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

ISBN 3-527-30260-3

H.-G. Elias (Ed.)

Vols. 1–4

ISBN 3-527-31172-6, 3-527-31173-4, 3-527-31174-2,

M. F. Kemmere, Th. Meyer (Eds.)

Supercritical Carbon Dioxide
in Polymer Reaction Engineering

ISBN 3-527-31092-4

M. Xanthos (Ed.)

Functional Fillers for Plastics

ISBN 3-527-31054-1

R. C. Advincula, W. J. Brittain, K. C. Caster, J. Ru
u˙˙he (Eds.)

Polymer Brushes

ISBN 3-527-31033-9

H.-G. Elias (Ed.)

An Introduction to Plastics
Second, Completely Revised Edition

ISBN 3-527-29602-6

Handbook of Polymer Reaction Engineering
Edited by
Thierry Meyer, Jos Keurentjes

Dr. Thierry Meyer
Swiss Federal Institute of Technology
Institute of Process Science
1015 Lausanne
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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8 2005 WILEY-VCH Verlag GmbH & Co.
KGaA, Weinheim
All rights reserved (including those of
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ISBN-13 978-3-527-31014-2
ISBN-10 3-527-31014-2


A principal difference between science and engineering is intent. Science is used
to bring understanding and order to a specific object of study – to build a body of
knowledge with truth and observable laws. Engineering is more applied and practical, focused on using and exploiting scientific understanding and scientific principles to make products to benefit 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 examples of polymeric products commercialized without adequate understanding of the
chemistry and physics of the underlying polymerization. Polymer reaction engineers, faced with detriments in process safety, product quality or product cost, become the driving force behind many polymer science developments. As such, polymer reaction engineering is more a collaboration of polymer science and reaction
engineering. A collaboration where polymer reaction engineers develop a firm understanding 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 defines 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 offers 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 first section is devoted to the science
and chemistry of the major types of polymerization. Included are step and chain
growth polymerizations with chapters devoted specifically to several different chain
growth methods. The central section of the middle chapters is dedicated to polymer reaction engineering tools and methods. The very important topics of safety
and process control are detailed and help frame the conditions through which successful 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-



mers through man-made and natural change are discussed. The details of polymer
end use are also presented.
This tome represents the first published handbook on polymer reaction engineering and should be well received in academia and industry. Polymer reaction
engineering became recognized as a separate engineering discipline in the 1970’s.
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
Philadelphia, Pennsylvania


Volume 1


List of Contributors





Polymer Reaction Engineering, an Integrated Approach
Th. Meyer and J. T. F. Keurentjes
Polymer Materials 1


A Short History of Polymer Reaction Engineering 4
The Position of Polymer Reaction Engineering 5
Toward Integrated Polymer Reaction Engineering 7
The Disciplines in Polymer Reaction Engineering 9
Polymerization Mechanisms 11
Fundamental and Engineering Sciences 12
The Future: Product-inspired Polymer Reaction Engineering
Concluding Remarks 15
References 15
Polymer Thermodynamics
Theodoor W. de Loos
Introduction 17



Thermodynamics and Phase Behavior of Polymer Solutions 18
Thermodynamic Principles of Phase Equilibria 18
Fugacity and Activity 18
Equilibrium Conditions 20
Low-pressure Vapor–Liquid Equilibria 21
Flory–Huggins Theory and Liquid–Liquid Equilibria 21
High-pressure Liquid–Liquid and Vapor–Liquid Equilibria 25
Activity Coefficient Models 29
Flory–Huggins Theory 30




Hansen Solubility Parameters 32
Correlation of Solvent Activities 34
Group Contribution Models 35
Equation of State Models 39
The Sanchez–Lacombe Lattice Fluid Theory
Statistical Associating-fluid Theory 44
SAFT and PC-SAFT Hard Chain Term 44
SAFT Dispersion Term 45
The PC-SAFT Dispersion Term 46
SAFT and PC-SAFT Applications 47
Extension to Copolymers 48
Conclusions 50
Notation 52
References 54


Polycondensation 57
Ma´rio Rui P. F. N. Costa and Rolf Bachmann
Basic Concepts 57
A Brief History 57



Molecular Weight Growth and Carothers’ Equation 59
The Principle of Equal Reactivity and the Prediction of the Evolution of
Functional Group Concentrations 62
Effect of Reaction Media on Equilibrium and Rate Parameters 62
Polycondensation Reactions with Substitution Effects 64
Exchange Reactions 66
Ring-forming Reactions 67
Modeling of Polymerization Schemes 68
Mass Transfer Issues in Polycondensations 69
Removal of Volatile By-products 69
Solid-state Polycondensation 80
Interfacial Polycondensation 82
Polycondensation Processes in Detail 85
Polyesters 85
Structure and Production Processes 85
Acid-catalyzed Esterification and Alcoholysis 86
Catalysis by Metallic Compounds 87
Side Reactions in Aromatic Polyester Production 89
Side Reactions in the Formation of Unsaturated Polyesters 90
Modeling of Processes of Aromatic Polyester Production 91
Modeling of Processes for Unsaturated Polyester Production 92
Polycarbonates 93
General Introduction 93
Interfacial Polycondensation 94
Melt Transesterification 96
Polyamides 98




Introduction 98
Kinetic Modeling 98
Nonoxidative Thermal Degradation Reactions 100
Process Modeling 101
Polymerizations with Formaldehyde: Amino Resins (Urea and
Melamine) and Phenolics 102
Formaldehyde Solutions in Water 102
Amino Resins 102
Phenolic Resins 107
Epoxy Resins 108
Polyurethanes and Polyureas 109
Modeling of Complex Polycondensation Reactions 113
Overview 113
Description of Reactions in Polycondensations of Several Monomers
with Substitution Effects 113
Equilibrium Polycondensations with Several Monomers 117
Kinetic Modeling of Irreversible Polycondensations 129
Kinetic Modeling of Linear Reversible Polycondensations 133
Notation 136
References 144
Free-radical Polymerization: Homogeneous
Robin A. Hutchinson
FRP Properties and Applications 153
Chain Initiation 154


Polymerization Mechanisms and Kinetics 156
Homopolymerization 157
Basic Mechanisms 157
Kinetic Coefficients 161
Additional Mechanisms 169
Copolymerization 179
Basic Mechanisms 179
Kinetic Coefficients 183
Additional Mechanisms 187
Diffusion-controlled Reactions 190
Polymer Reaction Engineering 193
Types of Industrial Reactors 195
Batch Processes 195
Semi-batch Processes 196
Continuous Processes 196
Mathematical Modeling of FRP Kinetics 197
Method of Moments 198
Modeling of Distributions 201
Reactor Modeling 203
Batch Polymerization 204




Continuous Polymerization 204
Complex Flowsheets 205
Computational Fluid Dynamics (CFD)
Model-based Control 206
Summary 206
Notation 206
References 209


Free-radical Polymerization: Suspension
B. W. Brooks


Key Features of Suspension Polymerization 213
Basic Ideas 213
Essential Process Components 214
Polymerization Kinetics 214
Fluid–Fluid Dispersions and Reactor Type 215
Uses of Products from Suspension Polymerization 216
Stability and Size Control of Drops 216
Stabilizer Types 217
Drop Breakage Mechanisms 218
Drop Coalescence 222
Drop Size Distributions 223
Drop Mixing 224
Events at High Monomer Conversion 228
Breakage of Highly Viscous Drops 229
Polymerization Kinetics in Viscous Drops 229
Consequences of Polymer Precipitation Inside Drops 230
Reaction Engineering for Suspension Polymerization 234
Dispersion Maintenance and Reactor Choice 234
Agitation and Heat Transfer in Suspensions 235
Scaleup Limitations with Suspension Polymerization 237
Reactor Safety with Suspension Processes 238
Component Addition during Polymerization 238
‘‘Inverse’’ Suspension Polymerization 239
Initiator Types 239
Drop Mixing with Redox Initiators 240
Future Developments 240
Developing Startup Procedures for Batch and Semi-batch Reactors 240
Maintaining Turbulence Uniformity in Batch Reactors 242
Developing Viable Continuous-flow Processes 242
Quantitative Allowance for the Effects of Changes in the Properties of
the Continuous Phase 242
Further Study of the Role of Secondary Suspending Agents 243
Further Characterization of Stabilizers from Inorganic Powders 243
Notation 243
References 244







Emulsion Polymerization 249
Jose´ C. de la Cal, Jose´ R. Leiza, Jose M. Asua, Alessandro Butte`, Guiseppe Storti,
and Massimo Morbidelli
Introduction 249
Features of Emulsion Polymerization 250
Description of the Process 250
Radical Compartmentalization 254
Advantages of Emulsion Polymerization 254
Alternative Polymerization Techniques 256
Kinetics of Emulsion Polymerization 258
Monomer Partitioning 259
Average Number of Radicals per Particle 260
Number of Polymer Particles 264
Heterogeneous Nucleation 264
Homogeneous Nucleation 266
Simultaneous Heterogeneous and Homogeneous Nucleation 267
Coagulative Nucleation 267
Molecular Weights 267
Linear Polymers 268
Zero–One System (Smith–Ewart Cases 1 and 2) 268
Pseudo Bulk System (Smith–Ewart Case 3) 270

Nonlinear Polymers: Branching, Crosslinking, and Gel Formation


Particle Morphology 273
Living Polymerization in Emulsion 275
Chemistry of LRP 275
Nitroxide-mediated Polymerization (NMP) 277
Atom-transfer Radical Polymerization (ATRP) 277
Degenerative Transfer (DT) 278
Reversible Addition–Fragmentation Transfer (RAFT) Polymerization


Polymerization of LRP in Homogeneous Systems 280
Kinetics of LRP in Heterogeneous Systems 282
Application of LRP in Heterogeneous Systems 284
Ab-initio Emulsion Polymerization 284
Miniemulsion Polymerization 285
Emulsion Polymerization Reactors 286
Reactor Types and Processes 286
Stirred-tank Reactors 286
Tubular Reactors 287
Reactor Equipment 288
Mixing 289
Heat Transfer 290
Reaction Engineering 290
Mass Balances 291





Heat Balance 292
Polymer Particle Population Balance (Particle Size Distribution)


Scaleup 295
On-line Monitoring in Emulsion Polymerization Reactors
On-line Sensor Selection 297
Latex Gas Chromatography 298
Head-space Gas Chromatography 298
Densimetry 298
Ultrasound 299
Spectroscopic Techniques 299
Reaction Calorimetry 302
Control of Emulsion Polymerization Reactors 305
Notation 312
References 317


Ionic Polymerization 323
Klaus-Dieter Hungenberg
Introduction 323



Anionic Polymerization 325
Anionic Polymerization of Hydrocarbon Monomers – Living
Polymerization 326
Association Behavior/Kinetics 326
Molecular Weight Distribution of Living Polymers 331
Side Reactions 336
Copolymerization 338
Tailor-made Polymers by Living Polymerization – Optimization 341
Industrial Aspects – Production of Living Polymers 343
Anionic Polymerization of Vinyl Monomers Containing Heteroatoms


Anionic Polymerization of Monomers Containing Hetero Double Bonds


Anionic Polymerization via Ring Opening 346
Cationic Polymerization 351
Cationic Polymerization of Vinyl Monomers 351
Cationic Ring-opening Polymerization 353
Conclusion 356
Notation 357
References 359


Coordination Polymerization 365
Joa˜o B. P. Soares and Leonardo C. Simon


Polyolefin Properties and Applications 365
Introduction 365
Types of Polyolefins and Their Properties 366



The Importance of Proper Microstructural Determination and Control
in Polyolefins 369
Catalysts for Olefin Polymerization 372
Ziegler–Natta, Phillips, and Vanadium Catalysts 378
Metallocene Catalysts 379
Late Transition Metal Catalysts 381
Polymerization Kinetics and Mechanism with Coordination Catalysts


Comparison between Coordination and Free-radical Polymerization




Polymerization Kinetics with Single-site Catalysts 383
Homopolymerization 383
Copolymerization 388
Polymerization Kinetics with Multiple-site Catalysts 392
Long-chain Branch Formation 395
Single Particle Models – Mass- and Heat-transfer Resistances 399
Macroscopic Reactor Modeling – Population Balances and the Method
of Moments 408
Homopolymerization 408
Copolymerization 413
Types of Industrial Reactors 416
Gas-phase Reactors 420
Slurry Reactors 422
Solution Reactors 423
Multizone Reactors 425
Notation 425
References 428
Mathematical Methods 431
P. D. Iedema and N. H. Kolhapure
Introduction 431

Discrete Galerkin h–p Finite Element Method 432
Method of Moments 435
Introduction 435
Linear Polymerization 435
Nonlinear Polymerization 438
Comparison of Galerkin-FEM and Method of Moments 440
Classes Approach 444
Introduction 444
Computing the CLD of Poly(vinyl acetate) for a Maximum of One TDB
per Chain 444
Multiradicals in Radical Polymerization 446
Pseudo-distribution Approach 449
Introduction 449
CLD/DBD for Mixed-metallocene Polymerization of Ethylene 451




Formulation of Pseudo-distribution Problem 451
Construction of the Full 2D Distribution 456
CLD/Number of Terminal Double Bonds (TDB) Distribution for
Poly(vinyl acetate) – More than one TDB per Chain 458
General Case 458
TDB Pseudo-distribution Approach for a Maximum of one TDB per
Chain 466
TDB Pseudo-distribution Approach for More than one TDB per Chain


Radical Polymerization of Ethylene to Low-density Polyethylene (LDPE)

Introduction 469
Radical Copolymerization 473
Introduction 473
Balance Equations 474
Probability Generating Functions 480
Introduction 480
Probability Generating Functions in a Transformation Method 480
Probability Generating Functions and Cascade Theory 481
Monte Carlo Simulations 485
Introduction 485
Weight-fraction Sampling of Primary Polymers: Batch Reactor,
Transfer to Polymer 486
Example 490
CSTR with Transfer to Polymer 491
Comparison of Galerkin-FEM Classes Model and CSTR with Transfer
to Polymer 492
Batch Reactor, Terminal Double Bond Incorporation 493
CSTR, Terminal Double Bond Incorporation 497
Incorporation of Recombination Termination 498
Incorporation of Random Scission, Linear Chains, Batch Reactor 498
Combined Scission/Branching 501
Scission in a CSTR 501
Prediction of Branched Architectures by Conditional Monte Carlo
Sampling 502
Introduction 502
Branched Architectures from Radical Polymerization in a CSTR 503
Branched Architectures from Polymerization of Olefins with Single
and Mixed Branch-forming Metallocene Catalysts in a CSTR 505
Introduction 505
Single-catalyst System 505
Synthesis of Topology 505
Mixed-catalyst System 508
Mathematical Methods for Characterization of Branched Architectures

Graph Theoretical Connectivity Matrices



Characterization of Architectures by Radius of Gyration 511
Characterization of Architectures by Seniorities and Priorities 512
Computational Fluid Dynamics for Polymerization Reactors 517
Introduction 517
Modeling Challenges 517
Development and Optimization of Modern Polymerization Reactors

Benefits of CFD 519
Limitations of CFD 519
Integration of CFD with Polymerization Kinetics 520
Classification and Complexity of CFD Models 521
Treatment of Polymerization Kinetics 522
Illustration of Homogeneous Reactor Model Formulation
Target Applications 523
Illustrative Case Studies 523
Concluding Remarks 528
Acknowledgments 530
References 530


Scaleup of Polymerization Processes
E. Bruce Nauman


Historic and Economic Perspective 533
The Limits of Scale 533
Scaleup Goals 534
General Approaches 535
Scaleup Factors 537
Stirred-tank Reactors 537
Design Considerations for Stirred Tanks 541
Multiphase Stirred Tanks 542
Stirred Tanks in Series 542
Tubular Reactors 543
Static Mixers 545
Design Considerations for Tubular Reactors 546
Extruder and Extruder-like Reactors 549
Casting Systems 549
Concluding Remarks 550
Notation 550
References 551



Volume 2


Safety of Polymerization Processes
Francis Stoessel
Introduction 553


Principles of Chemical Reactor Safety Applied to Polymerization
Cooling Failure Scenario 554






Criticality Classes Applied to Polymerization Reactors 557
Description of the Criticality Classes 558
Heat Balance of Reactors 559
Heat Production 559
Heat Exchange 560
Heat Accumulation 561
Convective Heat Transport due to Feed 561
Stirrer 561
Heat Losses 562
Simplified Expression of the Heat Balance 562
Dynamic Control of Reactors 562
Thermal Stability of Polymerization Reaction Masses 563
Specific Safety Aspects of Polymerization Reactions 564
Kinetic Aspects 564
Thermochemical Aspects 565
Factors Leading to Changing Heat Release Rates 568
Cooling of Polymerization Reactors 570
Indirect Cooling: Heat Exchange Across the Reactor Wall 570
Hot Cooling: Cooling by Evaporation 574
Importance of the Viscosity 578
Chemical Engineering for the Safety of Polymerization Processes


Batch Processes 579
Semi-batch Processes 580
Initiation 581
Feed 582
Final Stage 583
Practical Aspects 583
Continuous Processes 584
Concentration Stability 584
Particle Number Stability 584
Design Measures for Safety 585
Process Design 586
Reactor Design 586
Control of Feed 587
Emergency Cooling 587
Inhibition 588
Quenching 588
Dumping 588
Controlled Depressurization 588
Pressure Relief 588
Time Factor 589
Conclusion 589
References 590
Notation 591




Measurement and Control of Polymerization Reactors
John R. Richards and John P. Congalidis
Introduction 595
Definitions 595
Measurement Error 597
Measurement Techniques 598
Temperature 599
Resistance Thermometers 599
Thermocouples 600
Expansion Thermometers 601
Radiation Pyrometers 601
Pressure Measurement 602
Weight 604
Liquid Level 605
Flow 608
Densitometry, Dilatometery, and Gravimetry 617
Viscosity 619
Composition 620
Surface Tension 622
Molecular Weight Distribution (MWD) 622
Particle Size Distribution (PSD) 623
Sensor Signal Processing 625
Sensors and Transmitters 625
Converters 626
Indicators 626
Filtering Techniques 627
Regulatory Control Engineering 627
General 627
Process Dynamics 630
First-order System 631
Second-order System 632
High-order and Dead Time Systems 636
First-order Plus Dead Time System 636
Integrating System 638
Integrator plus Dead Time System 639
Controllers 639
Proportional Control 640
Integral Control 641
Derivative Control 641
PI, PD, and PID Control 642
Digital Controllers 642
Controller Tuning 644
On–Off Controllers 646
Self-operated Regulators 647
Valve Position Controllers 650






Single-loop Controllers 650
Digital Control Systems 650
Actuators 652
Advanced Control Engineering 656
Feedforward Control 659
Steady-state Model Feedforward Control
Ratio Control 660
Cascade Control 661
Feedforward–Feedback Control 663
State Estimation Techniques 666
Model Predictive Control 668
Batch and Semi-batch Control 669
Operation and Variability 669
Statistical Process Control 671
Future Trends 671
Notation 672
References 675


Polymer Properties through Structure
Uday Shankar Agarwal


Thermal Properties of Polymers 679
Crystalline and Amorphous Polymers 680
Influence of Polymer Structure on Crystallizability of Polymers 682
The Glass Transition Temperature 683
Influence of Polymer Structure on Tg of Polymers 684
The Crystallization Temperature and the Melting Point 686
Tuning Polymer Crystallization for Properties 686
Morphology of Crystalline Polymers 688
Tailoring Polymer Properties through Modification, Additives, and
Reinforcement 690
New Morphologies through Block Copolymers 691
Polymeric Nanocomposites 692
Polymer Conformation and Related Properties 692
The Chain Conformation 692
Solubility of Polymers 694
Dilute Solution Zero-shear Viscosity 695
Polymers as Dumbbells 696
Polymers as Chains of Beads and Springs 697
Viscosity of Concentrated Solutions and Melts 698
Nonlinear Polymers 699
Rigid Rod-like Polymers 701
Polymer Rheology 702
The Viscous Response: Shear Thinning 702
Normal Stresses during Shear Flow 703
Extensional Thickening 705





The Elastic Response 706
Ideal Elastic Response 706
Rubberlike Elasticity 706
The Viscoelastic Response 707
Linear Viscoelasticity in Dynamic Oscillatory Flow 709
Influence of Polymer Branching Architecture in Bulk Polymers 711
Polymers as Rheology Modifiers 712
Rheological Control with Block Copolymers 714
Polymer-like Structures through Noncovalent Associations 715
Summary 715
Notation 716
References 718


Polymer Mechanical Properties
Christopher J. G. Plummer
Introduction 721
Long-chain Molecules 721





Simple Statistical Descriptions of Long-chain Molecules 722
Elasticity 724
Deformation of an Elastic Solid 724
Thermodynamics of Rubber Elasticity 725
Statistical Mechanical Approach to Rubber Elasticity 727
Viscoelasticity 729
Linear Viscoelasticity 729
Time–Temperature Superposition 734
Molecular Models for Polymer Dynamics 736
Nonlinear Viscoelasticity 740
Yield and Fracture 741
Yield in Polymers 741
Models for Yield 744
Semicrystalline Polymers 746
Crazing and Fracture 748
Conclusion 752
References 755
Polymer Degradation and Stabilization
Tuan Quoc Nguyen
Introduction 757


General Features of Polymer Degradation 759
Degradative Reactions 759
Initiation 760
Propagation 760
Chain Branching 761
Termination 762
Some Nonradical Degradation Mechanisms 763





Physical Factors 763
Glass Transition Temperature 764
Polymer Morphology 766
Degradation Detection Methods 767
Mechanical Tests 768
Gel Permeation Chromatography 771
Fourier Transform Infrared Spectroscopy 773
Magnetic Resonance Spectroscopy 775
Nuclear Magnetic Resonance (NMR) 775
Electron Spin Resonance (ESR) 776
Oxygen Uptake 776
Chemiluminescence 778
Thermal Degradation 778
Thermal Stability 779
Polymer Structure and Thermal Stability 779
Computer Simulation 780
Thermal Oxidative Degradation of Polypropylene 782
Initiation 782
Propagation 784
Chain Branching 785
Termination 786
Secondary Reactions 786
Formation of Volatile Compounds 788
Homogeneous versus Heterogeneous Kinetics 789
Applications of Thermal Degradation 790
Analytical Pyrolysis 790
Introduction of New Chemical Functionalities 791
Chemical Modification of Polymer Structure 791
Metal Injection Molding (MIM) 792
Recycling 792
Photodegradation 793
Absorption of UV Radiation by Polymers 793
The Solar Spectrum 796
Photo-oxidation Profile 796
Influence of Wavelength: the Activation and Action Spectrum
Photodegradation Mechanisms 802
Photoinitiation 802
The Norrish Photoprocesses 803
Photo-Fries Rearrangement 803
Radiolytic Degradation 805
Interaction of High-energy Radiation with Matter 805
Radiation Chemistry 807
Radiolysis Stabilization 810
Applications 811
Radiation Sterilization 812



Controlled Degradation and Crosslinking 812
Mechanochemical Degradation 813
Initiation by Mechanical Stresses 813
Effect of Tensile Stress on Chemical Reactivity 813
Breaking Strength of a Covalent Bond 814
Rate of Stress-activated Chain Scission 815
Extrusion Degradation 816
Applications 817
Control and Prevention of Aging of Plastic Materials
Antioxidants 818
Radical Antioxidants 818
Hindered Amine Stabilizers (HAS) 819
Peroxide Decomposers 821
Photostabilizers 822
PVC Heat Stabilizers 823
Other Classes of Stabilizers 824
Metal Deactivators 824
Antiozonants 824
Lifetime Prediction 824
Conclusions 826
Notation 827
References 830


Thermosets 833
Rolf A. T. M. van Benthem, Lars J. Evers, Jo Mattheij, Ad Hofland, Leendert J.
Molhoek, Ad J. de Koning, Johan F. G. A. Jansen, and Martin van Duin
Introduction 833
Thermoset Materials 833
Networks 834
Advantages 835
Curing Resins 835
Functionality 835
Formulation 836
Production 837
General Areas of Application 837
Phenolic Resins 838
Introduction 838
Chemistry 838
Resols 840
Novolacs 840
Epoxy-novolacs 841
Discoloration 841
Production 842
Properties and Applications 842
Amino Resins 843



XXI 16.6.1 16.5.3 16.4 16.4.3 16.5.1 16.7.1 16.XXII Contents 16.1 16.3 16.5.5 16.3 16.4 16.2 16.2 16.2.5 Introduction 843 Chemistry 843 Polymerization Chemistry 845 Production 848 Properties and Applications 849 Epoxy Resins 849 Introduction 849 Chemistry 850 Cure 851 Production 853 Standard Liquid 853 Taffy Process 854 Advancement Process 854 Properties and Applications 855 Alkyd Resins 855 Introduction 855 Chemistry 856 The Alkyd Constant 858 Autoxidative Drying 858 Production 859 Properties and Applications 861 Short Oil Alkyds 861 Long Oil Alkyds 861 Medium Oil Alkyds 861 Alkyd Emulsions 861 The Inversion Process 862 Saturated Polyester Resins 862 Introduction 862 Chemistry 863 Production 865 Monitoring the Reaction 865 Properties and Applications 866 Powder Coatings 866 Application 867 Crosslinking 868 Advantages 869 Unsaturated Polyester Resins and Composites Introduction 869 Chemistry 869 Crosslinking 871 Styrene Emission 871 Vinyl Ester Resins 873 Production 874 Reinforcement 875 Fillers 878 869 .5.2 16.1 16.1 16.2.3 16.1 16.3 16.2.1 16.5 16.6.4 16.6.7 16.2 16.3.1 16.2.3 16.4 16.6.2 16.3 16.1 16. 16.3.7 16.4 16.5 16.3.4 16.9.8 16.Contents 16.3.1 Design Considerations: Mechanical Properties of Composites 886 Acrylate Resins and UV Curing 889 Introduction 889 Chemistry 890 Production 891 Epoxy Acrylates 891 Polyester Acrylates 891 Urethane Acrylates 892 Inside-out 893 Outside-in 894 Comparing Inside-out with Outside-in 894 Stabilization 894 Dilution 895 Safety 895 Properties 895 Introduction to UV Curing 896 General Introduction to UV-initiated Radical Polymerization 896 Photoinitiators for Radical Polymerization 897 Resin 897 Reactive Diluent 898 Curing Process 899 Cationic Curing 900 Base-mediated Curing 901 Rubber 901 Introduction 901 Types of Rubber 902 Polymerization 903 Crosslinking 904 Sulfur Vulcanization 904 Peroxide Curing 905 Processing 906 Properties and Applications 907 Advantages and Disadvantages 907 XXIII .8.7.5 16.6.3 16.2 16.4 16.3 16.8 16.10 Processing 879 Hand Lay-up and Spray-up 882 Continuous Lamination 882 Filament Winding 882 Centrifugal Casting 882 Pultrusion 883 Cold-press Molding 883 Resin Infusion 883 Resin-transfer Molding 883 Hot-press Molding 883 Casting.9.8.3 16.5.9 16.8 16. and Coating (Non-reinforced Applications) 886 16.6 16.6 16.7 16.7.2 16.1 16. Encapsulation.3.2 16.7.4 16.4.1 16.1 16.3 16.9.5 16.8.1 16.4 16.9.7.

Spinning 912 Synthetic Yarns 914 Titer: Tex and Denier 914 Tenacity and Modulus: g denierC1.XXIV Contents 16.3 17.2 Thermoplastic Vulcanizates Notation 908 References 909 17 Fibers 911 J. 17.1 17. A.4.4.1 17.4.5 17.4.4 17.4.2 17.2 17. and Industrial Yarns 917 Physical Structure 918 Fiber Polymers: Choice of Spinning Process 920 Polymer Requirements 920 Selection of Spinning Process 920 Spinnability 922 Melt Spinning 923 Extrusion 923 Polymer Lines and Spin-box 924 Spinning Pumps 925 Spinning Assembly 926 Filtration 926 Spinning Plate 926 Quenching 928 Finish 929 Spinning Speed 931 Winding 931 Drawing 931 Relaxation and Stabilization 934 Process Integration 934 Rheology 934 Shear Viscosity 934 Elasticity 936 Elongational Viscosity 936 Process Calculations 936 Mass Flow 937 Volume Flow 937 Extrusion Speed and Elongation in the Spin-line 937 Pressure Drop over the Spinning Holes 938 907 .2.3 17.3 17.3 17.7 17.2 17.2 17.2.13 17.1 17.1 17.12.4 Introduction 911 A Fiber World 911 Scope of this Chapter 912 Fiber Terminology 912 Definitions: Fibers.3.4.2 17.13. Carpet. N texC1 . 17.9. Juijn 17.2 17.1 17.1 17.1 17.4.7 17.10 17.4.2 17. or GPa 915 Yarn Appearance 916 Textile.11 17.3 17.5 17. Filaments.1.1 17. 17.4.2 17.1 17.4.6 17.3 17.3. PET) 938 PET Polymer 938 Spinning of PET 939 PET Staple Fiber 939 PET Textile Filament Yarns 940 PET Industrial Yarns 940 Polyamide (PA6 and PA66) 941 PA Polymer 941 PA Spinning 941 PA Staple Fiber 942 PA Textile Filament Yarns 942 PA Industrial Yarns 942 Polypropylene (PP) 943 PP Polymer 943 PP Spinning 943 PP Staple Fiber 943 PP Split Fiber 943 PP Filament Yarns 944 Solution Spinning 944 Preparation of Spinning Dope 944 Dry Spinning 944 Cellulose Acetate 945 Acrylics 946 Poly(vinyl alcohol) 946 Wet Spinning 946 Viscose Rayon 948 Acrylics 951 Poly(vinyl alcohol) 952 Comparison of Melt and Solution Spinning 953 High-modulus. 17.16.5 17.3 17.4 17.7.1 17.5 17.7.1 17.5 17.5.2 17.4.4 17.2 17.Contents 17.3 17.14.14 17.2.1 17.4.4. High-strength Fibers 956 Air-gap Spinning 956 Aramids 956 Other Liquid-crystalline Polymers 960 Gel Spinning 961 Theory 961 Gel Spinning of Polyethylene 962 Other Gel-spun or Superdrawn Fibers 964 Carbon Fiber 965 Carbon Fiber from PAN 965 Carbon Fiber from Pitch 966 Applications of Carbon Fibers 966 Other Advanced Fibers 966 Notation 967 Acknowledgments 969 References 969 XXV .5.16 17.7 17.5.3 17.3.5 17.3 17.4.1 17.1 17.2.15 17.2 Polyester (Poly(ethylene terephthalate). 17.4 17.4.2 17.4.

1 18.4 19.1 18.2 18.4.1 18.1 19.1 18. Barandiaran and Jose´ M.4 18.3 19.2 19.7 20 20.1 18.1.1 18.2.2 18.4.1 18.4.3 18.1.2. and Dirk J.3 Removal of Monomers and VOCs from Polymers Marı´a J.4 18.2 20.5 19.XXVI Contents 18 18.2.5 19 19.and Microstructuring of Polymers 995 Christiane de Witz.2 19.6 19.1 20.2.4. Cees Bastiaansen. 18.4 18. Asua Introduction 971 Polymer Melts and Solutions 972 Devolatilization 973 Fundamentals 973 Implementation of Devolatilization 975 Equipment 975 Polyolefins 979 Waterborne Dispersions 979 Post-polymerization 980 Modeling Post-polymerization 981 Devolatilization 981 Modeling 982 Rate-limiting Steps 985 Devolatilization under Equilibrium Conditions Equipment 986 Combined Processes 988 Alternative Processes 989 Summary 989 Notation 990 References 991 971 986 Nano. Broer Introduction 995 Patterning Techniques 996 Photoembossing 998 Materials and their Photoresponsive Behavior 999 Single-exposure Photoembossing 1001 Dual-exposure Photoembossing 1007 Complex Surface Structures from Interfering UV Laser Beams Surface Structure Development under Fluids 1010 Conclusion 1012 Acknowledgments 1012 Notation 1013 References 1013 Chemical Analysis for Polymer Engineers 1015 Peter Schoenmakers and Petra Aarnoutse Introduction 1015 Process Analysis 1017 Near-infrared Spectroscopy 1017 In-situ Raman Spectroscopy 1018 At-line Conversion Measurements 1020 1007 .2 18. Carlos Sa´nchez.2 19.

4 1047 Polymer Processes in Supercritical Carbon Dioxide 1048 Interactions of Carbon Dioxide with Polymers and Monomers 1050 Solubility in Carbon Dioxide 1051 Sorption and Swelling of Polymers 1052 Phase Behavior of Monomer–Polymer–Carbon Dioxide Systems 1054 Polymerization Processes in Supercritical Carbon Dioxide 1055 Polymer Processing in Supercritical Carbon Dioxide 1058 Extraction 1060 Impregnation and Dyeing 1061 Ultrasound-induced Radical Polymerization 1062 Ultrasound and Cavitation in Liquids 1063 Radical Formation by Cavitation 1065 Cavitation-induced Polymerization 1067 Bulk Polymerization 1067 Precipitation Polymerization 1069 Emulsion Polymerization 1070 Cavitation-induced Polymer Scission 1072 Synthesis of Block Copolymers 1073 Concluding Remarks and Outlook for the Future 1074 Acknowledgments 1076 Notation 1076 References 1077 Index 1083 XXVII .3.3.1 21.1 21.3 20.3.2 21.5 Polymer Analysis 1022 Basic Laboratory Measurements 1022 Conversion 1022 Detailed Molecular Analysis 1023 FTIR Spectroscopy 1023 NMR Spectroscopy 1024 Mass Spectrometry 1025 Polymer Distributions 1030 Molecular Weight Distributions 1030 Functionality-type Distributions 1034 Chemical Composition Distributions (CCDs) 1037 Degree of Branching Distributions 1040 Complex Polymers (Multiple Distributions) 1041 Notation 1044 References 1045 21 Recent Developments in Polymer Processes Maartje Kemmere Introduction 1047 21.3.2 20.5 21.3 21.2 21.3 21.2.2 20.1 20.1.3 21.2 21.1 20.Contents 21.2 20.1 21.3.2 21.3 21.2.3 20.1 21.3.

including Swiss cheese fondue and Dutch ‘‘Friese nagelkaastaart’’ in a friendly home setting. Editing this book has also been a starting point for the editors to become friends. roughly one year later. we are sure that this book represents the state of the art in polymer reaction engineering. Very rapidly we were convinced that we needed a completely new book. With these contributions. In June 2003 we had completed the list of contributors. Canada and the USA. The quality an edited book like this very much depends on the quality of the individual contributions. coming from Europe. It has been a great pleasure for us to see that all authors have taken their writing jobs very seriously. Maybe we were just lucky. Reading books. that has also been the case for this book.XXIX Preface Freshly started as chairman and secretary of the Working Party on Polymer Reaction Engineering it never crossed our mind to edit a book on this subject. We are convinced that the multidisciplinary and synergetic approach presented in this book may act as an eye-opener for research and development activities going on in strongly related areas. This changed when Wiley-VCH asked if the working party would be able to provide a translation of the Handbuch der Technischen Polymerchemie. We hope the reader will take advantage of this approach. and for some chapters we hired authors from other institutions. we would like to thank Karin Sora and Renate Doetzer from Wiley-VCH . written in 1993 by Adolf Echte. Finally. where the references given in the various chapters may be a starting point for further reading. Many of the working party members directly agreed to participate. covering the field of polymer reaction engineering in a modern. It is intended to attract equally readers that are new in the field as well as readers that may be considered expert in some of the topics but want to broaden their knowledge. Now. broad and multidisciplinary approach. others needed somewhat stronger persuasion techniques. Of course things may not always work out the way you plan. the new handbook is there. We have seen numerous examples from which the frustration is quite obvious. but not exactly. We decided to do so. you often read the preface as well. but we have greatly enjoyed doing this. From that perspective also Francine and Maartje have had their part both of the workload but also of the fun of all this.

They really know to find the balance between waiting and pushing in order not to diverge too far from the schedule. fall 2004 Thierry Meyer & Jos Keurentjes . Lausanne & Eindhoven.XXX Preface for their help with the editing process.

Asua The University of the Basque Country Institute for Polymer Materials (POLYMAT) Paseo Manuel Lardizabal 3 20018 Donostia-San Sebastia´n Spain Dr.XXXI List of Contributors P. Broer Philips Research Laboratories Prof. U. University of Amsterdam Nieuwe Achtergracht 166 1018 WV Amsterdam The Netherlands Dr. 3 20018 Donostia-San Sebastia´n Spain Dr. M. Bachmann Bayer AG ZT-TE-SVT 51368 Leverkusen Germany Prof. R. J. W. J. M. C. S.O. Box 902 5600 AX Eindhoven The Netherlands . J. Barandiaran The University of the Basque Country Institute for Polymer Materials (POLYMAT) Manuel Lardizabal. Box 513 5600 MB Eindhoven The Netherlands Prof. Aarnoutse Polymer-Analysis Group Department of Chemical Engineering (ITS) Faculty of Science. Holstlaan 4 5656 AA Eindhoven The Netherlands and Eindhoven University of Technology Den Dolech 2 5600 MB Eindhoven The Netherlands and Dutch Polymer Institute (DPI) P. M. Agarwal Polymer Technology Group Department of Chemical Engineering and Chemistry Eindhoven University of Technology P. D.O. Bastiaansen Eindhoven University of Technology Den Dolech 2 5600 MB Eindhoven The Netherlands Prof.

B1 67056 Ludwigshafen Germany . de Loos Delft University of Technology Faculty of Applied Sciences Department Chemical Technology Julianalaan 136 2628 BL Delft The Netherlands C. W. s/n 4200-465 Porto Portugal Dr. C. J. du Pont de Nemours and Company DuPont Central Research and Development Experimental Station Wilmington. A.XXXII List of Contributors Polymer Technology Department of Chemical Engineering and Chemistry Eindhoven University of Technology P. 3 20018 Donostia-San Sebastia´n Spain Prof. F. T. J. K. N. Brooks Loughborough University Department of Chemical Engineering Loughborough Leicestershire. Holstlaan 4 5656 AA Eindhoven The Netherlands Dr.I.O. Hungenberg BASF AG Polymer Technology. L. Costa Faculty of Engineering University of Porto Rua Roberto Frias.-D. P. de Witz Philips Research Laboratories Prof. W. Congalidis E. B. P. Hofland DSM Coating Resins Ceintuurbaan 5 8022 AW Zwolle The Netherlands Dr. de Koning DSM Research Oude Postbaan 1 6167 RG Geleen The Netherlands Dr. de la Cal The University of the Basque Country Institute for Polymer Materials (POLYMAT) Paseo Manuel Lardizabal. Evers DSM Melamine Oude Postbaan 1 6167 RG Geleen The Netherlands Dr.und Bioingenieurwissenschafften Gruppe Morbidelli ETH Hoenggerberg/HCI F135 8093 Zurich Switzerland Dr. ETHZ Institut fu¨r Chemie. A. Butte` Swiss Federal Institute of Technology Zurich. J. R. DE 19880 USA Dr. A. J. LE11 3TU United Kingdom Dr. M. Box 513 5600 MB Eindhoven The Netherlands Prof.

ETHZ Institut fu¨r Chemie. Juijn Research Institute Department QRI P. J. F. Box 513 5600 MB Eindhoven The Netherlands Prof. Mattheij DSM Melamine Oude Postbaan 1 6167 RG Geleen The Netherlands Dr.O. Molhoek DSM Coating Resins Ceintuurbaan 5 8022 AW Zwolle The Netherlands Prof. Market St. M. DE 19898-0001 USA Dr. Iedema Department of Chemical Engineering University of Amsterdam Nieuwe Achtergracht 166 1018 WV Amsterdam The Netherlands Prof.List of Contributors Prof. R.O. A. J. ISP-GPM 1015 Lausanne Switzerland L. Keurentjes Process Development Group Eindhoven University of Technology P. M. Wilmington. Leiza The University of the Basque Country Institute for Polymer Materials (POLYMAT) Paseo Manuel Lardizabal 3 20018 Donostia-San Sebastia´n Spain Dr. T. G. A. R. Kolhapure DuPont Engineering Research and Technology 1007 N. Kingston. Kemmere Process Development Group Department of Chemical Engineering and Chemistry Eindhoven University of Technology P. Jansen DSM Research Oude Postbaan 1 6167 RG Geleen The Netherlands Dr. Box 9600 6800 TC Arnheim The Netherlands Dr.O. H. D. T. A. J. P. Ontario K7M 2G9 Canada N. J. Box 513 5600 MB Eindhoven The Netherlands J. Meyer Swiss Federal Institute of Technology Institute of Process Science EPFL. Hutchinson Department of Chemical Engineering Queen’s University Dupuis Hall. F. 19 Division St. F. Morbidelli Swiss Federal Institute of Technology Zurich. J.und Bioingenieurwissenschaften Gruppe Morbidelli ETH Hoenggerberg/HCI F135 8093 Zurich Switzerland XXXIII .

T. J. L. Box 902 5600 AX Eindhoven The Netherlands Prof. Richards E. Nguyen Laboratory of Polymers (LP) Ecole Polytechnique Fe´de´rale de Lausanne 1015 Lausanne Switzerland J. Simon Department of Chemical Engineering University of Waterloo 200 University Avenue West Waterloo.und Bioingenieurwissenschaften Gruppe Morbidelli ETH Hoenggerberg/HCI F125 8093 Zurich Switzerland .O. University of Amsterdam Nieuwe Achtergracht 166 1018 WV Amsterdam The Netherlands Prof. C. Nauman The Isermann Department of Chemical and Biological Engineering Rensselaer Polytechnic Institute Troy. G. C. J. NY 12180 USA Dr. Q. Stoessel Swiss Institute for the Promotion of Safety and Security Chemical Process Safety Consulting Klybeckstrasse 141 WKL-32. DE 19880 USA Dr. Storti Swiss Federal Institute of Technology Zurich. Sa´nchez Eindhoven University of Technology Den Dolech 2 5600 MB Eindhoven The Netherlands and Dutch Polymer Institute (DPI) P. Soares Department of Chemical Engineering University of Waterloo 200 University Avenue West Waterloo.322 4002 Basel Switzerland Prof. P. E. Ontario N2L 3G1 Canada Prof.XXXIV List of Contributors Prof. J. R. du pont de Nemours and Company DuPont Engineering and Research Technology Experimental Station Wilmington. B. I. Schoenmakers Polymer-Analysis Group Department of Chemical Engineering (ITS) Faculty of Science. C. Plummer Laboratory of Composite and Polymer Technology (LTC) Ecole Polytechnique Fe´de´rale de Lausanne 1015 Lausanne Switzerland Dr. ETHZ Institut fu¨r Chemie. P. B. F. Ontario N2L 3G1 Canada Prof.

T .O. Box 513 5600 MB Eindhoven The Netherlands Dr. R.List of Contributors Prof. van Benthem Coating Technology Department of Chemical Engineering and Chemistry Eindhoven University of Technology P. M. van Duin DSM Research Oude Postbaan 1 6167 RG Geleen The Netherlands XXXV . A.M.

cover a wide range of properties from soft packaging materials to fibers stronger than steel. In terms of volumetric output. The consumption per capita has also increased over the years to a worldwide average of approximately 20 kg per annum in the year 2000. Edited by T. act as insulators for electricity and heat. 1. 1950 1960 1970 1980 Year 1990 2000 0 2010 Polymer production and the evolution of the population since 1940 [1].1). an Integrated Approach Th. Keurentjes 1. 25 120 Annual Production 106 to/an 20 100 Consumption. 109 people 0 1940 Fig. F. Meyer. and allow for relatively easy processing. Handbook of Polymer Reaction Engineering.1 1 Polymer Reaction Engineering. The enormous growth of synthetic polymers is due tot the fact that they are lightweight materials.1. Meyer and J. J. KGaA. 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. Weinheim ISBN: 3-527-31014-2 . Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. T. the production of polymers exceeds that of iron and steel.1 Polymer Materials Synthetic polymers can be denoted as the materials of the 20th century. kg/hab 15 80 60 10 40 5 20 World Population .

cling film. polyamide (PA). ‘‘boil-in-bag’’). textile fibers.1. 1. electrical insulators. These non-plastic applications account for about 14% of all thermoplastics consumed. crates. Thermoplastics are used not only in the manufacture of many typical plastics applications such as packaging and automotive parts.2.1. microwave-proof containers. guttering. low-density polyethylene (LDPE). mattresses. phenolics. thermal insulation. Applications and 2002 Western European markets for the major thermoplastics [1]. coatings. parts with complex shapes can be made at low cost and at high speed by shaping polymers or monomers in the liquid state. automotive parts ABS/SAN PMMA 788 317 Moreover. battery cases. appliances. wallpaper. polystyrene (PS and EPS). Applications and 2002 Western European markets for the major thermosets [1]. Thermoset Market [10 3 tonnes] Applications PU Phenolics 3089 912 coatings. toys. It has to be noted. bathroom units. E&E components. containers. The major thermoplastics include high-density polyethylene (HDPE). pipes. SAN). toys. and polyurethanes (PU). a growth of about 9% as compared to 2001 [1]. credit cards. toys. automotive parts. bags. The most important applications of thermoplastics are summarized in Table 1. The polymer market can be divided into thermoplastics and thermosets. toys film for food packaging (oil. electrical components window frames. pipes bottles. cheese. tape cassettes. polypropylene (PP).4 million tonnes in 2002. cups and plates.2. automotive parts. The major thermosets include epoxy resins. medical products containers. The total Western European demand for thermoplastics was 37. but also in non-plastic applications such as textile fibers and coatings. boats Epoxy resins 420 . pipes film. flooring. automotive components. finishes. vehicle seats general appliance moldings. cable insulation. for which the major applications are summarized in Table 1. Thermoplastic Market [10 3 tonnes] Applications LDPE 7935 PP 7803 PVC 5792 HDPE 5269 PET PS/EPS 3234 3279 PA 1399 pallet and agricultural film. textile fibers general appliance moldings transparent all-weather sheet. polyethylene terephthalate (PET). Tab. an Integrated Approach Tab. 1. sports equipment. housewares. bottles.2 1 Polymer Reaction Engineering. electrical components adhesives. industrial wrappings and films. film food packaging electrical appliances. hightemperature engineering applications. poly(vinyl chloride) (PVC). cushions. poly(methyl methacrylate) (PMMA) and styrene copolymers (ABS. adhesives.

Agriculture 2.2% Electrical and electronics 7. Irrigation and 3 . for example for insulation. Automotive industry Motorists want high-performing cars combined with reliability. however. piping. fuel efficiency. It is interesting to note that. and are therefore increasingly being substituted for other materials. about 1% below the 2001 value. competitive pricing. comfort. and. they play only a marginal role. and easy to process. for example for polymeric solar cells and holographic films.2. also contributing to a 10% reduction in passenger fuel consumption across Europe. The major application areas of polymers can be defined as follows (Figure 1.1 Polymer Materials Domestic 22. Although polymer packaging ranks first in terms of units sold. The total Western European market for thermosets was 10.5% Packaging 38.6% Fig. safety. 1. In 2002 this sector accounted for 17. Lightweight polymeric materials are increasingly used in this sector (Daimler Benz’s Smart is a nice example).4 million tonnes in 2002. while the number of applications in this field is increasing. increasingly.0% Large industry 5. Packaging The packaging sector remains the largest consumer of synthetic polymers.2). reassurance about the impact on the environment.6% of the total polymer consumption. flexible. that about one-third of the market for thermosets is for relatively smallscale specialty products. the weight of the polymers used per unit is decreasing.1% Plastic consumption in 2002 by industry sectors in Western Europe [1]. This is mainly due to the fact that these materials are lightweight. Building and construction Polymeric materials are used in the building and construction sector.3% Building and construction 17. approximately 38% of the total market. Electrical and electronic industry Many applications in this field arise from newly designed polymeric materials. it is only third if judged on weight. Agriculture As agricultural applications account for about 2.1. and window frames.5% of the total of synthetic polymers consumed in Europe.3% Automotive 7.

Early in the 20th century (1920). were processed to manufacture useful products. 1. some of which are still being used today. In the 1930s many research groups (for examples see refs. celluloid) concept of macromolecules postulated by Staudinger first systematic synthesis of polymers synthesis of polyamides (nylon) by Carothers at DuPont discovery of polyethylene at ICI (Fawcett and Gibson) synthetic rubbers and synthetic fibers stereospecific polymerizations by Ziegler and Natta. Till) development of polycarbonate discovery of PPO at GE by Hay and commercialization of PPO/PS blends (Noryl2 ) liquid-crystalline polymers superstrong fibers (Aramid2 . In those times no polymers were produced synthetically. light-emitting) metallocene-based catalysts. In the 19th century.4 1 Polymer Reaction Engineering.2 A Short History of Polymer Reaction Engineering In Table 1. This practice was often based on experimental discoveries. Tab. such as cellulose. 3–7) developed models for the chain length distribution in batch reactors resulting from different polymer chemistries. 1. 19th century 1920 1930–1940 1940–1950 1950–1960 1960–1970 1970–1980 1980–1990 1990–2000 2000– natural polymer and derivatives (vulcanized rubber. and polymeric films and greenhouses can increase horticultural production substantially. The use of socalled ‘‘super absorbers’’ for increased irrigation efficiency in arid areas can be considered an important emerging market.3 a comprehensive overview of the major developments in the polymer industry is given. making it possible for Ford to develop the automotive market. the first empirical description of macromolecules was developed by Staudinger [2]. in 1839 Goodyear discovered by mistake the sulfur vulcanization of natural rubber. and starch. a methodology that was further developed in the 1940s leading to more complex and comprehensive models. Fischer. At the same time. The history of polymers in brief. polyethylene) functional polymers (conductive.3. new methods were developed to determine the specific characteristics of these materials. an Integrated Approach drainage systems provide effective solutions to crop growing. novel polyolefins hybrid systems (polymer/ceramic. polymer/metals) Nature-inspired catalysts synthesis of polymers by bacteria and plants . Hevea brasiliensis latex (natural rubber). polymers produced by Nature. the birth of polypropylene discovery of polymer single crystals (Keller. As an example.

