process, in most cases at least
partly before the complete decomposition of the xanthate groups. Draw ratios
may be low for rayon staple ber. Tire cord is drawn to an elongation of 1213%
and a tenacity of about 500 mN tex
1
. Note that these are conditioned values; in a
wet state the high-modulus character is lost; the tenacity becomes lower (400
mN tex
1
) and the elongation much higher (25%).
A few alternatives for the derivatization of cellulose have been found recently: di-
rect dissolution of cellulose has been developed. For textile lament yarns, dissolu-
tion in N-methylmorpholine oxide (NMMO) is possible. The process is applied by
Courtaulds and Lenzing. A solution in formic acid/phosphoric acid was found to
have lyotropic behavior and tire yarns with very interesting properties could be pro-
duced (patented by Michelin). It even proved possible to use phosphoric acid alone
(patented by AKZO), but the process was never commercialized.
Yarns spun from solution have a dierent crystalline structure (cellulose II) than
natural cellulose (cellulose I). The dierence is that cellulose I has two intermolec-
ular hydrogen bonds formed parallel to the glucosidic bond, whereas cellulose II
has only one parallel hydrogen bond. The main eect is a large dierence in crystal
modulus: 130180 GPa for cellulose I, 6090 GPa for cellulose II. All attempts to
produce man-made bers with a cellulose I structure, and hence an even higher
modulus, have remained unsuccessful, however.
Applications of viscose rayon The main application of rayon is as staple ber.
Spinning is carried out from clusters of spinnerets and bundles are processed col-
lectively as a tow. Rayon staple ber is applied unblended, but is also used in
blends with cotton and/or polyester, in outerwear. Filament yarns have become a
950 17 Fibers
minor product; one may still nd them applied in lining fabrics. Rayon tire cord
has survived the strong competition with polyester, at least in Europe. Rayon has
an unproblematic adhesion to rubber, a high modulus, and a perfect fatigue behav-
ior, and therefore remains the ideal reinforcement for high-speed radial tires.
17.5.3.2 Acrylics
The crystallinity of acrylic bers is rather ill-dened. Polyacrylonitrile (PAN) is
known to be atactic, but the very strong polar interactions of the nitrile groups
give PAN a denite crystalline behavior. In water a melting endotherm slightly be-
low 200
C is measured and an extrapolated dry melting point could be as high as

320
C, above the decomposition temperature. This nding of melting point de-

pression by water has led to suggestions that PAN could be melt-spinnable when
water, or another plasticizer, is added to the polymer. So far, the technique has
been considered too complicated for technical realization, however.
In practice, the crystalline character of pure PAN is a problem for dissolution,
drawing, and dyeing in various stages of acrylic processing. Therefore comono-
mers (in acrylics) are added to reduce the crystallinity. Yarns containing b85%
acrylonitrile are called acrylics. Comonomers that are often used are methyl ac-
rylate and vinyl acetate. Yarns with less than 85% acrylonitrile are called moda-
crylics. In this case halogen-containing comonomers are often used, such as vinyl
chloride, vinylidene chloride, and vinyl bromide, obviously to improve the ame re-
sistance of the yarn.
For dissolution of acrylics highly polar solvents are required to disrupt the inter-
molecular bonds between the nitrile groups. Frequently used organic solvents are
dimethylformamide (DMF) and dimethylacetamide (DMAc). The polymer concen-
tration is about 20%. The spinning bath is water, in most cases mixed with the or-
ganic solvent being used, in order to slow down the coagulation and precipitation.
An alternative is the use of concentrated solutions (50%) of sodium thiocyanate
(NaSCN) in water. The spinning bath then is a dilute solution of NaSCN in water.
Acrylic solutions have the tendency to gel with time, a thermoreversible process.
For spinning it is an advantage to have gelation rather than precipitation of the l-
aments. As a result of the gelation, as-spun acrylic laments maintain the cross-
section of the spinning holes, but are very porous. A density of 0.40.5 g cm
3
is
usual, while the density of a drawn and dried ber is 1.17 g cm
3
. The voids are
very small (0.11 mm), and collapse during drawing and drying.
Most acrylic production is for staple ber. Huge spinning plates with up to
60 000 holes are used, and tow drawing and crimping are included in the process.
Drawing takes place in a hot-water bath, which is possible because the wet glass
transition temperature is about 75
C. The above-mentioned porosity of acrylics is

used to control luster. Dried yarns are very lustrous but can be made dull again by
a hot wet treatment.
Applications of acrylics The largest application is in ber yarns for clothing (espe-
cially sweaters), home furnishings, covers, and blankets. The lament titers vary
between 1.3 and 17 dtex, the higher titers being for carpets. Tenacities are modest
(200300 mN tex
1
), and elongations are between 30 and 60%. The tenacity may
seem low, but acrylics are still clearly stronger than wool.
Filament textile acrylics seem to have lost the competition with polyester and
nylon.
There is an interesting industrial application in outdoor fabrics, based on the
perfect UV stability of acrylics, which are used for awnings, tents, automobile up-
holstery, and outdoor furniture. These products are often pigment-dyed, for better
lightfastness. A further step is when hot drawing is applied. Yarns with low como-
nomer levels can be drawn to ratios of 10 or more. Such yarns are used as precur-
sors for carbon ber production (see Section 17.7.3), but may also be applied as
such, for asbestos replacement.
17.5.3.3 Poly(vinyl alcohol)
PVA is produced by hydrolyzing poly(vinyl acetate). PVA ber is an almost exclu-
sively Japanese product; some production takes place in Korea and China, based on
Japanese technology. The ber has Vinylon as a general name and Kuraray is the
largest producer (Kuralon). Poly(vinyl alcohol) is water-soluble, which makes the
choice of a solvent easy. And, of course, it has proved possible to make the bers
water-insoluble.
Wet spinning solutions contain about 15% polymer and are spun above 70
C,
because otherwise premature gelation would take place. The spinning bath (for
PVA) is an almost saturated solution of sodium sulfate in water, at 4050
C. Note
that this is not the usual solventnonsolvent situation. Diusion of water out of
the lament is rapid, diusion of the salt into the laments relatively slow. The
polymer concentration increases and solidicaton is by gelation. The solidication
is slow, however much slower than for viscose rayon, for example. Therefore, the
spinning speeds are low. Fairly exceptional are the vertical spinning machines,
spinning upward, with the spinning bath moving in co-current ow in a tube
around the yarn bundle (see Figure 17.20). The spinning holes are small (100
150 mm).
Hot drawing of PVA, at 210240
C, takes place after drying. Draw ratios (> 10)

and tenacities achieved (> 900 mN tex
1
) are high, and the resulting yarns are
highly crystalline (4050%) and no longer water-soluble. For staple ber the draw
ratios may be lower, and a heat treatment for 0.53 min at 210230
C is given to
further crystallize the bers.
For complete insolubility in water, the hydroxyl groups can be made to react with
formaldehyde to a maximum degree of 85%. This takes 1020 min, however, and
only seems interesting in tow processing.
An alternative spinning bath for PVA contains alkali (NaOH, b20%), which pen-
etrates more rapidly into the laments. The polymer concentration in the spin-
ning dope is somewhat higher (18%) and higher molecular weights are used.
The laments solidify more homogeneously and remain round. This process al-
lows even higher draw ratios than spinning in a sulfate bath, for example
DR > 15 and tenacity > 1300 mN tex
1
. For further improvement of water insolu-
952 17 Fibers
bility, small amounts of boric acid may be added to the spinning solution, inducing
crosslinking between chains. This seems to be the preferred route to high-tenacity
lament yarns. The term gel spinning is often used for spinning PVA according
to this route (see Section 17.7.2).
Applications of PVA The largest application of PVA bers is in paper and non-
woven fabrics, where a fraction of water-soluble ber is often used as a binder. Fur-
ther applications are in twines, ropes, fabrics (tatami mats), and tarpaulins. Gel-
spun, very strong, PVA bers have become an important replacement for asbestos
in cement reinforcement.
PVA lament yarns are used almost exclusively in industrial applications where
high strength is important, such as in shing nets, ropes and cables, reinforce-
ment of (high-pressure) hoses, and conveyor and transmission belts. PVA is not
suitable as a tire cord, however, because of its inadequate fatigue behavior.
17.6
Comparison of Melt and Solution Spinning
Having given a rough technical outline of melt and solution spinning, we can now
make a comparison between the speed spinning controlling mechanisms for the
two processes: cooling for melt spinning, and diusion of solvents for solution
spinning. We rst make a simple analysis of the ber formation processes, neglect-
ing sublayer eects outside the laments. An example of the situation is shown for
cooling (melt spinning) in Figure 17.21 (at the top).
Initially, the temperature will be at throughout the lament (at the spinning
temperature, for example 300
C) and the surrounding cooling air temperature is

assumed to be constant (20
C). Gradually a temperature prole will be formed in

Fig. 17.20. Spinning machine for PVA (reproduced from Ref.
2c): 1, vertical spinning machine, spinnerets at the bottom; 2,
3, 4, spinning bath circulation; 5, 6, godets; 7, washing; 8,
drying; 9, drawing; 10, heat treatment; 11, winder.
the lament; the surrounding air remains at 20
C. This situation is shown in the

gure. For solidication of the laments we would like to have a temperature in
the center of, say, 100
C. The initial temperature dierence (300 20 280
C)
must be reduced to 100 20 80
C. In relative terms, which are used in a Fourier

analysis of such a cooling process, the desired dimensionless temperature is
80=280A0:3.
For solution spinning, the analysis proceeds similarly, but now in terms of con-
centrations instead of temperatures. For example, we assume an initial solvent
concentration of 0.8 (polymer concentration 20%) and solidication at c 0:3
0 D/2
T
center
T
outside
0 D/2
c
center
c
outside
Cooling of a filament
Fourier number Fo=at D
2
a ~ 10
6
m
2
s
1
Simple approach: no sublayer
Extraction of solvent from a filament
Fourier number Fo=Dt/ D
2

D ~ 10
9
m
2
s
1

Realistic approach: sublayer
Fig. 17.21. Comparison of melt and solution spinning.
954 17 Fibers
(70% polymer concentration). We assume the spinning bath consists of pure non-
solvent; hence the solvent concentration c 0 around the laments. The desired
dimensionless concentration then is: 0:3=0:8A0:375, not very dierent from
the value for the dimensionless temperature in the cooling process.
We proceed to the Fourier analysis for the cooling and extraction/diusion pro-
cesses. The dimensionless Fourier number for cooling is Fo at=D
2
, with a
thermal diusivity (a l=rC
p
), t time required for cooling and D diameter
of a lament. The thermal diusivity is of the order of 10
6
m
2
s
1
. The Fourier
number for diusion processes is Fo Dt=D
2
, with D diusion coecient,
t time and D diameter. Diusion coecients in dilute systems are of the order
of 10
9
m
2
s
1
.
The dierence by a factor of 1000 between the values of thermal diusivity and
diusion coecient can only be compensated for by adapting the values of t=D
2
.
As a rst approximation, laments in solution spinning should, for example, be
made ten times thinner and process times ten times longer than in melt spinning.
For cooling we had a dimensionless temperature of 0.3. A Fourier plot then
shows a value of Fo at=D
2
0:1. If we have an average diameter in the cooling
process of 250 mm (2:5 10
4
m) we can calculate the necessary cooling time:
t A6 ms. For wet spinning we would nd t A50 ms. Experienced spinners will
say that the typical dierence between melt and wet spinning is correct, but that
both answers are one order of magnitude wrong. Both melt spinning and wet spin-
ning are slower by a factor of about 10 than calculated with our model, which is too
simple.
The mistake that we have made is obvious: we have neglected the speed limita-
tion in the sublayer, or, even worse, in sublayers that touch each other in a bundle
of laments. Figure 17.21 (at the bottom) is a graph showing a prole in the la-
ment and in the sublayer around the lament. The example is for concentration as
the parameter, for solution spinning, but the same graph can be used for cooling
by using T instead of c.
Exact calculations become much more complicated, but a few qualitative state-
ments can be made. In sublayers we are dealing with diusion: of molecules in
an air layer (cooling process and dry spinning) or of solvent molecules in a liquid
layer (wet spinning). The mobility of molecules in a gas is much greater than in a
liquid. For the three types of processes we thus have:
melt spinning: fast conduction in the lament, fast diusion in the gas sublayer;
dry spinning: slow diusion in the lament, fast diusion in the gas sublayer;
wet spinning: slow diusion in the lament, slow diusion in the liquid sub-
layer.
After all, the consequences for lament titers and diameters and process speeds do
not dier very much from our rst rough estimate. Melt-spun laments may have
a titer of 15 dtex, but 2030 dtex is still possible. Their eventual diameters range
from 10 to 50 mm, but they are spun from much larger holes. Dry- and wet-spun
laments often have a titer of 1.7 dtex (13 mm), and are usually spun from holes
smaller than 100 mm. Wet spinning speeds are limited to a maximum of 300400
m min
1
, whereas melt-spun yarns can be wound at speeds up to 8000 m min
1
.
Dry-spinning speeds are in between, at 5001000 m min
1
. Typical data are shown
in Table 17.6.
Not surprisingly, there are always exceptions to the rule. For example, acrylic
carpet bers up to 17 dtex are wet-spun, evidently from much larger holes and at
lower speeds than are indicated in Table 17.6!
17.7
High-modulus, High-strength Fibers
In the last three decades of the 20th century many advanced bers were developed
(see the surveys in Refs. 8 and 9). Carbon ber may be described as an inor-
ganic ber, but is produced by aftertreatment of organic bers, usually acrylic
yarns. High-modulus, high-strength bers were developed from sti-chain poly-
mers showing liquid-crystalline behavior in solution or melt. Aramid yarns spun
from solution became an important product. How exible-chain polymers can be
superdrawn was discovered, and gel-spinning of polyethylene was developed, add-
ing a valuable product to the spectrum of high-tenacity bers.
17.7.1
Air-gap Spinning
17.7.1.1 Aramids
Aramid yarns (Kevlar of DuPont, Twaron of TeijinTwaron) are produced from
poly( p-phenylene terephthalamide), PPTA (2), which is specially developed for
ber spinning and not used in any other application. DuPont had experience
with poly(m-phenylene isophthalamide) in a ber product called Nomex for high-
temperature applications. The polymer is produced in dimethylacetamide and the
solution is dry-spun. This cannot be done with the sti-chain parapara analogue
PPTA. The polymer does not dissolve in organic solvents. A special polymerization
route had to be developed, and the discovery of lyotropic behavior of concentrated
solutions in sulfuric acid then led the way to the production of a magnicent new
ber material.
Tab. 17.6. Typical process data for melt and solution spinning.
Process Typical spinning
hole size
[mm]
Average speed
in spin-line
[m min
C1
(m s
C1
)]
Height of spin-line
or length of bath
[m]
Residence time
in spin-line
[s]
Melt spinning 250500 3000 (50) 5 0.1
Dry spinning 50100 300 (5) 5 1
Wet spinning 5075 30 (0.5) 0.5 1
956 17 Fibers
N N
O O
H H
n

(2) PPTA (Kevlar, Twaron)
The polymerization of PPTA starts at low temperature (10
C) with a solution of
p-phenylene diamine (PPD) in a mixture of N-methylpyrrolidone (NMP) and cal-
cium chloride [10]. The second monomer, terephthaloyl dichloride, TPC, is in-
jected as rapidly as possible. A fast condensation reaction takes place, hydrochloric
acid being the condensate. Much heat is evolved and a high cooling capacity is re-
quired to keep the temperature below 50
C. An oligomer is formed that becomes

insoluble in the reaction medium at a degree of polymerization of about 10. In the
rubbery mass further condensation must be enforced by vigorous mixing with
a powerful stirrer. After neutralization, washing, and drying a yellow polymer,
with a degree of polymerization of 70100, is obtained in an irregular powder
form.
Dissolution of the polymer powder in water-free sulfuric acid can be achieved by
freezing the acid and blending it with the powder. This dry blend melts at 60
70
C. An alternative is direct dissolution in a kneader.

The key invention for aramid spinning was the discovery of the liquid-crystalline
behavior (lyotropy) of PPTAsulfuric acid systems at polymer concentrations above
10%. Morgan (Monsanto) was the rst to describe spinning of fully aromatic poly-
mers from concentrated solutions (in organic solvents), but did not report their
liquid-crystalline behavior [11]. Kwolek (DuPont) patented optically anisotropic
solutions of PPTA in sulfuric acid [12] and Blades (DuPont) further specied the
use of an air gap in the spinning process [13].
An example of the liquid-crystalline behavior is shown in Figure 17.22, in which
the viscosityconcentration relationship of a solution in a shear eld is plotted. Do-
mains of oriented chains are formed and these domains are easily oriented in a
ow eld (like tree-trunks in a river). An elongational deformation is much
more eective for achieving a high orientation. In Figure 17.23 the elongational
phenomena during spinning, and their eect on molecular orientation, are shown.
The polymer solution is spun at about 85
C. The polymer concentration is about

20%. Domains ow into the spinning hole and orient. The spinning holes are
shaped to promote elongational ow: they have a conical entrance and a tapered
capillary. In this way almost complete orientation is achieved. The laments are
quenched in cold water, which should not touch the spinneret because the spin-
ning solution would then immediately freeze in. This makes an air gap between
the spinneret surface and spinning bath necessary. An air gap is more often ap-
plied in other wet spinning processes, but in this case there is an additional very
important function. A draft of 515 times is applied over the air gap of about
1 cm. The solidication in the cold bath is immediate: the end speed of the process
is already achieved at 1 mm below the water surface. The elongational rate in the
air gap is comparable with the situation of a drawing neck in cold drawing of
Fig. 17.22. Lyotropic behavior of PPTA in sulfuric acid.
Fig. 17.23. Orientation of aramid in spinning hole and air gap.
958 17 Fibers
exible-chain polymers. One can imagine how benecial this draw over the air gap
is, to complete the molecular orientation in the laments.
Solidication of the aramid laments is called coagulation but is in fact a
simple freezing-in of the solution. It is not a speed-limiting step. The subse-
quent removal of sulfuric acid from the solid laments in the washing process is
diusion-controlled, however, and hence relatively slow.
Thus, the rest of the spinning process is careful washing, neutralization, further
washing, drying, and winding. The standard titer of aramid yarns is 1670 dtex f
1000 (1.7 dtex lament titer). The elongation at break is around 3%, the tenacity
2100 mN tex
1
, and the modulus b50 N tex
1
(75 GPa).
Filaments of 1.7 dtex and density 1.45 g cm
3
have a diameter of 12 mm. Assum-
ing a draft over the air gap of 515 and a polymer concentration of 20%, and
neglecting changes in density, we can make an estimate of the spinning hole diam-
eter by means of Eq. (10); hence D
hole
60100 mm.
D
hole
D
lament
DR=c
0:5
10
Fibers with an even higher modulus are produced by a post-treatment of PPTA
bers above 400
C under high tension, reducing the elongation to 1.52% and en-

hancing the modulus to above 100 GPa. Special bers for ballistics may be spun
through smaller holes, and have ner laments, for example <1 dtex.
The aramid process as described is a wet spinning process, but a fairly strange
one. Extrusion, polymer lines, and ltration are like those in melt spinning. The
heart of the spinning process, spinneretair gapspinning bath or coagulator,
is very specic for aramid, but would also be found on machines for other lyotropic
systems. The section after the coagulation again deviates from a normal wet spin-
ning process. Since the laments are not deformable, high tensions can be applied
but drawing is not necessary.
The construction material for PPTA in the melt-spinning section can be a nor-
mal steel because 100% sulfuric acid is not very corrosive. In places with high
shear (extruder screw, spinning pumps), nitrated steel, stainless steel, or even ce-
ramic inserts will be used, however. As soon as the acid becomes diluted, corrosion
becomes very severe. Spinning plates are therefore made of gold/platinum or with
capillary inserts of this material. The construction materials for the spinning bath
and washing sections are stainless steel, PVC, PP, or glass.
Technora There is one aramid product with a deviating composition. Teijins
Technora (3) is produced from terephthaloyl dichloride (TPC) and a 50:50 mixture
of two aromatic diamines: PPD (as in PPTA) and 3,4
0
-diaminodiphenyl ether. This
kinked monomer has the advantage that the polymer remains dissolved in the
polymerization solvent (NMP/CaCl
2
). The solution can be spun directly, but is not
liquid-crystalline! After washing and drying the yarn is drawn at high temperature
(> 500
C) to a high ratio (> 10). In fact Technora is an example of superdrawabil-

ity (see Section 17.7.2), which is surprising for a fully aromatic polymer, but the
high temperature makes the chains drawable.
N N
H H
O
O
N
N O
H
H

n

x y
(3) Technora (x=y 0:5=0:5)
Applications of aramids Large elds of application for aramid yarns are: antibal-
listics (bulletproof vests, armored plates); reinforcement of rubber (high-pressure
hoses, conveyor and transmission belts; limited application in automobile tires
because the material is expensive, but wide application in bicycle tires, on account
of its puncture resistance); ber-reinforced composites (aircraft interiors, sports
goods); reinforcement of optical cables; ropes and cables; protective clothing (re-
workers, metalworkers, butchers). Maybe the largest application of aramid ber,
however, is asbestos replacement, in clutches, brakes, and gaskets. To this end la-
ments are cut into short bers and brillated in a mill. The resulting pulp can be
blended with the resins and minerals to produce the clutch faces and brake linings.
For replacement of asbestos in gaskets lament yarns can be applied, in the form
of thick cords or fabrics.
17.7.1.2 Other Liquid-crystalline Polymers
Higher moduli and strength than in aramid can be reached with polymers having
even stier chains. We may call them semi-ladder polymers. Examples are the
polyazoles polybenzothiazole (PBT, 4) and polybenzoxazole (PBO, 5); the latter
yarn is produced on small scale by Toyobo (Zylon). An other example is M5 (6),
a semi-ladder polymer with higher polarity, yet having a very high modulus; the
product is developed by Magellan Systems International, in the USA. PBO and
M5 are polymerized in polyphosphoric acid and air-gap spun from this solution.
N
S S
N
n

N
O O
N
n

(4) PBT (5) PBO
N-H
N N-H
N
N
n

O H
OH
(6) M5
960 17 Fibers
17.7.2
Gel Spinning
17.7.2.1 Theory
Some exible polymers can be drawn to (much) higher ratios than are achieved in
a standard process. In the 1970s many publications were issued on the superdraw-
ability of, especially, polyethylene. Ward and co-workers (University of Leeds, UK)
showed [14] that polyethylene can be drawn 30 times, and that the modulus in-
creased linearly with the draw ratio, up to values of 60 GPa, but the tenacities re-
mained modest, a1 GPa. The undrawn laments or lms (strips) were melt-spun.
Too high a molecular weight gave spinnability problems, and, moreover, lower mo-
lecular weights were found to be more easily drawable. Careful drawing seemed to
be the key to high drawablity, in the sense that the drawing speed had to be low
and/or the drawing path long. In other words, one should have a low elongational
rate, _ ee dv=dx. For comparison, elongational rates in common drawing processes
of melt-spun yarns are in the order of 50500 s
1
. For superdrawing, values of
0.11 s
1
are preferred, for example a homogeneous drawing on a hotplate of 1 m
at a speed of 1 m s
1
(60 m min
1
).
Superdrawability also proved applicable to polypropylene and slightly more polar
polymers, such as polyoxymethylene (POM) [15].
At the same time Pennings (DSM, later of the University of Groningen, The
Netherlands) studied the ber formation from dilute solutions of high molecular
weight polyethylene. He started with bers formed in a Couette device: these were
stirring-induced ber crystals, with the famous shish-kebab structure [16]. The
best properties were obtained when bers were slowly withdrawn from a gel layer
on a rotor. The molecular weight was above 10
6
, the polymer concentration about
1%, the ber growth rate below 1 m min
1
, the moduli around 125 GPa [17], and
tenacities far above 1 GPa.
Smith and Lemstra (DSM, The Netherlands) combined the ideas of superdraw-
ability and working with dilute solutions of (ultra-)high molecular weight poly-
ethylene, and added the essential function of a continuous spinning process [18].
Gel spinning was born.
To explain the concept of gel spinning and superdrawing, it is necessary to intro-
duce the notion of entanglement of chains. If two chains form a loop, the disentan-
gling of one of those chains depends on the length between the entanglement
point and the chain end. A short chain end will fairly rapidly diuse through the
network of neighboring polymer chains and slip through the entanglement point,
without chain break. The reptation time necessary for disentanglement scales
with (MW)
3
, according to De Gennes [19]. For a polyethylene chain end with a mo-
lecular weight of 100 000 (approximately 4000 monomer units), the time would al-
ready be in the order of one second, a very high value for a drawing process.
The consequences for gel-spinning are:
A high molecular weight is required for an eventually high draw ratio. Draw ratio
scales as DR@MW
0:5
. In gel spinning the molecular weight is higher than in
superdrawing of melt-spun polyethylene by a factor of about 10. One may thus
expect a draw ratio of 3010
0:5
A100, which is close to reality.
The number of entanglements must be reduced, but a few should remain to give
the material coherence. This is only possible by working from a dilute solution.
Concentrations of 510% seem realistic; for ultra-high modulus products an
ultra-high molecular weight (g10
6
), and an even lower concentration (25%),
will be selected to keep the material spinnable.
Figure 17.24 depicts a scheme for the gel spinning process.
17.7.2.2 Gel Spinning of Polyethylene
Gel-spun polyethylene is produced by DSM in cooperation with Toyobo (Dyneema)
and Honeywell, formerly Allied Signal (Spectra). From the relevant patents it is
fairly obvious that dierent solvents are used: a volatile solvent in the Dyneema
process and a nonvolatile solvent in the Spectra process.
A nonvolatile solvent must be completely removed before drawing, by extraction
with a volatile solvent. The dried laments have a xerogel structure, a dry, porous
structure which collapses during drawing. A volatile solvent can be partly removed
in the spinning step, but may well be further removed by evaporation and squeez-
ing out in the drawing step.
Dyneema yarns have lament titers of 12 dtex, Spectra laments are coarser
(411 dtex). Filaments of 2 dtex with a density of 0.97 g cm
3
have a diameter of
16 mm. How is this diameter produced? If we assume a draw ratio of 100 and a
concentration of 10% we can calculate the diameter of the undrawn gel laments
from Eq. (10) to be D
gel; undrawn
D
drawn
DR=c 16100=0:1
0:5
506 mm. We
High molecular weight, dilute solution, few entanglements

Gel formation by crystallization

Extraction of solvent (before or during drawing) superdrawing

Gel crystals are melted and rebuilt, entanglements give coherence
Fig. 17.24. Scheme for gel spinning.
962 17 Fibers
may further take into account that the density of the spinning solution is lower
than that of the drawn laments (@0.8 g cm
3
versus 1.0 g cm
3
), and that there
may be some draft in the spin-line. A realistic estimate of the spinning hole diam-
eter will thus be about 1000 mm, greater than in most melt spinning processes!
The spinning solution extruded from the large holes is above 100
C, in order to
keep the polymer in solution and to keep the viscosity acceptable. Fiber formation
for gel spinning by quenching is relatively rapid: solidication is by crystallization,
rather than by evaporation or extraction of solvent. Complete removal of solvent
from the thick laments proceeds much more slowly. The quench liquid can sim-
ply be water and the spinneret cannot be immersed in the water bath because the
spinning solution would then freeze in. An air gap must be used, as in aramid
spinning, but without the function of increasing the molecular orientation.
The extraction step depends on the solvent used. The nonvolatile solvent (high-
boiling, and acting as a plasticizer) must be removed completely before drawing.
One can imagine that most of a volatile solvent would be removed in the initial
stages of the drawing process (at 100130
C): at least, this is how DSM (and

Toyobo) illustrate it in a simplied process scheme presented in articles and
folders (see Figure 17.25).
The process scheme for gel-spun PE shows a stirred vessel for making up the
spinning solution, but the use of a kneader in a continuous operation should
be possible. It also suggests the integration of spinning and drawing, but this is
improbable. As discussed in Section 17.7.2.1. the superdrawing process must
be careful and slow. Even for very long drawing ovens, an end speed of
200 m min
1
seems a limit. (As an example, at this speed, 3.3 m s
1
, and an
oven length of 33 m one would have an elongational rate ( _ ee dv=dx) of 0.1 s
1
).
The spinning speed would then have to be about 23 m min
1
. This is technically
dicult and economically unattractive. The output per hole would be as low as 0.4
g solution min
1
(0.04 g polymer per minute). A ten times higher output is tech-
nically feasible. The technical implication then is that spinning and drawing must
Fig. 17.25. Gel spinning process (reproduced from Ref. 8).
be separate steps; there should be ten times more drawing than spinning posi-
tions. This can be realized if a collective drawing process is used, such as a warp
of yarns drawn in a wide oven.
Applications of gel-spun PE Many applications overlap with those of aramid.
Polyethylene has the advantage of its lower density and often a higher tenacity.
This is important in ballistics and protective clothing, where Dyneema and Spectra
nd wide application. A special feature in armored plates is the Spectra Shield
or Dyneema UD construction: arrangements of laments in unidirectional layers
bonded by thermoplastic layers in between; the UD layers are arranged crosswise.
This construction is more eective than woven structures in ballistic protection.
A second large application, especially of Dyneema, is in marine twine, ropes,
and nets, where it replaces polyamide and polyester yarns. Outstanding tenacity,
abrasion resistance, UV stability, and low density (oating in water) give it a com-
petitive edge, even at about ten times the selling price of the melt-spun yarns!
Gel-spun polyethylene is too low-melting (about 140
C) to be applied in rubber
reinforcement. In composites the curing temperature should not exceed 130
C,
and a surface treatment is required for sucient adhesion. Finally, performance
under constant load is restricted because of creep limitations.
17.7.2.3 Other Gel-spun or Superdrawn Fibers
The ultra-high draw ratios for polyethylene are not found for any other polymer,
which may not be surprising because the interchain interactions in polyethylene
are so low. This makes molecular rearrangements in a drawing process easy. This
polarity concept was worked out by Smook and co-workers [20]. They took values
of maximum draw ratios from the literature and their own experience. For the
value of the polarity of a polymer the cohesive energy was taken, which is the en-
ergy required to make a polymer chain completely free from interactions with its
neighbors. This factor was made dimensionless by taking the ratio with RT
d
, T
d
(K) being the drawing temperature, and R the gas constant. The best relationship
was found to be Eq. (11), where l represents the draw ratio DR; this is plotted in
Figure 17.26.
ln l
max
360 expE
coh
=RT
d
0:5
11
Note the maximum value for polyethylene (PE) at ln l 4:6, implying a draw ratio
of 100. The polar polymers, polyester and polyamide(s), which are not superdraw-
able and not candidates for a gel spinning process, are at the other extreme. There
is an interesting group of polymers with intermediate polarity and drawability,
however: polypropylene (PP; DR 47.5), poly(vinyl alcohol) (PVA; DR 30), poly-
acrylonitrile (PAN; DR 28), poly-l-lactic acid (PLLA; DR 20).
The very good drawability of polypropylene was mentioned when discussing
that polymer; it is not gel-spun, but-melt spun bers are also highly drawable.
Poly(vinyl alcohol) is wet-spun, and special versions of this process, at Kuraray,
964 17 Fibers
with high molecular weight polymer, are indeed gel-spun; the bers replace asbes-
tos in cement reinforcement. Polyacrylonitrile, or a copolymer with a low comono-
mer level, is drawn 1015 times in the production of precursor for carbon ber.
17.7.3
Carbon Fiber
Carbon bers are not directly spun but are the product of a complicated aftertreat-
ment. Nowadays, most carbon bers (90%) are produced from an acrylic precursor.
Cellulose rayon is no longer applied as a precursor. Production from pitch has
been developed, but is still a small-volume business.
17.7.3.1 Carbon Fiber from PAN
Most textile acrylics contain 1015% comonomers. For carbon ber precursors
lower comonomer levels are used (about 5%); comonomers are selected that pro-
mote the reactions in the aftertreatment (methyl acrylate, itaconic acid). Wet spin-
ning is preferred because the cross-section can be controlled better then. In dry
spinning skin formation can hardly be prevented and eventually the cross-section
collapses into a dog bone shape, which is not desirable in carbon ber applica-
tions. Precursor laments are drawn to much higher draw ratios (b10) than tex-
Fig. 17.26. (Super)drawability of exible-chain polymers (reproduced from Ref. 20).
tile yarns. Precursor laments must be free from solid particles; sharp ltration of
spinning solutions is therefore required. Textbooks even mention spinning under
clean room conditions.
The aftertreatment proceeds in three steps: cyclization, oxidation, and
carbonization/graphitization. All steps are carried out under tension. In the cycli-
zation step (around 200
C) N-containing rings are formed, in a ladder structure:

PAN, Orlon, is transferred into Black Orlon. This rst step is still without
loss of material. In the second step this structure is made unmeltable by careful
oxidation and stabilization, at temperatures between 200 and 300
C. Some hydro-
gen is removed, carbonyl groups and double bonds are formed, and the aromatic
character is increased. The third step is a pyrolysis reaction carried out in an inert
atmosphere, at temperatures which are gradually increased from 400 to 1700
C
and further to 2800
C. Below 1000
C most volatile products are formed, such as

H
2
O, HCN, NH
3
, CO, CO
2
, N
2
, and so on. Note that the nitrogen content of PAN
is about 28%, while the weight loss of PAN to carbon ber is about 50%.
The term graphitization is not really correct because a true graphite structure
is not formed. The graphite layers, condensed ring systems, are indeed there, but
the layers are not strictly coordinated. This mist in the coordination of layers is
called turbostratic. Nevertheless, carbon bers are often referred to as graphite -
bers, especially in the USA.
17.7.3.2 Carbon Fiber from Pitch
Pitches can be produced from petroleum and coal tar, preferably from the rst
feedstock. A useful pitch should have a mesophase character, which means that it
must contain ordered, liquid-crystalline domains. The mesophase content can be
increased by solvent extraction. A pitch would typically have a molecular weight of
1000 (20 aromatic rings) and a melting point of 300
C.
Pitch can be spun at about 325
C and must then be aftertreated. The cyclization

step necessary for a PAN precursor can be omitted in this case. Stabilization by air
oxidation and carbonization/graphitization proceeds as for a PAN precursor, but
the amount of volatiles is much lower because the pitch does not contain nitrogen.
17.7.3.3 Applications of Carbon Fibers
Carbon bers are used almost exclusively in composites. Two main types are of-
fered: one with high strength (1.93.9 N tex
1
tenacity, 140 N tex
1
modulus) and
one with a high-modulus (2.2 N tex
1
tenacity, 280 N tex
1
modulus). Carbon ber
moduli are much higher than those of aramid and gel-spun polyethylene.
17.7.4
Other Advanced Fibers
One class of HMHS bers has not been mentioned: liquid-crystalline polyesters,
thermotropic polymers, melt-spun. In the 1970s and 1980s many compositions
were studied, in most cases fully aromatic polyesters, in one case PET enriched
with large quantities of p-hydroxybenzoic acid (pHBA). Only one product sur-
966 17 Fibers
vived and became a small commercial product: Vectra(n) polymer was developed
by Celanese; the ber is now produced by Kuraray. The polymer has a 75:25 com-
position of pHBA and HNA, the latter being the code for 2,6-hydroxynaphthoic
acid. Mechanical properties are on the level of a standard-type aramid.
There are many polymers with high-temperature resistant bers, most of them
with textile properties (low tenacity, high elongation) (see Table 17.7). Their appli-
cation is in insulation, hot gas ltration, and suchlike. Large products are meta
meta aramid (Nomex, Teijin-Conex) and polybenzimidazole (PBI). Smaller prod-
ucts are poly(phenylene sulde) (PPS), several aromatic polyketones (for example
poly(ether ether ketone), PEEK) and aromatic polysulfones; see Reference 9, Chap-
ters 8 and 9.
Notation
Symbol Name Unit
a thermal diusivity m
2
s
1
c concentration (of spinning solutions) (or %)
C
p
specic heat kJ

C
1
kg
1
_ gg shear rate s
1
D diameter (of spinning holes) mm
D diusion coecient m
2
s
1
DR draw ratio
Tab. 17.7. Survey of properties of HMHS bers (PET, PA, glass and steel are included for
comparison).
Fiber Density
[g cm
C3
]
Elongation
[ %]
Tenacity
[N tex
C1
] [GPa]
Modulus
[N tex
C1
] [GPa]
Aramid (standard) 1.45 3.5 2.1 3.0 5060 7287
Aramid (HM) 1.45 2.5 (1.5) 2.1 3.0 75 (115) 109 (167)
Technora 1.45 4.4 2.2 3.2 50 72
Vectran 1.40 b3.3 2.02.5 2.83.5 4662 6587
PBO 1.56 1.5 3.7 5.8 180 280
PE (standard) 0.97 3.5 2.62.8 2.62.8 90 90
PE (HM) 0.97 33.5 ca. 3.5 ca. 3.5 120 120
C-ber, HS 1.8 1.52.0 1.93.9 3.57.0 ca. 140 ca. 250
C-ber, HM 1.8 0.7 2.2 3.9 ca. 280 ca. 500
C-ber, pitch 2.1 0.22.0 0.51.0 1.02.0 19380 40800
Polyester 1.38 1015 ca. 0.8 1.1 ca. 10 ca. 14
Polyamide 1.18 1825 ca. 0.8 0.95 ca. 5 ca. 6
E-glass 2.55 1.83.2 0.61.2 1.53.0 28 72
S-glass 2.5 4.0 1.2 3.5 35 87
Steel 7.8 a0.27 a2.1 27 210
Notation 967
E elongation at break (in TE
0:5
) %
E
coh
cohesive energy kJ kmol
1
_ ee elongational rate s
1
f overall orientation factor (0 < f < 1)
f
a
amorphous orientation factor (0 < f
a
< 1)
f
c
crystalline orientation factor (0 < f
c
< 1)
F
v
volume ow m
3
s
1
or cm
3
min
1
F
m
mass ow kg s
1
or g min
1
h melt viscosity Pa s
[h] intrinsic viscosity dL g
1
L length (of spinning holes) mm
l thermal conductivity kJ m
1
C
1
s
1
l draw ratio (DR)
n index of refraction
Dn birefringence
P pressure Pa or bar
DP pressure drop Pa or bar
r density kg m
3
or g cm
3
R gas constant 8.3143 kJ K
1
kmol
1
T tenacity at break (in TE
0:5
) mN tex
1
T temperature