1. mass. flexible) and a solid material. However. for example. this can be expected to require polymer reaction engineering developments that are as yet difficult to foresee. Also. an issue that was solved. Current developments include the mimicking of nature (enzymes) for the synthesis of quite complex polymers like natural silk. metallocene catalysts were developed for polyolefin production that surpassed the Ziegler–Natta catalysts in terms of selectivity and reactivity [15. partly inspired by World War II. for example. 1. by using an inert solvent as a heat sink or by flashing of monomer followed by condensation outside the reactor. 9]. Processes were classified as homocontinuous and heterocontinuous. The development of catalysts based on transition metals by Ziegler and Natta [11] allowed the development of stereospecific propylene polymerization processes and ethylene polymerization in the 1950s. This included various liquid crystalline polymers leading. polycarbonate and (somewhat later) poly(propylene oxide) (PPO) were developed. to be produced in extremely large quantities. The development of functional polymers for the conduction of light and electricity and optical switches also started then [13]. physics. This pioneering approach also acted as a catalyst for the further development of polymer reaction engineering (PRE). Additionally. In the same period. In the 1990s. various hybrid materials were combining properties of both the polymer (lightweight. 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. Several process schemes were developed at that time. and mathematics) and engineering knowledge (transfer of heat. leading to materials with specific properties applicable. This was followed by the development of synthetic rubbers and synthetic fibers. The main characteristic of the polymers developed so far was that they were bulk materials. of which some are still in use. In the near future this will probably lead to highly effective and flexible polymer solar cells [14]. and momentum) to 5 . as protective coatings [17]. The major problem in process development has been to deal with the heat of polymerization. In the 1970s. Denbigh [10] was one of the first to introduce chemical reaction engineering concepts into polymer science by considering polymerization reactions at both the chemical and at the process levels. 16]. for example. biology.3 The Position of Polymer Reaction Engineering Around 1940. bacteria and plants are being modified to produce polymers of interest [18]. to the production of superstrong fibers such as Aramid2 / Kevlar 2 [12]. a paradigm shift occurred when polymers with more specific properties started to be produced.3 The Position of Polymer Reaction Engineering Traditional chemical reaction engineering has its basis in the application of scientific principles (from disciplines such as chemistry. which could be metal (conductive) or ceramic (insulating). depending on the mixing level. In the same period.

which is summarized in Figure 1.4. Less energy demanding processes Integrated heat recovery 1990 Multidisciplinarity 2000 2010 Changing priorities in industrial chemical engineering research.to nanoseconds. and process technology. from which it is obvious that the micro and macro scales are not related to the same time scale [20]. that is. 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. new concepts will be required to provide a basis for sustainable future developments. Safety should now be considered as an intrinsic plant property rather than a responsive action. thermodynamics. 1. the use of renewable resources and processes based on ‘‘green’’ solvents. PRE plays a crucial role in the transfer of information across the boundaries of different scale regions and to provide a comprehensive and coherent basis for the description of these processes [19]. which is represented by the middle portion of Figure 1. As depicted in Figure 1. modeling. using phe- . PRE problems are often of a multi-scale and multifunctional nature to achieve a multi-objective goal. mechanics. there is a direct link between time and size scale. and the plant needs to be flexible to be able to respond quickly to changes in the market. an Integrated Approach Energy Raw material Safety Natural gas Coal. safety. Last but not least. a shift toward a multidisciplinary approach can be observed. Engineers have traditionally been working at the meso scale. and societal importance. Oil Capacity Pollution control Water Process Scientific methodology Quality control Air Flexible production Recycling Clean processes Optimization Green solvents Intensification From empiricism to strategy 1980 Renewable feedstock Integrated and inherent safety Plant operation Market Fig.6 1 Polymer Reaction Engineering.3. industrial. physics. For PRE this implies the combination of several disciplines such as polymer chemistry.3. characterization. As an example. As a result of this changing focus. whereas process system integration evolves on the scale of years. molecular dynamics calculations are addressing a time scale in the order of femto. the solution of problems of practical. To deal with more stringent requirements in terms of energy consumption requires a shift from heat loss minimization toward novel intensified process concepts that intrinsically require less energy. Since the 1970s.4. a changing focus in chemical reaction engineering can be observed.

of process or plant engineers. the ‘‘micro-region’’ has traditionally been the domain of physicists and chemists. In the past. rather.4 Toward Integrated Polymer Reaction Engineering Time scale System integration Environmental. whereas the ‘‘macro-region’’ has been the field. Today these limits are pushed in two directions. both toward a more fundamental understanding and at the same time toward a more global scale. Although there is not necessarily a direct connection between them. and synergetic approach can lead to successful developments. and will also strengthen the multidisciplinary approach. Efforts to push these limits will induce innovative developments leading to emerging technologies and products. there exists a common core in which the different disciplines make their own specific contribution to a general objective. PRE can be defined as the science that 7 . In general terms. PRE is composed of many disciplines all linked together. parallel. The frontiers in PRE are determined by what we know. and these frontiers are moving with growing knowledge.4 Toward Integrated Polymer Reaction Engineering As will be obvious from the foregoing discussion. Today. nomenological and continuum models.5). and are able to quantify. understand. but they have a common gateway (see Figure 1. 1.1. it becomes obvious that only using a multidisciplinary. Global modeling Years Engineering design Process models Days Continuum Models Heterogeneous Minutes Phenomenological Models Microstructure Milliseconds Molecular level Elementary reactions Molecular modeling Chemical equilibrium Nanoseconds Picoseconds Atomic level Fundamental Quantum techniques Quantum chemistry Femtoseconds 1Å 10Å 100Å 1µm 1mm 1m 1km Size scale Fig. Activities in PRE with their corresponding time and size scales. 1. competences.4. Polymer reaction engineering will play an essential role as the core and the coordinator of this complex process. and experience. These disciplines can be either mature or emergent.

The selection of the proper chemistry and technology should include an evaluation of environmental. Disposal Modeling and simulation Polymer Reaction Engineering (PRE) Process integration optimization New products Polymer chemistry Reaction kinetics Post-reaction processes Novel processes Nano-. MicroBio- Measurement and control Fig. safety. Raw materials Fig. 1. 1.7). We can either consider it like a black box (Figure 1. and economic parameters.6) or we can try to define the interconnected disciplines that compose this black box (Figure 1.6. brings molecules to an end-use product.5.8 1 Polymer Reaction Engineering. Provided the required product properties can be met. End use product . questions regarding the possible use of renewable resources and minimizing the energy requirement will have to be answered. Moreover. Defining PRE in this manner appears to be very close to the procedure of life cycle analysis (LCA) [21]. we expect that sustainability is the common denominator for all the disciplines involved 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. an Integrated Approach Materials sciences Thermodynamics Novel processes Inherent safety Materials Application Environment Recycling. The expanding sphere of polymer reaction engineering. Polymer Reaction Engineering PRE as a black box process.

planet.5 The Disciplines in Polymer Reaction Engineering 9 Sustainability Materials sciences Thermodynamics Raw materials Novel processes Inherent safety Materials Application Energies Needs Environment Recycling.1. and the different process and raw material alternatives. MicroBio- Novel processes Measurement and control Renewable Fig.5 The Disciplines in Polymer Reaction Engineering The different disciplines involved in PRE can be represented using the academia– industry dichotomy (Figure 1.9).8) [22] leads to an optimization of all the parameters involved and a reduction of the costs. The interests of the two types of players are not identical: the differences are similar to the differences in their mission statements. Disposal Profit Modeling and simulation Laws Economy Satisfaction Integrated PRE Knowledge Process integration optimization New products Polymer chemistry Reaction kinetics Post-reaction processes Nano-. Life cycle analysis is a tool assisting decision making in the engineering process. . LCA is an instrument driven by environmental considerations against a background of technical and economic specifications. This seems to be contradictory at first sight. we can observe that a great overlap is present in the middle zone. LCA includes the information on the history of the materials used. 1. The LCA-based PRE methodology (Figure 1. Nevertheless. Products The integrated approach for sustainable PRE. and involves the so-called 3P concept (people.7. the use of this approach will lead to a ‘‘sustainable integrated PRE’’. but integrating all the aspects often leads to cost reductions. as well as the final product requirements. 1. In our view. and profit).

sewage synthesis processing Evaluation leads to closed loop assessment of costs Fig. methods.technical .ecologic . tools.material . thus providing a strong basis for partnership.10 1 Polymer Reaction Engineering. These disciplines are interconnected by a synergetic and multidisciplinary approach. where interests.economic . . an Integrated Approach waste management Specification .safety recycling Balances raw material product use . 1. As stated above. and systems. and com- Academia Fundamental kinetics Novel technologies Thermodynamics Molecular modeling Measurement and control Reactor design Environment Polymer physics Polymer chemistry Safety Quality assurance Applied modeling Process modeling Market economics Industry Fig.8. 1. PRE is composed of a large number of disciplines.9.energy . Overlap of industrial and academic disciplines. which are described in more detail in the following chapters of this handbook. and knowledge are similar.waste . Life cycle analysis of parts.emission . products.

Product-driven PRE. In step-growth polymerization (like polycondensation).5 The Disciplines in Polymer Reaction Engineering 11 Polycondensation Fig.10 it will be obvious that only teamwork. This could be expressed by an orthogonal representation (Figure 1. and polyamide[6].10. Condensation polymers are the result of a condensation reaction between monomers. with or without the formation of a condensation by-product (Chapter 3). This type of reaction is generally sensitive to thermodynamic equilibrium and requires the removal of the by-product. From Figure 1. and engineering aspects involved. These mechanisms differ basically with the time scale of the process. High molecular weights are already obtained at low monomer conversion.6) the result of the intermolecular condensation of hexamethylenediamine and adipic acid.10) where polymer sciences are linked with engineering sciences. which is often volatile. mercial products are the final achievement resulting from this methodology. can lead to the final objective. unlike step-growth polymerization. 1. the polymer chain growth proceeds slowly from monomer to dimer. based on an orthogonal relationship between science and engineering. until the final polymer size is formed at high monomer conversions. . Every type of polymerization will have its own specific features. and so on. Also.1 Polymerization Mechanisms Polymerization reactions can be classified depending on the reaction mechanism involved and can be either step-growth or chain-growth. (Nylon 6) which is the product of intramolecular condensation of a-caprolactam. (Nylon 6. which is in great contrast to step-growth polymerizations.5. In chain-growth polymerization (like ionic or free-radical polymerization). models.6]. Both the chain lifetime and the polymerization time are often in the order of hours. bringing together several fields of expertise. chain-growth polymerization requires the presence of an active center. 1. macromolecules grow to full size in a much shorter time (seconds being the order of magnitude) than required for high monomer conversion. Examples of polymers produced by condensation are polyamide[6.1. trimer.

2 Fundamental and Engineering Sciences Apart from the various polymerization mechanisms involved. such as peroxides. g-irradiation. depending on the number of functional groups per monomer. Polyolefins are often produced by this kind of reaction where the catalyst (Ziegler– Natta. In ionic polymerizations a cation or anion is the active site (Chapter 7). to produce new products. solvents. they are very sensitive to impurities present in the monomer or solvent. propagation. Radicals can be formed by the homolytic bond rupture of initiators (molecules sensitive to homolytic cleavage.10. complex media) have to be characterized by several specific analytical tools (Chapter 20). various transfer mechanisms. precipitation. which makes it possible to build polymers with a defined tacticity. and chemical engineers is required to take full advantage of this fundamental knowledge. Chapters 4 and 5) or heterogeneously (emulsion. . A close collaboration between chemical physicists. Chapter 6). photosensitive molecules. such as X-rays. and termination. an Integrated Approach The polymers produced by condensation reactions can be either linear or nonlinear. or bisazo compounds) or by complex mechanisms creating radicals from monomer units using thermal or high-energy sources. a large number of other disciplines will have to be involved. These reactions generally evolve at low temperatures (even as low as 120 C) due to the high reactivity of ions. Coordination polymerizations require a transition metal catalyst (Chapter 8). or UV. This process is often used to build tailor-made copolymers. chemists. Free-radical polymerization (FRP) can be performed homogeneously (in bulk. or suspension.5. from which phenomena such as phase behavior and partitioning can be derived. such as metallocenes. it provides information on the interaction between the various components present in the reaction mixture. 1. ESR. according to the matrix depicted in Figure 1. Also. bulk. Techniques such as NMR.12 1 Polymer Reaction Engineering. This type of polymerization usually comprises several steps: initiation. solution. This information is usually accessible by using the appropriate equation of state for a given system studied. Nowadays a great research effort is devoted to the synthesis of new transition metal-based catalysts. Also. Polymer solutions (solid. for example) acts as the active site but also as the steric regulator. solution. These reactions are not always terminated. Thermodynamics is essential to understand the physicochemical properties of the individual reactants. The polymerization process can be performed in bulk (liquid or solid state) or as an interfacial polymerization. and products involved (Chapter 2). A heterolytic process leads to charged parts of molecules that can induce the polymerization by nucleophilic or electrophilic processes. so lead to living polymerization. The active site is always a radical that can be unstable (classical FRP) or stabilized as in pseudo-living FRP.

and chemical and mechanical properties. In polymer reaction engineering. It is based on models that can be physical or chemical. Often the scaleup process begins with a scaledown approach in order to have reliable and representative equipment already at the laboratory scale. ultrasonic sensing. and living species). economic aspects are usually taken into consideration also. a tremendous effort has been observed in the development of new in-line analytical techniques. calorimetry. often in combination. The main characteristics being analyzed are the chain length distribution. All the processes aiming to lower the residual VOC content in the product are denoted as ‘‘removable’’ (Chapter 18). and so on). Safety deals with a wide variety of technological aspects with respect to the environment (water. the final product needs specific and often customer-based analysis. Since the early 1990s. It is used to simulate the reaction and the process system in order to shorten the time for development. chromatography. tacticity. laser. Polymer mechanics (Chapter 14) usually concerns the final product rather than the polymerization reaction. Raman. morphology. moment methods or equations based on population balance are often used. heat transfer and mixing can be considered as two major issues in this perspective. descriptive or more fundamental. Scaleup is a widely used term to define the methodology that allows scaling up of a process from small to larger scale (Chapter 10). for example). viscometry. Nevertheless. depending on 13 . as polymers are usually judged on their end-use properties (Chapter 13). Measurement and control are indispensable to achievement of a robust and safe process (Chapter 12). This is described more specifically for two application areas. To describe the development of the molecular weight distribution upon reaction. These processes can differ from each other. chromatography. and diffraction or electrical methods. namely the use of thermosets for coating applications (Chapter 16) and the production of polymeric fibers (Chapter 17). soil. independently of the reaction kinetics.1. Modern computing techniques such as computational fluid dynamics and process simulation become more and more important in the optimization of process parameters and the equipment hardware. particle size. All these techniques tend to lead to safer and more robust processes while increasing productivity and product quality at the same time. degree of branching.5 The Disciplines in Polymer Reaction Engineering electron microscopy. IR. Modern process development intrinsically includes safety and environmental aspects in all stages of the development. However. air. Modeling is probably the tool of excellence for engineers (Chapter 9). and laser diffraction are widely used to determine polymer properties. Scaleup is always dependent on the system studied and requires a proper understanding of the performance of process equipment involved at different scales. Safety cannot be treated as a separate discipline as it is already integrated from the early chemistry and process development (Chapter 11). electrophoresis. Volatile organic compound (VOC) content in the final product is related to product properties and legislation (FDA approval in the USA. composition. New control schemes appear where the reaction is performed just below the constraint limits. semiempirical or empirical. including spectroscopy (UV.

post-process reaction. The latter includes process intensification as a methodology. As a rule of thumb. Devolatilization. and extraction are some of the methodologies employed for this purpose. two years is often considered long. 25]. when product concepts are still being created. the shift is toward process innovations to reduce cost price.6 The Future: Product-inspired Polymer Reaction Engineering Innovation times in industry have shown a steady decrease since the 1970s. This is due to the fact that in an early phase of the lifetime of an industry. this is followed by a morphological analysis [26]. Currently. there is a strong emphasis on the synthesis of novel functional polymers shaped on a nano scale (Chapter 19) and the development of sustainable production processes (Chapter 21). including an idea about the microstructure. the use of ‘‘green’’ solvents. oxidation and mechanic stresses are the main contributors to product degradation. it has been emphasized that a need exists to refocus chemical engineering toward productdriven process engineering [24. 1. Currently. This period continues until a dominant design has emerged and opportunities for radical product innovation decrease. . chemical engineering has been the basis for polymer reaction engineering in the past. and the use of renewable resources. an Integrated Approach the techniques involved. A key characteristic of this approach is the fact that it avoids the classical ‘‘unit operation trap’’. Next. As has been discussed above. a functional analysis is performed to determine the lowest number of transformations needed to create the product. In this way. In this phase. Finally. The wishes of the consumer and consumer-perceived product properties have to be translated into physical and chemical product properties.14 1 Polymer Reaction Engineering. Many of the new processes under development are focusing on one or more of these topics. the rate of product innovation exceeds the rate of process innovation. Temperature. This sequence of events is the core of product-inspired polymer reaction engineering. because it does not fix the mindset to consider only traditional reactor design and separation process steps to build a process. In recent discussions. The half-time of product innovation (time-to-market) in the early 1970s was about ten years. the main physical attributes of a product are determined. Classic thinking is that process development becomes increasingly important as industry matures [23]. This acceleration of innovation time is the result of competitive pressure in the market. for which the use of supercritical fluids is currently being implemented on an industrial scale. Stability and degradation of polymers (Chapter 15) become relevant especially during post processing or moulding processes. so there is a high reward for being first. however. the first company to enter the market with a new product can get up to 60% of market share. 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. a conceptual process design exercise is performed to generate possible process routes to achieve the desired product properties.

J. 1073. Am. A. 10. Physik. Mater. R. 1934. 2002. Holzkamp. Chem. 665. Goodall. W. T. King. 70. 508.. van Duren. W. Adv. A.. 40. Breil. Martin. 80. 15 16 17 18 19 20 21 22 23 24 25 26 Kivits. Flory. Kuhn. J. 1999. IJzendoorn. H. E. 1934..). Kaminsky. L. 1955. Metallocene-catalyzed polymers. E.. in: Comprehensive Polymer Science. Macromolecules. Can. J. 1072. Faraday Soc. R. Ziegler. 1975. Abernathy. F. D. B. H. US Patent 2 130 948. 32. 1947. Chem. Morgan. Given the volume of polymer production. Utterback. 379. Wei.. Chem. 912. AIChE J. 104. S. Chem. M. References 1 Association of Plastics Manufacturers 2 3 4 5 6 7 8 9 10 11 12 13 14 in Europe. Hummelen. 49. Polymers for electronic applications. Morrissey. H. Am. H. B. J. 1937. 2002. Eng. B30. J. Chem. K.. M. 2202. Kwolek. 1995. J. Moggeridge. O. 43. G. Denbigh. Springer Verlag. AIChE Monograph Ser. P. Faraday Soc... J. 1930. Technol. L. Azapagic.F. P. W. Eng. this will allow the development of sustainable new polymer processes. Goodrich. Cambridge.. Benedikt. 53. Z. Eyerer.7 Concluding Remarks In the foregoing we have presented a general framework for sustainable polymer reaction engineering. 648. 2003. W. Carothers. 12. Appl. Aggarwal (Ed. K. G. 2001. 1935. T. A. 1920. 2003. 293. Funct. Chem. it will be of major importance that environmental and safety issues become an integral part of the development process. 7.. J. vol. Eng. Pergamon Press.. Soc.. Trans. 1994. S. Berichte de Deutschen Chem. R.References 1. Ind. A. 1. Chem. Penlidis. Staudinger. Annual report. Rispens. J. K. 72.. Cambridge University Press. Ind. 1998.) Transition metals and organometallics as catalysts for olefin polymerisation. G. 1987. 1936.. 15 . W.. Leewis. 54. 1996.. 1989. C. 1503. 1877. Berlin. Sapre. 15. 58. M. Oxford. W. 63. M. Chemical product design. C. 1974. Rev. Eng. P. H. Comp. J. Sasabe. W. E. Cussler. Ber. 67. Chem. H. K. In combination with tools such as life cycle analysis and product-inspired PRE. 541. H. 197. 56. V. J.. J. L. Res. E. Mater. Chem. Its most important characteristic lies in the concerted multidisciplinary approach. Sinke. Soc. Cussler. 1936.. 73. J. L. 1978. H. Gibson. Howells. H. Chem. J. Angew. C. Dostal. Janssen. J. rather than focusing on individual competencies. Gesellsch. E. J.. R. Fawcett. Brecksville. Soc. 34. L. 8. J. Polym. J. Trans. Schulz. Mark. 385. L. J. Wada. P. Chalmers. H. 1982. Sinn (Eds. Loos. 1. J. 386. Katzer.

The pressure must be high enough to keep the ethylene in solution. The reactor pressure chosen must be high enough to dissolve the polymer in its monomer. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. such as the number-average molecular weight Mn or the weight-average molecular weight Mw .17 2 Polymer Thermodynamics1 Theodoor W. Edited by T. LDPE has to be separated from unreacted ethylene. 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. which is a copolymer of ethylene and a 1-alkene. also. The reactor conditions are limited at high temperature by the onset of a liquid–liquid phase split. the pure solvent and the polymer have rather different free 1) The symbols used in this chapter are listed at the end of the text. Weinheim ISBN: 3-527-31014-2 . under ‘‘Notation’’. characterized by a lower critical solution temperature. for example random copolymers and block copolymers. In practice reactor pressures are higher than 200 MPa. Hydrocarbons are used as solvents in this process. Many polymers are produced by solution polymerization. KGaA. Another well-known example is the production of low-density polyethylene (LDPE). A polymer is not a single component but a multicomponent mixture characterized by a molecular weight distribution or by average molecular weights. Handbook of Polymer Reaction Engineering. From a thermodynamic point of view polymer solutions are complicated solutions. and the comonomer content may vary. Since the conversion of ethylene to LDPE is incomplete. and at low temperature by crystallization of LLDPE. de Loos 2. solvent recovery and the removal of traces of solvent from the polymer product are important factors in these processes. Meyer. J. In the case of a copolymer different types of copolymers are possible. which is recycled to the reactor. Solvent choice. which involve a high-pressure vapor–liquid flash. An example is the production of linear low-density polyethylene (LLDPE). In this process ethylene is compressed together with an initiator and the LDPE is formed by radical polymerization. To save energy this is done by pressure reduction in two steps.1 Introduction The phase behavior of polymer solutions plays an important role in polymer production and processing.

. In this chapter it is not possible to give an in-depth treatment of the thermodynamics of polymer solutions. where g is the molar Gibbs energy. see Refs. (3). These functions are C closely related to the Gibbs energy. X nai ¼ constant ð1Þ a mai ¼ mib ¼    ¼ mpi for i ¼ 1. Because of this.18 2 Polymer Thermodynamics volumes. C dmi 1 RT ln fi at constant T C fi lim ¼ 1 P!0 Pi ð4aÞ ð4bÞ . N ð2Þ The chemical potential of component i in phase a is defined by Eq. is defined by Eq. If this condition is combined with the condition that the total number of moles of component i is constant in a closed system [Eq. (4a) together with (4b). fi .1 Thermodynamic Principles of Phase Equilibria The equilibrium conditions for phase equilibria can be derived in the simplest way using the Gibbs energy G. where nai is number of moles of component i in phase a]. . According to the second law of thermodynamics. 1–6. the equilibrium conditions given by Eq.2 Thermodynamics and Phase Behavior of Polymer Solutions 2. (1). T. For further reading. . 2.2 Fugacity and Activity In the thermodynamic treatment of phase equilibria. The fugacity of component i in a mixture. . polymer–solvent systems often show a liquid–liquid phase split. nj0i 2.2. (2) can easily be derived for a system of p phases and N components [7]. auxiliary thermodynamic functions such as the fugacity coefficient and the activity coefficient are often used. 0 X 1 q nai g a B C i @ A mai ¼ ð3Þ qnai P.2. the total Gibbs energy of a closed system at constant temperature and pressure is a minimum at equilibrium. 2.

T. (9)]. The fugacity coefficient fi is defined by Eq. xÞ ai 1 0 fi ðP. N ð8Þ C The activity a i is defined as the ratio of fi and the fugacity of component i in the standard state fi 0 at the same P and T [Eq. x 0 Þ ð9Þ An ideal solution is defined by Eq.  C ð P RT dP ð6Þ Vi  RT ln fi ¼ P 0 0X 1 "  # n i RT ð V C @ A qP RT þ RT ln i RT ln fi ¼   ð7Þ qn V PV i V. the equilibrium relation in Eq. T. is a measure of the deviation from ideal solution behavior. (4). a iid 1 x i ð10Þ The activity coefficient of component i. T. T. . C C C fi a ¼ fi b ¼    ¼ fi p for i ¼ 1. gi [Eq. so the fugacity of a nonideal liquid solution can be written as Eq. (13).2 Thermodynamics and Phase Behavior of Polymer Solutions C According to this definition.2. n j0i 19 . gi 1 ai a iid ð11Þ C fi ¼ x i gi fi 0 ð12Þ The activity coefficient gi can be calculated from a model for the molar excess Gibbs energy g E. (12). nj0i y According to Eq. C C fi fi ¼ Pi ð5Þ The fugacity coefficient can be calculated from an equation of state by Eq. (11)]. (8). 2. 0 X 1 E q n g i B C @ A i ð13Þ RT ln gi ¼ qn i P. (6) or (7) [8]. . (2) can be replaced by Eq. (5) and is a measure of the deviation from ideal gas behavior. Eq. C fi ðP. . . fi is equal to the partial pressure Pi in the case of an C ideal gas. (10).

we have conditions according to Eqs. (14) and (15). C C fi 0 ¼ fi 00 or ðx i gi fi 0 Þ 0 ¼ ðx i gi fi 0 Þ 00 ð21Þ . (6) or (7). (16). respectively. fi L ðP. fi L A Pisat ð17Þ 2. we get Eq. so the simplest form of Eq. (15). TÞ ¼ fi V ðPisat . (16) or (17) C and ji with Eq. TÞ exp ðP viL dP Pisat RT ! ð15Þ Combining Eqs. fi L ðPisat . TÞ exp ðP dmiL Pisat RT ! ¼ fi L ðPisat . x i and yi are the liquid-phase and vapor-phase mole fraction of component i. TÞ ¼ fVi ðPisat . L fi ðP. (4a) we obtain Eq. where viL is the molar volume of pure liquid i. On the vapor-pressure curve of a pure component. in which fi 0 is calculated with Eq. x i gi Pisat ¼ yi P ð20Þ In the case of low-pressure liquid–liquid equilibria (LLE) the equilibrium condition is given by Eq.20 2 Polymer Thermodynamics In this approach the standard state fugacity fi 0 of a liquid component is usually the fugacity of the pure liquid component. and is closely related to the vapor pressure Pisat of that component. so Eq. (14). (18) is usually written as Eq.2.3 Equilibrium Conditions For low-pressure vapor–liquid equilibria (VLE) the equilibrium condition of Eq. (21). (17) holds. C C fi L ¼ fi V ð18Þ C x i gi fi ¼ yi ji P ð19Þ 0 The truncated virial equation or the ideal gas equation is often used as the equation of state. TÞ ¼ fVi ðPisat . TÞPisat exp ðP viL dP sat RT Pi ! ð16Þ At low pressure the fugacity coefficient and the exponential term are close to 1. (20). TÞPisat ð14Þ From Eq. In the latter case all fugacity coefficients are 1. (19) is Eq. TÞ ¼ fi L ðPisat . (19).

5 Flory–Huggins Theory and Liquid–Liquid Equilibria The Flory–Huggins 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. where wi and Mi are the weight fraction and molecular weight of component i. If for both liquid phases the standard fugacity is chosen as the pure liquid component. gs and Ws can be obtained from a correlation of experimental data using a suitable model or from a predictive model (see Section 2. (27).2.2 Thermodynamics and Phase Behavior of Polymer Solutions The two liquid phases are indicated by prime ( 0 ) and double prime ( 00 ).2. (26). (22). the equilibrium conditions for low-pressure vapor–liquid equilibria of polymer solutions as given by Eq. ðx i gi Þ 0 ¼ ðx i gi Þ 00 ð22Þ For the calculation of high-pressure vapor–liquid equilibria or liquid–liquid equilibria an equation of state is always used for both phases and the equilibrium condition used is given by Eq. N X wj gi wi ¼ ¼ Mi Wi x i M j j¼1 ð26Þ 2. or in a case where the weight fraction of polymer wp is used as a composition variable as in Eq. P ¼ xs gs Pssat ð24Þ P ¼ ð1  wp ÞWs Pssat ð25Þ The relation between a mole fraction based activity coefficient gi and a weight fraction based activity coefficient Wi of component i is given by Eq. (25). (21) reduces to Eq.3). (23). respectively.4 Low-pressure Vapor–Liquid Equilibria Since polymers have no vapor pressure and as a consequence the vapor phase does not contain polymer. (24). (20) are only applicable to the solvent s as in Eq.2. where Ws is the weight fraction based activity coefficient of the solvent. Eq. The Flory–Huggins expression for the Gibbs energy of mixing Dmix G for Ns moles of solvent and Np moles of polymer is given by Eq. C C fi a ¼ fi b or C C ðx i ji PÞa ¼ ðx i ji PÞb or C C ðx i ji Þa ¼ ðx i ji Þb ð23Þ 2. Dmix G ¼ Ns ln js þ Np ln jp þ js jp ðNs þ rNp Þw RT ð27Þ 21 .

in which ess . because of this. respectively. (30) and (31). but at high values of r gs becomes practically independent of r. respectively. In the original formulation of the Flory–Huggins theory Dmix G increases with decreasing temperature. This is illustrated in Figure 2. The figure shows that with increasing r. Per mole of lattice sites. and esp are the interaction energies between two solvent molecules. The expressions for the mole fraction based activity coefficients of solvent and polymer are Eqs. Equation (27) is derived using many assumptions and approximations (for a discussion. fs and fp .22 2 Polymer Thermodynamics The first two terms on the right-hand side of Eq. (29). (27) represent the so-called combinatorial entropy of mixing. respectively. js and jp are the segment fractions of solvent and polymer. In practice w. is used as an adjustable. the temperature maximum of . 8). The segment fractions of solvent and polymer are then equal to the volume fractions of solvent and polymer. and a solvent molecule and a polymer segment. (28). which leads to a liquid–liquid phase split with an upper critical solution temperature. js ¼ Ns Ns þ rNp and jp ¼ rNp Ns þ rNp ð28Þ According to the original Flory–Huggins theory w is given by Eq. the activity coefficient of the solvent is strongly dependent on r for low values of r. see Ref. the two-phase region increases in size and becomes more asymmetric. the entropy of mixing of a polymer–solvent system is much less than for a solvent–solvent system. defined by Eq. epp . the Flory–Huggins interaction parameter. polymer–solvent systems show a stronger tendency to demix than solvent– solvent systems. temperature-dependent parameter.1. two polymer segments. The critical point. This implies that the equilibrium pressure of low-pressure VLE for polymer–solvent systems is hardly dependent on the molecular weight of the polymer. and the third term is an approximation for the enthalpy of mixing. which shows schematically the influence of r on the location and shape of the liquid–liquid two-phase region. (30). wz ð2esp  ess  epp Þ T ð29Þ Often r is approximated by the ratio of the molar volumes of pure liquid polymer and pure solvent.     jp 1 þ 1  jp þ jp2 w ln gs ¼ ln ð1  jp Þ þ r r ð30Þ ln gp ¼ ln½ð1  jp Þr þ jp   ðr  1Þð1  jp Þ þ rð1  jp Þ 2 w ð31Þ As can be seen from Eq. but on the basis of this rather simple expression many features of the phase behavior of polymer solutions can be explained.

Calculated from the Flory– Huggins theory.60 φp Fig. higher temperature.90 r=10 1. (32). and jp ¼ 0.50 r=1000 0. At r ¼ y the critical point is found at a limiting value of w ¼ 12 . 2.30 0. and lower values of jp .20 0.40 0.60 χ r=100 0.00 0.40 0. (27)].2. Liquid–liquid equilibria for polymer–solvent systems at different polymer chain lengths r. where G is the Gibbs energy per mole of lattice sites]. qG qjp ! ¼ P. w crit   1 1 2 1 þ pffiffi ¼ 2 r jpcrit ¼ 1 pffiffi 1þ r ð33Þ ð34Þ 23 . T ! q2G ¼0 qjp2 ð32Þ This leads to Eqs.70 0.50 0.10 0. (33) and (34) for the Flory–Huggins expression [Eq. the two-phase region.1. T ¼ y. shifts with increasing r to lower values of w.2 Thermodynamics and Phase Behavior of Polymer Solutions 0. This follows directly from the critical point conditions [Eq.00 0.80 0.

4) [13]. another possibility is that the UCST and LCST never meet and that each liquid–liquid region shows a (different) y temperature for r ¼ y. 12]. the UCST and LCST approach each other. show a second region with liquid–liquid immiscibilty (Figure 2. According to these authors the reason for the occurrence of this LCST is the large difference in thermal expansion of pure liquid polymer and pure solvent. This type of behavior is found for polystyrene–methylcyclohexane [14]. Delmas and Patterson [10] calculated binary critical curves of polymer–solvent systems using the Flory equation of state [11. This phenomenon can not be explained on the basis of the original Flory–Huggins theory.5. which shows a closed-loop region of liquid–liquid immiscibility. In some cases.2. The resulting phase diagram is presented in Figure 2.24 2 Polymer Thermodynamics The theta temperature y is the highest possible upper critical solution temperature (UCST) within the framework of the Flory–Huggins theory. Many polymer–solvent systems.6. Another type of LCST is connected to specific interactions like hydrogen bonding. However. at temperatures above the UCST. If the molecular weight of the polymer is increased. T L1+L2 L L1+L2 Solvent φp Polymer Liquid–liquid equilibria showing a low-temperature two-phase region with a UCST and a high-temperature twophase region with a LCST. which leads to an increasing difference in free volume with increasing temperature and an LCST-type liquid–liquid phase split at temperatures below the critical point of the solvent. which is characterized by the occurrence of a lower critical solution temperature (LCST) [9]. This type of phase diagram is not predicted by the original Flory–Huggins theory. This type of LCST is found at temperatures below the UCST. this can lead to the phase diagram of Figure 2. .3. in which the liquid–liquid region has the shape of an hourglass.2). 2. Fig. as in the polystyrene–acetone system (Figure 2. either. see Figure 2.

In the case of curve a.2 Thermodynamics and Phase Behavior of Polymer Solutions T L1+L2 L L L1+L2 Solvent Fig. In going from case a to case c. The liquid–liquid–vapor curve is found in many cases very close to the vapor-pressure curve of the pure solvent because the polymer concentration in the vapor phase and in the solvent-rich liquid phase is low. increasing molecular weight of 25 .2.5. the mixture at low temperature shows a liquid–liquid region characterized by UCST behavior and at high temperature a liquid–liquid region characterized by LCST behavior. T diagram. At higher pressures the phase behavior is as represented by Figure 2. As discussed in Section 2.2. which separates the liquid–liquid region from a vapor–liquid region.2.7 shows schematically the phase behavior of a binary polymer solution at constant composition in a P. In the case of curve c the cloud point curve is found at much higher pressure and no longer shows a minimum. In this case the cloud-point curve shows a pressure minimum. Curve b shows the case where the low-temperature liquid–liquid region and the high-temperature liquid–liquid region are merged into a single liquid–liquid region. At pressures below this minimum. The curve that separates a liquid–liquid region from the one-phase liquid region is often called a cloud-point curve. the mutual solubility of polymer and solvent decreases. hourglass-shaped two-phase regions are found. An example of this behavior is shown by the polystyrene–acetone system [15] (see Figure 2. 2. φp Polymer Hourglass-shaped two-phase liquid–liquid equilibria. Stronger polymer–polymer or solvent–solvent interactions lead to a lower mutual solubility. 2.6 High-pressure Liquid–Liquid and Vapor–Liquid Equilibria Figure 2.2. Both twophase regions are bounded at low pressures by a three-phase liquid–liquid–vapor curve.8). while stronger polymer–solvent interactions lead to a higher mutual solubility [15].3.

Reproduced with permission from Ref. and pentane.9. propane. Fig. which shows that with increasing molecular weight of the solvent the cloud-point pressure increases and dP=dT of the cloud-point curves change sign from positive to negative. Since ethylene is a worse solvent than ethane. the polymer also leads to a decrease in mutual solubility for the same polymer– solvent system. 13.4. 2.26 2 Polymer Thermodynamics Liquid–liquid equilibria in the polystyrene–acetone system at the indicated polystyrene molecular weights (in g mol1 ). Ehrlich and Kurpen [17] determined cloud-point curves of 5 wt. the cloud point pressures for the system ethylene þ LDPE [18. An example of this effect is given by Zeman and Patterson [16] for the polystyrene–acetone system. 19] are higher than for the system .% LDPE in ethane. These results are reproduced in Figure 2. A similar effect is observed when the chain length of the solvent is increased. butane.

but the solvent-rich phase is liquidlike at low temperature.2. the polymer is more soluble in the higher molecular weight solvent. 14. For this type of systems it is not possible to make a clear distinction between vapor–liquid equilibria and liquid–liquid equilibria. 2. but vaporlike at high temperature. ethane þ LDPE. which is shown by the shift of the LCSTtype cloud-point curve to higher temperatures. and plus octane (see Figure 2. The polymer-rich phase can be considered to be a liquid phase.2 Thermodynamics and Phase Behavior of Polymer Solutions Fig. In this case also. 27 .10). plus heptane. Reproduced with permission from Ref. Liquid–liquid equilibria in the polystyrene– methylcyclohexane system at the indicated molecular weights of polystyrene (in g mol1 ).5. An increased degree of branching of the polymer leads to a better mutual solubility [21]. [20] measured cloud-point curves for LLDPE systems plus hexane. De Loos et al.

6.7. 2.and high temperature regions of demixing have merged. .28 2 Polymer Thermodynamics T L1+L2 φp Solvent Fig. showing a minimum Fig. cloud pressure. without a minimum cloud pressure. the broken curves are liquid–liquid vapor curves. L Polymer Closed-loop liquid–liquid equilibria. The full curves are cloud-point curves. (c) system in which the lowand high-temperature regions of demixing have merged. c P b a a T P. 2.and hightemperature regions of demixing. (b) system in which the low. T phase diagram for a constant composition polymer–solvent system: (a) system with separate low.

7 [22–25]. 26] and the difference 29 . To improve this situation a concentration-dependent w-parameter can be introduced and also the temperature dependence of w can be made more complicated than in Eq. 16.2.3 Activity Coefficient Models Fig. The addition of an anti-solvent such as a supercritical gas also produces changes in the phase diagram to one like Figure 2. Liquid–liquid equilibria in the polystyrene–acetone system at the indicated pressures. M ¼ 20400 g mol1 . The terms representing the combinatorial entropy of mixing.8. in this case the liquid–liquid–vapor equilibrium is represented by a region instead of by a curve. Reproduced with permission from Ref. 2.3 Activity Coefficient Models In practice the original Flory–Huggins theory is not accurate enough for a quantitative representation of polymer–solvent phase equilibria. the first two terms in Eq. (27). However. (29). can be replaced by results from more accurate theories [4. 2.


2 Polymer Thermodynamics

Cloud-point isopleths of LDPE in various n-alkane
solvent at 5 wt.% polymer. The short dash–long dash curve is
the solidification boundary of LDPE. Reproduced with
permission from Ref. 17.

Fig. 2.9.

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 polydispersity of the polymer.
The system-dependent parameters in these models can be adjusted to experimental data or predicted from a group contribution approach [4, 26].

Flory–Huggins Theory

For a solution of a polydisperse polymer with m polymer components in one solvent, the Flory–Huggins expression for the Gibbs energy of mixing per mole of lat-

2.3 Activity Coefficient Models

Fig. 2.10. Cloud-point curves of poly(E-co-1-octene)–n-alkane
systems at P ¼ 3 MPa. Mn ¼ 33 kg mol1 , Mw ¼ 124 kg mol1 ,
Mz ¼ 420 kg mol1 . The systems show LCST phase behavior.
Reproduced with permission from Ref. 20.

tice sites can be written as Eq. (35). The sum is only over the polymer components,
ji is the segment fraction of polymer component i, and jp ¼
ji ¼ ð1  js Þ is the
overall polymer segment fraction.
Dmix G
¼ js ln js þ
ji ri1 ln ji þ js jp g sp


g sp ¼ f ðT; jp Þ


To avoid confusion with the polymer–solvent 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 [27–29].
g sp ¼ a þ

þ cT þ djp þ ejp2

g sp ¼ a þ
1  djp





2 Polymer Thermodynamics

g sp ¼

þ c ln T
1  djp


We can derive Eq. (38) for the solvent, and Eq. (39) for polymer component i,
where rn is number-average chain length of the polymer, which is defined by Eq.
(40) and which is proportional to the number-average molecular weight of the

qg sp 2
lnðxs gs Þ ¼ ln js þ 1 
j þ g sp  js
rn p
qjp p  

ri jp
qg sp 2
lnðx i gi Þ ¼ ln ji þ 1 
ri js þ ri g sp  jp
qjs i

rn ¼

n i ri




Using Eqs. (37) and (38), vapor–liquid and liquid–liquid equilibria can be calculated as discussed above. Reference 5 gives details of liquid–liquid equilibrium calculations in polydisperse polymer–solvent systems. In Figure 2.11 the experimentally determined phase behavior of three PEG–water 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 fitted
to the data [29].
The description of the influence of pressure on polymer–solvent phase behavior
is also possible using a pressure-dependent g sp [27, 30–32]. However, this approach
is purely empirical.

Hansen Solubility Parameters

According to the regular solution theory of Hildebrand the w-parameter can be approximated by Eq. (41) [8], where vs is the molar volume of the solvent and ds and
dp 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 simplifications are involved, the results of this model can be considered as only a rough estimate. Following the slogan ‘‘like dissolves like’’, a good solvent for a polymer is a solvent for
which ds and dp have similar values.

ðds  dp Þ 2


2.3 Activity Coefficient Models

Fig. 2.11. Closed-loop liquid–liquid equilibria in the PEG–
water system. Symbols: experimental data, M ¼ 3:35 kg mol1
(0), M ¼ 8 kg/mol (5), M ¼ 15 kg/mol (4); curves fitted using
Eq. (37c). Reproduced with permission from Ref. 29.

Hansen suggested refining 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].

½ðds; d  dp; d Þ 2 þ ðds; p  dp; p Þ 2 þ ðds; hb  dp; hb Þ 2 


Recently, Lindvig et al. [34, 35] showed that Eq. (42) systematically overestimates
the infinite dilution activity coefficient of the solvent and proposed an alternative
expression, Eq. (43).

½ðds; d  dp; d Þ 2 þ 0:25ðds; p  dp; p Þ 2 þ 0:25ðds; hb  dp; hb Þ 2 




2 Polymer Thermodynamics

These authors showed that for a number of polymer–solvent system with a ¼ 0:6
this method performs similarly to group contribution methods using volume fractions to represent the segment fractions in the Flory–Huggins model. Values of
solubility parameters are tabulated by Barton [36].

Correlation of Solvent Activities

The combination of Eq. (35) with one of the Eqs. (36) or similar empirical equations is not very successful for describing the phase behavior of polymer–solvent
systems with strong interactive species and of systems which only differ in molecular weight. Since the mid-1990s activity coefficient models have been proposed
based on a combination of the Flory–Huggins type of expression for the combinatorial entropy of mixing and segment-based local composition models to account
for the contribution from energetic interactions (the residual contribution to the
activity coefficient).
In 1993 Chen [37] proposed a correlative model that used a combination of the
Flory–Huggins expression for the combinatorial entropy of mixing and the nonrandom two-liquid (NRTL) theory [38]. The same approach was followed by Wu
et al. [39]. These authors used Freed’s expression [41, 42] for the combinatorial
entropy of mixing, which is more accurate than the Flory–Huggins expression, in
combination with the NRTL theory. The nonrandom factor model of Haghtalab
and Vera [42] was modified by Zafarini-Moattar and Sadeghi [43] for polymer solutions. In 2004, Pedrosa et al. [44] suggested use of the UNIQUAC theory [45] instead of the NRTL theory and tested various combinations of combinatorial contributions 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 produce the best correlations of experimental VLE data and can also be used to predict
the influence of the molecular weight of the polymer on polymer–solvent VLE.
As an example we will give here the expression for the activity coefficient 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 coefficient of the solvent is given by Eq. (44).
ln gs ¼ ln gscombfv þ ln gsres


The combinatorial/free-volume term is given by Eq. (45).
ln gscombfv ¼ ln

f fv
þ1 s

The free-volume fraction fsfv is calculated from Eq. (46).


2.3 Activity Coefficient Models

fi ¼ X i fv
xj vi



The free volume of a component is defined by Eq. (47), where vi is the molar
volume of liquid component i, vi; 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].

vi ¼ ðvi  vi; vdW Þ p





The residual term is given by Eq. (49) together with Eqs. (50), where asp and a ps are
adjustable interaction parameters, a is the NRTL-nonrandomness parameter,
which was fixed by Pedrosa et al. at 0.4.

tps Gps

tsp Gsp2

ðXs þ X p Gps Þ 2 ðX p þ Xs Gsp Þ 2 

a ij
tij ¼ exp
and Gij ¼ expðatij Þ


qs X p2


X i is the effective mole fraction of segments of species i and qi is the effective segment number of species i, which are given by Eqs. (51) and (52); rs ¼ 1 and rp ¼ r.
x i qi
Xi ¼ X
xj q j



qi ¼ ri 1  2a 1 



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 coefficients 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



2 Polymer Thermodynamics

of experimental data. This makes the group contribution methods purely predictive. However, since details of molecular structure are not considered, group contribution methods for activity coefficients are in general less accurate than correlative
Oishi and Prausnitz [47] proposed writing the solvent activity coefficient for
polymer–solvent systems as the sum of three terms [Eq. (53)].
ln gs ¼ ln gscomb þ ln gsfv þ ln gsres


The combinatorial contribution gscomb accounts for differences in size and shape
of the molecules. The free-volume contribution gs accounts for changes in free
volume due to mixing, caused by the large difference between the free volumes of
pure solvent and polymer. For ordinary liquid mixtures in far from critical conditions, this term is usually negligible. The residual contribution gsres accounts for
energy interactions. In the approach of Oishi and Prausnitz, the combinatorial contribution is represented by the Staverman–Guggenheim expression, a modification
of the Flory–Huggins 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 entropic free volume model of Elbro et al. [52] and Kontogeorgis et al. [53], and the
group contribution Flory (GC–Flory) model of Bogdanic et al. [54, 55], which is a
modification of the model of Chen et al. [50].
In the entropic-free volume model, the activity coefficient of the solvent is given
by Eqs. (44)–(48) with p ¼ 1 [52]. The residual contribution is represented by the
residual contribution of the UNIFAC model with temperature-dependent interaction 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 GC–Flory model, the solvent activity coefficient is calculated from Eq.
The combinatorial term is calculated by means of the original Flory–Huggins expression, Eq. (54).
ln gicomb ¼ ln

þ1 i


The free-volume and residual terms are calculated from a modification of the original Flory equation of state, Eq. (55), where ~v is the reduced volume, defined by Eq.

RT v~1/3 þ C E attr 

v v~1/3  1


2.3 Activity Coefficient Models

v~ ¼



The molar hard-core v  is calculated from the pure component hard-core molar
volumes vi 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 ¼


x i vi


x i Ci




The pure component hard-core volumes and C parameters are calculated from the
group contribution expressions in Eqs. (59) and (60),

vi ¼ 21:9662

m Rm



Ci ¼



CT0 ; n þ CT; n



T T0 



X n Cn0



where un is the number of groups of type n in molecule i and T0 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 qi ,
the surface area of molecule i, is given by Eq. (62)
E attr ¼




yj expðDeji /RTÞDeji

zqi x i 6
4eii þ


yk expðDeki /RTÞ 5



v~  1 X X ðiÞ
un CT; n 
3R ln
qi ¼


n Qn



Q n is the normalized van der Waals surface of group n, as in UNIFAC. The interaction energy parameters eji and Deji are given by Eqs. (63), in which eij0 is calculated from a group contribution expression [Eq. (64), together with Eq. (65)].
eij ¼



Deij ¼ eij  eii




2 Polymer Thermodynamics

eji0 ¼





yðn jÞ enm



enm ¼ ðenn emm Þ 1/2 þ Denm


In these expressions the volume fraction fi of molecule i, the segment fraction yi
of molecule i, and the segment fraction yðiÞ
n of n in molecule i are defined by Eqs.
fi ¼ X i 
xj vj



x i qi
yi ¼ X
xj q j



u Q
Xn n
n ¼
m Qm



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 contribution in the activity coefficient are Eqs. (69) and (70).


ln gires

v~i  1
Ci ln
¼ 3ð1 þ Ci Þ ln 1/3
v~  1
1 4 1
½eii ð~
¼ zqi
vÞ  eii ð~
vi Þ þ 1  ln
yj expðDeji /RTÞ
X yj expðDeji /RTÞ





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 eji 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 GC–Flory model. The result of the correlation is almost perfect. The predicted
solvent activities by the GC–Flory model are also very close to the experimental
values. In Figure 2.13 a comparison is shown of experimental solvent activity

2.4 Equation of State Models

Fig. 2.12. Activity of benzene in the poly(propylene oxide)–
benzene system at 347.85 K. Mn ¼ 500 kg mol1 . Symbols:
experimental data; curves: UNIQUAC correlation and GC–Flory
prediction. Reproduced with permission from Ref. 54.

coefficients at infinite dilution and predictions by the GC–Flory model [54] for
homopolymer–solvent systems, demonstrating that the results of predictions are
good. The predictions for copolymer solutions are slightly worse [55].


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 equations of state for polymer systems, including a discussion of their theoretical background, has been given by Lambert et al. [6]. One of the first equations of state that
was used to model the high-pressure phase behavior of polymer–solvent 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 UCST phase behavior.
The perturbed hard-chain theory (PCHT) was developed by Prausnitz and coworkers [57–59]. It can be considered as an improvement of the approach of Flory


2 Polymer Thermodynamics

log Ω∞cal


log Ω∞exp
Fig. 2.13. Comparison of calculated activity coefficients at
infinite dilution using the GC–Flory model with experimental
values for many polymer–solvent systems. 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 temperature [57–60]. Here, we will discuss only the two equations of state methods:
the relatively simple Sanchez–Lacombe (S–L) lattice fluid model [61, 62], and the
statistical associating-fluid theory (SAFT) [63, 64], which has now become one of
the standard equations of state for polymer solutions.

The Sanchez–Lacombe Lattice Fluid Theory

Like the Flory–Huggins model, the Sanchez–Lacombe lattice fluid theory is based
on the assumption that segments of solvent molecules and polymer molecules occupy 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.

2.4 Equation of State Models

The resulting equation of state for a pure component is given by Eq. (71).   

p~v~ 1
¼  1 þ v~ ln 1  



The reduced volume v~, the reduced pressure p~, and the reduced temperature T~ are
defined by Eqs. (72a)–(72c).
v~ ¼

n0 þ rn


p~ ¼




T~ ¼ 


The parameters with an asterisk ( ) are the so-called characteristic parameters. In
practice r, the number of segments per molecule, e  , the interaction energy parameter, and v  , the molar volume of a lattice site, are used as the independent purecomponent parameters; n is the number of moles of the component and n0 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 ¼ 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 parameters r; e  , and v  are composition-dependent. Neau [65] gives an overview of different 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 ¼ j and which can fitted to binary experimental data.


v ¼
e ¼


x i ri


ji vi


ji jj

eii ejj ð1  k ij Þ


The segment fraction ji of component i is given by Eq. (76).
x i ri
ji ¼ X
x i ri




2 Polymer Thermodynamics

Fig. 2.14. Corresponding states behavior of various liquid–
polymer PVT data according to the Sanchez–Lacombe model.
Symbols represent experimental data; curves are calculated
from Eq. (71). Reproduced with permission from Ref. 62.

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 coefficient for the SL
model is Eq. (77).

2.4 Equation of State Models   

ln j^i ¼ ln z þ ri 2 
ln 1 
1 nr qe  

v~T~ e  qn i nj 0n i

xj r j


nr qv
v  qn i


nj 0n i


The compressibility factor z is given by Eq. (78).

¼ r


In Figure 2.15 [66] experimental isothermal cloud-point curves of the linear low
density polyethylene þ hexane system are compared with the results of a fit of
these data using the Sanchez–Lacombe 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 fit 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


P / MPa


450 K
470 K
490 K
Critical Point
Cloud Point
Critical Point





Weight fraction LLDPE
Isothermal cloud-point curves of LLDPE þ n-hexane.
Symbols: experiments; curves: modified Sanchez–Lacombe fit.
Fig. 2.15.





2 Polymer Thermodynamics

represented by 36 pseudo-components. The SL theory is very well able to describe
the experimental phase behavior.