C
T
d
drawing temperature (in Figure 17.25) K
T
d
decomposition temperature

C
T
g
glass transition temperature

C
T
m
melting temperature

C
Acronyms
BCF bulked continuous lament
DCM dichloromethane
DMAc dimethylacetamide
DMF dimethylformamide
DR draw ratio
FOY fully oriented yarn
HMHS high-modulus, high-strength bers
HNA 2,6-hydroxynaphthoic acid
HSS high-speed spinning
HSSDW high-speed spin-draw winding
HTS hot-tube spinning
LSS low-speed spinning
MFI melt ow index
NMMO N-methylmorpholine oxide
NMP N-methylpyrrolidone
PA polyamide
968 17 Fibers
PA66, PA6 polyamide 66, polyamide 6
PAN polyacrylonitrile
PBI polybenzimidazole
PBO polybenzoxazole
PBT poly(butylene terephthalate); polybenzothiazole
PEN poly(ethylene naphthalate)
pHBA p-hydroxybenzoic acid
PLLA poly-l-lactic acid
POM polyoxymethylene
POY partly oriented yarn
PP polypropylene
PPD p-phenylene diamine
PPS poly(phenylene sulde)
PPTA poly( p-phenylene terephthalamide)
PTT poly(trimethylene terephthalate)
PVA poly(vinyl acetate); poly(vinyl alcohol)
SDW spindraw winding
SDBW spindraw bulk winding
TPC terephthaloyl dichloride
Acknowledgments
The information in this chapter was gathered during 25 years service at Akzo Fi-
bers Research and recently updated, extended, commented upon, and improved
by former colleagues now working for Acordis and TeijinTwaron.
References
1 Ullmanns Encyclopedia of Industrial
Chemistry, 5th Edition, VCH Verlag,
Weinheim, 1987: bers, A10, pp. 451
655, A11, pp. 184; high-performance
bers, A13, pp. 123; cellulose and
cellulose esters, A5, pp. 375459; silk,
A24, pp. 95106; wool, A28, pp. 395
421.
2 International Fiber Science and
Technology Series, Marcel Dekker, New
York: (a) Volume 7, M. Lewin, E. M.
Pearce (eds.), Fiber Chemistry, 1985
(polyester, polyamide, acrylic, poly-
propylene, polyvinyl alcohol, wool,
silk, cotton, rayon, cellulose acetate);
(b) Volume 4, H. A. Krassig, J. Lenz,
H. F. Mark (eds.), Fiber Technology,
1984 (from lm to ber); (c) Volume
6, I. Sakurada (ed.), Polyvinyl Alcohol
Fibers, 1985; (d) Volume 10, J.-P.
Donnet, R. C. Bansal (eds.), Carbon
Fibers, 2nd Edition, 1990.
3 B. von Falkai (ed.), Synthesefasern,
Verlag Chemie, Weinheim, 1981.
4 F. Fourne, Synthetische Fasern, Carl
Hanser Verlag, Munich, 1995.
5 M. Mayer, Chapter 17: Fiber
Extrusion, in F. Hensen (ed.), Plastics
Extrusion Technology, Hanser Pub-
lishers, Munich, 1981.
References 969
6 A. Ziabicki, Fundamentals of Fibre
Formation, John Wiley, New York, 1976.
7 A. Ziabicki, H. Kawai, High-Speed
Spinning, John Wiley, New York, 1985.
8 T. Nakajima (ed.), Advanced Fiber
Spinning Technology, Woodhead
Publishing, Cambridge, 1994.
9 J. W. S. Hearle (ed.), High-
Performance Fibres, Woodhead
Publishing, Cambridge, 2001.
10 T. J. Veerman, L. Vollbracht, US
patent 4 308 374, 1981 (AKZO).
11 H. S. Morgan, US patent 3 414 645,
1966 (Monsanto).
12 S. L. Kwolek, Netherlands patent 6
908 984, 1969 (DuPont).
13 H. L. Blades, Netherlands patent 7
205 836, 1971 (DuPont).
14 G. Capaccio, T. J. Chapman, I. M.
Ward, Polymer 1975, 16, 469 (and
numerous other publications).
15 E. S. Clark, L. S. Scott, Polym. Eng.
Sci. 1974, 14(10), 682.
16 A. J. Pennings, J. M. A. A. van der
Mark, H. C. Booij, Kolloid-Z. 1970,
237, 336.
17 A. Zwijnenburg, Thesis, University
of Groningen, 1978.
18 P. Smith, P. J. Lemstra, UK patent 2
051 661, 1979 (Stamicarbon).
19 P.-G. de Gennes, Scaling Concepts in
Polymer Physics, Cornell University
Press, 1979.
20 J. Smook, G. J. H. Vos, H. L. Doppert,
J. Applied Polym. Sci. 1990, 41, 105
116.
970 17 Fibers
18
Removal of Monomers and VOCs
from Polymers
1
Mar a J. Barandiaran and Jose M. Asua
18.1
Introduction
The polymerization of monomers rarely proceeds to completion and there is inevi-
tably a level of unreacted monomer remaining in the polymer. The presence of re-
sidual monomer is undesirable, particularly when the monomers are toxic, which
is the case for vinyl chloride and acrylonitrile. Monomers such as acrylates and
methacrylates can also have strong (and oensive) odors, and the residual volatile
components may form an explosive mixture during transportation and storage.
Contamination with unreacted monomers is a problem particularly when the poly-
mer is used for food packaging, as well as in biomedical applications and in inte-
rior paints. Moreover, polymers may contain small amounts of nonpolymerizable
compounds that result from impurities in the raw materials or by-products formed
from side reactions during the polymerization process. The presence of such non-
polymerizable compounds results in an increase in the level of the residual volatile
organic compounds (VOCs) in the polymer and can adversely aect its ultimate
properties. In addition, many polymers are produced in the presence of organic
solvents, which are considered VOCs and must be eliminated before use.
The increasingly strict environmental regulations [1, 2] and the higher market
sensitivity to environmental and health issues are pushing the polymer manufac-
turing industry to reduce the amount of monomers and VOCs in polymers. Reduc-
tion of VOC emission can also lead to better workplace conditions, reduce risks of
re, reduce nuisance, and lead to economic savings. The industrial importance of
VOC removal is reected in the large number of patents that can be found in the
literature. The open literature, however, is scarce. The review in 2002 by Araujo et
al. [3], which summarized the principal methods employed for reducing residual
monomer content, and the books edited by J. A. Biesenberger [4] and R. J. Albalak
[5] reviewing the various aspects of polymer devolatilization, must be highlighted.
Several denitions of VOC have been oered. The European Union (EU) in Di-
ISBN: 3-527-31014-2
971
rective 1999/13/EC [6] denes a VOC as any organic compound with a vapor pres-
sure equal or greater than 10 Pa at 293.15 K. The U.S. Environmental Protection
Agency (EPA) [7] denes the term VOC as any organic compound that participates
in atmospheric photochemical reactions. Those two denitions can lead to contra-
dictory situations. This is the case for acetone, an organic solvent common in poly-
mer production, that is considered to be a VOC following the EU denition, while
it is exempted by the EPAs criterion.
The understanding of the origin of residual monomers and VOCs will help to
design strategies to polymerize up to very high monomer conversions (the higher
the monomer conversion, the less residual monomer) while simultaneously avoid-
ing the formation of new VOCs by side reactions. However, economic constraints
that limit the polymerization time as well as intrinsic characteristics of the poly-
merization technique (such as solution polymerization) always yield systems con-
taining VOCs. Therefore, post-treatments are necessary in order to fulll the legis-
lation and market requirements. Both the polymerization strategy and the type of
post-treatment strongly depend on the polymerization process used for the manu-
facture of the polymer. The problems associated with monomer and VOC removal
in highly viscous polymers produced by mass and solution polymerizations are dif-
ferent from those encountered in low-viscosity, heterogeneous aqueous dispersion
systems. Therefore, this chapter will be organized according to the dierent poly-
merization processes. It is focused on polymers produced by chain polymerization.
In polycondensation, the problem concerns only very specic cases, such as the
removal of ethylene glycol in some poly(ethylene terephthalate) routes, or the re-
moval of phenol in phenolic resins; the problems associated with these removals
are similar to those found in the treatment of polymer melts. Section 18.2 is de-
voted to monomer and VOC removal from polymer melts and solutions. Monomer
removal in polyolens is described in Section 18.3, and nally the treatments for
VOC removal in waterborne dispersions is discussed (see Section 18.4).
18.2
Polymer Melts and Solutions
Polymers produced by mass and solution polymerization, including the polycon-
densation processes, represent about 45% of the total synthetic polymer production
[8]. In a bulk process, polymerization at high conversions is complicated by the ef-
fect of viscosity on initiator eciency, monomer diusion, and heat transfer. The
eciency of the initiator radicals can be dramatically lowered due to the cage eect
resulting from the low mobility of the radicals, leading to a decrease in the poly-
merization rate. On the other hand, in polymerizations taking place at tempera-
tures below the glass transition temperature of the polymer, the mobility of the
monomer molecules is restricted, causing a severe decrease in the polymerization
rate (glass eect).
The use of higher temperatures would reduce the viscosity of the system, thus
avoiding some of the drawbacks associated with high viscosities. However, high
972 18 Removal of Monomers and VOCs from Polymers
temperatures have deleterious eects on the properties of the polymer, such as a
decrease in the molecular weight and degradation of the polymer. Furthermore,
some free-radical polymerizations suer a substantial depropagation at tempera-
tures above a certain level (ceiling point). This phenomenon is quite well known
for methyl methacrylate. Biesenberger et al. [9] showed that sustained exposures
in a vented extruder at temperatures higher than 250
C caused poly(methyl meth-

acrylate) to depolymerize to methyl methacrylate.
On the other hand, in spite of the much lower viscosities of solution polymeriza-
tion, the economically achievable conversion is limited because, due to the low
monomer concentration, the polymerization rate is extremely low at high conver-
sions, and consequently unaordable process times are required.
18.2.1
Devolatilization
Polymer devolatilization is a separation process in which residual VOCs are re-
moved from the polymer matrix by application of a reduced pressure (lower than
the equilibrium partial pressure of the volatile component), and/or heat. Stripping
agents are also commonly used.
18.2.1.1 Fundamentals
Devolatilization of molten and solution polymers generally involves rst the trans-
port by diusion of volatiles to a polymer/vapor interface and then the transport of
volatiles to a gas stream through the boundary layer.
The rate of removal of the volatiles through the interface can be expressed by Eq.
(1), where A is the interfacial area and N
VOC
is the ux of the VOC through the
interface given by Eq. (2).
dVOC
dt
N
VOC
A 1
N
VOC
Dcj
interface
2
Equation (2) requires the concentration prole of the VOC in the polymer melt
that can be calculated from the material balance in the polymer melt. Assuming
that the convective ux is negligible, Eq. (3) expresses this balance, where D is the
diusion coecient of the volatile in the polymer matrix.
qc
qt
Dc 3
The diusion coecient depends on both the temperature of the system and the
concentration of volatiles, and can be estimated through the VrentasDuda free-
volume theory [10].
The boundary conditions representing the diusion process are:
t 0 c c
0
t > 0 c
interface
c
e
c
0
being the initial interface volatile concentration. In the devolatilization of poly-
mer solutions and polymer melts, the diusion of the volatiles through the poly-
mer is usually the rate-controlling part of the process [4]. Therefore, the volatile
concentration at the interface, c
e
, is in equilibrium with the concentration of the
volatile in the gas phase. The equilibrium concentration is related to the partial
pressure of the volatile in the gas phase, P
1
, by means of Henrys law, Eq. (4),
where H, the Henrys law constant, depends on the temperature, pressure, and
nature of the volatile.
c
e

P
1
H
4
The interfacial area between the polymer and the gas phase is one of the key
parameters in the devolatilization processes, because the rate of VOC removal is
proportional to it. The devolatilizers are designed to maximize this interface area.
For free-bubble devolatilization, the area of the polymer lm that is exposed to de-
volatilization can be calculated, taking into account the geometry of the equipment.
Based on those principles, several models to describe the devolatilization in single-
screw extruders [1114] and twin-screw extruders [15, 16] have been presented.
However, bubbles are produced in most of the devolatilization processes. Bub-
bles can be formed when the polymer melt is exposed to a pressure lower than
the partial pressure of the monomer or the solvent in equilibrium with the poly-
meric solution. Those bubbles are composed of monomer and solvent. After for-
mation, the bubbles grow by diusion of monomer or solvent from the polymeric
solution, and ultimately they separate from the polymer melt, releasing the mono-
mer and solvent.
Bubbles can also be formed when stripping agents are introduced into the poly-
mer melt/solution under pressure. If the vapor pressure of the stripping agent is
higher than the equilibrium partial pressure of the volatile, gas bubbles composed
mainly of the stripping agent will be produced. In this case, devolatilization in-
volves diusion of the volatiles to the surface of these bubbles. The area of the
bubbles is determined by the interplay between bubble nucleation, growth, coales-
cence, and rupture. Under these circumstances the determination of the interface
area is not straightforward. Direct visual observation of foaming in dierent types
of devolatilizers has been reported by numerous authors [1721].
Several models for foam-based devolatilization are available. The fundamentals
are reviewed by Lee [22]. Bubble nucleation during devolatilization of polymer
melts has been explained by homogeneous nucleation [23, 24], heterogeneous nu-
cleation [2527], and a mixed-mode nucleation [28]. Yarin et al. [29] considered a
secondary nucleation.
Models that account for the growth of the bubbles, assuming either a single
spherical bubble growing in an innite sea of liquid [30, 31] or many spherical
bubbles growing together with a thin shell of liquid surrounding them [32], have
been developed. More complete models consider bubble motion, coalescence, and
rupture [26, 33, 34].
18.2.1.2 Implementation of Devolatilization
The foregoing equations show that devolatilization may be accelerated by acting on
the diusion coecient, the thermodynamic equilibrium, or the interfacial area.
The diusion coecient depends on the temperature of the system and on the
concentration of volatiles. An increase in the temperature results in an increase in
diusivity and a decrease in viscosity, both benecial for devolatilization. However,
many polymers are thermally sensitive, so there may be a practical upper limit on
the temperature to which the polymer may be exposed, as higher temperatures
may degrade the polymer. Heat stabilizers have been used to enhance the thermal
stabilization [35].
On the other hand, the diusion coecient through the polymer strongly de-
creases as the concentration of the volatile approaches to zero. This drawback can
be overcome by introducing an inert substance (usually water), which increases the
free volume of the polymer, enhancing the molecular diusion of the volatile to be
removed [3641]. Furthermore, the inert reduces the partial pressure of the volatile
in the gas phase, increasing the driving force for devolatilization. Adding an im-
miscible liquid to the melt presents the additional advantage that the total vapor
pressure of the system increases, and therefore the temperature and volatile con-
centration needed to produce bubbles in the polymer solution is lower.
Recently the use of supercritical uids in processing polymers has received
much attention, because supercritical devolatilization has the potential for pro-
ducing high-purity products with lower energy [4244]. The high solubility of the
volatiles in the supercritical uid enhances the driving force for devolatilization.
When the polymer is exposed to the supercritical uid, it is swollen, and the free
volume in the polymer is increased so that diusion of the volatiles out of the poly-
mer is enhanced.
18.2.1.3 Equipment
There exists a wide variety of devolatilization equipment. According to Biesen-
berger [4], the processes can be classied into two main categories: non-rotating
or still equipment, and rotating equipment, in which devolatilization is enhanced
by mechanical agitation.
Nonrotating equipment, such as the falling-strand [5, 29, 45, 46] (Figure 18.1)
and falling-lm [5, 47] devolatilizers, include mainly ash evaporators and other
equipment with specic congurations of the ash chamber, aimed at increas-
ing the exposed interfacial area between the gas and the polymeric phase. In this
equipment, the polymer melt/solution is preheated before entering the ash cham-
ber, where the conditions of pressure and temperature are such that the volatiles
boil. Vaporization of volatiles is prompted by continuous removal of their vapor
through the vacuum outlet port of the ash tank.
In those processes three dierent regimes can be distinguished [48]. Each of
them has a dierent rate-limiting mechanism, which depends mainly on the dier-
ence between the equilibrium partial pressure of the volatile in equilibrium with
the melt (P
1
) and the total pressure within the vacuum chamber (P). This dier-
ence (P
1
P) is often called the degree of superheat, SH.
The rst regime, termed free boiling, occurs when SH is large and the liquid
viscosity is low. This usually happens under volatile-rich conditions. Vapor bubbles
initiate and grow very fast, causing convective mixing that enhances mass transfer
to the vapor phase. Under this regime, the temperature of the melt can rapidly
drop if there is not an external energy input, since the latent heat of evaporation
is provided by the sensible heat of the devolatilization mass. For example, under
adiabatic conditions an MMAPMMA melt at 250
C will drop approximately 15
C
for every 10 wt.% of the melt that vaporizes. As the melt temperature drops, P
1
will
drop and the degree of superheat will diminish. On the other hand, melt viscosity
will rise, due to both the removal of volatiles and the temperature drop. These ef-
fects cause bubble growth and movement to slow down and the free-boiling regime
gradually fades out.
The second regime is termed bubble growth and the rate-controlling mecha-
nism is the bubble initiation and growth. The volatile removal rate is slower than
in the previous case, and consequently cool-down is reduced. Melt viscosity in-
creases due to depletion of the volatile.
In the third regime, where the viscosity of the melt is very high and the degree of
superheat has been reduced due to depletion of volatiles and temperature drop,
bubbles are hardly formed and existing bubbles grow very slowly. Under these cir-
cumstances, the rate of volatile loss is very slow, as it is controlled by the molecular
diusion at the melt/vapor interface. Therefore, for a very low level of volatiles,
ash devolatilizers are not ecient.
Vacuum
Devolatilized
melt
Feed
Heating jacket
Strands
l
l
i j
Fig. 18.1. The falling-strand devolatilizer.
Nonrotating equipment is ecient for low-viscosity polymer solutions contain-
ing large amounts of volatiles, and particularly useful when dealing with shear-
sensitive polymers. However, care must be taken to ensure that they do not have
stagnant areas where the polymer could degrade. Excessive foam expansion and
polymer entrainment in the volatile vapor stream could be serious problem. Those
systems are not operable with solutions that upon ashing retain enough solvent
to form a sticky mass, such as in the case of rubbery polymer solutions, because
the equipment has little self-cleaning and can become fouled up [49]. On the other
hand, low volatile concentrations can hardly be achieved with those equipment,
since very long residence times would be required to overcome their poor mass-
transport eciency, which would increase thermal degradation of the polymer.
Multi-slit devolatilizers [5052] were designed to overcome the problem of long
residence times of the polymer at high temperatures. In this process, the poly-
meric solution is fed through an assembly of heated slits which discharge into a
ash chamber where vacuum is maintained.
Rotating equipment is used for devolatilization of highly viscous polymer melts/
solutions. The rotating parts serve not only to spread and move the polymer for-
ward along the devolatilizer but also to generate and renew the polymer/gas phase
interface. Typical devices are wiped-lm evaporators and screw extruders.
The wiped-lm evaporators (Figure 18.2) employ a rotor with an array of blades
attached to the rotor shaft which transport the polymer melt through the evapora-
tor, forming lms. As the product goes down along the wall, bow waves developed
by the rotor blades generate a highly turbulent ow, resulting in optimum heat
and mass transfer. The melt and the vapor ow either in the cocurrent fashion
VOC removal
Devolatilized
melt
Feed
Heating
jacket
t
i
Fig. 18.2. The wiped-lm evaporator.
(mainly for removing highly volatile contents) or in countercurrent (for removing
low-volatility contents). The combination of the short residence time, narrow resi-
dence time distribution, high turbulence, and rapid surface renewal permits the
wiped-lm evaporator to successfully handle heat-sensitive, viscous (up to 10
4
Pa s) and fouling-type uids. This equipment is also used as a nal reactor in poly-
condensation reactions, where the low molecular weight species produced in the
reaction must be removed to achieve high molecular weights.
The screw extruders used for devolatilization (Figure 18.3) present a vent zone
with a deep channel, where the polymer is exposed to vacuum. Due to the clear-
ance between the barrel and the screw ight, a thin layer of polymer is deposited
in the barrel as the screw ight rotates. Evaporation may occur either at the surface
of the rotating melt pool or at the surface of the deposit lms. Bubbles can be gen-
erated inside the melt pool. Due to high viscosity, they hardly diuse through the
pool. However, as the pool rotates, some of them reach the exposed pool surface,
increasing the devolatilization eciency.
Both single- and twin-screw extruders have been used for devolatilization.
Counter-rotating, non-intermeshing twin-screw extruders have been widely used
in the isolation of polymers from solutions, emulsions, and suspensions, and
in the devolatilization-driven reactive extrusion processes [53]. Co-rotating, inter-
meshing twin-screw extruders have been also used as bulk and solution nishing
devolatilizers [54]. One of the main advantages of the twin screw over the single
screws is its ability to oer additional surface removal for lm exposure and the
excellent interchange of pool and lm polymer. On the other hand, the area under
the vent of a single extruder is vulnerable to stagnation, while the twin-screw ge-
ometry reduces this possibility. However, design of twin-screw extruders is more
complicated and they are more expensive than the single-screw extruders.
Although selection of the devolatilization system is not an easy issue, Figure 18.4
presents a guide based on the heat sensitivity, viscosity, concentration, and eco-
nomics.
Feed
hopper Vacuum

Metering
Devolatilization
Metering Feed
Fig. 18.3. A single-screw extruder.
18.3
Polyolens
Polyolens are nowadays one of the most important groups of commercial poly-
mers, with a consumption of about 100 million tons per year, which represents
more than 40% of the total word production of polymers [55]. Because the main
monomers involved in the production, ethylene and propylene, have very high va-
por pressure, these polymers are produced under pressure. Therefore, the residual
monomers are easily removed by depressurization and recirculated to the poly-
merization zone. However, in the slurry and solution processes the polymerization
medium is a solvent. In those cases, the polyolen solution or slurry leaving the
reactor is discharged into a vessel at lower pressure to ash o the solvent and un-
reacted monomers. The slurry from the polymerization reactor can also pass di-
rectly to a centrifuge where most of the volatiles are removed and recycled to the
reactor. Further removal of solvent residues is achieved by passing a heated stream
of inert gas (mainly nitrogen) through the bed of pellets.
In the gas-phase processes, the polymer is discharged into a cyclone separator,
from which residual monomers are recovered and recompressed.
18.4
Waterborne Dispersions
Probably the main step to eliminate VOC in the polymer industry has been the
substitution of solvent-based systems by waterborne products. Nowadays, about
5% of the polymers are produced by aqueous dispersion processes, mainly by sus-
pension and emulsion polymerization [8]. The water-based polymers, however, are
not totally free of monomer and VOCs, since the reaction does not reach comple-
tion and VOCs arising from impurities in the raw materials or from by-side reac-
tions can be present. There are two main ways to reduce the residual monomer
content in waterborne polymers: post-polymerization or/and devolatilization.

Preconcentration
(Dilute product)
Concentration
(Viscous heat sensitive)
Devolatilization
(Highly viscous)
Trace devolatilization
(Very high viscosity)
Viscosity (Pa.s)
1 50 10
3
2 10
4
5 10
4

Flash evaporator
Falling
strand
evaporator
Wiped-film evaporator
Vented extruder
Fig. 18.4. Criteria for choosing the devolatilizer equipment.
In order to develop ecient post-polymerization and devolatilization operations,
it is critical to know where the residual monomer and VOCs are located, that is, if
they are mainly in the polymer particles or in the aqueous phase. Table 18.1 (in
Section 18.4.2.1) summarizes the partition coecients (dened as the ratio be-
tween the concentrations of monomer/VOC in the polymer particles and in the
aqueous phase) measured for several monomers and VOCs in latexes. It can be
seen that the monomers are mainly located in the polymer particles. On the other
hand, water-soluble VOCs such as acetaldehyde and tert-butanol are mainly in the
aqueous phase. It is worth pointing out that the partition coecient decreases (that
is, the monomer partitioning shifts toward the aqueous phase) as the average
monomer concentration in the system decreases [56, 57].
18.4.1
Post-polymerization
Post-polymerization consists of adding, after the end of the main polymeriza-
tion process, fresh radical-generating systems to polymerize the residual monomer.
Even though residual monomers may be post-polymerized using radiation [58, 59],
post-polymerization is mainly carried out using initiators.
In suspension polymerization, the initiator must be oil-soluble. Those initiators,
in order to be fed into the reactor, are commonly dissolved in an organic solvent,
which increases the VOC content. On the other hand, the most important mono-
mers (styrene, methyl methacrylate, and vinyl chloride) polymerized in suspension
yield polymers with a high glass transition temperature (T
g
). The polymerization
temperature is usually below the T
g
, and hence the polymerization rate decreases
sharply at high conversions due to the glass eect. Increasing the temperature of
the reactor above the T
g
could be a way to improve the monomer conversion. How-
ever, this would imply temperatures higher than the boiling point of the water,
and in addition, long exposures to high temperatures could degrade the polymer.
Therefore, post-polymerization does not seem a promising way to reduce the resid-
ual monomer in suspension polymers.
In emulsion polymerization, any kind of free-radical initiation system may, in
principle, be used for post-polymerization. However, some alternatives seem to be
preferable. Thus, although both thermal and redox initiation systems may be used,
and attempts to enhance the activity of thermal initiators by using ultrasound have
been reported [60], redox systems are preferred because these systems generate a
higher ux of radicals, in particular under mild conditions, leading to shorter post-
polymerization times. A wide variety of oxidants and reductants can be combined
in dierent redox systems [61, 62]. Ideally, radicals should have easy access to the
place where the monomer is located. Because the residual monomer is mainly lo-
cated in the polymer particles [57], oil-soluble initiators seem promising. However,
as explained above, their addition would increase the VOC content. Consequently,
water-soluble redox systems are more convenient. Ilundain et al. [63] demonstrated
that independently of the water solubility of the monomer, water-soluble redox
initiators yielding hydrophobic radicals (such as organic hydroperoxides) were ad-
vantageous for monomer removal by post-polymerization. The reason is that the
hydrophobic radicals can enter directly into the polymer particles whereas the hy-
drophilic radicals must undergo a number of propagation steps before becoming
hydrophobic enough to be able to enter into the polymer particle. These growth
processes take rather a long time, because under post-polymerization conditions
the monomer concentration in the aqueous phase is very low, and the oligoradicals
suer bimolecular termination leading to low initiator eciency.
Emulsion polymerization is commonly used to produce lm-forming polymers,
and hence it is generally carried out at temperatures above the T
g
of the polymers.
Therefore, propagation does not become diusion-controlled [64], and the kinetics
of post-polymerization is not inuenced by the reaction temperature dierently
than the emulsion polymerization stage [65].
The main advantages of post-polymerization treatments are that they can be
carried out either in the polymerization reactor or in the storage tank, and no addi-
tional equipment is needed. However, only the polymerizable residual volatiles can
be eliminated, and in some cases new VOCs are produced from secondary reac-
tions. Thus, formaldehyde is formed when sodium sulfoxylate formaldehyde is
used as the reductant [66] and acetone and tert-butanol are formed when tert-butyl
hydroperoxide is used as the oxidant [67]. In addition, inorganic water-soluble ini-
tiators may be deleterious to both stability and water sensitivity of the lm formed
with the latexes.
It is worth mentioning that some initiator systems may modify the polymer
microstructure [68, 69], which can be either a problem or an opportunity to extend
the range of properties achievable with a given aqueous dispersion of polymers.
18.4.1.1 Modeling Post-polymerization
The processes involved in post-polymerization can be summarized as follows. The
radicals that are generated in the aqueous phase must add some monomeric units
in order to become hydrophobic enough to enter into the particles. This critical
value is referred as z, and is a function of both the monomer hydrophobicity [70]
and the type of radical formed from the initiator. The radicals may suer bimolec-
ular termination in the aqueous phase. On the other hand, the radicals inside the
particles can propagate, terminate, or desorb. Under post-polymerization condi-
tions, however, the radical desorption rate is negligible because, due to the low
monomer content in the particles, the probability of generating small free-radical
species by chain transfer to monomer is very low. A mathematical model based
on the mechanisms summarized above is available [71]. Optimal strategies aiming
at achieving maximum monomer removal with minimum formation of VOCs have
been reported [71].
18.4.2
Devolatilization
Devolatilization of aqueous polymer dispersions is usually carried out using a
stripping agent (steam and nitrogen are the most commonly used; air can also be
used, but explosive vapor mixtures can be produced). Figure 18.5 summarizes the
devolatilization process in a stirred tank using a stripping agent, which is usually
fed in continuously until the volatile content is reduced to the desired level.
18.4.2.1 Modeling
From a microscopic point of view, devolatilization of aqueous-phase dispersions is
a mass-transfer process, which involves the following steps: (1) diusion of the
VOCs to the particle surface; (2) transfer from the polymer surface to the aqueous
phase; (3) diusion through the aqueous phase; and (4) transfer from the aqueous
phase to the gas phase (Figure 18.6) [72].
Stripping agent
(steam, nitrogen,.)
Vapor +VOCs
Bubble
Polymer particle
Aqueous phase
Fig. 18.5. The stripping of latexes.
Fig. 18.6. Processes involved in the devolatilization of waterborne dispersions.
Assuming that the contact between the particles and the bubbles is negligible,
and that the ow of the gas phase may be described by a well-mixed continuous
system, the overall mass balances of the VOC in the dierent phases are given by
Eqs. (5)(7), where V
i
is the volume of the phase i (w water phase, p polymer
particles, g gas phase); C
i
is the concentration of the VOC in the phase i; C
i; ej
is the concentration of the VOC in the phase i that would be in equilibrium with
the actual concentration of the VOC in phase j; K
pw
represents the overall mass-
transfer coecient between the polymeric phase and the water phase, K
wg
is the
mass-transfer coecient between the aqueous and the gas phase; A
pw
and A
wv
are
the interfacial areas between the polymer particles and the aqueous phase and be-
tween the aqueous phase and the gas phase, respectively; y is the molar fraction of
the VOC in the euent; and G is the molar ow rate of the stripping gas.
Polymer particles:
d
dt
V
p
C
p
K
pw
A
pw
C
p
C
p; ew
5
Aqueous phase:
d
dt
V
w
C
w
K
pw
A
pw
C
p
C
p; ew
K
wg
A
wg
C
w
C
w; eg
6
Gas phase:
d
dt
V
g
C
g
K
wg
A
wg
C
w
C
w; eg
Gy 7
In the devolatilization of polymers in aqueous dispersion, the equilibria are ex-
pressed in terms of the partition coecient of the dierent VOCs between the
polymer particles and the aqueous phase, k
p
w
, and the Henrys law constant (H)
for the partitioning of VOCs between the aqueous phase and the gas phase. There-
fore, the equilibrium concentrations can be calculated from Eqs. (8) and (9).
C
p; ew
k
p
w
C
w
8
C
w; eg

P
T
y
H
9
Tables 18.1 and 18.2 present the values of those coecients under devolatilization
conditions (residual VOC content lower than 5000 ppm) for some monomers com-
monly used in emulsion polymerization and for the main VOCs found in those
latexes after polymerization.
The polymer particle/aqueous phase interfacial area can be obtained from the
particle size measurements, but the total transfer area between the aqueous and
gas phases is dicult to measure. The degree of dispersion of the gas in a liquid is
a function of several factors such as the geometry of the contact equipment, the
agitation device and speed, the viscosity of the medium, and the gas ow rate. In
addition, the physical-chemical properties of both phases, derived by the presence
of surfactants or electrolytes in the medium, aect the interfacial area. The deter-
mination of the mass-transfer coecients is not straightforward either. For the
water/gas phase, the uncertainty of the estimation of both the interfacial area and
the mass-transfer coecient is overcome through the evaluation of the volumetric
mass-transfer coecient, K
wg
A
wg
. Estimated values from dierent authors are pre-
sented in Table 18.3.
The polymer particles/aqueous phase mass-transfer coecient can be deter-
mined through the Frossling equation [73], where Sh is the Sherwood number, Re
the Reynolds number, and Sc the Schmidt number.
Sh 2:0 aRe
b
Sc
c
10
It is worth pointing out that few studies took into account the pseudoplastic behav-
ior of the polymeric dispersions [74, 75]. There is little and sometimes contradic-
tory information about the presence of the additional gas phase on the solidliquid
mass-transfer coecients. Sanger et al. [76] observed that in a bubble column, K
pw
increased upon increasing the gas ow rate. Grisa et al. [77], observed just the
opposite in a stirred tank; this was attributed to reduction of the eective power
Tab. 18.1. Polymer particle/aqueous phase coecients under devolatilization conditions
calculated by R. Salazar [100].
Monomer Polymer system T [
C] k
p
w
Monomer content of
particles (50 wt.% solids) [ %]
VAc poly(vinyl acetate) 65 10.5 91.3
VAc VAc/BA/AA 65 10.9 88.2
BA BA/S/AA 65 240 99.6
n-Butanol VAc/BA/AA 65 2.5 71.4
Acetaldehyde VAc/BA/AA 65 0.5 33.3
tert-Butanol VAc/BA/AA 65 0.5 33.3
Tab. 18.2. Henrys law constants at 65
C
calculated by R. Salazar [100].
Compound H [k Pa]
VAc 26
Butyl acrylate 29
Acetone 3
n-Butanol 1.5
per unit volume used to mix the dispersion. Kim et al. [78, 79] measured experi-
mentally the K
pw
of vinyl acetate diusion into poly(vinyl acetate) and polystyrene
latex particles using a vapor-phase addition method. Values in the range of
5 10
7
7 10
7
cm min
1
were obtained for diusion of vinyl acetate into 160
nm PS latex particles.
18.4.2.2 Rate-limiting Steps
For suspension polymers, which are commonly high-T
g
polymers and present
small polymer particle/aqueous phase interfacial areas, the diusion through the
particle and the transfer from the particle surface to the aqueous phase are often
the rate-limiting steps [80]. The ease of removal depends mainly on the polymer
particle size, particle size distribution (the presence of large particles increases the
diusion time through the particle largely), and the presence of glassy particles.
High temperatures speed up devolatilization.
For emulsion polymers, the monomer devolatilization rate is often limited by the
mass transfer through the interface between the aqueous phase and the gas phase
[57]. For these systems, diusion in the polymer particles is fast because the T
g
of
the polymer is low and the particle size is small. In addition, the mass transfer
from the particles to the aqueous phase is fast because of the huge interfacial
area. For water-soluble VOCs such as acetaldehyde and tert-butanol, the rate-
limiting step is also the mass transfer through the liquid/gas interface. Therefore,
all the process variables that increase the interfacial area between the aqueous
phase and the gas phase, such as agitation, geometry of the sparger, or gas ow
rate, would improve devolatilization [81].
However, the stripping of emulsion polymers may cause a substantial fraction of
the surfactant added to the system to desorb from the polymer particles to form
foam, thus leaving the system susceptible to coagulation. Furthermore, the me-
Tab. 18.3. Estimated mass transfer volumetric coecients.
Equation Estimated
K
vw
A
vw
[m
3
s
C1
]
Reference
K
wg
A
wg
0:02218P
g
=V
L
0:5
u
0:6
s
4:4 10
6
118
K
wg
A
wg
d
i
D
21:2
d
2
i
Nr
m
e