Statistical Associating-fluid Theory

The statistical associating-fluid theory (SAFT) developed by Chapman et al. [63, 64]
is based on the thermodynamic perturbation theory of Wertheim [69]. Since it
first appeared, many different versions of SAFT have been published. The different
SAFT versions and their application have been reviewed by Muller and Gubbins
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 energy a res, which is the difference between the molar Helmholtz energy of the system 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 ¼ a  a ig ¼ a hc þ a disp þ a assoc


From this expression the pressure and chemical potential can be derived [Eqs.
(80) and (81), respectively] using standard thermodynamic relationships
(A ¼ n i a).  

qV T; n 

mi ¼
qn i V; T; nj0i


For polymer solutions the association term is normally not used. The two SAFT
versions discussed here do not explicitly account for polarity and differ only in the
way the dispersion contributions are calculated.
SAFT and PC-SAFT Hard Chain Term
In the molecular picture behind SAFT a chain consists of mi hard-sphere segments. These hard-sphere segments are bonded by covalent bonds. The hardsphere 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

2.4 Equation of State Models

given by Eq. (82), where m is the average chain length of the molecules in the mixture [Eq. (83)] [64].
a hc
a hs a chain


x i mi


The hard-sphere contribution a hs is represented by the Boublik–Mansoori hardsphere equation of state for mixtures of hard spheres, Eq. (84) [74, 75].

a hs
6 z23 þ 3z1 z2 z3  3z1 z2 z32
þ 2  z0 lnð1  z3 Þ
RT pr
z3 ð1  z3 Þ 2


In this equation zk is given by Eq. (85), where r is the number density, dii is
the temperature-dependent hard-sphere diameter obtained from Eq. (86); mi , the
hard-sphere diameter si, and the energy parameter ei are pure component parameters.
p X
x i mi ðdii Þ k
zk ¼ r

dii ðTÞ ¼ si 1  0:12 exp


The chain term a chain is given by Eq. (87), where gðdii Þ hs is the so-called hardsphere radial distribution function at close contact [Eq. (88)] [74, 75].
a chain X
x i ð1  mi Þ ln½gðdii Þ hs 

d i d j 2 3z22
ð1  z3 Þ d i þ d j ð1  z3 Þ
d i þ d j ð1  z3 Þ 3


SAFT Dispersion Term
In the Huang and Radosz version of SAFT [71, 72] the Chen–Kreglewski dispersion term is used. This term is obtained from a fit to the physical property data of
argon and is given by Eq. (89) [76], where t is a constant equal to 0.74048. The constants Dij are given by Chen and Kreglewski [76]. 

i   j
4 X
a disp X
i¼1 j¼1




2 Polymer Thermodynamics

For mixtures, the van der Waals one-fluid mixing rules or the volume fraction mixing 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.




uij 3
kT ij

x i xj dij3



dij ¼ 

x i xj

di þ dj


uij ¼ ð1  k ij Þ uii ujj


The volume fraction mixing rules are given by Eq. (93), with volume fractions defined by Eq. (94).
fi fj


x i mi d 3i
fi ¼ X
xj m j d 3j



The combing rule for uij is again given by Eq. (92).
The PC-SAFT Dispersion Term
In SAFT the dispersion term represents the interactions between individual segments, 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 defined by Eqs. (96) and (97).

a disp


a i ðmÞh i
¼ 2prm 2
8h  2h 2
20h  27h 2 þ 12h 3  2h 4
¼ prm 1 þ m
þ ð1  mÞ
ð1  hÞ 4
ð1  hÞ 2 ð2  hÞ 2 






bi ðmÞh i



2.4 Equation of State Models

The reduced fluid density h is defined by Eq. (98), in which NAv is Avogadro’s

rmd 3


The parameters a i and bi are dependent on m, as Eqs. (99) and (100) state.
a i ðmÞ ¼ a 0i þ

ðm  1Þðm  2Þ
a 1i þ
a 2i


bi ðmÞ ¼ b0i þ

ðm  1Þðm  2Þ
b1i þ


The constants a 0i –b2i are fitted to the thermophysical properties of n-alkanes and
are given by Gross and Sadowski [73].
SAFT and PC-SAFT Applications
Both SAFT and PC-SAFT contain pure component parameters: the energy parameter e or u, the hard-sphere diameter s, or the hard-sphere volume v 00 , and the number of segments m per molecule. For small (solvent) molecules these parameters
are obtained from a fit of vapor pressure data and saturated liquid volume data.
Since they do not have a vapor pressure, this fit is not possible for polymers, and
the pure component polymer parameters are obtained from a fit to PVT data of the
molten polymer or from a fit 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 fitted 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 þ HDPE are
compared with modeling results using SAFT and Sanchez–Lacombe models. In
both cases k ij is taken to be linearly dependent on temperature. Due to the polydispersity 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 figure 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 PCSAFT. 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 þ solvent systems at constant polymer concentration. The pure LDPE parameters were fitted to the experimental
data of ethane þ LDPE. These parameters were subsequently used to describe the
LDPE þ ethane, þ propene, þ propane, þ butane, and þ 1-butene systems, using a



2 Polymer Thermodynamics

Fig. 2.16. Isothermal cloudpoint curves of the
HDPE þ ethylene system. Mn ¼ 43 kg mol1 , Mw ¼ 118
kg mol1 , Mz ¼ 231 kg mol1 . Symbols: experimental data;
curves: modeling results: (a) SAFT model; (b) Sanchez–
Lacombe model. Reproduced with permission from Ref. 77.

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 concentration.
Extension to Copolymers
For the modeling of the phase behavior of copolymer–solvent systems, the copolymer can be treated as a homopolymer with effective pure component parameters.
Examples of this approach are given by McHugh and co-workers [79, 80]. The disadvantage of this approach is that the pure component polymer parameters depend
on the type and composition of the copolymer. Pure component polymer parameters are obtained from binary polymer–solvent 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
[81–83], in which the copolymer parameters are estimated on the basis of the molecular weight and structure only. For an AB-type copolymer there are three binary
interaction parameters, the interaction parameters between A segments and segments of the solvent molecule, the interaction parameter between B segments

2.4 Equation of State Models

Fig. 2.17. Isothermal cloud-point curves of the
HDPE þ ethylene system. Mn ¼ 43 kg mol1 , Mw ¼ 118
kg mol1 , Mz ¼ 231 kg mol1 . Symbols: experimental data;
curves: modeling results. Reproduced with permission from
Ref. 78.

and segments of the solvent molecule, and the interaction parameter between A
and B segments. The first two binary interaction parameters can be obtained from
the phase behavior of the two homopolymer systems, while the third has to be
fitted to some copolymer–solvent data. Once these parameters are known, predictions can be made for copolymer–solvent systems with the same type of copolymer
but with a different copolymer composition. The same approach was followed by
Gross et al. [84] for the PC-SAFT model. The result is known as copolymer PCSAFT. 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
Figures 2.19 and 2.20 show experimental cloud-point curves and PC-SAFT modeling of the ethylene þ poly(E-co-EA) and ethane þ poly(E-co-BA) systems, respectively [85], at a polymer concentration of 5 wt.%. The model correctly predicts
the change in the location of the cloud point with changing comonomer concentration in the polymer. Especially interesting is the ethylene þ 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.



2 Polymer Thermodynamics

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
permission from Ref. 78.



Polymer–solvent systems behave in many respects in the same way as systems of
low molecular weight components. Differences between polymer–solvent 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
different molecular weights, and that there is a large difference between the free
volumes of the solvent and of the polymer.
The thermodynamic models for polymer–solvent 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 adjustable parameters in these models are fitted to experimental data, reliable predictions can be made for other conditions, for example at a different temperature or
for a system with the same solvent and the same type of polymer with a different

2.5 Conclusions

Fig. 2.19. Constant composition cloud-point
curves for poly(E-co-EA)–ethylene systems with
different repeat-unit compositions at 5 wt.%
polymer. The copolymer molecular weight is in

the range 113–157 kg mol1 . Symbols:
experimental data; curves: PC-SAFT
calculations. Reproduced with permission from
Ref. 85.

molecular weight. Vapor–liquid-equilibria can be predicted with different group
contribution models. Most recent models give reliable predictions of comparable
accuracy for different polymer–solvent 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 liquid–liquid equilibria
is more difficult than for vapor–liquid equilibria. This also holds for polymer–
solvent systems. Reliable prediction methods are not available. The correlation of
liquid–liquid data using the extended Flory–Huggins type models [27–29] gives
reasonably good results. Again, once the adjustable parameters in these models
are known, predictions can be made for other conditions.
High-pressure fluid-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 fitted to data. Small variations in these parameters in
general have a large influence on the predicted phase equilibria. The most promising models for high-pressure phase equilibria of polymer solutions are the SAFT
and the PC-SAFT ones.


Constant composition cloud-point curves for poly(E-co-BA)–ethylene systems with different repeat-unit compositions at 5 wt. 2. radial distribution function Gibbs energy NRTL parameter Gibbs energy per mole of lattice sites Boltzmann’s constant binary interaction parameter number of polymer components. molar Helmholtz energy Helmholtz energy number of external degrees of freedom temperature-dependent hard-sphere diameter constant fugacity molar Gibbs energy. Reproduced with permission from Ref. curves: PC-SAFT calculations.% polymer. Symbols: experimental data.52 2 Polymer Thermodynamics Fig.20. The copolymer molecular weight is in the range 155–283 kg mol1 . interaction parameter. 85. Notation Symbols a A C d DC f g G Gij G k k ij m M n activity. number of segments molecular weight number of moles .

volume fraction fugacity coefficient chemical potential activity coefficient (weight fraction basis) temperature-independent hard-sphere diameter NRTL interaction parameter. surface area normalized van der Waals surface number of segments in a molecule number-average chain length gas constant normalized van der Waals volume absolute temperature energy parameter molar volume volume weight fraction mole fraction segment fraction lattice coordination number. (85)] reduced density number of groups interaction parameter Subscripts d hb i. b. p g d e y jC f m W s t z h u w NRTL nonrandomness parameter phase activity coefficient (mole fraction basis) solubility parameter. compressibility factor Greek a a. density energy parameter theta temperature. polar solvent van der Waals 53 . y X z number of components correction factor pressure effective segment number.Notation N p P q Q r rn R Rm . constant in SAFT density-related variable [Eq. Rn T u v V w x. segment fraction segment fraction. j mix p s vdW dispersion hydrogen bonding component mixing polymer.

Butterworth. 1953. vapor  @ assoc attr chain comb crit disp E fv hc hs id ig L res sat V Acronyms LCST LDPE LLDPE LLE NRTL PCHT poly(E-co-BA) poly(E-co-EA) SAFT S–L UCST VLE lower critical solution temperature low-density polyethylene linear low-density polyethylene liquid–liquid equilibria nonrandom two-liquid perturbed hard-chain theory poly(ethylene-co-BA) poly(ethylene-co-EA) statistical associating-fluid theory Sanchez–Lacombe lattice fluid model upper critical solution temperature vapor–liquid equilibria References 1 P. Danner. DIPPR/AIChE. Elsevier. 1956. 3 H. USA. Cornell University Press. Polymer Solutions. Tompa. 2 H. M. Fujita. High. indicates characteristic parameter reduced association attraction chain formation contribution combinatorial critical dispersion excess free volume hard chain hard sphere ideal mixture ideal gas liquid residual saturated gas. Flory. UK. The Netherlands. Polymer Solutions.54 2 Polymer Thermodynamics Superscripts 0 standard state hard core. 1990. Handbook of Polymer Solution Thermodynamics. S. 4 R. Principles of Polymer Chemistry. J. . 1993. P. USA.

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from which stems the still-used concepts of addition and condensation polymerizations. its formation was also an example of polycondensation. N. under ‘‘Notation’’. Handbook of Polymer Reaction Engineering. Costa and Rolf Bachmann 3. by reaction to create a bond between inert chemical moieties by splitting off a smaller molecule (a condensation). 1) The symbols used in this chapter are listed at the end of the text.57 3 Polycondensation1 Ma´rio Rui P. Weinheim ISBN: 3-527-31014-2 . These expressions became widely used. KGaA. it fell into oblivion a little later. Phenol–formaldehyde (in the form of resins and varnishes) was the first commercial product (in 1907) consisting of an entirely synthetic polymer [2].1 A Brief History The concept of producing larger molecules starting from smaller ones containing suitable groups (such as carboxyls and hydroxyls). Flory [5] justly criticized this terminology. Meyer. In his famous book. since closely related polymerization mechanisms involving reactions of groups with active hydrogen atoms with epoxides and isocyanates do not lead to the splitting of a byproduct.1. can be traced back to the middle of the nineteenth century [1]. he proposed a classification into ‘‘step growth’’ and ‘‘chain growth polymerization’’. in spite of the good impact the work had at that time. even if they are quite vague. Edited by T. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. but this early development was purely empirical and contributed very little to scientific progress. It paved the way to the systematic study aimed at producing synthetic fibers carried out by Carothers at DuPont in the late 1920s and early 1930s [4]. F.1. Staudinger’s concept of the existence of macromolecules came two decades later [3]. much better would be ‘‘random’’ and ‘‘sequential’’ polymerization [6]. It was discovered when preparing oligomers of ethylene glycol. but.1 Basic Concepts 3. J. A survey of important examples of polycondensation reactions can be found in Table 3.

Functional groups or monomers Connecting group By-product aCOOH Carboxylic acid aOH hydroxyl aCOOa ester H2 O aCOOR Ester aOH hydroxyl aCOOa ester RaOH aCOOH Carboxylic acid aNH2 primary amine aCONHa amide H2 O ClCOCl/aCOCl Phosgene/chloroformate aOH hydroxyl O O C HCl O carbonate Na2 S/aSNa Di-sodium sulfide monomer/sodium sulfide end group aCl chloro end group (as in ClC6 H4 Cl) aSa sulfide NaCl NaOa Sodium alkoxide/phenoxide.. and their condensation reactions shown in the last two rows of Table 3. 3.N 0 -dialkylurea AraCH2 OH Aromatic methylol Ar 0 aCH2 OH aromatic methylol AraCH2 aAr 0 HCHO In some polycondensations. . Thus. new functional groups are created by reactions of the monomers. aCl chloro end group.3. aOa ether NaCl NaO CH3 C CH3 aNbCbO Isocyanate Cl ONa O S O aOH hydroxyl Cl O O C none NH urethane aNbCbO Isocyanate aNH2 primary amine O C NH none NH urea CH CH2 O 1.1 occur in later stages of formaldehyde/urea and formaldehyde/phenol polymerizations (see Section 3. e. methylol end groups are formed by the initial reactions of formaldehyde with other monomers.2-epoxide aCH2 OH Methylol aNHa secondary amine none OH N CH2 CH b-hydroxy-t-amine (NH2 )2 CO/NH2 CONHa urea/N-alkylurea CH2NH O C H2 O NH N. A survey of technically important polycondensation reactions.1.g.g.58 3 Polycondensation Tab.4). e..

needed for use as fibers) are possible only by reaching high conversions when monomer molecular weights are a few hundreds. (2) and (3). For instance. With two different monomers. Mn ¼ MAXA þ rMBYB  2pMW 1 þ r  2p ð3Þ High molecular weights (say. (4) is obtained. Starting with 1 mol of monomer AXB. p  MW . Mn ¼ MAXB  pMW 1 p ð2Þ With two monomers. the conversion of reference groups A. yielding Eq. Polymer mass per mole of AXB is equal to its molecular weight MAXB .1 Basic Concepts 3. (2) and (3) by replacing the molecular weights of monomers by 1 and the molecular weight of by-product by 0. The effect of ring formation on Mn of open chain molecules can be taken into account by introducing pc . Well-known relationships for number-average degree of polymerization xn are obtained from Eqs. this reaction leads to a decrease of one polymer molecule (comprising the starting monomers). (3). and later in polyamidations. (2). Eq.1. stoichiometric ratios very close to unity are also needed. minus the mass lost in byproduct formation.2 Molecular Weight Growth and Carothers’ Equation Carothers was mainly interested in polyesterifications. on introduction of the initial stoichiometric ratio r ¼ ½B0 /½A0 between mole concentrations of groups A and B. A count of the polymer molecules and their mass in the system can easily be carried out with the help of p. allowing the number-average molecular weight (mass of polymer/moles of polymer) to be predicted. of compounds with the structures AXA and BYB. and thus do not create a ring. in which X and Y are inert chemical moieties whereas A and B are the active carboxyl and hydroxyl or amine groups. giving rise to a connecting ester or amide group Z and splitting off a by-product (water) W [Eq.3. above 20 000. (1)]. Mn ¼ MAXA ð1  pc Þ þ ðr  pc ÞMBYB  2ð p  pc ÞMW 1 þ r  2ð p  pc Þ ð4Þ 59 . when there are two monomers AXA and BYB. in Eqs. the remaining moles of polymer are 1  p. a similar reasoning leads to Eq. the conversion of end groups yielding rings. or sometimes AXB. AþB!ZþW ð1Þ If reacting groups A and B do not belong to the same molecule.

Monomers with three or more functional groups lead to the formation of branched polymers. Prediction of pc and the average molecular weight of rings is not a trivial task. and similar heavier elements lower in the periodic table) can result. Fig.7). (5). versus conversion p of A groups with monomer functionalities f ¼ 2 and f ¼ 3. P. 3. Notice that.4. of average degrees of polymerization and weight fraction of finite molecules (sol fraction) for the single monomer polycondensations of XA3 and XA2 . x½Px /½X  ¼ f ð fx  xÞ! xp x1 ð1  pÞ xð f 2Þþ2 x!ð fx  2x þ 2Þ! ð5Þ .1 are presented classical predictions (see Section 3. the sol is nearly pure unconverted monomer. low-value maxima (4 if f ¼ 3) at gel point are observed with these nonlinear polycondensations. for equilibrium or batch reaction starting from monomer. Recent experimental results show this concept is not valid in the case of irreversible polycondensations (see Section 3. Stockmayer [7] has obtained the distribution for the fractions of the initial monomer units present in each finite polymer molecules (Eq. where Px is the set of isomers with x repeating units X). which require high conversions for obtaining high values of x n .60 3 Polycondensation Average degrees of polymerization and sol fraction in XA f polycondensations without intramolecular reaction. except when five. in contrast with linear polycondensations. A network of macroscopic dimensions (a gel) appears for high enough conversions and monomer branching.1.1. In Figure 3. Close to full conversion.or six-membered rings (or higher in the case of rings containing Si. Carothers has stated that the fraction of rings in bulk polycondensations is negligible.3).

(6)]. branched oligomers which will be later used to form networks. 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. in contrast to the general Stockmayer distribution. which decreases monotonically (see Figure 3. but always dominated in number and even in weight by the lower molecular weight species. or else low molecular weight. 3. x½Px /½X  ¼ xð1  pÞ 2 p x1 ð6Þ This latter distribution has a relative maximum for x G x n. the even more notorious Schulz–Flory [8] distribution is obtained [Eq. It is also possible to prepare low molecular weight mixtures of ring molecules for further reactive processing (using. for instance.1 Basic Concepts Fig. whereas nonlinear polycondensations lead to extremely broad distributions near the gel point. In any case. anion polymerization). If the functionality f ¼ 2. and possible change of functionality due to side reactions. Equilibrium distributions of monomer units x ½Px =½X  for XA f polycondensations without intramolecular reaction versus conversion p of A groups with monomer functionalities f ¼ 2 and 3. consideration of initial stoichiometry. is essential to predict average molecular weights.3.2. and to avoid premature gelation in the processes described here. mainly linear polymers. This chapter concentrates on processes for making either high molecular weight.2). starting 61 .

1. (9).3 The Principle of Equal Reactivity and the Prediction of the Evolution of Functional Group Concentrations Carothers’ successful synthesis of high molecular weight. regardless of the polymer molecule to which they belong. as often happens. Flory in order to assess the effect of molecular weight on chemical kinetics would eventually lead to the establishment of the principle of equal reactivity. RA ¼ k½A½B ð7Þ Equation (7) states that a single apparent second-order rate constant k should describe all intermolecular reactions of the involved groups A and B for a certain concentration of catalyst(s) (which may be A or B themselves) and solvent. through Eq. the apparent first-order reverse rate constant k Z is related.7).4 Effect 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 formation of rings. aliphatic polyesters could only be carried out thanks to his care in reducing the effect of the hydrolysis reaction through use of high vacuum. If the end groups have polarities and/or hydrogen acceptor or do- . If the reaction is reversible. (8)] for RA should be used. 3. (7). k Z ¼ k½W /K ð9Þ 3. J. RA . a more general expression [Eq. to apparent equilibrium ratio K and by-product concentration ½W .1. of end groups A by an irreversible reaction reaction with groups B can be written as Eq. by dilution with inert solvents and a suitable catalyst (see also Section 3. Schulz [10] in Germany. A change of composition of the reaction medium will often cause k also to change. a by-product W exists.62 3 Polycondensation with monomers [8] or even with recycled polymer [9]. RA ¼ k½A½B  k Z ½Z ð8Þ In the case where. the specific rate of consumption. Further research carried out by his former collaborator P.1. has been led by G. V. A parallel research. Assuming there is no mutual interference of end groups in the same molecule (which does often happen with groups attached to aromatic rings). which also has contributed to the establishment of the same concept and to the prediction of equilibrium chain length distribution (CLD). The discussion of these otherwise interesting processes falls outside the scope of this chapter.

Progress in computational quantum mechanics should ultimately make the practical use of these correction methods more widespread. but its empirical character and lack of available parameters at high temperatures limit drastically its usefulness. Known examples are the apparent increase in reactivity with conversion in esterifications and the strong effect of water concentration on apparent equilibrium and rate constants in amidation systems (see Sections 3.3.3. (10). tr ¼ t0 exp½b g ðTÞx n  bg ¼ b g0 T  T0 ð11Þ Function b g ðTÞ is empirical and could be different from that in Eq. epoxies being the most studied.1 and 3. (11) relating structural relaxation time tr to number-average degree of polymerization x n . leaving aside the long-used ‘‘free volume’’ concept. 63 . the topological limit [14] when unreacted groups in network are too far apart to meet. It is based upon the Adam–Gibbs [17] entropy theory of glass transition. Solvent or bulk media effects can be modeled by taking advantage of group contribution methods [12]. 13 for an example). B. Multiple kinetic experiments with different media compositions are needed in order to compare the free energy of interaction involving the hypothetical transition state group (see Ref. which will be observed as a dependence on conversion or stoichiometric ratio.1 Basic Concepts nor affinities very different from the bonds. There is for the moment no published use of this theory to fit apparent kinetic constants. Formation of more covalent bonds by polymerization decreases the number of available statistical configurations of the chemical system. A new theory for describing this phenomenon. No such studies have ever been tried with polymerization reactions. it is possible to observe a limiting conversion. Should some thermodynamic model of the chemical system be available. as discussed in the reviews by Mita and Horie [15] and Dusˇek [14]. Rate constants will fall before reaching the topological limit if glass transition temperature Tg is attained (the glass effect).3. K ¼ K0 gA gB ½Z½W  ¼ g Z gW ½A½B ð10Þ This kind of computation can be done using the UNIFAC contribution group method [11]. a function only of temperature) through Eq.3 respectively). was recently put forward by Corezzi et al. This situation occurs with many thermosetting systems of practical interest. (11) [16]. Z and by-product W would allow the apparent equilibrium ratio K to be related to the thermodynamic K 0 (a true constant. this is likely to lead to changes in the value of apparent constant k. suggesting Eq. knowledge of activity coefficients g of chemical groups A. thus decreasing configurational entropy. In nonlinear polycondensations. [16].

This behavior has been recognized in urea/formaldehyde formation (see Section 3. Four different rate constants ki are needed to describe forward reactions. based on the Rabinowitch equation for diffusional effects on chemical reactions [Eq. 4) are required to describe reverse reactions: . A first-shell substitution effect (FSSE) is the simplest kind of departure from ideal behavior. . 3.3. diffusion control of chemical reactions may be specific. It is the situation where reactivity is affected only by the reaction of the functional groups attached to the same monomer unit. and possibly an equal number of apparent rate constants (kiZ . For instance. i ¼ 1 . Examples of this approach will be discussed along with their respective chemical systems (bulk polyester and polyamide formation).64 3 Polycondensation A possible suggestion is the following (untested) correlation with yet another two parameters. must be tried.4. Lacking a better alternative. but also to the units linked to that one. when the bond formation rate depends on the mobilities of individual reacting molecules or substructures. as reactivities of functional groups in monomers are often different from the reactivities of end groups in polymers because of mutual steric. 1/k ¼ 1/k 0 þ Cg tr ð12Þ In Dusˇek’s terminology.1.2). A second-shell substitution effect (SSSE) occurs when the reactivity of a functional group is affected by the reaction of all the groups attached not only to the same monomer unit. resonance. or else nonspecific. Linear polycondensations AXA þ BYB with FSSEs in both root units X and Y are examples found in some important processes. Experimental evidence points toward prevalence of nonspecific rate control: for instance. FSSEs are encountered in many polycondensations. It is seen that the glass effect could be taken into account using a similar procedure. or electrostatic interactions.5 Polycondensation Reactions with Substitution Effects When the reaction of a functional group changes the reactivity of its neighbors. a glycol HOaXaOH shows no substitution effect in an esterification 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 substitution effect exists. gel conversion in epoxide resin cure is the same regardless of glass effect [18]. such as the esterification of terephthalic acid and ethylene glycol leading to poly(ethylene terephthalate) (PET). . for a given starting composition. k 0 and Cg . (12)]. when the reaction rate depends only on the average properties of the system. an empirical dependence of rate parameters on conversion.

There is no closed set of rate equations in terms of the concentrations of functional groups ½AXA. This example illustrates several difficulties encountered in modeling reversible polycondensation reactions with substitution effects. and ½ZP . For instance. (15). RAXA ¼ 4k1 ½AXA½BYB  2k2 ½AXAð½ZD  þ ½ZB Þ þ k Z ð½ZD  þ ½ZA Þ RBYB ¼ 4k1 ½AXA½BYB  2k3 ½BYBð½ZD  þ ½ZA Þ þ k Z ð½ZD  þ ½ZB Þ RZD ¼ 4k1 ½AXA½BYB  ½ZD ½2k2 ½AXA þ 2k3 ½BYB þ k4 ð2½ZD  þ ½ZA  þ ½ZB Þ  k Z ð½ZD   ½ZA   ½ZB Þ ð15Þ RZA ¼ 2k2 ½AXAð½ZD  þ ½ZB Þ þ 2k4 ½ZD 2  ½ZA ð2k3 ½BYB þ k4 ½ZB Þ  2k Z ½ZA  RZB ¼ 2k3 ½BYBð½ZD  þ ½ZA Þ þ 2k4 ½ZD 2  ½ZB ð2k2 ½AXA þ k4 ½ZA Þ  2k Z ½ZB  65 .3. ½ZA . for further details see Section 3. a repeating unit X with its pendent chemical groups) is formed by destruction of either of the sequences ZB XZP YZP or ZB XZP YZA (which are dyads. ½W  ¼ 1 (dimensionless) should be used in Eq. ½ZD . An FSSE model taking into account reverse reaction must consider equality of rate constants of reverse reactions k1Z ¼ k2Z ¼ k3Z ¼ k4Z ¼ k Z . sets of two connected repeating units) by reverse reactions at the rightmost Z group as written above. Introduction of more complex chemical entities does not alleviate the problem. A major problem is the possible change in the nature of bonds because another bond connecting a different unit has been destroyed. ½ZB .1 Basic Concepts k1 AXA þ BYB T AXZY B þ W k1Z k3 AXZ þ BYB T BYZX Z þ W k3Z k2 AXA þ BYZ T AXZY Z þ W k2Z k4 ð13Þ AXZ þ BYZ T ZXZY Z þ W k4Z Recall that apparent first-order rate constants of the reverse reactions kiZ are related to the apparent second-order rate constants of the forward reactions ki through the apparent equilibrium ratios Ki and the concentrations of by-product: Ki ¼ ki kiZ ½W  ð14Þ If there is no by-product. this demands knowledge of the concentrations of triads. even with the help of the two stoichiometric restrictions ½X  ¼ ½AXA þ ½ZD  þ ½ZA  þ ½ZP  and ½Y  ¼ ½BYB þ ½ZD  þ ½ZB  þ ½ZP . rates of formation of groups can be written as shown in Eqs. (14).4. ½BYB. In fact.5. one needs the concentrations of dyads. In order to predict the concentrations of monads. and so on. as happens with isocyanate þ hydroxyl reactions. the above kinetic model considers SSSEs for the reverse reaction. Since ½ZA  ¼ 2½AXZA YZA XA þ ½AXZA YZP  and ½ZB  ¼ 2½BYZB XZB YB þ ½BYZB XZP . sequence ZB XZB (a particular kind of monad. This hierarchy of equations can not be broken without obtaining the whole chain length distribution.

as these reactions can be safely neglected. but a reshuffling of pieces of the reacting molecules takes place. k1 XA þ YC T XZ1 Y þ W k1Z E k12 k2 XB þ YC T XZ2 Y þ W k2Z ð16Þ XA þ X 0 Z2 Y T XZ1 Y þ X 0 B E k21 These reactions modify the counts of functional groups of similar chemical nature (for example. such as the acidolysis and aminolysis reactions present in polyamidations. 3. .6 Exchange Reactions Exchange reactions without formation of by-products. Kotliar has presented a general review of these reactions [19]. 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. can be described through Eqs. E k12 K1 ¼ E k21 K2 ð17Þ This operation will reduce the number of kinetic parameters in the kinetic scheme. The exchange of bonds Z1 and Z2 (necessarily formed with a common by-product W). In order not to violate the condition of chemical equilibrium. only exchange reactions involving an end group and a bond should be of any importance. even for just the prediction of basic characteristics of the chemical system. do not increase number-average molecular weight. Also. but also may lead to added mathematical difficulties. the equilibrium ratio of the exchange reaction must be in accord with Eq. In this example. If there is only a single kind of bond. but can be an important cause of relaxation of chain length distributions toward the equilibrium. such as the concentrations of functional groups. descriptions of substitution effects not only require knowledge of more kinetic parameters. which consists of checking the formation of the same final products through successive equilibria but with different intermediate stages. there is no net creation or destruction of functional groups or bonds. several of the various equilibrium constants can also be related through a reasoning due to Gordon and Scantlebury [20] for the XA f polycondensation. (17).66 3 Polycondensation In conclusion. (16). 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.1. distinguishable kinds of amides/amines/carboxylic acids).

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. according to the schemes represented in Eqs. not closeness to stoichiometry of the reagents. The rationale for this unexpected concentration of rings is the irreversible character of their formation.3.7 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 counterparts. k c ðnÞ L n !  Cn þ W cZ ð18Þ k k aE L m þ Cn !  L mþn cE ð19Þ k ðnÞ Except for small rings.1 Basic Concepts 3. (18) and (19). or by a ‘‘back-biting’’ reaction.1. should be identical to their open-chain counterparts. Unfortunately. describing the addition of rings to the end of chains through the exchange reactions. (20)–(21). recent studies by Kricheldorf [24. presence of both kinds of end groups in the same molecule will inevitably lead to competition of ring formation with respect to polycondensation. analogous to the exchange reactions discussed in the previous section. Cn is a ring with n bonds and L n is a linear molecule containing n  1 bonds. According to the Jacobson–Stockmayer theory. In what follows. Their theory has later been refined [22. 25] using MALDI mass spectroscopy have in several circumstances detected quite an appreciable concentration of ring molecules. 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 findings. The limiting factor for molecular weight increase becomes ring formation. valid for gaussian chains (and therefore only for rings with at least some tens of bonds. Unless there is a slight excess of some of the end groups. so this is not a major factor in those systems. The reverse constants depend on the size of the ring. and k aE . k Z and k E respectively. For irreversible polycondensations. Measured ring concentrations for thermodynamically controlled (reversible) polycondensations in bulk are usually only a few percent. The formation of that ring moiety can occur by intramolecular reaction of functional groups. kjc ðnÞ ¼ kj k c ðnÞ ð20Þ 67 . and bulk media or with low solvent concentration) k c and k cE should be related to the corresponding parameters for intermolecular relations through Eqs. representing breakage of bonds in the ring. 23] as it provides a good test for statistical–mechanical treatments of chain molecules. rate constants k cZ .

4 and 3. see Sections 3. the small contributions of the distances of the ends of functional groups b were assimilated to the length of a bond. and NAL is the Avogadro– Lo¨schmidt number. 35]. Alternative approaches to Gordon’s branching theory have later been developed. Exchange reactions also drive molecular weight distributions toward equilibrium.68 3 Polycondensation kijcE ðnÞ ¼ kijE k c ðnÞ k c ðnÞ ¼ 1 ð3/2pnb 2 Þ 3/2 NAL ð21Þ ð22Þ In Eq. (22). an equilibrium constant of cyclization K c ðnÞ can be defined from the equilibrium in Eq. can be tackled using this approach. Systems at chemical equilibrium are amenable to description by the domain of calculus of probabilities known as the theory of branching processes [27]. 28] recognized that nonlinear polymers in the absence of intramolecular reaction can be described by a Galton–Watson branching process. Use of statistical–probabilistic methods for describing polycondensations started with Flory. but lacks the power of the older theory in many situations. Relatively complex chemical systems. who used them to compute the equilibrium chain length distribution of linear systems and later was able to predict gelation conditions for multifunctional monomers.4.8 Modeling of Polymerization Schemes Methods for predicting molecular weight distributions at chemical equilibrium and for irreversible polycondensations are presented with some detail below. 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 [31–33] could be computed. Stockmayer [7] could extend this method to the computation of chain length distributions and average molecular weights of nonlinear polymers. K c ðnÞ ¼ ½Cn ½L m  ¼ k c ðnÞ/n ½L nþm  ð23Þ 3. Many reactions of great technological interest. .4.4. (23). Applicability of statistical–probabilistic methods far from chemical equilibrium cannot be guaranteed. If there is only one kind of bond. mainly the so-called recursive method [34. Gordon [20. presenting substitution effects.3 and 3.1.5 are a better choice. such as melt polyesterifications. became tractable. which is in a number of ways simpler to understand and use. increasing the practical importance of such an approach.4. Batch reactions starting from monomers can sometimes be described by the same solutions.4. and the kinetic approaches described in Sections 3.

So. For a more detailed discussion. It is possible to establish closed sets of rate equations for those fragments in many important cases (the main difficulty being the presence of higher-order substitution effects). together with a short analysis of the much simpler case of linear polycondensations with a single kind of bond (a single monomer AXB or two monomers with different groups AXA þ BYB).4. 3.  Reaction and removal of by-product are intimately connected. the main discrepancies occurring as far as the concentrations of the first linear oligomers are concerned. polycondensations are easier to simulate by Monte Carlo than other polymerizations.2 Mass Transfer Issues in Polycondensations This section deals with situations where mass transfer effects of by-products (devolatilization.5.1. however. Nevertheless. since all reactions have more or less the same time scale. which should be carefully tracked by the kinetic model. It is noteworthy that CLD in those chemical systems (and probably in similar alternating polyesterifications and polyamidations) is nearly always fairly close to equilibrium. The main factor controlling the CLD should be the presence of multifunctional impurities. it differs from the devolatilization of other polymers in a number of ways. These simulations are invaluable for investigating the effect of space correlations between reacting groups and their effect on ring formation and elastic properties [37].  Removal of volatiles takes place during the whole course of the reaction. Prediction of the whole CLD should be possible only with Monte Carlo methods. with their usual drawbacks [36]. Monomers may be removed in substantial quantities. solid-state polymerization) and monomers (interfacial polymerization) become so important as to cause a spatial change in polymer molecular weight distributions. 3.2. For reversible polycondensations. Prediction of molecular size distribution (which hopefully can be determined by size exclusion chromatography) is also a useful result [38] which is difficult to obtain otherwise. see Section 3.1 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.3.2 Mass Transfer Issues in Polycondensations Reversible polycondensations can be tackled using the concept of molecular fragments introduced in Section 3.5.  69 . a method which predicts those concentrations correctly is what is really needed in practice.

in which PW is the equilibrium vapor pressure of by-product W. which at high dilutions can be treated independently. for example. they may be obtained by using a combination of vacuum and inert stripping gas. but even so partial pressures of some millibars for polyester and polycarbonate processes are required.99. PW is the vapor pressure of pure W. (26)]. the infinite dilution is not applicable and the multicomponent Flory–Huggins equation [Eq. the yYi are their mole fractions. and of the order of hundreds for polyamides. Here the fYi are the volume (or segment) fractions of the various components. The high temperature of the processes increases the vapor pressure of the by-products and their equilibrium solubility decreases. For instance. 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. and WW is its weight fraction activity coefficient. 0 1 W Yi ¼ N N Y þ1 f Y þ1 Y þ1 N Y þ1 X X X B C f NX rP Yj expB VYi þ fYi wij  Yi yYi fYk wjk C @ A rYi V y Y Y j i j¼1 k¼ jþ1 j¼1 j¼1 ð26Þ j0i At high conversions. (24) is useful below the critical temperature of the byproduct. (25). not because of low diffusivities D of the by-products (in the range 109 to 1011 m 2 s1 ). These low partial pressures and consequently nearly infinite dilution often justify the application of Henry’s law to describe the vapor–liquid equilibrium according to Eq. Equilibrium constants are of the order of unity for polyesters and polycarbonates. In order to obtain end-group conversions above 0. a possi- . and consequent mass transfer coefficients. i ¼ 1 up to NY being the volatile components and the polymer being component NY þ 1. or product entrainment. given the densities of melt and by-product respectively as rP . VYi the molar volumes.70 3 Polycondensation In the first stages of the reaction. (24). HW is its Henry constant for the polyS mer melt (in the usual range of 10–1000 bar). but because of low interfacial areas. mass transfer resistance to by-product removal is a key factor. rW . At low conversions. WW ¼ rP expð1 þ wÞ rW ð25Þ Similar expressions hold for the volatile monomers. when some thermodynamic model is available. wW is mass fraction in the melt. and the wij the binary interaction parameters. Flory–Huggins theory leads to Eq. should be used instead. foaming. this implies a concentration of by-product ½W  below 104 times the concentration of bonds in the former two systems. reversible polycondensates readily form boiling liquids and care has to be taken to avoid removal of monomers. S PW ¼ HW wW ¼ PW WW wW ð24Þ The second part of Eq.

Stirring helps the formation of bubbles by cavitation and breaks existing bubbles. where the impeller blades throw the polymer melt against the inner surface of the vessel (Figure 3. but can conversely bring about problems for chains which break under shear. vented extruders being a common choice.  Falling-strand or falling-film evaporators. Inert gas injection will also help (but loss of volatile monomers becomes more difficult to counterbalance). According to the mechanism of creation of film. Vented extruders work using a similar principle in their central section (where deeper screws lead to partial filling of the channel) and their reactor models can be considered a variant of this class.3). Fig. and special film-forming equipment must be used. Other processes consist of simple unstirred bubble columns. The basic design of these latter systems consists in a partially filled horizontal cylindrical vessel in which the reaction mixture moves axially with the help of a screw or a rotor with blades. Diagrammatic representation of a wiped-film reactor. these reacting mixtures at the beginning of the processes resemble boiling liquids. increasing interfacial area. in which the disks periodically dip into the pool of reacting mixture. Equipment for devolatilization of residual monomers and solvents without chemical reaction is used in most polymerization processes. 71 . leaves it exposed as a thin film to the gas phase for a short time t f .3.3. The impeller periodically extracts part of the bulk liquid. as well as other specially developed devices that we discuss next. with different kinds of stirrers. and remixes it again with the main stream as it flows toward the outlet. such as polybutylene terephthalate. high-viscosity polymers.  Rotating disk contactors (RDCs) (Figure 3. 3. subjecting it to a high shear rate (in the range 10 3 –10 4 s1 ) in the gaps between their tips and the wall. The polymer film they carry is exposed to the gas phase before being mixed again with the bulk liquid.2 Mass Transfer Issues in Polycondensations ble solution is the use of different continuous stirred reactors (CSTRs) in series. These mechanisms become inefficient for high enough molecular weight with the consequent higher viscosity (above 200 Pa s). This high shear is favorable to conveying pseudoplastic. They are also used in the final stages of reversible polycondensations [39].4). In either case. three classes of devices can be distinguished [40–42]:  Wiped-film reactors (WFRs) [43].

The flux of small molecules has a negligible convective contribution. It considers polymer molecules immobile. time-averaged mass transfer coefficient of . in moles per unit area and unit time. it is possible to predict mass transfer coefficients for simple geometries and to take into account possible coupling with chemical reactions. (27). For instance.72 3 Polycondensation Fig. one using a driving force in terms of mole concentrations. There are two equivalent alternative definitions [Eq. q½Yi  a ¼ kfYi ð½Yi   ½Yi   Þ ¼ kfY ðaYw  aYi Þ N_ Yi ¼ DYi i qy jy¼0 ð28Þ Combining this expression with the microscopic mass balances in the polymer film. considered to lie at y ¼ 0). and mass transfer occurs along the y direction with a plane geometry. 3. the diffusive flux of evaporation N_ Yi . Diagrammatic representation of a rotating disk contactor. only the diffusional flux with respect to the polymer needs be considered. and the microscopic mass balance of a generic volatile component (usually. the other in terms of activities (asterisks mark a concentration or activity value at the interface. a by-product) Yi and a group A i belonging to the polymer may be written. as in Eq.4. if the polymer film is immobile. has a constant depth L. The currently used description of homogeneous diffusion of volatile by-products in polymer media during reversible polycondensations is due to Secor [44]. q½Yi  ¼ DYi ‘ 2 ½Yi  þ RYi qt ð27Þ q½A i  ¼ RA i qt As the resistance to mass transfer in the gas phase may be neglected. will be obtained with the help of a mass transfer coefficient kfYi . neglecting density variations. (28)]. but not always.

It assumes plug flow in the pool. ½A i jt¼0 ¼ ½A i 0 ½Yi jy¼0 ¼ ½Yi   . this yields the well-known result [Eq. (27) with initial and boundary conditions as given in Eqs. tÞ dt qy jy¼0 ½Yi 0  ½Yi   In view of the kinds of gas–liquid contact described above. A time-averaged mass Volatile by-product x y JT Low M polymer inlet Polymer outlet z=0 Fig. sffiffiffiffiffiffiffi DYi pt f ð30Þ kfYi ¼ 2 Pell and Davis [45] were the first to actually measure a diffusion coefficient for a volatile by-product of a polycondensation. 46. ½Yi jt¼0 ¼ ½Yi 0 . using PET formation in films of varying depth (although obtaining values of D much higher than those nowadays accepted).5) is due to Amon and Denson [47] (Ault and Mellichamp [46] considered that all the polymer was in the film) and was developed for WFRs. (30)] for the time-averaged mass transfer coefficient. z z=L y 73 . The first model associating the axial transport along the reactor (direction z) with the cross-flow transfer of volatile by product (direction y) (see Figure 3.3. and is replaced by fresh fluid after an exposure time t f .2 Mass Transfer Issues in Polycondensations volatile species kfi after an exposure time t f would be computed by solving Eq.5. Simple model for a WFR. For an infinite film depth L and negligible chemical reaction. an obvious model is provided by the penetration theory (infinite depth L). q½Yi  ¼0 qy jy¼L DYi ð tf kfYi t f ¼ 0 ð29Þ q½Yi ð y. where a portion of fluid with uniform concentration profile is suddenly exposed to the gas phase. An early example of discussion of coupling of diffusion/chemical reactions in these systems may be found in Ref. 3. which implies a negligible hold-up of the liquid in the film. (29).

since its thickness is low. (33). q½Yi f qt þ ux q½Yi f qx ¼ DYi q 2 ½Yi f qy 2 ðL q½Yi  q½Yi  ux þ uz ¼ R Yi þ qt qz L q½A i  q½A i  ux þ uz ¼ RA i þ qt qz L ½Yi jz¼0 ¼ ½Yi 0 ðtÞ 0 þ RYi q½A i f qt þ ux q½A i f qx ¼ RA i ½Yi f ðt.74 3 Polycondensation transfer coefficient is obtained at each axial position by solving Eqs. where the ½A i f and ½Yi f are the concentrations of the species in the film. yÞ dy  u z ½A i  ð33Þ ½A i jz¼0 ¼ ½A i 0 ðtÞ ½Yi f jx ¼0 ðt. where u z is the axial superficial velocity (volumetric flow rate of polymer Q divided by cross-section area of the pool) and a v is the film area per unit volume. (32). zÞ ¼ ½Yi ðt. Fundamental studies on fluid mechanics and mass transfer without reaction are reported in Refs. y. yÞ dy  u z ½Yi  ðL 0 ½A i f ðt. 0Þ ¼ ½Yi   With some modifications. where d T is the inner barrel diameter. zÞ ½A i f jx ¼0 ðt. the exposure time would be calculated [47] through Eq. zÞ ¼ ½A i ðt. a model of single-screw vented extruders can also be developed. leading to Eqs. uz d½Yi  ¼ RYi  kfYi a v ð½Yi   ½Yi   Þ dz uz d½A i  ¼ RA i dz ð31Þ ½Yi jz¼0 ¼ ½Yi 0 Since the main mass transfer area is the film on the barrel wall. We will present here a slightly extended version of the treatment by Roberts [49] and Biesenberger and Sebastian [50]. tf ¼ Lx pd T n_ ð32Þ A better model [48] takes into account the movement of the film along the wall with velocity u x ¼ pd T n_ between coordinates x ¼ 0 and x ¼ L x and therefore adds a convection term. 51 and 52. (31). zÞ q½Yi f qy ¼0 jy¼L ½Yi f ðt. and the mass balance of the pool is written as Eqs. L x is the film perimeter (L x G pd T . . if the nip is small) and n_ is the screw rotational speed in rotations per unit time. (27) and (29). There is no need to consider cylindrical geometry for the film. y.

6. the film width is h/2. a fraction passes through the space between the barrel and the screw. with a fraction fL filled with liquid. d ¼ pd T fL cos y ð35Þ t f ¼ ð1  fL Þ/n_ ð36Þ The concentrations ½A i f ðzÞ and ½Yi f ðzÞ respectively for nonvolatile and volatile components in the film. are obtained by solving Eq. back-mixed at axial position z. is given by Eq. where h is the clearance. ð34Þ vT ¼ pd T n_ sin y The film which is wiped from the channel re-enters at a distance d upstream of its departure point given by Eq. (27) for t ¼ t f with initial conditions described by Eqs. As the movement of screw pushes the polymer pool. If the fluid is Newtonian. the coordinate z will be taken along this helicoidal path. (35) [50] and the time of exposure of the film t f is given by Eq. ½A i jt¼0 ¼ ½A i ðz þ dÞ ð37Þ 75 . 3. in which y is the angle of the screw. Dimensions of the channel will be LW (width) by H (depth). The average transverse velocity of the screw dragging the film. (37) (a more exact model would consider convection as in Eq. (34). A scheme of flow and mass transfer in single-screw vented extruders. forming the desired evaporating film. also illustrating some key geometrical parameters. with a total length LB /sin y. Scheme of flow and mass transfer in single-screw vented extruders. As polymer flows inside the channel along a trajectory in a helix.2 Mass Transfer Issues in Polycondensations Unwrapped views: Film Fig. (36). vT .6.3. is shown in Figure 3. (33)): ½Yi jt¼0 ¼ ½Yi ðz þ dÞ.

t fP ¼ H pd T n_ sin y ð39Þ Another integration of Eq. since the J compartments with liquid hold-ups Vm j can be approximated as CSTRs.5. and few fundamental studies [54] have been carried out. in which b 1 ¼ 0. and the gas phase will be considered well mixed with uniform temperature (see Figure 3. (38). the exposure time of the pool may be estimated through Eq. Q j . thanks to the possibility of using reduced space times. mass balances at a steady state of volatile and nonvolatile components in the jth compartment ( j ¼ 1. Twin-screw extruders have the advantage of being self-cleaning and can work with extremely high viscosity. J) may be written as in Eqs. which has been attributed to the very low liquid hold-up and consequent lack of coverage. will be divided into a fraction b j going back to CSTR j  1 and 1  b j going to tank j þ 1. Taking into account the possibility of back-flow. Thus. except for the first CSTR. Rates of mass transfer have been predicted for a co-rotating twin screw using penetration theory and experiments have been done with a transparent device (for observing whether bubbles were present or not in the devolatilization zone). (27) for t ¼ t fP with a trivial modification of Eq. above 10 6 Pa s [53]. the overall volume flow rate leaving the jth CSTR. (39). use of staged models for describing rotating disk contactors is a natural choice [55]. In contrast to WFRs and vented extruders. Their detailed modeling is more difficult than with single-screw devices. . (40). making them a good choice for polyamide and polyurethane final stages of reaction. the mass balances in the channel taking into account also the devolatilization from the pool (mass transfer coefficients kfpYi ) thus becomes those given in Eqs. uz kfpYi d½Yi  vT h ¼ RYi þ ð½Yi   ½Yi   Þ ð½Yi f  ½Yi Þ  dz fL LW H fL LW uz d½A i  vT h ¼ RA i þ ð½A i f  ½A i Þ dz fL LW H ½Yi jz¼0 ¼ ½Yi 0 ð38Þ ½A i jz¼0 ¼ ½A 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. as penetration theory predicts. Q Jþ1 ¼ 0. 49 and 50. Also according to Refs. but were three times lower than theoretical predictions.7).76 3 Polycondensation Assuming plug flow in the channel (a trivial change would be to add an axial dispersion coefficient). Also. Observed results of kf a v were proportional to the speed of rotation to the power of 0. (30) will provide an estimation of the mass transfer coefficients of the pool kfpYi .

(42). because polymer staying there will degrade due to secondary reactions to possibly discolored or gelled material. Local film thickness and hold-up have been correlated to physical properties (surface tension. viscosity) and geometrical parameters [57]. Staged model of an RDC. Q j1 ð1  b j1 Þ½A i j1 þ Q jþ1 b jþ1 ½A i jþ1 ¼ Q j ½A i j  RA i Vm j Q j1 ð1  b j1 Þ½Yi j1 þ Q jþ1 b jþ1 ½Yi jþ1 ð40Þ ¼ Q j ½Yi j  RYi Vm j þ kfYij avj Vm j ð½Yi j  ½Yi   Þ Mass transfer coefficients can be computed using penetration theory as described above.2 Mass Transfer Issues in Polycondensations Fig. Residence time distribution has been shown to become narrower when viscosity grows [58].7. in view of the complexities introduced by polymer viscoelasticity. strands and films become very thin and may be completely depleted of 77 . but this correlation should only be used as a first approximation [40]. [56] obtained correlations for hold-up and mixing time in RDCs.3. Interfacial area [58] can be correlated with relative filling level H/d T and the number of disk rings per unit length ( J/LT ) [Eq. Efficient surface renewal is achieved by shear thinning during the fall [59].  2 0:5 kf dR d n_ ¼ 1:59 R Sh ¼ D D ð42Þ Falling-film or falling-strand devolatilizators receive increasing attention as they require no heavy and expensive machinery: Polymer is simply pumped through small slits or holes. Fractional dead space (between 0 and 18% for their experimental data) can be predicted from the mixing time. (41)]. av ¼ J 1:72  1:87H/d T LT 0:085 þ 0:955H/d T ð41Þ An experimental study on mass transfer in disk-ring contactors of diameter dR using low-viscosity acrylamide solutions as a model fluid [60] has led to the correlation of Eq. and product quality may be seriously harmed. This dead space should obviously be kept to a minimum. 3. Murakami et al.

but this is often not the case. So. Depletion or possible tearing determine the optimal height of strands/ films for a given viscosity and initial film diameter. only high supersaturation will restart boiling. equal to the sum of the partial vapor pressures due to inert gases and volatile components if physical equilibrium and gas-phase ideality hold. foam grows until a limiting volume is reached. Of course. thin rods. an additional component of interfacial area is provided by the gas bubbles. Rates of mass transfer in the presence of foaming were about 40 times higher than in the bubble-free regime. rbc ¼ 2s Pb  Pme ð43Þ Bubble nucleation in polymer media is usually heterogeneous [62]. Favelukis et al. 54. (43) [50]. which can result from sparging with inert gas (widely used for devolatilization without chemical reaction) or from boiling. it is possible that no bubbling occurs if the pressure is high enough or the content of volatiles is too low. internals. The Laplace–Kelvin equation predicts that an isolated gas bubble should redissolve if its size is below a critical threshold. or grids. in many practical situations there are already small air bubbles in the polymer. when it forms. An important recent result is that. regardless of initial volatile content and presence of stripper gas [66]. such as wires. and conversely it should grow if its radius r b exceeds the critical value given by Eq. In all these devices. Guides to the strands/films. Once the source of heterogeneous nucleation is spent. It starts when shear stress manages to detach the small bubbles which are stuck in cracks and crevices of vessel walls. will further enhance the role of the reaction while reducing the effect of shear thinning and tearing. 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. because neither pool nor film is well stirred – which could explain the failure of predictions in Ref. A predictive theory for bubble nucleation was developed in this same research [64]. and thus the devolatilization section in vented extruders should . and they will start foaming too. or suspended dust. Trace devolatilization with the help of a stripper agent has a greatly enhanced efficiency. 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). Reaction considerably increases the efficiency of these devices (by a factor of up to ten) as it replenishes the volatile by-product. [63] have confirmed this view. Pme 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]).78 3 Polycondensation volatiles. and Pb is the pressure inside the bubble. where s is the surface tension. Observed rates of mass transfer are often several times higher than predicted [50] and this discrepancy has been linked to the presence of bubbles. Measured values of mass transfer rates without bubbling are three times lower than predicted by penetration theory.

a v ¼ pdb2 Nb Vm ð46Þ Q g tf Nb ¼ Vb The observed bubble frequency agreed with the theoretical predictions. (45)] as the rising time of a bubble in the melt (at height hR above the gas injection point).   1/4  15mQ g 3/4 4p 2rg 3    Q g d b 1/2 2gd b ub ¼ 1þ Cd u b Vb Vb ¼ Cd ¼ ð44Þ 16 þ1 Re In these equations m.3. The mass transfer coefficient was predicted using penetration theory. (46)]. r. suggesting that for some problems ‘‘classical’’ Chemical Engineering of the 1960s can still help in present-day industrial and scientific problems. as also did the profiles of x n versus reaction time. An experimental and theoretical model has also been presented [68] and will be briefly summarized here. and the crux is the prediction of the mass transfer rate of by-product (phenol). respectively. and the exposure time was computed [Eq.2 Mass Transfer Issues in Polycondensations have enough room for that expansion. 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). are the viscosity and density of the liquid. and Cd is the drag coefficient. The reactor was a rotating disk contactor for making bisphenol A (BPA) polycarbonate. The reactor model uses a staged approach. d b is the bubble diameter. 79 . It is interesting to finish this complex section with such a case study. tf ¼ hR ub ð45Þ The interfacial area per unit volume was obtained from the number of bubbles Nb and the melt volume Vm [Eqs. and residence time should also be sufficient to allow the final density to be reached. The two relationships expressed in Eqs. (44) for the volume of a gas bubble Vb as a function of the gas flow rate Q g [69] and of its rising velocity u b in a laminar regime [70] were the key data. g is the acceleration of gravity.