1:11
m
e
rD

0:5
d
i
u
s
s

0:447
m
g
m
e

0:694
0:14 10
6
119
K
wg
A
wg
d
2
i
D
1:41 10
3
d
2
i
Nr
m

0:67
m
rD

0:5
rN
2
d
3
i
s

1:29
0:91 10
6
120
K
wg
A
vg
d
2
i
D
0:06
d
2
i
Nr
m
e

1:65
m
rD

0:5
N
2
d
i
g

0:19
mu
s
s

0:6
Nd
i
u
s

0:33
F
F 1 2:0lN
0:5
0:67
0:83 10
6
121
K
wg
A
wg
8:48 10
8
u
0:56G0:08
G
N
2:7G0:2
N > 30 rpm 5:3 10
6
122
chanical agitation and the creation of large gas/liquid interfacial areas promote co-
agulation. In addition, the solids content of the dispersion can vary due to either
the evaporation of some water or the condensation of steam.
18.4.2.3 Devolatilization under Equilibrium Conditions
Under some circumstances, such as when the bubble size is very small and low
gas ow rates are used, the concentrations of the VOCs in all phases are at ther-
modynamic equilibrium. In this case, the removal kinetics of the VOCs is given by
Eq. (11) [8284], where t is the removal time and k is the apparent removal rate
constant, given by Eq. (12) [84]. M
w
is the water molecular weight, E is the mass
of latex in the devolatilizer, and X is the mass fraction of polymer in the latex.
C
C
0
e
kt
11
k
GM
w
H=P
T
E X k
p
w
r
w
r
p
1
!
1
" # 12
This prediction was found to be valid for dierent processes, such as the stripping
of styrenebutadiene latexes when a constant steam sparge rate was used [83, 85],
and acrylic copolymers at dierent solids contents and steam sparge rates [84].
Equations (11) and (12) show that devolatilization is strongly aected by the ther-
modynamic equilibria of the VOCs between dierent phases. High values of the
polymer particles/aqueous-phase partition coecient imply that the concentration
in the aqueous phase will be low and hence it will be dicult to remove the VOC
from the particles. Similarly, a low value of the Henrys law constant means that
the concentration of VOCs in the gas phase is low and hence, devolatilization will
be dicult. Figure 18.7 shows the kinetics of devolatilization of vinyl acetate, acet-
aldehyde, and n-butanol in a VAc/BA/AA latex, and that of BA in a BA/S/AA latex
by stripping in laboratory-scale equipment, under equilibrium conditions. It can be
seen that the devolatilization of BA was slow due to the high anity (high k
p
w
) of
BA to the polymer particles. The removal of n-butanol was also very slow because
of its high solubility in the aqueous phase and low vapor pressure (a low value of
the Henrys law constant).
18.4.2.4 Equipment
Although ash devolatilization has been applied for removal of high-volatility
monomers, such as vinyl chloride from poly(vinyl chloride) [8688] or butadiene
from polybutadiene [89], most of the processes described in the literature include
the use of a stripping inert gas (usually steam) to improve the devolatilization
eciency.
Several types of equipment have been proposed to allow fast devolatilization
without aecting the stability of the dispersion and avoiding foaming. Englund
[83] reviewed the dierent latex strippers used in commercial practice. Batch,
semibatch, and continuous tanks, using countercurrent or cross-ow gas [9093],
packed or perforated columns in countercurrent ow [9498], and tubular devola-
tilizers [99] have been used.
Continuous steam stripping using countercurrent ow of an aqueous dispersion
and steam requires less steam than batch and cross-ow systems, although the
equipment needs considerable space. On the other hand, the column continuous
countercurrent stripper requires the least steam of all the processes, and little oor
space. This type of stripper is attractive because the short residence time allows
short exposure to high temperatures, decreasing the risk of degradation. They are
used extensively in suspension processes, such as the production of poly(vinyl
chloride). Those stripping systems, however, are dicult to apply to latexes, be-
cause of severe foam formation, and the risk of coagulation due to the shear and
the relatively high viscosity of the latex. The low T
g
of most of the latexes is an ad-
ditional drawback for using column stripping systems. In these cases, tank reac-
tors are much more convenient.
The undesirable foaming can be suppressed by lowering the temperature, but
this reduces the recovery of the low boiling point substances. Chemical defoaming
agents may be used, but they may accelerate thermal degradation of the polymer
when it is processed at an elevated temperature (as occurs with the polyvinyl chlo-
ride) and their use adds contaminants to the latex. One way to control foam forma-
tion is by a sudden increase of the pressure. This method has been proven to be
very ecient in the stripping of acrylic latexes in tank reactors [100]. Many eorts
have been devoted to the design of the devolatilizer to overcome this problem. The
injection of the steam at a point in the autoclave such that it passes through the
0
0.2
0.4
0.6
0.8
1
0 30 60 90 120 150 180
C
o
n
v
e
r
s
i
o
n
Time (min)
Fig. 18.7. Kinetics of devolatilization of vinyl
acetate, acetaldehyde, and n-butanol in a
VAc/BA/AA latex, and that of BA in a BA/S/AA
latex: g, acetaldehyde; k, VAc; c, n-butanol
removal rate by devolatilization from a
VAc/BA/AA latex; , BA removal rate from
BA/S/AA latex, under the same devolatilization
conditions [100].
dispersion uncondensed has been found very convenient [101]. In other cases,
the gas to be drawn o is passed through porous lter elements [102] or through
a condenser adapted to the top of the packed tower [94]. Other authors [90]
claimed to feed the aqueous latex as a spray to avoid the contact of the droplets
of spray with the side wall of the chamber, and therefore to avoid foaming, which
otherwise could cause ooding of the descending latex.
18.4.3
Combined Processes
Devolatilization is an adequate technique to remove both residual monomer and
nonpolymerizable volatiles. However, this method is of limited eciency for the
removal of very hydrophobic monomers, for which high ow rates of the stripping
gas should be used to appreciably reduce the monomer content, with the corre-
sponding increase in cost, and risk of foaming and coagulation. Under these cir-
cumstances, combination of post-polymerization and devolatilization is an attrac-
tive alternative.
Some authors have proposed treating the dispersion initially by post-
polymerization followed by stripping devolatilization [103105]. Taylor [106]
claimed a treatment in which devolatilization and post-polymerization proceeded
concurrently. Salazar et al. [57] have compared the performance of concurrent
combined strategies for removal of monomer and VOCs with those of other strat-
egies including post-polymerization, devolatilization, and post-polymerization fol-
lowed by devolatilization. The results obtained for the removal of BA and the
VOCs present in BA/S/AA commercial latex are shown in Figure 18.8. It can be
0
0.2
0.4
0.6
0.8
1
0
C
o
n
v
e
r
s
i
o
n
Time (min)
30 60 90 120 150 180
Fig. 18.8. Inuence of the strategy on the eciency of removal
of BA from a BA/S/AA commercial latex: k, devolatilization;
g, post-polymerization; c, simultaneous post-polymerization
and devolatilization.
observed that the simultaneous process resulted in the highest eciency of re-
moval for monomer. For the nonpolymerizable VOCs, almost the same eciency
was obtained in all the strategies using devolatilization.
18.4.4
Alternative Processes
In addition to those conventional techniques widely applied in the industry, other
alternatives that try to overcome the problems associated with the use of chemicals
in post-polymerization or the high energy consumption associated with devolatili-
zation have been implemented. The modication of the unreacted monomer into a
harmless compound, or into a product easier to devolatilize, has been applied to
reduce the VOC content. Ozone was found advantageous for vinylic monomer,
because it can easily break the double bond and is innocuous [107, 108]. On the
other hand, it could also attack the double bond of the polymer chain, causing the
degradation of the polymer. Biological degradation through the use of peroxide-
generating enzymes was also shown to be able to reduce residual monomer in
latex [109, 110]. This process, however, is very slow.
Adsorbents, such as active carbon particles [111, 112], zeolites [111, 112], poly-
meric adsorbents [111], or ion exchangers [111], have been proven to be useful for
VOC reduction in latexes. This treatment, however, requires additional equipment
and the regeneration of the adsorbent.
Extraction of the VOCs with suitable solvents has been also extensively investi-
gated. Treatment with organic solvents was found valid for particular cases, such
as the removal of high-boiling organic compounds [113] or preparation of poly-
meric hydrogels [114]. Application of supercritical uids to cleaning processes
was presented in 1998 as an alternative to monomer removal in the near future
[115]. Kemmere et al. [116, 117] studied the potential of a post-polymerization pro-
cess based on supercritical carbon dioxide to remove methyl methacrylate from
poly(methyl methacrylate). This process is attractive since CO
2
is very abundant,
relatively inexpensive, and environmentally benign on this scale of use.
18.5
Summary
For polymer melts and solutions, the diusion of the VOCs from the polymer to
the polymer/vapor interface is the rate-limiting step. This limitation is more pro-
nounced for highly viscous melts. Therefore, the devolatilizers must be designed
to increase both the diusion coecient of the volatiles and the polymer/vapor
interfacial area. This is achieved by using stripping agents, and equipment with
rotating parts that generate and renew the interfacial area. Vented screw ex-
truders are recommended for devolatilizing highly viscous systems. Wiped-lm
evaporators can handle polymer melts with viscosities up to 10
4
Pa s, and ash
18.5 Summary 989
and falling-strand devolatilizers are recommended for low-viscosity polymers (vis-
cosities up to 1 Pa s).
Residual monomer present in polyolens is easily removed by depressurization.
The solvent used in the slurry and solution processes is commonly eliminated by
ash evaporation and subsequent contact with a heated inert gas stream.
There are two main ways to reduce the VOC content in waterborne dispersed
polymers: post-polymerization and devolatilization. Post-polymerization can only
be applied to emulsion polymers. Water-soluble redox initiators yielding hydropho-
bic radicals have been found to be advantageous for monomer removal by post-
polymerization. In suspension polymers the devolatilization is limited by both the
diusion through the particle (because of the usually high T
g
of the polymer) and
the mass transfer from the particle surface to the aqueous phase (because of the
large particle size that results in a relatively small interfacial area). Therefore, the
temperature and the polymer particle size play an important role in the devolatili-
zation eciency.
In the devolatilization of emulsion polymers, the mass transfer between the
aqueous phase and the gas phase is frequently the rate-determining step. Conse-
quently, the agitation, the gas ow rate, and other process variables or design
characteristics that increase the interfacial area between the aqueous phase and
the gas phase will improve the devolatilization. However, care must be taken to
avoid foaming and coagulation. Column continuous countercurrent strippers are
often used in devolatilization of suspension polymers, while stripping in tank reac-
tors is more convenient for low-T
g
lm-forming latexes.
Notation
A interfacial area [m
2
]
c concentration of the VOC [mol m
3
]
c
e
volatile concentration at the interface [mol m
3
]
D diusion coecient [m
2
s
1
]
d
i
impeller diameter [m]
E mass of latex in the devolatilizer [kg]
G molar ow rate of the stripping gas [mol s
1
]
g gravitational constant [m s
2
]
H Henrys law constant [kPa]
K overall mass transfer coecient [m s
1
]
k
p
w
partition coecient between the polymer particles and the aqueous phase
M
w
water molecular weight [kg mol
1
]
N agitation speed [s
1
]
N
VOC
ux of the VOC through the interface [mol m
2
s
1
]
P
1
partial pressure of the volatile in the gas phase [kPa]
P
g
power applied to the system [W]
Re Reynolds number
Sc Schmidt number
SH degree of superheat
Sh Sherwood number
T
g
glass transition temperature [
C]
u
g
linear gas velocity [m s
1
]
u
s
supercial gas velocity [m s
1
]
V volume [m
3
]
X mass fraction of polymer in the latex
y molar fraction of the VOC in the euent
Greek
r density [kg m
3
]
m viscosity [Pa s]
m
e
eective viscosity [Pa s]
s interfacial tension [Nm s
1
]
Subscripts
g gas phase
p polymer particle
w water phase
Acronyms
AA acrylic acid
BA butyl acrylate
S styrene
VAc vinyl acetate
VOC volatile organic compound
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19
Nano- and Microstructuring of Polymers
1
Christiane de Witz, Carlos Sanchez, Cees Bastiaansen, and
Dirk J. Broer
19.1
Introduction
Nano- and microstructures are essential for the growth of well-established tech-
nologies, such as microelectronics, but also for the development of emerging
new ones in the elds of biology, nanotechnology, and information and communi-
cation technology. Since the early 1970s the production of microelectronic silicon
chips has been a driving force of paramount importance for the development of
micropatterning techniques. Traditionally, this eld has focused on optical lithogra-
phy in which a polymer lm is structured using light. The patterned polymer is
then used to implement and integrate the functional components of the microchip
in the silicon wafer. The semiconductor industry focuses on reducing the feature
size of transistors and on reaching higher integration densities for faster computa-
tion, higher performance, and cheaper production [1]. Besides microelectronics,
miniaturization and high-throughput production of complex structures are also
required for electro-optical and electronic devices (LCD, LED, FET), nano- and
micro-electromechanical systems (MEMS), denser memories, and biosensors or
biological arrays [2]. New patterning techniques and materials need to be explored
in order to sustain the historical trend in size reduction in the semiconductor
industry and in order to make real advances. For this, polymers are an extremely
attractive platform due to their ease of processing and their tailorability, which
allows ne-tuning of the properties for each application. As an example, the
possibility of patterning polymers with special functionalities such as electrical,
(semi-)conductivity, electroluminescence, piezoelectric, and/or dielectric properties
is important for the development of plastic electronics. Well-dened structured
polymer surfaces also nd their application in optical and electro-optical devices
[38]. For instance, special reectors, made of a polymer lm with a well-designed
relief structure and coated with a thin-lm metallic mirror, redistribute incoming
ISBN: 3-527-31014-2
995
light in a very controlled way and are widely used in reective and transective
liquid crystal displays. Periodic relief structures are also widely employed in trans-
missive gratings to control light in transmission or reection [7, 8]. First, we will
briey review dierent strategies for the patterning of polymer structures and, sub-
sequently, we will focus on new patterning techniques such as photoembossing.
19.1.1
Patterning Techniques
Photolithographic techniques make use of electromagnetic (EM) radiation (UV,
DUV, EUV or X-ray photons) to generate a latent image in a photopolymer [9].
The image of a mask can be transferred, either by putting it in direct contact with
the photoresist and subsequently irradiating with collimated light or by projecting
the image with the help of appropriate optics. Methods involving multibeam holog-
raphy have also been explored [10]. Independently of the irradiation method, the
EM radiation exposure induces a change in solubility in the exposed areas. A sub-
sequent development step in a solvent removes material locally and a relief struc-
ture is obtained. This technique suers from certain intrinsic limitations such as
diraction or, in the case of projection lithography, the depth of focus. The resolu-
tion of optical lithography increases if the wavelength of the EM radiation is re-
duced. The use of KrF lasers (248 nm) allows the routine fabrication of features
in the order of 200 nm. In order to reduce the size of these features, shorter wave-
lengths need to be used. ArF excimer lasers working at 193 nm can lead to resolu-
tions of 150 nm. Shorter wavelengths such as 157 nm (F2 excimer lasers) can be
employed. New grades of modied fused silica have been developed showing weak
absorption in this wavelength region, making possible the production of litho-
graphic masks. Calcium uoride meets also the requirements for implementing
the optics for the illumination and projection systems [11]. More problematic is
the use of EUV and X-ray lithography, due to the lack of transparent materials
to generate the masks and the necessary optics for the lithographic process. One
possibility is to use masks with openings in a stencil instead of the conventional
lithographic masks consisting of metallic (for example, chromium) patterns sup-
ported on a transparent substrate. Reection-instead of transmission-based optics
also needs to be implemented. Besides the typical problems of UV lithography,
damage to the mask is also induced during exposure. Although the use of these
high-resolution lithographies (EUV and X-ray) has been demonstrated in a labora-
tory scale, their use in mass production is still restricted because of their high cost.
In all the cases described the development of appropriate polymeric photoresists is
of crucial importance. For example, the resolution can be enhanced by using re-
sists with a nonlinear response that make possible the fabrication of features with
a size below the diraction limitation of the photolithographic technique [12, 13].
Electron beams (EBs) can also be employed for the ne-scale (tens of nano-
meters) patterning of polymer structures, because of their short (de Broglie) wave-
length [14]. Here the charged character of the writing particles limits the resolu-
tion because of interparticle electrostatic interactions that produce scattering and
996 19 Nano- and Microstructuring of Polymers
therefore lack of resolution. Another important drawback of this technique is that
the patterning is performed with a writing procedure and, consequently, the pro-
duction of structures is laborious and expensive; this restricts their use to very spe-
cic applications. Some projection systems are being investigated in attempts to
obtain a high-throughput production of patterned structures by EB lithography
[15]. Other related techniques involve ion or uncharged particle beams [16].
Other non-photolithographic techniques, such as imprinting (or embossing) or
cast molding, have had a large technological impact in dierent industrial sectors.
In the case of imprinting, a rigid master is pressed against an unstructured poly-
mer lm [17]. Afterward the master is released and its inverse replica is obtained.
Some popular applications of this imprinting technique are the holograms such as
those used in safety features in the security industry (credit cards, passports, and
money) and compact disks (CDs) [18]. It is also possible to obtain these inverse
replicas by casting a polymer precursor onto the master; after curing this is re-
leased to obtain the desired inverse structure. These techniques can reach resolu-
tions of tens of nanometers. The aspect-ratio of the replicated structures with high
throughput and reproducibility is limited to values of around 1, although higher
values have been reached. Among the physical origins of this limitation are the
adhesion forces between the mold and the inverse replica, and their mechanical
and thermal properties.
Nanomachining and nanomanipulation techniques using scanning probe micro-
scopes (SPMs) have been shown to be feasible for the patterning of polymers on a
nanometer scale [19]. Polymer lms have been modied by using high-force AFM.
In this case the tip indents into the material, generating a hole in it. Surface pro-
les consisting of not only lines and dots but also more complex three-dimensional
structures in a gray-scale fashion have been demonstrated. Attempts to overcome
the serial nature of this AFM-based lithography have also been made (Millipede
project from IBM) using arrays of independent cantilevers (up to 1024 tips). In this
case the hole formation rate (bit rate) is thermally assisted by heating the tip. Den-
sities of storage up to 200 Gbytes inch
2
[31 Gbytes cm
2
] have been achieved us-
ing this system. The movement of individual polymeric chains has also been con-
trolled, showing the power of this new nanolithography. Other nanomanipulation
techniques under development involve highly focused beams (optical tweezers)
able to control the position of polymeric microbeads [20].
The techniques described above are known as top-down approaches that make
use of available technologies to reduce the size of the features of the patterned
structures. On the other hand, bottom-up techniques make use of the self-
assembly concept to build up structures over several length scales. For example,
periodic templates are generated using polymer microbeads of monodispersed
size [21]. The steric repulsion between beads promotes the formation of controlled
three-dimensional packed crystalline structures. These templates, or equivalent
ones made of inorganic materials, can be used subsequently to generate the in-
verse polymeric opal also [22]. Another self-organization approach involves phase
separation of block copolymers [23]. In this case the dierent natures of the blocks
can induce their segregation, giving way to well-dened, long-range structures
(lamellas, spheres, cylinders) with sizes that range from several to hundreds of
nanometers, well controlled by the length of the dierent blocks. Although they
are intrinsically attractive, these techniques have important limitations for the ad-
vanced patterning of complex structures because of the diculty of controlling the
size, position, shape, and directionality of the growth structure.
Soft lithography is being investigated extensively for the large-scale generation of
relief structures in metallic substrates. In microcontact printing, which is a sub-
technique of soft lithography, an elastomeric stamp with a relief structure is used.
The stamp is impregnated with a monolayer of a reactive ink containing, for exam-
ple, thiols or silanes. The relief structure is then brought into conformal contact
with a noble metal substrate (silicon or silica may also have been used). In the con-
tact areas, a reaction occurs between the ink and the substrate, and an ink mono-
layer is obtained which acts as an etch-resist [24, 25]. Although this procedure is
intended to be used to pattern metal layers, it has also been employed in the struc-
turing of polymers. For example, the selective growth of polymer in the reacted
areas has been demonstrated [26]. The reacted monolayer on the substrate can
also act as a surface tension pattern to deposit polymers selectively.
We have briey reviewed some of the most signicant available technologies for
generating patterns in polymers. Each of them has specic advantages and de-
ciencies with respect the feature size, processability, high-throughput capability,
cost eectiveness, and functionality of the nal patterned structure. These and
other new techniques need to be developed further in order to overcome existing
problems.
19.1.2
Photoembossing
As an example of a patterning technique in polymers, we will discuss in more
detail photoembossing, a photolithographic technique for the generation of poly-
meric relief structures. In this particular case, the relief structure develops as a re-
sult of a material ux induced by a local polymerization. The material ux deforms
the surface of the lm, which is permanently xed by the photoinitiated crosslink-
ing process without the interference of a solvent development step [9, 27, 28].
Therefore this principle is attractive in an economic sense for applications that re-
quire the structuring of large surfaces.
The maskwise or holographic exposure of a thin lm consisting of a blend of
monomers in the presence of a photoinitiator induces a ux of material to the
exposed (high UV intensity) areas; this may be accompanied by a counterux of
other material to the dark (low UV intensity) regions [2932]. When the ux and
counterux are equally balanced in volume, a modulation in composition is ob-
tained, whereas the surface of the lm remains at. This process is used suc-
cessfully, for instance, to make volume holograms based on refractive index modu-
lation [33, 34]. If there is an unequal volume ux, the surface of the lm will
become modulated because of a volume expansion of the exposed area and a corre-
sponding volume reduction of the dark areas, or vice versa. This principle is ap-
plied to make surface holographic gratings. The process in itself is understood and
can be described quantitatively in terms of the change in the spectrum of chemical
potentials of the various components during the UV exposure and polymerization
[35].
Enhancement of this eect can be achieved with a blend that consists of a poly-
mer and a polyfunctional monomer. In that case the polymer forms a stationary
phase whereas the monomer diuses to the exposed areas, resulting in pro-
nounced surface proles. A general drawback is that the structures form during
exposure. This causes changes of the light path during exposure because the de-
forming surfaces refract the light in a continuously changing way during the for-
mation of the surface relief. It is possible to overcome this problem by creating a
latent image in the lm during which the formation of a surface relief is mini-
mized. The structure is then formed in a subsequent processing step, for example
heating. This is established by using a blend of a polymer and a monomer which
has low monomer mobility during the formation of the latent image because of its
high viscosity or because of its glassy state. Diusion and polymerization are then
largely inhibited. The exposed areas contain a high concentration of reactive par-
ticles, such as free radicals, that are conned to a very localized space. Only when
being heated the mobility is greatly increased and diusion and polymerization are
enabled. This then very rapidly deforms the surface to its desired shape, controlled
by diusion parameters and free surface energy. The process, which we will refer
to further as photoembossing, is shown schematically in Figure 19.1. The blends
may also contain a thermal initiator that initiates polymerization in the dark area
simultaneously or later when heated at higher temperatures, thus xing the sur-
face structure. An additional, but very important, advantage is that contact mask-
ing can be applied because the lm is solid and does not stick and thus cause de-
terioration in the mask and the lm.
An interesting feature of this process is that by the use of multiple lithographic
exposures before the thermal development of the structures, complex surface pro-
les can be generated. For this multiple exposure technique the fact that the
surface prole is not formed before the thermal treatment is optimally benecial,
since the second masking step can also be performed on a solid, at surface, en-
abling easy mask alignment. In the rest of the chapter we will discuss structure
formation during single and multiple lithographic or holographic steps, and show
some examples of photoembossed structures. A newly developed method to en-
hance the aspect ratio of the relief structures will also be shown.
19.2
Materials and their Photoresponsive Behavior
A typical formulation for the production of photoembossed structures contains a
polymer base material, a polyfunctional monomer, a photoinitiator, and, optionally,
a thermal initiator. For the coating process, solvents are added. The blend is com-
posed so that after evaporation of the solvent a solid, tack-free lm is formed, al-
19.2 Materials and their Photoresponsive Behavior 999
lowing contact mask exposure. An example of a blend consists of poly(benzyl
methacrylate) as the base polymer and di-pentaerythritol tetraacrylate as the mono-
mer. The polymer/monomer ratio is typically 1:1. Poly(benzyl methacrylate) is a
solid polymer and has a glass transition of around 54
C. It blends easily and homo-

geneously with the monomer. Polyfunctional acrylates like di-pentaerythritol
tetraacrylate are viscous liquids and basically act as plasticizers for the polymer. If
the monomer concentration is too high, the blend becomes tacky. Typically, thin
lms are formed by spin coating or by a doctor blade and the solvents are removed
by heating for 10 min at a temperature well below the decomposition temperature
of the initiators: in the case described, this is 80
C.
Figure 19.2 shows the dierential scanning calorimetry (DSC) traces of a sample
after application as a thin lm in the sample holder and drying at 80
C to remove
the solvent. From DSC the sample appears stable up to 120
C, above which the

thermal initiator activates the thermal polymerization of the acrylate monomer,
UV radiation at RT
photomask
solid reactive blend
spun from solution
substrate, e.g. glass or plastic
free radicals immobilized by polymer
solvents evaporated
at T < 80
o
C (in dark)
two-step heating at
T = 80
o
C and 130
o
C
solid polymer film
with fixed surface
Fig. 19.1. Schematic representation of the photoembossing process.
which reveals itself as the large exothermic peak in the DSC thermogram. When
the sample is exposed to UV light before heating, polymerization already starts
above 30
C. An isothermal DSC scan for 60 min during the UV exposure at 20
C
showed no signicant conversion of the acrylate monomer. This indeed shows that
monomer mobility at this temperature is very limited, inhibiting further polymer-
ization. Only when heated above 30
C, monomers are gaining diusional freedom

in order to allow propagation of the polymerization. Upon further heating, mono-
mer conversion proceeds up to a temperature of around 8090
C above which a
small decrease is seen, most probably due to a diminishing concentration of free
radicals due to termination. At temperatures above 120
C the polymerization prop-

agation rate increases again because of free radical generation from the thermal
initiator.
19.3
Single-exposure Photoembossing
The process of latent activation as demonstrated by photo-DSC is also exactly what
happens when a thin lm of the sample is exposed to UV through a mask. In that
case a latent image is formed at the exposed sites consisting of free radicals of the
photoinitiator with only minor conversion of the acrylate groups. Only after heat-
ing does further polymerization take place. The typical processing sequence has
been shown in Figure 19.1. First a thin lm is spun on a glass substrate. The lm
thickness is typically 3 mm after evaporation of the solvent by moderate heating at
80
C without premature polymerization. Cooled down to room temperature, the

0
0.5
1
1.5
2
2.5
-50 0 50 100 150 200 250
Temperature (
o
C)
E
x
o
t
h
e
r
m
i
c

h
e
a
t

f
l
u
x

(
m
W
)
0 min
10 min
60 min
Fig. 19.2. DSC traces of the reactive photoembossing mixture
(pre-heated in the dark at 80
C to remove solvents) measured

after 0, 10 and 60 min of pre-exposure with a UV lamp (365 nm,
5 mW cm
2
).
lm is exposed to 365 nm light from a mercury lamp (365 nm bandpass lter, 2.5
mW cm
2
) through a mask. After this exposure the surface deformation is present,
but is very small in relation to the desired structure. The exposed area contains a
high concentration of free radicals, immobilized by the viscous matrix. By heating
the lm to 80
C, well above the glass transition temperature, monomer mobility is

enhanced and the polymerization reaction sets in. This polymerization induces dif-
fusion of the monomer to the exposed areas without noticeable counterdiusion of
polymeric material. This process swells the exposed areas, whereas the unexposed
Before
heat treatment
After heat
treatment (80
o
C)
Fig. 19.3. Interferometric microscope picture of a sample
surface exposed with a UV dose of 0.2 J cm
2
through a
checkerboard mask (feature size 10 mm) before and after heat
treatment (5 min, 80
C).
areas are depleted. Figure 19.3 shows interferometric microscope picture of a sur-
face before and after the heating step. Before heating, but after UV exposure, the
surface remains relatively unstructured and at. Directly upon heating, the surface
develops itself into the relief that was imposed by the checkerboard mask. Note
that in these gures the aspect ratio is heavily exaggerated: in a lm of 3 mm
high, dierences of 1 mm are easily feasible. The structure obtained is xed perma-
nently either by a ood UV exposure or by heating to 130
C, at which temperature
the thermal initiator nishes o the polymerization reaction.
The surface prole that is created is determined by a set of parameters. First of
all, of course, the mask dimensions are important, but exposure conditions (dose,
temperature) and heat treatment conditions have also been proven to matter. Some
examples of surface structures obtained by various mask congurations are shown
in Figures 19.4 and 19.5. The structure size can be varied between approximately 1
and 20 mm. Below these dimensions the structures become small and the process
is hindered by the normal limitations of lithographic processes, such diraction.
At larger dimensions the diusion lengths of the monomer become too great, re-
sulting in high edges and deeper central parts of the relief (compare, for instance,
the two top AFM pictures in Figure 19.4), a phenomenon that is perfectly under-
stood from the models available for this process [35]. The shape can also be af-
fected to some extent by the exposure dose, as can be seen by comparing the two
lowest AFM structures in Figure 19.4, in which an overdose of UV light has re-
shaped the structures that are obtained.
The inuence of the exposure energy on the height of the structures is demon-
strated in Figure 19.6. This gure again demonstrates that surface deformation of
the samples takes place only to a minor extent when they are kept at room temper-
ature, even for a prolonged period of 24 h. The minor relief formation under these
conditions is practically independent of the UV dose, but during heating, in this
case in one step directly to 130
C, the structures develop and the UV dose appears

to be of great importance. Too low energy gives only a small eect, for the obvious
reason that photoinitiator conversion is low. A maximum in structure height is ob-
tained at UV doses between 100 and 200 mJ cm
2
. At higher doses the structure
height decreases again. This is explained by the fact that at doses that are too high
(overexposure) some cross-exposure of the intended dark area cannot be avoided.
At the same time the exposed area becomes too crosslinked, thus hindering further
diusion in a later stage of the process.
Next to the UV dose, the periodicity also seems to have an inuence on the fea-
tures height, as is demonstrated in Figure 19.7. In general, smaller dimensions
lead to a lower relief height. This can be understood in terms of monomer decit
at smaller pitches. At greater periodicities, for instance above 20 mm, the structures
have some problems lling the whole exposed area, and swelling occurs predomi-
nantly near the edges. The diusion in the reacting medium apparently occurs typ-
ically on a length scale of some micrometers. Further optimization outside this
preferred region is still possible, and an optimum balance between diusion and
polymerization reaction can be found at other diusion and curing temperatures.
However, comparing the results of the single-step (130
C) baking procedure with


Mask design

AFM of structure after heating step

p = q = 8 m
p = q = 10 m
overexposure
p = q = 10 m
p = q = 20 m
100 m
50 m
0 m
50 m
0 m
100 m
590 nm
100 m
50 m
0 m
50 m
0 m
100 m
480 m
100 m
50 m
0 m
50 m
0 m
100 m
1260 m
100 m
50 m
0 m
50 m
0 m
100 m
0 m
510 m
0 m
1020 m
Fig. 19.4. Examples of mask designs and the surface relief that
they generate after UV exposure and thermal treatment (10 min,
80
C; 10 min, 130
C).

Mask design

AFM of structure after heating step

p = q = 10 m
p = q = 10 m
p = q = 3 m
p = 20 m
q = 5 m
100 m
50 m
0 m
0 m
50 m
100 m
0 m
724 m
100 m
50 m
0 m
0 m
50 m
100 m
102 nm
0 nm
100 m
50 m
0 m
0 m
50 m
100 m
280 nm
0 nm
100 m
50 m
0 m
0 m
50 m
100 m
1200 nm
0 nm
Fig. 19.5. Examples of mask designs and the surface relief that
they generate after UV exposure and thermal treatment (10 min,
80
C; 10 min, 130
C).
0
200
400
600
800
1000
1200
0.00 0.10 0.20 0.30 0.40
Exposure energy (J/cm
2
)
L
a
t
t
i
c
e

h
e
i
g
h
t

(
n
m
)
Fig. 19.6. Surface relief heights after exposure through a line
mask with a periodicity of 20 mm and an aperture of 50% after
storage in air at RT for 25 h (c) and after a subsequent
heating step at 130
C in air for 5 min (k).

0
200
400
600
800
1000
1200
1400
0.00 0.10 0.20 0.30 0.40
Exposure energy (J.cm
2
)
L
a
t
t
i
c
e

h
e
i
g
h
t

(
n
m
)
mask with periodicities of 5 mm (c), 10 mm (D), and 20 mm
(k). The lms were exposed at RT and heated to 80
C for
5 min, and subsequently to 130
C for another 5 min.

the dual-step (80 and 130
C, respectively) reveals that the one-step process is about

as eective as the dual-step procedure. This leads to the conclusion that the bal-
ance in diusion and polymerization kinetics is in favor of diusion.
19.4
Dual-exposure Photoembossing
Figure 19.3 has already shown that the surface of the reactive polymer lm re-
mains almost at before the heating step. This is conrmed in Figure 19.6, which
shows that the height of the structures before the heating step, even after pro-
longed storage at room temperature, remains below 100 nm. The fact that the pris-
tine structures are small means that the optical behavior of the initially at lm is
hardly aected by the exposure. This is very relevant for controlling structure
shape during the exposure step. A surface that deforms redirects the rays of the
masked image, or in other words the surface proles start acting as a lens. But
the fact the surface prole remains almost unaected is of even greater importance
if one wants to employ a second exposure superimposed on the rst one. The pro-
cedure to perform this double exposure can be as follows. A rst exposure though
mask 1 is given at a dose somewhat smaller than the dose corresponding to the
maximum prole as shown in Figures 19.6 and 19.7. Then mask 1 is removed
and mask 2 is brought into place while the lm is maintained at room tempera-
ture. A second exposure is performed with a dose equal to the dose of the rst
exposure step. The lm now contains the latent images of two masks which will
develop during the heat-diusion step at 80
C or higher. Figure 19.8 shows some

examples of the masks that are used and the resulting surface proles obtained.
The structures that were presented individually in Figures 19.3 and 19.4 are now
superimposed, one on top of the other. The AFM pictures show that the formation
of complex structures is very readily possible and that the second structure is not
hindered in its resolution by the presence of the rst structure. In the experiments
shown, equal doses for the two mask exposure steps are used. Of course, one has
the freedom to choose them dierently and play with the dominance of each mask
step. In the case where UV doses are selected at the maximum sensitivity for a sin-
gle exposure or higher dose, it must be realized that local overexposure of doubly
exposed areas then lead to smaller features as well.
19.5
Complex Surface Structures from Interfering UV Laser Beams
Patterned irradiation can also be obtained by means of holographic exposure. In
this case two beams (or possibly three or more) coming from a laser are made to
interfere in the area of the sample. In order to do this, a conventional holographic
setup is employed. The s-polarized UV beam (351 nm) from an Ar laser is split in
two equal-intensity beams. These are made to overlap again, obtaining as a result a
Mask used for
1
st
exposure
Mask used for
2
nd
exposure
AFM of resulted structure
p = q = 10 m
p = q = 3 m p = q = 10 m
p = q = 10 m
p = q = 3 m
p = q = 3 m
p = q = 32 m
p = q = 8 m
100 m
50 m
100 m
0 m
0 m
50 m
212 nm
0 nm
100 m
50 m
100 m
0 m
0 m
50 m
148 nm
0 nm
100 m
50 m
100 m
0 m 0 m
50 m
204 nm
0 nm
100 m
50 m
100 m
0 m
0 m
50 m
150 nm
Fig. 19.8. Surface relief structures as measured by AFM after
two mask exposures of equal UV doses.
sinusoidal spatial modulation of the light intensity in the interference region (Fig-
ure 19.9). The period of the modulation can be adjusted by changing the angle be-
tween the two beams. In Figure 19.10 a sinusoidal surface relief grating is shown
with a periodicity of around 1 mm, such as is obtained by exposing the sample to a
holographic interference and subsequently heating to 80
C as described above.
Multiple holographic exposures can also be performed. As an example, Figure
19.11(a) shows a beat structure obtained by sequential exposures with two holo-
graphic gratings with close periods. First a holographic grating with a period of
1.5 mm is recorded. Afterward a second one with a period of 1.62 mm is registered.
The subsequent heating step reveals a beat structure with a period of about 20 mm,
the same as the beat that is obtained by addition of the two recorded sinusoidal
Fig. 19.9. Schematic representation of the holographic setup.
Fig. 19.10. Surface relief grating after holographic exposure
and thermal treatment (10 min, 80
C; 10 min, 130
C).
intensity proles, as shown in Figure 19.11(b). In Figure 19.12 we see the result of
exposing a lm with two gratings perpendicular to each other, giving a square lat-
tice.
19.6
Surface Structure Development under Fluids
The formation of surface relief structures starting with a at lm involves an in-
crease in surface, which is counteracted by the free surface energy. Consequently
(a)
(b)
0 20
0.00
0.02
0.04
0.06
0.08
0.10
R
e
l
i
e
f

h
e
i
g
h
t

(
m
)
Position (m)
10
Fig. 19.11. (a) Surface relief beat structure
due to sequential double holographic exposure
with two grating interference patterns of
dierent periods and equal doses and thermal
treatment (10 min, 80
C; 10 min, 130
C).
(b) Schematic representation of the result of
the addition of two waves of equal amplitude
but dierent periods, L
1
and L
2
.
the surface energy is a limiting factor for the generation of these relief structures
[28]. A new process has been developed to reduce interfacial interactions, favoring
the formation of new surface and achieving in this way enhanced aspect ratios in
the photoembossed structures. The use of a contact uid during the development
of the relief structure enhances the aspect ratio of the photoembossed structures by
a factor almost 2. The eect of this process is shown in Figure 19.13. Irradiation of
the lm is performed through a lithographic mask (transparent and dark lines
Fig. 19.12. Surface relief structure due to sequential double
holographic exposure with two orthogonal grating interference
patterns of equal UV doses and thermal treatment (10 min,
80
C; 10 min, 130
C).
0 10 20 30 40
0.0
0.5
1.0
1.5
2.0
R
e
l
i
e
f

h
e
i
g
h
t

(
m
)
Position (m)
0 10 20 30 40
0.0
0.5
1.0
1.5
2.0
R
e
l
i
e
f

h
e
i
g
h
t

(
m
)
Position (m)
mask with a periodicity of 10 mm and an aperture of 50% after
development: (a) without silicon oil; (b) with silicon oil on top.
19.6 Surface Structure Development under Fluids 1011
with a period of 10 mm). After the exposure and before the baking step, half of the
sample is covered with a drop of silicon oil, which wets the photosensitive lm but
does not diuse into it; the other half of the sample remains uncovered. The bak-
ing is then performed at 80
C for 10 min, after which the sample is cooled to room

temperature. The silicon oil is removed by rinsing the whole lm with heptane. It
has been checked by infrared spectroscopy of the lm and of the liquids employed
that neither the silicon oil nor the heptane swells or dissolves the photosensitive
lm. The photoembossed structure is xed by a second heating step at 130
C for
another 10 min. Figure 19.13 shows the surface prole of (left) the part cured in air
and (right) the part cured with silicon oil on top and subsequently rinsed with hep-
tane. The relief height is noticeably higher (almost double) in the part cured in
contact with the uid. The dierences in shape of the developed surfaces are also
remarkable. Whereas the surface baked in air shows a rounded top part, as driven
by the minimization of the surface area under the action of the surface tension, the
one baked in contact with the uid shows a atter top part and sharper edges. In
addition, the top at part corresponds quite well to the irradiated region of 5 mm.
By using this special process, relief structures that reproduce the features of the
mask with improved delity have been obtained. The research presented in this
paragraph is patent pending (inventors: Dick Broer, Carlos Sanchez, and Cees Bas-
tiaansen; applicant and owner: Dutch Polymer Institute (DPI)).
19.7
Conclusion
The generation of latent images by adjusting the monomer mobility during the UV
exposure step and the subsequent development of surface structures by polymer-
ization at higher temperatures provide accurate control over polymer surfaces.
The fact that the surface deforms only after the exposure step prevents structure
blur by refraction and diraction defects, and enables multiple exposures, creating
complex surfaces by multiple mask steps before heat development, or by combined
holographic exposures. Reduction of interfacial interactions makes possible to ob-
tain higher aspect ratios and more sharply dened features in the photoembossed
structures.
Acknowledgments
We acknowledge Mrs. G. N. Mol, Mr. H. Nulens, Sasha Alexeev (NT-MDT) and
Dr. B. van de Zande for their help, with the DSC measurements, the AFM mea-
surements, and the interferometric microscope images. The research of Carlos
Sanchez, Cees Bastiaansen, and Dirk Broer forms part of the research program of
the Dutch Polymer Institute (DPI), project DPI#298.
Notation
Acronyms
AFM atomic force microscopy
CD compact disk
DPI Dutch Polymer Institute
DSC dierential scanning calorimetry
DUV deep UV
EB electron beam
EUV extreme UV
FET eld-eect transistor
LCD liquid crystal display
LED light-emitting diode
MEMS micro-electromechanical system
SPM scanning probe microscope
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20
Chemical Analysis for Polymer Engineers
1
Peter Schoenmakers and Petra Aarnoutse
20.1
Introduction
Polymer reaction engineers have basically two dierent needs for polymer analysis
[1]: they want to follow the polymerization process, and to characterize the result-
ing polymer. These two types of analysis can be classied as process analysis and
polymer analysis, respectively; dierent objectives are associated with each of them
(Table 20.1). Process analysis enables the chemical engineer to monitor the poly-
merization process. For example, (s)he may want to follow the monomer conver-
sion or the polymer molecular weight during the reaction. Process control can be
realized if the results of the process monitoring are translated into specic actions.
Polymer analysis concerns the product that results from the polymerization pro-
cess. For example, the physical and chemical (molecular) properties may be com-
pared with given specications. The results of such analyses may also be used to
tune the polymerization process, either for future (batch) reactions or during a
continuous polymerization process. Arguably, the ultimate objective of the polymer
reaction engineer is to optimize the polymerization process, using either type of
measurement.
The dierent sets of objectives and requirements for the two types of analysis
imply that they are performed in quite dierent manners. Process analyses are
preferably carried out on-line (in the reactor) or at-line (in the immediate vicinity
of the reactor). Polymer analyses are typically performed in the laboratory. It is
also typical for dierent analytical techniques to be used (Figure 20.1). These will
be discussed in somewhat greater detail in subsequent sections of this chapter. We
will rst discuss the process analysis techniques (bottom left in the gure) in Sec-
tion 20.2. The polymer analysis techniques will be discussed in Section 20.3.
It should be noted that Figure 20.1 deals with chemical analysis as does the re-
mainder of this chapter. Physical measurements of, for example, the melt viscosity
of a polymeric product are very common (at-line) process monitoring tools, but
they are beyond the scope of the present chapter.
ISBN: 3-527-31014-2
1) The abbreviations used in this chapter are
listed at the end of the text, under Notation.
1015
Tab. 20.1. Objectives of the two types of chemical analysis for polymer reaction engineering.
Process analysis Polymer analysis
Engineering objectives process monitoring
process control
process optimization
product characterization
product control
process optimization
R&D objectives polymerization mechanism
reaction kinetics
reaction mechanisms
structureproperty relationships
Analytical objectives fast response
high precision (repeatability)
representative data
quality and amount (detail)
of information
(often) high accuracy
(correct information)
Laboratory
Multidimensional and
Hyphenated systems
At-line On-line
Monomer concentration (GC or LC)
Near - IR
spectroscopy
NMR spectroscopy
FT-IR
spectroscopy
Polymer
separations
Raman spectroscopy
Mass spectrometry
Gravimetry, Titration
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.