Pilati et al. A practical difficulty is the possible tendency of the particles to stick. linear. taking into account the change in the volume of the reaction media affecting functional group concentrations. Another problem may be the sublimation of oligomers. which is also covered in the review by Pilati [71]. is present in industrial processes since early 1970’s.2 Solid-state Polycondensation Current industrial processes for the production of high molecular weight. as in nylon-6. low molecular weight polymers to high molecular weight ones. [72. in a batch SSP. the polymer has to be in a powdery form. occurring below the melting temperature of high polymer. use solid-state polycondensation (SSP) for their last stages. a maximum in molecular weight versus time is expected. but well above the glass transition temperature.  Equilibrium CLD holds locally. One of the several optimization problems of these processes is to specify an economical starting particle size. We will disregard polycondensation of crystalline monomers. Because of the need to provide enough interfacial area to allow the removal of volatile by-products. This is the kind of process that will be treated in this section: the polycondensation of semi-crystalline.  Chemical reactions follow the same kinetics as in melt. as simplified models seem to have arrived at their limits. aromatic polyesters and polyamides.8):  All chain end groups belong to the amorphous regions. A precrystallization step for PET. which will make the process unfeasible. for use as plastics and fibers. and this maximum will occur at shorter times and will lead to lower molecular weights as the temperature is increased. owing to the selectivity gain of polycondensation with respect to degradation reactions.2. 3. The key assumptions made in order to interpret SSP are due to Gostoli. to make it attain at least 40% crystallinity before SSP starts.80 3 Polycondensation The design and operation of most polycondensation reactors for devolatilization of volatile by-products (namely vented extruders) is clearly a very difficult problem because of the complexity of the flows (with or without foaming). and by adding glass beads. Therefore. which may clog the bed. The main reason for using SSP is the achievement of molecular weights higher than would be possible in melt polycondensation. It is counteracted by starting with polymers with sufficiently high crystallinity.  The overall polydispersity of polymer will be greater than the equilibrium value (2 . 73] (see Figure 3. Further progress is likely to require a heavy use of computational fluid dynamics. No reactions occur in crystalline regions.

for linear polycondensations) because of the radial profile of Mn in the diffusioncontrolled regime. An unavoidable complication is thus the description of the build-up of the crystalline phase. (47). Phase separation in solid-state polycondensation. values of 1. effective diffusion coefficients DYie (for fluxes with respect to the total geometric area) are decreased relative to the values in the melt DYi because of the obstruction due to the crystalline phase at a volume fraction fcr and because of the tortuosity factor tD (which depends on the structure of the solid. 3. the relationship is given in Eq.8. B are the end groups. The rate of crystallization is often described by the Avrami equation [Eq.2 Mass Transfer Issues in Polycondensations Fig. Mallon and Ray [74] have put forward in- 81 . which affects mass transfer and chemical reactions by increasing functional group concentrations in the amorphous phase. In the same way as in heterogeneous catalysis. W is volatile by-product. wcr ¼ 1  expðkcr t ncr Þ ð48Þ The exponent ncr is a function of nucleation and growth type. DYie ¼ DYi 1  fcr tD ð47Þ Notice that volume and mass fractions wcr of the crystalline phase are different because of the slight difference in density with respect to the amorphous phase.3. A.5 to 3 being common). (48)]. which is not constant for the entire course of crystallization.

6 in a moving bed reactor. and the other monomer. Either the neutral form of AXA is in an appreciable amount (in the case of amines). Mallon and Ray have published a brief discussion of idealized models of these reactors [75]. depending on economic details. 3. Industrial-scale SSP is carried out in moving packed bed. considering its complex geometry and its start-up and shutdown operation [76].3 Interfacial Polycondensation Typical chemical systems are fast reactions between two difunctional monomers. in order to use the same kinetic rate laws [Eqs.2. Here we do not follow the notation in Ref. rather. with low water solubility (acid chloride. (27) has to be modified in order to take into account the variable reaction volume due to polymer crystallization. (49)] as in the melt. A model for SSP of nylon-6. or a phase transfer catalyst is needed (as in polycarbonate synthesis). we use concentrations and rates of reaction per unit volume of amorphous phase instead of concentrations per unit volume of particle ½A i p ¼ ½A i /ð1  fcr Þ. The microscopic mass balance of polymer functional groups and volatile components given in Eqs. The first monomer (diamine. bisphenolate) is dissolved in a water solution (in alkaline media in both cases). 74. fluidized bed. and so on.   q½ð1  fcr Þ½Yi  1  fcr ¼ ‘ DYi ‘½Yi  þ ð1  fcr ÞRYi qt tD ð49Þ q½ð1  fcr Þ½A i  ¼ ð1  fcr ÞRA i qt Examples of the use of this approach with PET and nylon-6. The chain extension of water dispersions of isocyanates with water-dissolved amines. Fluidized beds have a serious drawback because of the high consumption of gas needed to keep the bed in a fluidized state. AXA þ BYB. can be found in Ref. Another common feature among these chemical systems is the presence of a parasite reaction consuming end groups B by reaction with water. and residence time distribution is unfavorable to high conversions. 74. Stirred beds in series are a possible solution. in order to make polyurea dispersions.6. including a successful comparison with available experimental data. shares some similarities with the former (amine þ acid chloride) systems. since ionized forms will not dissolve in the organic phase. is usually dissolved in an organic solvent.82 3 Polycondensation stead of Avrami equation an empirical rate law in terms of residual amorphous phase volume fraction. A decrease in the pH is often used to quench interfacial polyamidation. phosgene). can serve as a guide for dealing with more complex real-life situations. . and stirred bed reactors.

Karode et al. the organic phase is continuous in this latter case. the first attempt at predicting molecular weight distributions for more typical interfacial polycondensation systems is due to Karoda. the adjective ‘‘interfacial’’ is thus rather misleading. Also with the exception of polycarbonates. Furthermore.9). Kulkarni et al. 90]. as they are completely soluble in the methylene chloride solvent chosen for their production. the diffusion coefficient of AXA in organic solvent þ BYB. So. Models have for a long time concentrated on describing the velocity of consumption of water-soluble monomer and consequent rate of film growth [83–87]. This work will be the basis of the analysis next presented in this section. the rate of movement of the interface between the organic phase and the precipitated polymer film is considered to be slow. such as membranes [80–82] and microcapsules [83–87]. These studies show that the reaction occurs in a layer close to the interface. Instead of solving microscopic mass balances for the concentration profiles. interfacial polycondensation is mostly used in the production of specialty products. assuming a molecular weight of up to a few hundreds. so that a pseudo-steady approximation for the diffusion of AXA through the polymer film and for diffusion of BYB inside the organic phase should be valid. 78 and 79. In most cases (namely polyamides and polyureas). 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 ½Bb ¼ 1 kmol m3 . (50). the characteristic reaction time for consumption of monomer AXA is of the order of 104 to 102 s. and precipitates as soon as it forms.2 Mass Transfer Issues in Polycondensations Addition of a monofunctional chain stopper to the organic phase is advisable in order to control the final M n . the polymer is insoluble in monomer BYB or in its solvent. [89. 83 . 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. which is a rather exceptional situation for interfacial polycondensations.3. Also. polymerization occurs in a thin shell beneath the film of precipitated polymer. [89. often yielding a shell through which AXA has to diffuse. Although a possible framework for describing the simpler case of polycarbonate formation has been presented by Mills [88]. Mass balances of monomers in the reaction zone and in bulk aqueous and organic phases resulting from these assumptions are given in Eqs. 90] use average concentrations in the reaction zone and consider its thickness LR constant (see Figure 3. based on experimental data by Johnson [91]. should be of the order of 1010 to 1011 m 2 s1 . Early important contributions on interfacial polycondensations are described by Morgan [77] as well as in Refs. Polycarbonates are an exception. and this yields a characteristic width of reaction zone LR ¼ 108 to 107 m. Reaction is very fast and mass transfer resistance is an important factor. on the organic side. In the absence of polymer.

 Hi is the ratio of monomer concentration in the polymer film to concentration in the organic phase. with the help of a mass transfer coefficient kf BYB (which can be obtained by penetration theory).9. aq DAXA dt Lp Vorg d½BYBblk ¼ av.  Vaq and Vorg are the volumes of aqueous and organic phases and av. org are their interfacial areas per unit volume (trivially related). LR d½AXA He ½AXAblk  Hi ½AXA ¼ LR RAXA þ DAXA dt Lp LR d½BYB ¼ LR RBYB þ kf BYB ð½BYBblk  ½BYBÞ dt ð50Þ d½AXAblk He ½AXAblk  Hi ½AXA Vaq ¼ av. Bulk LR x Bulk organic phase Model for interfacial polycondensation. aq . Introduc- . No mass transfer resistance is assumed to exist outside the polymer film (although it can be easily included). av. org kf BYB ð½BYBblk  ½BYBÞ dt There are two partition coefficients He and Hi for monomer AXA: He is the ratio of bulk concentration in the aqueous phase ½AXAblk to concentration in the outer interface of polymer film (thickness L p ). but it is considered inside the organic phase. 3.84 3 Polycondensation [AXA]blk [BYB]blk [BYB]blk He [AXA]blk [AXA] [BYB] Hi [AXA] [BYB] LP Swollen aqueous polymer phase film Reaction zone Fig.

3 Polycondensation Processes in Detail 3. Molecular weight depends on the competition between reaction and precipitation of polymer: a more powerful solvent should lead to higher molecular weight. remarked upon by P. this approach has given an important new insight on these processes. 3. their mass balances can be written as Eq. J ¼ A. (51). high molecular weight (M n between 15 000 and 100 000). W.3. taken as independent of molecular weight for n > 1) [93].1 Polyesters Structure and Production Processes Two kinds of polyesters will be discussed in this section: 3.1. The earlier paper by Karode et al. n (nil for n ¼ 1.4).3. [92] with a phenomenological rate of nucleation k nuc. it also tries to fit the diffusion coefficient of monomer in the polymer film DAXA .4. In spite of its limitations in predictive power (a natural consequence of the complexity of the phenomena involved). IJ d½Pn  ¼ RPnIJ  k nuc. as it postulates a constant width of the reaction zone. 85 . this model needs the rate of nucleation k nuc .3. used as plastics and fibers. it has also to fit the kinetic parameters. could at last be explained by this model – 40 years later. nucleation giving better crystallinity. The ‘‘saturation’’ concentrations of polymer species are taken as the values of their concentrations in the lower branch of the spinodal curve for the liquid–liquid equilibrium with organic solvent. [89] considered only spinodal decomposition. Morgan. crystalline. B. the most important being poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT). considered as an adjustable parameter. Besides thermodynamic data on the liquid–liquid equilibria of polymer/solvent and hydrophilic monomer polymer/solvent. C dt ð51Þ Polymer precipitation is taken into account through the model of Kamide et al.3 Polycondensation Processes in Detail ing the rates of reaction of polymer species (see Section 3. The existence of a sharp maximum of average molecular weight as a function of the concentration of monomer in the organic phase when the two monomer fluxes toward the reaction zone are balanced. Film thickness is predicted through the overall mass balance of precipitated polymer.1  Linear. A coherent film 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 permeation properties should depend on the mode of phase separation. n ð½PnIJ   ½PnIJ sat Þ I. and.

it is first-order with respect to hydroxyls and. involving mixed anhydrides [94]. isophthalic acid. In spite of being the first reaction ever studied [95]. (52) to the whole range of concentrations of functional . and generic nonidealities will introduce changes in the apparent values of the kinetic constants in Eq. Acid-catalyzed Esterification and Alcoholysis The two main reactions in these processes are esterification and alcoholysis. In their extensive review.86 3 Polycondensation  Unsaturated low molecular weight (Mn between 1000 and 10 000). In a few special cases. namely phthalic and maleic anhydrides. which share similar mechanisms. Acidolysis reactions have a different mechanism. or thermosetting materials by themselves (alkyd resins). and a great variety of multifunctional alcohols. Esterification also occurs in high-temperature alcoholysis of aromatic esters. 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. Esterification was shown to be acid-catalyzed. natural fatty acids or triglycerides. as carboxyl end groups are formed by side reactions. 3. (52). with respect to carboxyls. Fradet and Mare´chal [97] have found that the overall order of esterification in the chemical literature is claimed to vary from zero to six! It is nevertheless useful to have some relationship.2 R COOH ¼ kscat ½OH½COOH 2 ðno foreign acidÞ R COOH ¼ kfcat ½OH½COOH½Cat-H ðstrong foreign acid Cat-HÞ ð52Þ However. This stage is slightly exothermal and care is needed to avoid sudden boiling of the reacting mixture. these rate laws can only be observed at low concentrations of hydroxyl and carboxyl groups. but proposal of other kinetics has continued. Experimental verification of these rate laws is more delicate than it seems at first sight (the effect of reverse hydrolysis reaction must be adequately taken into account or eliminated by the experimental set-up) and has been repeated by Hamann et al. otherwise a higher dielectric constant. even empirical. They are prepared from several monomers.1. The basic kinetic model for polyesterification was established by Flory and is summarized in his classic book [5].3. and should also be considered in the kinetic modeling of these processes. its order is either one in the presence of foreign strong protic acids. (52)]. they may be saturated and/or linear for use as macromonomers in the production of polyurethanes or other polymers. with a hypothetical tetrahedral intermediate. or two in their absence [Eq. Kinetic parameters of this reaction (apart from selectivities with respect to hydroxyls) are usually not needed. [96]. esterification has been under investigation ever since. and much knowledge has accumulated. Their rate is comparable to the esterification reactions only above 250 C. even if some points are still less clear. association through hydrogen bonds. Reactions between anhydrides and alcohols are much faster than carboxyl þ alcohol reaction. that could extend the validity of Eq. used as macromonomers for synthesis of thermosets (polyester resins). adipic acid. often branched.

Ge.3  Metals of groups II–III (such as Zn.3. both for esterification and alcoholysis. Metals in metallic complexes can catalyze esterification and alcoholysis through two distinct mechanisms [117]: 3. metallic salts are currently used as catalysts. such as lithium hydroxide. complex the oxygen in carbonyl esters preferentially. because of the low solubility of the diacid). Even volatile catalysts such as methanesulfonic acid are avoided. coordinate with the acylic oxygen of esters. 99]. (53) the empirical parameter a is a function of the initial stoichiometric ratio r.and cross-catalysis by two carboxyl groups.  Metals of groups III–VI (namely Ti. [100] and Zetterlund et al. can also be used. [101] have also presented interesting experimental data on the simultaneous self. Catalysis by Metallic Compounds Self-catalyzed esterification is often too slow to be of practical use. the total rate reaction 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. 106] and Chung [107]. In their modeling of unsaturated polyester resin formation. Ce.3. (53) where p is carboxyl conversion) has been proposed by Chen and Wu [98. Bi). It was theoretically linked to the dependence of the dissociation equilibrium constant of the carboxylic acid on the dielectric constant of the medium and to the dependence of the latter on the carboxylic acid concentration through conversion p. Pb). they show there is an anti-synergistic effect: that is.3 Polycondensation Processes in Detail groups. Strong bases. but for alcoholysis only (as in polycarbonate formation). and such a relationship (Eq. Beigzadeh et al. Sb. and strong protic acids are not advisable. who found volcano-shaped relationships with different optima of activity of the several metals in terms of metal electronegativity according to Tanaka [108] for the glycolysis of dimethyl terephthalate 87 . [102] or Lehtonen et al. A good fit of experimental data has been obtained with the parameter a varying in the range 0.2 to 1. especially because hydroxyl-terminated polymers are either sought or are a consequence of the process (aromatic polyesterifications are carried out with a large excess of hydroxyls at the beginning of the process. Therefore.2– propanediol. Mn.2 both for the self-catalyzed and the foreign acid-catalyzed esterifications of adipic acid with different diols. dialkyltin oxides R2 SnO and carboxylates such as dibutyltin dilaurate. [103]. usually introduced as carboxylates.1. namely those formed by the addition of maleic and phthalic anhydride to 1. usually introduced as alkoxides. as they would catalyze polymer hydrolysis if allowed to remain with the polymer. Zetterlund et al. [101] have also found the Chen–Wu relationship more useful than the rather cumbersome empirical models of Paatero et al. Their activity with respect to esterification and alcoholysis has been compared by Habib and Ma´lek [105. k ¼ kA expðapÞ ð53Þ In Eq.

and other associations. 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. the ratio kEG /kHE much depends on the catalyst (it may vary from 1 to 5) and even on the catalyst concentration. but the order with respect to the catalyst becomes zero at catalyst concentrations over a few millimoles per gram (no power rate law [114]). and other aromatic and aliphatic esters is now becoming better understood. kEG HOCH2 CH2 OH þ XCOOCH3 !  XCOOCH2 CH2 OH þ CH3 OH kEG =KEG kHE ð54Þ ! XCOOCH2 CH2 OH þ XCOOCH3    XCOOCH2 CH2 OOCX þ CH3 OH kHE =KHE Besnoin and Choi [112] were the first to actually use experimentally measured oligomer concentrations to validate this kinetic scheme for Zn catalyst. BHET. A key step was to recognize that in systems such as DMT þ ethylene glycol (EG) there are two reversible alcoholysis reactions. It is noteworthy that. It is also active at surprisingly low concentrations [117]. trimers. which cannot be explained unless polynuclear complexes participate in the reaction. even at temperatures below ambient. Alcoholysis of DMT.3-propanediol. because it is little inhibited by carboxyls and hydroxyls (which poison Sb) and also efficiently catalyzes esterification. These complexes exchange alkoxide groups very rapidly. There are also studies for DMT þ 1. as was soon confirmed and perfected by others [113–117]. the reactivity of hydroxyl groups in monomer and in hydroxypropyl chain ends is the same [118]. There are striking differences [109. These reactions are first order with respect to the esters and hydroxyls.88 3 Polycondensation (DMT) and for the polycondensation of bis(2-hydroxyethyl) terephthalate (BHET). 110] between the two groups of metals as regards sensitivity to inhibition by carboxyls (which poison the first group) or by hydroxyls (which poison the second group).4-butanediol with Ti and divalent metal catalysts. Moreover. Mixtures of divalent metal catalysts can have considerable synergistic effects [117]. Titanium has the best balance of properties. the other in the attack of the hydroxyethyl ester groups which produces oligomers detected by HPLC [Eq. toxicity (a problem for Sb) and price (expensive Ge will nevertheless yield a white polymer). and are more complicated than for acidcatalyzed reactions. one consisting in the attack of methyl esters either by EG or the hydroxyethyl end groups. The choice of catalyst also depends on secondary reactions (Ti causes yellowing).6-naphthalenedicarboxylate þ 1. for which an order of one with respect to Ti and the hydroxyl and ester . A much more careful analysis [117] has considered the catalyst concentrations and the differences between the catalyzed reactions. Kinetic models have to take into account both the existence of these polynuclear complexes and the poisoning phenomena. (54)]. The metal responsible for the catalysis is usually involved in several complexes. in the similar system dimethyl 2.

Side Reactions in Aromatic Polyester Production The important side products formed in nonthermooxidative secondary reactions in PET formation are acetaldehyde. is detectable by its flavor in drink bottles. Dialkyltin catalysts (such as dibutyltin dilaurate) have catalytic properties for esterification and alcoholysis similar to Ti and Zr [123]. together with carboxyl end groups. On the other hand. DEG units decrease the melting point. vinyl end groups. O C 89 . The SnaC bond is fairly stable. even at parts-per-million level. OH C O CH O + CH2 Vinyl end group formation from PET. probably due to formation of insoluble products.3 Polycondensation Processes in Detail groups has been reported [119]. Nowadays these catalysts are often used in alkyd resin production. the influence of catalysts and stabilizers) cannot be found in the open literature. Knowledge of this chemistry has obvious economic advantages. and diethylene glycol (DEG) units. Too much water will lead to a drop in activity [110]. The analysis of rate data is more difficult because of the relatively high importance of the secondary reaction leading to THF formation (see below). These structures are more active than the monomeric titanate [120].3.1): 3. it is possible to prepare catalysts that are quite insensitive to deactivation by vestiges of humidity [124]. Carboxyl end groups promote hydrolytic and thermal instability. Vinyl esters and acetaldehyde lead to chromophoric products. hydroxyl. and many details (for example.3. Acetaldehyde. these side reactions lead to a decrease in molecular weight. and Ti (at a concentration of a few parts per million) [121]. Models for Ti-catalyzed esterification are still more complex. crystallinity and thermal stability. thanks to the added flexibility provided by the organic group and the possibility of oligomerization. Side reactions can be minimized to a certain extent by choice of operating conditions and catalysis.1. R 0 O)aTiOa structures (unless the hydroxyl excess is large). No simple first-order rate law with respect to hydroxyls and carboxyls was found in that research. but there is a slight inhibition effect by the ester groups. Additionally.1. The increase in activity brought about by vestiges of water has also been observed both for Ti and Zr (this latter is even more active) in the model reaction of octadecanoic acid þ octadecanol [122]. Thermal scission of ethylene diester groups is a likely source of carboxyl and vinyl end groups [125] (Scheme 3. Order one was found with respect to acid. but the upper acceptable temperature limit is around 220 C. which is particularly undesirable for product use in markets such as tire cord and soft drink bottles. Titanates are hydrolyzed by water and form oligomeric a(RO.4 O C O O H C CH O CH2 Scheme 3.

the other important side reaction is Ordelt reaction [131–133] (see Scheme 3. The presence of a hydroxyl ester group is indispensable. The analogous intramolecular etherification is the source of side product dioxane [125] (see Scheme 3.4-butanediol disadvantageous. Further alcoholysis of vinyl esters yields acetaldehyde [Eq. C CH2 O O CH2 + H O + CH2 CH2 OX O C CH2 O CH2 CH2 O CH2 OX Formation of DEG moieties in PET.90 3 Polycondensation This is a first-order reaction.5 . the formation of 1-butenyl end groups (Scheme 3. making production of PBT by direct esterification of terephthalic acid and 1. 3. Both reactions are reversible and acid-catalyzed. Side Reactions in the Formation of Unsaturated Polyesters A recent review on the chemistry of unsaturated polyesters has been published by Malik et al. Poly(butylene terephthalate) is also subject to analogous side reactions [128].5). with no effect of catalysts or additives.3).3. This latter reaction is not affected by the metallic catalyst.4) followed by splitting-off of 1. as it can be shown experimentally that DEG forms in negligible amounts if ethylene glycol is heated alone in the absence of acid catalysts [126].6) which increases branching and consumes double bonds. (a)]. [129]. Besides cis–trans isomerization [130]. O C OCH2CH2 O OH O + C OH CH2 CH2 O O CH2 CH2 CH2CH2 Scheme 3. but is catalyzed by the carboxyl end groups.3.2. O C O O C OH Scheme 3.3-butadiene or tetrahydrofuran (Scheme 3. Reimschuessel [127] has suggested the attack of ethylene glycol or a hydroxyethyl end group as a possible source of the DEG moieties (see Scheme 3.2). XCOOCHbCH2 þ HOCH2 CH2 OOCY ! XCOOCH2 CH2 OOCY þ CH3 CHO ðaÞ DEG units are observed to form mainly in the first stages of the process.1. Dioxane formation in PET.

6 91 . CH2 O H2C CH CH2 + HO O C O C Vinyl end group formation from PBT. Earlier models for continuous processes based on DMT [134. their qualitative conclusions should still hold. CH2 CH2 CH2 CH2 O THF splitting-off from PBT.3.4. HC CH R OH + COOR'' R'OOC Scheme 3. They show it is possible to optimize conversion and minimize formation of side products.3 Polycondensation Processes in Detail O H CH2 CH2 C O CH CH2 C O CH2 O OH + C O H2C CH CH CH2 Scheme 3. should be described by a similar approach. Yamada et al.1. O C O Scheme 3.5. A brief discussion of their main assumptions and predictive capacities follows. Several models have been developed. only the specific aspects of the initial process stages still needs to be covered. for which no published process models have been found. on process performance. 135] study the influence of variables. reactor temperatures.6. Modeling of Processes of Aromatic Polyester Production Continuous processes are currently used in the manufacture of PET. PBT production. the first reactor in the train (‘‘esterification’’ reactor) is operated at a higher pressure and 3. and average residence times for CSTRs in series connected with distillation columns. Even if kinetics and physical equilibria are now much better known. As TPA has a low solubility because of its high melting point. OH + C O CH2 CH2 CH2 CH2 HO RO HC CH2 R'OOC COOR'' Ordelt reaction. [137] have presented models of the direct esterification process of terephthalic acid (TPA) with ethylene glycol (Figure 3. Since polycondensation in solid-state and in film-forming devices has been analyzed previously. such as the initial stoichiometric ratio.10). [136] and more recently Kang et al.3. with the aim of contributing to a better design and operation.

Polyester resins should ideally be produced with a certain predefined viscosity in their solution in acrylic/vinyl monomers and with a known. which is not a minor task in view of the large number of parameters needed. and the amounts of each one should be known. no actual plant data to validate these conclusions. is achieved by decreasing residence time in the ‘‘finishing’’ wiped-film reactor. no thermodynamic model has been used for predicting the solubility of TPA. by adding MgO) in order to thicken the solution. temperatures. and a few recent studies have appeared in this area [101. Minimizing vinyl ester formation. and pressures. reproducible. Most of the DEG units are shown to be produced essentially in the esterification and pre-polycondensation reactors. Also. 3. but for now they only aim at predicting the concentrations of functional groups. Trans double bonds are much more reactive in free-radical polymerization.3. Carboxyl end groups are in some processes further converted to metal carboxylates (typically.92 3 Polycondensation Fig. only an interpolation between values in pure ethylene glycol and different oligomers. There are. but increasing the residence time in the solid-state polymerization reactor. it is worth developing models for these processes. with very little change afterwards. so it is also important to control their concentration. The calculations show it is also possible to optimize conversion and minimize side reactions by a choice of average reaction times. distribution of double bonds. 3. Simple model for WFR used for the direct esterification process of terephthalic acid (TPA) with ethylene glycol. 104]. thus improving molecular weight and product quality. which is operated at a lower temperature under a stream of inert gas. An integrated view of recent processes for PET has presented by Yao and Ray [138]. although without taking into account the influence of alcoholysis and acidolysis on monomer concentrations. temperature than the ‘‘pre-polycondensation’’ reactor in order to counterbalance this lack of solubility.10.7 . Modeling of Processes for Unsaturated Polyester Production Nava gives a brief description of the industrial processes [139].1. Modeling of the full process requires consideration of the losses of volatile monomers (lack of reliable vapor–liquid equilibria data is a problem). Therefore. however. and the aforementioned problems of taking into account the low solubility of isophthalic and terephthalic acids are also pending. The kinetic model uses a ‘‘fragment’’ approach similar to what was recommended in previous sections.

and side reactions of the double bonds in fatty acids. it is often necessary to look for initial amounts of monomers which satisfy stoichiometric constraints (such as mole ratio and fatty acid content).3 Polycondensation Processes in Detail Description of the branched structure of the resins is less problematic than in the case of alkyds. Vacuum and inert gas sparging is also used in different stages. These carbonates have low melting points and thermal resistance and are not commercially interesting as stand-alone thermoplastics. namely lack of data for liquid–vapor and liquid–solid equilibria and associated mass transfers.2 Polycarbonates General Introduction Polycarbonates are polyesters of carbonic acid formed by reaction of diols (aromatic.3. as specifications often require less than 1 mg g1 KOH acid value. The usual problems found in previously discussed polyesterifications. a nonnegligible amount of intramolecular reaction. so the molecules are almost comb-like and the approximations used by Yang and Pascault [140] should be reasonable. but the properties of the products seemed uninteresting.3. according. Therefore. will not lead to gelation. Catalysts (mostly alkyltin salts) are used to convert most of the carboxyl groups. Modeling of alkyd resin production is a rather formidable task because of the high number of distinguishable chemical groups. Thus the main routes to polycarbonates were established early. 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]. to fatty acid content. Low molecular 3. These predictions are not very accurate. The first preparations of polycarbonates were reported by Einhorn in 1898 [155]. connected to partial condensers in order to recover volatile glycols. by reaction of phosgene with resorcinol or hydroquinone in a pyridine solution. The same plant usually produces different varieties of resins. Industrial processes [141–143] use batch stirred reactors.1 93 . Around 1930 aliphatic polycarbonates were studied by Carothers and van Natta [157]. the branched structure of the polymer. but good data on intramolecular reactions and differences of reactivity of functional groups will be needed if better control of physico-chemical properties is sought. and meanwhile keep an acceptably high M n (for instance). aliphatic or a mixture of both) with a derivative of carbonic acid. are also present. Monomers may be added in several steps to overcome solubility problems.2. 3. Long reaction times are sometimes avoided through different techniques for eliminating residual carboxyls. New compositions are often sought in order to improve end use properties or to compensate for fluctuations of raw material prices. Bischoff and van Hedenstro¨m in 1902 [156] obtained the same aromatic polycarbonates via transesterification with diphenyl carbonate (DPC). because the conversion of double bonds by Ordelt reaction is in the range 10 to 20%. Azeotropic distillation with xylene (for instance) is often used. for instance.3.

Following the work of Whinfield and Dickson [158]. ONa + n COCl2 -2n NaCl O CH3 C CH3 O C O n Overall stoichiometry of bisphenol A polycarbonate formation.3. The original processes – phosgenation in pyridine solution and melt transesterification – were soon replaced by interfacial polycondensation with phosgene.94 3 Polycondensation weight. Interfacial Polycondensation In the interfacial process. It has thermal stability up to over 300 C as well as excellent mechanical. are widely used as a diol component for the synthesis of polyurethanes and polyurethane– urea elastomers. and birefringence were achieved with different (co)monomers [163. 164].8). Improvements of several polymer properties such as heat resistance. aliphatic polycarbonates with hydroxy end groups. who in 1941 succeeded in preparing high molecular weight. The synthesis proceeds in two steps: phosgenation of BPA forming oligomeric carbonates with phenolic and chloroformate end groups. melt flow.2-di(4hydroxyphenyl)propane] by Schnell at Bayer [159. inherent fire resistance. non–phosgene-based and environmentally more attractive transesterification process revived in the 1990s. and polycondensation of the oligomers (see Scheme 3.7. It still remains the predominant production process although interest in the simpler. high molecular weight polycarbonate derived from bisphenol A [BPA. For the phosgenation.2. or 2. however. and food compatibility. problems with the earlier melt carbonates. high melting polyesters. an aqueous alkaline BPA solution and an organic phase containing phosgene. 160] and shortly afterwards by Fox at General Electric [161]. the chemistry of polycarbonates was re-examined.5 million tons per year. However. which proceeds at low temperatures and allows the easy production of high molecular weight polymer. The overall reaction is shown in Scheme 3. BPA and phosgene react at the boundary of two immiscible liquids. BPA polycarbonate (BPA-PC) proved to be an outstanding engineering thermoplastic that differs from the other polyesters in that it is noncrystalline with a high glass transition temperature (about 150 C) and retains its high transparency and toughness after molding. could be overcome. and electrical properties. Approximately 12% is produced by transesterification and the percentage is expected to increase. BPA-PC remains the commercially most important polycarbonate. The presentation here focuses on the engineering aspects of BPA homopolymer production.7. This led to the preparation of a linear. Polycarbonate demand has enjoyed steady growth and total production capacity in 2003 was about 2. 3. BPA is first dissolved in an . optical. 164–171. in particular the poor resin color. Detailed reviews of the synthesis and application of polycarbonates are given in Refs.2 CH3 C CH3 n NaO Scheme 3.

. p-cumylphenol) is added as a chain terminator to control the molecular weight of the final polycarbonate. [173] and Kosky et al. including solventless precipitation.8.. At high BPA concentrations a fourth solid phase may be present [172]. Detailed mechanistic studies of the catalyst reaction were performed by Aquino et al. . spray drying. In the polycondensation step. 176] and its rate depends on mixing as well as on pH and the volume ratio of the organic and aqueous phases. Intensive mixing with dispersion and redispersion is required throughout the reaction stages.3. Several processes for devolatilization are in use. m m m O C ... The amines react with the chloroformate end groups to form intermediate quaternary acylium salts which then react with phenolate to form carbonate and OH ions. The following phenomena contribute to the reaction process: 95 . * . aqueous alkaline solution as sodium bisphenolate. * n Na 4 NaOH * . n * O + NaCl + NaCl Na + NaCl + Na2CO3 + H2O Formation of polycarbonate by interfacial polycondensation.. The final polycondensation stages are catalyzed by tertiary amines. p-tert-butylphenol.. hydrolyzing the chloroformate end groups. Reaction partners are now end groups (chloroformate and phenolic aOH. The reaction is started by dispersing the two phases. * . Phosgenation is generally mass transfer-limited [175.. The reactions can be carried out in batch in stirred tank reactors or continuously in series of CSTRs and tubular reactors. and phosgene is dissolved in a solvent of chlorinated hydrocarbons (such as dichloromethane and monochlorobenzene) which also dissolves polycarbonate. and vacuum extrusion in devolatilizing extruders. both rates still show the same dependencies due to the interfacial nature of the reaction... the brine phase is separated and the polymer solution washed to remove residual amine and base. * . Although the polycondensation reaction of end groups is slower. a monofunctional phenol (such as 3–5 mol% phenol.. [174]. see above) and reaction rates decrease. or to form a urethane in a side reaction [164]. Part of the phosgene is hydrolyzed with NaOH to NaCl and Na2 CO3 and an excess of phosgene (10–20 mol%) is required to compensate for hydrolysis and provide an excess of chloroformate end groups for the following reaction step.. m m m O C Cl + O C Cl + NaO O C Cl + Scheme 3... Numerous variations of the interfacial process have been published. Alternatively. falling-strand devolatilization.3 Polycondensation Processes in Detail * ... liquid–gas phosgene (boiling point 4 C) is fed into a slurry of BPA in the presence of an organic solvent. Reaction temperatures are between 20 and 50 C and the pH is kept between 9 and 13 by the addition of NaOH. steam precipitation. * . After the reaction is complete..

Intrinsic (kinetic) reaction rates. they show how mass transfer limitations can lead to a higher polydispersity or a higher oligomer content. so that the by-product phenol has to be removed for the reaction to proceed. Monofunctional phenols with better solubility in the organic phase show a better efficiency as chain terminators. Rates always depend on mixing. Both types of emulsions. drying. Formation of bisphenol A polycarbonate by transesterification. oil in water (o/w) as well as water in oil (w/o).3.9. the molecular weight distribution in interfacial synthesis is kinetically controlled and may be far from thermodynamic equilibrium. can be found. . however. The only by-product. The partition of phenols between the phases and its pH dependence [177]. The type of emulsion.1 hPa may have to be applied for the final stage. In two parametric studies Mills [179] and Munjal [180] have tried to model the full molecular weight distribution of polycarbonate. 3.96 3 Polycondensation      Dispersion of the two phases. Melt Transesterification The melt process is based on the transesterification of diphenylcarbonate (DPC) and BPA (see Scheme 3. Varying the ratio of mass transfer/kinetic rates. The process. Effective kinetic rate constants can be formulated as a function of energy dissipation or interfacial area. is removed and can be recycled to the production of DPC or BPA. With improved quality of the starting materials and improved high-viscosity reactors these temperatures no longer affect polycarbonate quality and most grades can now be produced via the melt process. The transesterification is a reversible reaction with an equilibrium constant close to unity. Silva and Kosky [178] studied the reaction of hydrolysis taking into account the different phases and the partitioning of BPA between them. The melt process requires no solvent and polycarbonate is produced directly without the need for cleaning. phenol.9).3 O n HO OH + n OCO O O OC + 2n OH n Scheme 3. Mass transfer to and across the boundaries. Due to the low reaction temperature and the use of chain terminator. Pressures below 0. and devolatilization.2. requires high temperatures (190–320 C) so that the polymer remains molten and the viscosity can still be handled.

and equilibrium concentration ½Yi   at the interface). Ji ¼ kfi a v ð½Yi   ½Yi   Þ ð55Þ Mass transfer coefficients may be obtained by fitting to process data. High surface renewal rates are achieved by small holes. Mass transfer and hence the speed with which phenol can be removed are reduced with increasing viscosity.3. (55). production capacity (reaction time). excess DPC has to be used at the beginning of the reaction. 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 [149–151]. Conversion is driven by the removal of phenol and the pressure is successively reduced while the temperature is increased. [152]. These may be wiped-film evaporators. Apart from surface renewal. with the mass transfer rates per unit volume Ji of component Yi . or on a simple relationship for the mass transfer of each volatile component Yi (Eq. For a semi-batch operation for the first stages. a high fraction of phenol end groups reduces the concentration of one reaction partner and hence reaction rates [146]. The relative DPC loss compared to phenol removal is quite high for these stages. and of the solubility of DPC and phenol in polycarbonate by Webb [153]. Simple reactors such as CSTRs. or phosphonium-salts) are mixed together with the DPC and BPA and the reaction is started at the lower temperature. Unfortunately. 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. in falling-strand evaporators the melt is simply pumped through small holes. This means that an optimal process is neither entirely mass-transfer nor kinetically controlled. optimal variations of pressure and temperature can be calculated based on the above relationships plus the assumption of phase equilibrium. The melt process depends on the reaction rates. mass transfer is de- 97 . single.3 Polycondensation Processes in Detail Small amounts of basic catalyst (< 0. Including DPC loss. 150]. reactors of the rotating disk type or falling-strand evaporators [145. the thermodynamic phase equilibrium. interface area per unit volume a v . Reactors are needed that provide a high rate of surface renewal. The effect of shear thinning films can also be achieved in rotating disk reactors with disks that contain holes. mass transfer coefficient of component i kfi . and unwanted side products in a cost function. the optimization leads to a balancing of mass transfer and reaction rate. Detailed mechanistic studies of the Li-catalyzed melt process have been published by Choi et al.or twin-screw extruders.01 mol% of alkyl-ammonium. tubular reactors or falling-film evaporators can be used for the first stages. The balancing of reaction versus mass transfer rate can similarly be applied for the last stages. and mass transfer between the phases. The liquid–gas equilibrium has to take into account at least two components: phenol and DPC. Therefore. Whereas the first three reactor types create surface actively. To avoid side reactions that impair product quality. A high fraction of phenol end groups compared to OH end groups is desirable for product quality. continuous process [154]. but also by shear thinning of the falling strands [59]. 149.

but no model exists for taking into account the group interactions. The chemistry of their formation is similar to that observed for the aforementioned crystalline linear polyamides.3 Polyamides Introduction Since their discovery by Carothers [181].3. low molecular weight. and these kinetics are now much better understood. Much more data are available on nylon-6 formation. It obviously changes the activity coefficients of functional groups. Because of the obvious identity in average chemical group composition of both polymers.6 reaction are due to Ogata [183. it should be possible to reconcile both kinetic laws [188]. The activity of water can be directly measured from knowledge of its vapor pressure. 3.3. An alternative is the determination of diffusion constants using molecular dynamics simulations [148].3. nylon-6.3. which does not present these problems. 3. Aliphatic. branched polyamides of dimer fatty acids with di. 191. Aromatic polyamides are specialty products [182]. and it has been claimed that a correlation based upon a Flory– Huggins model can predict it [190]. concentrations of hypothetical species having been used throughout that paper. 185–187. aliphatic polyamides such as nylon-6. 184]. or by hydrolytic polymerization of lactams. Degradation reactions of nylon-6. and data on nylon-6 are in the opposite situation. However.1 Kinetic Modeling The only published kinetic data on nylon-6. which are produced by solution or interfacial processes from acid chlorides and amines.12 system.3. Apparent equilibrium and kinetic constants in these systems are seen to depend on water concentration. and there is in general a great scarcity of information on the amide þ acid reaction. [189] lies in the empirical correlation 3. Measurement of diffusion coefficients is difficult because of the parallel reaction.3) complicate the interpretation of kinetic data at higher temperatures. McAuley et al. The crux of the treatment by Schaffer et al.6 data have been obtained at high water concentrations and relatively low temperatures. Some interesting ideas can be found in Ref.98 3 Polycondensation termined by diffusion. such as in Refs.3. used for high-performance fibers and composites. have some interest as engineering plastics. but no thermodynamic model has ever been used to completely describe the mixture.and triethylenediamine are among the most widely used curing agents for epoxide resins. Schaffer.2 . [189] have recently obtained experimental data on the nylon-6. but no actual thermodynamic model has been developed.6 and nylon-6 are important textile fibers and plastics. Similar polyamides produced by melt reaction of aliphatic diacids þ diamines.3. and will also be discussed in this section.6 through adipic acid chain ends (see Section 3.

(57)]. a dependence on [COOH] might be added in Eq. (57) is rewritten as Eq. and only the ratio g A ¼ mA /bA can actually be found from experimental data.or second-order rate law: R CONH R CONH      Ec 1 1 ½H2 O½CONH  ¼ kc0 exp  ½COOH ½NH2 ½COOH  Ka R T T0     Ec 1 1 ½H2 O½CONH  ½NH2 ½COOH  ð60Þ ¼ ku0 exp  Ka R T T0 99 . K a0 . However.3. this is not needed. K a ¼ K 0 gH2 O ðbA þ mA ½H2 OÞ ð57Þ It is seen that parameter bA is absorbed by the unknown thermodynamic constant. activity coefficients are based on mole fractions. as no effect of the mole ratio [COOH]/[NH2 ] on the apparent equilibrium constant has ever been detected. Eq. and g A ) have been fitted simultaneously with a mass transfer time constant for water k m. (56). (58).3 Polycondensation Processes in Detail expressed by Eq.6Þ ¼ exp 6:390  T ð58Þ Choosing a reference temperature T0 ¼ 549 K. and activation energy Ec and pre-exponential factors kc0 or ku0 describing forward reaction through a third. The correlations found for the activity coefficient of water are given in Eqs. (56). such as [H2 O] and [COOH]. K a ¼ K a0 K a0    1 þ g A ½H2 O DH 1 1  exp  gH2 O /gH2 O ðT0 Þ R T T0   bA DH DS exp  ¼ þ RT0 R gH2 O ðT0 Þ ð59Þ Parameters describing equilibrium (DH. Insertion of the above relationship into the mass action law provides a relationship between apparent equilibrium constant K a and true thermodynamic constant K 0 [Eq. where bA and mA are assumed to be constant parameters. gCOOH gNH2 ¼ bA þ mA ½H2 O gCONH ð56Þ As the overall composition of the system may be described by two variables. (59).   3613 ðNylon 6.12Þ gH2 O ¼ exp 9:624  T gH2 O   2258 ðNylon 6. appropriate to their experimental set-up.

Their approximate correlation matrix can be found in the same reference. As in esterifications. Mallon and Ray [191] have suggested that its initial rate is determined by the presence of impurities. The reason might be a nonideality effect similar to the one observed in esterifications.6 3:19  104 24. which yields ku0 ¼ 2:64  10 7 mg mol1 h1 and has a similar sum of weighed squared residuals. Parameter Units Estimate 95% confidence interval DH K a0 gA Ec kc0 km kcal mol1 – g mmol1 kcal mol1 g 2 mmol2 h1 h1 1. The authors state the parameters thus obtained for nylon-6. but also in kinetic modeling. There are several studies concluding that the apparent order of reaction changes from two to three as conversion grows. whereas aminolysis has the much smaller activation energy of 13 kcal mol1 .2 G0:45  102 G7.1 2:03  102 22.42 G6. Equilibrium and rate parameters for nylon formation. Thus.12 should hold for the other aliphatic polyamides. acidolysis is slower and is explained by a mechanism involving the formation of intermediate anhydrides.12 relative to nylon-6. there is little change in parameters for the second-order model. The same authors have also remarked that the rate constant of addition of caprolactam to amine end groups is about what would be expected for an aminolysis reaction.3 G1. The rate of aminolysis was shown to be first order in carboxylic acid.6.5 in nylon-6. just correcting the equilibrium constant. which is lower by a factor of 0. Its activation energy is 27 kcal mol1 . It shows that parameters describing equilibrium are highly correlated with g A . and the pre-exponential factor is highly correlated with k m .3. which have not yet been reported at the time of writing.82 63. and experimental confirmation has not yet been possible [191]. Hydrolysis of caprolactam is autocatalytic. 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 3.2. Miller [192] has carried out an experimental study on aminolysis and acidolysis reactions using carefully dried model compounds. These results are valuable not only for dealing with block polymers. Further. but the only usable data concern the equilibrium concentrations.4 to 0.4 The optimum values of parameters for the third-order model are shown in Table 3.2. it is not yet possible to determine the reaction order without performing experiments with excess of diamine or diacid.100 3 Polycondensation Tab. It should also be possible to predict the concentrations of higher cyclic oligomers.3 .7 G0:71  104 G15.3. particularly with cyclic lactams: a narrow CLD will not occur because of the reorganization brought about by aminolysis.

3. and to get rid of it in the later stages.H2 O CH2 H2C C O k1 CH2 . A slow deamination reaction has also been shown to occur. XNHCO(CH2)4COOH k1 O NH Y O O C X NH k2 C O CH2 CH2 C k3 . Process Modeling Recent progress in kinetic and reactor modeling make it possible to assist the reactor design and process operations with unprecedented exactness. since the equilibrium constant of the former is much greater. 196]. and also to crosslinking.H2O Z Z + 2 NH3 Nonoxidative thermal degradation of nylon-6. either from carboxyl end groups or by intrachain reaction. as explained by the simplified mechanism in Scheme 3. The reason is the much reduced sensitivity of polyamides to by-product removal as compared to polyesters.3. Since the early 1970s. X N k4 + 2 NH2 Z Y + NH2 XNH CH2 CH2 X . Nylon-6. with a decrease in molecular weight. which consists in adding just as much water as is needed to start polymerization. but the gain was minor compared to what happened with PET.11 [195.4 101 .CO2 N Scheme 3. There is an interesting optimization problem inherent to this process. also degrades in the absence of oxygen.3. 194]. Losses of CO2 and NH3 lead to an imbalance of end groups.10) [193. X X HO C N OH O C CH2 CH2 N X CH2 k2 H2C CH2 CH2 Scheme 3. many researchers have modeled nylon-6 processes [197]. to a much greater extent than nylon-6. Because of 3.6 process [138] looked for improvements based on expansion of the solid-state polymerization.3 Polycondensation Processes in Detail Scheme 3.CO 2 CH2 C H2C H2C CH2 CH2 CH2 Nonoxidative thermal degradation of nylon-6. A recent analysis of the nylon-6. as reviewed by Kumar and Gupta [198]. N O C . Cyclopentanone units are created. and it eventually gels. a nuisance for dyeing.

have lead to a simple model of the VK column.3. melamine. A simple and widely used reactor is the VK column (simplified continuous column). Under such conditions. An alternative is a hot-water extraction step. in order to reduce the average molecular weight and prevent precipitation of paraformaldehyde. essentially a vertical tube at atmospheric pressure [193. nearly all the formaldehyde is transformed into methanediol and higher oligomers (see Scheme 3. which usually contain some methanol.2 . The bottom one-third of the columns has a homogenizing function. solid polymer (paraformaldehyde). Extensive pilot-plant tests carried by Jacobs and Schweigman [199]. 199]. Amino Resins Reaction between a water solution of formaldehyde with urea. and more conveniently as 37% or 55% water solutions. The various equilibrium constants have been measured using NMR [202] and a model describing the vapor–liquid equilibrium in that system has been developed.3.3. 3. usually end-capped by methanol. 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. HOCH2OH (CH2O)x+1OH + H2O HOCH2OCH3 (CH2O)x+1OCH3 + CH3OH Formaldehyde/water/methanol equilibria.1 HCHO + H2O (CH2O)xOH + HOCH2OH HCHO + CH3OH (CH2O)xOH+ HOCH2OCH3 Scheme 3. 3. It may be sold as a low molecular weight.4 Polymerizations with Formaldehyde: Amino Resins (Urea and Melamine) and Phenolics Formaldehyde Solutions in Water Formaldehyde is a gas at room temperature. These reactions are not very fast at room temperature: characteristic reaction times are of the order of minutes. and further data from industrial plant.102 3 Polycondensation the autocatalytic nature of the caprolactam hydrolysis. not only physical but also chemical. consisting in one or two CSTRs in series. Other designs [200] have improved performance by preventing water evaporation at the top of the column through the use of above-atmospheric pressure.4.12.4. back-mixing increases conversion. and similar molecules (such as acrylamide) leads to hydroxymethylation of the nitrogens 3. through the aminolysis reaction [201]. stirred by the boiling action of water leaving the reactor mixture in the top zone. followed by a plug-flow reactor.12). which will also extract higher cyclic oligomers.

is still a major market. Formation of melamine resins is much less reversible and therefore food contact with them is allowed.14.13. this matter needs to be solved. Laminated sheets (tables and counter tops) are a major application for melamine resins. Both de Jong and de Jonge. are important markets discussed in Ref. Coatings. Kumar and Sood [208] have proposed an FSSE model for the early stage of this polycondensation.. have considered that hydrolysis reactions are unimolecular. 203. the rest being nearly all produced from melamine (1). Melamine. Available experimental data could not decide for any of the alternatives. and UF oligomers by de Jong and de Jonge [204–206]. leather tanning and foundry binders. (c)]. since the water concentration was always the same. for which methanol. formaldehyde. Kumar and Sood [208] have considered it could be bimolecular. taking advantage of their extreme hardness and heat resistance. A major problem with the use of UF resins is their formaldehyde emission due to hydrolysis. it is more expensive. (b)] and further condensations produce the so-called amino resins [Eq. and Price et al. where their five urea monads U0 . which stay in the outer decorative surface. XaNH2 þ HCHO ! XaNHaCH2 OH ðbÞ XaNHaCH2 OH þ YaNH2 ! XaNHaCH2 Y þ H2 O ðcÞ NH2 N H2N N N NH2 1 Scheme 3. of which 80% are based on urea [203].3 Polycondensation Processes in Detail [Eq. . U4 have been kept but three formaldehyde monads have been used instead of two. . their first big application. because higher initial concentrations of formalde- 103 . Melamine resins are therefore chosen when one can get an appreciable benefit from their better hydrolytic or thermal resistance. textile finishing.3. Urea–formaldehyde (UF) resins are mainly used as adhesives for wood. Molding compounds. Since melamine is made from urea and ammonia. Besides earlier classic data on the kinetics of reactions between urea. which seems to be reasonable. A modified version of that model introduces the groups presented in Scheme 3.or butanol-etherified resins are usually employed. Formation of tetrasubstituted urea is known to be negligible. [207] at higher temperatures in a sealed reactor are of immediate use to establish a kinetic model of the chemical system. only experiments by Price et al. paper additives.

7. 30 and 40 C. 9.2. Chemical transformations according to this new model are shown in Scheme 3. 10) at temperatures 20. such as Ref. 209.14. Although only at low temperatures. for 15 values reported by Landqvist with different buffers (pH 6.104 3 Polycondensation U0 = O C H2N O C U3= H2N F0 = H O C NH2 U1 = U4 = N H2N O C U2 = NH- -HN O C NH- O C -HN N F2 = -CH2- F1 = -CH2OH H Scheme 3.68. Since the only information in the experimental data of Price et al. U 0 + F0 k1 → ←  k U 1 + F1 + W k6 → U 0 + F1 h2 k U 1 + F0 2 → U + F1 + W ←  2 k k U 1 + F1 h1 7 → U + F2 + W ←   2 k h2 k U 1 + F0 5 → ←  k k U 3 + F1 + W U 1 + F1 h1 U 2 + F0 k4 → ←  k → h1 Scheme 3. A possible simplification consists in distinguishing only rate constants of forward reactions according to the number of hydrogens involved. and kh1 (this one measured from the rate of formation/hydrolysis of both monomethylol urea and dimethylolurea) are nevertheless available from other sources. Monads in the FSSE model of urea/formaldehyde polycondensation. it is not possible to estimate rate constants k6 to k10 from them. k3 . . hyde are often used nowadays. k6 ¼ 2k7 ¼ 4k10 and k8 ¼ k9 . reducing the number of unknown parameters. [207] is formaldehyde concentration versus time.15.and dimethylolurea: the rate constants per mole of the chemical substances should be double for dimethylolurea.15. The value of this ratio is 1.42. standard deviation 0. and therefore k1 ¼ 2k2 ¼ 4k5 and k3 ¼ k4 . ←   k U 3 + F2 + W k U 4 + F1 + W U 2 + F1 h1 ←  k 8 → h2 9 → U + F2 + W ←   4 k h2 k5 U 3 + F0 U 1 + F2 + W ←   k h1 k10 U 4 + F1 + W U 3 + F1 → ←   k U 4 + F2 + W h2 Kinetic scheme of FSSE model of urea/formaldehyde polycondensation. rate constants k1 . A crucial check of the FSSE hypothesis is the equality of the first-order hydrolysis constants of methylol groups in mono.

or intermolecular ether bonds are destroyed with liberation of formaldehyde at acid pH. the rate constants for the reaction of methylenediurea with formaldehyde or monomethylolurea are identical.16. and SSSEs should be needed for fully describing this chemistry. For these reactions. we will keep using the above model in the discussion. respectively. O C N N CH2 N N CH2 O C NH-CH2OCH2N O C O N CH2 O C N + H2O + H2O 2 Reactions at alkaline pH in urea/formaldehyde polycondensation. but unfortunately it seems there might be no such thing as a single ‘‘aCH2 OH’’ group. In the same work.9 according to de Jong and de Jonge. 211]. NMR shows that these intra. and there is a decrease of about 3 in the forward rate constants of the successive substitutions.3. For simplicity. At high temperatures and alkaline pH. 218. So. (61) [204]. though. Rate constants are known to depend on pH (although not much between pH 4 and 9). Interestingly. 2 HOCH2N N HOCH2 O C O H Scheme 3. reaction between methylols was found negligible (the temperature was at most 50 C).and dimethylolurea [206].16). there seems to be enough evidence to take FSSEs into account for urea. ki ¼ ki0 þ kiOH bOH c þ kiH bHþ c ð61Þ Rate constants k6 to k10 in this scheme can be estimated from data of reactions in acid media between urea. to those observed for urea þ formaldehyde and urea þ monomethylolurea [210. the terms ki0 . respectively. so these constants should be written as in Eq. 105 . mono. methylol groups form methylol ether bridges and uron rings 2 (Scheme 3. the reactions are very slow at pH > 4. kiOH can be neglected. according to both research studies. The equilibrium constants of the first and second hydroxymethylations of urea are. 990 and 253 at 35 C. there is catalysis by OH and Hþ . the activation energy of the hydrolysis is the same (20 kcal mol1 ). The preparation and possible industrial uses of uron UF resins may be found in Ref. More recent work has concentrated on analysis supported by quantitative 13 C NMR [212–216] and size exclusion chromatography [217] has completed this view of the chemistry.3 Polycondensation Processes in Detail However. that ratio is 6.

The functionality of melamine is six. Melamine resins have a similar chemistry. Gelation may be physical. which lead possibly to ladder structures. who succeeded in providing evidence not only of hydroxymethylation. Amino resins are nearly always made in batch processes. also considering reaction reversibility. while keeping the properties of products (such as wood panels) at an acceptable level. because of the much higher temperatures than in resin synthesis.3. the reaction medium resembles a colloidal dispersion [219]. the main difference being the reduced importance of hydrolysis reactions. mass. Direct analysis of methylene ether bridges has also been performed by NMR [226]. Except at low conversions. in the case of wood panel manufacture). As with UF.  addition of urea to decrease the final stoichiometric ratio to 1 to 1. acid condensation at pH 4 to 5. consisting of thermostated reaction kettles connected to a condenser. [223]. Notice that it should be integrated with the modeling of the cure stage (a complex combination of heat.  The goal is to reduce formaldehyde emissions [222]. alkaline addition of formaldehyde. . Modeling of the process has increased its potential importance in this context. They are prepared using two stages. Cure is performed with ammonium chloride as catalyst.5. Methylene bridges are also formed only at acid pH. and equilibrium constants are 100 to 200. the process has also become more difficult to control. There is no experimental validation. and acid polycondensation. Its chemistry is not fully understood. and mechanical modeling.and base-catalyzed (sensitive to pH). because of the daunting complexity of the chemistry. before or instead of being chemical [220]. A simplified model (no reaction reversibility) of melamine–formaldehyde formation based on Tomita’s kinetic scheme [225] has been presented [227] and afterwards extended to reaction in a CSTR [228]. 225]. but the difficulties of putting it into practice are considerable. but it is noteworthy for the use of a program to calculate the CLD of a nonlinear reversible polycondensation in order to overcome the astronomical number of reaction possibilities in the rates of formation of individual oligomers. that should not be overlooked. formaldehyde addition is acid.106 3 Polycondensation Another question. which also acts as a formaldehyde scavenger. Since the formaldehyde/ urea molar ratio had to be decreased. is the incomplete solubility of the polymer in water. but also of the formation of methylene and methylene ether bridges using polarography. The initial stage of the melamine/formaldehyde reaction has been studied by Nastke et al. The current method of synthesis has three stages [221]:  synthesis of methylolated oligomers at pH 8 to 8. with a negative substitution effect of about 40% [224.

which have a different and much less branched structure than resols.  novolacs. Scheme 3. Mn. These catalysts complex phenol and methanediol and lead to formation of omethylolphenol in a first step.17).3. Phenolic resins are mainly used as wood adhesives. with a formaldehyde/phenol stoichiometric ratio between 0. Mg). laminates. The branching density is low because nonterminal rings are less reactive. This is caused by molecular coiling. which are highly branched. Novolacs can be made using either strong acid catalysts (sulfuric acid is preferred) or at pH 4 to 7 using carboxylates of divalent metals (such as Zn.18). H O M2+ OH CH2 OH OH OH .4. .. Novolacs prepared with acid catalysts have a more random structure.2 to 3.8.H2 O + OH Formation of ortho-directed methylene bridges.3. They are low molecular weight (500–5000) thermoplastics. abrasives. which is especially important in high ortho-novolacs. O CH2 H O H H O CH2 CH2 Hypothetical intramolecular hydrogen bonds in novolac resins. molded parts. low molecular weight (150–1500) polymers with a formaldehyde/phenol stoichiometric ratio between 1.17.18. 107 .M2+ CH2OH .. Nonterminal units are often assumed to stay CH2 O O H O H H CH2 Scheme 3.5 and 0.M2+ OH CH2 .3 Polycondensation Processes in Detail Phenolic Resins Two subclasses have to be distinguished [229]: 3. further crosslinked with hexamethylenetetramine. Phenol groups tend to associate through hydrogen bonds and change the molecular conformation (Scheme 3. and rigid foams. insulating varnishes. or more randomly distributed (in the case of Zn). Subsequent addition steps may also be orthodirected (Scheme 3.3  resols.H2 O . formed at alkaline pH. made at acid pH.

such as Ref. The most widely used epoxy resins are formed through the reaction between epichlorohydrin (ECH. a total of 19 can be distinguished [235. . will not be discussed in this section. such as amines. formaldehyde can be fed continuously in order to increase safety. and carboxylic acids. Reaction is exothermal (DH ¼ 80 kJ mol1 ). and relatively small batch reactors ( 2 to 10 m 3 ) are usually preferred. Number-average and weight-average molecular weights have been predicted using the ‘‘recursive’’ approach. thanks to Zavitsas and collaborators [233]. The research information [237. will be presented. [231]. assuming irreversible reactions. Fairly good agreement of model and experimentally measured functional group concentrations in resol formation at various stoichiometric ratios has been claimed [239] and it is expected that a trustworthy quantitative description of these systems may eventually be achieved. sometimes with a small amount of inert solvent (aromatics are inert only if they carry deactivating groups).3. a 1.2-epoxide. therefore yielding a great variety of potentially useful polymers. owing to the several different aromatic reaction sites and substitution effects [234]. a brief review of processes to make the macromonomers containing epoxy groups.5 Epoxy Resins The three-membered cyclic ether group oxirane. and used as coatings and adhesives. and lump together all isomers with the same unit counts. Resol reactors have been the subject of studies. Mathematical models describing formation of novolacs both in batch and continuous reactors have been developed by Frontini et al. which requires extensive use of 13 C NMR and synthesis of model compounds. Experimental determination of the necessary structural and kinetic parameters is a huge task. 240. 238] allows modeling of these reacting systems to be elaborated with better chemical support. Nearly all of them are thermosetting.19) and bisphenol A. Instead. Concentrations of fragments have been computed. 3. A Monte Carlo method [232] can also be used in order to obtain a more detailed description at molecular level. or an epoxy group reacts with substances containing an active hydrogen group. or can be polymerized with anion or cation initiators. Their cure processes. The initial addition of formaldehyde to phenol in alkaline media could for the first time be successfully described.108 3 Polycondensation preferentially inside the molecular coils and decrease their reactivity because of this. and has mainly been carried out through measurement of individual oligomer and functional group concentrations. 3 in Scheme 3. Validation of these predictions is plagued by experimental difficulties. which should be considered in close connection with the method of producing the final material. the so-called epoxy resins. [230] and Kumar et al. In novolac production. Resol formation in further reactions is a complex process. concerning operation in accident situations. Heat of reaction is removed using water reflux. 236]. They consider the existence of at most one methylol group per molecule. phenols.

CH3 C CH3 HO -NaCl OH OCH2CHCH2O n CH3 C CH3 OCH2CH CH2 O Formation of epoxy resin by reaction of bisphenol A with epichlorohydrin. with A ¼ aOH.19.6 Polyurethanes and Polyureas Urethane polymers were discovered by Baeyer in 1937 [246.20. intramolecular ring formation has been measured. Branching formation occurs to a low extent and can usually be neglected. [242] and Gao [243]. the reaction can be described as a linear irreversible polycondensation AXA þ BYC. In this system. and both constants have been determined both for the catalyzed and noncatalyzed reaction. The similar epoxidation of novolacs with ECH has been additionally studied by Oyanguren and Williams [244].3 Polycondensation Processes in Detail ClCH2CH CH2 O 3 + CH3 C CH3 CH2 CHCH2O O Scheme 3.20. The activation energy of the branching reaction was found to be higher (20 as compared to 18 kcal mol1 ) than that of chain extension. Its kinetics has recently been studied by Smith and Ishida [276].3. 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 catalyst. The kinetics has been studied by Enikolopyan et al. and eventually gelation occurs. bifunctional. 4 109 . such as hydrolysis and alcoholysis of chlorine and epoxides in ECH. 4 in Scheme 3. among others. These reactions create molecules with functionality one or even zero. epoxy resin. This process leads to branching.3. and must of course be minimized. The so-called ‘‘taffy process’’ consists in the two-phase reaction of an alkaline solution of bisphenol A with ECH in stoichiometric excess [241]. Addition of alcohols to isocyanates. due to the reaction of the pendent hydroxyl group with epoxide. 247]. B ¼ aCl. using the addition of alcohols to isocyanates leading to carbamates (or urethanes). and C ¼ epoxide (ECH and oligomers have different reactivities). with the goal of producing a higher molecular weight. The main reaction as described above is accompanied by side reactions. 3. R NCO + HO R' R N O C O R' H Scheme 3.

R 6 H Reaction of urethanes with isocyanates leading to allophanates. Addition of primary amines to isocyanates. alkoxides. As the amine reacts again with isocyanate. Isocyanate groups also react to form uretdiones 9. R NCO + H2N R R' N O C NH R' 5 H Scheme 3.23.23) and with ureas.24. this reaction will lead to branching.110 3 Polycondensation The analogous. + CO2 H H Reaction of water with isocyanates. They are mainly used in the production of foams. leading to biurets 7 (Scheme 3. as will consecutive reactions with carbamates. which stabilize the foam even before the system .21). leading to the thermostable isocyanurate ring 8. occurs with basic catalysts (multifunctional amines. R NCO + R N O C NH R' R N H O C NH R' C N O Scheme 3.24). Most urethane polymers are thermosets [247. and so on) through allophanate intermediates [252–254] (Scheme 3. reaction with primary amines produces Nsubstituted ureas 5 (Scheme 3.22. This is an equilibrium reaction.22). Trimerization of isocyanates.25). taking advantage of the reaction of water and of the precipitation of insoluble ureas. carboxylates. leading to allophanates 6 (Scheme 3. O C O R' R 7 H Reaction of ureas with isocyanates leading to biurets.26). 248].21. much faster. R NCO R + H2O N O C O H H R N Scheme 3. Reaction with water produces an amine and carbon dioxide through an unstable carbamic acid intermediate (Scheme 3. R NCO + R N O C O R' R N H C N O Scheme 3. which is mainly important at high isocyanate concentration (Scheme 3.

Another important use is the fabrication of plastics by RIM (reaction injection molding) (see Figure 3.3 Polycondensation Processes in Detail R N O C O C N O R' R' + R NCO R N H O C O O C N O R R R H N C O R O N N N R R + R' OH O 8 Scheme 3.25. Rigid foams use more branched polyols than do flexible foams. additives such as surfactants and demolding agents. blowing agents. They are most often starshaped poly(oxypropylene). in combination with shorter polyols such as glycerine. and water. . Formation of isocyanurates.11).11. 3. O C 2 R NCO R N N R C O Scheme 3. which exploits the very fast reaction which can be Fig. 111 9 Formation of uretdiones.or hydroxyethyl-capped branched polyols of molecular weight of the order of a few thousands are preferred. Amine. Scheme for an RIM machine with a jet impingement mix-head (on a very exaggerated scale). in its recirculation and injection modes.26. gels chemically.3.

a short diol such as 1. which is possible provided the thermodynamics is favorable: this means a high enough concentration and chain length of ‘‘hard’’ blocks. Many polyurethanes are block polymers prepared with a diisocyanate. Most often. poly(butadiene) or other.4 should deal with them without difficulties. or a diamine (the chain extender). tertiary amines. An important and desirable feature of polyurethanes and polyureas is the phase separation of the small isocyanate/chain extender blocks. We will nevertheless give a few hints of the reaction engineering of the production of polymers and macromonomers based on this chemistry. also prevents correlation of rates of reaction by simple proportionality or even power-law relations. 259]. From the point of view of the prediction of structure. 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. 258. and thermoplastic elastomers (including elastic fibers) can therefore be obtained. the preparation is performed in two steps: firstly. It might be thought that modeling of polyurethane processes would be relatively straightforward.4. metallic or tertiary amine catalysts being ineffective in this case. selfcatalyzed) reactions may sometimes be fast enough in practice: isocyanate reactions with amines are so fast that only recent studies using stopped-flow methods could lead to useful data [255. binders. which is particularly well adapted to the fabrication of big. or their loose complexation by products or reagents.112 3 Polycondensation achieved either with amines or with hydroxyls. The whole production cycle can take less than one minute from injection to demolding. and a diol with molecular weight between 500 and 4000. Formation of isocyanurates causes a reorganization of the CLD akin to what happens in reversible polycondensations because of exchange reactions. which shares some characteristics with solid-state polycondensation. allophanate and biuret formation is reversible at temperatures above 130 C [252]. In reality. reaction of the longer polyol with the isocyanate. these processes will not be discussed in this section. 251] is by far the best understood.6-hexanediol. and fibers. 256]. The excellent book by Macosko [249] extensively covers this technology. Self-association of metallic catalysts. and has been tackled through the use of Monte Carlo methods [257. polycarbonate. As often happens with polymerization reactions. coatings. The catalysis of isocyanate reactions has been extensively studied because of its critical importance in many of these processes. then with the chain extender in the second stage. and also to complex elastomeric objects (viscosity is very low during mold filling). Reactors for these processes range from simple batch or continuous stirred tank .4-butanediol or 1. Noncatalyzed (or rather. other relevant uses are adhesives. Catalysis of isocyanate reaction with hydroxyls [250. thermoplastic elastomers. this brings about a complex problem. polyester. based on a polyether. or a combination of the two [250]. in the presence of catalysts such as dibutyltin carboxylates. As with the other thermosets in this chapter. given that reactions are mostly irreversible and the methods described in Section 3. molded parts. These ‘‘hard’’ blocks act as physical crosslinks at a temperature lower than their melting point. flat.

3.4.4. Owing to the strong exothermicity of the main reaction. alternating polycondensation is discussed in Section 3. including more complex molecular fragments (monads. to tubular reactors with static mixers or extruders.2 Description of Reactions in Polycondensations of Several Monomers with Substitution Effects 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.4. Many processes at low temperature and in homogeneous phase can nevertheless be analyzed through the methods described in Section 3.1 Overview Rate equations allowing the prediction of concentrations of reactive groups. Mathematical difficulties grow considerably in the presence of SSSEs.2 are useful in order to predict average numbers of bonds for each monad. Prediction of molecular weight distributions for reversible. 3.5.4 Modeling of Complex Polycondensation Reactions 3. There seems to be no alternative to Monte Carlo methods for dealing with reversible nonlinear polycondensations or even linear polycondensations where more than two kinds of bonds are present. as they now stand. cooling has to be used in order to prevent side reactions from becoming too important. The presence of rings is also allowed. In Section 3. needed for predicting average molecular weights. allowing prediction of average molecular weights before or after gelation. 3.4. The results of Section 3. Knowledge of the distributions of numbers of bonds connecting repeating units makes it possible to describe molecular structure at chemical equilibrium. Stoichiometric coefficients are introduced in order to obtain a fairly general formalism. for irreversible reactions or systems with at most FSSEs if reversible reactions exist. Irreversible polycondensations can be tackled quite easily using a general kinetic approach developed in Section 3. later exploited in Section 3. dyads and so on) from mass balance equations are established in Section 3. and even molecular weight distributions (lumping together isomers with the same numbers of groups).4.4.4 Modeling of Complex Polycondensation Reactions reactors for very low molecular weight or solvent-based processes.4.4. linear. using the theory of branching processes. the main results concerning molecular weights and network properties of chemical systems verifying FSSEs are presented. because the same molecular entity has to be labeled in a dif- 113 . The existence of substitution effects seriously complicates the task.

Vectors e. incident on monomer units Xzi . In some of these NR reactions. A total number NW of by-products Wi will be considered for the sake of generality. NR þ ‘‘half-bonds’’. e i A 1 . . . . the vectors z and h. We introduce the following nomenclature for the species (monomer units or functional groups) and vectors h. Zeþi monomer units. will be related through hgiþ ¼ zeþi and hgi ¼ zei . . ei A 1 . . A giþ 1 A½iþ Zeþi 1 Z½iþ We i 1 W½i Xh i 1 X½iA Xzi 1 X½iZ ð62Þ . NZ The NA functional (or end) groups A i will be distinguished (even if chemically similar) according to the monomer unit Xh i where they are attached. but because its neighbors have reacted. as happens for instance if a carboxylic acid reacts with glycerol. Hence. the notation given by Eqs. . . The directed bonds associated with ZiR will be named Zei and Zeþi . This definition allows for more than one possible kind of bond between two given monomer units. of sizes NZ . such as in the case of self-condensations of silanols in silicone formation and of methylols in formaldehyde polymerizations. defining respectively their incident and adjacent monomer units. eþ and e . which possesses distinguishable primary and secondary hydroxyls. e i . The number of such reactions in this subset will be defined as NRs . h is yet another vector of indices. gþ and g have sizes NR . For each bond.114 3 Polycondensation ferent way. e storing their indices: Xh i A gi . giþ A 1 . which will be coincident for the NRs reactions considered above. there is a total number of NZ ¼ 2NR  NRs kinds of directed bonds Z i . A giþ We i Z iR Zei . . NX functional groups which react forming bond ZiR . the set of monomer units and bonds are the vertices and edges of a directed graph (or digraph). (62) (loosely inspired by indirect addressing of computer assembly languages) will be used hereafter. . not because it has intrinsically changed. an end group may react with itself. g. NR reactions involving pairs of functional groups create connections between monomer units. using yet another pair of vectors of indices. h i A 1 . There is a one-to-one correspondence between directed bonds and half-bonds hanging from the repeating units at each side. with size NA . . indices gi . it is useful to define a positive sense in the direction of the unit with higher or equal index. So. possibly (with the well-known exceptions of epoxides and isocyanate reactions) also forming by-products. In order to avoid multiple levels of indexing in equations. therefore contains the indices of the repeating units to which each directed bond points. i A 1 . of size NZ . NW bonds. Vector z. NA by-products. By-product We i is formed by the reaction between functional groups A gi and A giþ creating the bond ZiR .

5 and 3. in such cases we will introduce a nil by-product W0 (assuming that the indices are counted starting from one) with a constant unit concentration.1. the exchange of bonds ZiR and ZjR . to functional groups An and oriented bonds Zn coming out of the monomer unit in which stood A½i .4. igi iei i i moreover. by definition there is no substitution effect. (66). This trick only works with FSSEs. but it helps in situations such as the thermal decomposition of urethanes or ureas. NR ). ki A½i þ A½iþ T Z½i þ Z½iþ þ W½i ð64Þ kiZ To account for first-shell substitution effects (FSSEs). i ¼ 1. they would be written with an algebraic notation as in Eqs.5) are much more difficult to describe. all other stoichiometric coefficients are nil. 115 . and. can be described through Eqs. kijE  þ þþ X  A½i þ X þ Z½ j Z½ jþ X þþ !  X Z½i Z½iþ X þ A½ j X E kji  X A½iþ þ X þ Z½ j Z½ jþ X þþ kijEþ ð66Þ  !  X Z½i Z½iþ X Eþ þ þ A½ jþ X þþ kji In the presence of FSSEs. nigA  ¼ n þ ¼ 1. Aþ Zþ Z No FSSE means that. which are first-order reactions. related to the former through the equilibrium ratios Ki and the concentration of the corresponding by-product. ninZ correspond. (63). In the absence of FSSEs. Likewise. If the groups react independently. (64). as well as apparent first-order rate constants of the backward reactions (kiZ ).4 Modeling of Complex Polycondensation Reactions For the NR reactions which create new bonds from functional groups and also (very often) a by-product. (65)] can be written. necessarily forming the same by-product (e i ¼ ej ). for every reaction i. By convention. if it exists. The condensation reaction creating a bond (the same as two half-bonds) can be written as Eq. ninZþ. respectively. kiZ ¼ ½W½i  ki Ki ð63Þ This may look rather artificial. and a similar convention is used for ninAþ .3. nW in . it is useful to introduce the stoichiometric coefficients of by-products. according to Eq. Higher-order substitution effects (see Sections 3. we will introduce apparent second-order rate constants of the forward reaction (ki . using stoichiometric coefficients n: NW NA NZ X X X ðninA þ ninAþ ÞAn þ nW ðninZ þ ninZþ ÞZn ¼ 0 in Wn þ n¼1 n¼1 ð65Þ n¼1 ninA . a more general expression [Eq. nie ¼ n þ ¼ 1. (67).

and they are nil if there are no substitution effects. If there is only a single kind of bond. as shown by the cancellation of the stoichiometric coefficients in Eq. respectively. The relative rate of change of reaction volume RV can be . connected to the root unit X  where either AEþþ ZEþþ AEþþþ ZEþþþ . (67). but a reshuffling of pieces of the reacting molecules takes place. connected to the root unit X þþ where stood the living group A½ j or A½ jþ. Rates of production by chemical reaction of the various groups are obtained using Eqs. nijn . nijn are the changes in A½i or A½iþ were attached. respectively. distinguishable kinds of amides/amines/carboxylic acids). nijn are the changes in the numbers of groups ficients nijn attached to root unit X þ which gets connected to the unit where stood the attacking group. nijn . The above reactions modify the counts of functional groups of similar chemical nature (for example. The other stoichiometric coefAEþ ZEþ AEþþ ZEþþ . nijn are the changes in numbers of functional groups An and bonds Zn . (68)–(70). and nijn numbers of functional groups An and bonds Zn . nijn . R An ¼ NR X ðninA þ ninAþ Þðki ½A½i ½A½iþ   kiZ ½Z½iþ Þ i¼1 þ NR X NR X e EA EAþ EAþþ de ij ½kijE ½A½i ½Z½ jþ ðnijn þ nijn þ nijn Þ i¼1 j¼iþ1 EA EAþ EAþþ þ njin þ njin Þ þ kjiE ½A½ j ½Z½iþ ðnjin R Zn ¼ ð68Þ NR X ðninZ þ ninZþ Þðki ½A½i ½A½iþ   kiZ ½Z½iþ Þ i¼1 þ NR X NR X e ZA ZAþ ZAþþ de ij ½kijE ½A½i ½Z½ jþ ðnijn þ nijn þ nijn Þ i¼1 j¼iþ1 ZA ZAþ ZAþþ þ njin þ njin Þ þ kjiE ½A½ j ½Z½iþ ðnjin RWn ¼ NR X Z k i nW in ð½A½i ½A½iþ   ki ½Z½iþ Þ ð69Þ ð70Þ i¼1 The reaction volume changes mostly because of by-product removal. there is no net creation or destruction of functional groups or bonds. nijn .116 3 Polycondensation NA X AE AEþ AEþþ ðnijn þ nijn þ njin ÞAn þ n¼1 NZ X ZE ZEþ ZEþþ ðnijn þ nijn þ nijn ÞZn ¼ 0 n¼1 ð67Þ NA X NZ X AEþ AEþþ AEþþþ ZEþ ZEþþ ZEþþþ ðnijn þ nijn þ nijn ÞAn þ ðnijn þ nijn  nijn ÞZn ¼ 0 n¼1 n¼1 AE ZE Stoichiometric coefficients nijn . and little because of density changes.

117 . one may need only some of the moments of the aforementioned distributions for making a few calculations.4 Modeling of Complex Polycondensation Reactions estimated as the sum of products of the molar volume of by-products by their rate of elimination by phase change. (71). All isomeric trees with the same counts of groups are lumped into the same chemical species leading to vector count distributions with NZA ¼ NZ þ NA independent variables. A kinetic method may be used for this prediction. hopefully easier to translate into computer programs. In fact. respectively. of size NZA .2. 3. we will introduce a more straightforward description. and other polymer properties. The mass balances of the functional groups in a batch reactor can thus be written as Eqs.3 Equilibrium Polycondensations with Several Monomers Instead of the elegant but often error-prone Gordon’s notation. Notice that the molecular graphs have to be considered as digraphs.4. unless higher-order substitution effects have to be tackled) are mutually connected. (71)] until close to steady state. These computations assume there is some way of predicting how molecular fragments (usually monads. molecular weight distributions. it is necessary to know the distributions of the numbers of bonds connecting the fragments. d½An  ¼ RAn  RV ½An  dt ð71Þ d½Zn  ¼ RZn  RV ½Zn  dt A convenient way of computing the concentrations of groups at chemical equilibrium consists in integrating the system of ODE [Eq. This has been one of our motivations for presenting the formalism in Section 3. but mainly as a means to avoid solving equations derived from mass action laws for concentrations of fragments. for each kind of fragment.4. xA Þ with counts of end groups and directed bonds xA and xZ . The goal is to obtain a set of formulae for predicting average molecular weights. valid for generic chemical systems.3. Each directed bond Z i is supposed to start a pendent chain Vi ðxZ . More specifically. otherwise xZ would be meaningless: it would be impossible to know the counts of the monomer units according to their chemical nature. Variables sA and sZ will be often ranged together as subvectors of a vector s. Vectors of dummy Laplace variables sA and sZ will be associated with the counts of unreacted groups and directed bonds.

Aj F ðsÞ ¼ s1 Aj qF X½ jA q log sA j  qF X½ jA q log sA j js¼1 X X ½ jA ½ jA ¼ s1 A j LA j ðsÞ/lA j NZA ð77Þ . xA groupsgsZ1 1    sAN A A xAN ¼0 A J ¼ Xi. xA Þ ¼ NZ NA X X ðMX½ jZ þ MZ j ÞxZ j þ MA j xA j j¼1 ð74Þ j¼1 X i ðxZ . (72). (75). and half-bonds. ZijZX ¼  1 if j ¼ zi 0 if j 0 zi ð73Þ The chemical system is further described through knowledge of the molar fractions of monomers or monomer units. xA Þ is. yX i . sA Þ and F Z i ðsZ . M½Vi ðxZ . as stated in Eq. respectively MX i .1. Hence. MA i and MZ i . Zi ð76Þ These pgf values are mutually related through Eqs. an unreacted group A i or a directed bond Z i [Eq. sA Þ ¼  xZ1 ¼0 y X y X y X  xZN ¼0 xA1 ¼0 Z y X xAN ¼0 A xZ xAN PfJ is connected to xZ . (76)]. in which 1N means a vector with N components equal to 1.5. (77) and (78).118 3 Polycondensation Vector xX containing the counts of the monomer units can be obtained from xZ through Eq. y X F J ðsZ . xA Þ of a tree Vi ðxZ . xA groupsg ¼ ½X i ðxZ . sA Þ be the probability generating functions (pgf ) of the counts of the different kinds of connecting and unreacted functional groups directly linked to a unit X i . (73). can be thought of as a probability: the probability that a certain repeating unit is attached to those counts of groups. (summing to 1) and of the molecular weights of monomer units. Ai. Its concentration. a monad with vectors of group counts xZ and xA . unreacted groups. xX ¼ ðZ ZX Þ t xZ ð72Þ ZZX is a matrix containing the incidence vectors z defined by Eq. (74). xA Þ can be computed through Eq. PfX i is connected to xZ . F A i ðsZ . the molecular weight M½Vi ðxZ . xA Þ/½X i  ð75Þ Let F X i ðsZ . normalized by the concentration of repeating units X i . according to the concept introduced in Section 3. sA Þ.

with equal and independent groups A. will be often needed. 119 .4 Modeling of Complex Polycondensation Reactions F Z j ðsÞ ¼ s1 Zj qF X½ jZ q log sZ j  qF X½ jZ q log szj js¼1 X X ½ jZ ½ jZ ¼ s1 Z j LZ j ðsÞ/lZ j ð78Þ NZA Notice the use of L with lower indexes for the derivatives of the pgf values with respect to the logarithms of dummy Laplace parameters. are presented in Table 3. MP . B not reacting with C (such as adipic acid þ glycerol. is introduced in Eqs. and of unreacted functional groups A j . the conversion of A groups.3. or C. (79). If a pgf relative to the count of monomer units is desired. as well as of l for their moments.3. p. A reacting with B or C. (80) and (81). (83). and can be obtained using Eqs. lZX ij . B. sZ ¼ ZZX sX ð79Þ The average numbers of bonds Z j . F X ¼ ½ð1  pÞsA þ psZ  f F Z ¼ F A ¼ ½ð1  pÞsA þ psZ  f 1 lZX ¼ f p lAX ¼ f ð1  pÞ ð83Þ MP ¼ MX þ f pMZ þ f ð1  pÞMA Expressions for the less trivial case XA f þ YBg C illustrated diagrammatically in Figure 3. f ¼ g ¼ 2). (82). with constant reactivity of end groups A. a useful convention which will be encountered often in the rest of this chapter. can therefore be computed using Eq. MP ¼ NX X i¼1 " y X i MX i þ NZ X lZX ij MZ j þ j¼1 NA X # lAX ij MA j ð82Þ j¼1 For the classic self-polycondensation of XA f . lAX ij . attached to a monomer unit X i . for a vector of dummy Laplace variables sX . lZX ij ¼ lAX ij ¼ qF X i q log sZ j js¼1 NZA qF X i q log sA j js¼1 NZA ð80Þ ð81Þ The mass of polymer per mole of monomer units. it can be found by obtaining the pgf with respect to the counts of directed bonds with Eq.12.

3. . (85)]. 3. sA Þ. sA  i ¼ 1. (86). . Probability generating functions F describing polycondensation XA f þ YBg C and its gelation condition. this leads to the well-known result of Eq. " # " # ½ð1  pA ÞsA þ pAB sZAB þ pAC sZAC  f F XX X F ¼ ½ð1  pB ÞsB þ pB sZBA  g ½ð1  pC ÞsC þ pC sZCA  F XY 2 3 F ZAB 6 ZAC 7 6F 7 FZ ¼6 7 4 F ZBA 5 F ZCA 2 AA 3 F 6 A 7 A 6 F ¼4 F B 7 5 2 Gelation condition gpBg pACg þ ðg  1Þ pBg pABg þ pCg pABg ¼ F AC ½ð1  6 ½ð1  6 6 4 ½ð1  ½ð1  2 ½ð1  6 4 ½ð1  ½ð1  3 pB sZBA  g1 ½ð1  pC ÞsC þ pC sZCA  7 pB sZBA  g 7 7 f 1 5 pAB sZAB þ pAC sZAC  f 1 pAB sZAB þ pAC sZAC  3 pA ÞsA þ pAB sZAB þ pAC sZAC  f 1 7 pB ÞsB þ pB sZBA  g1 ½ð1  pC ÞsC þ pC sZCA  5 g pB ÞsB þ pB sZBA  pB ÞsB þ pB ÞsB þ pA ÞsA þ pA ÞsA þ 1 f 1 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). . NZ ð84Þ The vector v of the NZ probabilities of extinction (the fractions of finite pendent chains) v ¼ Vð1NZA Þ contains the solutions of system (84) for s ¼ 1NZA . Tab. Gelation occurs when system (84) has a double root v ¼ 1NZA for s ¼ 1NZA. (84)] for the pgf of pendent trees of the different kinds: Vi ðsZ . implying that its Jacobian becomes nil [Eq. The theory of branching processes leads to a system of NZ algebraic equations [Eqs. " # qF Z i  I ¼ j½LzZj i ð1NZA Þ  Ij ¼ 0 qnj ð85Þ For the polycondensation of a single monomer.3. sA Þ ¼ sZ i F Z i ½VðsZ . . . Example of proposed notation: polycondensation XA2 þ YB2 C.12.120 3 Polycondensation Fig.

3.3. if there is only one kind of monomer unit and so just one kind of directed bond. These latter will have to be computed relative to the molar concentrations of the various groups or monomer units. Defining xZy as the count of infinite pendent chains and the correspondent dummy Laplace variable as sZy .4 Modeling of Complex Polycondensation Reactions pg ¼ 1 f 1 ð86Þ Prediction of the gel point for XA f þ YBg C is also presented in Table 3. which is the sum of the degrees of polymerization corresponding to the various monomer units (the components of vector xX ). ySX i . ySZ i and ySA i . and so me and ne can be computed using Eqs. respectively me and ne [260. Z. sA Þ ¼ sYi F Yi ½VðsZ . for an alternating polycondensation of two monomers. sA  Y ¼ Z. 1NA Þ Y ¼ X. sA Þ ¼ sX i F X i ½VðZZX sX . ySYi ¼ F Yi ðv. x2 Þ/½X1  with respect to x1 and x2 . GYi ðsZ . in which x is the degree of polymerization. A ð89Þ 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). A ð87Þ G X i ðsx . given the probabilities of extinction and the moments with respect to the numbers of pendent chains as previously defined. Notice that vector xZ with the counts of directed bonds has more information about the molecular composition. Since we are dealing with several kinds of units. an unreacted group A i . The pgf values of trees starting with a prescribed monomer unit X i . not directly molar concentrations of polymer molecules. sA  ð88Þ 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. There is a basic difficulty when trying to use Eqs. whereas EANCs are the chains linking EANJs (see Figure 3. For instance. These concentrations can be easily predicted. (90) and (91). and thus will come multiplied also by the number of those groups in the distributions. 1NA . EANJs are the intersection of at least three chains leading to the gel.13). an overall degree of polymerization can be defined. (87) and (88): they provide pgf values of monomer units or groups. (88) will provide the generating function of x½Px /½X  with respect to x. 121 . or a directed bond Z i . after gelation. (88) will provide the generating function of x1 ½Pðx1 . ½Px . (87) and (88). 261]. G X as computed by Eq. can be computed by replacing s ¼ 1NZA in the above equations to give Eq. sA Þ. (89). even as generating functions. G X 1 ðsZ1 . sZ2 Þ as computed by Eq. its pgf for the chains stemming out of a monomer unit X i is F X i ½v þ sZy ð1NZ  vÞ. are obtained from the theory of branching processes through Eqs. Fractions of units and groups of the various kinds in finite molecules (in sol). sA Þ.

. (93) and (94). 1NA Þ 2 i¼1 j¼1  NZ X NZ X ) nj nk ð1  nj Þð1  nk ÞLZXjiZk ðv. Elastically active and inactive junctions and chains in a polymer network. 1NA Þ  2 j¼1 k¼1 ne ¼ ð90Þ ( NX NZ X 1X ½X i  ½lZX ij  nj ð1  nj ÞLZXji ðv. and the pgf of counts of finite pendent chains connected to units or groups. sA Þ. 1NA Þ ð91Þ j¼1 k¼1 For instance. it is convenient to introduce the pgf of finite pendent chains.13. 1NA Þ j¼1 i¼1 ) NZ X NZ 1X Xi nj nk ð1  nj Þð1  nk ÞLZ j Zk ðv. assuming the so-called ‘‘phantom network’’ model. shear modulus Ge would be predicted for gaussian chains to be given by Eq. Ge ¼ RTðne  me Þ ð92Þ In the presence of gel. 1NA Þ  nj ð1  nj ÞLZXji ðv. ( NX NZ X X me ¼ ½X i  1  F X i ðv. (92). which can be found using Eqs. named V^i ðsZ . 3.122 3 Polycondensation Finite pendent chain Infinite pendent chain EANJ Junction EANC EANJ Chain connecting to gel Fig.

GM ðsM Þ ¼ y X X Mi sM wi ¼ NY X MY MA ^ M ðsM Þ. the various pgf values with respect to the different kinds of groups in the ^ X i ðsZ . 1NA Þ/ySYi Y ¼ Z. l^AX ij MA j MP ð99Þ j¼1 ð100Þ X y X j ySX j l^Z ji j¼1 MP wS ð101Þ 123 . sA Þ. (95).Zk ¼ LYZi j . (96) can be evaluated. . wS ¼ NX X y X i ySX i MX i þ j¼1 i¼1 wX i ¼ y X i ySX i MX i MP wS MZ i wZ i ¼ NZ X NX X l^ZX ij MZ j þ NA X !. sA Þ. wi .. the index i in the infinite sum sweeps all finite polymer molecules. sA Þ. for which the dummy Laplace variable associated with molecular weight is sM . G Eqs. . sA Þ ¼ F Yi ðn1 s Z1 . nNZ sZNZ .. relative to the overall mass of the polymer computed by Eq. The weight fraction of the sol wS . .Zk ðv. . sA  i ¼ 1. . A ð96Þ Pgf values of finite pendent chains with respect to molecular weight. sA Þ/ySYi ¼ F Yi ðv5sZ . the moments in Eq. Z. with respect to their molecular weight Mi . can be computed using molecules of the sol. sA Þ/ySYi Y ¼ X. sM A M þMX z Þ ¼ V^i ðsM z MA .. A i¼1 i¼1 The mass fractions of the units and groups in Eq. Z.3. the pgf values of the mass fractions of the polymer molecules in the sol. . A ð93Þ ^ ðsZ . ^Yi ðsZ . .4 Modeling of Complex Polycondensation Reactions F^Yi ðsZ . sM 1 . l^YZij . (99)–(102). . sM wYi sM i F^Yi ½V  ð98Þ Y ¼X. NZ V^i ðsZ . defined below. sA Þ ¼ F^Yi bV ^ ðsZ . . (97) (notice the conventional use of a power of a scalar to a vector): M ZN MZ þM V^Mi ðsM Þ ¼ V^i ðsM 1 X½1Z . sM Z þMX ½NZ Z MA MAN . sA Þ. . sM Þ ð97Þ Prediction of average molecular weights is now possible by introducing GM ðsM Þ. G ^Z i ðsZ . . G ^A i ðsZ .. sA Þ ¼ sZ i F^Z i ½V ð94Þ So. A ð95Þ After computing the probabilities of extinction. (98) above are relative to the mass of the sol. Z. . is therefore given by Eqs. sA Þ. (82). sA c G Y ¼ X. can be found 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. yP ¼ NX X y X i ySX i i¼1 NZ 1X 1 l^X i 2 j¼1 Z j ! ð104Þ The number-average molecular weight of the sol can thereafter be computed through Eq.124 3 Polycondensation MA i NX X X y X j ySX i l^A ji j¼1 wA i ¼ ð102Þ MP wS Before carrying out the evaluation of distributions and average molecular weights. . (105). the systems of linear algebraic equations (107)–(113) must be solved. and so on. the number of moles of polymer molecules per mole of monomer units before gelation is given by Eq. When it is taken into account that. (98) with respect to log sM and setting sM ¼ 1. (104)] is needed. can be now obtained through differentiation of Eq. NX X Mn ¼ y X i ySX i MX i þ NZ X MZ i l^ZX ij j¼1 i¼1 NX X y X i ySX i i¼1 þ NA X j¼1 NZ 1X 1 l^X i 2 j¼1 Z j ! ! MA i l^AX ij ð105Þ An expression for the number-average degree of polymerization of the sol follows from Eq. a special reasoning must be carried out in order to compute number-average molecular weight and degrees of polymerization. the more general expression [Eq. lMM . (103). yP ¼ 1  NX NZ X 1X yXi lZX ij 2 i¼1 j¼1 ð103Þ After gelation. one polymer molecule is consumed. (106)]. with the reaction of every pair of end groups in finite molecules. NX X xn ¼ y X i ySX i i¼1 NX X i¼1 y X i ySX i NZ 1X l^X i 1 2 j¼1 Z j ! ð106Þ The moments with respect to molecular weight lM . First of all.

Z. Z. qGM ¼ Mw q log sM jsM ¼1 " # NY NZ NA X X X X Y Z A ^Yi ¼ w Yi M Yi þ ðmj þ mj ÞlZ j þ MA j l^A ji lM ¼ Y ¼X. A ( NY X " w Yi MY2i j¼1 i¼1 þ þ 2MYi NZ NA X X ðmjZ þ mjA Þl^YZij þ MA j l^YZij ! j¼1 NZ X NZ X ðmjZ þ mjA ÞðmkZ þ mkA Þl^YZij Zk j¼1 k¼1 þ NZ X ðmjZZ þ 2mjZA þ mjAA þ mjMXZ þ mjMA Þl^YZij j¼1 þ2 NZ X NA X ðmjZ þ mjA ÞMAk l^YZij Ak j¼1 k¼1 þ NA X NA X j¼1 k¼1 MA j MAk l^AYjiAk þ NA X #) MA2 j l^AYji ð115Þ j¼1 Except for extremely simple polycondensations.3. formulae for predicting average molecular weights are very cumbersome and numerical evaluation is a must. 125 . A i¼1 j¼1 ð114Þ j¼1 lMM ¼ Mw MZ ¼ X Y¼X.4 Modeling of Complex Polycondensation Reactions j ½miZ  ¼ ½di  l^ZZ ij 1 ½MZ i þ MX½iZ  ½miA  ¼ j ½di  ð107Þ l^ZZ ij 1 ½l^ZAji ½MA i  ð108Þ " ½miZZ  ¼ j ½di  l^ZZ ij 1 2ðMZ i þ MX½iZ Þ NZ X mZl l^ZZli þ ¼ j ½di " ¼ j ½di ð109Þ " # NA NZ X NA X X Z i 1 Zi Zi Z ^ ^ ^  lZ j  ðMZ i þ MXX½iZ Þ MAm lAk þ m l MAm lZl Am  l^ZZ ij 1 NZ X NA X ð110Þ l¼1 m ¼1 m¼1 ½miAA  # Z ^Z i mZl mm lZl Zm l ¼1 m¼1 l ¼1 ½miZA  NZ X NZ X mlA MAm l^ZZliAm þ l¼1 m¼1 NA X NA X # MAl MAm l^AZliAm ð111Þ l¼1 m¼1 j ð112Þ ½miMA  ¼ ½di  l^ZZ ij 1 ½MA2 i  ð113Þ ½miMZX  ¼ ½di  l^ZZ ij 1 ½ðMX½iZ þ MZ i Þ 2  j Weight-average and z-average molecular weights are now obtained explicitly through Eqs. (114) and (115).

xw ¼ 1 þ pð2v  1Þ 1  p½1 þ vð f  2Þ xz ¼ 1 þ þ ð116Þ 2f pv þ f p 2 vð f  1Þð1  p þ pvÞ f 2 ð1  p þ 2pvÞ½1  pð f  1Þð1  p þ pvÞ f 2  ð f  1Þð f  2Þ p 2 v 2 ð117Þ ð1  p þ 2pvÞ½1  pð f  1Þð1  p þ pvÞ f 2  2 The number-average degree of polymerization x n is obtained through a stoichiometric reasoning as previously discussed [Eq. using the trapezium rule and Fast Fourier Transform for evaluating the sums [Eq.126 3 Polycondensation The weight-average and z-average degrees of polymerization. or unreacted functional groups can be obtained from Eq.1 have been computed using the above expressions. For the polycondensation of a single monomer XA f . 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. Analytical inversion by computing derivatives with respect to dummy Laplace variables on s ¼ 0 is feasible with the simplest chemical systems. (116) and (117). for which the resulting recurrence formulae are not too complex. as happens with the Stockmayer distribution. this leads to Eqs. It consists in computing the inversion contour integral on a circle C in a complex plane centered on the origin with radius jsj slightly below 1. (119)]. Numerical inversion of generating functions of the concentration distributions is y P s x ½Px  usually a better way to predict them. xn ¼ 1  p þ pv 1  p þ pvð1  f /2Þ ð118Þ Values of average degrees of polymerization versus conversion of end groups p shown for f ¼ 2 and f ¼ 3 in Figure 3. Unless the cost of evaluating GðsÞ ¼ x ¼0 is too high and more sophisticated methods based upon Laplace transform inversion are needed. ½Px  ¼   N 1 y X jsjx X 2pimx Gðsm Þ  exp  ½PxþNn jsj Nn N N m¼0 n¼1 ð119Þ . Pgf values of the various distributions with respect to the counts of monomer units. (98) by setting equal to one the molecular weight of the species in question and to zero the molecular weights of all the other species. bonds. 264 for a thorough analysis of round-off and truncation errors of similar approaches). an accurate evaluation can be obtained using the method independently developed by Mills [262] and ourselves [263] (see also Ref. x w and x z . (118)].

A recent surge on this approach has led to exploitation of other more complex but hopefully more efficient methods [265]. The evaluation of averages involving the distances of every pair of monomer units is required. [267]. which will be found afterwards from mass action laws. and a starting point for that purpose is the evaluation of the trail generating functions [31–33]. V ¼ F Zl ðVÞ ¼ b 0 sC0 ½sA ð1  ar Þ þ ar V f 1 þ y X b n sCn ½sA ð1  ar Þ þ ar V nð f 2Þ1 n¼1 G ¼ ð1  yc ÞsC0 ½sA ð1  ar Þ þ ar V f þ y X y Xc ðnÞsCn ½sA ð1  ar Þ þ ar V nð f 2Þ n¼1 b0 ¼ f ð1  yc Þ . summing 1  yc . Chemical equilibrium will be attained in two hypothetical stages: 1. Equilibrium polycondensation of a single monomer XA f taking FSSEs into account has been analyzed by Gordon and Scantlebury [268] using TBP. No other reactions of functional groups A occur. (119) can be neglected for large enough N or small enough jsj.4 Modeling of Complex Polycondensation Reactions The second term in Eq. Besides molecular weight distribution. and experimental results concerning the POCl3 /P2 O5 system have been successfully described. such as the angular dependence of light scattering intensity. The unreacted monomer and the rings start a polycondensation with an infinity of monomers with a single group A and different functionalities. yÞ at the end of this stage is assumed to be y Xc ðnÞ. which are f for the unreacted monomer coming from stage 1 and nð f  2Þ  1 for the rings. mainly developed for Laplace transform inversion. the generating function of the trees with either a ring or a unit not belonging to any ring can be found from TBP as shown in Eqs. More general calculations are better carried out using the method described by Kuchanov et al. and so more adapted to high average molecular weights. summarized below for the polycondensation of XA f (but only in the absence of gel). such as naphthalene. f  2yc bn ¼ ð f  2Þ y Xc ðnÞ f  2yc ð120Þ A pgf for the counts of repeating units X will result from substituting sC0 in Eq. Defining sCn as the dummy Laplace variables associated to the counts of rings (including sC0 for the count of units X in the chains connecting rings) and sZl as the variable counting the bonds not belonging to rings. (120) by sX and sCn by sXn. allowing the counting of path lengths. but no fused rings. All the rings are formed. 2. (120). are allowed and molecules look like ‘‘cactus’’ [266]. (119). The error of those formulae is more complex to control. Variable ar in the expressions (120) is the probability of 127 . it is also possible to access readily some information about the distribution of molecular sizes and other polymer properties. unlike Eq. The fraction of repeating units X in rings of size n ðn ¼ 1.3.

Gordon has not accepted that argument [271]. (121). and considers the molecular graphs to be embedded in ordinary three-dimensional space – not in a lattice. Stauffer. Taking cyclizations into account raises the question of introducing information about the spatial location of atoms in models of network formation. which reduces to the distribution found by Jacobson and Stockmayer in their classic paper [21] for f ¼ 2. starting with classic gelation theory and using TBP as a particular case. In bulk systems. one of the main contributors to the progress of percolation theory. has been developed by Kuchanov [272. In spite of its power. claiming that Gordon’s theory is inapplicable in the vicinity of gel point [270]. and the fraction of rings will increase.128 3 Polycondensation reaction of the unreacted functional groups after ring formation in stage 1. it has not become a widely used instrument for dealing with ‘‘real’’ complex chemical sys- . and to introduce the mass action laws for the rings. so the algebraic equations become integral equations. as is usually done in percolation theory. (23). Dependence of space coordinates is eventually eliminated by averaging. ½Px  ¼ ½X ð f  2yc Þ y Xc ðnÞ ¼ y X n¼1   ½xð f  1Þ!arx1 ð1  ar Þ xð f 2Þþ2 f ð1  yc Þ x f  2yc x!½xð f  2Þ þ 2! nK c ðnÞ n q . until it becomes practically unity. It is necessary to eliminate it. claiming his theory to be universal and capable of describing gel formation in any homogeneous system. The classic gelation theory described here considers a uniform distribution in space of all the chemical properties. Application of the approach described above could lead to improved modeling where small numbers of rings are present. gel points in bulk are affected by a few per cent due to cyclizations. has strongly criticized this view. A new theory. The final result. Dilution with an inert solvent will make [X] decrease without affecting the cyclization constants much. a phenomenon which has experimental support obtained using polysiloxanes as model polymers. [269]). ½X  nK c ðnÞq n ¼ ½X  yc . and elastic properties are also affected (that effect using TBP has been modeled by Dusˇek et al. the fraction of rings is usually only a few per cent. as it requires the application of graph theory in order to compute the concentrations of linear polymer molecules ½L n  in Eq. is Eq. q¼ f ð f  1Þar ð1  yc Þ f  2yc yc ¼ f ð p  ar Þ 2ð1  ar Þ ð121Þ A solution is also known for the analogous system of the alternating polycondensation XA f þ YBg [267]. This last step is not straightforward. Generating functions are replaced by generating functionals of the ensemble of positions of the functional groups and repeating units. 273]. With nonlinear polycondensations of aliphatic monomers.