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Fig. 20.1. The main analytical techniques used
in polymer reaction engineering. A distinction
can be made between on-line (process) and
o-line (product) analysis (left to right in the
gure). On-line techniques typically provide
limited information, whereas more detailed
characterizations can be performed in the
laboratory (bottom to top in the gure).
1016 20 Chemical Analysis for Polymer Engineers
Moreover, this is not meant to be an exhaustive treatment of all the possible
methods of chemical analysis. For example, a very exciting possibility for the direct
monitoring of free-radical polymerization reactions in a research environment is
electron spin resonance (ESR) spectroscopy [2]. This allows a direct measurement
of the concentration of radicals in the reaction mixture. In many cases catalysts
are used in polymerization reactions, and determination of the fate of the catalyst
during the reaction and in the product polymer may require specic analytical
methods. For example, a variety of techniques exist for determining residual traces
of metal catalysts in polymers. These include X-ray uorescence characterization
for solid polymers, and atomic absorption (AAS) and emission (AES) spectrometry
for polymer solutions. The treatment in this chapter stops at the primary product
of the polymerization reaction. Detailed studies on the structure and morphology
of the ultimate polymeric product are assumed to be the domain of polymer tech-
nologists, rather than polymer reaction engineers. Methods for analyzing additives
are also beyond the scope of the present chapter.
20.2
Process Analysis
Analyses during a polymerization reaction can be carried out with the aim of
understanding the process (for example, the polymerization mechanism and the
kinetics) or with the aim of process control. The former concerns research mea-
surements, for which the amount of information obtained and the accuracy of the
data are the prevailing criteria. The latter concerns true process analysis and the
response time is a prevailing criterion.
In principle, all kinds of spectroscopic techniques lend themselves to on-line
measurements. Only a very few are practical. Although low-eld NMR has been
used to measure various material properties by applying empirical relationships,
NMR is still not a realistic proposition for on-line measurements. Ironically, FTIR
spectroscopy suers from too much sensitivity. Typically, good spectra can be ob-
tained only from very thin polymeric lms (or solutions). Attenuated total reec-
tion (ATR) probes, in which only a fraction of the IR light penetrates a very short
distance into the sample, reduce the problem of excessive sensitivity. However, they
aggravate the problems of variations in the baseline and nonlinear response. The
latter problem also obstructs the use of UV spectrometry for monitoring polymer-
ization reactions. Of the remaining options, near-infrared (NIR) and Raman spec-
troscopy are the most attractive.
20.2.1
Near-infrared Spectroscopy
Near-infrared (NIR) spectra are not very informative. In comparison with conven-
tional (mid-)IR spectra, they are much less useful for identifying unknown com-
pounds and for diagnosing minor variations in the sample. NIR spectra contain
fewer bands and much less resolution. Also, the absorption coecients (sensitivity)
are much lower in the NIR wavelength range (typically 8001200 nm). In contem-
porary applications of NIR spectroscopy, the lower sensitivity is turned into an ad-
vantage: it makes it much easier to deal with the presence of strong IR absorbers,
such as water, and it helps to keep the response strictly linear. Also, the spectra of
individual compounds of a mixture turn out to be perfectly additive in NIR spec-
troscopy. Finally, unlike mid-IR spectra, NIR spectra typically show plenty of base-
line, which is essential for quantitative analysis. Thus NIR spectroscopy is perfect
for on-line analysis in almost all respects. The lack of resolution and of clearly
dened bands for specic components or functionalities remains a distinct dis-
advantage.
The combination of (near-)perfect linearity and spectral additivity and limited
specicity and resolution makes NIR a perfect match for multivariate calibration
methods or chemometrics. In this case calibration is not based on a single wave-
length (band) per component or functional group (one variable, thus univariate),
but on many wavelengths or entire spectra (many variables, thus multivariate).
The resulting spectrum is thought to be a linear combination of the individual
spectra. In most cases, the spectrum corresponding to the desired property is not
known. For example, the number of hydroxyl groups in a polymer can be charac-
terized using NIR and multivariate calibration [3]. This implies that the NIR anal-
ysis must be calibrated using a training set of samples with known concentrations.
The latter could be a set of (commercially) available reference materials or, more
commonly, a set of samples that are analyzed in parallel using an absolute (pri-
mary) method. The latter must be reliable and validated. Building good calibra-
tion models is a critical step in the process. If the sample exceeds the boundaries
of the training set, the NIR results are highly unreliable and may be grossly in-
correct. In case of systematic deviations from the training set (for example, when
a dierent catalyst is used in the polymerization process), recalibration is neces-
sary. The advantages of NIR in combination with multivariate calibration (rapid
on-line measurements) must be balanced against the disadvantages of indirect cal-
ibration.
NIR has been used to monitor the polymerization of acrylic acid [4], for the so-
lution polymerization of methyl methacrylate (MMA) in toluene [5], for following
the emulsion polymerization of MMA and butyl acrylate [6], and for monitoring
the copolymerization of MMA and N,N-dimethylacrylamide (Figure 20.2) [33]. The
density of linear low-density polyethylene was monitored using NIR and a partial
least-squares (PLS) calibration model [7].
20.2.2
In-situ Raman Spectroscopy
Raman spectroscopy is based not on absorption of light, but on inelastic scattering.
The wavelength of the scattered light is slightly changed because of its interaction
with molecules. The information obtained from Raman spectroscopy is in some
ways similar to that from IR spectroscopy (wavelength shifts in the micrometer
range) and in some ways very dierent (dierent selection rules). For example,
water is an infamous interference in mid-IR spectroscopy, but it is not detectable
by Raman spectroscopy. Raman spectroscopy shares some of the advantages of
NIR spectroscopy. It combines a relatively low sensitivity with a good linearity,
rendering it compatible with multivariate calibration. An advantage of Raman in
comparison with NIR is the much greater spectral resolution (narrower spectral
bands).
The greatest disadvantage of Raman spectroscopy in the analysis of polymers
and the monitoring of polymer reactions is the occurrence of uorescence, which
manifests itself as disturbances in the spectral background. Raman spectroscopy is
a relatively insensitive technique and because in light-scattering measurements
(other than absorption measurements) the sensitivity increases with the intensity
of the light source, lasers are commonly used in Raman spectroscopy. This also
implies that the incident wavelength is very well dened. In general, uorescence
eects are strongest at short wavelengths. Traditionally, Raman spectroscopy is per-
formed with lasers in the visible range as primary light sources. In FT-Raman near-
IR lasers are employed, which give rise to much less uorescence (Figure 20.3).
An attractive compromise is the use of a 785 nm laser, which reduces uorescence
while oering greater sensitivity than NIR lasers.
0
Offset
Correction
7000 6000 5000
Wave number [cm
1
]
1.6
1.2
0.8
0.4
A
b
s
o
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e

[
A
.
U
.
]
0
Fig. 20.2. Use of NIR spectroscopy in-line
reaction monitoring of copolymerization of
methyl methacrylate and N,N-
dimethylacrylamide [33]. Spectrometer:
BOMEM MB 155; the probe was connected to
the spectrometer using optical bers and a
BOMEM optical interface. The gure shows
calibration samples.
20.2.3
At-line Conversion Measurements
Although chromatography is an incredibly versatile (set of ) technique(s) for per-
forming analytical separations and quantitative analyses, the typical nature of a
polymerization mixture, containing both high molecular weight polymers and low
molecular weight monomers, causes serious complications. Polymer-containing
samples cannot be injected easily into simple gas chromatographs, because the
injector or, worse, the column will be seriously contaminated. Although several
elegant solutions exist (see Section 20.3.1.1), these cannot easily be implemented
and applied in at-line situations.
Liquid chromatography systems can deal more easily with the combination of
large and small molecules. Size exclusion chromatography (SEC; also known as
gel permeation chromatography, GPC) is especially suited for the analysis of poly-
mers, which are separated on the basis of their size in solution. Therefore, SEC is

1610 1620 1630 1640 1650 1660 1670 1680 1690 1700
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
x 10
-3
Wavenumber (cm
-1
)
A
r
b
i
t
r
a
r
y
R
a
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a
n
I
n
t
e
n
s
i
t
y
styrene
1,3-butadiene
poly(butadiene)
Fig. 20.3. FT-Raman spectra recorded during copolymerization
of 1,3-butadiene and styrene [34]. Spectrometer: Bruker IFS66
FTIR/FT-Raman spectrometer with Nd:YAG laser (1.5 W,
1064 nm), N
2
-cooled Ge detector. Early stages of the reaction
(only polybutadiene homopolymer formed).
often used for measuring molecular weight distributions (see Section 20.3.3.1).
The mechanism underlying SEC separations concerns the partial exclusion of
larger molecules from pores of the packing material. By inserting a column with
very small pores (an oligomer column) in the separation system, it is possible
to create sucient selectivity between the monomers and the smallest oligomers
present in the reaction mixture. If suitable detectors (suciently sensitive and,
ideally, linear) can be found for both the polymer and the monomer, then the con-
version can be elegantly measured by on-line SEC. The polymerization of styrene
is a good example (Figure 20.4) [8]. In this case, UV detection can be used conven-
iently.
There has been a recent trend toward performing fast SEC separations [9], in-
spired by the developments in combinatorial (polymer) chemistry and the asso-
ciated high-throughput experimentation. Fast SEC allows molecular weight dis-
tributions to be measured in one or two minutes. From both a practical and a
theoretical point of view, the possibilities for fast SEC are much greater than was
commonly believed until very recently. Fast SEC oers less resolution than conven-
tional SEC. It only oers a rough picture of the MWD and it can only be applied to
broadly distributed polymers. Yet the developments in fast SEC make it a feasible
technique for determining molecular weight distributions at-line.
Fig. 20.4. Use of SEC for conversion measurements.
Chromatograms of two polystyrene (Acros Organics,
M
w
1:4 10
5
g mol
1
, PDI 2:6) calibration samples
(conversion x 0:027 and x 0:401). Reprinted from Ref. [8].
20.3
Polymer Analysis
20.3.1
Basic Laboratory Measurements
20.3.1.1 Conversion
In the laboratory, residual monomer concentrations are typically measured by
some kind of chromatographic analysis; whether this is gas chromatography (GC)
or liquid chromatography (LC) depends largely on the type(s) of monomers used in
the polymerization process. Monomers that are gases or highly volatile liquids (for
example, alkenes, vinyl chloride, acrylonitrile) or UV-inactive (for example, acryl-
ates) are not readily compatible with LC. On the other hand, nonvolatile monomers
(for example, diacids, diamines, bisphenol A) are not amenable to GC.
When GC is being used, possible contamination of the system (injector and col-
umn) with nonvolatile polymeric material is the main issue. One option is to allow
direct introduction of a polymer-containing sample (solution), but to conne the
polymer to a removable part (liner) of the injection system. On some injection
systems (specically programmable-temperature vaporizers, or PTVs), a series of
injections may be performed before the quantitative analysis of monomer is jeop-
ardized and the liner needs to be replaced. Such an approach may be acceptable if
Fig. 20.5. Individual conversion proles of
methyl methacrylate (s) and vinylidene
chloride (c) in the batch solution
copolymerization of methyl methacrylate and
vinylidene chloride in dimethylformamide,
estimated by GC measurements of the vapor
composition of the reactor head space [35].
the total number of analyses that need to be performed is fairly small. Another,
much more sophisticated, option is the on-line coupling of an LC separation of
polymer and monomer (for example, using size exclusion chromatography; see
Section 20.2.3) with a GC analysis [10]. A fully automated system may be built
that allows large numbers of samples to be analyzed. However, LC-GC systems
are complicated to develop and to use in practice. High-level expertise is required
if one is to opt for such a solution.
An easier solution, that also allows complete automation, is head-space GC.
An example is shown in Figure 20.5. This technique is based on measuring vol-
atile components from the vapor phase above a nonvolatile matrix. In this case a
polymer-containing sample in a vial is placed in the system. The sample may be a
solid or a (viscous) liquid. In this case, the presence of a large amount of volatile
solvent may be a disadvantage. Water, especially, may cause insurmountable prob-
lems. In head-space GC the vapor phase may be analyzed after equilibrium with
the sample has been established (static head-space), or the sample may be purged
continuously and all volatile materials may be trapped at the column inlet, to be
released from there at the beginning of the analysis (purge and trap or dynamic
head-space). Head-space analysis (especially in the static mode) requires careful
calibration and validation, but once it is in operation fully automatic analyses can
be performed with relative ease.
20.3.2
Detailed Molecular Analysis
20.3.2.1 FTIR Spectroscopy
Infrared spectroscopy has long been one of the stalwarts of polymer analysis. One
reason is that polymers and IR spectroscopy are highly compatible. As a case in
point, thin lms of polystyrene have been used for many years as a reference sam-
ple for calibrating the wavelength scale of conventional IR spectrometers. In most
laboratories, conventional (dispersive) IR spectrometers have been replaced by
contemporary Fourier transform instruments. The latter typically yield a higher
resolution, a higher sensitivity, and a greater wavelength accuracy. The advent of
FTIR has spurred on the development of highly sensitive measurements on small
samples (for example, FTIR microscopy) and of very fast measurements.
The range of information that can be obtained from FTIR measurements is
summarized in Table 20.2. FTIR is still often used in polymer analysis, because
the measurements are easy and fast and because many dierent types of polymeric
samples can be measured with a minimum of sample preparation. However, FTIR
spectroscopy also has its weak points. The resolution in the spectra is usually not
limited by the quality of the spectrometer, but by the properties of the sample. In
samples of polymers many bands usually overlap and, while band assignments are
usually possible, the quantication of overlapping bands is dicult and prone to
errors. One signicant source of error is variation in the baseline of FTIR spectra.
Such variations can be attributed to the fact that in FTIR spectrometers the base-
line and the sample are not measured simultaneously. Also, spectral artefacts, such
as scattering by the sample, may result in changes in the baseline. Other problems
are possible nonlinearity in absorbance (or reectance) versus concentration curves
and the large dierences in sensitivity for dierent absorption bands. In fact, near-
IR spectroscopy is often preferred for routine quantitative measurements, be-
cause fewer problems are encountered with the linearity and with establishing the
baseline.
20.3.2.2 NMR Spectroscopy
Nuclear magnetic resonance spectroscopy probes the spins of specic atomic nu-
clei in a strong magnetic eld. The spin can be changed at very specic (resonance)
frequencies, which depend on the chemical environment of the nucleus. Thus,
NMR spectra provide very detailed chemical information on the structure of mole-
cules (Table 20.3). The dierences between the spin energy levels (with and against
the magnetic eld) are very small. This implies that the spins are almost evenly
distributed across the dierent levels (Boltzmanns law). Therefore, NMR is an
insensitive technique. The dierence between the energy levels, and thus the dif-
ference between the populations of the dierent levels, and hence the sensitivity
of the NMR measurements, can be increased by increasing the eld strength.
Therefore there is a continuous trend toward ever-higher eld strengths (and ever-
costlier instruments) in NMR spectroscopy. This is especially the case since (in so-
lution NMR) the resolution also increases with increasing eld strength. The two
most common nuclei that are studied in NMR spectroscopy are protons (
1
H) and
carbon (
13
C). The former has a natural abundance of almost 100%, but
13
C repre-
sents only about 1% of the carbon population. If only because
12
C cannot be ob-
served by NMR spectroscopy, the sensitivity of carbon-NMR is signicantly lower
than that of proton-NMR.
NMR spectroscopy yields quantitative data on the number of protons or (with
some precautions) carbon atoms that have a certain chemical environment. This
can be directly translated into chemical composition data (see Figure 20.6). For ex-
Tab. 20.2. Information that may be obtained from FTIR spectroscopy.
Type of information Comments
Chemical composition clear evidence on presence or absence of specic
functional groups
rapid conrmation of structure
chemical composition of copolymers, but
quantication can be dicult
End groups useful only for low MW polymers
Characterization of polymers
in many dierent forms
direct measurements on polymer lms
thicker objects though ATR or specular reection
(surface characterization)
easy characterization of powders (DRIFT)
IR microscopy for small spots
imaging techniques are emerging
ample, the numbers of aromatic and aliphatic protons in a copolymer of styrene
and isobutene unambiguously dene the chemical composition. Much more de-
tailed information is revealed by NMR spectroscopy about the specic structure of
the polymer. Many dierent measurement techniques have been developed that
reveal intricate details about the molecular structure [11], but these are beyond
the scope of the current chapter.
NMR spectroscopy can be used to study polymers in solution (solution NMR) or
as such (solid-state NMR). In the latter case, the resolution is typically much lower,
mainly because of sample anisotropy. To improve the resolution in solid-state NMR
the sample can be spun at a high frequency (in the kilohertz range) and at a
specic (magic) angle (54
) relative to the magnetic eld. The sensitivity can be

increased by transferring magnetization from
1
H to
13
C nuclei. The resulting tech-
nique is referred to as cross-polarization magic-angle spinning NMR (CP-MAS-
NMR).
20.3.2.3 Mass Spectrometry
Whereas (FT)IR and NMR spectroscopy have been essential tools for polymer anal-
ysis for decades, mass spectrometry (MS) only became truly relevant in the later
1990s, and the number of mass spectrometers in polymer analysis laboratories is
now increasing rapidly. Our current ability to characterize (very) large molecules
successfully can be seen as a small miracle. In many cases, we are now able to ion-
ize polymer molecules and to transport large molecular ions through magnetic or
electric elds with great integrity. The possibilities of contemporary MS are fantas-
tic. However, one must be aware that there are still severe limitations. The possibil-
ities and limitations of polymer MS will be briey reviewed in this section.
MS has been used in polymer analysis for many years, but these techniques
Tab. 20.3. Information that may be obtained from NMR spectroscopy.
Chemical composition highly detailed information on chemical structure and
composition
accurate quantitative data (% of specic protons; % of
specic carbon atoms) at levels above about 1%
Molecular architecture good, quantitative information on average chain
regularity (tacticity)
information on branching (at high branching levels)
easy distinction between random and block copolymers;
some information on average block length
Physical structure information on network mobility
some information on polymer morphology
Polymers in various forms solution NMR gives the best resolution
solid-state NMR (powders, particles, or small objects)
routinely possible
polymer melts studied occasionally
have relied on destruction of the polymer into smaller pieces or fragments.
Pyrolysis-GC-MS is a conventional method for polymer analysis and characteriza-
tion. The pyrolysis stage yields small, uncharged fragments of the polymer, such
as residual monomers, which can be separated by gas chromatography (GC) and
identied by MS. Pyrolysis-GC-MS yields useful information on the composition
of (co)polymers, the presence of additives, and suchlike. However, the results are
dicult to quantify. Similarly, in secondary-ion mass spectrometry (SIMS), the
polymer is rst fragmented using a beam of primary ions. The resulting fragments
are charged and these fragments are subsequently analyzed by MS. SIMS can yield
very useful (organic chemical) information on polymer surfaces (static SIMS), or it
can yield depth proles of materials (dynamic SIMS). In these conventional appli-
cations of MS in polymer engineering, only information on molecular fragments is
obtained, but none on the intact polymer molecules.
Fig. 20.6. 188 MHz
13
C NMR spectra of poly(n-butyl acrylate-
co-carbon monoxide-co-ethylene) samples with dierent
monomer compositions (indicated in the gure) [36].
The main breakthrough in polymer MS has been the development of soft ioniza-
tion methods. This implies that molecular ions are obtained and characterized.
During the formation of molecular ions, small ions (such as H
) may be ab-
stracted from the molecule, or adducts may be formed with small ions (for exam-
ple, Na
), but no fragmentation occurs and the resulting ion is highly representative

of the original polymeric molecule. Two important soft ionization techniques have
emerged in recent years, namely electrospray ionization (ESI) and matrix-assisted
laser desorption ionization (MALDI).
Electrospray ionization (ESI) ESI requires a polymer solution to be pumped
into the mass spectrometer, either as such or, conveniently, after a liquid-
chromatographic separation. In the latter case, a narrow, pre-separated fraction of
the polymer is introduced into the mass specrometer, which greatly enhances the
chances of obtaining useful mass spectra. The liquid is sprayed into the ionization
chamber under the simultaneous action of an electric eld of several kilovolts. The
solvent should have a signicant polarity and some ionic additives (salt or buer)
are typically present. It is not strictly necessary for the polymer itself to be dis-
solved in this polar solvent. Good results have been obtained by adding a separate
(immiscible) stream of solvent to the polymer solution through a T-piece just be-
fore the ESI interface [12].
The exact mechanism by which charged molecular ions are ultimately obtained
from the polymer solution has not yet been elucidated unequivocally. The spray is
formed at atmospheric pressure, but then passed into the vacuum part of the ion-
ization chamber, where the volatile components evaporate. This may result in a
concentration of (nonvolatile) ions in very small droplets, which then become un-
stable and explode to yield a series of individual ions, including the charged poly-
mers. An alternative mechanism, which seems to be supported by the fact that the
polar, salt-containing solvent does not need to be miscible with the polymer solu-
tion, entails the complete evaporation of all solvents, followed by ionization of the
polymer molecules in the gas phase.
In any case, molecular ions are formed that contain one (singly charged ions)
or more charges. The fact that multiply charged ions are being formed makes it
easier to analyze molecular ions of high molecular weight, because the behavior
of ions in mass spectrometers is determined by the mass-to-charge ratio (m=z)
rather than by the absolute mass. However, the presence of multiply charged ions
may signicantly complicate the resulting mass spectra and their interpretation.
Figure 20.7 shows an example of the application of ESI-MS for polymer analysis.
Table 20.4 summarizes the information that can be obtained using this technique.
Matrix-assisted laser desorption ionization (MALDI) In MALDI, the polymer is
mixed intensively (usually from a solution) with a matrix, and possibly with other
additives such as a salt. It is then deposited as a small spot on a target (MALDI
plate). The deposited mixture is irradiated by a laser pulse. The matrix is selected
such that it strongly adsorbs the laser light, heats up very rapidly, and induces the
transfer of a single charge (usually an adduct ion) to the polymer molecule. The
Extracted masses for every scan
3000
2500
2000
1500
1000
500
0
m
a
s
s

v
a
l
u
e
0 20 40
scan #
60 80 100 120 140
Fig. 20.7. Characterization of peruoro-
polyethers by on-line LC-ESI-MS [12]. LC
conditions: Column: Nucleosil silica (5 mm),
150 mm 2.1 mm i.d.; mobile phase:
0.120% methyl-t-butyl ether in 1,1,2-
trichlorotriuoroethane in 15 min; mass
spectrometry: Micromass time-of-ight MS
operated in negative-ion mode; capillary
voltage: 3 kV; desolvation temperature: 350
C;
source temperature: 120
C; cone-gas ow rate:
30 L h
1
; desolvation gas ow rate: 350 L h
1
.
ESI coniditions: 20 mL min
1
50:50 iso-
propanol/water added post-column; cone volt-
age: 50 V.
Tab. 20.4. Information that may be obtained from ESI-MS.
Absolute mass of molecular ions limited to polar polymers with molecular weight below
ca. 25 kDa
structural formulas may be obtained in the case of high-
resolution MS
Molecular-weight distribution only for (homo)polymers with a very narrow
distribution in terms of molecular weight, chemical
composition, and type of functionality
prior separations (e.g., SEC, LC) allow analysis of more
broadly distributed polymers by ESI-MS
Combined mass of end groups
(homopolymers)
can be obtained from series of MS peaks (one of more
dierent end groups)
may be complicated by adduct ions
may be facilitated by high-resolution MS
resulting spectra are quite variable in terms of the observed ions and their inten-
sities, but representative spectra can be obtained by summing or averaging the
spectra resulting from a large number of pulses. Only singly charged ions are ob-
served and there is usually little or no fragmentation, although MALDI is often
found to be slightly less soft (that is, more likely to induce fragmentation) than
ESI [13].
Polymers that are amenable to MALDI must have some degree of polarity
polyethene and polypropene are still essentially incompatible with the technique.
Another essential requirement is that the polymers be narrowly distributed in
terms of molecular weight, chemical composition, and functionality. If the molec-
ular weight distribution is not very narrow, then the smallest molecules will be
over-represented in the resulting mass spectrum (discrimination). If one type of
molecule is abundant, it may dominate the entire mass spectrum, completely sup-
pressing the ionization of polymeric components present in lower concentrations
(ion suppression). Selective ionization may also be observed in the case of varia-
tions in functional groups or end groups.
MALDI cannot easily be coupled on-line to separation techniques such as liquid
chromatography (LC), but it can be elegantly coupled o-line. Because of the high
sensitivity of MALDI, one drop of LC euent may be sucient to prepare excellent
MALDI spots.
Table 20.5 summarizes the information that can be obtained using this tech-
nique.
Types of mass analyzers There are quite a few dierent types of mass analyzers.
Conventional high-resolution MS exploits magnetic-sector instruments. Quadru-
pole instruments have become the aordable standard for the analysis of fairly
small components (up to about 1000 Da), although ion-trap systems have some
specic advantages, such as the possibility of performing high-sensitivity tan-
Tab. 20.5. Information that may be obtained from MALDI-MS.
Absolute mass of molecular ions limited to polymers with a certain minimum polarity,
up to quite high molecular weights, provided that
the sample is very narrowly distributed
Molecular weight distribution only for (homo)polymers with a very narrow
distribution in terms of molecular weight, chemical
composition, and type of functionality
prior separations (e.g., SEC, LC; usually carried out
o-line) allow analysis of more broadly distributed
polymers by MALDI-MS
Combined mass of end groups
(homopolymers)
can be obtained from series of MS peaks (one of more
dierent end groups)
may be complicated by adduct ions or fragmentation
may be facilitated by high-resolution MS
dem MS (MS-MS) or multiple MS (MS
n
) experiments with relative ease. The big
brother of the ion-trap instrument, the Fourier transform ioncyclotron resonance
(FT-ICR-MS, or simply FT-MS) spectrometer, oers extremely high resolution. It
has been gaining popularity, mainly thanks to the great advances made in protein
MS since the mid-1990s. However, use of FT-MS instruments is still the preroga-
tive of the elite few.
In contrast, another type of mass analyzer that was quite uncommon until re-
cently is now proliferating rapidly in the eld of polymer MS. Time-of-ight (ToF)
analyzers are based on the principle of measuring the time a specic ion requires
to travel a given length (in vacuum). The ight time is directly related to the m=z
value. The mass range of ToF analyzers is not fundamentally limited. Thus, poly-
mers of very high molecular weight can be analyzed after soft ionization. ToF ana-
lyzers are now the preferred type of instrument for the characterization of (natural
and synthetic) macromolecules, in combination both with ESI and with MALDI.
ToF combines a high sensitivity (due to a favorable duty cycle) with a broad mass
range and a high spectral resolution and accuracy. High-resolution versions of ToF
analyzers exploit the so-called reectron mode, in which the length of the ight
path is doubled. In addition, ToF-MS instruments have become much more acces-
sible and much more aordable in recent years. An example of the MALDI-ToF-
MS technique is shown in Figure 20.8.
20.3.3
Polymer Distributions
There are many ways to measure the average properties of a polymeric sample.
These will not be discussed extensively in this chapter. Among the techniques
used to measure average molecular weights are those that yield number averages
M
n
, such as end-group titrations and end-group analysis by NMR. Such tech-
niques work best at relatively low molecular weights. Static light scattering yields
a direct estimate of the weight-average molecular weight M
w
. It works best for
relatively high molecular weights (above ca. 20 kDa). Measurement of the intrinsic
viscosity may be used to obtain the viscosity-average molecular weight M
v
. If the
entire molecular weight distribution is measured, then all the desired averages and
the sample polydispersity (PDI M
w
=M
n
) can be readily calculated.
20.3.3.1 Molecular Weight Distributions
The most important molecular distribution is the molecular weight distribution
(MWD) or, equivalently, the molar mass distribution (MMD). Size exclusion chro-
matography (SEC; also known as gel permeation chromatography, GPC) is the out-
standing technique for measuring the MWD. In SEC, the retention time is related
to the molecular weight by constructing a suitable calibration curve (Figure 20.9)
based on the retention times (or volumes) of a set of narrowly distributed stan-
dards of known molecular weight. SEC separates on the basis of the size of mole-
cules in solution (the hydrodynamic volume), rather than on the molecular weight.
Thus, to measure accurate (in SEC terminology, absolute) molecular weights, it
is necessary that the calibration standards be chemically identical to the sample
polymer. Polystyrene standards should be used to construct a calibration curve for
polystyrene samples, PMMA standards for PMMA samples, and so on.
Unfortunately, suitable standards are not available for all polymers. For a num-
ber of homopolymers suitable standards are commercially available. However, for
copolymers it is notoriously dicult to determine absolute molecular weights by
SEC. Even if copolymer standards were available, there are many dierent mole-
cules (dierent combinations of molecular weight and chemical composition) that
exhibit the same hydrodynamic volume. Also, the size of polymer molecules in
solution is aected signicantly by other properties, for example the degree of
branching. For these reasons, SEC is often used to measure molecular weight
distributions relative to dierent standards, such as polystyrene. Such relative
measurements may be perfectly adequate for many purposes. For example, for
monitoring polymerization reactions and product specications the precision (re-
peatability) of the data tends to be much more important than their accuracy.
788.0 1216.8 1645.6 2074.4 2503.2 2932.0
104.1
104.1
104.1
104.1

I
n
t
e
n
s
i
t
y

(
%
)

Mass (amu)
100
773 1316 1859 2402 2945 3488

104.1
104.1
104.1
Mass (amu)
I
n
t
e
n
s
i
t
y

(
%
)

100
Fig. 20.8. MALDI-TOF-MS spectra of
polystyrenes, reective positive-ion mode,
DCTB as matrix and Ag
as a cationization
agent. Top: PS with two dierent end groups or
adduct ions. The two dierent series of peaks
dier by 104.1 amu, the mass of one repeat
unit styrene. Bottom: PS with four dierent end
groups [37].
Detectors for size exclusion chromatography The most common detectors used in
SEC are the UV absorbance detector (for polymer molecules that possess chromo-
phores) and the (dierential) refractive index detector (DRI or RI) for polymers that
do not (see Table 20.6). The latter is less convenient to use in practice, and less
sensitive. Therefore, the evaporative light-scattering detector (ELSD) is used in-
creasingly for characterizing non-UV-active polymers at low concentrations (for
example, polymeric contaminants or polymers separated by comprehensive two-
dimensional liquid chromatography). A serious disadvantage of the latter detector
is that its response increases exponentially with increasing polymer concentration
and is, therefore, highly nonlinear. The response of the ELSD also tends to vary
more strongly with the molecular weight of the sample polymer than those of the
UV and DRI detectors.
A very important option is the combination of SEC with techniques that allow
direct measurement of molecular weight, such as viscometry or light scattering
(Table 20.7). This in principle eliminates the need for narrow standards of ex-
actly the same polymer, and it alleviates the requirements on the SEC system, be-
cause slight variations in retention times due to variations in the ow rate or inter-
actions with the column can be negotiated. This is true for viscometric detection,
provided that accurate MarkHouwink constants (K and a) are available to trans-
50
100
500
10
6
10
5
10
4
10
3
Elution volume (ml) 10 4

P
o
l
y
s
t
y
r
e
n
e

M
o
l
e
c
u
l
a
r

W
e
i
g
h
t
10M
100
1M
100K
10K
1K
Fig. 20.9. SEC calibration curves for a series of columns with
dierent pore sizes (Polymer Laboratories, Church, Stretton,
Shropshire, UK; www.polymerlabs.com/gpc). Dierent columns
show good selectivity (shallow curves) across dierent
molecular weight ranges.
Tab. 20.6. General (concentration-sensitive) detectors for size exclusion chromatography.
Detector Abbrev. Strong points Weak points
UV absorbance UV sensitive
highly linear
only applicable for UV-absorbing
polymers
(Dierential) refractive
index
(D)RI universal
(all polymers)
not very sensitive
strong solvent signal
sensitive to temperature variations
needs reference cell
Evaporative light
scattering
ELSD universal
(all polymers)
highly sensitive
nonlinear response
response depends on polymer structure
and molecular weight
Tab. 20.7. Specic (molar mass sensitive) detectors for size exclusion chromatography.
Detector Abbrev. Strong points Weak points
Viscometry Vis direct measurement of
intrinsic viscosity
absolute MW using Mark
Houwink constants or
the universal calibration
principle
applicable only for M > (ca.)
5000
accuracy relies on accuracy
of MarkHouwink
constants or on quality of
SEC measurements
Light scattering
low angle
right angle
triple angle
multi-angle
LALS
[a]
RALS
TrALS
MALS
direct measurement of M
w
(for M > (ca.) 10 000)
multi-angle LS provides
direct measurement of
the root-mean-square
radius (for M > (ca.)
50 000)
sensitive to calibration
parameters (especially the
refractive index increment
dn/dc)
tedious calibration
procedure
Mass spectrometry
electrospray
ionization
[b]
ESI absolute molecular-weight
measurement
information on end groups
only applicable to polar
polymers
multiple ionization
complicates spectra
best for M < (ca.) 20 000
Matrix-assisted laser
desorption/
ionization
[c]
MALDI absolute molecular weight
measurement
information on end groups
applicable to narrowly
distributed polymers up
to very high M
only applicable to
moderately or highly
polar polymers
(very) narrowly distributed
samples are required (in
terms of MWD, FTD, etc.)
[a]
Sometimes called low-angle laser light scattering (LALLS).
Analogously, RALLS, TrALLS and MALLS may be found.
[b]
Electrospray ionization mass spectrometry can be coupled on-line
with SEC. However, this does require a miniaturized SEC system (ow
rate < 100 mL min
1
) or a ow splitting device after the SEC column.
[c]
MALDI is usually combined o-line with SEC. Samples from the
euent can be collected manually or by using a fraction collector.
Devices to facilitate deposition directly from the SEC system onto a
MALDI target plate are commercially available.
late the measured intrinsic viscosity ([h]) for the specic polymer (in the specic
solvent used and at the specic temperature of operation) into the molecular
weight through M Kh
a
. When measuring the light scattered by the polymer so-
lution to obtain the (weight-average) molar mass, the refractive index increment
(dn/dc) of the specic polymer in the specic solvent (at the temperature of opera-
tion) must be accurately known. Both an on-line viscometer and a light-scattering
instrument must be calibrated using known standards.
Both viscometry and light scattering require an independent measurement of the
concentration of the polymer. For this purpose, one of the concentration-sensitive
detectors (most often refractive index detection) is used in combination with the
molecular weight selective detector. Using a combination of several detectors is
common practice in SEC. A particularly powerful combination is to use refractive
index detection (to measure concentration), viscometry (to measure the intrinsic
viscosity), and light-scattering detection (to measure molecular weight), all together.
A RALS detector is typically used instead of a MALS detector. Therefore, the root-
mean-square radius of the polymer in solution cannot be measured directly and
the molecular weight of large polymer molecules (M > 100 000) requires an itera-
tive correction procedure.
The on-line combination of SEC with electrospray ionization MS (SEC-ESI-
MS) and the o-line combination of SEC with matrix-assisted laser desorption/
ionization (SEC//MALDI-MS) are relatively recent possibilities. For the time being,
SEC-ESI-MS is limited to polar polymers of relatively low molecular weight. In
contrast, SEC//MALDI-MS is applicable to almost all polymers (polyethylene
and polypropylene being the most notable exceptions), up to very high molecular
weights. The main requirement is that the polymer samples subjected to MALDI
should be narrowly distributed in terms of molecular weight, chemical composi-
tion, and functionality. The major problems of MALDI are discrimination and ion
suppression. Discrimination implies that the sensitivity (response) of the MALDI-
ToF-MS system varies with properties (for example, molecular weight, functional-
ity) of the polymer molecules. Ion suppression occurs when a particular type of ion
is present in a very high concentration and the sensitivity of less prevalent ions is
(dramatically) reduced. Because MALDI requires narrowly distributed samples and
because it is a very sensitive analytical technique, its (o-line) combination with
chromatographic separations is highly attractive.
20.3.3.2 Functionality-type Distributions
Size exclusion chromatography can be used to separate polymer molecules accord-
ing to their size in solution, and size can be converted to molecular weight by cali-
bration. SEC cannot be used to separate polymers according to chemical compo-
sition or functionality. For this purpose, interactive liquid chromatography (i-LC)
may be used. In i-LC the molecules of the analyte polymers interact with the mo-
bile phase and with the stationary phase in the column. Usually, thermodynamic
equilibrium is reached at any point in the column. The distribution of the polymer
molecules across the two phases can then be characterized by a distribution coe-
cient (K c
s
=c
m
, where c
s
is the concentration of the polymer in the stationary
phase and c
m
is its concentration in the mobile phase). The retention factor (k) is
proportional to the distribution coecient and to the phase ratio [Eq. (1), where V
R
is the retention volume, t
R
the retention time, V
0
is the column hold-up volume, t
0
the column hold-up time, V
s
the volume of stationary phase in the column, and
V
m
the volume of mobile phase.]
k
V
R
V
0
V
0
t
R
t
0
t
0
K
V
s
V
m
1
Retention in i-LC is thus directly related to the thermodynamic distribution coe-
cient. K can be expressed in terms of fundamental thermodynamic properties, that
is, the partial molar free energy associated with the transfer of one mole of analyte
from the mobile phase to the stationary phase (Dg), the corresponding partial mo-
lar enthalpy, and the corresponding entropy eect (Ds), according to Eq. (2), where
R is the gas constant and T the absolute temperature.
RT ln K Dg Dh TDs 2
Enthalpic (heat) eects arising from molecular interactions are reected in Dh.
SEC is a strictly entropic process; that is, Dh 0 and temperature has no signi-
cant eect on the elution volume.
Separation between chemically dierent polymers can be achieved if dierent
parts of the molecules (dierent co-monomers, end groups, functional groups) ex-
hibit dierent interactions with the mobile phase and the stationary phase in the
column. We can rewrite Eq. (2) for a homopolymer as Eq. (3), where we assume
that the partial molar free energy is built up from p contributions of monomeric
units ( p being the degree of polymerization) and the sum of all contributions
from end groups (or functional groups).
RT ln K Dg pDg
monomer

P
Dg
end groups
3
Because p is a large number for high M
r
polymers, reasonable distribution coe-
cients (and, therefore, reasonable retention factors) can usually be obtained only if
Dg
monomer
A0.
A special case is the situation in which Dg
monomer
0. In this case the distribu-
tion coecients and chromatographic retention factors are determined only by the
functional groups and they are independent of the chain length ( p). This situation
is known as liquid chromatography at the critical conditions or, simply, as critical
chromatography. It is eminently suitable for separating polymers based on func-
tionality. Figure 20.10 shows examples of the separation of functional poly(methyl
methacrylate)s [14, 18]. All PMMA molecules without OH groups are eluted with a
retention time of around 4 min in Fig. 20.10(a), irrespective of the molecular
weight and (possible) other end groups present (provided that the Dg values for
all the end groups other than OH are either negligibly small or very similar). The
polymers with one OH end group are all eluted at around 5 min and the bifunc-
3 4 5 6 7 8 9 10
Time (min)
E
L
S
D

r
e
s
p
o
n
s
e
PMMA 3,800
PMMA 28,300
PMMA-OH 3,310
PMMA-OH 20,740
HO-PMMA-OH (MD-1000X)
(a)
0 1 2 3 4 5 6
Time (min)
E
L
S
D

r
e
s
p
o
n
s
e
V37A
V37B
V37A0
V37A1
V37B2
V37B0
V37B1
(b)
Fig. 20.10. (a) Separation of end-functional
poly(methyl methacrylate)s based on the
number of end groups. Column: 150 mm
long 4.6 mm i.d., home-packed with Hypersil
silica (3 mm particles, 100 A
pore size); mobile

phase: 43% acetonitrile in dichloromethane;
temperature: 25
C; ow rate: 0.5 mL min

1
;
injection volume: 10 mL; sample concentration:
1 mg mL
1
in dichloromethane; detector:
evaporative light scattering [14]. (b) Separation
of end-functional PMMAs prepared by RAFT
polymerization [18]. Mobile phase: 40%
acetonitrile in dichloromethane; other
conditions as in (a).
tional (telechelic) PMMAs are eluted at around 8 min in Fig. 20.10(a). The elu-
tion proles of real samples can be translated into a functionality-type distribution
(FTD), provided the detector is suitably calibrated [1517].
The separation shown in Fig.10(a) has proven to be quite robust. However, this
is not usually the case for critical separations. Indeed, for carboxyl-functionalized
poly(n-butyl acrylates) it proved much more dicult to achieve genuine critical
chromatography [19]. Critical liquid chromatographic separations are not always
easy, but they can be highly rewarding, especially for determining FTDs.
Mass spectrometry (ESI-MS and MALDI-ToF-MS) is very useful for obtaining in-
formation on the total masses of various end group combinations present. In this
case Eq. (4) holds, where M
ion
is the observed mass for the polymeric ion, p is the
degree of polymerization, M
mon
is the mass of the monomeric unit, M
adduct
is the
mass of the adduct ion (typically added as a salt to the matrix/polymer mixture)
and
P
M
endgroup
is the sum of the masses of the end groups.
M
ion
pM
mon
M
adduct

P
M
endgroup
4
Very accurate and precise values of M
mon
and M
endgroup
can be obtained by MALDI.
Complicating factors are:
uncertainty in the true end group mass, which may equal

P
M
endgroup
, but also
P
M
endgroup
nM
mon
(where n is an integer);
the (broad) isotope pattern of large polymers, which, if not properly accounted
for, may cause errors in the values obtained for
P
M
endgroup
;
the possibility that several dierent end group combinations yield exactly or
nearly the same value for
P
M
endgroup
.
It is very dicult to obtain quantitative FTDs by MS. Because the response factors
are usually dierent for polymers with dierent end groups, highly specic refer-
ence materials (of accurately known composition) would be required.
In some cases capillary (zone) electrophoresis can be elegantly used to separate
polymers according to functionality, and to obtain accurate FTDs. This is especially
the case if the end groups are charged (in a suitable buer solution) or if they can
be derivatized to yield ionizable groups. Under suitable conditions, the eect of
the molecular charge on the electrophoretic mobility can be much greater than
the eect of the molecular weight [20].
20.3.3.3 Chemical Composition Distributions (CCDs)
For a copolymer, Eq. (3) becomes Eq. (5), where the subscript i depicts the dierent
monomeric units.
RT ln K Dg
X
i
p
i
Dg
monomer; i

P
Dg
end groups
5
It is dicult to achieve Dg
monomer; i
0 for one particular monomer (critical chro-
matography) by carefully adjusting the ratio of two components of the mobile
phase (a strong eluent and a weak eluent or nonsolvent). It is impossible to
nd conditions that are critical for several dierent monomers simultaneously.
Therefore, critical chromatography is much more useful for determining the
FTDs of functional (homo)polymers than for determining the CCDs of copoly-
mers. In the latter case, two options are open. One is to nd conditions at which
the separation is critical toward one type of monomer, while the second mono-
meric unit does not show any interaction, so that it is eluted under SEC conditions.
Such conditions have been applied to block copolymers. The block for which criti-
cal conditions are maintained is made invisible and the separation reects the
block length distribution of the second block [22]. There is some discussion in
the literature on whether any eect of the invisible block on the retention of the
polymer molecule can be avoided [2123].
The alternative (and more common) way to analyze copolymers is to resort to
gradient elution. In this case the composition of the mobile phase is changed over
time. At the initial composition, both monomers are highly retained (negative Dg).
When the eluent becomes stronger, the critical conditions for one of the mono-
meric units will be approached. At a later point in time, this will be the case for
the second monomer. In this way, a blend of polymers can be separated into its
constituents. Copolymers will be eluted according to their composition (Figure
20.11). In principle, gradient elution liquid chromatography can be used to obtain
CCDs of copolymers. Again, proper calibration of the detector is a signicant issue
if quantitative data are to be obtained.
i-LC separations can also be coupled to spectrometers and other highly informa-
tive detection devices. The situation is similar, but not identical, to that described
for SEC. In many cases, gradient elution is used: that is, the solvent changes as a
function of time. In that case hyphenation between i-LC and viscometry or light
scattering is horribly dicult. Gradient elution is not used with such devices.
Thus, it is dicult to determine the (average) molar mass as a function of the
chemical composition hM
r
ij
pol
. i-LC//MALDI-ToF-MS is a feasible technique; i-
LC-Vis and i-LC-LS are not realistic options. SEC-FTIR and SEC-NMR can in
principle be used to obtain the average composition as a function of molar mass
hj
pol
iM
r
. In principle it is possible to combine viscometry or light scattering
with critical chromatography. However, since the latter technique is more practical
for relatively low molar masses and the detection devices are most suitable for high
masses, this is not a perfect match.
Both LC-FTIR and LC-NMR can be applied in combination with solvent gra-
dients. In both cases there are some complicating factors. In the case of FTIR,
only solvent elimination interfaces can realistically be used. This implies that the
euent from the LC is sprayed into a (heated) evaporation chamber and that the
nonvolatile analyte polymers are deposited on a suitable substrate (for example, a
germanium disc). By moving the spray or the substrate, the entire chromatogram
can be recorded. Some authors have programmed the deposition conditions to ob-
tain optimal results for gradient elution LC-FTIR. However, as was mentioned ear-
lier (Section 20.3.2.1), it is not easy to obtain accurate quantitative results for the
copolymer composition using FTIR. In LC-NMR a solvent gradient causes severe
complications associated with the suppression of the solvent signal. While suppres-
sion techniques for gradient elution LC have been developed and applied success-
fully, the interferences in the spectrum are more serious than they are in isocratic
separations. In either case, LC-FTIR or LC-NMR, the amount of additional infor-
mation obtained is limited. The LC retention axis contains information on the
polymer composition. The information present in the spectra is related to this.
Although additional information on structural aspects may be obtained from both
FTIR and NMR spectra, the two information dimensions are far from orthogonal.
This is fundamentally dierent for the combination of i-LC with MS, either on-
line (most commonly using LC-ESI-MS) or o-line (most commonly using LC//
MALDI-ToF-MS). In that case, the LC axis contains mainly structural information,
whereas the MS axis provides information on the molar mass. A disadvantage of
this combination is that fractions resulting from the i-LC separation are expected
to be narrow in terms of their chemical composition distribution, but may be quite
broad in terms of their molar mass distribution. In critical or pseudo-critical i-LC
the very purpose of the separation is to elute all the dierent molar masses as one
Time (min)
-2
0
2
4
6
8
10
12
14
16
18
0 10 20 30 40 50 60 70 80
D
e
t
e
c
t
o
r

s
i
g
n
a
l

Fig. 20.11. Gradient elution liquid
chromatography of a mixture (blend) of a
number of copolymers. Column: Supelcosil
Discovery C
18
, 150 mm long 2.1 mm i.d.;
particle size: 5 mm; pore diameter: 180 A
;
temperature: 25
C; ow rate: 0.2 mL min

1
;
injection volume: 5 mL; sample concentration:
1.5 mg mL
1
; gradient from 5 to 95% THF
in acetonitrile. Peaks from left to right:
poly(methyl methacrylate) homopolymer, 20%
polystyrene-co-MMA, 40% PS-co-MMA, 60%
PS-co-MMA, 80% PS-co-MMA, PS
homopolymer.
peak. Such broad fractions are not really compatible with MS. As mentioned in
section 20.3.2.3, biased results are anticipated from the MS analysis of broadly dis-
tributed samples.
Better results are anticipated if fractions that are narrow both in chemical com-
position and in molar mass are subjected to mass spectrometry. Such fractions can
be obtained from two-dimensional separations (see Section 20.3.3.5).
20.3.3.4 Degree of Branching Distributions
When polymer molecules are branched, their size in solution decreases. This is
progressively the case with an increasing degree of branching. This also implies
that molecules of equal size in solution (and thus equal SEC retention times) can
have dierent molecular weights, depending on the degree of branching. SEC
alone is not capable of revealing both the MWD and the degree of branching dis-
tribution (DBD), because the two distributions are confounded. Other information
is required to yield information on the two parameters simultaneously. This extra
information may be obtained from light scattering or from viscosity data, and both
of these techniques can be readily combined on-line with SEC, yielding so-called
hyphenated systems that is, SEC-Vis (size-exclusion chromatography with visco-
metric detection) and SEC-LS (light-scattering detection). Static light scattering is
most commonly coupled with SEC, but in recent years the on-line coupling of
SEC and dynamic light scattering has become more readily available. The instru-
mentation for static light scattering is typically distinguished by the type and/or
number of measurement angles. Thus, we have low-angle light scattering (LALS)
and right-angle light scattering (RALS), as well as multi-angle light scattering
(MALS) and triple-angle light scattering (TrALS). Often an additional L is added
to the abbreviations, signifying the use of a laser source (for example, multi-angle
laser light scattering, MALLS). In any case (viscometry or light scattering) a
concentration-sensitive detector, typically a refractive index (RI) detector, is also
installed on-line. Also quite common is the use of both viscometry and light scat-
tering in combination with refractive index (RI) detection and SEC. Such a system
with three detectors is known as a TripleSEC system.
Branching parameters g
0
vis
are obtained from the ratio of the intrinsic viscosity of
the branched polymer h
br
(measured by viscometry) to that of the corresponding
linear reference polymer h
lin
(eluting at the same time) [Eq. (6)], or from the mo-
lecular weight of a linear reference polymer (as measured by light scattering) div-
ided by the molecular weight of the branched polymer [Eq. (7), where a is the
MarkHouwink coecient].
g
0
vis

h
br
h
lin
6
g
0
LS

M
lin
M
br
!
a
7
The average number of branches in polymer molecules as a function of the molec-
ular weight can be estimated from Eqs. (6) or (7) and the ZimmStockmayer equa-
tion [24].
20.3.3.5 Complex Polymers (Multiple Distributions)
We have already encountered several examples of confounded distributions. SEC
may not suce to obtain the MWD of a copolymer, because the molecules eluted
at any one time may have dierent molecular weights and dierent compositions
resulting in equal hydrodynamic volumes. Likewise, in the SEC separation of a
branched polymer the molecules eluted at any one time may have dierent molec-
ular weights and dierent degrees of branching, again resulting in equal hydro-
dynamic volumes. Just as the characterization of polymer distributions necessitates
polymer separations, the characterization of two-dimensional polymer distribu-
tions necessitates two-dimensional polymer separations. Only if two distributions
are fully independent do two separate one-dimensional separations suce. This is
the case if every chemical composition fraction exhibits the same MMD and every
molar mass fraction exhibits the same CCD. Because this is not usually the case,
one two-dimensional separation usually reveals (much) more information than two
one-dimensional separations.
Comprehensive two-dimensional liquid chromatography Two-dimensional liquid
chromatographic separations can be performed in the linear (heart-cut) format
or in the comprehensive mode. In the former case, one fraction (or a few fractions)
is (are) isolated from the sample and these are subsequently subjected to a second
separation. An advantage of this approach is that the specic fraction(s) can be
subjected to two (lengthy) high-resolution separations. A great disadvantage is
that only one or a few small fractions of the sample are extensively characterized.
In comprehensive two-dimensional liquid chromatography the entire sample is
subjected to two dierent separations. The word comprehensive is justied if
the nal (two-dimensional) chromatogram is representative of the entire sample
[25]. The recommended notation for linear (heart-cut) two-dimensional liquid
chromatography is LC-LC, whereas comprehensive two-dimensional liquid chro-
matography is commonly denoted by LC LC [25].
In the case of polymer separations, the MMD is usually one of the distributions
of interest. The second most important distribution is usually either the CCD or
the functionality-type distribution (FTD). This implies that SEC and i-LC are attrac-
tive candidates for the two dimensions in comprehensive two-dimensional liquid
chromatography. These two techniques can in principle be coupled in two dier-
ent orders (either LC SEC or SEC LC, with the rst dimension listed rst).
LC SEC has a number of prevailing advantages [26]. These include (i) the possi-
bility of performing high-resolution (gradient) LC in the rst dimension, (ii) the -
nite time of analysis in the second dimension, (iii) the greater choice of detectors
(because the separation in the second dimension is isocratic), (iv) the possibility of
changing the rst-dimension LC conditions without the need to re-optimize the
second-dimension conditions, (v) the relatively high concentration in the rst-
dimension i-LC system (not easily overloaded) and the relatively low concentration
in the second-dimension SEC system (more easily overloaded), and (vi) the greatly
reduced chance of breakthrough. If the rst dimension were SEC, the sample
(fraction) transferred to the second-dimension LC would be dissolved in a very
strong solvent, creating a great danger of detrimental breakthrough peaks [27].
A disadvantage is that the resolution in the second (fast-SEC) dimension is limited,
but the series of advantages prevails. Therefore LC SEC is now the commonly
employed technique.
If we are to maintain the separation (resolution) that has been achieved in the
rst dimension in the eventual LC SEC chromatogram, we need to collect a large
number of fractions. To maintain a reasonable overall analysis time, this implies
that the second-dimension separation should be fast and that the resolution that
can be obtained in this second dimension is limited. There have been signicant
developments toward fast SEC in recent years [9, 28] Moderate-resolution SEC
can be performed within one or two minutes. If we want to collect 100 fractions
from the rst dimension, this implies that typical LC SEC analysis times are of
the order of two to three hours. Indeed, these are the analysis times commonly en-
countered in practice.
If we wish to transfer the entire rst-dimension fraction to the second dimen-
sion, then the rst-dimension column should have a much smaller internal diam-
eter than the second-dimension column. Either a miniaturized rst-dimension
column can be used in combination with a conventional second-dimension col-
umn, or a conventional rst-dimension column can be used in combination with
a wide-bore (maxiaturized) second-dimension column. Both approaches have
been demonstrated successfully. The rst approach requires (very) much less sol-
vent, produces correspondingly less waste, and is compatible with most existing
LC detectors, including the molar-mass selective detectors (viscometry, light scatter-
ing) that are of great interest in polymer separations. The second approach puts
fewer demands on the chromatographic (rst-dimension) system in terms of
extra-column band broadening and it yields larger separated fractions for subse-
quent o-line analysis by other methods (for example, NMR).
Figure 20.12(a) shows an outline of a typical LC SEC system and Figure
20.12(b) shows an enlarged representation of the switching valve. A comprehensive
two-dimensional liquid chromatography system typically consists of two liquid
chromatographs that are interfaced by means of a switching valve. In the case of
LC SEC the rst dimension often features a gradient elution system; that is,
the composition of the eluent can be programmed during the run. The valve is
congured so that while one fraction is being analyzed, the next fraction is being
collected (Figure 20.12(b)).
Figure 20.13 features a contemporary example of an LC SEC separation [26]:
in this two-dimensional separation of a series of copolymer standards of known
molar mass and chemical composition, the rst (gradient elution LC) dimension
shows a high resolution, whereas the resolution in the second (SEC) dimension is
adequate. The two separations are seen to be nearly orthogonal (that is, separation
in the rst dimension is (nearly) completely based on the chemical composition,
whereas that in the second dimension is based on molecular size).
Comprehensive two-dimensional liquid chromatography has seen a strong in-
crease in popularity and in the number of applications in recent years. LC SEC
has been applied to a large number of problems in polymer science. For exam-
ple, the technique has been used to provide a detailed analysis of polystyrene
poly(methyl methacrylate) diblock copolymers [29], to analyze well-dened star
polylactides [30], and to study to the grafting reaction of methyl methacrylate onto
EPDM [31] or onto polybutadiene [32].
The main bottlenecks for the proliferation of LC SEC (and other two-
P
LC
W
SEC
Load
Inject
L1
L2
P
LC
W
SEC
Load
Inject
L1
L2
Loop 1
1
st
dimension
2
nd
dimension
6-way injection valve
sample
waste
PC
Detector (UV)
1
st
dimension column
2
nd
dimension column
Loop 2
(a)
(b)
Fig. 20.12. Instrumentation for comprehensive two-
dimensional liquid chromatography: (a) schematic of the
complete instrument; (b) preferred conguration of a 10-port
switching valve. Reprinted from Ref. [26] with permission.
dimensional polymer separations) are now in the development of suitable cali-
bration procedures and the associated software. Because suitable hardware for
LC SEC is already commercially available, signicant progress is expected in
this direction.
Notation
Acronyms
ATR attenuated total reection
CC critical (liquid) chromatography (or liquid chromatography at the
critical conditions of adsorption)
CCD chemical composition distribution
CP-MAS-NMR cross-polarization magic-angle spinning NMR
DRI dierential refractive index
ELSD evaporative light-scattering detector
ESI electrospray ionization
5
4
3
2
1
6 7 8 9
10
14
13
12
11
0.5 1 1.5 2 2.5 3 3.5 4
Time LC [hours]
1.3
1.1
1
0.9
T
i
m
e

S
E
C

[
m
i
n
]
0.8
Fig. 20.13. LC SEC-ELSD contour plot of a
mixture of homo- and copolymeric reference
materials: PMMA 2900 (1), 6950 (2), 28 300
(3), 127 000 (4), 840 000 (5); S-co-MMA 20% S
(6), 40% S (7), 60% S (8), 80% S (9); PS 2450
(10), 7000 (11), 30 000 (12), 200 000 (13), 900
000 (14). LC (rst dimension): C
18
column;
ow: 4 mL min
1
; gradient: 570% THF in
acetonitrile 0300 min (40
C). SEC (second

dimension): mixed C column; ow: 0.6
mL min
1
THF. Figure reprinted from Ref. [26]
with permission.
FTD functionality-type distribution
FT-ICR-MS Fourier transform ioncyclotron resonance mass spectrometry
FTIR Fourier transform infrared
GC gas chromatography
GPC gel permeation chromatography (same as SEC)
i-LC interactive liquid chromatography
IR infrared
LA(L)LS low-angle (laser) light scattering
LC liquid chromatography
LC LC comprehensive two-dimensional liquid chromatography
LC SEC comprehensive two-dimensional (liquid chromatography) (size
exclusion chromatography)
LS light scattering
MA(L)LS multi-angle (laser) light scattering
MALDI matrix-assisted laser desorption ionization
MS mass spectrometry
MMD molar mass distribution (equivalent to MWD)
MWD molecular weight distribution (equivalent to MMD)
NIR near infrared
NMR nuclear magnetic resonance
RA(L)LS right-angle (laser) light scattering
RI refractive index
SEC size exclusion chromatography
ToF time-of-ight
TrA(L)LS triple-angle (laser) light scattering
Triple SEC SEC with light-scattering, viscometry, and refractive index detec-
tion
Vis viscometry
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21
Recent Developments in Polymer Processes
1
Maartje Kemmere
21.1
Introduction
Currently, many industrial polymers are being produced in organic solvents. A typ-
ical production scheme for conventional polymer processes is shown in Figure
21.1, for which three sub-processes can be distinguished: the polymerization of
the monomers, the shaping of the raw polymer, and the post-processing of the
polymer. A major drawback of polymer processes in organic solvents is the ine-
cient removal and recovery of the solvents and monomers in each of the three sub-
processes. Often the solvent recovery requires more process steps and energy than
the actual production process, as indicated in Figure 21.1. For example, in the pro-
duction of butadiene rubber a typical production process applies a recycle of ap-
proximately four tons of solvent per ton of polybutadiene produced [1]. Another ex-
ample is the production of elastomers such as EPDM (ethylenepropylenediene
copolymer), for which typically 20 wt.% of polymer is dissolved in an excess of hex-
ane. Annually, these conventional polymer processes add substantially to the total
amount of discharged volatile organic compounds (VOCs) such as hexane and tol-
ISBN: 3-527-31014-2
polymerization shaping
S
SR
P
SR
solvent solvent
post-processing
PP
SR
solvent
monomers
final
product
S
SR
P
SR
PP
SR
t
S
SR
P
SR
PP
SR
t

Fig. 21.1. Conventional polymerization (P), shaping (S) and
post-processing (PP) steps based on organic solvents,
including signicant solvent recovery steps (SR).
1047
uene. Approximately 20 million tons of VOCs are emitted into the atmosphere
each year as a result of industrial activities [2].
For these reasons, increasing environmental awareness demands more sustain-
able polymer processes. Currently, several technologies are being investigated to
develop cleaner processes. These include the reduction and/or recycling of solvents
by closed-loop operation as well as switching to solvent-free processes, for instance
melt-phase polymerization [3]. However, these methods have their limitations, be-
cause many industries require process liquids for operations such as reactions,
separations, and processing steps. Therefore, the possibilities of alternative green
solvents to replace organic solvents are being explored, for which important ex-
amples are aqueous solvents, ionic liquids, uorous phases, and supercritical or
dense-phase uids [3, 4]. Obviously, each of these approaches exhibits specic ad-
vantages and potential drawbacks. Ionic liquids (room-temperature molten salts),
for example, have a vapor pressure that is negligible. Because ionic liquids are
non-volatile, their commercial application would signicantly reduce the present
VOC emission. In general, ionic liquids can be used in existing equipment at
reasonable capital costs [5]. Nevertheless, the cost price of the ionic liquid itself is
substantial. In addition, the separation of ionic liquids from a process stream is an-
other important point of concern. With respect to dense-phase uids, supercritical
water has been shown to be a very eective reaction medium for oxidation reac-
tions [6, 7]. Despite extensive research eorts, however, corrosion and investment
costs still form major challenges in these processes due to the extreme operation
conditions required (above 647 K and 221 bar). Particularly, supercritical carbon di-
oxide has made its appearance as an alternative to organic solvents, because of its
tunable nature, its excellent wetting characteristics, and its low viscosity [3].
Besides alternative reaction media, process and product research has resulted in
a number of new classes of polymers, such as dendritic and conductive polymers.
At the same time the application eld of polymers has been extended, ranging
nowadays from bulk materials such as polyethylene and polypropylene all the way
to specialty products, for example for biomedical applications. These developments
ask for well controlled polymerization processes. In this respect ultrasound has
proven to be a clean and safe technology for generating radicals in situ during the
polymerization reaction.
In this chapter supercritical carbon dioxide will be discussed in more detail as
one of the most promising green solvents for polymerizations. Subsequently, the
possibilities and challenges of applying ultrasound in polymer processes are de-
scribed. Finally, a short overview of the application potential of polymer processes
based on supercritical carbon dioxide or ultrasound technology will be given.
21.2
Polymer Processes in Supercritical Carbon Dioxide
A supercritical uid is dened as a substance for which the temperature and
pressure are above their critical values (see Figure 21.2A) [8, 9]. Above the critical
1048 21 Recent Developments in Polymer Processes
temperature, the line representing vapor and liquid coexistence has disappeared.
Therefore, supercritical uids can be regarded as hybrid solvents because the
properties can be tuned from liquid-like to gas-like without crossing a phase
boundary by simply changing the pressure or the temperature. The unique proper-
ties of supercritical uids provide opportunities for a variety of industrial pro-
cesses. In Table 21.1 [1013], the critical properties are shown for some com-
ponents, of which carbon dioxide and water are the most frequently used as
supercritical uids. In polymerization processes, supercritical ethylene and propy-
lene are also applied, where they act both as a solvent and as the reacting mono-
mer [14].
With respect to the development of sustainable polymer processes, supercritical
carbon dioxide (scCO
2
) has signicant potential as a substitute for organic sol-
vents. In addition to the environmental benets, scCO
2
has interesting physical
and chemical properties from an engineering point of view. These include its rela-
tive chemical inertness, readily accessible critical point, and highly tunable solvent
behavior. Moreover, carbon dioxide is nontoxic and nonammable. In Figure
21.2B, the density of CO
2
at dierent temperatures is plotted as a function of pres-
sure. The graph clearly shows that the modication of the density requires only
small changes in temperature or pressure just above the critical point. In general
terms, scCO
2
is a solvent with a low viscosity, high diusion rates, and no surface
tension [15]. The viscosity is in the range of 0.020.1 mPa s, where liquids have
viscosities of approximately 0.51.0 mPa s and gases approximately 0.01 mPa s,
respectively. Diusivities of solutes in supercritical carbon dioxide are higher than
in liquid solvents by a factor of up to 10. Binary diusion coecients of various
substances in scCO
2
have been determined experimentally as a function of CO
2
density [16]. Because of the high diusivity compared with ordinary solvents,
scCO
2
is often associated with high mass and heat transfer. Additionally, the
1
10
100
1000
10000
200 250 300 350 400
temperature (K)
p
r
e
s
s
u
r
e

(
b
a
r
)
solid
liquid
supercritical
fluid
gas
A
0
200
400
600
800
1000
30 50 70 90 110 130 150 170
pressure (bar)
d
e
n
s
i
t
y

(
k
g
/
m
3
)
280 K
300 K
310 K
330 K
400 K
B
Fig. 21.2. Projections of the phase diagram of carbon dioxide
A) in the pressuretemperature plane and B) in the density
pressure plane [8, 9].
above-mentioned properties are strongly pressure-dependent in the vicinity of the
critical point, making scCO
2
a highly tunable solvent.
For application of scCO
2
as a medium in polymer processes, it is important to
have insight into the specic system involved. In Section 21.2.1 a brief overview
of the interactions of carbon dioxide with polymers and monomers will be given,
including solubility in CO
2
(Section 21.2.1.1), sorption and swelling of polymers
(Section 21.2.1.2) as well as phase behavior (Section 21.2.1.3) of polymermono-
merCO
2
systems. Subsequently, an overview of processes involving polymeriza-
tion (Section 21.2.2) as well polymer processing (Section 21.2.3) in scCO
2
will be
discussed.
21.2.1
Interactions of Carbon Dioxide with Polymers and Monomers
The thermodynamic properties of pure substances and mixtures of molecules are
determined by intermolecular forces acting between the molecules or polymer seg-
ments. By examining these potentials between molecules in a mixture, insight into
the solution behavior of the mixture can be obtained. The most commonly occur-
ring interactions are dispersion, dipoledipole, dipolequadrupole, quadrupole
quadrupole, and specic interactions. For small molecules, the contribution of
each interaction to the intermolecular potential energy G
ij
r; T, is given by Eq. (1)
[12], where a is the polarizability, m is the dipole moment, Q is the quadruple
Tab. 21.1. Physical properties of various solvents [1013].
Solvent T
c
[K] P
c
[ bar]
Polarizability
a [ 10
C19
m
3
]
Dipole moment
m [ 10
C30
C m]
Quadrupole moment Q
[ 3:16 D10
C17
J
1/2
m
5/2
]
Methane 190.4 46.0 26 0.0
Ethane 305.3 48.7 45.0 0.0 0.7
Propane 369.8 42.5 62.9 0.1
Ethylene 282.4 50.4 42.3 0.0
Propene 364.9 46.0 62.6 0.4
Ethyne 308.3 61.4 33.3 0.0 3.0
Dimethyl ether 400.0 52.4 51.6 1.3
Sulfur hexauoride 318.7 37.6 54.6 0.0
Diuoromethane 351.6 58.3 24.8 2.0
Triuoromethane 299.3 48.6 26.5 1.7
Tetrauoromethane 227.6 37.4 28.6 0.0
Diuororethane 386.7 45.0 41.5 2.3
Hexauoroethane 293.0 30.6 47.6 0.0 0.7
Carbon dioxide 304.1 73.8 27.6 0.0 4.3
n-Hexane 507.5 30.1 118.3 0.0
Cyclohexane 553.5 40.7 109 0.3
Diethyl ether 466.7 36.4 87.3 1.3
Methanol 512.6 80.9 32.3 1.7
Acetone 508.1 47.0 63.3 2.9
moment and SI represents specic interactions such as complex formation or hy-
drogen bonding.
G
ij
r; T A C
1
a
i
a
j
r
6
C
2
m
2
i
m
2
j
r
6
kT
C
3
m
2
i
Q
2
j
r
8
kT
C
4
Q
2
i
Q
2
j
r
10
kT
SI
" #
1
The interactions work over dierent distances, with the longest range for disper-
sion and dipole interactions. Note that the dispersion interaction depends on the
polarizability alone, and not on the temperature. Consequently, an increased polar-
izability of the supercritical solvent is expected to decrease the pressures needed to
dissolve a nonpolar solute or polymer. Furthermore, at elevated temperatures, the
congurational alignment of directional interactions such as dipoles or quadru-
poles is disrupted by the thermal energy, leading to a nonpolar behavior. Hence, it
may be possible to dissolve a nonpolar solute or a polymer in a polar supercritical
uid. However, to obtain sucient density for dissolving the solutes at those ele-
vated temperatures, substantially higher pressures need to be applied. Additionally,
specic interactions such as complex formation and hydrogen bonding can in-
crease the solvent strength of the supercritical uid. These interactions are also
highly temperature-sensitive.
21.2.1.1 Solubility in Carbon Dioxide
The solvent strength of carbon dioxide for solutes is dominated by a low polariz-
ability and a strong quadrupole moment. Consequently, carbon dioxide is dicult
to compare with conventional solvents, due to this ambivalent character. With its
low polarizability and nonpolarity, carbon dioxide is similar to peruoromethane,
peruoroethane, and also methane. These uids are very weak solvents for many
components. Additionally, the acidity of carbon dioxide increases the solvent
strength for weakly basic solutes. In general, carbon dioxide is a reasonable solvent
for small molecules, both polar and nonpolar. For many components, with the
exception of water, complete miscibility can be obtained at elevated pressures.
However, the critical point of the mixture, which is the lowest pressure at a given
temperature where CO
2
is still completely miscible, rises sharply with increasing
molecule size. Consequently, most of the larger components and polymers exhibit
a very limited solubility in carbon dioxide. Polymers that do exhibit a high solubil-
ity in carbon dioxide are typically characterized by a exible backbone and high free
volume (hence, a low T
g
), weak interactions between the polymer segments, and a
weakly basic interaction site such as a carbonyl group [1720]. Examples of poly-
mers that are soluble in carbon dioxide and incorporate these characteristics in-
clude poly(alkene oxides), peruorinated poly(propylene oxide), poly(methyl acry-
late), poly(vinyl acetate), poly(alkylsiloxanes), and poly(ether carbonate).
To illustrate the inuence of the carbonyl group on the solubility of the polymer
in carbon dioxide, Figure 21.3 shows the dierence in cloud-point pressures for
polymethyl acrylate (PMA) and polyvinyl acetate (PVA) [17]. Structurally, these
polymers are very similar, but the carbonyl group in PVA is more easily accessible
to CO
2
, making it more susceptible to complex formation. As a result, the cloud-
point pressure of PVA is up to 1500 bar lower than that of PMA, even though the
molecular weight of PVA is four times higher than that of PMA, and its glass tran-
sition temperature is 21 K higher.
21.2.1.2 Sorption and Swelling of Polymers
Although the solubility of polymers in CO
2
is typically very low, the solubility of
carbon dioxide in many polymers is substantial. When the polymer comes into
contact with scCO
2
, the sorption of carbon dioxide by the polymers and the resul-
tant swelling of the polymer inuence the mechanical and physical properties of
the polymer. The most important eect is plasticization, that is, the reduction of
the glass transition temperature (T
g
) of glassy polymers. The plasticization eect,
characterized by an increased segmental and chain mobility as well as by an in-
crease in interchain distance, is largely determined by polymersolvent interac-
tions and solvent size [21]. The molecular weight of the polymer is of little inu-
ence on the swelling once the entanglement molecular weight has been exceeded.
The inuence of specic interactions of carbon dioxide with various groups in the
polymer on the swelling isotherms is shown in Figure 21.4 [22]. These polymers
all have a T
g
of approximately 378 K. Carbon dioxide shows little interaction with
the phenyl groups in polystyrene (PS), resulting in limited swelling. Substituting
one of the CH groups in styrene with a nitrogen atom renders the polymer some-
what basic, thereby increasing the swelling level as well as the swelling rate. Build-
ing carbonyl groups into the polymer has an even stronger eect. In the case of
poly(methyl methacrylate) (PMMA), the swelling level is doubled as compared to
PS. Besides the enhancing interactions with carbon dioxide, the sorption and swell-
poly(vinyl acetate) poly(methyl acrylate)
O
CH
3
O
O O
CH
3
0
500
1000
1500
2000
2500
280 320 360 400 440 480
temperature (K)
p
r
e
s
s
u
r
e

(
b
a
r
)
Liquid + Liquid
Fluid
PMA 31000
PVA 125000
3
3
0
500
1000
1500
2000
2500
280 320 360 400 440 480
temperature (K)
p
r
e
s
s
u
r
e