278] has shown that. ‘‘groups’’ An should include not only the unreacted functional groups. as even a basic but comprehensible description would be too extensive. Dusˇek [279] has pointed out that this behavior is even more visible when dealing with polyadditions (linear polyaddition leads to a Poisson CLD. Sarmoria and Miller [35] have tried to extend the ‘‘recursive approach’’ to systems presenting FSSE by considering network building starting from dyads and larger fragments. We will use NXZA as the number of kinds of groups in that generalized sense. and we leave it here only for reference. and even larger molecular fragments when needed. Kuchanov [277. and the statistical approach was preferred. In this approach. 3. But chemical systems can be found in which this latter idea does not provide useful results [281].4. but also the bonds and repeating units.4 Kinetic Modeling of Irreversible Polycondensations In his pioneering study of nonlinear polycondensation [7]. chemical engineers had to deal with semi-batch and continuous stirred tank reactors where the statistical approach. whereas a simplistic use of a statistical approach would lead to a geometrical/Schulz–Flory CLD) and has confirmed this result using Monte Carlo simulation of XA f polycondensation with FSSEs [280]. so a few papers appeared in the 1960s dealing with kinetically controlled linear polycondensations [274–276]. Stockmayer has already checked his statistical solution [Eq. for a long time no importance was attributed to the use of a kinetic approach for describing batch polycondensations starting from monomers. Hence. In reality. is cumbersome and error-prone. dt ½Px jt¼0 ¼ ½X . (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 Px with x repeating units X [Eqs. kinetic and statistical approaches give distinct results for average molecular weights and gel points. so that use of statistical approaches outside the description of chemical equilibrium now seems more like a waste of time. ( x1 d½Px  1X ¼k ½ yð f  2Þ þ 2½ðx  yÞð f  2Þ dt 2 y¼1 þ 2½Py ½Pxy   ½A½xð f  2Þ þ 2½Px  d½A ¼ k½A 2 .4 Modeling of Complex Polycondensation Reactions tems. 129 . (122)]. ) ð122Þ ½Ajt¼0 ¼ f ½X  The two solutions are identical. Of course. although possible.3.with polycondensations presenting FSSEs. Kuchanov’s kinetic approach divides polymer molecules into classes PðxÞ having a vectorial count of groups x.

as repeating units are also An moieties. leading to a version of Smoluchowski’s coagulation equation. which will not be presented. Insertion of Eq. such as a continuous stirred tank reactor (CSTR) with constant volume. are simplified through consideration of its generating function [Eqs. (125) into mass balance equations. (124). (126)]  NR X þ GRP ðsÞ ¼ ki G ni Gni i¼1 qG qG qG qG  ½A½iþ   ½A½i  q log s½i q log s½iþ q log s½i q log s½iþ   þ NR X i¼1 ki qG ðG   1Þ q log s½i   ni ð125Þ where J Gni ¼ N XZA Y n J snin J ¼ þ. which does not make sense now. (123)]. ki A½i   ! N XZA X nin An i ¼ 1. since it is no longer possible to include breakage or exchange reactions.130 3 Polycondensation It is possible to obtain a rate equation for the members of each class by adding the contributions of the various condensation reactions. . (68). 282 with the advantage of considering only the reactions actually taking place. (125).  ð126Þ n¼1 Equation (125) replaces a similar expression in Ref. the new general rate equation becomes Eq. Ring-forming reactions involving functional groups in the same monomer can be described by a simple extension of the preceding FSSE model. and not every combination of pairs of unreacted groups. just by considering unimolecular reactions and new fake functional groups. (127)]. . which are pairs of groups [Eq.  R An NR NR X X þ ¼ ðn þ n Þk ½A ½A  þ nin ki ½A½i    i ½i ½iþ in in i¼1 ð124Þ i¼1 The multiple sums in the rate of formation of PðxÞ. Adding the unimolecular reactions defined above. leads to a nonlinear first-order PDE [Eq. NR ð123Þ n¼1 The rate of formation of groups requires a modification of Eq.

in the prediction of the moments of ½Px  with respect to the counts of groups. setting s ¼ 1NZXA [Eqs. A much simpler problem. as Galina was apparently the first to remark [287]. 284–286. (126). lmn.. If GðsÞ is to be evaluated. numerical solution of Eq. (119). earlier examples being found in Refs.4 Modeling of Complex Polycondensation Reactions   NR qG X qG qG qG qG þ ¼ ki G G  ½A   ½A  ½iþ ½i ni ni qt q log s½i q log s½iþ q log s½i q log s½iþ i¼1  þ NR X ki i¼1 qG GF ðsÞ  GðsÞ ðGni  1Þ  RV G þ  q log s½i  t GðsÞjt¼0 ¼ G0 ðsÞ ð127Þ Solution of the above equation by the method of characteristics [283] is described in Ref.3. Differentiation of Eq. 131 . or if average degrees of polymerization in the presence of gel have to be predicted. the absence of gel. (126) with respect to log sn and setting s ¼ 1NZXA leads to an ODE system with known initial conditions. is P . a rate equation for the overall concentration of polymer ½P (zeroth-order moment) is obtained from Eq. dljkP dt ¼ NR X þ  þ k m ½ðn mk þ nmk Þðnmj þ nmj Þ½A½m ½A½mþ  m¼1 þ P P þ ðn mj þ nmj Þðl½mk ½A½mþ  þ l½mþk ½A½m Þ þ P P P P P P þ ðn mk þ nmk Þðl½m j ½A½mþ  þ L½mþ j ½A½m Þ þ l½m j l½mþk þ l½mþ j l½mk   þ NR X P  P    km ðl½m   j nmk þ l½m  k nmj þ ½A½m   nmj nmk Þ þ m¼1 ljkPF  ljkP t  RV ljkP ð128Þ As there is no gel. in order to take advantage of the numerical inversion formula Eq. which has a straightforward numerical solution [Eq. NR X ½Pf  ½P q½P ¼ ki ½A½i ½A½iþ   RV ½P þ t qt i¼1 ½Pjt¼0 ¼ ½P0 ð129Þ Number-average and weight-average molecular weights are found by the wellknown expressions (130). They will not be reproduced here. 282.. (129)]. for the sake of brevity. (128)]. (127) leads to a two-point boundary solution problem with twice as many unknowns as the number of derivative terms log sn (the number of active groups in the polymer).

or alternatively. where index n counts the most frequent kind of repeating units in the molecule: n1 X RPnAA ¼ k 4 RPnBB ¼ k 4 AA ½PmAA ½Pnm  þ2 m¼1 m¼1 n1 X n1 X BB ½PmBB ½Pnm  þ m¼1 " RPnAB ¼ k n1 X n X BB 4 ½PmAA ½Pnmþ1  m¼1 ! AB ½PmAA ½Pnm   2½PnBB ½A  ½PnAB ð½A ! AB 2 ½PmBB ½Pnm  m¼1 þ  2½PnAA ½B # n1 X AB ½PmAB ½Pnm  m¼1 þ ½BÞ  kc ðnÞ½PnAB  RCn ¼ kc ðnÞ½PnAB  RPnAC ¼ k 2 n X BC ½PmAA ½Pnmþ1  m¼1 RPnBC ¼ k 2 n1 X n1 X ! AC ½PmAB ½Pnm   ½PnAC ½B m¼1 AC ½PmBB ½Pnm  m¼1 RPnCC ¼ k þ n1 X þ n1 X ! BC ½PmAB ½Pnm   ½PnBC ½A m¼1 BC ½PmAC ½Pnm  m¼1 RA ¼ RB ¼ k½A½B  y X kc ðnÞ½PnAB  ð131Þ n¼1 Modern computers will not have much difficulty with the ‘‘brute force’’ approach of solving the mass balances after inserting the above relationships for n ¼ 1 up to an upper value N of a few hundreds or even thousands (notice that this implies 11N 2 þ OðNÞ multiplications and sums every time this set of rates of reaction is evaluated).132 3 Polycondensation N ZXA X Mn ¼ N ZXA N ZXA X X MAn ½An  n¼1 Mw ¼ ½P m¼1 n¼1 N ZXA X P MAm MAn lmn ð130Þ MAn ½An  n¼1 This approach can only deal with ring-forming reactions either for a limited number of the smallest rings. . in order that extrapolation of CLD and evaluation of the infinite sum using the last . . The important practical case of the irreversible polycondensation of AXA þ BYB þ BYC (C being an inert group) leads to the rate laws in Eqs. for linear polycondensations. . PnCC and rings Cn . PnAB . (131) for the molecules with the six possible combinations of end groups PnAA . A relatively large value of N is needed if the mole ratio is close to one.

It can be described by the rate laws of Eqs. RP1AA ¼ 4k1 ½P1AA ½P1BB   2k2 ½P1AA ð½P1AB  þ ½ZB Þ þ k1Z ½P1AB  þ k2Z ½ZA  RP1BB ¼ 4k1 ½P1AA ½P1BB   2k3 ½P1BB ð½P1AB  þ ½ZA Þ þ k1Z ½P1AB  þ k3Z ½ZB  RP1AB ¼ 4k1 ½P1AA ½P1BB   ½P1AB ½2k2 ½P2AA  þ 2k3 ½P1BB  ð132Þ þ k4 ð2½P1AB  þ ½ZA  þ ½ZB Þ  k1Z ½P1AB  þ 2k2Z ½P2AA  þ 2k3Z ½P2BB  þ 2k4Z ð½ZA  þ ½ZB   2½P2AA   2½P2BB Þ n b 2: AB RPnAA ¼ 2k2 ½P1AA ½Pn1  þ 2k4 n2 X AA ½PmAB ½Pnm   2½PnAA ½2k3 ½P1BB  þ k4 ð½P1AB  þ ½ZB Þ m¼1 "  ½PnAA ½2k2Z þ 2k4Z ðn  2Þ þ k3Z ½PnAB  þ k4Z ½ZA   n X # ð½PmAB  þ 2½PmAA Þ m¼2 AB  þ 2k4 RPnBB ¼ 2k3 ½P1BB ½Pn1 n2 X BB ½PmAB ½Pnm   2½PnBB ½2k2 ½P1AA  þ k4 ð½P1AB  þ ½ZA Þ m ¼1 "  ½PnBB ½2k3Z þ 2k4Z ðn  2Þ þ k2Z ½PnAB  þ k4Z ½ZB   n X m¼2 # ð½PmAB  þ 2½PmBB Þ 133 .4 Modeling of Complex Polycondensation Reactions equation of Eqs. Through more elementary reasonings. More recently. (131) may be done accurately. taking into account the times of birth of molecules. 3.5 Kinetic Modeling of Linear Reversible Polycondensations The reversible alternating polycondensation with FSSEs in both monomers (see Section 3. is a convenient case study for discussing problems of modeling this kind of systems. When the kinetic approach was at an early stage. it is nevertheless possible to estimate probabilities of extinction and thus network elastic properties [282] or average radius of gyration [290].3. it was thought that it could provide no information about polymer or network properties. a description of batch polycondensation using TBP which is rigorously equivalent to the one obtained by the kinetic approach was found [289].4.1. A more elegant method uses generating functions [288] and avoids the problem of the lack of closure of the above equations for any finite N. (132) and (133). so that the fundamental restriction does not hold.5). disregarding exchange reactions.

(134) and (135). (136). Only when the rate constants of reverse equations are equal do the above expressions simplify (FSSE for reverse reaction). On introduction of generating functions of the CLD. and the abovementioned difficulty disappears. the concentrations of end groups. and tetramers conform with Eqs. GAA ¼ y X s n2 ½PnAA  GBB ¼ n¼2 y X s n2 ½PnBB  GAB ¼ n¼2 y X s n2 ½PnAB  ½ZA  ¼ 2GAA ð1Þ þ GAB ð1Þ ½ZB  ¼ 2GBB ð1Þ þ GAB ð1Þ ½P2AA  ¼ GAA ð0Þ ½P2BB  ¼ GBB ð0Þ ð134Þ n¼2 ½P2AB  ¼ GAB ð0Þ ð135Þ The rate equations in terms of those generating functions become Eqs. defined in Eq. (134). RGAA ¼ 2k2 ½P1AA ðsGAB þ ½P1AB Þ þ k4 s 2 GAA GAB  2GAA ½2k3 ½P1BB  þ k4 ð½P1AB  þ ½ZB Þ  2k2Z GAA  2k4Z s þ k4Z qGAA þ k3Z GAB qs ½ZA   2GAA  GAB 1s RGBB ¼ 2k3 ½P1BB ðsGAB þ ½P1AB Þ þ k4 s 2 GBB GAB  2GBB ½2k2 ½P1AA  þ k4 ð½P1AB  þ ½ZA Þ  2k3Z GBB  2k4Z s þ k4Z ½ZB   2GBB  GAB 1s qGBB þ k2Z GAB qs . trimers. it is not possible to obtain a closed finite set of rate equations for the first oligomers – rate equations for oligomers with chain length n always depend on concentrations of oligomers with chain length n þ 1. in general.134 3 Polycondensation RPnAB ¼ 4k2 ½P1AA ½PnBB  þ 4k3 ½P1BB ½PnAA  n1 X þ k4 AB ½PmAB ½Pnm  þ4 n1 X ! BB ½PmAA ½Pnmþ1  m¼2 m¼1  ½PnAB ½2k2 ½P1AA  þ 2k3 ½P1BB  þ k4 ð2½P1AB  AA BB þ ½ZA  þ ½ZB Þ þ k2Z þ k3Z þ k4Z ð2n  3Þ þ 2k2Z ½Pnþ1  þ 2k3Z ½Pnþ1  " þ k4Z ½ZA  þ ½ZB   2 n X ½PnAB   2 m¼2 nþ1 X # ð½PmAA  þ ½PmBB Þ ð133Þ m¼2 It may be observed from these expressions that.

and GBB ðt. s 0 Þ. s 0 Þ. partial differential equations. s 0 Þ to GAA ðt. GAB ðt. relating initial values GAA ð0. ds ¼ 2sk4Z dt ð139Þ The relationship of Eq. 135 . sÞ. sÞ. (139)].4 Modeling of Complex Polycondensation Reactions RGAB ¼ 4k2 ½P1AA GBB þ 4k3 ½P1BB GAA þ k4 ½2½P1AB ðsGAB þ ½P1AB Þ 2 þ 4sGAA GBB   ½2k2 ½P1AA  þ 2k3 ½P1BB  þ k4 ð2½P1AB  þ ½ZA  þ ½ZB Þ þ s 2 GAB þ k2Z þ k3Z þ k4Z GAB  2k4Z s þ 2ðk2Z  k4Z Þ qGAB ½ZA  þ ½ZB   2ðGAB þ GAA þ GAB Þ þ k4Z qs 1s GAA  ½P2AA  GBB  ½P2BB  þ 2ðk3Z  k4Z Þ s s ð136Þ Rate laws for ½ZA  and ½ZB  become Eq. sÞ. RW ¼ 4k1 ½P1AA ½P1BB  þ 2k2 ½P1AA ½ZA  þ 2k3 ½P1BB ½ZA  þ k4 ½ZA ½ZB   k1Z ½P1AB   k2Z ½ZA   k3Z ½ZB   k4Z y X ½ð2n  4Þð½PnAA  þ ½PnBB Þ þ ð2n  3Þ½PnAB  n¼2 ¼ 4k1 ½P1AA ½P1BB  þ 2k2 ½P1AA ½ZA  þ 2k3 ½P1BB ½ZA  þ k4 ½ZA ½ZB   k1Z ½P1AB   k2Z ½ZA   k3Z ½ZB    3  k4Z ½X  þ ½Y   ð½ZA  þ ½ZB Þ  ½P1AA   ½P1BB   2½P1AB  2 ð138Þ Insertion of these rate laws in mass balances of ideal reactors (batch/plug flow or transient CSTR) leads to systems of semi-linear.3. first-order. GAB ð0. with a single family of characteristics [Eq. (137): RZA ¼ 2k2 ½P1AA ð½ZB  þ 2½P1AB Þ  2k3 ½P1BB ½ZA  þ k4 ð2½P1AB 2  ½ZA ½ZB Þ  k2Z ð½ZA  þ 2½P2AA Þ  k3Z ð½ZB   2½P2BB Þ   5 þ k4Z ½X þ ½Y þ ð½ZA  þ ½ZB Þ  ½P1AA   ½P1BB   2½P1AB  2 RZB ¼ 2k2 ½P1AA ½ZB  þ 2k3 ½P1BB ð½ZA  þ 2½P1AB Þ þ k4 ð2½P1AB 2  ½ZA ½ZB Þ  k2Z ð½ZA   2½P2AA Þ  k3Z ð½ZB  þ 2½P2BB Þ   5 þ k4Z ½X þ ½Y þ ð½ZA  þ ½ZB Þ  ½P1AA   ½P1BB   2½P1AB  2 ð137Þ A rate law for by-product [Eq. and GBB ð0. (138)] is usually required. (138) allows integration along characteristics.

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). respectively. (140). for t ¼ 0. GBB ðt. as there is no simple way of describing formation of chemical species through breaking of larger ones. by-product W and differential equations for GAA ðt. GAA ðt.136 3 Polycondensation but a serious problem remains: integration along characteristics and prediction of concentration of first oligomers have to be done at the same time. GI ð0Þ ¼ GI ðsþ Þ þ GI ðs Þ þ Oðes2 Þ I ¼ AA. GAB ðt. 291). s Þ and GBB ðt. (139). the CLD of these chemical systems will stay close to equilibrium (see Ref. GAB ðt. s Þ. Notation 1N av b vector with N components equal to one film area per unit volume [m1 ] length of a Kuhn segment connecting two half-bonds in the same repeating unit [m] . As s0 is to be found iteratively in order that the characteristic starting with s ¼ s0 will attain the prescribed value of s at the prescribed time t. it is easy to relate the auxiliary characteristics to the ‘‘main’’ characteristic sðtÞ starting with s ¼ s0 through Eq. such as CSTRs in series. but very straightforward to solve. sÞ. Two auxiliary characteristics sþ ðtÞ ¼ s ðtÞ. will eventually allow the evaluation of all unknown variables of this problem. If there are more than two functional groups per repeating unit. 1. Nevertheless. owing to their branched structure. s Þ. BB. sþ Þ. sÞ. GBB ðt. the balances of end groups ZA . are introduced in order to provide an accurate numerical estimation of oligomer concentrations through Eq. this is a boundary value problem. (139). Owing to Eq. the approach described above is no longer useful. sþ ðtÞ ¼ s ðtÞ ¼ es sðtÞ ð141Þ 2. in most situations resembling industrial practice. starting at sþ ¼ es js0 j and s ¼ es js0 j. GAB ðt. sþ Þ. sÞ. Only the solution with equal reactivity has been published [291]. sþ Þ. ZB . The resolution of a system of ODE comprising Eq. AB 2 ð140Þ Parameter es should be a small value (say 106 to 108 ). 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. (141). GAA ðt.

(12) [s1 ] binary diffusivity [m 2 s1 ] bubble diameter [m] diameter of ring (in a RDC devolatilizer) [m] inner diameter of tube. an unreacted group A i . . Hi ization relating. (126) Xi G ðsX . respectively. sA Þ. F Z i ðsZ . F A i ðsZ . the bulk concentration in the water phase and the concentration in the outer interface of the polymer film. or a half-bond Z i f monomer functionality (number of functional groups it contains) equilibrium zero strain shear modulus of polymer network [Pa] Ge GðsÞ moment generating function of molar concentrations of polymer molecules with respect to their counts of monomer units and unreacted functional groups J generating functions of stoichiometric coefficients of reaction Gni i ð J ¼ þ. sA Þ. respectively. sA Þ probability generating functions (pgf ) of the counts of the different kinds of connecting and unreacted functional groups directly linked to. an unreacted group A i . as defined by Eq. with a prescribed monomer unit X i . ei F X i ðsZ . sA Þ pgf of trees starting. a monomer unit X i .  Þ. respectively. sA Þ. G A i ðsX .Notation bA Cd Cg D db dR dT Ec ei empirical parameter in Eq. or of the barrel of an extruder [m] activation energy of amidation reaction [J mol1 ] index of by-product formed by reaction leading to bond Z iR . G Z i ðsX . A giþ reacting to create bond Z i gi . no byproduct if it is nil þ indices of ‘‘half-bonds’’ of bond Z iR e i . or a half-bond Z i GM ðsM Þ pgf of mass fractions of polymer molecules in a sol g acceleration due to gravity [m s2 ] ratio mA /bA [m 3 mol1 ] gA  þ indices of functional groups A gi . (56) (dimensionless) drag coefficient (dimensionless) parameter in Eq. and the concentrations in organic phase in the two interfaces of polymer film (dimensionless) Henry constant of component W in terms of pressure versus weight HW fraction [Pa] h clearance between the screw and barrel in a vented extruder [m] index of a repeating unit carrying functional group A i hi hR 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 mass transfer rate per unit volume of component j [mol m3 s1 ] Jj K apparent equilibrium ratio of bond formation from end groups (dimensionless) thermodynamic equilibrium constant of bond formation from end K0 groups (dimensionless) 137 . sA Þ. gi H depth of liquid in the channel of a vented extruder [m] partition coefficients of hydrophilic monomer in interfacial polymerHe .

(61) [mol m3 s1 ] rate constant of exchange reaction forming bond Z iR and destroying bond Z jR rate constants of exchange reaction forming bond Z iR and replacing bond Z jR . n kscat . (53) [mol m3 s1 ] rate constant of breakage of a bond in a ring molecule through reaction with a functional group [mol m3 s1 ] first-order rate constant of L n cyclization [s1 ] rate constant of formation of Cn by the back-biting cyclization reaction [s1 ] rate coefficient of crystallization in Avrami equation [sncr ] (see below) apparent first-order rate constant of breakage of a bond in a ring molecule [s1 ] third-order pre-exponential factors of amidation rate constant [kg 2 mol2 s1 ] mass transfer coefficient of species Yi in terms of molar concentrations [m s1 ] mass transfer coefficient of species Yi in terms of activities [mol m2 s1 ] noncatalytic contribution to the rate constant in Eq. A½i or A½iþ acid-catalyzed reaction constant in Eq. (12) [m 3 mol1 s1 ] empirical parameter in Chen–Wu relation. when the attacking group is. respectively. kfcat ku0 kZ kiZ ki L Lp LR LW Lx apparent equilibrium ratio of amidation (dimensionless) reference value of the apparent equilibrium ratio of amidation (dimensionless) apparent equilibrium ratio of cyclization [mol m3 ] apparent second-order rate constant [m 3 mol1 s1 ] parameter in Eq. kijEþ kiH kiOH km k nuc. Eq. (61) [m 6 mol2 s1 ] water mass transfer rate constant [s1 ] rate coefficients of nucleation of polymer species with chain length n [s1 ] rate constants of self-catalyzed and foreign acid-catalyzed esterification [m 6 mol2 s1 ] second-order pre-exponential factor of amidation rate constant [m 3 mol1 s1 ] apparent first-order rate constant of bond group breakage [s1 ] apparent first-order rate constant of breakage of bond group ZiR [s1 ] first-order rate constant of intramolecular reaction i destroying group A½i   [s1 ] film thickness [m] thickness of polymer film in interfacial polymerization [m] thickness of reaction zone [m] width of the channel in an extruder [m] film perimeter [m] . (61) [m 6 mol2 s1 ] catalytic term of hydroxyls in Eq.138 3 Polycondensation Ka K a0 K c ðnÞ k k0 kA k aE k c ðnÞ k cE ðnÞ kcr k cZ kc0 kfYi a kfY i ki0 kijE kijE .

(56) [mol1 m 3 ] mA number of functional (or end) groups NA Avogadro–Lo¨schmidt number [mol1 ] NAL Nb number of bubbles flux of component j [mol m2 s1 ] N_ j number of distinctive chemical bonds NR number of symmetrical chemical bonds NRs number of kinds of monomer units NX number of by-products NW number of volatile (or precipitating) components NY number of half-bonds NZ NZA ¼ NZ þ NA overall number of kinds of functional groups and half-bonds NZXA ¼ NZ þ NX þ NA overall number of kinds of functional groups. and half-bonds n_ screw rotational speed (as rotations per unit time) [s1 ] Avrami exponent ncr pressure inside a bubble [Pa] Pb local pressure over a bubble [Pa] Pme vapor pressure of W [Pa] PW S PW vapor pressure of pure W [Pa] p conversion of reference functional groups A conversion of functional groups A having given rise to rings pc Q volumetric flow rate of polymer [m 3 s1 ] volumetric flow rate of gas [m 3 s1 ] Qg R ideal gas constant [J mol1 K1 ] Re Reynolds number for the rising movement of a bubble rate of formation by chemical reaction of species j [mol m3 s1 ] Rj RV combined relative rate of change of reaction volume by chemical reaction and transfer of by-product [s1 ] r stoichiometric ratio in alternating polycondensations radius of a bubble [m] rb s vector of dummy Laplace variables associating sA and sZ (defined below) 139 . where i is an arbitrary  y index y P P Mn ¼ Mi ½Pi  ½Pi  number-average molecular weight of polymer i¼1 i¼1 mass of polymer per mole of monomer units [kg mol1 ] relative  ymolecular weight of by-product W y P P Mw ¼ Mi2 ½Pi  Mi ½Pi  weight-average molecular weight of polymer i¼1 i¼1  y y P P Mz ¼ Mi3 ½Pi  Mi2 ½Pi  z-average molecular weight of polymer MP MW i¼1 i¼1 empirical parameter in Eq. monomer units.Notation M Mi relative molecular weight relative molecular weight of generic polymer species i.

140 3 Polycondensation sA vector of dummy Laplace variables associated with the counts of unreacted functional groups dummy Laplace variables associated with the counts of rings (includsCn ing sC0 for the count of units X in the chains connecting rings) for the equilibrium polycondensation of a single monomer XA f sM dummy Laplace variable associated with molecular weight vector of dummy Laplace variables associated with the counts of halfsZ bonds dummy Laplace variable associated with xZy s Zy sZl dummy Laplace variable associated with the counts of bonds not belonging to rings for the equilibrium polycondensation of a single monomer XA f T absolute temperature [K] reference temperature [K] T0 t time [s] exposure time [s] tf exposure time of liquid in the pool of a vented extruder [s] t fP bubble rising speed [m s1 ] ub average velocity in directions x. sA Þ pgf of finite pendent chains Vi Vj molar volume of species j [m 3 mol1 ] ^ pgf of finite pendent chains Vi with respect to molecular weight VMi ðsM Þ overall melt volume [m 3 ] Vm volume of liquid in compartment j in a staged model of an RDC devoVmj latilizer [m 3 ] v vector of the NZ probabilities of extinction (the fractions of finite pendent chains) average transverse velocity of the screw dragging the film [m s1 ] vT wcr weight fraction of crystalline material weight fraction of j wj weight fraction of the sol. uz V volume of reacting mixture [m 3 ] volume of a bubble [m 3 ] Vb Vi ðsZ . relative to the overall mass of the polymer wS x degree of polymerization. sA Þ pgf of pendent chains Vi V^i ðsZ . the number of repeating units in a polymer molecule x coordinate along the perimeter. z [m s1 ] ux . when discussing mass transfer from a liquid flowing over a cylindrical wall [m] vector storing the counts of functional groups xA xi degree of polymerization of generic polymer species i. where i is an arbitrary  y index y P P xn ¼ x i ½Pi  ½Pi  number-average degree of polymerization of polymer i¼1 i¼1  y y P P xw ¼ xi2 ½Pi  x i ½Pi  weight-average degree of polymerization of polymer i¼1 i¼1 .

.. xJ .. .. . b g0 parameters in Eq.. . . qF I LIJ. xJ IðxÞ moments of distribuq log sJ . qF I I lJ.Notation xX xZ xZ y y yc yP ySX i .. q log sK ating functions) with respect to logarithms of dummy Laplace parameters y y P P q . where F ðsÞ is the moment generating function of vector distribution IðxÞ a ar 141 . after gelation 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 matrix defined in Eq. (53)] (dimensionless) probability of reaction of unreacted functional groups after ring formation in the first stage (absence of open-chain molecules) of a hypothetical two-stage equilibration of XA f b g . (73) from incidence vectors z defined below Cartesian coordinate parallel to the interface [m] index of the monomer unit to which half-bond Z i points Greek empirical parameter of Chen–Wu relation [Eq.. ySZ i y Xc ðnÞ ZZX z zi vector containing the counts of monomer units vector storing the counts of half-bonds number of infinite pendent chains connected to a junction Cartesian coordinate normal to the interface [m] overall molar fraction of repeating units X in rings for a single monomer polycondensation number of moles of polymer molecules per mole of monomer units before gelation and ySA i fractions of units and groups of the various kinds in finite molecules (in a sol). q log sK x1 ¼0 xN ¼0 I tions. . (11) describing the glass effect [K] fraction of volume flow rate in compartment j going to the preceding bj compartment j  1 activity coefficient of species j gj Flory–Huggins parameter (multicomponent mixture) wij DH enthalpy of reaction [J mol1 ] DS entropy of reaction [J mol1 K1 ] d upstream distance of re-entry of film wiped by the screw in a vented extruder [m] small starting value of s in characteristic line es y screw angle ratio of rate constants of similar intramolecular and intermolecular k c ðnÞ reactions [mol m3 ] q . . . .K ðsÞ ¼ derivatives of pgf F I ðsÞ (or other moment generq log sJ .K ¼ ð1N Þ ¼ . .

for the exchange reaction forming Z iR at the expense of Z jR AEþþ ZEþþ AEþþþ ZEþþþ nijn . connected to the root unit X þþ where the living group A½ j or A½ jþ was situated. nijn . respectively. nijn changes in numbers of functional groups An and bonds Zn . lMM Chemical symbols A. B functional groups A gi 1 A½i . for the exchange reaction forming Z iR at the expense of Z jR AEþ ZEþ AEþþ ZEþþ nijn . nijn changes in numbers of functional groups An and bonds Zn . nijn . (11) [s] t0 tortuosity for by-product diffusion in a solid polymer particle tD (dimensionless) volume fraction of crystalline material fcr volume fraction of j fj fraction of channel extruder filled with liquid fL w Flory–Huggins parameter (binary mixture) (dimensionless) weight fraction activity coefficient of W WW lM . connected to the root unit X  where either A½i or A½iþ were attached. respectively. for the exchange reaction forming Z iR at the expense of Z jR W nin stoichiometric coefficients of by-products for the reaction forming Z iR  nin stoichiometric coefficient of group An for the ith intramolecular reaction concentration of elastically active network chains [mol m3 ] ne density of j [kg m3 ] rj s surface tension [N m1 ] t space time based upon feed flow rate. nijn changes in numbers of groups attached to the root unit X þ which gets connected to the unit where the attacking group was situated. ninZ Zn coming out of the monomer unit in which A½i was situated for the reaction forming Z iR Aþ Zþ nin .142 3 Polycondensation first and second moments of molecular weight of distribution of polymer m dynamic viscosity [N m1 s1 ] concentrations of elastically active network junctions (EANJ) me [mol m3 ] n stoichiometric coefficient (the change in number of moles caused by chemical reaction) stoichiometric coefficients of functional groups An and oriented bonds ninA . nijn . nijn . A giþ 1 A½iþ functional groups reacting in bond Z iR formation . nin stoichiometric coefficients of functional groups An and oriented bonds Zn coming out of the monomer unit in which A½iþ was situated for the reaction forming Z iR AE ZE nijn . Vm /Q F for a CSTR [s] tr structural relaxation time [s] parameter in Eq.

nonvolatile. Z iR is the ith distinctive bond in the chemical system bond group in fragment AXZA YZ (polycondensation AXA þ BYB) ZA bond group in fragment BYZB XZ (polycondensation AXA þ BYB) ZB bond group in dimer AXZD YB (polycondensation AXA þ BYB) ZD Zei 1 Z½i . xA Þ pendent chain starting with a half-bond Z i and containing vector counts of bonds and functional groups. respectively. nonprecipitating ring molecule with n bonds Cn linear polymer molecule with n  1 bonds and a pair of active end Ln groups length of tube LT generic polymer species.Notation Aj active component (molecular species or fragment) j. Zeþi 1 Z½iþ ‘‘half-bonds’’ of bond Z iR ZP bond group in fragment ZXZP Z (polycondensation AXA þ BYB) Subscripts aq b blk c cr F g org sat aqueous of a bubble bulk critical crystalline in feed at gel point organic at saturation Superscripts * x used for describing values of concentration at the interface average value of x Acronyms BHET BPA bis(2-hydroxyethyl) terephthalate bisphenol A 143 . xZ and xA W by-product of condensation reaction We i 1 W½i by-product of condensation reaction leading to bond Z iR X. where i is an arbitrary index Pi IJ Pn linear polymer molecule with end groups I and J and n repeating units of the most frequent kind ½U  molar concentration of species U Vi ðxZ . Y monomer units Xh i 1 X½iA monomer unit carrying functional group A i Xz i 1 X½iZ monomer unit to which each half-bond Z i points volatile (or precipitating) component j Yj Z bond group.

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and the techniques used to construct mathematical representations of bulk and solution FRP. The description will also serve as a good base for the suspension and emulsion FRP chapters that follow. Multiple monomers can be easily copolymerized via FRP. This chapter will provide an overview of the kinetics and mechanisms. as described elsewhere (see Chapter 8).153 4 Free-radical Polymerization: Homogeneous1 Robin A. Meyer. used primarily in films and packaging applications. J. and is produced via high-pressure free-radical polymerization. 4. flooring material. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co.1 FRP Properties and Applications Polymers produced via free-radical chemistry include the following major families:  Low-density polyethylene (LDPE) and copolymers. KGaA.and terpolymers with acrylonitrile and butadiene.  Polystyrene and its co. LDPE has density of <0. and films and sheet. Weinheim ISBN: 3-527-31014-2 .  Poly(vinyl chloride) and copolymers. Homopolymer is used for packaging and containers. although requiring the absence of oxygen. It can be applied to almost all vinyl monomers under mild reaction conditions over a wide temperature range and. electronics.94 g cm3 . Hutchinson Free-radical polymerization (FRP) is one of the most important commercial processes for preparing high molecular weight polymers. while the acrylonitrile-containing polymers are used for various molded products in the appliance. polyethylenes of higher density (and polypropylene) are produced via transition metal catalysis. and 1) The symbols used in this chapter are listed at the end of the text. Handbook of Polymer Reaction Engineering. is tolerant of water. under ‘‘Notation’’. used primarily to produce pipe and fittings. Edited by T. leading to the preparation of an endless range of copolymers with properties dependent on the proportion of the incorporated comonomers.

and paper and textile treatment. and is terminated in the time scale of. In addition to these major product families. a few seconds.  Acrylic. The processing and end-use properties of the polymer depend upon the distributions of these characteristics. and the final polymer product is an intimate mixture of chains formed under time and/or spatially varying conditions. due to its transparency and weatherability. The defining characteristic of FRP is that the active centers are free radicals.2 Chain Initiation Free-radical polymerization. Polyacrylates and copolymers are used extensively in the adhesives and coatings markets.  Poly(vinyl acetate) and copolymers. FRP kinetics together with reactor design and operating conditions controls the composition and architecture of the polymer produced. suspension) or homogeneous (bulk. or semi-batch. Poly(methyl methacrylate) (PMMA). and windows. As with other chemistries. The free radicals that initiate polymerization are in most cases generated by thermal or photochemical homolytic cleavage of covalent bonds. Thus it is necessary to develop methods to relate the fundamental kinetic mechanisms of free-radical polymerization to these distributed characteristics. When the macromolecule stops growing it cannot generally react further (barring side reactions). and structural properties such as branch points and branch lengths. like other chain growth mechanisms. at most. 4. Commercial initiators include azo and peroxy compounds. used extensively in adhesives.and methacrylic-based polymers. a typical chain is initiated.  Fluoropolymers including polytetrafluoroethylene and copolymers. coatings. composition. involves the sequential addition of vinyl monomers to an active center. Each growing polymeric radical increases in size rapidly. is used extensively in signs. and are also combined with acrylonitrile to make acrylic fibers. the final product consists of a mixture of polymer chains with varying length. Styrene–butadiene is the most widely used synthetic rubber. used widely in the wire and cable industry. not just the average values. These dead chains have a residence time of minutes or hours in the polymerization reactor. The driving force for the dissociation of azo . and is considered ‘‘dead’’. solution) polymerization in a wide range of reactor configurations ranging from tubular to well-mixed tanks (and everything in between) in processes that may be continuous. batch. They also have many specialty applications as coatings due to their inertness and low-surface tension. there exist many other smaller-volume (but often high-value) polymeric products synthesized via free-radical chemistry. These products are manufactured via heterogeneous (emulsion. lighting fixtures.154 4 Free-radical Polymerization: Homogeneous automotive industries. grows to high molecular weight.

Pathway (a). The tert-butoxy radical formed in both pathways may decompose to acetone and a methyl radical. CN CN CN Decomposition of AIBN. as shown for 2. Many types of peroxides (R-O-O-R 0 ) are also utilized. In general. The preferred pathway depends on the nature of the R substituent. When an initiator decomposes. R ¼ C(CH3 )3 ) [1.2. 2]. as it plays a role in the efficiency of the primary radicals in initiating new polymer chains. tert-butyl peroxypivalate. In-cage reactions for pathway (a) in Scheme 4.1. dialkyl peroxides. concerted two-bond scission.2 0 -azobisisobutyronitrile (AIBN) in Scheme 4. R ¼ CH3 ). R CH3 + CO2 + CH3 Decomposition of tert-butyl peroxyesters. peroxide decomposition can yield both carbon. the latter being used mainly in water-based systems. peroxydicarbonates. abstract hydrogen atoms from other molecules (including O CH3 CH3 . the primary radicals are nearest neighbors surrounded by a ‘‘cage’’ of other molecules through which they must diffuse to escape from each other before they recombine. Once one radical leaves the cage it is extremely unlikely that the pair will encounter each other again.4. the formation of an acyloxy and an alkoxy radical via single bond scission. N N H3C N2 CH3 + 2 C CH3 CH3 CH3 CH3 Scheme 4.and oxygen-centered primary radicals that add to the carbon–carbon double monomer bond to form a new propagating chain.2.1.2 Chain Initiation 155 initiators is the formation of the stable nitrogen molecule and resonance stabilized tertiary radicals. Scheme 4. occurs for secondary and tertiary peroxyesters (for example.2 will lead to the re-formation of the original initiator molecule. or abstract a hydrogen atom to form tert-butanol. 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. The exact nature of the decomposition pathway is important. as illustrated for tert-butyl peroxyesters in Scheme 4. tert-butyl peroxyacetate. and inorganic peroxides such as persulfate. R O CH3 O O +O (a) CH3 CH3 CH3 O R O (b) CH3 . including diacyl peroxides. peroxyesters. is favored for structures in which the carbon atom in the a-position to the carbonyl group is primary (for example. The rate of peroxide decomposition as well as the subsequent reaction pathway is greatly affected by the nature of the peroxide chemical structure. Pathway (b).

followed by the extension to multi-monomer systems. This section starts with the derivation of appropriate kinetic expressions for a single monomer system. (1). The relative rates of these processes are dependent on both the nature of the primary radicals and the monomer system.3). with a low value indicating inefficient usage of the initiator and potentially a high formation rate of undesired by-products. as this is the most common means of generating radicals in industrial systems. . Dispersed throughout are up-to-date estimates for important free-radical polymerization rate coefficients.9.3 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. Complicating (but industrially important) secondary reactions are then introduced. as the rate of initiation can be controlled through the intensity and location of the light source. n ¼ 2 for most common initiators. 4.1.4–0. The mechanistic pathway followed will influence endgroup structures of the polymeric products. and descriptions of how they are obtained experimentally. with the fraction of primary radicals that initiate a new polymer chain a complex function of the reaction system. The kinetic descriptions in this chapter are developed for thermal unimolecular scission of a compound to yield two radicals. The above discussion highlights the fact that the simple initiation process of most polymer texts is the exception rather than the rule. where n is the number of moles of primary radicals generated per mole of initiator. and bear a brief mention at this point. And finally. Further details on initiator decomposition kinetics and mechanistic pathways can be found in the excellent monograph by Moad and Solomon [3]. formally defined by Eq. Initiators with multiple peroxide linkages ðn > 2Þ have been the subject of recent academic study [4]. Thermal initiation of monomers is an additional mechanism capable of forming primary radicals at higher temperatures. as discussed for styrene (see Section 4. affecting final properties such as thermal stability.3.156 4 Free-radical Polymerization: Homogeneous polymer) in the system. Other initiation systems are also available. Nonetheless. a redox (reduction–oxidation) process is often used to initiate chains in emulsion polymerization (see Chapter 6). f ¼ Initiation Rate of Propagating Chains nðRate of Initiator DisappearanceÞ ð1Þ The initiator efficiency is normally in the range 0. the kinetic treatment is usually simplified by the introduction of a fractional initiator efficiency ( f ). or recombine to form inactive compounds. Photoinitiators that produce radicals by ultraviolet irradiation are commonly used to initiate crosslinking and curing reactions in polymeric systems.

with rate coefficient k p ). in some cases. propagation. Chain stoppage may also occur via a transfer mechanism. and transfer to monomer and solvent or transfer agent.1 Homopolymerization Many commercial polymers. and LDPE. k td ) dead polymer chains. 4. where the growing radical abstracts a weakly bonded 157 .1 k Initiator Decomposition d I  →2 f I ∗ Chain Initiation i I ∗ + M  → P1 Chain Propagation Pn + M → Pn +1 k kp Chain Termination k By Combination tc Pn + Pm  → Dn+m By Disproportionation td Pn + Pm  → Dn + Dm k Chain Transfer k mon To Monomer tr Pn + M  → Dn + M * k mon i M * + M  → P1 k sol To Solvent or Agent Scheme 4. k tc ) or two (termination by disproportionation.3. The free-radical initiator (I) unimolecularly decomposes (with rate coefficient kd ) to form two primary radicals (I  ) with efficiency f. are synthesized via homogeneous free-radical polymerization of a single monomer. tr Pn + S → Dn + S * k sol i S * + M → P1 Basic free-radical homopolymerization mechanism.4. as shown in Scheme 4. structural characteristics such as branching level. Homopolymer properties are controlled by average chain length and chain-length distribution as well as.3.3. Bimolecular coupling of two growing chains results in the loss of two radicals from the system and the formation of either one (termination by combination. PMMA.3. Each reaction has an associated kinetic rate law expression and a specific rate coefficient. and chain growth continues via successive addition of monomer units to the radical center (chain propagation. including polystyrene.1.3 Polymerization Mechanisms and Kinetics 4. termination. The subscript n denotes the number of monomeric units in growing polymer radicals (Pn ) and dead polymer chains (Dn ). Chain initiation occurs when the primary radical adds to monomer M. Basic Mechanisms The basic set of FRP mechanisms includes initiation.

but this effect diminishes rapidly with chain length and has a negligible effect on the overall kinetics of the system.3 is that the rates of propagation. 3) are faster by a factor of 10 than addition to long-chain radicals [5].158 4 Free-radical Polymerization: Homogeneous atom (usually hydrogen) from monomer or other molecules (solvent or chaintransfer agent. A key assumption implicit in the formulation of Scheme 4. denoted by S) in the system to generate a dead polymer chain as well as a new radical that initiates another polymer chain. is a very fast chemical process that is controlled by the rate at which the two radicals find each other in the reaction system. most engineering treatments of FRP neglect this complex dependence. the length(s) of the radical(s) involved. the coupling of two polymeric radicals.1. (7)]. The nature of this diffusion control makes termination the most complex reaction in the polymerization process since the apparent rate coefficient can vary greatly with system conditions such as monomer conversion and solution viscosity (see Section 4. where d is the fraction of the termination events that occur by disproportionation. and thus the two events can also be expressed by the nomenclature of Eq.3). and termination reactions are independent of n. ½Ptot  ¼ y X ½Pn  ð7Þ n¼1 In some literature the right-hand side of the termination rate expression [Eq. see Section 4. 2.2. The set of rate laws that can be written from Scheme 4. The mode of termination – combination or disproportionation – has no effect on the overall termination rate. transfer. It is known that propagation and likely transfer reactions involving very short chains (n ¼ 1.3. d¼ k td k tc þ k td ð8Þ The following assumptions are widely accepted and usually valid in FRP systems: . Initiator Decomposition R d ¼ kd ½I ð2Þ Chain Initiation R init ¼ 2f kd ½I ð3Þ Chain Propagation R p ¼ k p ½M½Ptot  ð4Þ 2 Chain Termination R term ¼ ðk tc þ k td Þ½Ptot  ¼ k t ½Ptot  Chain Transfer R tr ¼ ðktrmon ½M þ ktrsol ½SÞ½Ptot  2 ð5Þ ð6Þ Here Ptot represents the concentration of all polymer radicals in the system [Eq. (2)–(6).3. (8). Chain termination. Although termination may also exhibit some chainlength dependence. For further discussion of the individual mechanisms of Scheme 4. k t ¼ k tc þ k td .3 is given by Eqs.3 and their rate coefficients. (5)] is written as 2k t ½Ptot  2 .

 With a continuous source of new radicals in the system. the total rate of polymer radical formation is given by (R init þ R tr Þ. since transfer events both consume and create a polymeric radical species. Table 4. This characteristic. is a result of the fast dynamics of radical reactions compared to that of the overall polymerization system.   ½Ptot  ¼  R init kt 1=2  ¼ 2f kd ½I kt 1=2 ð9Þ The consumption of monomer by chain-initiation or transfer events is negligible compared to that by propagation. called the long-chain hypothesis (LCH). the average number of monomer units on a living chain). (10)–(12). it leads to the well-known analytical expression for total radical concentration [Eq.3 Polymerization Mechanisms and Kinetics The small radical species I  . the average number of monomer units on a dead polymer chain formed at any instant) are given in Eqs. an equilibrium is achieved instantaneously between radical generation and consumption. (11) and (12) arises because termination by combination yields a single polymer chain such that the chain length of dead polymer formed (DPninst ) is greater than the chain length of polymer radicals (u) in the system at the same instant. must be true if high molecular weight polymer is being produced. the classic expressions for rate of polymerization (R pol ). respectively. These can be combined with Eqs. but are converted to polymeric radicals with 100% efficiency. proven to be true for almost all FRP conditions [6]. Under these (generally valid) assumptions. such that R init ¼ R term . (9)–(12) to illustrate the tradeoffs involved be- 159 . Thus. (9)]. M  . and S  are not consumed by side reactions and do not accumulate in the system.4. Often referred to as radical stationarity or the quasi-steady-state assumption (QSSA).  1=2 R pol 2f kd ½I ¼ k p ½M½Ptot  ¼ k p ½M kt u¼ Rp k p ½M ¼ R term þ R tr k t ½Ptot  þ ktrmon ½M þ ktrsol ½S DPninst ¼ k p ½M ðk td þ 0:5k tc Þ½Ptot  þ ktrmon ½M þ ktrsol ½S ð10Þ ð11Þ ð12Þ The difference between Eqs. The net formation of polymeric radicals is R init .1 lists the range of concentration and rate coefficient values typically encountered in homogeneous free-radical polymerization systems at low conversion. kinetic chain length (u. This result. Thus the rate of polymerization (disappearance of monomer) can be taken as equal to the rate of propagation (R pol ¼ R p ) with the rate of heat generation proportional to the rate of this exothermic reaction. and instantaneous degree of polymerization (DPninst .

this theoretical limit can only be approached in homogeneous FRP by reducing rates of polymerization to extremely low levels. limiting values of DPn are 10 4 –10 6 . In some cases. For bulk FRP with no solvent. This dictates the choice of initiator such that R init (the product of kd and [I]) is also of order 108 –106 mol L1 s1 . tween the desire for high throughput (R pol ) and the need to produce high MW (DPn ) polymer. solvent or any other species in the system. Final polymer MW and MWD (molecular weight distribution) are controlled by how the concentrations and kinetic coefficients in Eq. Thus after the first few seconds of polymerization.9 10 2 –10 4 10 6 –10 8 106 –104 106 –103 104 –102 1–10 1–10 [a] At low conversion. and by the end of a typical polymerization the concentration of dead chains is orders of magnitude higher than [Ptot ]. Typical values of coefficients and concentrations in low-conversion homogeneous FRP systems. so that [Ptot ] is of the order 108 –106 mol L1 . as calculated by the expression u=ðk p ½M). (12). (12) vary with polymer conversion. chain-transfer agents are added deliberately to limit and control polymer DPn . Coefficient/Concentration Typical range kd [s1 ] f k p [L mol1 s1 ] k t [L mol1 s1 ][a] ktrmon =k p ktrsol =k p [I] [mol L1 ] [M] [mol L1 ] [S] [mol L1 ] 106 –104 0.  The denominator of Eq. must be of the order 105 –108 chains L1 s1 in order to produce polymer with a DPn of 10 2 –10 4 .1. . 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 ¼ 103 – 10 0 ) and thus can be added in trace quantities (f 1 mol L1 ). the concentration of dead polymer chains is higher than that of polymeric radicals.  To produce high MW polymer (DPn of 10 2 –10 4 ) it is necessary to keep total radical concentration low. The use of transfer agents allows for independent manipulation and control of R pol and DPn . However. the rate of dead chain formation.  The theoretical MW limit for a system is controlled by transfer events. Individual polymer radicals exist on average only for a fraction of a second.4–0. 4. and is calculated by setting [Ptot ] to zero in Eq. For most systems both termination and transfer events play an important role in controlling polymer MW.  Transfer can occur to monomer. (12). but is only possible if the desired MW is less than that achieved for the corresponding transfer-free reaction.160 4 Free-radical Polymerization: Homogeneous Tab.

Although R pol and DPn are easily measured experimentally. (12) to give Eq.1. The following discussion highlights some of these advances.4. (10)] and DPn are both dependent on k 2p =k t . especially for individual rate coefficients [8. and solvent choice (see Section 4.4).2 1 0:5k tc ½Ptot  k td ½Ptot  ktrmon ktrsol ½S ¼ þ þ þ inst k p ½M k p ½M k p ½M kp DPn ¼ 0:5k tc R pol kp2 ½M 2 þ k td R pol kp2 ½M 2 þ ktrmon ktrsol ½S þ k p ½M kp ð13Þ R pol [Eq. It should be cautioned that these statements are generalities for a typical FRP system. and knowledge of how they vary with temperature. The emergence of specialized experimental techniques since 1988 has greatly improved this situation and led to an improved understanding of free-radical polymerization kinetics. Achievable values of R pol are also often limited by the heat removal capabilities of the reactor system. are required for model development and an accurate representation of multi-monomer systems.3) and the variation of k t with conversion and other system conditions (Section 4. it is not possible to resolve the quantities into estimates for individual rate coefficients. (13).3. as well as summarizing key FRP rate coefficients as expressed by the Arrhenius law [Eq. Kinetic Coefficients The coupling of polymer MW and polymerization rate is further illustrated via rearrangement of Eq. as the heat released by monomer addition is of the order 50–100 kJ mol1 .3. 9]. but at the expense of decreased polymer MW. These factors necessitate the use of more-powerful modeling techniques to quantitatively describe FRP systems (Section 4. Faster rates can be achieved by increasing R init .1. Eqs.3. with DPn also a function of mode of termination (disproportionation versus combination) and chain transfer. (9)–(12) provide an idea of the factors controlling rate and MW. and the assumption that radicals are not being consumed or retarded by adventitious impurities in the system. and the kinetic treatment is complicated by the occurrence of side reactions (Section 4. initiator.3). Approximately 10 3 –10 5 s are required to take a batch system to complete conversion.1. k i ¼ A i expððEi þ 0:1DVi PÞ=RTÞ ð14Þ 161 .2) as well as polymerization conditions. Rate coefficients vary with monomer. Yet individual values. 7). and are very useful for a qualitative examination of FRP systems.3 Polymerization Mechanisms and Kinetics  Initial rates of polymerization (monomer consumption rates) at low conversion are of order 104 –102 mol L1 s1 . Ref. Nonetheless. These factors have led to considerable scatter in rate coefficients reported in the literature (for example. 4. (14)].3. Even the estimation of the ratio k 2p =k t from R pol requires independent knowledge of initiator characteristics f and kd .

(16)]. This unimolecular reaction is characterized by a first-order rate coefficient (kd . (2) may be integrated to yield Eq.2). but still important for high-pressure LDPE systems. In order for high polymer to be formed the propagating radical must not be too stable: addition must occur at a sufficiently high rate in comparison with competing transfer and termination events. the time needed for the concentration to decrease to half of its initial value [Eq. All second-order rate coefficients are reported with units of L mol1 s1 . with T in K and P in bar. t 1=2 ¼ ðln 2Þ=kd ð16Þ 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 significantly during the course of an experiment. where special care must be taken to eliminate transient nonisothermal effects.4). ½I ¼ ½I0 expðkd tÞ ð15Þ The decomposition kinetics is often expressed by the half-life of the initiator. Propagation In general. Values of kd at a particular temperature and pressure can be determined by measuring initiator concentration as a function of reaction time using a technique such as infrared spectroscopy. Of special note is the recent work of Buback and co-workers that systematically examines not only how Ed and DVd vary with alkyl substituent for the peroxyester family (Scheme 4. Decomposition kinetics are summarized for a wide range of initiators in the Polymer Handbook [7] and in trade literature available from commercial suppliers. and thus decomposition rates are very temperature-sensitive: the t 1=2 of benzoyl peroxide drops from 13 h at 70 C to 0. Special care must be taken in handling and transport of thermal initiators. with ½I0 the initial concentration at t ¼ 0. The experimental difficulty increases as half-life shortens. Eq.2). for a constant-volume batch system. 2].4 h at 100 C. 2]. . while an initiator used for high-pressure ethylene polymerization typically has a half-life on the order of a few seconds. Activation energies for thermal homolysis of peroxide and azo compounds are in the range of 100–150 kJ mol1 . but also how the substituent choice affects the decomposition pathway and initiator efficiency [1.162 4 Free-radical Polymerization: Homogeneous Activation energies (Ei ) and volumes (DVi ) are reported with units of kJ mol1 and cm 3 mol1 respectively. The dependence on pressure is much less. chain growth or propagation proceeds in a highly selective manner to yield a polymer chain consisting of head-to-tail linkages (Scheme 4. s1 ) so that. especially those with faster decomposition rates. (15). Initiation Thermal scission of an initiator is the most common means of generating radicals in FRP (see Section 4. in the range of 0 to 15 cm 3 mol1 [1.

many prone to significant error [8. has greatly improved the reliability of k p data. (17) yields a direct estimate of k p from the experimentally-determined value of DP0 . What 163 .2 s. typically 0. 9].2 summarizes the Arrhenius parameters for free-radical propagation of a wide range of monomers. With known values for t 0 and [M] (kept constant.1.3. a mixture of monomer and photoinitiator is illuminated by short laser pulses separated by a time of t 0 . A number of nonsteady polymerization rate techniques have been introduced to measure k p .1. Data collected from various research laboratories around the world have been compiled in a series of papers for styrene [11] and methacrylates [12–14]. 3DP0 .3). as determined by PLP-SEC. Thus. a significant fraction of dead chains formed have a chain length DP0 corresponding to a lifetime of t 0 seconds [Eq. As a result.4. In this technique. These papers provide benchmark k p data for these monomer systems. is also increased. An extensive review by Beuermann and Buback [15] contains further discussion and data for additional monomers. with the radical concentration and the rate of termination both decreasing with time according to Eq. as samples are pulsed only long enough to allow a conversion of 1–3%). PLP-SEC has proven to be a very simple and robust experimental technique for determining k p and its temperature dependence. PLP produces a well-structured MWD with peaks at chain lengths of DP0 and its multiples. . Eq.01–0. .3 Polymerization Mechanisms and Kinetics R1 CH2 R1 + C R2 Scheme 4. Table 4. Propagation and termination (but no initiation) occur between pulses. DP0 ¼ k p ½Mt 0 ð17Þ Since radicals have a certain probability of surviving the laser flash and of terminating at a later pulse. 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. provided adequate care is taken with SEC analysis. The introduction of a new method. R1 CH2 C H2C R2 R2 R1 CH2 C R2 Free-radical chain propagation.4. when a new population of short radicals are generated by the next laser pulse. due to measurement difficulties arising from additional secondary mechanisms that occur (see Section 4. (17)]. (5). the relative concentration of polymer with chain lengths 2DP0 . and make recommendations for best experimental practices. illustrate the good agreement between facilities (typically 10–20%). that couples pulsed-laser-induced polymerization (PLP) with size exclusion chromatographic (SEC) analysis of the resulting polymer [10]. as shown in Figure 4. There is a high probability that these surviving radicals will be terminated at t 0 . The data for acrylates are limited. .