(
b
a
r
)
Liquid + Liquid
Fluid
PMA 31000
PVA 125000
Fig. 21.3. Cloud-point curves of carbon dioxidepoly(methyl
acrylate) and carbon dioxidepoly(vinyl acetate) with polymer
concentrations of @5 wt.% [17].
ing can also be increased by lowering the interchain interactions of the polymer.
This is illustrated by comparison of commercial semi-crystalline low-density poly-
ethylene (ldPE) [23] (40% crystallinity) with highly branched amorphous polyethyl-
ene [24] (<2% crystallinity). Although both polymers lack specic interactions
with carbon dioxide, the highly branched PE shows a strongly enhanced swelling
(up to 25 vol.%) in carbon dioxide, whereas the ldPE exhibits a low maximum
swelling (4 vol.%) at 323 K [25]. This is caused by the absence of crystallinity and
the increased free volume introduced by branching.
To study the CO
2
-induced plasticization, dierent techniques can be applied, for
example, gas sorption and polymer swelling [26, 27]; in-situ FTIR spectroscopy
[28, 29], NMR spectroscopy [30], and dynamic light scattering [31]. Two new tech-
niques for simultaneous sorption and swelling measurement have been proposed,
based on detection of the volume change of the polymer sample measured by mer-
cury displacement [32], and on gravimetric measurement [33], respectively.
The sorption and swelling of a wide variety of polymers in scCO
2
have been re-
ported in the literature. For example, Liau and McHugh [34] have investigated the
swelling of PMMA and sorption of CO
2
in PMMA at temperatures ranging from
313 to 343 K and at pressures up to 272 bar by using a camera to record the change
in length of the polymer sample. Wissinger and Paulaitis [26] have reported swell-
ing and sorption in glassy polymergas systems for CO
2
with polycarbonate (PC),
PMMA, and PS at temperatures between 306 to 338 K and pressures up to 100 bar.
Sada et al. [35] have studied the sorption and diusion of CO
2
in glassy polymer
lms of PS and PC over a temperature range of 293 to 313 K and pressures up to
30 bar by a pressure decay method. Berens et al. [36] have investigated the sorption

O O
CH
3
CH
3

N
poly(methyl methacrylate) polystyrene
poly(vinyl pyridine)
0
4
8
12
16
20
0 20 40 60 80 100 120
pressure (bar)
s
w
e
l
l
i
n
g

(
%
)
PMMA
PVP
PS

PMMA
PVP
PS
Fig. 21.4. Swelling isotherms of poly(methyl methacrylate),
polystyrene and poly(vinyl pyridine) in carbon dioxide at 308 K
[22].
behavior of the glassy polymers poly(vinyl chloride) (PVC), PC, PMMA, and PVA at
298 K up to 700 bar in the presence of liquid CO
2
through a simple gravimetric
procedure. Additionally, sorption and swelling data at 308 K have been reported
by Zhang et al. [37] and up to 100 bar for PMMA, PS, polyvinylpyridine and poly-
isoprene as well as for block copolymers of styrenemethyl methacrylate, styrene
vinylpyridine and styreneisoprene, respectively. Otake et al. [31] have measured
the swelling of a 50 nm monodisperse PS latex in water by CO
2
by dynamic light
scattering at 298 K at pressures up to 350 bar.
In general, the sorption and swelling of polymers by CO
2
are crucial eects in
designing polymer processes based a high-pressure technology, because important
properties such as diusivity, viscosity, glass transition, melting point, compressi-
bility, and expansion will change. The plasticization eect of CO
2
facilitates mass
transfer properties of solutes in and out of the polymer phase, which leads to
many applications: increased monomer diusion for polymer synthesis, enhanced
diusion of small components in polymers for impregnation and extraction pur-
poses, polymer fractionation, and polymer extrusion.
21.2.1.3 Phase Behavior of MonomerPolymerCarbon Dioxide Systems
One of the requirements for the development of new polymer processes based on
scCO
2
is knowledge about the phase behavior of the mixture involved, which ena-
bles one to tune the process variables properly to achieve maximum process e-
ciency. Important parameters in the phase behavior of the system are the solvent
quality, the molecular weight, chain branching, and chemical architecture of the
polymer, as well as the eect of end groups, and addition of a co-solvent or an
anti-solvent. The literature available on the phase behavior of polymers in super-
critical uids has been reviewed extensively by Kirby and McHugh [38].
The usual phase equilibrium issue in polymer systems consists of determining
whether phase separation occurs, and if it does, then what the phase compositions
are. Although measuring is still the most accurate way at present to obtain in-
formation about the phase behavior [3942], it is rather time-consuming. Most of
the experimental work described in the literature has focused on polymersolvent
systems rather than on non-solvents. For example, binary systems of linear and
branched polyethylenes in ethylene have been measured [40, 43]. In addition, the
eect of carbon dioxide as a non-solvent on polyolensolvent systems has been
studied [4447].
When thermodynamic models are used to correlate and predict phase equilib-
ria, the experimental eort can be reduced substantially. Modeling of polymer
supercritical uid mixtures is particularly challenging, as the model has to be able
to describe the behavior of a mixture containing molecules covering a wide range
of molecular weights, which is often referred to as the asymmetry of the system.
Additionally, the proximity to the critical point is dicult to model. There exist sev-
eral thermodynamic models suitable for the description of phase behavior of poly-
mer systems in supercritical media; see Chapter 3 for a detailed description of the
existing models. However, the SanchezLacombe equation of state (eos) and statis-
tical associating uid theory (SAFT) eos are the most commonly used.
The SanchezLacombe model [4850] is a lattice uid model in which each
component is divided into parts that are placed in a lattice. The dierent parts are
allowed to interact with a mean-eld intermolecular potential. By introducing an
appropriate number of vacant sites (holes) in the lattice, the correct solution den-
sity can be obtained. SAFT [5153] is based on the perturbation theory. The princi-
ple of perturbation theory is that rst a model is derived for some idealized uid
with accurately known properties, called the reference uid. Subsequently, the
properties of this model are related to those of a real dense uid. By expanding
this reference uid into power series over a specied parameter, the power terms
can be regarded as corrections or perturbations for the reference uid as com-
pared to reality. Obviously, the more the reference model approaches reality, the
smaller the corrections are. Therefore, the key issue for applying perturbation
theory is deriving the most suitable reference uid.
In general, the choice of a certain model to describe the phase behavior of a
polymermonomerCO
2
system is far from arbitrary, and depends on, among
other factors, the particular components involved and the required detail of the
description. The SanchezLacombe eos has the advantage that it is very tractable
and it is suitable for interpolation of data. On the other hand, the Sanchez
Lacombe model gives a poor description of systems containing specic interac-
tions, because it is a mean-eld theory with mixing rules assuming a random
mixture. For that reason specic interactions can only be introduced through a
temperature-dependent interaction parameter. Modeling with SAFT provides a
more rigorous approach, although it is more computationally intensive. Many
non-idealities can be incorporated in calculations with this eos. However, similarly
to SanchezLacombe, description of the binary polymerCO
2
system can be trou-
blesome using SAFT. As an example the SAFT eos and the SanchezLacombe eos
have been compared for the poly(ethylene-co-propoylene)ethyleneCO
2
system
[54]. Both models give a qualitative description of the increase in ethylenePEP
cloud-points upon addition of carbon dioxide as anti-solvent. For a quantitative cor-
relation with the SanchezLacombe model, a temperature-dependent interaction
parameter is required. Additionally, the parameter is determined for each individ-
ual cloud-point composition. For the SAFT model, one temperature-dependent
interaction parameter suces for all compositions. For this particular system, the
description of the phase behavior with the SAFT model is in better agreement with
the experimental data than the description with the SanchezLacombe model (see
Figure 21.5).
21.2.2
Polymerization Processes in Supercritical Carbon Dioxide
With respect to the possibilities of carbon dioxide as a reaction medium for poly-
merization reactions, extensive reviews have been published by Scholsky [55],
Shaer et al. [56], Kendall et al. [57], and Cooper [58]. Typically, a division is
made between homogeneous and heterogeneous polymerization in scCO
2
.
Both chlorouorocarbons (CFCs) and carbon dioxide appear to be very good sol-
vents for amorphous, low-melting uoropolymers. Since environmental restric-
tions have limited the use of CFCs drastically, carbon dioxide has become a highly
viable alternative solvent for the production of amorphous uoropolymers [59]. Ex-
amples of polymerization of uorinated monomers in a homogeneous reaction
medium of scCO
2
are the polymerization of uorinated acrylates (see, for example
Refs. 5961, uoroalkyl-derivatized styrene [62], uorinated vinyl and cyclic ethers
[63], and the telomerization of 1,1-diuoroethylene [64]. Other options to run a
1500
2000
2500
3000
3500
4000
310 315 320 325 330 335 340 345
temperature (K)
p
r
e
s
s
u
r
e

(
b
a
r
)
SL
A
1500
2000
2500
3000
3500
4000
310 315 320 325 330 335 340 345
temperature (K)
p
r
e
s
s
u
r
e

(
b
a
r
)
SAFT
B
Fig. 21.5. SanchezLacombe (A) and SAFT (B) correlation of
the cloud-point curves for the ternary system ethylenecarbon
dioxidePEP containing 10 wt.% PEP, as a function of
temperature and mass fraction of carbon dioxide: y, 0.05;
D, 0.10; j, 0.15; b, 0.20 [54].
polymerization under homogeneous conditions are to increase the temperature
and pressure until a one-phase system is obtained [65] or to add a co-solvent.
Except for certain uoropolymers and a few other examples of polymers that are
soluble in it, as given in Section 21.2.1.1, carbon dioxide exhibits a strong anti-
solvent eect for most high molecular weight polymers. This implies that the ma-
jority of the polymerization reactions, such as dispersion, emulsion, suspension,
and precipitation polymerization, involve heterogeneous polymerization. Examples
of dispersion polymerization in scCO
2
are the polymerization of MMA [66] and
styrene [67]. Beckman and co-workers have reported the inverse emulsion poly-
merization of acrylamide in scCO
2
[68]. Moreover, it is possible to synthesize
well-dened porous polymers by templating in scCO
2
water emulsions [69]. Mac-
roporous beads of trimethylolpropane trimethacrylate (TRIM) can be synthesized
by means of suspension polymerization [70]. Much work has been performed
on precipitation polymerization, such as the polymerization of vinyl ethers and
oxetanes [63], the continuous polymerization of vinylidene uoride as well as of
acrylic acid [71, 72], MMA polymerization initiated by ultrasound [73], the catalytic
polymerization of olens [74, 75] and the enzymatic polymerization to polycapro-
lactone [76]. An interesting extension in the application of scCO
2
for polymeriza-
tion purposes is the use of CO
2
both as a reactant and as a solvent in a copolymer-
ization with cyclohexene oxide [77].
From an engineering point of view several issues have to be addressed in order
to design polymerization processes based on scCO
2
. The previous sections have
emphasized the importance of the phase behavior of the system as well as the
sorption and swelling of the polymer. Additionally, in catalytic polymerization pro-
cesses the solubility and recycle of the catalyst are important. Moreover, when the
polymer-shaping step is to be included in the same equipment or the purication
of the polymer product, this will set additional requirements on the design. Obvi-
ously, mass and heat transfer have to be investigated. In general, supercritical u-
ids have gas-like viscosities and diusion rates, which allow for fast mass transfer.
In addition, the thermal diusivity of supercritical CO
2
is signicantly higher than
for gaseous CO
2
. The need for forced convection in order to facilitate sucient
mass and heat transfer during the polymerization process has to be determined
for each particular type of polymerization. If the process involves a precipitation
polymerization, for instance, the eect of polymer deposition on heat transfer sur-
faces forms a potential point of concern. Given the scale of most commercial poly-
merization processes, a translation from a batchwise operation as it is usually per-
formed on a laboratory scale toward a continuous process forms another important
consideration in the development of polymerization processes based on scCO
2
. As
an example, it has been suggested that the process concept of the catalytic polymer-
ization of olens in scCO
2
should include a loop type of apparatus [78], as de-
scribed by Ahvenainen et al. [79] (see Figure 21.6). Next to the requirements men-
tion above, this reactor design allows adjustment of the residence time to relatively
long values in order to obtain a reasonable conversion.
Although many new polymerization reactions have been discovered in scCO
2
since the early 1990s, the development of the engineering aspects of these pro-
cesses and the step toward pilot scale and industrial application had only just been
initiated in the last few years. The commercialization by DuPont of the production
of Teon2 (polytetrauoroethylene, PTFE) in scCO
2
is a promising example [80].
21.2.3
Polymer Processing in Supercritical Carbon Dioxide
Applications of supercritical uids in polymer processing can be divided into three
areas: applications where carbon dioxide does not interact with the polymer; and
processing of swollen, or dissolved, polymers. Schematically, this is shown in Fig-
ure 21.7 [81, 82]. In the rst of these areas, when no interaction with the polymer
occurs, which is typically the case for crystalline and rigid polymers, supercritical
carbon dioxide can be used as a cleaning solvent. Applications in this category
include precision cleaning of surfaces, degreasing, particle removal, and dry clean-
ing. In particular, dry cleaning is being investigated for widespread industrial
application, because traditional processes based on perchloroethylene are under
pressure due to health and environmental issues. Current research in this area is
focused on the development of low-cost nonuorous CO
2
-philic surfactants [18,
19] and on the development of membrane systems for the economical reuse of car-
bon dioxide [83].
In the case of moderate interactions of carbon dioxide with the polymer, substan-
tial levels of sorption and swelling can occur. The swelling of the polymer signi-
cantly enhances diusivities of solutes in the polymer matrix, allowing for rapid
extraction, impregnation, shaping, and blending processes. Extraction applications
include removal of residual monomers, solvents, and catalysts [84, 85]. An impor-
monomer
c
a
t
a
l
y
s
t
external recycle
CO
2
polymer
Fig. 21.6. Proposed process concept of a loop reactor used for
the catalytic polymerization of olens in scCO
2
[77].
tant application of impregnation of polymers is the dyeing of textiles and bers
[86, 87]. Other impregnation applications include impregnation of polymer matri-
ces with drugs for the production of controlled drug delivery devices [88]. Advan-
tages in this process are the low processing temperatures and the lack of organic
solvents, which need to be removed in post-processing steps. Applying scCO
2
for
shaping purposes is advantageous because the material properties can be tuned
by varying the supercritical solvent density. This enables the removal of the solvent
without passing a liquidgas interface, which would cause the structures formed
to collapse [89]. With respect to blending, an interesting application is in-situ poly-
merization in an existing polymer matrix after impregnation with a monomer and
an initiator to form polymer blends [90]. This enables the formation of polymer
blends that cannot easily be obtained by conventional methods, for example due
to large dierences in the melting temperatures of the pure polymers.
Applications in the third category, where the polymer is dissolved in the
supercritical uid, include coating processes as well as fractionation. For exam-
ple, various groups have worked on the RESS (rapid expansion from supercritical
solution)-based process for spray coating using supercritical carbon dioxide as a
solvent [9194]. The main advantage of these processes is the reduction of VOC
emissions. Methods of applying coatings from CO
2
involve dip or spray coatings,
solutions of coatings in a CO
2
atmosphere and dispersion coatings. An example
that has already been commercially developed is the Unicarb
TM
spray coating pro-
cess [95], which can use highly viscous coatings and results in a narrow droplet
size distribution. A potential drawback of spray coating processes using super-
critical carbon dioxide is the fact that most coating materials have a low solubility
in supercritical carbon dioxide. Consequently, co-solvents such as methanol are
needed to enhance solubilities. An alternative to the addition of co-solvents is the
use of stabilizers [96]. Typical stabilizer structures involve graft copolymers, per-
uoropolyether acid and polyether carbonates.
polymer and supercritical fluid
sorption and swelling dissolution of polymer
no interaction
applications:
precision cleaning
dry cleaning
applications:
extraction
impregnation
shaping
blending
effects:
plasticization (decrease T
g
)
crystallization (increase T
m
)
changes in mechanical
and surface properties
applications:
removal of low M
w
material to
improve properties
fractionation
coatings / paint
swelling of polymer
:
i i
i
i
r
i
u

i

Fig. 21.7. Interactions of supercritical uids with polymers,
and their applications in polymer processes [81].
An extensive review on polymer processing using supercritical uids by Kazar-
ian [21] includes the applications mentioned above. To illustrate the possibilities
of polymer processing with scCO
2
from an engineering point of view, two impor-
tant applications will be discussed in more detail, namely extraction (see Section
21.2.3.1) and impregnation (Section 21.2.3.2).
21.2.3.1 Extraction
Commercial-grade polymers contain a range of additives and contaminants such as
residual monomer, solvent, and catalyst residue. Before application of the polymer
in the end-product, manufactures need to remove these impurities from it, for in-
stance to meet environmental regulatory requirements or to improve the physical
polymer properties [58]. Supercritical uid extraction (SFE) has many advantages
over conventional cleaning techniques, such as a shorter extraction time, adjust-
able solvent strength by tuning the pressure, a wide range over which the extrac-
tion temperature can be varied, and less energy consumption [15].
A number of studies have been reported in supercritical extraction of polymer
additives, extraction of monomers and oligomers, and removal of residual solvent
from polymer foams [97], of which some examples will be given here. SFE can be
achieved in two ways: statically or dynamically. In a static extraction, the extraction
vessel is pressurized to the desired pressure with the extracting uid and subse-
quently left for a certain length of time, whereas during dynamic extraction the
supercritical uid passes continuously over the sample, extracting soluble com-
pounds and depositing them in a suitable solvent or on a solid trap. Cotton et al.
[98] used dynamic extraction for the extraction of Irgafos 168 and Irganox 1010
from a commercial-grade polypropylene matrix. The rate of extraction can be
hampered by two factors: the diusion of the additive through the matrix, or the
solubility of the extracted material in the supercritical uid, can be limited. Similar
results have been obtained by Lou et al. [99] for the supercritical extraction of poly-
ethylene by applying the two-lm theory. In general, if diusion through the poly-
mer matrix is the rate-limiting step in the extraction process, an enhanced extrac-
tion temperature will increase the extraction rate, because the diusion coecient
increases with temperature. Moreover, the plasticizing eect will signicantly en-
hance the diusion rates. If the rate-limiting step is the solubility of the solute
(extracted material) in the supercritical uid, the extraction rates can be enhanced
by either increasing the pressure (solvent strength) or by increasing the uid ow
rate [58].
Another example of supercritical uid extraction is the extraction of liquid crys-
talline 4,4
0
-dibutylazobenzene from a polystyrene matrices [100]. Furthermore,
Sekinger et al. [101] have investigated the feasibility of using SFE for extracting ad-
ditives from styrenebutadiene rubber (SBR) by determining the eects of density,
temperature, ow rate, and contact time on the extraction eciency. Kemmere et
al. [85] have developed a post-polymerization process which reduces the amount
of residual monomer in latexes using scCO
2
. Typically, the method comprises a
counterow process, in which part of the residual monomer is converted by the
increased diusion inside the polymer particles due to the swelling by scCO
2
. In
addition, the amount of residual monomer is further reduced by the extraction
capacity of scCO
2
[102]. Figure 21.8 shows the ow diagram of the extraction pro-
cess. A viability study, including equipment sizing and economic evaluation, has
shown that the removal of residual monomer from latex-products using scCO
2
in
principle yields a process which is both technically and economically feasible, and
capable of meeting future requirements [85]. Other examples of extrapolation of
SFE results obtained on a laboratory scale toward production equipment are de-
scribed by Brunner [103] and Perrut and co-workers [104].
21.2.3.2 Impregnation and Dyeing
The same properties that make scCO
2
attractive for extraction purposes can be ex-
ploited in the impregnation and dyeing of polymeric materials [105]. By applying
supercritical conditions, it is possible to impregnate polymers with pharmaceuti-
cals, avors, and fragrances, or with additives such as pigments, stabilizers, and
7
3
2
1
CO
2
from
supply tank
T: 15 C
P: 55 bar
F: 0.796 kg/s
HEX2
6 compressor
5 separator
4 extractor
latex
F:1.11 kg/s
T:60 C

MMA
latex
Start-up
pump
CO
2
recycle
T: 11C
P: 30 bar
P: 30 bar
T: 60C
P: 80 bar
HEX1
polymerization reactor
T: 11C
P: 30 bar
F: 0.0167 kg/s
F: 0.789 kg/s
1. Latex
pump
2. Centrifugal
pump
3. Heat
exchanger 1
4. Extractor 5. Separator 6. Compressor
(screw)
7. Heat
exchanger 2
flow
4.0 m
3
/hr
flow
3.45 m
3
/hr
heating duty
80.5kW
height
4.25 m
height
3.38 m
total power
53.66 kW
heating duty
(-)51.57 kW
head of feet
2592.0
head of feet
995.7
U
850.0 W/m
2
K
diameter
0.60 m
diameter
1.12 m
U
850.0 W/m
2
K
power
12.5 kW
power
3.44 kW
Tm
69.12 K
wall thickness
0.024 m
wall thickness
0.045 m
T
m

57.00 K
required area
1.4
required area
4.52
7
3
2
1

:

x
: /

-
2

P: 30 bar

:
:
t s
)

r

.

.
.

.

U

.

.

.

Fig. 21.8. Process ow sheet for the removal of residual
monomer from latex-products using scCO
2
[84].
plasticizers. A wide variety of polymer systems have been impregnated using
scCO
2
, for example PMMA [106], PS, PE, PC, PVC, and polypropylene (PP) [107],
and polydimethylsiloxane (PDMS) [108, 109], as well as poly(ethylene terephtha-
late) (PET) [110, 111].
The key parameter that determines the feasibility of the impregnation process is
the equilibrium distribution or partition coecient of the solute that is being im-
pregnated into the polymer. There are two dierent methods of supercritical uid
impregnation of additives into polymer products. The rst involves diusion of a
compound that is soluble in the supercritical uid. The impregnation takes place
when a polymer matrix is contacted with the supercritical uid containing the
solute. On depressurization, the CO
2
ows out of the polymer matrix, leaving the
solute trapped in it [112]. For example, Ma and Tomasko [113] have investigated
the impregnation of high-density polyethylene (hdPE) with the nonionic surfactant
N,N-dimethyldodecylamine-N-oxide using scCO
2
. They have observed that the pen-
etration and absorption into the polymer produces no structural changes or losses
of mechanical strength. However, as a result of the swelling by scCO
2
, the wetting
properties of hdPE are changed permanently, in contrast to conventional tech-
niques using an aqueous solution. In the second route to impregnation, the com-
pound typically has a low solubility in the supercritical phase; dyeing is a typical
example (see, for example, Refs. 106, 107, 111, 114).
As described earlier in Section 21.2.3, impregnation applications based on scCO
2
technology include polymer blending and the production of polymeric drug deliv-
ery devices. However, the largest application of impregnation with scCO
2
at pres-
ent is the dyeing of textiles and bers. The main motivation is the replacement of
large amounts of water in the dyeing process with benign scCO
2
, which can reduce
the wastewater in the textile industry signicantly [85, 86]. The ease of recovering
the carbon dioxide by reducing the pressure and recycling it without the necessity
to clean the carbon dioxide provides a strong environmental advantage. For these
reasons, there has been a signicant eort to commercialize supercritical uid dye-
ing of PET [112], for which the rst pilot plant has been built [115].
21.3
Ultrasound-induced Radical Polymerization
For the development of sustainable polymer processes, ultrasound is an interesting
technology, as it allows for polymerizations without the use of initiator. The radi-
cals are generated in situ by cavitation events [116, 117], which make possible a
clean and intrinsically safe polymerization reaction. As a result of the high strain
rates outside the bubble, cavitation can also induce chain scission [118, 119], which
provides an additional means to control the molecular weight of the polymer
produced. In Sections 21.3.1 and 21.3.2 the physical background of ultrasound-
induced cavitation and radical formation will be described. Subsequently (see
Section 21.3.3), an overview of the several types of ultrasound-induced polymer-
izations will be given, namely bulk, precipitation, and emulsion polymerization.
Finally, in Section 21.3.4, the breakage of polymer chains by cavitation will be dis-
cussed, including the possibility of synthesizing block copolymers.
21.3.1
Ultrasound and Cavitation in Liquids
Ultrasound passes through an elastic medium as a longitudinal wave, which is a
series of alternating compressions and rarefactions. This means that liquid is dis-
placed parallel to the direction of motion of the wave. Ultrasound comprises sound
waves typically in the range of 20 kHz to approximately 500 MHz. The frequency
( f ) and the acoustic amplitude (P
A; max
) are the most important properties to char-
acterize the pressure wave. The variation of the acoustic pressure (P
A
) of an ultra-
sound wave as a function of time (t) at a xed frequency is described by Eq. (2)
[120].
P
A
P
A; max
sin2 p f t 2
The use of ultrasound can be divided into two areas: low-intensity, high-frequency
ultrasound (2500 MHz, 0.10.5 W cm
2
) and power ultrasound with a high in-
tensity and a low frequency (20900 kHz, >10 W cm
2
); see Table 21.2. The rst
does not alter the state of the medium through which it travels and is commonly
used for nondestructive evaluation and medical diagnosis [121]. This type of ultra-
sound cannot be used for reactions. Contrarily, power ultrasound uses the energy
to create cavitations, which involve the formation, growth, and implosive collapse
of microscopic bubbles in a liquid. These bubbles are generated when the nega-
tive pressure during the rarefaction phase of the sound wave is suciently great
to disrupt the liquid. The implosive collapse of the bubbles can produce extreme
temperatures and pressures locally for very short times, due to compression of
the gas phase inside the cavity [122, 123]. These hot-spots can lead to irreversible
changes such as the formation of excited states, bond breakage, and the generation
of radicals. Power ultrasound is applied for cleaning purposes, treatment of kidney
stones, plastic welding, and chemical reactions [124].
Tab. 21.2. Overview of dierent types of ultrasound, including the various applications.
Power ultrasound,
20100 kHz
Sonophoresis,
20 kHz, low power
Therapeutic ultrasound,
1 MHz, high power
Nondestructive ultrasound,
I2 MHz, low power
Sonochemistry
Welding
Cleaning
Cell disruption
Sterilization
Kidney stones
transdermal drug
delivery
therapeutic massage
controlled release
aw detection
medical diagnoses
Sonochemistry comprises the chemical eects that are induced by power ultra-
sound. The ultrasound waves cause the molecules to oscillate around their mean
position in a liquid. During the positive-pressure cycle the distance between the
molecules decreases, while during the negative-pressure period the distance in-
creases. At a suciently high intensity a critical distance between the molecules
is exceeded during the negative-pressure period, and a cavity is formed [125]. Due
to the presence of nuclei such as dissolved gases and solid impurities, cavities are
formed at far lower sound pressures than theoretically predicted [126]. After the
formation of a cavity, a critical acoustic pressure has to be overcome to initiate the
explosive growth of this bubble. This explosive growth is followed by an implosive
collapse (see Figure 21.9). During this collapse, the contents of the bubble are
heated almost adiabatically, which leads to local short-lived hot-spots in the liquid.
Depending on the specic conditions, bubble wall velocities, and pressures and
temperatures in the bubble, can increase up to 1500 m s
1
, 200 bar and 5000 K,
respectively [127].
The acoustic pressure amplitude determines the growth of a cavitation bubble
and consequently the chemical eects upon collapse. The amplitude of the pres-
sure wave can be measured directly with a hydrophone or calculated using a calo-
rimetric method [128, 129], by which it is possible to determine the ultrasound
power (Q
US
) that is transferred to the liquid. With the ultrasound power, the den-
sity of the liquid (r), the speed of sound in the medium (v), and the surface area of
the ultrasound source (A
US
), the acoustic amplitude can be calculated according to
Eq. (3). The ultrasound intensity is the power input divided by the surface area of
the source [130].

0 10 20 30 40 50 60 70 80
0
50
100
150
200
250
300
350
400
R
a
d
i
u
s

(
1
0
-
6

m
)
Time (10
-6
s)
Formation
G
r
o
w
t
h
C
o
l
l
a
p
s
e
Hot-spot

Hot-spot
Fig. 21.9. Schematic representation of bubble
growth and collapse in water at ambient
pressure irradiated with ultrasound and
the resulting hot-spot due to adiabatic
compression. The radius of the cavitation
bubble as a function of time has been
calculated using the dynamic bubble model
based on the RayleighPlesset equation [136].
P
A; max

2 r v
Q
US
A
US
r

2 r v I
US
p
3
The Blake threshold pressure (P
B
) describes the critical pressure to initiate the ex-
plosive growth of a cavitation bubble [Eq. (4)] [131].
P
B
P
0
P
v

4
3
s
2
3

s
P
0
2
s
R
0
P
v

R
3
0
v
u
u
u
t
4
Equation (4) assumes that the external pressure (P
0
), the vapor pressure (P
v
), the
surface tension (s), and the equilibrium radius of the bubble (R
0
) determine the
negative pressure in the liquid required to start an explosive growth of a cavity
[132]. The Blake threshold pressure is based on a static approach and is only valid
when the surface tension dominates all dynamic eects, such as mass transfer and
viscosity. The inuence of the medium characteristics and the physical conditions
on the implosion can be calculated with a dynamic bubble model [120, 133]. The
dynamic movement of a bubble in a sound pressure eld can be described with the
RayleighPlesset equation. By combining the RayleighPlesset equation with a
mass and energy balance over the bubble, the temperature and pressure in the
bubble can be calculated [134136]. The model also describes the dynamic move-
ment of the bubble wall, which results in a calculated radius of the cavitation bub-
ble as a function of time (see Figure 21.9). The explosive growth phase and the col-
lapse phase of the bubble can be distinguished clearly. Moreover, when dynamic
eects are more important than the surface tension, the cavitation threshold can
be calculated with the dynamic model, while the Blake threshold pressure cannot
be used in these conditions.
21.3.2
Radical Formation by Cavitation
Because of the extreme conditions during a cavitation event, radicals can be
formed. Several parameters aect cavitation and thereby the polymerization reac-
tion, since the radical formation rate is directly inuenced by the cavitational col-
lapse. The number of radicals formed due to sonication is a function of the num-
ber of cavities created and the number of radicals that are formed per cavitation
bubble. The bubble wall velocity during collapse and the hot-spot temperature de-
termine the rate at which radicals are formed, both inside and outside a single bub-
ble. These two parameters depend on the physical properties of the liquid as well
as on the physical and chemical processes occurring around the cavity. The most
important properties and processes occurring in a cavitation bubble are depicted
schematically in Figure 21.10. The number of cavities is determined, for instance,
by the impurities in the liquid, the static pressure, the ultrasound intensity, and the
vapor pressure. This emphasizes the complexity of the inuences on the overall
radical formation rate [137, 138]. In the following sections, the eect of the most
important parameters will be discussed.
Reaction temperature When the reaction temperature is altered, the liquid proper-
ties will change. Although these properties (viscosity, surface tension, sound veloc-
ity, vapor pressure, and so on) all have an inuence on the chemical eect of cavi-
tation, the change in vapor pressure dominates the other liquid properties. As the
temperature is raised, the vapor pressure in the bubble is increased, which cush-
ions the implosion of the cavity. This results in a lower local temperature inside
the cavity at higher overall temperatures. Consequently, fewer radicals are formed
per cavitation bubble. On the other hand, a higher vapor pressure can lead to easier
bubble formation due to the decrease in the cavitation threshold. In most cases,
however, an increase in reaction temperature will result in an overall decrease in
the radical formation rate. Therefore, ultrasound-induced reactions exhibit the op-
posite behavior to common radical reactions [139].
Static pressure A high static pressure can prevent the formation of cavitation bub-
bles, as the Blake threshold pressure increases. This implies that fewer or no cavi-
tations are formed at higher static pressures. To counteract this eect a higher
acoustic pressure is required, which will result in a more violent collapse of a cav-
itation bubble.
Viscosity At increasing viscosities the growth and collapse of a cavitation bubble
is retarded, due to the higher drag of the liquid. At a certain viscosity the drag force
becomes too high and the bubble has insucient time to grow to a critical radius.
Fig. 21.10. Schematic representation of a cavitation bubble,
including the processes and physical properties that determine
the cavitation process.
If this radius is not reached, no collapse will occur. Additionally, the higher viscos-
ity slows down the collapse, which makes it possible for heat to be transferred to
the liquid. Due to this heat transfer, lower hot-spot temperatures are reached and
subsequently fewer radicals are being generated.
Ultrasound intensity At rst the radical formation rate will increase to a maxi-
mum with increasing ultrasound intensity [137]. This is caused by the higher
cavitation intensity per bubble and the larger number of cavitation bubbles. At
ultrasound intensities that are too high, however, a cloud of cavitation bubbles is
formed near the ultrasound source, due to which the pressure wave is no longer
transmitted eciently to the liquid. As a result, the cavitation intensity and conse-
quently the radical formation rate decrease with a continued increase in intensity
[137]. An optimum radical formation rate with ultrasound intensity can thus be
found.
Ultrasound frequency The frequency of ultrasound has a signicant eect on
the cavitation process. At very high frequencies (>1 MHz), the cavitation eect is
reduced as the inertia of a cavitation bubble becomes too high to react to fast-
changing pressures. Most ultrasound-induced reactions are therefore carried out
at frequencies between 20 and 300 kHz. Typically a frequency of 20 kHz is used
for ultrasound-induced polymerizations and polymer scission reactions [140].
21.3.3
Cavitation-induced Polymerization
Generally, free-radical polymerization consists of four elementary steps: initiation,
propagation, chain transfer, and termination. When ultrasound is used to initiate
polymerization, radicals can be formed both from monomer and from polymer
molecules. This implies that due to radical formation by polymer scission an addi-
tional elementary step is involved in ultrasound-induced polymerization, as indi-
cated in Figure 21.11.
The radicals from polymer and monomer are generated by two dierent mecha-
nisms. The monomer molecules are dissociated by the high temperatures inside
the hot-spot, whereas the polymer chains are fractured by the high strain rates out-
side the bubble [141]. The majority of the radicals in an ultrasound-induced poly-
merization reaction originate from the polymer chains [142]; see Figure 21.12. It
has to be noted that the radicals are only formed in the immediate vicinity of the
ultrasound source where cavitation occurs. Subsequently, these radicals are dis-
persed throughout the reactor. In the literature several types of ultrasound-induced
polymerizations have been reported, namely bulk, precipitation, and emulsion
polymerization.
21.3.3.1 Bulk Polymerization
Most ultrasound-induced bulk polymerizations are performed at room tempera-
ture [143]. This low temperature is chosen because radical formation induced by
ultrasound appears to be more ecient at lower temperatures [128]; see also Sec-
tion 21.3.2. In contrast to conventional thermal initiators such as potassium persul-
fate, ultrasound can initiate a polymerization reaction at ambient temperatures. It
should be noted, however, that the propagation rate increases with an increasing
temperature. Therefore, a suitable well-tuned system has to be chosen to optimize
ultrasound-induced polymerization. In the literature, several bulk polymerizations
initiated by ultrasound have been reported; examples are the polymerization of
methyl methacrylate [116, 144, 145], ethyl methacrylate [146], n-butyl methacrylate
[117, 141], and styrene [147]. Since the basic reaction kinetics are well known [144,
148] the ultrasound-induced polymerization of MMA is by far the most studied
system. Typically, the resulting molecular weight of the PMMA obtained is in the
range 1 10
5
6 10
5
g mol
1
.
An important parameter during ultrasound-induced bulk polymerizations is the
viscosity. As the reaction proceeds, the polymer chains formed cause a dramatic
increase in the viscosity, resulting in slower growth and collapse of the cavity. As
Initiation
M + Cavitation 2 R ] [ 2 M k R
dmon i

Propagation
n
+ M M
n+1
] [ ] [
n p p
M M k R

Chain Transfer
to monomer
M
n
+ M M
n
+ M ] [ ] [
n ctm ctm
M M k R
to polymer
M
n
+ M
m
M
n
+ M
m
] [ ] [
m n ctp ctp
M M k R
Termination
by combination
M
n
+ M
m
M
n+m
] [ ] [
m n tc tc
M M k R
by disproportionation
M
n
+ M
m
M
n
+ M
m
] [ ] [
m n td td
M M k R

Polymer Scission
M
n
+ Cavitation M
m
+ M
n-m
] [ 2
n dpol d
M k R
M
.
.
.
. .
. .
=
=
=
=
=
=
=
Fig. 21.11. Reaction mechanism of ultrasound-induced radical
polymerization, assuming intrinsic polymerization and avoiding
thermal initiation.
the cavitations become less eective, the radical formation rate both from mono-
mer and from polymer will decrease. Subsequently, the reaction rate decreases as
shown in Figure 21.13. At a conversion of approximately 20% the collapse is no
longer suciently strong to induce hot-spot temperatures that are able to generate
monomeric radicals. Moreover, the strain rates outside the collapsing bubble are
not large enough to produce polymeric radicals by polymer scission [116]. As a
consequence, the polymerization ultimately stops at this conversion, which repre-
sents a serious drawback for the development of ultrasound-induced bulk polymer-
ization toward industrial application.
21.3.3.2 Precipitation Polymerization
As described in Section 21.3.3.1, ultrasound-induced bulk polymerizations are
limited to relatively low conversions, because a strong increase in viscosity upon
reaction hinders cavitation. In order to obtain higher conversions, precipitation
polymerization forms a potential solution. Because the polymer produced is pre-
cipitated from the reaction medium, the viscosity and consequently the radical for-
mation rate are expected to remain virtually constant. From this perspective, liquid
carbon dioxide is a suitable reaction medium, because most monomers have a high
solubility in CO
2
, whereas it exhibits an anti-solvent eect for most polymers.
Moreover, CO
2
is regarded as an environmentally friendly compound, which is
nontoxic, nonammable, and naturally abundant. Since higher pressures are re-
quired for CO
2
to act as an anti-solvent [56, 149], the possibility of ultrasound-
induced cavitation in pressurized carbon dioxide systems has been studied [73, 150].
0 1 2 3 4 5
5.0x10
-10
1.0x10
-9
1.5x10
-9
2.0x10
-9
2.5x10
-9
3.0x10
-9
K
d

M
M
A

(
1
/
s
)
Weight % PMMA
MMA
5.0x10
-5
1.0x10
-4
1.5x10
-4
2.0x10
-4
2.5x10
-4
3.0x10
-4
3.5x10
-4