8 27.d.9 23. 11.0 16.8 DP0 0.7 17..4 22. but also the similar behavior within a monomer family.2. DP0 is determined from the inflection point of the peak.d.7 11. k p at 50 C/1 atm [L molC1 sC1 ] .0 20.7 17.d.7 16.5 5 5.5 Log MW A typical PLP-generated MWD. n. All methacrylates exhibit a similar temperature (Ep of 21 to 23 kJ mol1 ) and pressure (DVp of 15 to 17 cm 3 mol1 ) dependence.2 2DP0 1 wt log(MW) 164 0. and the k p values for alkyl methacrylates at 50 C increase with increasing size of the alkyl ester group (methyl to dodecyl) by a factor of less than 2.4 Free-radical Polymerization: Homogeneous 1.5 22.5 4 4.[a] ˚ Monomer Ep [kJ molC1 ] DVp [cm 3 molC1 ] Ap [L molC1 sC1 ] Ethylene Styrene Methyl methacrylate Butyl methacrylate Dodecyl methacrylate Glycidyl methacrylate Cyclohexyl methacrylate 2-Hydroxypropyl methacrylate Vinyl acetate Methyl acrylate Butyl acrylate Dodecyl acrylate 34.7 n.7 1:47  10 7 1:66  10 7 1:81  10 7 1:79  10 7 6625 22 900 27 900 32 000 [a] All values taken from Ref. 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. Fig. 4.0 22. 4.4 17.0 12.1.0 10.4 0.2 n. Arrhenius k p parameters for various monomers determined by PLP-SEC. although the activation energies (17 to 18 kJ mol1 ) and volumes (10 to 12 cm 3 mol1 ) are lower than for methacrylates.3 32. obtained by differentiating the distribution. is striking is not only the large variation in k p and activation energies between monomer families.2 0 3.0 15.5 6 6. not determined.1 16. 1:88  10 7 4:27  10 7 2:67  10 6 3:78  10 6 2:50  10 6 6:19  10 6 6:29  10 6 3:51  10 6 54 238 648 757 995 1230 1204 1504 20. 15. and the values of k p at 50 C Tab.9 21.5 16. The alkyl acrylate family exhibits exactly the same trends.6 0.

While some progress has been made in relating activation energy to reaction enthalpy corrected for polar and resonance factors [17].6 6. The PLP-SEC method has also been utilized to show that there is little to no solvent influence on propagation kinetics of most monomers [15].4. unless otherwise indicated. the propagation kinetics of acrylic acid in water is a strong function of concentration.5 4. 4. is found in the data contained in the Polymer Handbook [7].3 Polymerization Mechanisms and Kinetics are 30 to 40 times greater.1[b] 4. a result that may be explained by a change in local monomer concentration around the propagating radical center [16]. more work is required for quantitative predictions. since the errors introduced are not large. Most measurements of k t have been carried out at low monomer conversion.7 15. Arrhenius kt parameters for various monomers. Nonetheless.1 4. as much as an order of magnitude. Termination With independent measures of k p available. However. 15.7 4.3.3. The propagation behavior is affected more significantly by electron-donating or -withdrawing substituents present in functional monomers such as glycidyl and 2-hydroxypropyl methacrylates.6 14 15 15[b] 15[b] – 20 16 21 1:6  10 9 2:2  10 9 4:3  10 8 8:5  10 7 2:8  10 7 – 6:0  10 9 5:1  10 8 2:1  10 7 2:9  10 8 2:0  10 8 9:4  10 7 1:9  10 7 6:2  10 6 (5–50)  10 7 [c] 5:1  10 8 1:2  10 8 1:1  10 7 [a] All values taken from Ref.3. equal to MMA value. Significant scatter. k t can now be estimated from the lumped ratio of k 2p =k t . Termination rates in FRP are always diffusion-controlled so that the apparent value of k t depends on the conditions under which it has been measured. the possibility of correlating the coefficient with the structural characteristics of the propagating radicals and monomers is receiving attention. including the lengths of the radicals involved in the reaction. see Section 4. the assumption of chain-length independence is usually made for modeling of commercial FRP systems.0 1.3. The uncertainty Tab. as reflected in the vinyl acetate k t data in Table 4. and thus it is useful to tabulate available data in this regime.[a] ˚ Monomer Et [kJ molC1 ] DVt [cm 3 molC1 ] At [L molC1 sC1 ] k t at 50 C/1 atm [L molC1 sC1 ] Ethylene Styrene Methyl methacrylate Butyl methacrylate Dodecyl methacrylate Vinyl acetate Methyl acrylate Butyl acrylate Dodecyl acrylate 4. For a more detailed discussion of the diffusion-controlled nature of the termination reaction. With accurate estimates of k p now available. including its strong conversion dependence. [b] Assumed 165 . [c] From Ref.1[b] – 6. 7. Specialized techniques involving pulsed-laserinduced polymerization have also been developed to yield accurate estimates of the ratio k p =k t [15].

as it affects the molecular architecture of the polymer formed. while the latter can be an important reaction impacting MWD and . and always causes a reduction in u and DPninst . The mode of termination is also of importance. and 2 if chains are terminated by disproportionation or chain transfer. these are taken from the recent review by Beuermann and Buback [15]. and thus some of its properties. termination by combination results in head-to-head linkages in the polymer chain. (8)] is difficult to measure.8 for a-methylvinyl monomers such as the methacrylates and 0.5.05–0. The reported activation energies and volumes are consistent with the diffusion-controlled nature of the reaction. It can occur to all of the substances present in the polymerization system. but is difficult to verify within the scatter of the data [19]. but transfer to initiator and dead polymer can also occur.3 are based on PLP studies. Polymer polydispersity (Mw/Mn ) is 1. Scheme 4. Chain transfer Chain transfer in radical polymerization involves the transfer of the radical center from a polymeric radical to another molecule.5 if all chains are terminated by combination of two radicals. Note the large difference in magnitude between values for styrene. and have a higher level of accuracy (within a factor of 2). (5) for the termination rate. R2 R1 R1 CH2 CH CH2 + C CH R2 Free-radical chain termination by combination and disproportionation. The rest of the data in Table 4. This has been attributed to differences in segmental diffusion rates and/or steric hindrance of the large ester side groups. The relative importance of termination by disproportionation versus combination expressed by d [Eq. The former is often neglected since [I] is small relative to the concentration of other species.5. R1 R1 CH2 + C R2 C R2 CH2 R1 R1 CH2 C C R2 R2 Scheme 4.5–0. adjusted to conform to the convention used in Eq. As shown in Scheme 4. A weak temperature dependency has been proposed.3 includes only transfer to monomer and solvent (or added transfer agent). and methyl acrylate (k t of 1  10 8 –5  10 8 L mol1 s1 ) and values for dodecyl acrylate and dodecyl methacrylate (@0:5  10 7 –1  10 7 L mol1 s1 ).166 4 Free-radical Polymerization: Homogeneous arises from a number of measurement and interpretation factors [18]. methyl methacrylate.2 for styrene and acrylates [3]. whereas disproportionation results in the formation of an unsaturated end group that may undergo further reaction. The value depends largely on the structure of the monomer: d is in the range of 0.

The form of this equation leads to the definition of a chaintransfer constant C for each species.4. The rate and MW equations in Section 4.4 summarizes values for a few typical solvents and CTA compounds at 50 C.1. As well as reducing chain length. This assumption is valid for transfer to most species. Eq.3) are incorporated as end groups in the final polymer product.3 Polymerization Mechanisms and Kinetics final polymer properties (see Section 4. since a changing ratio of ½S=½M will cause a corresponding drift in polymer MW.3.3. and Eqs. If the low-conversion polymerization rate is significantly decreased. The chain-transfer ability of a compound can be studied by varying its concentration while holding all other variables fixed. 1 1 k sol ½S ¼ þ tr DPn ðDPn Þ0 k p ½M ð18Þ A plot of 1=DPn against ½S=½M should yield a straight line with slope k trsol =k p and intercept 1=ðDPn Þ0 . 7). By stopping the reaction at very low conversion such that concentrations and diffusion-controlled k t values (and thus R pol and DPninst ) are kept constant.1. where ðDPn Þ0 is the average chain length measured in the absence of transfer agent. For very active compounds (for example. Table 4. (19). solvent is added not for its chain-transfer ability. (18).3. within about the same time period as that required for a propagation step (k imon A k isol A k p ). Thus values for Ctrsol may vary widely from a low of 106 –104 to a high of 101 –10 1 . including monomer. in Eq. and can be verified by examining whether addition of the transfer agent has an effect on polymerization rate. In such cases careful control of CTA addition to the system is required. In other systems. Solvent/transfer agent For some homogeneous FRP systems. telomerization (formation of low-MW species) will occur rather than polymerization.1 were derived assuming that the radicals formed by transfer reinitiate new polymeric radicals quickly. (13) can be rearranged as Eq. kp Ctrmon ¼ ktrmon kp ð19Þ It is these ratios and their temperature dependence that are tabulated in standard references (for example. the fragments from the transfer reactions (I  and M  in Scheme 4. but as a diluent to control viscosity and/or heat transfer.3). If it is added at higher concentrations.3. a small amount of chain-transfer agent (CTA) is added specifically to control and reduce the MW of the polymer. the species is classified as a retarding agent or inhibitor. see Section 4. thiols and halogenated compounds) with Ctrsol > 101 it is necessary to account for the consumption of CTA during the course of the polymerization. (9)–(13) no longer describe the kinetics of the system. depending on the number of weakly bonded atoms (generally hydrogen or halogen) on the transfer agent and their ease of abstraction. Ref. Ctrsol ¼ ktrsol . Most organic compounds have low transfer rates (Ctrsol of 106 –104 ) so that 167 .1.

The Polymer Handbook [7] and the monograph by Moad and Solomon [3] provide a summary of available data for a wider range of monomer–CTA (solvent) pairings. the transfer process involves H-atom abstraction to form an unsaturated new radical. assuming the absence of all other transfer and termination events. Abstraction reactions from organic solvents generally have higher activation energies than propagation.6 2  105 1  104 6  105 4  102 2  104 1.0[b] values at 50 C [7].4. 4. as solvent). and are difficult to measure experimentally since the ratio with propagation (R trmon =R p ) is independent of [M].[a] Benzene Toluene Ethyl acetate Triethylamine CCl 4 1-Butanethiol Styrene Methyl methacrylate Methyl acrylate Vinyl acetate Ethylene[b] 2  106 1  105 5  104 5  104 1  102 20 4  106 2  105 1  105 8  104 2  104 0.6.8 50 9  104 [b] 1:3  102 [b] 5  103 [b] 1:8  102 [b] 1. O H2C C O O C CH3 CH2 O C CH3 CH2 + H Free-radical chain transfer to monomer (vinyl acetate). For monomers that contain aliphatic hydrogens such as vinyl acetate and (meth)acrylates. Monomer Transfer to monomer cannot be avoided.0[b] 6. aliphatic compounds that yield tertiary radicals will be more effective transfer agents than those that produce secondary radicals. The polymer chain that grows from this radical thus contains an unsaturated end group that may undergo further reaction.168 4 Free-radical Polymerization: Homogeneous Tab. as shown for vinyl acetate in Scheme 4. react faster with nucleophilic radicals such as styrene or vinyl acetate than with (meth)acrylates.6. 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. [b] Ethylene values at 130 C and 1360 atm [20]. 22]. Transfer constants (k trsol =k p ) to solvents and transfer agents at 50 C. with (Etr  Ep ) in the range of 20–50 kJ mol1 [21. there can be an order of magnitude range in literature data. used as MW-controlling agents due to their high transfer rates. Transfer to monomer rates are generally very low. Halomethanes and thiols. For a given radical type. and the maximum upper limit of chain length that can be achieved in a polymerization is Ctrmon . The details of the mechanism depend upon the specific monomer involved.5 1  104 2  103 2  104 4  102 0. Table 4.5 summarizes O CH2 O O C CH3 C + H Scheme 4. O H2C C H C CH2 . [a] Representative transfer is important only when they are present in high concentration (that is.

 k therm L2 mol 2  s  ¼ 2:2  10 5 expð114:8=RTÞ ð20Þ 169 . (20)] [27].[a] Styrene Methyl methacrylate Butyl acrylate Vinyl acetate Ethylene[b] C trmon E tr C E p [kJ molC1 ] Reference 5  105 2  105 6  105 2  104 4  104 [b] – 23. unless otherwise noted.1.3 Polymerization Mechanisms and Kinetics Tab. Other mechanisms are more system specific.7 15. followed by the subsequent hydrogen transfer to a third styrene molecule to form two radicals that can initiate polymerization (Scheme 4. Acrylates and methacrylates have also been reported to undergo thermal polymerization. Generally the rate of radical generation by these processes is very low – negligible compared with R init from the added initiator.2 – 43. or by reactions involving trace impurities in the system.3 Thermal initiation Primary radicals in most FRP systems are generated by scission of an added initiator. This complex mechanism can be approximated by a third-order dependency on styrene concentration [Eq. Ctrmon increases with temperature.5. [a] Representative the range of values found in the literature. exhibits significant thermal polymerization at temperatures of 100 C or more. Indeed. These additional mechanisms complicate the kinetic analysis and often play an important role in controlling polymerization rate and polymer structure under typical industrial operating conditions. 4. Styrene. dependent not only on the choice of monomer but also the process operating conditions.9 7 23 24 7 25 values at 50 C. Additional Mechanisms The basic mechanisms of Scheme 4. 4. k therm 3M ! 2I  R therm ¼ k therm ½M 3 . as the rate of thermal initiation is sufficient to make an industrially viable process [26]. but is believed to involve the reversible formation of a dimeric species by a Diels–Alder reaction. The mechanism behind the thermal polymerization of styrene is still under debate.3.4. [b] At 250 C and 2000 bar. values reported in Ref. however. but at a significantly slower rate than styrene. Transfer constants (k trmon =k p ) to monomer. 7 can show an order of magnitude range.3 are common to and occur in every FRP system. it is not necessary to add initiator to styrenic systems at high temperatures. Free-radical polymerizations can also be initiated by the monomer itself. with (Etrmon  Ep ) in the range of 10–40 kJ mol1 .7).

Retardation and inhibition Some substances retard or suppress free-radical polymerization by reacting with primary or polymer radicals to yield nonradical products or radicals that are too stable to add further monomer. as shown schematically in Figure 4. can take different forms and thus must be considered on a case-by-case basis.3. in which R  represents I  or Pn ) that may form. In many academic studies. at which time polymerization proceeds at a normal rate. R inhib ¼ kinhib ð½Ptot  þ ½I  Þ½Z ð21Þ Ideally an inhibitor (Z) stops all polymerization until completely consumed (R inhib g R p ). The kinetic expressions (Section 4. since the excess of initiator-generated radicals quickly consumes the inhibitor. polymerization rate is slowed (retardation) or stopped completely (inhibition).170 4 Free-radical Polymerization: Homogeneous + CH CH + + Scheme 4.2. although the preexponential factor has been increased by a factor of 2–3 to fit 260–340 C data obtained in a more recent study [26].2). (21). polymerization will proceed at a lower rate until all of the retarding species is consumed (curve a in Figure 4. Thermal initiation of styrene. the slowing of polymerization rate by consumption of radicals. This expression from the mid-1970s has stood the test of time. Retardation. monomer is distilled or passed over a column to remove inhibitor before polymerization. If R inhib is of similar magnitude to R p . hydroquinone.7. This purification 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. kinhib R  þ Z ! dead products. Phenolic inhibitors (for example. By decreasing the concentration of reactive radicals in the system.1) cannot be applied since termination is no longer the . monomethylhydroquinone) are commonly added to monomers at parts-per-million levels in order to prevent polymerization during transport and storage by rapidly and effectively scavenging any radicals (Eq.1.

4.2. 4. Good practice requires the removal of air by sparging or freeze–thaw cycles before a reaction is started. R pol . the retardation effect will last the duration of the polymerization (curve b in Figure 4.2). and the extra mechanisms must be included when deriving expressions for [Ptot ]. k sol tr Pn + S → Dn + S * k sol i S *+ M → P1 k sol t S *+ Pn → Dn Scheme 4. vinyl acetate) than (meth)acrylates [3].8. In addition to the slower reaction rate with monomer to form a polymer radical. nitrogen) or refluxing solvent. retarded.8). which can vary with monomer type. However. 171 . and exclusion of air during polymerization by operating under an inert atmosphere (for example. As solvent/transfer agent is generally not completely consumed. application of radical stationarity yields R init ¼ R term þ R inhib .3 Polymerization Mechanisms and Kinetics Conversion Normal Polymerization Inhibition a b Retardation Time Conversion–time plots for normal. subsequent monomer addition can occur in some systems. Retardation cases a and b are described in the text. The degree of retardation depends on the value of k isol . A different form of retardation occurs when a radical species formed from transfer (S  in Scheme 4. and DPn . many carbon-centered radicals show much lower reactivity toward vinyl esters (for example. Fig. sole mechanism of radical consumption.3) reinitiates at a slow rate. Retardation of polymerization by solvent or transfer agent. Explicit balances must be written for S . and inhibited free-radical polymerizations. Oxygen inhibits or retards vinyl polymerizations by the formation of peroxy radicals that are generally unreactive. the termination of S  with other radicals in the system may also need to be considered (Scheme 4. this copolymerization forms polymeric peroxides that affect the thermal stability of the final polymer product.

Ethylene. Table 4. where DHp represents the enthalpy and DSp represents the entropy change upon propagation.  DHp ¼ Ep  Edep . polymerization can only occur spontaneously when DGp is negative. but is typically in the range of 100 to 140 J mol1 K1 . For some systems. depropagation is negligible at typical reaction temperatures. vinyl acetate. the enthalpy and entropy terms for propagation are delicately balanced so that depropagation has a significant effect on polymerization rate (R pol ) at higher temperatures [Eqs. kdep R dep ¼ kdep ½Ptot  ð22Þ The relative importance of the reverse reaction is governed by the free energy change. the polymerization rate becomes zero: Tc ¼ DHp DSp þ R ln½M ð25Þ It also provides a link between the thermodynamic and kinetic coefficients according to Eqs. the monomer concentration for a particular temperature at which the effeceff tive propagation rate coefficient (k p ) and polymerization rate become zero [Eq.6 also contains estimates of Tc calculated at ½M ¼ 1 mol L1 . to define the ceiling temperature Tc at which. DSp ¼ R ln Ap A dep  þ R lnð½MÞ ð26Þ Values of DHp for common monomers are tabulated in Table 4.6. DSp is more difficult to measure experimentally. however. With most common monomers. and acrylates have very high values. (25). (22)]. 7. DGp ¼ DHp  TDSp . K eq ¼     kp DGp DHp DSp 1  ¼ exp ¼ exp ¼ ½Meq kdep RT RT R ð24Þ This equation can also be rearranged to Eq. (23)]. (24)]. for a given monomer concentration. and depropagation does not occur under viable polymerization condi- . an expanded list may be found in Ref.172 4 Free-radical Polymerization: Homogeneous Depropagation The addition of a radical to a double bond – the propagation reaction – is potentially a reversible process [Eq. R pol ¼ R p  R dep ¼ ðk p ½M  kdep Þ½Ptot  ¼ kpeff ½M½Ptot  kpeff ¼ k p  ð23Þ kdep ½M Examining the reaction from a thermodynamic viewpoint leads to the definition of ½Meq . kp Pn þ M Ð Pnþ1 . (26).

0 1000/T (K -1) Fig. [b] Calculated tions.4 2.4 2. Tab. 4.2). as seen by comparing values for a-methylstyrene to styrene and methacrylates to acrylates.4.3 Polymerization Mechanisms and Kinetics Depropagation behavior of common monomers. the highest temperature examined.2 3.0 2.4 3. The addition of a methyl group to a monomer greatly reduces Tc .2 3 2.8 log[kpeff (L/mol-s)] 3. 28. eff Figure 4.6 173 . assuming DSp ¼ 120 J mol1 K1 . is used for some commercial processes [26].2.8 3.4 3.8 2. This temperature range. 4. the temperature dependence of kdep may be estimated directly from 4 3.2 2. 3. a-Methylstyrene Styrene Methyl methacrylate Methyl acrylate Vinyl acetate Ethylene [a] From ˚ CDH p [kJ molC1 ] [a] Tc [ C][b] 35 73 56 80 88 102 19 335 194 394 460 577 Ref. Effective propagation rate coefficient for bulk dodecyl methacrylate measured by PLP. Experimental data are taken from Ref.6 2. With known Arrhenius coefficients for propagation (Table 4. The line indicates the forward rate coefficient (k p ) calculated according to the Arrhenius parameters of Table 4. while higher than that generally employed for styrene polymerization.3 is a plot of k p measured for dodecyl methacrylate (bulk monomer) by eff the PLP-SEC technique [28].6 2. k p is 1 1 1 1 4000 L mol s . Styrene has a slightly lower ceiling temperature and depropagation must be considered above 250 C. At 180 C. less than half of the k p value of 9400 L mol s extrapolated from the lower-temperature data.6 3. 7.6.3. for ½M ¼ 1 mol L1 .

The depropagation behavior of many methacrylate monomers is similar [28]. c ! Dn. and depropagation must be considered at temperatures above 120 C. depending upon the number and distribution of the branches along the polymer backbone as well as their length. with each repeat unit linked to two others. especially for systems with low monomer concentration [29]. is a key component to manipulation and control of polymer structure. discussed in the next subsection. can have significantly different physical properties than their linear counterpoints. those in which the repeat units are not linked solely in a linear array. The common feature is the re-activation of a dead polymer chain.9. b þ Pm. The reaction of a polymeric radical with another polymer chain. Branched polymers.9. and thus has no effect on DPn . these reactions significantly broaden the polymer chain-length distribution. cþ1 . An additional subscript can be added to track the number of long-chain branches formed [Eq. Addition of monomer to the mid-chain radical produces a polymer with a branch point. Long-chain branching All of the mechanisms presented to this point do not change the basic linear architecture of the polymer chains. Long-chain branch formation by chain transfer to polymer. can occur by three distinct mechanisms. or intermolecular reactions. therefore. or long-chain branching. Intermolecular transfer to polymer The transfer of a radical center from a polymeric radical to another polymer chain is shown in Scheme 4. b þ Dm. with the length controlled by the number of propagation events before chain transfer or radical– radical termination occurs. The rate expression in Eq. Understanding the mechanisms by which these branches are formed. (27) is written assuming that all repeat units on all R1 R1 CH2 + C CH2 C CH2 CH2 CH2 + H H R1 R1 CH2 C R1 R1 CH2 + H2C CH R1 CH2 C CH2 H2C R1 CH Scheme 4. Branches can be formed either by intramolecular reactions. pol mk tr Pn. As well as creating branched structures. pol pol R tr ¼ k tr ½Ptot m1 ð27Þ This reaction does not change the number of monomer units that have been polymerized or the number of polymer chains in the system. CH2 C CH2 .4 Free-radical Polymerization: Homogeneous 174 these data. (27)]. The corresponding values for DHp (54 kJ mol1 ) and DSp (123 J mol1 K1 ) agree well with thermodynamic estimates.

Long-chain branching (LCB) levels are usually quite low. This has two important consequences. and chain scission (discussed later in this section) create polymer chains with terminal unsaturation (denoted in Eq. (28)]. as seen in Eq. Transfer constants to polymer (Ctr ¼ k tr =k p ) are not as readily determined as other transfer constants because the process does not decrease DPn .3 Polymerization Mechanisms and Kinetics dead polymer chains have an equal probability of reaction. but seldom occurs in styrene and methacrylate systems. the relative importance increases with temperature. and acrylate [36. pol ¼ R pol p ¼ k p ½Ptot ½Dtot  ð30Þ 175 . First. Like other transfer events. bþcþ1 . leading to a significant scatter pol in reported Ctr values [7]. The reaction can be important in systems with very reactive radicals such as ethylene [30–32]. the importance of transfer to polymer increases with polymer conversion (x p ) in the system.4. the total concentration of polymerized monomer units in the system [Eq. b þ Dm. Reaction with unsaturated polymer chains Termination by disproportionation. making it difficult to employ NMR. 38] are often used. but to the number of repeat units contained in the chains. can add to a growing radical to form a long-chain branch. transfer to monomer. even low levels of branching can increase polydispersity values (Mw/Mn ) to 5–15 compared to 2–3 for linear polymers. (30) by D ¼ ). pol kp ¼ Pn. such as the acetate methyl pol pol hydrogens on poly(vinyl acetate). but may also involve other easily abstracted H-atoms. as represented by m1. c ! Pnþm. vinyl acetate [33–35]. b  ð28Þ n¼1 b¼0 Note that the reaction is not proportional to the number of chains in the system. longer polymer chains – those with more repeat units – are more likely to participate in a branching reaction than short chains. m1 ¼ y X y X n½Dn. Transfer to polymer usually occurs via abstraction of a methine hydrogen as shown in Scheme 4. As well as conversion. this leads to a broadening of the molecular weight distribution reflected by an increase in the weight-average MW (Mw ). Since the re-activated chains increase in length through subsequent propagation. (29) by looking at the ratio of branching to monomer consumption.9. pol pol pol k tr x p R tr k ½Ptot m1 ¼ tr ¼ R pol k p ½Ptot ½M k p ð1  x p Þ ð29Þ Thus polymerizations operating at high monomer conversion will have significantly higher branching than low-conversion systems. Indirect methods such as multi-detector SEC [32. 37] polymerizations. Second. less than 2 per 1000 repeat units. sometimes called macromonomers. These reactive chains. the importance of transfer to polymer depends upon the monomer system.

10). Reaction with multifunctional monomers Another way to introduce branching is through addition of a multifunctional monomer to the polymer system. (31). affecting both DPn and DPw . Scheme 4.11. Reaction of the first dou- O C OCH3 C + C CH2 O O CH2CH2 O C O C CH2 H2C C C CH3 H3C H3C CH3 C CH2 O CH2 O CH2CH2 O C O C H3C CH3 CH3 C O C CH2 C H3C OCH3 + O C H2C C C CH2 C C O O CH2 CH2 O O O CH3 C C CH2 H3C CH3 Addition of ethylene glycol dimethacrylate to a methyl methacrylate radical. This reaction is fundamentally different than transfer to polymer in several respects.11. as shown in Scheme 4. The pendent double bond is attacked by another polymer radical to form a crosslink. An example is the addition of small levels of ethylene glycol dimethacrylate (EGDMA) to methyl methacrylate (MMA). to propagation is controlled by the ratio ½Dtot pol pol ¼ Rp k p ½Ptot ½Dtot  ¼ k p ½Ptot ½M R pol ð31Þ Unlike transfer to polymer.4 Free-radical Polymerization: Homogeneous 176 R1 CH2 + C R1 R1 H2C CH2 C C R1 CH2 C R2 R2 Long-chain branch formation by addition to a terminally unsaturated polymer chain. 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 ¼ =½M according to Eq. Reaction with terminally unsaturated chains can be important in vinyl acetate [33] and highertemperature methacrylate [3] polymerizations.10. CH2 O O H2C CH2 O O C C CH3 CH2 . the mechanism combines two polymer chains (and all of their repeat units) into one. It is an addition rather than a transfer (H-abstraction) reaction (Scheme 4. Scheme 4.

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 150–300 C [30]. polymer. There is strong evidence to suggest that monomer addition to the resulting mid-chain radical. Addition of higher levels leads to an interconnected branched. due to its higher stability. LDPE density is 0. This level of SCB significantly decreases the polyethylene crystallinity and gives LDPE some of its unique properties. occurs via the formation of a six-membered ring. The addition of a small amount of difunctional monomer such as EGDMA to MMA [39. in addition to the common butyl branch in LDPE. with the second reactive site remaining as a pendent double bond. where the number of short-chain branches is in the range of 20–50 per 1000 ethylene repeat units.4. Reaction of this pendent bond with another polymer radical creates a branched structure termed a crosslink. often called back-biting. 42]. 41. since the branch is tetrafunctional rather than trifunctional in nature. Monomer addition to the new radical structure creates a short-chain branch in the polymer. Short-chain branching (intramolecular transfer to polymer) Intramolecular H-atom abstraction. COOBu COOBu COOBu R CH CH CH C COOBu COOBu COOBu COOBu R CH H HC COOBu CH COOBu CH C H CH COOBu Formation of a mid-chain radical by intramolecular chain transfer to polymer.3 Polymerization Mechanisms and Kinetics 177 ble bond incorporates EGDMA in the PMMA chain. ethyl and 2-ethylhexyl branches have been identified using 13 C NMR [30. along with the observed high concentration of branch points formed at conditions of very low polymer concentration during nBA homopolymerization [36].12 for butyl acrylate (nBA). Multiple back-biting events lead to other SCB structures. or network. indicates that the intramolecular (back-biting) mechanism is also important in acrylate polymerizations. This result.92 g cm3 compared to 0. as shown in Scheme 4.12. Thus the mechanism affects nBA polymerization rate as well as polymer structure [37]. 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 hydrogen abstraction from a CH2 unit in the backbone [43]. 40] or divinylbenzene to styrene is a means to increase polymer MW without decreasing radical concentration. is much lower than addition to a chain-end radical [44].98 g cm3 for linear polyethylene. Scheme 4. The same type of back-biting reaction has also .

Scission is a dominant mechanism in styrene polymerizations at 260–340 C [26]. short-chain branch formation. yielding a short-chain radical or a short-chain unsaturated trimer species. ð32Þ RSCB ¼ kptert ½M½Q tot  ð33Þ 0:5kb ¼ Q n ! Dn2 þ P2 0:5kb Q n ! Pn3 þ D3¼ . Scheme 4. and b-scission for butyl acrylate polymerization [47]. and also occurs during LDPE production [30]. but is shown to be important at 140 C [29. kbb Pn ! Q n . Chain scission The radical structure formed by intra. Scission events can occur in any system where mid-chain radicals are formed. . Under higher-temperature conditions. The scission can occur in either direction. Kinetic treatment of these more complex mechanisms is often difficult. Scission of midchain radicals formed via intermolecular transfer to polymer can have a significant effect on the breadth and the shape of polymer MWD [46]. scission is more temperature-activated than H-abstraction and thus becomes important only at elevated temperatures.178 4 Free-radical Polymerization: Homogeneous been shown to occur during styrene polymerization at high temperatures (260– 340 C) [26]. However. The reaction is not believed to occur during butyl acrylate polymerization at 75 C [37]. As well as lowering polymer MW. R b ¼ kb ½Q tot  ð34Þ The kinetic coefficients are estimated by measuring the level of quaternary carbons (equated to short-chain branch level) and terminal unsaturations (D ¼ ) by NMR. R bb ¼ kbb ½Ptot  kptert Q n þ M ! Pnþ1 þ SCB.13. as discussed previously (see Scheme 4.or intermolecular transfer to polymer is less reactive than a chain-end radical. 45]. the scission event produces an unsaturated chain end that can react further. the radical can undergo b-fragmentation (chain scission) as shown in Scheme 4.10). COOBu COOBu COOBu CH2 C CH CH COOBu COOBu COOBu CH CH COOBu + HC COOBu CH2 COOBu CH C H COOBu COOBu CH COOBu CH CH + COOBu COOBu H2C C HC COOBu CH2 b-Scission of butyl acrylate mid-chain radical.13 for butyl acrylate [45]. Equations (32)–(34) are a network of reactions developed to treat intramolecular transfer.

2 Copolymerization Reaction of two or more monomers by free radical polymerization is an effective way of altering the balance of properties of commercial products. the presence of more than one type of monomer adds an extra degree of complexity to the kinetics. FRP leads to the formation of statistical copolymers. but not necessarily polymeriza4.3. 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). This assumption provides a good representation of polymer composition and sequence distribution.2. 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 improved oil and grease resistance. 4. Developing a set of mechanisms to describe how radical structure affects termination and transfer rates is required to represent copolymer chain length and molecular weight distributions.3. a-Methylstyrene cannot be homopolymerized to form high-MW polymer due to its low ceiling temperature (see Table 4. The different monomers form different radical structures. many questions still remain: does the mid-chain radical terminate at the same rate as chain-end radicals. The adhesive and cohesive properties of coatings resins are balanced by controlling the mix and relative proportions of monomers in the recipe. that the identity of the penultimate unit on the radical does not affect its reactivity. where the arrangement of monomers within the chains is dictated purely by kinetic factors. and the relative rates of chain growth depend on the structure of both monomer and radical. These and other similar observations can be understood by considering copolymerization mechanisms and kinetics. Vinyl acetate polymerizes about 30 times more quickly than styrene (see Table 4. However. While the mechanism provides improved understanding of this complex system. and does the mid-chain radical scission with equal probability in each direction? The reaction engineering challenge is to consider the set of mechanisms required to represent the basic rate behavior and polymer architecture of the system without introducing unneeded complexity. what is the reactivity of the unsaturated chain end. reactivity of a monomer in copolymerization cannot be predicted from its behavior in homopolymerization. yet is readily incorporated into copolymer at elevated temperatures.3 Polymerization Mechanisms and Kinetics Termination of the mid-chain radical (Q n ) is also considered in the scheme.2). that is.4.1 179 . The most common treatment of free radical copolymerization kinetics assumes that the reactivity of the polymer radical depends solely on the nature of its terminal monomer unit. Basic Mechanisms In copolymerization. yet the product is almost pure polystyrene if the two monomers are copolymerized together in a 50:50 mixture.6).

The dead polymer and radical-i chains of length n (Dn and Pni ) are made up of a mixture of the monomer types in the system. This so-called terminal model is widely used to model free-radical copolymerization according to the set of mechanisms in Scheme 4.3.2). k Initiator Decomposition d I  →2 f I ∗ Chain Initiation j I ∗ + M j  → P1 j Chain Propagation ij Pni + M j → Pn +j 1 ki kp Chain Termination ktc By Combination ij Pni + Pmj → Dn + m By Disproportionation ij Pni + Pmj → Dn + Dm ktd Chain Transfer To Monomer ktrmon ij Pni + M j  → Dn + P1 j ktrsol To Solvent or Agent i Pni + S → Dn + S * k isol j S * + M j → P1 j Basic free-radical copolymerization mechanism. However. such that kt ¼ k tij for all i and j. assuming terminal radical kinetics. For a two-monomer system assuming the long-chain hypothesis. with their relative amounts governed by the copolymer composition equation developed below. (35). as indicated by subscripts.180 4 Free-radical Polymerization: Homogeneous tion rate (see Section 4. The rate coefficients for transfer and termination reactions can also be dependent on the nature of the radical center. In this scheme monomer-j (denoted by Mj ) adds to the initiator primary radical to form a polymer radical of type-j and unit length.14 are binary parameters. Scheme 4. Most of the kinetic coefficients in Scheme 4.2. the consumption rates of the two monomers are written as in Eqs. Chain growth occurs by addition of Mj to radical-i (Pni ) with the propagation rate coefficient k pij dependent on both radical and monomer type. Thus the polymerization behavior of three or more monomers can be estimated reliably from knowledge of the corresponding binary copolymerizations. dependent on the radical and monomer type.14. since radical–radical termination is a diffusion-controlled reaction. the rate coefficient cop can usually be assumed to be independent of radical type.14. 1 2 ½M1  þ k p21 ½Ptot ½M1  R pol1 ¼ k p11 ½Ptot 1 2 R pol2 ¼ k p12 ½Ptot ½M2  þ k p22 ½Ptot ½M2  ð35Þ .

1 ½Ptot  k p21 ½M1  2  ¼ k ½M  ½Ptot p12 2 ¼ Fpinst 1 ð38Þ r1 f12 þ f1 f2 þ 2 f1 f2 þ r2 f22 ð39Þ r1 f12 Equation (39) defines the composition of the copolymer formed at any instant during polymerization. Reactivity ratios also control copolymer sequence distribution. (40)]. and substitution and rearrangement leads to the well-known polymer composition equation [Eq. (Fpinst i Fpinst 1 Fpinst 2 ¼ 1 2 R pol1 k p11 ½Ptot ½M1  þ k p21 ½Ptot ½M1  ¼ 1 2 ½M  R pol2 k p12 ½Ptot ½M2  þ k p22 ½Ptot 2 ð37Þ Application of the quasi-steady-state assumption yields the ratio of the radical types as in Eq. (42) and (43). (39)]. i ½Ptot ¼ y X ½Pni  ð36Þ n¼1 The ratio of the two consumption rates dictates the instantaneous composition ) of the polymer being formed [Eq. Copolymer properties depend on the distribution of the monomer units along the chain as well as the average composition. P12 ¼ 1  P11 ¼ f2 r1 f1 þ f2 ð41Þ Similar expressions.4. Eqs. can be derived for addition to radical-2: 181 . P11 ¼ 1 k p11 ½Ptot ½M1  1 1 ½M  k p11 ½Ptot ½M1  þ k p12 ½Ptot 2 ¼ r1 f1 r1 f1 þ f2 ð40Þ The probability P12 that an M2 unit follows an M1 is given by Eq. where f1 and f2 are the mole fractions of M1 and M2 in the monomer mixture. (41). The probability P11 that an M1 unit follows an M1 unit in the copolymer is equal to the rate of M1 M1 formation divided by the sum of the rates of all additions to radical-1 [Eq. (36)]. and monomer reactivity ratios r1 and r2 are defined as k p11 =k p12 and k p22 =k p21 . (37)].3 Polymerization Mechanisms and Kinetics i where Ptot represents the concentration of all polymer radicals of type-i in the system [Eq. (38). and is dependent only on the ratios of the propagation rate coefficients and not on their absolute values.

n 1 NðM2 . n i 1 NðM1 . The overall rate of monomer consumption is given by Eq. (39). the fraction of M1 contained in isolated diads is 2P11 P12 . the fraction of triads is 2 P12 . fri [Eq. valid for long-chain polymer.182 4 Free-radical Polymerization: Homogeneous P22 ¼ 2 k p22 ½Ptot ½M2  2 2 ½M  k p22 ½Ptot ½M2  þ k p21 ½Ptot 1 P21 ¼ 1  P22 ¼ ¼ r2 f2 r2 f2 þ f1 f1 r2 f2 þ f1 ð42Þ ð43Þ These probabilities can be used to calculate NðM1 . 1  P11 P12 N2 ¼ 1 1 ¼ 1  P22 P21 ð45Þ Implicit in these expressions is the approximation. that the number of M1 M2 linkages in a chain is equal to the number of M2 M1 linkages. n i Þ ¼ P11 P12 . Fpinst 1 Fpinst 2 ¼ N1 N2 ð46Þ Substitution and rearrangement of this equation yields the polymer composition equation. 1 2 1 2 R pol ¼ k p11 ½Ptot ½M1  þ k p21 ½Ptot ½M1  þ k p12 ½Ptot ½M2  þ k p22 ½Ptot ½M2  ! 2 2 XX ¼ k pij fri fj ½Ptot ½Mtot  ð47Þ i¼1 j¼1 The fraction of radical-i in the system. (45) and the fraction of all M1 units contained in a sequence of length n i is n i 1 2 2 P12 . where [Mtot ] indicates the total monomer concentration (½M1  þ ½M2 ). (48)] can be calculated from Eq. nj Þ ¼ P22j P21 ð44Þ Thus the fraction of M1 sequences that consists of an isolated M1 unit is P12 . and so forth. the same is not true for polymerization rate. . This is simply the probability of having ðn i  1ÞM1 M1 linkages followed by an M1 M2 linkage. The number-average length of M1 sequences (N 1 ) is given by P11 Eq. Thus it is possible to estimate reactivity ratios for binary copolymers from triad distributions measured by NMR analysis. according to Eq. the fraction of all M1 sequences that are exactly n i units long. (47). n i Þ. Eq. (46)]. Thus the ratio of M1 to M2 units in the chain must equal the ratio of the respective average sequence lengths [Eq. (38). (44). the fraction that consists of isolated M1 M1 diads is P11 P12 . that is. While copolymer composition and sequence distribution are only functions of the reactivity ratios. n i P11 N1 ¼ 1 1 ¼ .

3. The scatter for these ratios is much less than found in k p and k t data. the total radical concentration.4). (50).1. (47) is analogous to the homopolymerization rate expression [Eq. is calculated from an overall radical balance similar to Eq. k pcop ¼ r1 f12 þ 2f1 f2 þ r2 f22 ðr1 f1 =k p11 Þ þ ðr2 f2 =k p22 Þ ð51Þ Using Eqs. (51). NMR measurement of sequence distributions provides additional information about chain microstructure. (9) and given by Eq. (39) must be used [50]). or if the experimental system does not remain homogeneous (often observed with acid monomers). the copolymerization reaction rate can be analyzed as for cop homopolymerization (see Section 4. 49]. ½Ptot  ¼     R init 1=2 2f kd ½I 1=2 ¼ cop cop kt kt ð49Þ The form of Eq. with a copolymer-averaged rate coefficient for propagation (generalized for a system with Nmon different monomers) defined in Eq. summarized in Ref.3 Polymerization Mechanisms and Kinetics fri ¼ i Ptot Pi ¼ tot 2 þ Ptot Ptot 1 Ptot ð48Þ [Ptot ].3.2 183 . 4.4. (10)].2. There is a large body of published r1 –r2 data for monomer pairings. application of the QSSA [Eq. Kinetic Coefficients The traditional method for determining reactivity ratios involves determination of copolymer composition for a range of monomer feeds at very low conversion. (38)] and simplification lead to Eq. but suffers from greater experimental noise and signal assignment uncertainty from tacticity effects. but care still must be exercised when extracting values from this and similar compilations. Some error can arise from the methodology used to estimate r1 and r2 from Fp1 versus f1 data. The estimation is best accomplished by nonlinear least squares techniques [48. 7. 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 sufficiently high for f1 to deviate significantly from the zero-conversion value (in which case an integrated form of Eq. (47)–(51). that is. measuring Fp1 as a function of f1 . with k p now a function of monomer composition. (49). k pcop ¼ Nmon X Nmon X k pij fri fj ð50Þ i¼1 j¼1 For a two-monomer system.

Table 4.058 0.7. alternative kinetic models that include the formation of monomer complexes have been developed to represent these systems [3.02 0.8: While r1 (1 ¼ ethylene) values for alkyl methacrylates.058 1. or the observed reactivity ratios in the system vary with monomer concentration or solvent choice.4 0. Monomer reactivity ratios at 50 C[a]. styrene–maleic anhydride). and vinyl acetate systems.058 0. The majority of systems. 4. 7. 54]. Monomer reactivity ratios for ethylene (monomer-1) systems at 240 C and 2000 bar [53.0 7 11 4 8 1.4 the relationship between polymer and monomer composition is plotted for various copolymer systems: Tab.03 40 20 6 – values Ref. There are only a few systems for which the terminal model upon which Eq. Monomer-2 r1 r2 Alkyl methacrylates Methacrylic acid Alkyl acrylates Acrylic acid Vinyl acetate [a] 0.058 0. are well behaved and well represented by the terminal model. r1 is tabulated horizontally and r2 vertically. 7.8. with the composition data of various systems fitted well by a single curve [52]. however. and methacrylic acid could not be distinguished within experimental error [53]. methyl. . The resulting polymers exhibit an alternating structure (for example. It is informative to consider some of the implications of these values. In Figure 4. Values for ethylene copolymer systems at typical production conditions are summarized in Table 4. 51].4 0. dodecyl) exhibit a family type behavior. Reactivity ratios for alkyl methacrylates and acrylates (for example. butyl. alkyl acrylate. 4.0 [a] From Ref. alkyl methacrylate.7 summarizes values of reactivity ratios for styrene. alkyl acrylates. (39) is based does not provide a good description of copolymer composition.03 0. Since they often include a polar monomer with strong electron-withdrawing or electron-donating properties.2 0.6 – 0. Monomer-1 Monomer-2 Styrene Alkyl methacrylate Alkyl acrylate Vinyl acetate [a] Representative Styrene Methacrylate Acrylate Vinyl acetate – 0. there were significant differences in the r2 values [54].8 2.184 4 Free-radical Polymerization: Homogeneous Tab.2 – 0. acrylic acid.

9 0.4 0. and styrene. 185 .3 Polymerization Mechanisms and Kinetics 1 0. the ratios tend to approach unity as demonstrated for styrene–butyl acrylate [55].  With both r1 and r2 less than unity (styrene–acrylate.7 0. For the case where r1 ¼ r2 ¼ 1:0 (ethylene–vinyl acetate.3 0. and ethylene copolymer systems [53. With increasing temperature.6 0. Eth ¼ ethylene).7 Fp 1 0. the greater the deviation between polymer and monomer composition.8 0.6 0.  Reactivity ratios exhibit a weak temperature dependence that is often difficult to measure. Sty ¼ styrene.1 0 0. VAc ¼ vinyl acetate. The system has an azeotropic composition at which the copolymer composition is exactly equal to the monomer composition. the monomers have equal reactivity to propagation and will be incorporated into polymer at the same ratio as they are in the monomer phase (Fp1 ¼ f1 ). methacrylates. MA ¼ methyl acrylate.4. butyl acrylate–methyl methacrylate [56]. The temperature dependence of the latter agrees well with activation energies reported for addition of monomers to small radicals [57]. the copolymer will always be richer in monomer-1 than in the monomer phase.0 0.0 f1 Fig. Relationship between monomer composition f1 and corresponding instantaneous polymer composition Fpinst for 1 various monomer pairings (MMA ¼ methyl methacrylate. styrene–methacrylate).4 0.2 0. Systems that exhibit this behavior include methacrylate–acrylate polymerizations. cross-propagation is favored over homopropagation and the copolymer tends toward an alternating structure. or acrylates polymerized with vinyl acetate or ethylene. 4. 54].5 0.  Where r1 > 1 and r2 < 1.9 1.8 0. so that monomer-1 will become depleted in a batch polymerization.5 0. The further the reactivity ratios deviate from unity. methacrylate– methacrylate).4.1 0.3 MMA-Sty MMA-MA MMA-VAc Eth-VAc 0.2 0.

90 1. including styrene–methacrylate [51. e) [62] and MMA–styrene (---. Lines are calculated assuming terminal-model kinetics and points are experimental data for: MMA–nBA (—. cop k p . however.0 10.5. with the deviation substantial in some cases.00 f 1 (MMA) Fig. 61]. it does not provide as good of a description of polymerization propagation behavior. Many common systems show deviation from terminal propagation kinetics.5. 59].0 kp 186 100.80 0.10 0. Relationship between monomer composition f1 and corresponding copolymer-averaged propagation rate coefficient.40 0.70 0.0 0.00 0. provides a good representation of this behavior [Eqs.0 cop (L/mol-s) 10000. (52)]. 62] systems. As cop shown in Figure 4. and acrylate–methacrylate [52. C) [59] at 20 C.50 0. which accounts for the influence of the penultimate monomer unit of the growing polymer radical on the propagation kinetics [51]. Careful experimental work by Fukuda and co-workers [51]. The ‘‘implicit penultimate unit effect’’ model.4 Free-radical Polymerization: Homogeneous 1000. k pcop ¼ k p11 r1 f12 þ 2f1 f2 þ r2 f22 ðr1 f1 =k p11 Þ þ ðr2 f2 =k p22 Þ k p ½r1 f1 þ f2  ¼ 111 r1 f1 þ ½ f2 =s1  k p22 k p ½r2 f2 þ f1  ¼ 222 r2 f2 þ ½ f1 =s2  ð52Þ .20 0.60 0. the measured k p values can be higher or lower than the terminal model predictions. While the terminal model effectively represents copolymer composition for most systems. with further evidence obtained by applicacop tion of the PLP-SEC technique to measure k p . 4.30 0. Rate abnormalities have previously been attributed to termination reactions and represented by introducing physically unrealistic cross-termination mechanisms [58]. styrene–acrylate [60. demonstrated that the rate deviations are due to the inadequacy of the terminal model to describe propagation.

(For a discussion of transfer to monomer in copolymer systems. (53)]. called radical reactivity ratios. 11 r11 21. 22 r22 12.1. k p211 k p111 s1 ¼ s2 ¼ k p122 k p222 ð53Þ A value of greater than unity for si indicates that a comonomer unit-j in the penultimate position increases the addition rate of monomer-i to radical-i compared to the homopolymerization case. the kinetic studies summarized in this section indicate that adcop ditional parameters and penultimate radical fractions are required to represent k p cop and kt . with frij ði. When the deviation of propagation kinetics from the terminal model is taken into account.3 also occur in multi-monomer systems.3 Polymerization Mechanisms and Kinetics The extra parameters s1 and s2 . cop f þ kt0:5 f þ kt0:5 f þ kt0:5 f ðkt Þ 0:5 ¼ kt0:5 11. with the cross-termination coefficients k t 12. it is necessary to track the four possible penultimate radical types in the system.4. 63] that accounts for the influence of polymer composition on segmental diffusion is required to fit recent acrylate– cop methacrylate low-conversion kt data [63.3 187 . The kinetics of diffusion-controlled termination in copolymerization is also difficult to study. however. styrene–acrylate. 2Þ the penultimate radical fraction. capture the effect of the penultimate unit on the addition rate of monomer [Eqs. The kinetics of depropagation. and chain scission are strongly influenced by not only the nature of the monomer and terminal radical. Additional Mechanisms The secondary mechanisms presented for homopolymerization in Section 4.2. (54)]. cop kt ¼ Nmon X Nmon X i¼1 j¼1 k tij fri frj . j ¼ 1. The original interpretation of low-conversion rate data was based on a chemically controlled model utilizing a cross-termination factor [Eq. 12 r12 ð55Þ While the terminal model and reactivity ratios provide a good description of copolymer composition. cop the estimates for kt become well behaved and bounded by the homotermination values [51]. chain transfer to polymer. and other systems cop such that kt was greater than either homotermination value. but also the penultimate unit on the polymer radical. 21 fitted to experimental data). 65. 12 and k t21. 21 r21 22. F¼ k t 12 k t 11 k t22 ð54Þ Assuming terminal propagation kinetics. It is expected that this situation will change as more data become available. A penultimate model [51. (55).3.) These mechanistic complexities are often not considered when developing FRP models for polymer reaction engineering applications. In order to use this representation (Eq. 64]. the best fit for F was found to be much greater than unity for styrene–methacrylate.3. 4. see Ref.

and general expressions have been developed for the situation where all four of the propagation reactions are reversible [66.6).4 Free-radical Polymerization: Homogeneous kp 11 → ~~~ M 1M 1 . Depropagation in copolymerization affects polymer composition. (56) (compare with Eq. depropagation of monomer-1 will occur only if an M1 unit is also in the penultimate position. (25) and Table 4. Depropagation of radical-1 becomes a competitive process with addition of monomer-2. (57). 69]. 70]. Depropagation must be considered when examining the kinetics of starved-feed semi-batch copolymerization involving methacrylates at the highertemperature conditions typically used to produce acrylic coatings [29. (37) in the absence of depropagation). 67]. the relative rates of monomer consumption are given by Eq. The effect of depropagation becomes larger as total monomer concentration decreases and as the fraction of the depropagating monomer in the system increases. With Scheme 4. Thus MMA can be successfully copolymerized with ethylene at 290 C [57]. ~~~ M 1 ⋅ + M 1   → 188 kdep 11 kp12 ~~~ M 1 ⋅ + M 2 → ~~~ M 1M 2 . this is represented by Eq. with monomer-1 units at the radical end becoming irreversibly trapped in the growing chain as soon as monomer-2 adds. Addition of a non-depropagating monomer (M2 ) to the system disrupts this behavior.15. Furthermore. kp 21 ~~~ M 2 ⋅ + M 1   → ~~~ M 2 M 1 . and polymerization rate. For the case of intermolecular chain j transfer (long-chain branching). sequence probabilities. Depropagation It is not possible to produce high MW homopolymer close to the ceiling temperature of the monomer (see Eq. and a-methylstyrene with various comonomers at temperatures well above its ceiling temperature [66.15.15. where m1 represents the total concentration of polymerized monomer-j units in the system and . Lowry [68] first derived the composition expressions for the situation where only one monomer depropagates. Scheme 4. kp 22 ~~~ M 2 ⋅ + M 2  → ~~~ M 2 M 2 . depropagation to the less-stable M2 radical can be assumed to be unlikely (kdep21 A 0). 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. Depropagation in copolymerization for the case where M2 does not depropagate and M1 depropagates only when an M1 -unit is in the penultimate position. as illustrated by Scheme 4. Fpinst 1 Fpinst 2 R pol1 ¼ ¼ R pol2 fr11 ½P 1  fr11 þ fr21 tot 1 ½M  þ k ½P 2 ½M  k p12 ½Ptot 2 p22 tot 2 1 2 k p11 ½Ptot ½M1  þ k p21 ½Ptot ½M1   kdep11 ð56Þ The ratio fr11 =ð fr11 þ fr21 Þ accounts for the fraction of radical-1 that ends in a 11 diad.