K
d

P
M
M
A

(
1
/
s
)
PMMA
Fig. 21.12. Radical formation rate constants from MMA and
PMMA as a function of the weight percentage of polymer
dissolved at a temperature of 293 K and an ultrasound intensity
of 62 W cm
2
[142].
During pressurization of a liquid, the Blake threshold pressure [Eq. (4)] in-
creases, which implies that higher acoustic pressures are needed to produce cavita-
tions. Obviously, no cavitation occurs when the Blake threshold pressure exceeds
the maximum acoustic pressure that can be applied with the currently available
equipment. The vapor pressure of the liquid, however, can counteract the static
pressure (see Figure 21.14). As a result of this, the Blake threshold is reduced in
liquids with a high vapor pressure, such as CO
2
, ethylene, and ammonia. This en-
ables cavitation at increased static pressures [73, 150]. Additionally, the dynamic
movement of the bubble in pressurized CO
2
has been calculated using the dy-
namic bubble model based on the RayleighPlesset equation. According to the cal-
culations, the bubble exhibits a similar movement to that of water at ambient pres-
sure. To validate these simulations, cavitation experiments have been performed
in pressurized CO
2
MMA systems using the radical scavenger 1,1-diphenyl-2-
picrylhydrazyl [151]. The radical formation rate appears to be in the order of
1:5 10
4
s
1
, from which no noticable dierence occurs upon varying the
MMACO
2
ratios. Moreover, ultrasound-induced polymerizations of MMA in
CO
2
-expanded MMA have resulted in high molecular weight polymers [151].
21.3.3.3 Emulsion Polymerization
The generation of radicals by ultrasound can also be applied in emulsion polymer-
ization, which comprises a free-radical polymerization in a heterogeneous reaction
system, yielding submicron polymer particles in a continuous aqueous phase. Ul-
trasound can be applied for emulsication purposes as well as at higher conver-
sions in the emulsion polymerization process.
0 1 2 3 4
0.0
2.5
5.0
7.5
10.0
C
o
n
v
e
r
s
i
o
n

(
%
)
Time (h)
298 K
313 K
Fig. 21.13. Conversion development of an ultrasound-induced
bulk polymerization of MMA at 298 and 313 K [150]. The
broken lines indicate the initial reaction rate.
At the beginning of the polymerization, emulsication and nucleation govern
the course of the process. The monomer droplets have to be small enough to pro-
vide a negligible resistance to monomer transport from the droplets through the
aqueous phase to the growing polymer particles. Only in the case of sucient
emulsication, can intrinsic polymerization kinetics be assumed. This implies
that in conventional emulsion polymerization vigorous stirring is required to dis-
perse the monomer droplets. When ultrasound is applied as an energy source
for emulsication, a very uniform emulsion of small monomer droplets is ob-
tained without additional stirring. The high implosion velocity of the cavitation
bubbles ensures that the monomer droplets are well dispersed. A special case in-
volves mini- or microemulsion polymerization. Depending on the surfactant sys-
tem used and the emulsication induced by ultrasound, the monomer droplets
become so small that they can serve as nucleation loci. In ordinary emulsion poly-
merization, the main locus of nucleation is within the monomer-swollen micelles.
Typically, polymer particles produced by ultrasound-induced emulsion polymeriza-
tion have a diameter of approximately 50 nm [152, 153].
During emulsion polymerization induced by ultrasound, the redundancy of ini-
tiator is advantageous in terms of process control and safety. Moreover, initiator
residues do not contaminate the product. In contrast to ultrasound-induced bulk
polymerizations, high conversions can be obtained in ultrasound-induced emul-
sion polymerization [154, 155]. Since a heterogeneous reaction system is involved,
in which the polymer is insoluble in the continuous aqueous phase, the viscosity of
the water phase does not increase upon reaction. The cavitation events occur in the
continuous phase, producing radicals mainly from water and surfactant molecules
275 280 285 290 295 300 305
0
10
20
30
40
50
60
70
Blake threshold H
2
O
Blake threshold CO
2
Vapour pressure H
2
O
Vapour pressure CO
2
P
r
e
s
s
u
r
e

(
b
a
r
)
Temperature (K)
Fig. 21.14. Calculated Blake threshold and vapor pressure for
water and carbon dioxide at 58.2 bar [73].
[156]. Subsequently, the oligomeric radicals enter the monomer-swollen polymer
particles and continue to polymerize. Examples of ultrasound-induced emulsion
polymerization are described for styrene [153, 155, 157], methyl methacrylate
[152, 156, 158161], and n-butyl acrylate [162] and the copolymerization of vinyl
acetate and butyl acrylate is also reported [154].
21.3.4
Cavitation-induced Polymer Scission
In terms of product properties, the molecular weight distribution is an important
characteristic of polymers. In the polymer industry a post-processing step is often
applied to alter the molecular weight of the polymers, for example for the peroxide-
induced degradation of polypropylene [163]. In this process, fracture of the poly-
mer chain occurs at a random site. An alternative method is ultrasound-induced
polymer scission, which involves a much better-controlled, nonrandom process
[119]. This enables relatively straightforward production of the desired molecular
weight as well as the formation of block copolymers, as described in Section 21.3.5.
It has been shown that ultrasound-induced polymer breakage is a direct conse-
quence of cavitation because, under conditions that suppress cavitation, no degra-
dation is observed. In this nonrandom scission process the polymer is fractured at
the center of the chain [164, 165]. This is clearly shown in Figure 21.15, in which a
polymer with a molecular weight of 90 kg mol
1
is produced from a polymer with
an initial molecular weight of 180 kg mol
1
. It is often thought that the extreme
temperatures inside the bubble upon implosion contribute to the degradation.
10
4
10
5
0
1
2
3
4
5
6
0 min
5 min
10 min
20 min
40 min
d
w
t
/
d
(
l
o
g
M
)
Molecular weight (g/mol)
Fig. 21.15. Molecular weight distributions of an ultrasound-
induced polymer scission of PMMA into MMA with an initial
M
n
of 18:0 10
4
g mol
1
[151].
However, temperature degradation implies a random process and thus does not ex-
plain the scission in the middle of the chain.
Ultrasound-induced chain fracture arises from the high strain rates on the poly-
mer chain upon implosion. The nonrandom fracture in the middle of the chain by
cavitation can only occur when the polymer chain is in a nonrandom conformation
and thus completely stretched [166, 167]. In the absence of an external force a poly-
mer chain in solution is randomly coiled. Upon bubble collapse, the entire mole-
cule will move along with the uid. However, due to the velocity prole near the
cavities, friction between the polymer chain and the liquid will occur. Under su-
ciently strong ow conditions, the solvent drag force causes extension of the poly-
mer molecule and nally full stretching. If the polymer chain is stretched, the
maximum stress due to the drag force will be in the center of the polymer chain,
which is in analogy with ow-induced polymer scission [168]. If the drag force on
the stretched polymer molecule exceeds the bond strength, scission will occur in
the middle of the chain; otherwise the chain is not fractured and a limiting molec-
ular weight (M
lim
) is reached [169]. This limiting molecular weight is no longer
fractured as the forces acting on the chain are smaller than the force required to
break a bond.
The kinetics of ultrasonic scission can be directly ascribed to the implosion
velocity of the cavitation bubbles and the polymer that is fractured. The scission
rate and the limiting molecular weight are thus inuenced by the ultrasonic wave,
the solvent properties, and the polymer structure. The inuence of ultrasound in-
tensity, liquid viscosity, and liquid temperature on the degradation rate and the
limiting molecular weight have been studied by Price et al. [170]. A higher inten-
sity results in a faster scission and a lower limiting molecular weight. Lower tem-
peratures and lower viscosities have similar inuences on the scission rate and
M
lim
. These three eects can be ascribed to the higher implosion velocity, which
induces higher strain rates around the bubble and therefore lead to a lower limit-
ing molecular weight and a higher scission rate.
The initial molecular weight of the polymer inuences neither the implosion ve-
locity of a cavity nor the limiting molecular weight that is reached. However, the
molecular weight has a large inuence on the fracture rate of the polymer chains.
A higher scission rate is observed for polymers with a higher initial molecular
weight [170]. This is a consequence of the higher solvent drag force on the longer
chains. As a result, narrow molecular weight distributions can be produced by
ultrasound-induced polymer scission, because a high molecular weight polymer is
fractured faster. Independently of the initial molecular weight, a similar limiting
molecular weight is obtained for dierent experiments, as the nal conditions are
equal after several breakage events of the higher molecular weight polymers [167].
21.3.5
Synthesis of Block Copolymers
An interesting application of ultrasound-induced scission and polymerization is
the synthesis of block copolymers, which are used in many applications where dif-
ferent polymers are connected to yield a material with hybrid properties [171], for
instance as a compatibilizing agent between immiscible polymers [172]. Anionic
and living radical polymerization reactions are the most important techniques for
synthesis of block copolymers. Alternatively, ultrasound can be used to produce
these block copolymers, for which two dierent methods are applicable.
The rst route to synthesis of block copolymers by ultrasound starts with the
dissolution of a homopolymer in a dierent monomer [173]. Subsequently, ultra-
sonic scission of the polymer chains generates polymeric radicals, which initiate
the polymerization reaction with the monomer present. In this way ultrasound
provides the controlled formation of block copolymers, examples of which are poly-
ethylene with acrylamide [173], and PMMA with styrene [174]. Secondly, dissolv-
ing two dierent homopolymers in a nonreactive solvent can lead to block copoly-
mers as well (see Figure 21.16). In this case, the polymeric radicals generated have
to undergo termination by cross-combination [170, 175]. If no cross-combination
occurs, the original homopolymers are reproduced again. The advantage of the
second method is that block copolymers can be produced from homopolymers of
which the polymermonomer systems are immiscible. Using this approach the
synthesis of the block copolymer of polystyrene and poly(methyl phenyl silane)
[170] as well as the block copolymer of poly(vinyl chloride) and poly(acrylonitrile-
co-butadiene) [171] has been described.
21.4
Concluding Remarks and Outlook for the Future
In this chapter, supercritical carbon dioxide and ultrasound have been discussed as
two examples of emerging technologies in polymer processes. Replacing the tradi-
tional organic solvents with supercritical carbon dioxide provides possibilities for
Ph
Ph
Ph
Ph
Ph
Ph
)
)
)
)
n
n
n

ultrasound
ultrasound
Ph
Ph
) ( )
n n
n
Fig. 21.16. The production of a block copolymer from two
homopolymers with ultrasound [117].
the development of sustainable polymer processes. Additionally, the tunability of
the solvent and the relatively easy separation of the polymer from the reaction
medium are important advantages. However, applying scCO
2
as a clean solvent
in polymer processes is not the simplest route, because it implies, among other
things, high-pressure equipment, complex phase behavior, new measurement
techniques, and the development of novel process concepts rather than extending
the conventional technologies. Currently, there is a lack of integrated tools between
the research on a laboratory scale and the industrial-scale application, mainly
caused by the absence of pilot-scale facilities. Recent innovative tools, such as
supercritical reaction calorimetry [176] on the liter scale, could ll this gap by al-
lowing the determination of engineering, process, scaleup, and safety data [177].
Additionally, several process design calculations have shown that polymer pro-
cesses based on scCO
2
technology can be economically feasible, depending on the
value of the product and the process conditions. Moreover, further developments
will reduce costs of supercritical application substantially. It is expected that the
major application of supercritical carbon dioxide will rst be in the food and phar-
maceuticals industry because of additional marketing advantages, such as the
GRAS (generally regarded as safe) status. Nevertheless, the fact that DuPont is
commercializing the production of uoropolymers in scCO
2
illustrates the possi-
bility of applying supercritical uid technology in polymer processes as well. In
addition, the long-existing ldPE tubular process (approximately 2500 bar, 600 K)
proves that a high-pressure polymerization process performed on a large scale can
survive in a highly competitive eld.
With respect to controllability of polymerization processes, ultrasound has sig-
nicant potential as a clean and safe technology. After the production of most
types of polymers, catalyst and initiator residues contaminate the product. Since
ultrasound generates the radicals in situ, no initiator or catalyst is required to start
a polymerization reaction. In addition, high-temperature free-radical polymeriza-
tion is emerging in order to avoid the use of initiators that will remain present in
the polymer chain at the end of the process [178]. The mechanism of thermal ini-
tiation at high temperatures is still not well described. However, in analogy with
initiation by ultrasound at low temperatures, high-temperature processes open
the route for the sustainable production of polymers composed only of monomer
units. An additional advantage of ultrasound is the intrinsically safe operation,
because turning o the electrical power supply will immediately stop the radical
formation and consequently the polymerization reaction. Besides polymerization,
polymer scission can also occur through irradiation with ultrasound, due to the
rapid ow around a cavitation bubble. At a suciently small chain length, further
fracture of the polymer is prevented. In this way ultrasound-induced polymer scis-
sion provides an additional means to control the molecular weight of the product.
At the moment the major challenge of ultrasound-induced polymer processes is
the scaleup, mainly in terms of energy conversion of the ultrasound generator
to the probe. Although no large-scale industrial polymerization process based on
ultrasound exists yet, commercial applications in other elds such as ultrasound
cleaning and sterilization prove that ultrasound is a readily available technique
21.4 Concluding Remarks and Outlook for the Future 1075
and relatively simple to implement in existing industrial equipment. Still, the ap-
plication of ultrasound for polymerization purposes requires a thorough, multi-
disciplinary understanding of both ultrasound parameters and liquid properties,
including physics, chemistry, and engineering.
In general, the various subjects in this chapter have been addressed from an en-
gineering point of view, for which industrial application is one of the important
issues. Although signicant eort is being put into new developments by a large
number of research groups, the development trajectory from the concept idea, via
the laboratory, bench, and pilot scale, toward industrial implementation is often
long and not easy. To reduce the boundaries between the academic approach and
industrial practice, collaboration between industrial R&D, research institutes, and
universities is essential to reduce costs and to exploit existing know-how and exper-
imental facilities, as well as to reduce the development time. Given the economics
of an emerging technology as compared to long-existing processes, it is a challenge
to implement new process concepts at reasonable costs. For these reasons, in the
short term the number of large-scale industrial polymer processes based on super-
critical uid or ultrasound technology will be limited, for which stimulation from
government and research consortia can contribute substantially to facilitate the
development trajectory. Nevertheless, the progress made in research today will en-
able the development of sustainable and well-controlled polymer processes for the
future.
Acknowledgments
The author thanks Marc Jacobs and Martijn Kuijpers for their contribution to this
chapter.
Notation
A
US
surface area of ultrasound source [m
2
]
f frequency [Hz]
I
US
ultrasound intensity [W/cm
2
]
P
0
external pressure [bar]
P
A
acoustic pressure [bar]
P
A; max
maximum acoustic amplitude [bar]
P
B
Blake threshold pressure [bar]
P
c
critical pressure [bar]
P
v
vapor pressure [bar]
Q quadrupole moment [J
1=2
m
5=2
]
Q
US
ultrasound power transferred to liquid [W]
R
0
equilibrium radius of cavitation bubble [m]
T
c
critical temperature [K]
T
g
v speed of sound in medium [m s
1
]
a polarizability [m
3
]
G
ij
potential energy [J]
m dipole moment [C m]
v speed of sound in medium [m s
1
]
r density [kg m
3
]
s surface tension [N m
1
]
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171 I. W. Hamley, Block copolymers, in
Technology, John Wiley, New York,
2002.
172 T. J. Mason, Sonochemistry, The Uses of
Ultrasound in Chemistry, CRC Press,
Cleveland, 1990.
173 H. Fujiwara, J. Tanaka, A.
Horiuchi, Polymer Bulletin, 1996, 36,
723.
174 G. Schmidt-Naake, M. Drache, M.
Weber, Macromol. Chem. Phys., 2002,
15, 203.
175 H. Fujiwara, Polymer Bulletin, 2001,
47, 247.
176 S. Fortini, F. Lavanchy, Th. Meyer,
Macromol. Symp., 2004, 206, 79.
177 F. Lavanchy, S. Fortini, Th. Meyer,
Organic Process Research Development,
2004, 8(3), 504.
178 P. Nising, Th. Meyer, Ind. Eng.
Chem. Res., 2004, 43, 7220.
References 1081
Index
a
AAS, see Atomic absorbtion spectroscopy
AES, see Atomic emmision spectroscopy
Ab-initio calculation 781
Abstraction reaction 784
AC, see Air-to-close valve
Accelerated weathering test 824
Accumulation 556, 580
Acetaldehyde 89
Acid-catalyzed esterication and alcoholysis
86
Acidolysis 86, 100
Acid strength 900
Acid value 860, 865
Acoustic amplitude 1064
Acoustic attenuation spectroscopy 624
Acrylate resins 889
Acrylated oils 891
Acrylic bers 946
Acrylic solutions 951
Acrylics 951
Action spectrum 800
Activated anionic mechanism 348
Activation energy 565, 744, 747
Activation spectrum 799
Activation volume 744
Activity 18
Activity coecient 19, 29, 34
Actuator 629, 652
Adaptive control 664, 668
A/D converter 626
Additives 836
Adiabatic polymerizer 662
Adiabatic temperature rise 308, 546, 565
Adsorbents 989
Advanced control 657
Advancement process 109, 854
AES, see Atomic emission spectroscopy
After-oils 930
Aging prevention for plastic material 818
Agitation requirement 289
Agitator 289
Agitator power 534
Air-gap spinning 921, 956
Air-to-close (AC) valve 652
Air-to-open (AO) valve 652
Alarm 589, 626
Alcohol-isocyanate reaction 893
Alcoholysis, acid-catalyzed 86
Alcoholysis process 857
Alkyd constant 858
Alkyd emulsions 861
Alkyd resins 855
Aminolysis reactions 100
Amino resins 843
Amorphous orientation 919
Amorphous phase 682
Analog lter 627
Analytical pyrolysis 790
Analytical techniques, overview 1016
Analytical tools 12
Anhydrides 86
Anionic polymerization 325
Anisotropic crystallization 918
Anisotropy 886
Antagonistic eect 826
Anti-misting agent 714
Antioxidant 818
Antiozonant 824
Antirad 810
Anti-reset windup 643
AO, see Air-to-open valve
Apolar rubbers 896
Apparent shear rate 934
Apperant equilibrium constant 99
Applications of acrylics 951
Applications of aramids 960
Applications of carbon bers 966
ISBN: 3-527-31014-2
1083
Applications of gel-spun PE 964
Applications of PVA 953
Aramid 921, 956, 959
Aramid2/Kevlar2 5
Aspect ratio 888
Association behavior 326327, 330, 715
Association number 328329
Atactic polystyrene 721
At-line analysis 1015
At-line conversion measurement 1020
Atomic absorbtion spectroscopy (AAS) 1017
Atomic emission spectroscopy (AES) 1017
Attraction term 37
Autoacceleration 762
Automatic control 650
Auto-oxidation mechanism 782
Autoxidative drying 858
Auxiliary devices 596
Average branching density 491
Average copolymer composition 478
Average molecular weight 123, 269
Average number of radicals per particle 258,
260
Average sequence length 474
Average value 597
Axial-ow 289
Azeotrope 859
Azeotropic distillation 865
Azo initiator 154
Azomethine structure 841
b
Back-biting 67, 189
Backow 648
Backhole 927
Balances 604
Base-mediated curing 901
Basicity of HAS 821
Batch control 669
Batch copolymerization 478
Batch emulsion polymerization 251
Batch polymerization 204
Batch process 195, 579
Batch reactor 335, 669
Bead 216, 233, 238
Beer-Lambert law 607, 618
Bellows pressure gauge 602
Belt balance 605
Belt process 353
Bernoulli equation 607, 611
Bias 640
Bidirectional ber 879
Bifunctional initiator 334, 1035
Bimetallic thermometer 601
Bimodal distribution 343
Bimolecular deactivation 386
Binary format 626
Binomial distribution 456
Birefringence 919
Birth conversion 495
Bisphenol-A 850
Bisphenol-A glycidyl resins 841
Black body 601
Black orlon 966
Blake threshold pressure 1065
Blending process 1058
Block copolymer 335, 338, 342, 344, 351,
690, 714, 1073
Block copolymer application 691
Block diagram 629
Block length distribution 1038
Boltzmann superposition principle 730731
Boltzmanns law 1024
Bonds 114
Bottom-up technique 997
Boublik-Mansoori hardsphere equation 45
Branch point 504, 711
Branched architecture 472, 502
Branching 272, 445
Branching behavior 700
Branching distribution 672
Branching moment distribution 454
Branching parameter 1040
Branching process theory 13
Breakage 218, 229
Breaking strength of a covalent bond 814
Breakthrough in SEC systems 1042
Brittleness 855
Bubble coalescence 974
Bubble growth 974, 976
Bubble nucleation 78, 974
Bubble pressure method 622
Bulk (compression) modulus 725
Bulk molding compound (BMC) 883, 885
Bulk polymerization 1067
Buoyancy method 606
Burgers vector 747
Buttery valve 654
c
Cactus 127
Cage eect 765
Calorimetry 297
Capacitance measurement 608
Capillary electrophoresis 1037
Capillary hydrodynamic fractionation (CHDF)
624
Capillary number 221
1084 Index
Capillary viscometer 619
Capsule 603
Carbenium ion 352
Carbon ber 791, 956, 965, 966
Carbon nanotubes 692
Carbon NMR 1024
Carboxilic anhydrides 853
Carboxylic acids 853
Carpet yarn 916917, 926
Cascade control 650, 660
Cascade theory 480482
Casting 886
Casting system 549
Catalan number 484
Catalysis by metallic compounds 87
Catalyst 451, 842, 1075
Catalyst activity 377
Catalyst deactivation mechanism 375
Cationic curing 900
Cationic photoinitiator 897
Cavitation 654, 1063
Cavitation-induced polymerization 1067
Ceiling temperature 172, 565
Cellulose acetate 944945
Cellulose rayon 965
Cellulose triacetate 921
Central lter 926
Centrifugal casting 882
CFD, see Computational uid dynamics
CHDF, see Capillary hydrodynamic
fractionation
Chain branching 761
Chain conformation 692
Chain growth 564
Chain-growth polymerization 11
Chain mobility 765
Chain orientation 766
Chain retraction 741
Chain scission 190, 714, 771, 803, 809
Chain transfer 166
Chain-transfer constant 167
Chain-transfer mechanism 374
Chain-transfer reaction 775
Chain transfer to hydrogen 386
Chain transfer to polymer 188
Chains of beads and springs 697
Chain walking mechanism 382
Characteristic ratio 723
Charlesby-Pinner plot 809
Check valve 648
Chemical analysis 1015
Chemical composition distribution (CCD)
390, 394, 1037
Chemical defect 795
Chemical defoaming 987
Chemical degradation 758
Chemical derivatization 774
Chemical distribution 341
Chemical engineering 14
Chemical heterogeneity 339
Chemical reaction engineering 5
Chemical resistance 874
Chemicrystallization 766
Chemiluminescence 778, 789
Chemometric analysis 301
Chromatographic retention 1035
Chromel/alumel electrode 601
Chromophore impurities 795
Chromophores 793
Classes approach 444
Closed-loop control 305
Closure problem 438
Cloud-point 1051
CMC, see Critical micelle concentration
Coagulation 294, 946, 959
Coagulation risk 987
Coagulative nucleation 253, 267
Coating process 1059
Coaxial device 620
Cobalt irradiation 806
Co-condensation 845
Cold drawing 932
Cold-press molding 883
Column hold-up volume 1035
Combined scission/branching 501
Comonomer distribution 344
Compartmentalization of radicals 254
Compatible blends 811
Complex owsheets 205
Complex modulus 731
Composite formation 692
Composition measurement 620
Composition of copolymer 292
Composition of monomer 292
Compositional drift 670
Comprehensive two-dimensional LC
instrumentation 1043
Compressibility factor 43
Compressible ow 613, 625
Compton scattering 807
Computational uid dynamics (CFD) 205,
290
Computer simulation 780
Concentrated solutions and melts 698
Concentration of monomer in the polymer
particles 258
Concentration of radicals in the aqueous phase
262
Index 1085
Concentration-sensitive detector 1033
Concerted multidisciplinary approach 15
Condensation 11
Condensed mode 421
Conditional Monte Carlo sampling 502
Conductivity measurement 621
Cone-and-plate viscometer 620
Connectivity 472, 482, 502
Contact ion pairs 324
Contact thermometer 599
Continuos stirred tank reactor (CSTR) 584
Continuous lamination 882
Continuous operation 536
Continuous polymerization 204
Continuous steam stripping 987
Control loop 629
Control of feed 587
Control system 629
Controlled degradation and crosslinking
812
Controlled depressurization 588
Controlled reaction 546
Controlled thermal degradation 791
Controlled variable 628, 639
Controller 628, 639
Controller action 640
Controller gain 640
Controller output 640
Controller tuning 644
Conversion of monomer 291
Converter 626
Cooling 570, 689
Cooling belt 842
Cooling coil 570
Cooling experiment 573
Cooling rate 686
Cooling speed 929
Coordination catalyst 373
Coordination polymerization 12
Coordinator 7
Copolymer 225, 241, 243
Copolymer averaged rate, coecient for
propagation 183
Copolymer composition 338
Copolymerization 179, 338, 413, 451, 473
Copolymer sequence distribution 181
Copolymer-solvent systems phase behavior of
48
Copper/constantan electrode 601
Corded yarn 913
Coriolis owmeter 617
Couette device 961
Couette-Taylor reactor 288
Coulter-counter particle size analyzer 623
Counter 609
Covalent polarized bond 324
Covalent species 352
Crack advance 750
Crack formation 769
Crack tip 750
Cracked specimen 750
Craze-bulk interface 748
Craze bril 749
Craze length 748
Craze nucleation 749
Craze stress 749
Crazing 748
Creep behavior 709
Creep response 708
Critical-angle refractometer 621
Critical length for entry of radicals 267
Critical liquid chromatographic separation
1037
Critical micelle concentration (CMC) 264,
622
Criticality classes 558
Cross-aggregation 329
Crosslink denition 177
Crosslink density 834
Crosslinked polymer 748749
Crosslinkers 467
Crosslinking 272, 771, 809, 868, 871
Crosslinks 834
Cross model 703, 740
Cross-tie bril 750
Crystaf, see Crystallization analysis
fractionation
Crystal thickness 689
Crystalline domains 688
Crystalline morphology 688, 690
Crystalline orientation 919
Crystalline phase 682, 766
Crystalline polymer 681, 688
Crystallinity 1053
Crystallizability 682
Crystallization 680, 686, 918
Crystallization analysis fractionation (Crystaf )
369
Crystallization enhancement 687
Crystallization rate 687
Crystallization reduction 687
Crystallization temperature 686
CSTR, see Continuos stirred tank reactor
Cumulative distribution 407
Cure 835
Curing 564, 871
Cyclic monomers 346
Cyclization of side chains 763
1086 Index
d
D/A converter 626
Damping function 741
Data highway 651
DCS, see Distributed control system
Deadband 647
De-aeration of the melt 924
Dead chain 467
Dead time 636, 639
Deborah number 708
Decomposition 337, 556, 564
Defoaming agent 987
Degradation detection method 767
Degradation reaction of nylon-6 100
Degree of aggregation 329
Degree of branching distribution (DBD)
1040
Degree of crystallinity 766
Degree of polymerization 126, 159
Degree of superheat 976
Delustering 916
Dendrimers 712
Denier 914
Denisov cycle 820
Dense grafting 712
Densimetry 297298
Density balance 617
Depolymerization 356, 566, 973
Depropagation 172, 973
Depropagation in copolymerization 188
Derivative controller (D controller) 641
Derivative kick 642
Derivative mode lter 642
Derivative time 641
Detection time 589
Detector for SEC 1032
Development process 2
Development trajectory 1076
Deviation 597
Deviation variable 632
Devolatilization 971
Diacids 865
Dialkyltin catalyst 89
Diaphragm pressure gauge 603
Diaphragm valve 652
Dibutyltin dilaurate (DBTDL) 893
Dicyclopentadiene (DCPD) 873, 903
Diethylene glycol 89
Diethylenetriamine 853
Dierential refractometer 621
Diusion constant 764
Diusion control 230
Diusion-controlled chain termination 165,
229
Diusion-controlled reaction 190
Diusivity 1049
Digital control system (DCS) 642
Diglycidyl ether of bisphenol-A (DGEBPA)
850, 873
Digraph 114
Dilatant 619
Dilatometer 619
Dilute solution 696
Dimensional temperature dependance 1003
Dimensionality 431
Dimethylol urea rate of formation 104
Diols 864
Dioxane 90
Dipole moment 1050
Direct esterication process 91
Dislocations 747
Dispersion polymerization 256, 1057
Dispersion term 4546
Disproportionation 166, 440
Distributed control system (DCS) 627, 651,
668, 672
Distribution coecient 1034
Distribution of active polymer chains 269
Distribution of feed 535
Distribution of inactive chains 269
Distributive properties 431
Disturbance variable 628, 640
Doi and Edwards model 738, 740
Doolittles equation 734
Dormant end group 345
Double-screw reactor 356
Drag-reducing agent 714
Draw ratio 748, 932933
Drawing 931
Drop coalescence 222, 235
Drop-in technology 373
Drop mixing 224, 240
Drop size 216
Drop size distribution 222223, 227
Drop stabilizer 214, 223
Dry spinning 921, 944, 955
Dual-exposure photoembossing 1007
Dulling agent 916
Dumbbell model 697, 703
Dumping 588
Dyads 64
Dyeing 1061
Dynamic control 553
Dynamic head-space 1023
Dynamic light scattering 624
Dynamic modulus 731
Dynamic oscillatory ow 709
Dynamic SIMS 1026
Index 1087
Dynamic stability 584
Dyneema 962, 964
Dyneema process 962
e
EKF, see Extended Kalman lter
Elastic behavior 936
Elastic polymer 706
Elastically active network chain 121
Elastically active network junction 121
Elastomer 725, 727729, 739, 901
Elastomeric green strength 715
Electro-chemical potential method 621
Electron beam accelerator 806
Electron beam lithography 996
Electron spin resonance (ESR) spectroscopy
776, 1017
Electronic balance 605
Electro-pneumatic valve positioner 650
Electrospray ionization (ESI) 1027, 1033
Electrostatic spraying 867
Eleostearic acid 856
Elimination reaction 324, 337
Elongation rate 936
Elongational viscosity 936
Embrittlement 749
Emergency cooling 575, 587
Emerging technologies 7
Emulsication 1071
Emulsion polymer 985
Emulsion polymerization 249, 980, 1057,
1070
Emulsion polymerization reactor 286, 305
End conversion 494
End-to-end distance 723, 738
End-to-end distance of polymer coil 693
End-to-end vector 723, 727, 738
Energy dissipation by the stirrer 578
Energy dose 1003
Energy requirement 8
Energy transfer 808, 811
Enforced cooling 928
Enolization 345
Entanglement 729, 738740, 749
Enthalpy balance 292
Entropic free volume model 36
Environmental and safety issues 15
Environmental aspects 13
Environmentally friendly 255
Enzymatic polymerization 1057
EPDM, see Ethylene-propylene-diene rubbers
Epichlorohydrin (ECH) 108, 850
Epidemic model 790
Epitaxial crystallization 687
Epoxy acrylates 891
Epoxy resins 108, 849
Epoxy-novolacs 841
Equal percentage 652
Equation of state model 39
Equilibrium equations 259
Equilibrium monomer concentration 347,
354
Equilibrium morphology 274
Error 628, 640
Ester enolate anion 345
Esterication 86, 863
Esterication acid-catalyzed 86
Ether bridges 845, 839
Ethoxylation 351
Ethylene 451
Ethylene oxide 349
Ethylene-propene-diene (EPDM) 368, 902
5-Ethylidene-2-norbornene (ENB) 903
Evaporative light-scattering detector (ELSD)
1032
Exchange of bonds 115
Exchange reaction 66
Excited state quencher 808
Exothermic reaction 541, 565
Expansion factor 613
Expansion thermometer 601
Exponential smoothing lter 627
Exposure time 74
Extended Kalman lter (EKF) 667
Extensional thickening 705
External impurity 795
Externally applied stress 767
Extraction of VOC 989
Extruder 75, 76, 549
Extrusion 816, 866, 923, 937
f
Fail safe 587
Failure scenario 554
Falling-lm devolatilizer 975
Falling-strand devolatilizer 975
False twist operation 916
Fatty acid 855
Fatty acid process 857
Feedback controller 628
Feedforward control 659, 666
FENE, see Finitely extensible nonlinear elastic
Fiber modulus 915
Fiber polymers 920
Fiber reinforcement 886
Fiber tenacity 915
Fiber terminology 912
Fiber yarn 913, 917
1088 Index
Fibers, denition 912
Fibril 748
Fibril extension 748
Fibril formation 920
Ficks second law 798
Filament 913
Filament number 915
Filament textile acrylics 952
Filament titer 914
Filament winding 882
Filament yarn 913
Fillers 692, 878
Film-formation temperature 273
Film-forming equipment 71
Filter constant 642
Filter package 926, 935, 938
Filtration 926
Finish 929
Finish roll 930
Finite element method 432
Finitely extensible nonlinear elastic (FENE)
dumbbell model 703
First dimension separation 1042
First-order system 632
First-order system plus dead time (FOPDT)
636, 645
First-shell substitution eect (FSSE) 64
Flame retarding agents 849
Flash evaporator 975
Flexibility 866
Flexibilization of amino-resins 849
Flexible foams 111
Float method 606
Flooding 575
Flory distribution 442
Flory-Huggins, multicomponent 70
Flory-Huggins theory 21, 30
Florys chain length distribution 387
Flow-induced degradation 817
Flow measurement 608
Fluidized-bed reactor 82, 417, 420
Fluorescence eect 1019
Fluoropolymer 1057
Foam 111
Foam formation 987
Foam-based devolatilization 974
Food preservation 812
FOPDT, see First-order system plus dead time
Force balance 614
Force eld calculation 782
Formaldehyde 108, 346, 838
Formalin solution 842
Formulation 250
Fouling 570, 925
Fourier analysis 954
Fourier number 955
Fourier transform IR spectroscopy (FTIR)
621, 1023, 1024
Fourier transform ion-cyclotron resonance
spectrometer 1030
Fractionation 1059
Fracture 741742, 748
Fracture behavior 751
Fracture resistance 740, 750751
Fragment 472
Fragmentation 178, 190
Fragmentation in polymer analysis 1027,
1029
Free boiling 976
Free-bubble devolatilization 974
Free ions 324
Free-radical polymerization 1067
Free-radical polymerization, heterogeneous
12
Free-radical polymerization, homogeneous
12
Free-radical polymerization mechanism 157
Free volume 734735, 764
FSSE, see First-shell substitution eect
FTIR, see Fourier transform IR spectroscopy
Fugacity 18
Fugacity coecient 19, 42
Fully oriented yarn (FOY) 933, 940
Fumaric acid 871
Functional monomer 250
Functionality 835
Functionality-type distribution (FTD) 1034,
1041
g
Galerkin hp method 434
Gas chromatograph feedback controller 666
Gas chromatography (GC) 297298, 621,
1022
Gas-phase process 416
Gas-phase reactor 420
Gas-phase stirred-bed reactor 417
Gate valve 656
Gauss normal dierential distribution function
598
Gaussian chain 707
GC, see Gas chromatography
Gel 272
Gelation 714, 837
Gel eect 193, 568569
Gel permeation chromatography (GPC) 622,
664, 771, 1020
Gel point 128, 771, 835
Index 1089
Gel spinning 921, 961, 962
Gel-spun polyethylene 918 964
General-purpose nishes 930
Generation 487
Geometric similarity 295, 534, 536
G-factor 808
Glass lament 875
Glass transition 721, 732733, 735, 745, 683,
764, 901
Glassy polymer 742743, 750
Glycerol 856
Glycidyl group 841, 850
Glyptals 857
Gold distribution 333334
GPC, see Gel permeation chromatography,
see also SEC
Grade transition 669
Gradient elution liquid chromatography
10381039, 1042
Graft copolymers 232
Graph theory 502
Graphite nanosheets 692
Graphitization 966
GRAS (generally regarded as safe) 1075
Gravimetric method 619
Gray 808
Green solvent 1048
Grotthus-Draper law 793
Group contribution Flory model 36
Group contribution methods 35
h
Hagen-Poiseuille law 619
Half-bonds 114
Half-life 162
Half-sandwich metallocene 381
Hand lay-up process 882
Hansen solubility parameters 32
Hard sphere term 44
Hardening 835
Hardness 895
HAS, see Hindered amine stabilizer
HCSTR, see Homogeneous continuous stirred
tank reactor
HDC, see Hydrodynamic chromatography
HDPE, see High-density polyethylene
Head-space gas chromatography 1023
Heart-cut 1041
Heat accumulation 561, 581
Heat balance 292, 554, 559, 562
Heat-balance calorimetry 303
Heat-ow calorimetry 303
Heat loss 562
Heat release 559
Heat removal 194, 560
Heat resistance 779
Heat-resistant polymer 780
Heat-sensitive substrate 869
Heat-shrinkable product 813
Heat stabilizer 975
Heat transfer 214, 227, 235236, 242, 290,
539, 972
Heat-transfer coecient 293, 560
Heat-transfer resistance 400
Heaviside step function 632
Helmholtz energy 44
Helmholtz free energy 726
Henrys constant 974
Henrys law 974
Heterogeneous kinetics 789
Heterogeneous nucleation 252, 264
Heterogeneous oxidation 789
Heterogeneous polymerization 1055
Heterogeneous reaction model 827
Heterolytic bond scission 760
HEUR, see Hydrophobically associting
polymer
Hexamethylenetetramine (HMTA) 838
Hexamethylolmelamine 841
Hierarchical approach 658
High monomer conversion 972
High-density polyethylene (HDPE) 366
High-energy radiation 805
High-impact polypropylene 417
High-impact propylene/ethylene copolymers
368
Highly branched popylethylene 1053
High-modulus high-strength bers (HMHS)
917
High-pressure laminate 843
High-pressure liquid-liquid equilibria 25
High-pressure vapor-liquid equilibria 25
High-speed spin-draw winding (HSSDW)
941
High-speed spinning (HSS) 931
High-temperature gel permeation
chromatography 369
High-tenacity ber 956
Hildebrand theory of 32
Hindered amine stabilizer (HAS) 819
Hindered phenols 818
HMTA, see Hexamethylenetetramine
Holdup scaling factor 537
Hollow particle 273
Holographic photoembossing 1007
Homocondensation 845
Homogeneous continuous stirred tank reactor
(HCSTR) 335
1090 Index
Homogeneous continuous stirred tank reactor,
oscillating feeds 343
Homogeneous deformation 749
Homogeneous nucleation 252, 266
Homogeneous polymerization 1055
Homolytic degradation 760
Hookean elasticity 708
Hookes law 724725
Hosiery yarn 926
Hot cooling 574
Hot drawing 932
Hot-press molding 883
Hot-tube spinning (HTS) 932, 940
Hybrid polymer particles 256
Hybrid polymer-polymer particle 273
Hydride elimination 385
Hydrodynamic chromatography (HDC) 624
Hydrogen bonding 767
Hydrolysis 866
Hydrometer 617
Hydroperester 783
Hydroperoxide 761, 783, 858
Hydrophobically associating polymer (HEUR)
715
Hydrostatic method 607
Hydroxyl value 865
Hydroxymethylation 102
Hyperbranched polymer 712
i
I-controller 641
Ideal elastic response 706
Ideal measured value 597
Ideal PID controller 643
IMC, see Internal model control
Implicit penultimate unit eect 186
Impregnation 1058, 1061
Increase in viscosity 195
Indicator 597, 626
Induction period 777
Industrial-scale SSP 82
Industrial yarn 916917, 924, 926, 928
Inferential control 668
Innite dilution 70
Infrared spectroscopy (IR) 620, 660
Inherent viscosity 664
Inhibition 170, 588
Initiator eciency 156, 972
Initiator residue 1075
Initiation 162, 581, 583, 760, 802
Inorganic powder 243
Inorganic solid 217
Input/output (I/O) 651
Insertion polymerization 903
Inside-out technology 893
In-situ Raman spectroscopy 1018
Instantaneous average molecular weight
269
Instantaneous property 387
Instrument gauge 597
Integral conrtroller 641
Integral of the timeweighted absolute error
(ITAE) 644
Integral of the timeweighted absolute error
tuning rules 645
Integrating process 638
Integrator plus dead time process 639
Interactive liquid chromatography (i-LC)
1034
Interfacial process 94
Interlacing 916
Interlocks 589
Intermolecular chain transfer 356
Intermolecular transfer to polymer 174
Internal impurity 795
Internal model control (IMC) 668
Internal viscosity 765
Interparticle heat transfer 400
Interparticle mass transfer 400
Intramolecular chain transfer 356
Intramolecular H abstraction 784
Intramolecular ring-forming reaction 67
Intramolecular transfer 189
Intraparticle heat transfer 400
Intraparticle mass transfer 400
Intrinsically safe operation 1075
Inventory scaleup factor 543
Inverse emulsion polymerization 256
Inverse polymerization 239
Inversion process 862
Ion pair 324, 352
Ion pair association 715
Ion supression 1029
Ionic liquid 1048
Ionic polymerization 323
Ionization constant 352
Ionization method 621
Ionomer 715
Ion-trap system 1029
iPP, see isotactic polypropylene
Iron/constantan electrode 601
Irreversible polycondensation 132
Irreversible termination transfer 331
Isolation valve 648
Isophorone diisocyanate (IPDI) 893
Isotactic polypropylene (iPP) 746, 798
Isothermal cloud-point curves 43
Isothermal operation 579
Index 1091
ITAE, see Integral of timeweighted absolute
error
j
Jacobsen-Stockmayer theory 348
k
K-BKZ (Kaye-Bernstein, Kearsley, and Zapas)
formalism 741
Kevlar 956
Kinetic chain length 159
Kinetic energy correction factor 612
Kneaders 356
Kolmogorov length 221
Kubelka-Munk equation 797
l
Labile structure 775
Laboratory measurement 1022
Lactamate anion 348
Lambert-Beer law 797
Laminar ow scale 539
Laminar plug ow reactor 335
Laminate ooring 849
Laplace-Kelvin equation 78
Laser for Raman spectroscopy 1019
Late transition metal catalyst 373, 381
Latent heat of evaporation 574
Latent radical image 1001
Latex 987
LCB, see Long-chain branch
LDPE, see Low-densisty polyethylene
Length truncation 434
Level measurement technique 606
Life cycle analysis 9
Lifetime prediction 824
Limiting molecular weight 1073
Limiting swelling 259
Limiting temperature 347
Linear AB step polymerization 480
Linear chain 498
Linear energy transfer 807
Linear low-density polyethylene (LLDPE) 17,
367
Linear polycondensation, kinetically controlled
129
Linear polymer 268
Linear polymerization 435
Linear scission 473
Linear viscoelasticity 709, 729, 740741
Linearly elastic dumbbell model 703
Linoleic acid 856
Liquid chromatography (LC) 1022
Liquid-crystalline behavior 957
Liquid-crystalline polymer 960
Liquid-lled thermometer 601
Liquid level measurement 605
Lithium-based polymerization 327
Living anionic polymerization 690
Living chain 467
Living polymer 331
Living polymerization 325326
LLDPE, see Linear low-density polyethylene
Logarithmic relationship 800
Long oil alkyds 861
Long-chain approximation 410
Long-chain branch (LCB) 174, 371, 395, 902
Long-chain hypothesis 159
Longitudinal modulus 888
Loop circulation 570
Loop reactor 288
Lorentz-Lorenz law 621
Loss modulus 710, 731
Loss of control 563
Low angle light scattering (LALS) 1033, 1040
Low-density polyethylene (LDPE) 17, 153,
366
Low molecular weight polyamine 853
Low-pass lter 627
Low-pressure liquid-liquid equilibria 20
Low-pressure vapor-liquid equilibria 2021
Low styrene content resin 872
Lower critical solution temperature 24
Lytropic behavior 956
m
Macrocycle 348, 355
Macroheterogeneity 789
Macromolecular brush 712
Macromolecules empirical description 4
Macromonomer 175
Macroparticle 401
Macroscopic property 750
Magnetic-inductive owmeter 617
MALDI, see Matrix-assisted laser desorption
ionization
Maleic anhydride 871
Manipulated variable 311, 628, 640
Manual control 650
Mark-Houwink relation 696
Mass analyzer, type 1029
Mass balance 117, 290
Mass ow 613, 616, 937
Mass polymerization 972
Mass spectrometer 622
Mass spectrometry (MS) 1025, 1037
Mass-to-charge ratio 1027
Mass-transfer coecient 983
1092 Index
Mass-transfer process 982
Master 662
Master curve 734
Mastication of rubber 817
Matrix-assisted laser desorption ionization
(MALDI) 1027, 1029, 1033
Maxiaturized second-dimension column
1042
Maximum drop diameter 219
Maximum technical temperature (MTT) 557
Maximum temperature of the synthesis
reaction (MTSR) 556
Maxwell model 707, 709, 711
Mean square radius of gyration 693
Measurement and control 13
Measurement chain 596
Measuring error 597
Mechanical energy 561
Mechanical energy balance 607
Mechanical modulus 683
Mechanical tests 768
Mechanism for radical entry 261
Mechanochemical degradation 813
Mechanochemical synthesis 818
Medium oil alkyds 861
Melamine resins 106
Melamine-formaldehyde (MF) resins 843
Melamine-urea-formaldehyde (MUF) resins
8
Melt ow index (MFI) 935
Melt index 620, 664
Melt spinning 920, 922923, 926, 953, 955
Melt viscosity 740
Melting point 686
Metal catalysts 373, 381
Metal deactivator 824
Metal injection molding (MIM) 792
Metallocene 5, 373, 451, 483
Metallocene catalyst 371, 379
Metastable morphology 275
Method of characteristics 131
Method of moments 198, 406, 408, 410, 413,
435
Methodology 9, 11
Methylene bridge 839, 845
Methylol groups 840
Micelle 251
Microdomain 789
Microemulsion polymerization 256, 1071
Microheterogeneity 789
Microparticle 401
Micro-region 7
Microscopic mass balance 72
Microstructure 326
Microstructure/property relationship 250
Microwave radar 608
Mid-chain radical 177, 190
Mid-chain scission 772
Midrange infrared spectroscopy (MIR) 297,
300
Mie scattering 624
MIM, see Metal injection molding
Miniaturized rst-dimension column 1042
Miniemulsion polymerization 256, 1071
MIR see Midrange infrared spectroscopy
Mixing 195, 227, 242, 289
Mixing rules 41
Mixing time 538, 540
Modacrylics 951
Model identication 637
Model predictive 671
Model predictive control (MPC) 668, 672
Model-based control 206, 664
Modeling of distributions 201
Modern process 13
Molar mass sensitive detector 1033
Molecular dynamics simulation 782
Molecular weight averages 622
Molecular weight distribution (MWD) 267,
331, 341, 622, 664, 771, 1021, 1030, 1031,
1072
Moment distribution 476
Monad 64
Monitoring techniques 298
Monodispersed micron-size particles 257
Monomer composition 292
Monomer concentration 258
Monomer droplet 251
Monomer feed 582
Monomer partitioning 259
Monomer reactivity ratio 181
Monomethylol urea rate of formation 104
Monomolecular deactivation 386
Monoradical assumption 446
Monte Carlo 202, 485, 790
Mooney viscometer 620
Morphology 217, 232233
Morphology of block copolymers 691
Morse potential 814
Morton-Flory-Huggins equation 260
Moving-average lter 627
Moving packed-bed reactor 82
MPC, see Model predictive control
MTT, see Maximum technical temperature
Multi-angle light scattering (MALS) 1033
Multiaxial stress state 749
Multidirectional bers 879
Multidisciplinary approach 7, 10
Index 1093
Multiexposure photoembossing 1007
Multigrain model 401, 413
Multinomial distribution 120
Multi-objective goal 6
Multiphase stirred tank 542
Multiple distributions 1041
Multiple holographic exposure 1007
Multiple-site catalyst 392
Multiple steady state 656
Multiplicity 584
Multiplicity of solution 563
Multi-product plant 657
Multiradicals 467
Multi-slit devolatilizer 977
Multitubular polymerization reactor 543
Multivariable 664
Multivariate calibration 1018
Multi-way partial least squares (PLS) 671
Multi-way principal component analysis (PCA)
671
Multizone circulating reactor 425
Multizone reactor 419
n
Nanoclay 692
Nanocomposites 692
Nanomanipulation 997
Nanoparticles dispersion 692
Nanophase separation of block copolymer
melts 714
Nanostructured material 692
Narrow-band 602
Nascent crystallization 687
Natural rubber (NR) 902
Near-infrared (NIR) spectroscopy 297, 300,
10171019
Negative feedback 640
Neopentyl glycol 865
Newtonian uid 571, 708
Newtonian viscous behavior 708
Newtons law of viscosity 619
Nitrile rubber (NBR) 902
Nitrogen inerting 900
Nitroxide radical 819
NMR, see Nuclear magnetic resonance
Nomex 956
Non wovens 206
Nonlinear controller 311
Nonlinear polymer 272, 699
Nonlinear viscoelasticity 740741
Nonpolymerizable compounds 971
Nonradical degradation mechanisms 763
Nonrandom factor model 34
Nonrandom two-liquid (NRTL) theory 34
Non-reinforced applications 886
Non-self-regulating 631
Normal stress dierences 741
Norrish photoprocess 787, 803, 897
Novolac application 107, 840, 842
Nozzle 611
Nuclear magnetic resonance (NMR) 621,
775, 1024
Nucleating agents 687
Nucleation 747
Nucleation rate 295
Number-average chain length 412
Number fraction 489
Number of monomer units 473
Number of polymer particles 264
Numerical fractionation 202
Numerical inversion of generating functions
126
Nylon-6 98, 101
o
O-line analysis 1042
Oset 641
Olen copolymerization 388
Oleic acid 856
Oligomer column 1021
On-aim 657
One component formulation 836
On-line analysis 1015
On-line monitoring 296
On-line sensor selection 297
On-o controller 646
Onset temperature 308
Optical clarity 688
Optical pyrometer 602
Optical scanning electron microscopy 623
Optimization 306
Orange peel eect 868
Organic solvent 1047
Orice plate 611, 613
Orlon 966
Oscillatory baed reactor 234, 239
Osmotic pressure 694
Output unit 596
Outside-in technology 894
Oval gear owmeter 609
Oval wheel counter 610
Overcooling 583
Over-damped 632
Overlapping chains 694
Overshoot 646
Oxidation resistance 907
Oxidative degradation 798
Oxirane 850
1094 Index
Oxygen diusion constant 798
Oxygen inhibitor 894
Oxygen uptake 776
Ozone absorption 796
p
PA, see Polyamide
Palmitic acid 856
Panel board 627, 650
Paper coating 256
Paracrystalline 920
Paran 872
Paraformaldehyde 102
Parallel lter 926
Parametric sensitivity 562, 580
Particle board 849
Particle fragmentation 401
Particle morphology 273
Particle nucleation 264
Particle size distribution (PSD) 223, 234
235, 294, 623, 672
Particle size stability 584
Partition coecient 259, 1062
Partly oriented yarn (POY) 940
PCA, see Multi-way principal component
analysis
PC-SAFT application 47
PD controller 642
Pendent chain 117
Pentaerythritol 856
Peracids 774, 783, 788
Performance 14
Peroxide 155, 774, 871
Peroxide curing 905
Peroxide decomposer 821
Peroxy radicals 762
Personal computer (PC) controller 651
Phantom network 122
Phase behavior 1054
Phase equilibria 18
Phenol 838
Phenolic resins 838
Phillips catalyst 373, 378
Phosgenation 94
Photodegradation 793
Photoembossing 9981001
Photo-Fries rearrangement 803
Photoinitiated radical polymerization 896
Photoinitiation 802, 897
Photo-ionization 621
Photolabile base 897
Photolithographic techniques 996
Photo-oxidation 793, 796, 855
Photoresponse 999
Photostabilizer 822
Physical association 715
Physical degradation 757
Physical properties 571
Physicochemical degradation 758
PI controller 642
PID controller 642, 645
PID feedback controller 659
Piezoelectric pressure transducer 604
Piezoresistive pressure transducer 604
Planar zigzag (trans) conformation 681
Planck radiation law 602
Plasticization eect 1052
Platinum thermometer 600
PLS, see Multi-way partial least squares
Plug 652
Plug ow reactor 335
Pneumatic position controller 650
Pneumatic pressure 598
Pneumatic signal 598
Point-contact 606
Poiseuilles law 938
Poisson distribution 333334, 750
Polar additive 326, 343
Polar hydrogel 896
Polarizability 1050
Polarographic method 621
Polyacetal 346
Polyacrylonitrile (PAN) 951
Poly(alkyl methacrylate) 712
Polyamide (PA) 917, 923, 941, 942
Polybenzothiazole (PBT) 960
Polybenzoxazole (PBO) 960
Poly(butyleneterephthalate) (PBT) 938
Polycarbonate 733
Polycondensation 11, 95, 132, 432, 481, 547,
863, 869, 972
Polydispersity 333, 335, 622
Polyester 687, 853, 891, 923
Polyesterication 859
Polyetherimide 780
Polyethylene (PE) 682, 687, 920
Poly(ethylene terephthalate) (PET) 685, 687,
938940
Poly(ethylenenaphthalate) (PEN) 938
Polyhedral silsesquioxane (POSS) 692
Polyimide 780
Polyisobutene 734
Polymer branching 711
Polymer coil size 693
Polymer composition 179
Polymer composition feedback controller 666
Polymer conformation 692, 784
Polymer degradation, physical factor 763
Index 1095
Polymer distribution 1030
Polymer line 924, 935
Polymer melt 972
Polymer microstructure 249
Polymer microstructuring 995
Polymer morphology 766
Polymer nanostructuring 995
Polymer particle 252
Polymer processing 1058
Polymer reaction engineering development 5
Polymer reaction engineering disciplines 9
Polymer reaction engineering history 4
Polymer recycling 792
Polymer scission 1072
Polymer solution thermodynamics 18
Polymer-like structures 715
Polymeric additive 714
Polymeric uid 703
Polymeric material 3
Polymeric network 834
Polymerization-induced diusion 999
Polymerization kinetics 377, 383
Poly(methyl methacrylate) (PMMA) 154, 682,
685, 733, 1036
Poly(m-phenylene isophthalamide) 956
Polyolen 365, 979
Polyoxyalkylene 349, 353
Polyoxymethylene (POM) 346, 356, 961
Poly(p-phenylene terephthalamide), (PPTA)
956
Polypropylene (PP) 367, 682, 923, 943, 964
Polypropylene degradation 782
Polystyrene 153, 920
Polystyrene lms 1023
Polystyrene-poly(methyl methacrylate) analyzer
1043
Poly(tetrauoroethylene) (PTFE) 682, 812,
1058
Polytetrahydrofurane (THF) 356
Poly(trimethylene terephthalate) (PTT) 938
Polytropic reaction 579
Polyurea 109
Polyurethane 109
Poly(vinyl acetate) (PVA) 154, 217, 224, 232,
444, 458, 683
Poly(vinyl alcohol) 683, 946, 952
Poly(vinyl chloride) (PVC) 216, 230, 686, 744,
823, 920
Population balance 262, 408409, 414, 432
Porosity 231232, 237
Positional form 643
Post-polymerization 980
Post-processing 13
Post-treatment of VOCs 972
Pot life 871
Potassium alkoxide 350
Powder coating 866
Power consumption 289
Power number 236
Power ultrasound 1063
PRE, see Polymer reaction engineering
Precipitation 714
Precipitation polymerization 1057, 1069
Precursor particle 267
Predici 202
Prediction of the gel point 121
Pre-polymerized catalyst 401
Pressure drop 536, 938
Pressure limitation 546
Pressure measurement 602
Pressure-reducing valve 648
Pressure relief 588
Pressure temperature level and ow (PTLF)
658
Preventive measure 586
Primary initiation 802
Primary particle 401
Primary polymer 485, 503
Primary reactor 662
Primary recycling 792
Principle of equal reactivity 62
Principle of similarity 295
Probabilities of extinction 120
Probabilities of reaction 120
Probability generating functions 480
Process development 5
Process gain 632
Process or measured variable 628
Process scheme 5
Process system integration 6
Process under development 14
Production rate 116, 297
Product quality 290, 297
Productivity 583
Products-by-process 249
Programmable logic controller (PLC) 651
Propagation 162, 760
Propagation rate coecient 327
Proportional band 641
Proportional controller (P controller) 640
Propoxylation 351
Protection strategy 558
Protective coatings 861
Protective eect 808
Proton NMR 1024
Pseudo bulk 270
Pseudo distribution 445, 449, 451, 458, 473
Pseudo-kinetic rate constant 414
1096 Index
Pseudoplastic 619
Pulsed-ow reactor 288
Pulsed-laser-induced polymerization 163
Pultrusion 883
Pure delay 636
PVT behavior of polymer melts 41
Pyrolysis 790
Pyrolysis-GC-MS 1026
q
Quadrupole instrument 1029
Quadrupole moment 1050
Quantization error 626
Quasi-elastic light scattering (QELS) 623
Quasi-steady-state assumption (QSSA) 159,
489
Quench collar 929
Quencher 823
Quenching 588, 927
Quick opening 652
p-Quinone structures 841
r
Radial cooling 928
Radial ow 289
Radiation chemistry 807
Radiation-induced grafting 812
Radiation pyrometer 601
Radiation sterilization 811
Radical antioxidant 818
Radical chain polymerization 890
Radical entry 260
Radical exit 262
Radical formation 1065
Radical photoinitiator 897
Radical polymerization technique 690
Radical reactivity ratio 187
Radical-scavenging stabilizer 818
Radical site 444
Radioactive gamma-ray 607
Radiolytic degradation 805
Radiometrically 618
Radius of gyration 502
Radius tap 613
Raman spectroscopy 297, 300, 621, 660
Ramp function 638
Random polymerization 57
Random scission 498, 771772
Range 597
Rapid expansion from supercritical solution
1059
Rapid stress-induced crystallization 687
Rate laws 158
Rate-limiting steps 985
Rate of crystallization 81
Rate of nucleation 85
Rate of polymerization 159, 258
Rate of termination 262
Rate theory 815
Ratio control 660
Ratio of specic heat 613
Rayleigh-Plesset equation 1065
Rayleigh scattering 623624
Rayon tire cord 951
Reaction calorimetry 302, 572, 580, 667,
1075
Reaction diusion 192
Reaction dynamics 567
Reaction engineering 14
Reaction injection molding (RIM) 111
Reaction injection molding process 349
Reaction order 329
Reaction temperature 1066
Reactive diluent 889, 898
Reactor blends 368, 417
Reactor temperature control 664
Recirculated loop reactor 343
Recirculating tubular (loop) reactor 353
Recombination 440
Recombination termination 498
Recursive method 68
Redox initiation system 980
Reduced uid density 47
Reduction of risk 585
Redundant system 586
Ree-Eyring model 744
Reux 575
Reux condenser 290
Refractive index 297, 621
Refractive index detector (DRI or RI) 1032,
1040
Regulating aps 654
Regulator 628
Reinforced composites 879
Reinforcement 875
Reinforcing material 692
Relative gain array (RGA) 665
Relative reaction rate 498
Relaxation 934
Relaxation time 702, 732733, 735, 737
Renewable resource 8
Repeatability 597
Replication 997
Replication phenomenon 401
Reptation 738
Reptation time 739
Reset time 641
Reset windup 641
Index 1097
Residence time distribution (RTD) 235, 242,
287, 491
Residual monomer 971, 1060
Resin 835
Resin infusion 883
Resin stability 848
Resin-transfer molding 883
Resistance temperature detector 599
Resistance thermometer 599
Resols 107, 840
Restrictor device 611
Retardation 170
Retarded cooling 929
Retention factor 1035
Reversibility 347
Reversible alternating polycondensation with
FSSE 133
Reynolds number 219, 237
Rheological behavior 696, 715, 934
Rheological control 714
Rheological eects of branching 700
Rheology 294, 502, 702
Rheology modier 712
Ricinic acid 856
Right-angle light scattering (RALS) 1033,
1040
Rigid foams 111
Rigid rod-like polymer 701
RIM, see Reaction injection molding
Ring-opening oxidation 805
Ring-opening polymerization 346
Ring-opening reaction 852
Risk parameter 307
Risk-reducing measure 586
Root mean square end-to-end distance 693
Rotameter 614, 616
Rotated helical conformation 681
Rotating disk contactor 71
Rotating lters 926
Rotating lobe owmeter 610
Rotating vane meter 611
Rotating viscometer 619
Rouse model 697, 703, 736737
Rouse relaxation time 738
Rovings 875
Rubber 343
Rubber elasticity 721, 725, 727, 729
Rubberlike elasticity 706
Rubbery plateau 722, 729, 739, 743
Runaway incident 307, 553
Russell mechanism 778
s
Safe operation 307
Safe region 308
Safety 13, 290, 296
Safety barrier 575
Safety valve 648
SAFT, see Statistical association uid theory
Sampling of monomer units 504
Sampling period 643
Sanchez-Lacombe lattice uid theory 40
Sanchez-Lacombe model 1055
Satellite drops 221, 224
Scalability 533
Scale 597
Scaleup 237238, 295, 560, 569
Scaleup criterion 296
Schulz-Flory 61, 334, 336
Scission 762, 771, 785
Scission probability distribution function 772
Scission rate 1073
Seat 652
SEC, see Size exclusion chromatography,
see also Gel permeation chromatography
Secondary initiation 802
Secondary particle 401
Secondary reaction 786
Secondary reactor 662
Secondary recycling 792
Secondary relaxation 733, 744, 749
Secondary relaxation temperature 749
Secondary suspending agent (SSA) 231232,
243
Secondary-ion mass spectrometry (SIMS)
1026
Second-order system 635
Second-shell substitution eect 64
Seeding 569, 585
Segmental diusion 191
Segregated stirred tank reactor 336
Segregation 235, 241
Self-assembling behavior 690
Self-operated regulator 647
Self-polycondensation 119
Self-regulating 630
SEM, see Scanning electron microscopy
Semi-batch control 669
Semi-batch operation 580
Semi-batch process 196
Semi-batch reactor 335, 670
Semicontinuous reactor 254
Semi-crystalline low-density polyethylene
(ldPE) 1053
Semicrystalline polymer 682, 688, 722, 725,
733, 743, 746, 751
Semi-ladder polymers 960
Seniority/priority distribution 502
1098 Index
Sensible heat 561
Sensing element 596
Sensitivity to inhibition 87
Sensitizer 895
Sensor 596
Sensor signal processing 625
Sequence distribution 179
Sequence length 478
Sequence length distribution 473
Sequential polymerization 57
Set point 628, 640
Set-point trajectory 306
Settling time 646
Shape-forming process 687
Shear compliance 730
Shear ow 703
Shear force 578
Shear modulus 725, 730, 747
Shear rate 938
Shear thickening 619
Shear thinning 619, 702, 740
Shear viscosity 934
Sheet molding compound (SMC) 883
Shewhart (x-bar) chart 671
Shift factor 734736
Shish-kebab structure 961
Short-chain branch 382
Short oil alkyds 861
Short-chain branching (intramolecular
transfer to polymer) 177
Shoulder 467
Shrinkage 934
Shrinkage control 885
Silicone acrylates 892
SIMS, see Secondary-ion mass spectrometry
Single charged ions 1027
Single-exposure photoembossing 1001
Single-loop controller 627, 649651
Single-screw extruder 924, 974, 978
Single-site catalyst 383
Single-train process 534
Singular value decomposition analysis (SVD)
665
Size distribution 220
Size-exclusion chromatography (SEC) 622,
664, 1020, 1021, 1033
Sizing 875
Skin formation 948
Slave 662
Slurry process 416, 422
Smart transducer 604, 625
Smith-Ewart Case 263264
Soft lithography 998
Solar spectral irradiance 796
Solar spectrum 796
Solid-state NMR 1025
Solid-state polycondensation (SSP) 80
Solubility 694, 1051
Solution NMR 1025
Solution polymerization 972
Solution process 416, 423
Solution spinning 921922, 944, 953
Solvent-based system 979
Solvent or bulk media eect 63
Solvent-separated ion pair 324
Solvent/transfer agent 167
Sonic densitometer 618
Sonic velocity 654
Sonochemistry 1064
Sorption of polymer 1052
Sound speed 1064
Span 597
Sparged reactor vessel 542
Spatial location of atoms in models of network
formation 128
Specic gravity 617
Specic heat 683
Specically programmable-temperature
vaporizer (PTV) 1022
Spectra process 962, 964
Spectra lament 962
Spectroscopic technique 299
Spectrum 1018
Spherolite 747
Spin stretch factor 937
Spin-box 925
Spin-draw bulk winding (SDBW) 934
Spin-draw winding (SDW) 933
Spinnability 922
Spinning 913, 918, 925, 931, 938
Spin-trapping 776
Spray coating 1059
Spray tower 343
Spray-up process 882
Spring 652
SSP, see Solid-state polycondensation
Stabilization 894
Stabilizer 216217
Staged models for describing rotating disk
contactor 76
Standard 596597
Standard deviation 598
Standard liquid 853
Staple ber 913
Stark-Einstein law 793
Star-shaped block copolymer 344
Starved feed 670
State estimator 667
Index 1099
State variable 305
Static head-space 1023
Static light scattering 624
Static mixer 545
Static pressure 1066
Static SIMS 1026
Statistical associated uid theory (SAFT) 44,
47, 1054
Statistical copolymer 338
Statistical process control 671
Staudinger 4
Steady-state model feedforward control 660
Steam stripping 987
Stearic acid 856
Stefan-Boltzmann law 601
Stem position 652
Step growth 565
Step-growth polymerization 11
Step response 632
Steric factor 784
Stiening behavior 707
Stiness 887
Stirred-bed gas-phase reactor 421
Stirred-bed reactor 82, 417, 420
Stirred-tank continuous mode 286
Stirred-tank reactor 286, 537
Stirred-tank reactor batch mode 286
Stirred-tank reactor semibatch mode 286
Stirred tanks in series 542
Stirrer power 561
Stockmayers distribution 61, 388, 406
Stoichiometric coecient 115
Storage modulus 710, 731
Strain 709
Strain gauge 604605
Strain rate 1073
Strands 875
Stress-activated chain scission 815
Stress-concentrating eect 750
Stress gradient 749
Stress intensity factor 750
Stress relaxation behavior 708
Stress-induced chemical reactivity 813
Stress-induced morphologies 767
Strip-chart recorder 627
Stripping 985
Stripping agent 973
Stuer box texture 916
Styrene 871
Styrene polymerization 169
Styrene-butadiene copolymers (SBR) 902
Styrene-butadiene latexes 986
Sulfur vulcanization 904
Supercritical carbon dioxide 10481049
Supercritical uid 975, 989
Supercritical uid extraction (SFE) 1060
Supramolecular organization 759
Surface energy 259
Surface tension 622
Surface tension reduction 1010
Surfactant 251, 862
Surlyn 715
Suspension polymerization 213, 239, 980,
985, 1057
Sustainability 8
Sustainable integrated PRE 9
Sustainable new polymer processes 15
Swelling 575576, 1052
Synergetic approach 7
Synergistic eect 826
Synthetic cellulose yarn 914
Synthetic polymer 1
Synthetic polymer material 5
Synthetic staple ber production 914
Synthetic yarn 914
Synthetic yarn spinning 916
t
Tay process 109, 854
Tandem reactor technology 417
Tangled yarn 917
Taylored polymer 691
Technora 959
Temperature control 567, 579
Temperature measurement 599
Temperature rising elution fractionation (Tref )
369
Tensile strength 705
Terminal double bond incorporation 497
Terminal double bond (TDB) 444
Terminal double bond moment distribution
459
Terminal double bond propagation 454
Terminal model 180, 388
Termination 165, 324, 337, 477, 762
Tertiary recycling 792
Tetrahydrofuran 90
Tetramethylolmethane 856
Tex 914
Textile lament yarn 917
Textile yarn 916917, 924, 933
Thermal behavior 679
Thermal conversion 560, 580
Thermal degradation 778
Thermal expansion coecient 683
Thermal initiation 169, 980
Thermal oxidative degradation of
polypropylene 782
1100 Index
Thermal polymerization of styrene 169
Thermal runaway 254, 546
Thermal stability 575, 779
Thermal stabilization 821, 975
Thermal time constant 574
Thermocouple 600
Thermocouple pyrometer 601
Thermodynamic model 1054
Thermodynamics 12
Thermoplastic elastomer 112
Thermoplastic vulcanizates 907
Thermoplastics 23
Thermosets 2, 833
Thermosetting 833
Thin layer resin 897
Throughput scaling factor 537
Time-averaged probability 258
Time constant 632
Time-independent bril failure criterion 750
Time-of-ight (ToF) analyzer 1030
Time-temperature superposition 734, 736
Time to maximum rate under adiabatic
conditions 557
Tire cord 940
Titer 914
Tobolsky and Eyring model 815
Topological scission 472
Topology 502
Total radiation pyrometer 602
Totalizer 605
Trail generating functions 127
Transducer 596597
Transesterication 863
Transesterication of diphenylcarbonate (DPC)
and BPA 96
Transfer of information 6
Transfer of proton 337
Transfer reaction 325, 338, 352
Transfer-to-monomer 168, 386
Transfer-to-polymer 449
Transformation variable 480
Transition metal 761
Transition-state theory 781, 815
Translational diusion 192
Transmitter 596597, 625
Transparent semicrystalline polymer 688
Transverse modulus 888
Tri-block copolymer 342
Triethylenetetramine 853
Trim 652
Trimethylolpropane 856
Trimethylolpropane trimethacrylate (TRIM)
1057
Trioxane 355
Triple angle light scattering (TrALS) 1033
Triple-detector instrument 623
TripleSEC system 1040
Tromsdor eect 568
Troutons ratio 936
True thermodynamic constant 99
Tube model 738739, 741
Tubular reactor 287, 343, 543, 546
Tuning fork densitometer 617
Tuning rules 646
Turbidimetry 624
Turbine owmeter 611
Turbulence 218, 235, 242
Turbulent regime 539
Twaron 956
Twin-screw extruder 924, 974, 978
Two component formulation 836
Two-dimensional liquid chromatography
1041
Two-dimensional separation 1042
Two-phase ow 588
Two-point controller 647
u
Ultimate gain 646
Ultimate period 646
Ultra-high molecular weights 257
Ultrasound 297, 299, 980, 1057, 1062
Ultraviolet (UV) absorbance 794, 822, 1032
Ultraviolet curing 869, 896, 899
Ultraviolet detector 624
Ultraviolet lamp 899
Ultraviolet lithography 996
Ultraviolet region 621
Unidirectional ber 879
UNIFAC model 36
Unimolecular reaction 130
UNIQUAC theory 34
Univariate calibration 1018
Unsaturated polyester resin 869
Unzipping 773
Upper and lower control limit 671
Upper critical solution temperature 24
Urea-formaldehyde (UF) resin 843
Urethane acrylate 892, 894
Uron UF resin 105
UV, see Ultraviolet
v
Valve characteristic 652653
Valve coecient 653
Valve position controller 650
Valve resistance 631
Valve stem 652
Index 1101
van der Waals 722
van der Waals mixing rules 46
Vanadium catalyst 379
Vapor velocity 576
Velocity form 643
Velocity gradient 705
Venturi tube 611, 613
Vibrating ow U-tube 618
Vibrating-reed viscometer 620
Vinyl chloride 217, 220, 224, 227
Vinyl content 326
Vinyl ester resin 873
5-Vinylidene-2-norbornene (VNB) 903
Vinyl polymerization 541, 546
Viscoelastic response 707
Viscometric detection 1032
Viscometry 1033
Viscose rayon 948, 950
Viscosity 213, 229, 240, 571, 578, 695, 698,
702, 734, 740, 746, 860, 1049, 1066
Viscosity index improvement 714
Viscosity measurement 619
Viscous force 219
Viscous shear 218, 221, 243
Visible region 621
Vitrication 848
VK column 101
Volatile compounds 788
Volatile organic compound (VOC) 971, 989,
1047
Volume ow 937
Volume fraction 696
Volume fraction mixing rules 46
Volume scaleup factor 533
Volumetric ow 612, 616
Volumetric ow rate 294
Volumetric growth rate 294
von Mises criterion 743, 749
w
Water-based nish 929
Waterborne dispersions 979
Water tolerance 848
WAXD, see Wide-angle X-ray diraction
Weber number 218219, 237
Weight distribution in interfacial synthesis
96
Weight measurement 604
Weight-average chain length 413
Weight-average molecular weight 125
Weight-fraction sampling 486
Wet spinning 921922, 946, 955
Wicker-tube reactor 288
Wide-angle X-ray diraction (WAXD) 681
Wiens law 601
Wilson correlation 576
Wilson plot 572
Winders capacity 931
Winding 931
Wiped-lm evaporator 977
Wiped-lm reactor 71
WLF equation 736, 746
Work hardening 729, 742743, 747
x
Xerogel structure 962
y
Yarn appearance 916
Yield 725, 741, 743744, 746, 748
Yield drop 742
Youngs modulus 722, 887
z
Z-average degree of polymerization 126
Z-average molecular weight 125
Z-domain 480
Zener element 732
Zero-one system 268
Zero-shear viscosity 715
Ziegler-Natta catalyst 370, 372, 378, 903
Ziegler-Natta EP(D)M polymerization 903
Ziegler-Nichols controller tuning parameter
646
Zimm model 698, 737
Zimm regime 699
Zimm-Stockmayer equation 1040
Zylon 960
1102 Index

Handbook of Polymer Reaction Engineering

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Handbook of Polymer Reaction Engineering

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Handbook of Polymer

C) due to the high reactivity of ions. Also,

is calculated from the pure component hard-core molar

) are the so-called characteristic parameters. In

, the interaction energy param-

are composition-dependent. Neau [65] gives an overview of dier-

hard core, indicates characteristic parameter

C as well as excellent mechanical, optical, and electrical properties, in-

C) so that the polymer re-

C, and there is a decrease of about 3 in the for-

, so these constants should be written as

C). For these reactions, the terms k

C [252]. Formation of isocyanurates causes a reorganization of the CLD akin

where stood the living group A

which gets connected to the unit where stood the attack-

which gets connected to the unit where the attacking

omvarsky, Polym. Bull.

C and a laser repetition rate of 10 Hz. DP

C. Most organic compounds have low transfer rates (C

C [7]; there can be an order of

C and 1360 atm [20].

C or more. Indeed, it is not necessary to

C, unless otherwise noted; values

C and 2000 bar.

C. This temperature range, while higher than that generally

C, the highest temperature examined, k

C, especially for systems with low monomer

C [30], where the number of short-chain branches is in

C [37], but is shown to be important

C [29, 45]. Scission is a dominant mechanism in styrene polymerizations

C and 2000 bar [53, 54].

C [57], and a-methylstyrene with various comonomers at temperatures well

C). More recent studies were aimed to reduce

angled blade turbine. Multiple impel-

of non-associated polystyryllithium is calculated with the

C. In Ref. 48 data for

C assuming n = 2 for styrene and n = 2

Fig. 7.2. Fraction a of non-associated species as a function

C [13]), but contrary to styrene, the side

C in toluene (10 kg) with various

C in toluene (10 kg) with various

C, which make them hardly accessible in industrial applications. The t-butyl

C [215]. For such high rate coe-

C in boiling ethylene to remove the heat of

C. The polymerization rate is controlled by initiator feed and cooling is

C) in precipitating agents or in bulk, and are carried out

C) or tubular reactors (15003500 atm, 140180

C, for instance) [21, 22]. Phillips catalysts are used in

Fig. 8.19. Comparison of the monomer propagation step in

Fig. 8.27. Mechanism of long-chain branch formation with coordination catalysts.

Fig. 9.13. Principle of probability generating functions and

C, p @10003500 atm), these

C. As seen in Figure 9.29(b), center-mode initiator injection causes sharp

C, respectively. The poor

DHr =RTA0 =51:3

C but becomes problematic

C DT. There are many solutions. In a

C feed to control the

C. This leads to the possibility of parametric sensitivity and thermal run-

C, a hydrodynamic instability occurs at a smaller tube diameter

C. The parameter in the plot is the

The process temperature (T

The maximum temperature of synthesis reaction (MTSR) depends essentially

The temperature at which the TMR