The overall back-biting rate must be corrected for the sequence probabilities [Eqs. Thus it is not uncommon for the intermolecular transfer to polymer rate of one pairing (for example. cþ1 . (40)–(43)] at the chain end.16. j m1 ¼ y X y X nj ½Dn. Scheme 4. b . COOBu C H3C H COOBu C CH COOBu 189 . 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. COOBu COOBu C C R H COOBu COOBu COOBu CH CH C C R HC H CH COOBu COOBu COOBu C C R H H3C COOBu C COOBu COOBu COOBu C R HC COOBu Back-biting reaction in high temperature copolymerization of butyl acrylate and butyl methacrylate (R ¼ H or CH3 ). according to Eq. In the case of acrylate (1)/ methacrylate (2). c ! Dn. vinyl acetate) are more likely to abstract from a polymer chain than styrenic or methacrylate radicals.3 Polymerization Mechanisms and Kinetics nj represents the number of monomer-j units on a particular chain of length n [Eqs.16 [70]. (58)]. pol mj k tr j ij pol Pn. acrylate. b þ Pm. The situation is more complicated in the case of intramolecular transfer.i b þ Dm. as shown in Scheme 4. Thus back-biting can occur only for two monomer sequences (M1 M1 M1 and M1 M2 M1 ) at the radical end. acrylate radical to acrylate monomer unit) to dominate the system.4. which occurs through the formation of a six-membered ring. with pol the overall transfer rate R tr decreasing rapidly with increasing content of the lessreactive monomer. and acrylate and vinyl acetate monomer units on a chain are more likely to have an H-atom abstracted. n¼ n¼1 b¼0 Nmon X R tr ¼ Nmon X Nmon X j pol i k trij ½Ptot m1 ð57Þ i¼1 j¼1 ð58Þ nj j¼1 Active radicals (ethylene. (59).

17.16. Scheme 4. Fragmentation after intramolecular transfer results in the formation of a longchain radical and trimer species or a dimer radical and an unsaturated dead chain (Scheme 4. Consideration of all possible pathways and structures becomes complex.3 Diffusion-controlled Reactions The kinetic schemes in this chapter have been written assuming that k t is independent of the sizes of the radicals involved in the termination reaction. Chain scission There is evidence that the rate of b-fragmentation of a mid-chain radical is affected by the nature of the units adjacent to the mid-chain radical.13).17. Thus it was deduced that fragmentation greatly favors the generation of tertiary (methacrylate chain end) radical species. H-abstraction only happens to the acrylate unit.3. It was observed that the number of the unsaturated end groups per chain is increased by increasing the methacrylate content in the polymerization. two types of fragmentation with different reaction rates are possible. [72] studied the copolymerization of cyclohexyl acrylate and methyl methacrylate at high temperatures. This is not . If the adjacent units are acrylate and methacrylate. CH3 CH3 C CH2 HC C CH2 fast CH2 C + CH2 H2C CO2CH3 CO2CH3 CO2CH3 CO2CH3 CO2CH3 CH2 C HC CO2CH3 CH3 slow C CH2 C CH2 CO2CH3 CH2 CO2CH3 + HC CO2CH3 Fragmentation of a mid-chain radical with adjacent MA and MMA units (after Ref. Harada et al.190 4 Free-radical Polymerization: Homogeneous 1 R bb ¼ kbb ½Ptot ðP11 P11 þ P12 P21 Þ ð59Þ Back-biting mechanisms have also been examined for styrene/acrylate [71] and ethylene copolymer systems [43]. a result in agreement with the high rate of fragmentation observed in methacrylate macromonomer systems [73]. 72). 4. but the resulting model requires no additional parameters from the homopolymerization back-biting/scission case and provides a good representation of high temperature acrylate–methacrylate copolymerization [70]. as illustrated in Scheme 4. As in Scheme 4.

the errors involved by neglecting the dependence of k t on radical chain length are not large. Through the application of pulsed-laser experimental techniques [15] and a critical examination of available data [18].6 shows the three to four orders of magnitude decrease in k t typically observed.8 0. cannot be neglected. strictly true.0E+03 1. In this region k t is of the order of 10 8 L mol1 s1 for many common monomers (Table 4.6. 4.4.2 0.3 0. since the termination rate is limited by the rates at which the radical ends can encounter each other.5 0. and the two chains diffuse together quickly. has led to a large scatter in reported values. the internal reorganization of the chain that is required to bring the reactive ends together. and MW) and the lengths of the two terminating radicals. The rate of reaction is controlled by segmental diffusion. the apparent rate coefficient is affected not only by pressure and temperature.0E+09 1.0E+07 1.4 0.1 0. polymer concentration.0E+06 1. Solvent choice can have a significant effect on the value [18]. For most commercial free radical polymerization. as well as experimental difficulties in measuring k t .0E+05 MMA nBA DA 1.0E+04 1. The change in k t with conversion (increasing viscosity). For a diffusion-controlled reaction. butyl acrylate (nBA). Typical variation of k t with conversion for methyl methacrylate (MMA). however.3 Polymerization Mechanisms and Kinetics 1. Figure 4. The usual division is as follows:  Low conversion: the system viscosity is still low.7 0. even at low conversion [7]. This complex behavior.0E+08 kt (L/mol-s) 1.9 1 Conversion Fig. and dodecyl acrylate (DA). Based upon data from [15]. 191 . with the value remaining relatively constant up to 10– 20% conversion. the situation is starting to improve.3). The shape of the curve reflects the changing nature of the rate-controlling diffusion mechanism.0E+02 0 0.6 0. but also by system viscosity (a function of solvent.

and reaction diffusion.3.  Very high conversion: at high conversion. (60)]. RD ð60Þ The subscripts SD. It is observed experimentally that addition of a powerful chain-transfer agent to MMA lowers polymer MW and system viscosity. RD is set proportional to propagation. called reaction diffusion. translational diffusion. leads to a second plateau region in the k t versus conversion plot. k t. The latter treatment relates the chain diffusivity to the system free volume vf by Eq. or free volume. SD can be set to the low conversion values summarized in Table 4. The overall behavior of k t with conversion is often modeled as a composite of the various diffusional processes [Eq. (62). The variation of low-conversion k t with polymer composition in copolymer systems can be represented by Eq. the propagation reaction and apparent initiator efficiency [75] may also become diffusion-controlled. TD as a function of system viscosity. (55). (61)]. and k t. conversion. The rate of reaction is controlled by how quickly the two chains find each other among the tangle of dead polymer chains in the system. with parameters Ci fitted to experimental data. TD z C1 expðC2 vf Þ ð62Þ This effect of polymer MW on system viscosity may be captured by expressing C1 as a function of Mw . k t. TD þ k t. If the glass transition temperature of the reaction mixture exceeds the reaction temperature. 1 1 1 ¼ þ k t k t. Even lower k t values are measured for termination during polymerization of sterically hindered monomers such as the itaconates [74] and acrylate trimer species [44]. with k t proportional to k p ð1  x p Þ. the system may become so viscous that the polymer radicals move more quickly through propagation (addition of new monomer units) than by translation. SD k t. affected by the lengths of the reacting chains as well as the system viscosity.  Medium to high conversion: the large increase in system viscosity with polymer formation leads to a change in the controlling mechanism.192 4 Free-radical Polymerization: Homogeneous Lower values of 10 6 L mol1 s1 for dodecyl (meth)acrylate is attributed to shielding of the radicals by the long-chain dodecyl ester groups. TD. This phenomenon. thereby in- . This so-called center-of-mass or translational diffusion mechanism is complex. The value of k t can drop by several orders of magnitude in this regime. for these monomers k t remains relatively constant up to 60% conversion [64]. k t. and RD refer to segmental diffusion. with proportionality coefficient CRD fitted to experimental data [Eq. RD ¼ CRD k p ð1  x p Þ ð61Þ Many semi-empirical approaches have been used to model k t.

4 0.4. The severity of the gel effect is directly related to the magnitude of the decrease in k t .2 MMA nBA 0. The sharp increase in rate seen for MMA. This accelerated rate is accompanied by a large heat release that can be difficult to remove from the viscous reaction system. (9)] and a corresponding increase in R pol [Eq. and one that produces dozens of differ- 193 .8 Conversion 0.3 0.4 Polymer Reaction Engineering 1 0. creasing k t .5 0. Typical time–conversion plots for methyl methacrylate and butyl acrylate batch polymerizations. The large decrease in k t at intermediate conversion results in an increase in radical concentration [Eq. (13)] for systems where MW is controlled by termination.6 0. while addition of a small amount of EGDMA crosslinking agent has the opposite effect [39].4 Polymer Reaction Engineering The design of an industrial polymerization process begins with a clear understanding of objectives and an appreciation of constraints. (10)] that causes an upward curvature in the time–conversion plot (Figure 4.1 0 0 500 1000 1500 2000 time (s) Fig. 4. Details and variations of this modeling approach can be found in the literature [40. The decrease also leads to an increase in DPninst [Eq.9 0.7 0.7.7). known as the gel effect. as seen by comparing the nBA and MMA rate profiles in the figure. is due to the large decrease in k t with conversion. Design and operation requirements are very different for a process manufacturing several grades of a high-volume commodity homopolymer. A good model for k t is necessary to capture the time–conversion behavior in homogeneous batch FRP systems. 76–79]. 4.

Invariably the end-use properties are a product of not one but several structural features. and therefore it takes longer for desired changes (for example decreasing the reactor temperature) to occur. Design of a process involves several decisions such as the type of reactor used. and termination [see Eq. propagation. provided the reactor . and so on.194 4 Free-radical Polymerization: Homogeneous ent (and often new) low-volume higher-value products of varying composition and structure. and the ensuing relationships are usually restricted to a narrow range of materials. The difficulty of characterizing polymer structure on-line makes design of a robust easy-to-operate process especially important. (Values of DHp for common monomers are tabulated in Table 4. Knowing the extent to which deviations from the target value of a property affect the manufacturer’s ability to sell that product is a critical piece of design information. (10)] is on the order of 80 G 15 kJ mol1 . Heat removal Free-radical polymerizations are highly exothermic. with adiabatic temperature rises for bulk monomers typically @200–500 C. Heat removal is also an important issue to consider during process scale-up.) In addition. degree of branching/branching distribution. the flow and contacting patterns for the reagents. therefore establishing relationships is a complex task. the overall activation energy for a radical polymerization. This may in itself not be a serious problem.6. any of these properties can simultaneously be product specifications. If there is a process disturbance leading to a thermal runaway condition. Unlike many chemical systems. the system dynamics become increasingly slow. The resulting temperature increase can pose serious safety concerns such as reactor overpressurization and possible explosion. This poses the challenge of relating structural features to properties. and sequence length distribution. there will naturally be some degree of process variability that will translate into product variability. copolymer composition/copolymer composition distribution. As reactor size increases. Heat removal and mixing issues are two key factors that strongly influence design and operation of homogeneous FRP processes. the choice of homogeneous versus heterogeneous process types. Depending on the nature of the product. off-spec polymeric material cannot be easily recycled or altered by downstream unit-operations. calculated from the activation energies of initiation. The sudden and dramatic increase in the heat produced in the gel-effect region can result in loss of effective temperature control. the polymer is ultimately not sold on basic structural characteristics but rather on end-use properties. In an industrial polymerization environment. However. Establishing structure–property relationships remains an active area of research. the heat generation rate can exceed the heat removal rate to such an extent that the reaction behaves close to adiabatically. Typical product specifications for a homogeneous FRP process may include average molecular weight/molecular weight distribution. 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. requiring processes to be designed to safely release the pressure prior to failure (rupture) of the process equipment.

4. styrene) employ more than one reactor in series. mixing) occur sufficiently fast for overall behavior to be dictated primarily by reaction kinetics. where the high-temperature conditions make for very fast reactions (for example. and composition in radical polymerizations by homogenizing local concentration gradients. By having large surface areas available for heat transfer.3.4. When the polymerization is complete. thereby providing safer and more robust operation. PMMA can be polymerized in large sheets. However. as scale increases. No material is added to or removed from the reactor during operation. For example.3) as well as the heat removal and quality of mixing in the system. kinetic and transport effects become increasingly coupled. and is therefore a potentially powerful design tool for controlling properties such as molecular weight distribution. molecular weight. initiator half-life of <1 s) on the order of characteristic mixing times.1 195 . Homogeneous FRP reactions offer a particularly challenging problem because of the large increase in viscosity accompanying the conversion from bulk monomer (@1 cp for liquids) to polymer (> 10 5 cp). since different reactor configurations and agitators will be required as the viscosity increases. adequate temperature control is achieved without the need to provide mixing during polymerization. Batch Processes All of the reactants are added to the reactor prior to starting the polymerization. copolymer composition distribution. and so on).1. Mixing Mixing can directly affect the kinetics. Varying the contacting pattern can dramatically alter the local reaction conditions (for example. large variations in the temperature profile can translate into differences in the final product properties. However. Mixing can also be an issue at lower viscosities such as those found in LDPE systems. In small-scale experiments. chaintransfer agents.4 Polymer Reaction Engineering cooling system is able to maintain control. including monomers. categorized by the method by which the reactants are added to the reaction vessel. particularly molecular weight distribution. Some processes are designed to not require mixing. the contents are discharged and the reactor prepared for 4. and degree of branching. including thermal runaway. but it can also indirectly play an important role through its role in reducing thermal gradients in a reactor. Solution polymerizations offer low viscosity but the trend in industry is to eliminate (or greatly reduce) the use of organic solvents. The increase in viscosity can greatly affect the reaction kinetics (see Section 4. the rate of polymerization can also be controlled. albeit at a higher than desired temperature. Other bulk polymerizations (for example. The monograph by Biesenberger and Sebastian [80] provides an excellent discussion of thermal effects. initiators. concentrations of individual species. 4. Because of the ability to manipulate local monomer concentrations.1 Types of Industrial Reactors There are three major classifications of chemical processes.4. most transport phenomena (heat transfer.

meaning all reactant concentrations and process conditions (temperature. 4. although much progress has been made in automating many of the reactant weighing. For polymerizations with more than one monomer. For operations where changes to the formulation or the polymerization conditions are common. resulting in higher rates of transfer to polymer and branching reactions. and reactants are added during reaction in order to control a desired property (for example molecular weight distribution. and discharging steps to minimize this interval. and products and unconsumed reactants are removed. batch processes have the advantage of being flexible and readily adaptable to new products. Automation has also improved reproducibility of batch reactions.1. drift can be substantially reduced by maintaining a (near) constant concentration ratio of the respective monomers in the reactor. Usually only a portion of the total reactant charge is initially fed into the reactor. pressure. initiators. The polymerization is then started. The process may take place in a single reactor or in a train (series) of reactors in which the monomer conversion is gradually increased. Two of the most common applications for semi-batch operation in homogeneous FRP are control of copolymer composition distribution and control of reaction rate. the relative consumption rates of the different monomers will be governed by their respective reactivities.or terpolymers (for example coatings) is also readily done using this type of approach. From an economic perspective. but offer the least control over the polymerization. Production of low molecular weight co. possibly resulting in broad copolymer composition distributions and inhomogeneous product.3 . continuously. This mode of operation also ensures that at any time the monomer concentration in the reactor is low. In a batch reaction. and it is common practice to add monomer(s). This can be an enormous advantage for certain types of properties if the reactor is 4.4. copolymer composition drifts according to the inherent reactivities of the monomers. However in semi-batch operation. Most continuous processes are operated at ‘‘steady-state’’ conditions. copolymer composition distribution) or the reaction rate.4. and so on) are time-invariant. A potential concern with operating in a starved mode is that polymer concentrations are high. Batch polymerizations are the simplest to run.1. charging. Any reactant can be fed. Semi-batch Processes These processes (also called semi-continuous) are similar to batch processes.196 4 Free-radical Polymerization: Homogeneous the next batch. batch polymerizations suffer from downtime between batches. and therefore the maximum potential hazard in the event of a thermal runaway reaction is minimized. Molecular weight distribution drift is therefore a common phenomenon and can lead to very broad distributions in the final product.2 Continuous Processes Reactants are fed. except that reactants can be added and/or products removed during the polymerization. Initiator and monomers are continuously fed in the desired ratio to provide composition and MW control while maintaining starved conditions (low monomer concentration) in the reactor. Another feature of batch polymerizations is that reactant concentrations change throughout the polymerization. and/or chain-transfer agents.

For simple 197 . continuous processes are favored because of their low operating cost. to help discriminate between kinetic and physical (for example. 81]. For large-volume polymers with a limited number of variations to the polymerization conditions (for example. Although a few historical references are included. formulation changes). the focus of this section is the development of fundamental models based upon first-principles descriptions of chemical and physical phenomena. A good process model can be used to predict the influence of operating conditions on reaction rate and polymer properties.2 Mathematical Modeling of FRP Kinetics Mathematical modeling is a powerful methodology to improve the understanding and operation of polymer processes. 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. more uniform product quality. Wherever possible. the main focus is on advances made since the mid-1990s. Thus. to guide (along with appropriate experimentation) the selection and optimization of standard operating conditions for existing and new polymer grades. and optimization. it would be totally inappropriate for design of a new process or to choose operating conditions for a new polymer grade. followed by a discussion of issues related to reactor modeling. high throughput rates. the attempt often leads to valuable insights that can aid process and product development.4. narrower molecular weight distributions can be produced in a well-mixed continuous reactor for linear polymer systems than in batch systems. The modeling approach and level of detail should be dictated by the application.4 Polymer Reaction Engineering also well mixed (no spatial variations). pressure) and species concentrations from a defined set of kinetic mechanisms. a dynamic model is required to examine how properties change as a function of time. examples have been selected to emphasize industrial application.3 are presented first. Whereas an empirical model linking measured inputs and outputs may be the best solution for control of an existing industrial reactor. and simplicity of operation. in the end. to perform design and safety studies. Although a perfect description of an actual process is. and to understand and optimize transitions and other dynamic behavior (that is. While empirical modeling has its uses. there is no molecular weight distribution drift. Branching reactions. heat and mass transfer) effects. Techniques to model the FRP mechanisms and kinetics of Section 4. On the other hand. process control). 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. The mechanisms to be included in a model depend upon its end-use. to train plant personnel. The objective of kinetic modeling is to build a description of how polymer architecture and polymerization rate depend on reaction conditions (temperature. because concentrations are constant. 4.4. however. scale-up. to guide process development from lab to pilot-plant to full-scale production. an unattainable goal. and no composition distribution drift.

(27)]. Its introduction. Construction of moment balances allows the tracking of average polymer properties: for molecular weight this would be Mn (number-average). initiator. Many of the moments have precise physical meanings. To track polymer molecular weight.2. Method of Moments The equations in Section 4. while useful for examining rate of polymerization and instantaneous chain length. 81.4. and the creation and reaction of terminal double bonds. such as the density of short. all mechanisms that include radical transfer must also be included. 84]. (63) and (64). 4. and possibly Mz . Additional balances are needed to follow other molecular properties. and radical–radical termination. end-group functionality. . 85]. it is only necessary to consider those that consume monomer.3. Mw (weight-average). Only the basics of the mathematical treatment for a homopolymerization system will be given here: more details can be found in recent comprehensive reviews [83.or long-chain branches. eliminates the moment closure problem created by the LCB mechanism [40. Consider a free radical system that includes the basic set of mechanisms shown in Scheme 4. One of the challenges in modeling polymerization systems is how to reduce a very large number of individual species (living and dead chains with lengths from 1 to >10 5 . propagation. (65)].3 as well as long-chain branching [Eq.198 4 Free-radical Polymerization: Homogeneous mass and energy balances. they do not provide a means of tracking higher MW averages that are strongly affected by long-chain branching reactions.1 lj ¼ y X n j ½Pn  ð63Þ n j ½Dn  ð64Þ n¼1 vj ¼ y X n¼1 It is also helpful to define moments for the bulk polymer (mj ). often with other distributed attributes such as the number of branch points) to a tractable solution. the total polymer in the system including live radicals [Eq. and radicals – initiation. however. The classical approach to this problem is to reduce the system of equations through definition of the principal moments of the various distributions [82]. are not written in an appropriate form for substituting into a generalized reactor model. The moments for the radical (l j ) and dead (zj ) polymer distributions are defined in Eqs. mj ¼ y X n j ð½Dn  þ ½Pn Þ ð65Þ n¼1 With ½Dn  g ½Pn  there is little difference in magnitude between mj and zj . and for branched systems it is possible to track the number-average (B n ) and weight-average (B w ) number of branches per chain. In addition.

3). dead chains. ( RPn ¼ 2f kd ½I þ ktrmon ½M ) y y X X sol ½Pj  þ ktr ½S ½Pj  dðn  1Þ j¼1 j¼1 þ k p ½Mð½Pn1   ½Pn Þ ( ktrmon ½M  þ ktrsol ½S ) y X þ ðk td þ k tc Þ ½Pj  ½Pn  j¼1 y y X X pol pol þ k tr n½Dn  ½Pj   k tr ½Pn  j½Dj  j¼1 ( R Dn ¼ ktrmon ½M pol þ k tr ½Pn  ( RPn þDn ¼ þ ktrsol ½S y X ) y n1 X 1 X þ k td ½Pj  ½Pn  þ k tc ½Pj ½Pnj  2 j¼1 j¼1 pol j½Dj   k tr n½Dn  j¼1 2f kd ½I þ ð67Þ j¼1 y X ½Pj  ð68Þ j¼1 ktrmon ½M ) y y X X sol ½Pj  þ ktr ½S ½Pj  dðn  1Þ j¼1 j¼1 þ k p ½Mð½Pn1   ½Pn Þ ! y n1 X 1 X ½Pj  ½Pn  þ k tc ½Pj ½Pnj   k tc 2 j¼1 j¼1 ð69Þ The origin of the various terms in these balances should be evident by looking at the mechanisms of Scheme 4. Mn ¼ m w m1 . m0 Mw ¼ m w m2 .3 and Eq. The Kronecker delta function [dðxÞ ¼ 1 if x ¼ 0 and sðxÞ ¼ 0 if x 0 0 ] accounts for the generation of new polymeric radicals (P1 ). m1.4 Polymer Reaction Engineering The zeroth live moment. Similarly. l 0 . and total chains of length n. These moment definitions collapse the infinite set of equations for polymeric species into a manageable subset used to calculate MW averages.4. accounting for all of the consumption and generation terms from the kinetic mechanisms [Eqs. where m w is the molecular weight of the monomeric repeat unit [Eqs. m 0 is the concentration of all polymer chains in the system. and m1 is the concentration of monomer units bound in all polymer chains. and m 2 will be developed for the calculation of Mn and Mw . equations for the kinetic expressions for m 0 . and the terms for transfer to polymer account for the probabil- 199 . (27). (66)]. m1 Mz ¼ m w m3 m2 ð66Þ For this example. The first step is to formulate balances for live radicals. is the concentration of polymer radicals in the system (denoted by [Ptot ] in Section 4. and the first live moment. is the concentration of monomer units contained in all growing radicals. (67)–(69)]. l1 .

and leads to Eqs. 86. The Hulburt and Kutz [88] method is often used to approximate z3 . (70)–(78) for the moments. Live moments: Rl 0 ¼ 2 f kd ½I  ðk td þ k tc Þl02 Rl1 ¼ 2f kd ½I þ ktrmon ½Ml 0 þ ð70Þ ktrsol ½Sl 0 þ k p ½Ml 0 pol  fktrmon ½M þ ktrsol ½S þ ðk td þ k tc Þl 0 gl1 þ k tr ðl 0 v2  l1 v1 Þ Rl2 ¼ 2f kd ½I þ ktrmon ½Ml 0 þ ktrsol ½Sl 0 ð71Þ þ k p ½Mðl 0 þ 2l1 Þ pol  fktrmon ½M þ ktrsol ½S þ ðk td þ k tc Þl 0 gl2 þ k tr ðl 0 v3  l2 v1 Þ ð72Þ Dead moments: 1 R v0 ¼ ktrmon ½Ml 0 þ ktrsol ½Sl 0 þ k td l02 þ k tc l02 2 ð73Þ pol R v1 ¼ fktrmon ½M þ ktrsol ½S þ ðk td þ k tc Þl 0 gl1  k tr ðl 0 v2  l1 v1 Þ R v2 ¼ fktrmon ½M þ ktrsol ½S þ ðk td þ k tc Þl 0 gl2 þ k tc l12  pol k tr ðl 0 v3 ð74Þ  l2 v1 Þ ð75Þ Bulk moments: 1 Rm 0 ¼ 2f kd ½I þ ktrmon ½Ml 0 þ ktrsol ½Sl 0  k tc l02 2 ð76Þ Rm1 ¼ 2f kd ½I þ ktrmon ½Ml 0 þ ktrsol ½Sl 0 þ k p ½Ml 0 ð77Þ Rm 2 ¼ 2f kd ½I þ ktrmon ½Ml 0 þ ktrsol ½Sl 0 þ k p ½Mðl 0 þ 2l1 Þ þ k tc l12 ð78Þ The set of moment expressions to be considered consists of either the live and dead moments [Eqs. (71). The expression for termination by combination accounts for the possibility of creating Dn from any combination of two smaller radical fragments whose lengths sum to n. (70)–(75)] or the live and bulk moments [Eqs. The next step in the procedure is to substitute these species balances into the moment definitions in Eqs. while it is common practice in the literature. Choice of the former. (63)–(65). assuming that the molecular weight distribution can be represented by a truncated series of Laguerre polynomials by using a gamma distribution weighting function [Eq. suffers from the problem that the equations for l2 and z2 depend on z3 . (71) and (76)– (78)]. The use of generating functions [82.200 4 Free-radical Polymerization: Homogeneous ity that transfer to a certain chain Dn is proportional to chain length n. (79)]. v3 ¼ v2 ð2v0 v2  v12 Þ v0 v 1 ð79Þ . substituting m1 and m 2 for z1 and z2 in Eq. 87] eliminates the tedium (and possible errors) of performing the required series summations. (70).

4. 85–87]. as well as how a second distributed quantity (for example. Recent advances in modeling tools now make it possible to simulate the complete MWD. it is the standard methodology used in process simulation packages (see. Scheme 4. substitution of the kinetic expressions for the moments into reactor balances. a recursive relationship can be derived for Pn and Dn from Eqs. The set of moment equations developed here can be extended to include additional complex mechanisms.4 Polymer Reaction Engineering Using the bulk moments not only eliminates the need for this approximation.2 wninst ¼ ðt þ 0:5ðn  1Þbðt þ bÞÞðt þ bÞn t¼ k td ½l 0  þ ktrmon ½M þ ktrsol ½S . While adequate for most situations. For discussion regarding the final step of model development. (76)–(78). An additional balance [Eq. (30). since it is easy to implement as part of larger-scale reactor modeling. Furthermore.11) [40]. crosslinking (Scheme 4. pol RLCB ¼ k tr l 0 m1 ð80Þ Thus.10] [81]. Mw . Modeling of Distributions The major limitation of models based on the method of moments is that they only track average quantities. (70). for example. In the absence of long-chain branching and employing the QSSA. more detail may be needed if the objective of the study is to improve our knowledge of the kinetics – for example. (67) and (68). 90. but also reduces the set of equations by one. that is. and LCB density. LCB) varies with chain length.2.4. k p ½M b¼  1 1þbþt k tc ½l 0  k p ½M n ð81Þ ð82Þ 201 . since Eq. the kinetic and modeling assumptions can be tested more rigorously through a detailed comparison with full molecular weight distributions (MWDs) measured experimentally.4. (81) and (82) for the weight-fraction distribution of polymer formed at any instant in time [92]. or to incorporate chain-length dependent termination kinetics into the mechanistic scheme.3. a set of six equations [Eqs. leading to Eqs. (80)] can be added to either set of equations to track the concentration of LCB formed by the transfer to polymer mechanism. 40. (71). or by defining additional moment quantities (for examples. 85). 91). those without any branching. (72) is not required to solve for Mw . Refs. see Refs. and (80)] can be used to collapse the molecular weight distribution into its principle averages to calculate Mn . In such cases. such as reactivity of terminal double bonds [Eq. either by defining copolymer-averaged rate coefficients as in Eqs. The methodology can also be extended to copolymerization systems. see Section 4. and chain b-scission following intermolecular H-abstraction [89].4. 81. (50) and (54) [6. The modeling of complete MWDs has long been possible for linear polymer systems. to examine the combined effect of chain-scission and long-chain branching on polymer architecture.

This seminal work identifies a succession of branched polymer generations based on the degree of complexity of their architecture. The authors conclude that a more accurate approximation is obtained by classifying the chains according to their number of branches. It has been shown that this classification scheme leads. to errors in the shape of the overall MWD: through comparison with distributions calculated by rigorous numerical solution. and the resulting MWD solved using Monte Carlo techniques [93]. a chain from the first generation can only progress to the second by joining (through crosslinking. [95] have shown that the definition of generations proposed by Teymour and Campbell can create an artificial high MW shoulder due to the accumulation of chains with a wide distribution of the number of branches (and thus high polydispersity) in the first branched generation. These expressions can be integrated to follow the evolution of the MWD with time or conversion and compare against experimental data. (83). A second group of models is based upon the ‘‘numerical fractionation’’ concept developed by Teymour and Campbell [94]. as was done by Balke and Hamielec [92] for batch isothermal FRP of MMA. due to the interaction of the polymer radical and dead polymer chain distributions through reaction (for example. Unfortunately. the generations were defined 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 first generation by participating in a branching event. the probabilities of connections between primary polymer molecules (the linear chain that would exist if all of its branch points were severed) is calculated. the values for instantaneous DPn and DPw are given by Eqs. an important quantity often presented experimentally. . Butte´ et al. Both Monte Carlo [96] and a modified numerical fractionation technique [95] can also be used to calculate the LCB number as a function of chain length. The complete MWD is approximated by combining the MWDs for individual generations which themselves are reconstructed from the leading moments assuming a distributional form. The methods for modeling MWDs with branching can be divided into three main groups. terminal double bond polymerization. crosslinking). in certain cases.5 if termination by combination is the only chain-ending mechanism (t ¼ 0). the methodology cannot be easily extended to branched systems. has been greatly advanced through the efforts of Tobita. Assuming a given set of mechanisms. Thus. DPninst ¼ 1 .202 4 Free-radical Polymerization: Homogeneous Assuming the formation of long-chain polymer (t þ b f 1). or termination by combination) with another molecule from the same generation [94]. utilizing Monte Carlo techniques. tracking the population of chains in each generation using the method of moments. Numerical fractionation was specifically developed to examine the problem of gel formation in polymer systems. H-abstraction. and 1. t þ 0:5b DPwinst ¼ 2t þ 3b ðt þ bÞ 2 ð83Þ The instantaneous PDI is 2 for a system where there is no termination by combination (b ¼ 0). terminal double bond polymerization. The first.

r and c p are the density and heat capacity of the mixture. (70) and (71) for the live moment balances.4. For a wellmixed reactor system. Eqs. These new modeling capabilities. qin and qout are the inlet and outlet volumetric flow rates. Rtrsol ¼ ktrsol ½Sl 0 in the solvent balance. will hasten progress to a better understanding and representation of complex polymer architecture [46.4. Eq.4 Polymer Reaction Engineering The commercial software Predici2 package uses yet another numerical technique. in combination with improved characterization techniques. (10) for the monomer and energy balance. (76)–(78) for the bulk moment balances. 4. In 2000.2 are substituted into overall material and energy balances to construct a model to represent an FRP process. in Þ  ðqout ½l i Þ þ VRl i dt ð87Þ dðV½m i Þ ¼ ðqin ½m i.4. in Þ  ðqout ½m i Þ þ VRmi dt ð88Þ dðVrc p ðT  Tref ÞÞ ¼ ðqin ðrc p Þin ðTin  Tref ÞÞ  ðqout ðrc p Þout ðT  Tref ÞÞ dt þ ðDHp ÞVR pol  Q ð89Þ In these balances. 203 . calculating MWDs using a discrete Galerkin technique with variable grid and variable order [97]. dðV½MÞ ¼ ðqin ½Min Þ  ðqout ½MÞ  VR pol dt ð84Þ dðV½IÞ ¼ ðqin ½Iin Þ  ðqout ½IÞ  VR d dt ð85Þ dðV½SÞ ¼ ðqin ½Sin Þ  ðqout ½SÞ  VRtrsol dt ð86Þ dðV½l i Þ ¼ ðqin ½li. the package was extended to follow branch point concentrations as a function of chain length through the introduction of balance equations [98]. and Eqs. (2) for the initiator balance. (84)–(89) comprise the general system of equations for homopolymerization. 99]. and Q is the rate of heat removal from the reactor system.3 Reactor Modeling The kinetic expressions of Section 4. 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 perform detailed kinetic modeling. which must be accompanied by appropriate initial conditions and a volume balance. V is the reactor volume. Eqs. The various source terms have been presented earlier: Eq.

and should not be neglected when solving the material balances.3. (93).1 dV V dr ¼ dt r dt ð90Þ Volume contraction due to the difference in polymer and monomer densities can be as high as 20% for bulk polymerization.204 4 Free-radical Polymerization: Homogeneous Batch Polymerization Inflow and outflow terms are set to zero. Eq. namely Eq.2 ðqout ½l 0 Þ ¼ Vð2f kd ½I  k t ½l 0  2 Þ ð92Þ For most cases. dx p ¼ dt kp 1=2 kt ! 2f kd ½I0 1  ex p !1=2   kd t ð1  x p Þ exp  2 ð91Þ Continuous Polymerization Equations (84)–(89) can be solved to provide a description of the dynamic behavior of a continuous well-stirred system. Eq. ½l 0  ¼   2f kd ½I 1=2 kt ð93Þ [I] can be calculated from the steady-state solution of Eq. for l 0. (94). (83). Analytical solutions may be derived for the steady-state case by setting all derivative terms to zero. (90)]. (92) results for l 0. but the change in volume with conversion must be considered for the constant-mass system [Eq. the radical lifetime is much shorter than the average residence time. Thus outflow of radicals can be neglected. 4. where y ¼ V=qout is the reactor residence time and e ¼ ðrout  rin Þ=rout is the fractional density change between inlet and outlet streams. resulting in the familiar expression. ½I ¼ qin ½Iin  ½Iin  ¼ qout þ Vkd ð1 þ ykd Þð1  eÞ ð94Þ Substitution of these expressions into the monomer balance leads to a nonlinear relationship between conversion and y [Eq. Assuming no inflow of radicals. (95)]. Solution of the initiator balance and substitution into the monomer balance lead to a differential equation for conversion. where the volume contraction factor is defined as e ¼ ðrfinal  r0 Þ=rfinal where rfinal is the system density at 100% conversion of monomer to polymer and r0 is the initial density of the system. 4. (91).3. Eq.4.4. .

short-chain branching. Models for multifeed tubular systems also include heat transfer and pressure drop along the length of the system [103]. Kolhapure and Fox [106] incorporated a more complete kinetic scheme to allow the prediction of polymer MW. Complex Flowsheets These are often constructed to represent systems with nonideal mixing and fast reaction. generally conducted in a homogeneous phase consisting largely of supercritical ethylene monomer.3. Advances in computing power have allowed the complexity of these models to increase. and introduce the potential of thermal runaway. by examining the importance of initiator distribution at the injection point. much of the work is focused on high-pressure ethylene polymerization systems. this advancement shows enormous promise. polydispersity. More recently. LCB and reaction with terminal double bonds broaden the MWD significantly [81]. (83). A major challenge is incorporating both macromixing (turbulent diffusion and convection) as well as micromixing (molecular diffusion) into the representation [104]. The first efforts in this area [104.4 Polymer Reaction Engineering x p ¼ yk p l 0 ¼ y kp 1=2 kt ! 2f kd ½Iin  ð1  eÞð1 þ ykd Þ 1=2 ð95Þ Assuming no inflow of polymer into the reactor and the long-chain hypothesis. A classic example is the high-pressure high-temperature free radical production of ethylene copolymers. Although not yet applied to polymerization systems.4 205 .4. These CFD studies can point the way to improved reactor design and operation. and termination reactions. These conditions make for very fast reactions (for example. Recent models of these systems combine a detailed description of polymerization kinetics with a complex flowsheet of continuous well-mixed tanks in series with recycle to represent mixing in a multizone. The general strategy is to ‘‘tune’’ the model (based upon a set of proposed kinetic mechanisms captured by the method of moments) by fitting kinetic coefficients and mixing and heat transfer parameters to a set of industrial data.3 Computational Fluid Dynamics (CFD) CFD simulation is emerging as an alternative and more fundamental approach to examining polymerization systems with complex mixing and reaction. 4. for example.3. 105] concern themselves with the prediction of temperature and conversion profiles in the reactors. the pol steady-state values for DPn and DPw in the absence of LCB (k tr ¼ 0) are given by Eq. and average branching number. An article in 2000 discussed the implementation of CFD calculations within a process simulation package [107]. and then to use the model to interpret and optimize industrial operating conditions. promote numerous side reactions (long-chain branching. multifeed autoclave reactor [100–102].4. to simplify the calculational load they consider only initiation. 4. initiator half-life of <1 s). and defining conditions for stable reactor operation [106]. propagation. Once again.4. and chain scission).

XXX ¼ mon. A review by Congalidis and Richards [108] provides a good summary of literature focusing on this difficult issue. Notation Ai CtrXXX pre-exponential factor for mechanism-i ratio of chain-transfer rate coefficient (k trXXX . (19)] . in conjunction with a strong experimental program. and large-scale homogeneous FRP processes are often limited by transport effects. The use of empirical models has utility in the control of polymerization reactors. In many cases. Promising technologies for homogeneous FRP include living radical polymerization chemistries and polymerization in supercritical carbon dioxide.5 4. the implementation of detailed fundamental models is not warranted for control application. In most cases. in Refs. transport phenomena such as heat and mass transfer become more difficult. pol. molecular weight. together with an ability to relate measurements to functional properties. simple models can often be combined with limited on-line measurements (for example. the next several years may see the emergence of new industrial technologies. 109–112) to improve control performance. sol) to propagation [Eq. The adoption of new technology requires identifying an application or product for which the new technology is clearly advantaged. Mathematical modeling. Continuing development of new measurement techniques. As reactor size increases.206 4 Free-radical Polymerization: Homogeneous Model-based Control Model-based control of polymerization systems has also garnered its share of attention. While many current free-radical polymerization processes have been in industrial use for years. for further discussion.5 Summary Polymer reaction engineering issues can pose major challenges for industrial-scale polymer synthesis. These processes will require a detailed understanding of polymerization kinetics combined with fundamental reaction engineering principles. Fundamental models can also be used to test empirical models developed for control purposes [113]. The goal of these efforts is the development of robust strategies to guide and control the manufacture of polymer safely and reproducibly in the face of unmeasured disturbances and frequent product grade transitions. the final reaction rate. and successfully overcoming the numerous scaleup challenges in converting the process to industrial scale. However. and can be an important contributor to product quality and process robustness. and copolymer composition are determined by the coupled effects of reaction kinetics and transport phenomena. will be a critical area of future research.3. The main challenge in controlling polymerization systems is the lack of on-line measurements of polymer structure.4. 4. see Chapter 12 of this book. is a powerful means to improve our mechanistic and process understanding.

nj Þ fraction of monomer-i sequences that are exactly nj units in length probability of unit-j following unit-i in a polymer chain Pij cp Dn¼ Dn. (1)] mole fraction of monomer-i in the monomer mixture mole fraction of polymer radicals ending in monomer unit-i mole fraction of polymer radicals ending in monomer unit-j with penultimate unit-i [I] initiator concentration [mol L1 ] equilibrium propagation–depropagation constant K eq rate coefficient for intramolecular H-abstraction [s1 ] kbb kd rate coefficient for initiation decomposition [s1 ] rate coefficient for depropagation [s1 ] kdep rate coefficient for primary-radical initiation [L mol1 s1 ] ki rate coefficient for inhibition [L mol1 s1 ] k inhib rate coefficient for propagation [L mol1 s1 ] kp rate coefficient for addition of monomer-j to radical-i [L mol1 s1 ] k pij rate coefficient for addition of monomer-k to penultimate radical-ij k pijk [L mol1 s1 ] cop kp copolymer-averaged propagation rate coefficient [L mol1 s1 ] eff effective propagation rate coefficient. b DPn DPw Ei Fpinst i f fi fri frij 207 . corrected for depropagation kp [L mol1 s1 ] pol rate coefficient for radical addition to a terminally-unsaturated chain kp [L mol1 s1 ] tert addition rate of monomer to mid-chain radical [L mol1 s1 ] kp rate coefficient for termination [combination þ disproportionation) kt [L mol1 s1 ] cop kt copolymer-averaged termination rate coefficient [L mol1 s1 ] rate coefficient for termination by combination [L mol1 s1 ] k tc rate coefficient for termination by disproportionation [L mol1 s1 ] k td rate coefficient for thermal initiation of styrene [L 2 mol2 s1 ] k therm rate coefficient for transfer to species XXX (mon. sol) [L mol1 s1 ] k trXXX rate coefficient for radical b-scission [s1 ] kb [M] monomer concentration [mol L1 ] equilibrium monomer concentration [mol L1 ] [M]eq Mn number-average molecular weight [g mol1 ] weight-average molecular weight [g mol1 ] Mw molecular weight of the reaction mixture [g mol1 ] mw Ni number-average length of monomer-i sequences NðMi .Notation heat capacity [kJ kg1 K1 ] dead polymer chain of length n with terminal unsaturation dead polymer chain of length n with b branch points number-average degree of polymerization weight-average degree of polymerization activation energy for mechanism-i [kJ mol1 ] mole fraction of monomer-i contained in polymer chains being formed initiator efficiency [Eq. pol.

s1 ¼ k p211 =k p111 ) temperature [K] ceiling temperature of monomer [ C] initiator half-life [s1 ] reactor volume [L] weight fraction of chains of length-n fractional monomer conversion to polymer inhibitor concentration [mol L1 ] Greek b DGp DHp DSp DVi d e zk y lk mk ratio of chain termination (combination) to propagation [Eq. sol) [mol L1 s1 ] rate of change of moment l i [mol L1 s1 ] monomer reactivity ratio for radical-i (for example. b [Ptot ] i ] [Ptot Qn qin qout Rd R dep R inhib R init RLCB Rp pol Rp R pol R term R therm R trXXX Rl i ri [S] si T Tc t 1=2 V wn xp [Z] polymer radical of length n polymer radical of length n with b branch points total concentration of radicals [mol L1 ] total concentration of polymer radicals of type-i [mol L1 ] mid-chain polymer radical of length-n (formed by intramolecular or intermolecular H-abstraction) reactor inlet volumetric flow [L s1 ] reactor outlet volumetric flow [L s1 ] rate of initiator disappearance [mol L1 s1 ] rate of depropagation [mol L1 s1 ] rate of inhibition [mol L1 s1 ] rate of radical generation from initiator [mol L1 s1 ] rate of long-chain branch formation [mol L1 s1 ] rate of propagation [mol L1 s1 ] addition rate of terminally unsaturated polymer chains mol L1 s1 ] total rate of monomer consumption [mol L1 s1 ] rate of radical–radical termination [mol L1 s1 ] rate of thermal initiation of styrene [mol L1 s1 ] rate of transfer to species XXX (mon.208 4 Free-radical Polymerization: Homogeneous Pn Pn. (82)] free energy change of polymerization [kJ mol1 ] heat of polymerization [kJ mol1 ] entropy of polymerization [J mol1 K1 ] activation volume for mechanism-i [cm 3 mol1 ] fraction of termination by disproportionation volume contraction factor kth moment of the dead polymer chains [mol L1 ] average residence time [s] kth moment of the polymer radicals [mol L1 ] kth moment of the total (dead þ radical) polymer chains [mol L1 ] . r1 ¼ k p11 =k p12 ) solvent (transfer agent) concentration [mol L1 ] radical reactivity ratio for monomer-i in the penultimate copolymerization model (for example. pol.

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KGaA. Handbook of Polymer Reaction Engineering.213 5 Free-radical Polymerization: Suspension1 B. Uniform mixing and temperature control are difficult 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. Brooks 5. poly(methyl methacrylate). Meyer. Although the drop viscosity increases with monomer conversion. expandable polystyrene. W. These include poly(vinyl chloride). J. 5. the effective viscosity of the suspension remains low and efficient agitation is possible.1 Key Features of Suspension Polymerization Many important polymers are made commercially via suspension polymerization of vinyl monomers. The annual polymer production from suspension processes is very high. The conditions that are necessary to achieve those goals can be predicted from the kinetics of homogeneous free radical polymerization (see Chapter 4). heat transfer from large reactors is usually poor because the ratio of surface area to volume decreases as the reaction mass increases. Edited by T. In suspension polymerization. drops of a monomer-containing phase are dispersed in a continuous liquid phase. Weinheim ISBN: 3-527-31014-2 . The polymerization rate must be reasonably high and the polymer product must have the correct molecular weight distribution. Monomer solubility in the continuous phase is often low and polymer is produced inside the drops.1. under ‘‘Notation’’. styrene–acrylonitrile copolymers and a variety of ionexchange resins and specialist materials. If the continuous 1) The symbols used in this chapter are listed at the end of the text. But those conditions cannot be obtained easily in large-scale production when bulk processes are used. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. The ratio of surface area to volume for small drops is relatively high and local heat transfer is good.1 Basic Ideas There are two key requirements for any commercial free radical polymerization process.

Sometimes chain-transfer agents are added also. see Section 5. The continuous phase is often regarded as chemically inert. and Arshady [7]. simple rate expressions may not be applicable because the values of some rate coefficients diminish at high polymer concentrations (see Section 5. That assumption may be valid if the monomers and initiator are virtually insoluble in the continuous phase. Suspension stability is maintained by good agitation and by the use of drop stabilizers. Therefore. because the actual composition of the drops may then be unknown.1. molecular weight distributions. those stabilizers participate in the polymerization process. Brooks [4].2. but drop stabilizers are usually present in it and.2). Removal of the stabilizing agents.1. and copolymer composition. 5. the use of those relationships is not straightforward if one. which include reaction rates. That permits effective control of temperature and of those variables which depend on temperature. Suspension polymerization usually requires larger reactor volumes than bulk processes because the vessels often contain about 50% of the continuous phase. [6]. after polymerization. to form graft copolymers). However. and copolymer compositions can be predicted from conventional kinetic schemes. For a discussion of stabilizer types. may not be complete and some contamination of the final product is sometimes inevitable.2 Essential Process Components The chemical events that occur inside drops of the dispersed phase are similar to those found in bulk polymerization. then the instantaneous copolymer composition can be predicted from idealized relationships which apply to homogeneous systems. Bieringer et al. and polymer. Then. The drops contain monomer (or monomers). . radical generators (often called initiators). of the monomers is partially soluble in the continuous phase.214 5 Free-radical Polymerization: Suspension phase is aqueous and well mixed. heat transfer from the reactor is also good.3. Yuan et al. When all the monomers in a suspension polymerization are virtually immiscible with the continuous phase. 5. But drop stabilizers may react with species inside the drops (for example. Suspension polymerization has been reviewed previously by Munzer and Trommsdorff [1]. polymerization rates. Warson [3]. It is often assumed that the polymerization chemistry which occurs in the dispersed phase is identical to that which occurs in the equivalent bulk process. polymer molecular weight. The effective monomer concentrations.3 Polymerization Kinetics Higher conversions of monomers can be accommodated more readily in suspension processes than in bulk processes because suspensions are more mobile than molten polymers. [5]. Vivaldo-Lima et al. or more. [2].1. in some cases.

1. methacrylic acid. MAA. p-acetoxystyrene. VC. or semi-batch.4. might be predicted if the appropriate partition coefficients for the two phases can be obtained. 4). Apparent reactivity ratios obtained directly from suspension polymerization experiments may not be identical to those expected from the equivalent bulk processes if some monomer migrates to the continuous phase.85 1. Apparent reactivity ratios in solution and suspension copolymerization (reproduced with permission from Ref. methyl methacrylate. 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 copolymerization of styrene and acrylonitrile [9]. 215 . 5. methyl acrylate.18 0. then simultaneous emulsion polymerization may occur when free stabilizer remains in the continuous phase [12.1). Dispersions in tubular flow reactors are difficult to maintain and a continuous stirred tank would produce drops containing partially polymerized material that would coalesce in the receiving equipment.75 1.47 1.4 Fluid–Fluid Dispersions and Reactor Type Batch. 5.1 Key Features of Suspension Polymerization Tab.68 0.99 70 0. reactors are often used for suspension polymerization on an industrial scale.63 1. of acrylonitrile and methyl acrylate. If the initiator in suspension polymerization is slightly soluble in water.0 60 1. MMA. But sometimes their use is limited because they do not account for changing physical properties of drops or for the presence of drop stabilizers.02 0. acrylonitrile. Ashady et al.23 2.0 1. AN.1. which should be used in these relationships. Monomer 1 Monomer 2 AS S AN MA VC VA MMA MAA r1 (soln) r2 (soln) r1 (susp) r2 (susp) Temp [ C] 1. styrene. [10] found values for reactivity ratios that were not expected from results observed in bulk or solution copolymerization.7 0. were different from those obtained from either solution or emulsion polymerization. vinyl chloride.54 50 1.5. 13].35 1. MA.1 compares reactivity ratios obtained from solution copolymerization with those observed in suspension copolymerization. VA. S. Many of the published studies on drop behavior in agitated liquid–liquid dispersions are applicable to suspension polymerization.63 0. vinyl acetate. new types of flow reactors are being developed for suspension polymerization (see Section 5.07 69 Abbreviations: AS. Table 5. Izumi and Kitagawa [11] showed that reactivity ratios for suspension copolymerization. However.

The energy required to disperse monomer drops is lower than that required to break up the finished polymer. drop size depends on the physical properties of the two phases. such as poly(vinyl chloride) (PVC). There. the size range of the final product particles is very important. Heat transfer rates to polymer particles during extrusion and mass transfer rates of plasticizers in particulate polymers both depend on particle size. If a polymer product is required in particulate form. For example. Interfacial tension and drop stability depend largely on the nature of the drop stabilizer. initial drop diameters can be as large as 1–2 mm [1]. however. Some polymers. Also. That is why suspension polymerization is used for the largescale production of PVC. Drop stability against coalescence depends largely on the ability of the stabilizer to form a thin protective film at the interface. In that case. that problem is avoided. The effect of the elastic properties is enhanced by increasing the concentration of the suspending agent. But particle size can also be important when the polymer is to be converted to a macroscopic object. the nature of the suspension flow. . 5. the phase ratio. If no stabilizer were used to protect the drops. range between 10 and 100 mm. During suspension polymerization. That gives the drops better elastic properties [14]. Expandable polystyrene beads are also made by suspension polymerization. a ‘‘critical surface coverage’’ is established and a further increase in the suspending agent concentration will have a very little effect on the drop stability [15].216 5 Free-radical Polymerization: Suspension 5. bead diameters affect flow rates through ion-exchange columns. When a product is to be used in ‘‘bead form’’. and the condition of the phase interface. drop size control before polymerization is easier to achieve than particle size manipulation of granulated polymer.1. 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. In suspension polymerization.2 Stability and Size Control of Drops For many applications. Suspension polymerization provides a good route to functionalized particles such as those used in ion-exchange resins. are immiscible with their monomers. coagulation is largely confined to the drop interiors and aggregation of polymerizing drops is restricted. the suspension would be unstable and the final polymer particles would reach an undesirable size. and the final particle sizes. At that point.5 Uses of Products from Suspension Polymerization Advantages of suspension polymerization are not restricted to temperature control. the initial drop diameters. until a certain surface coverage of the drops is reached. Subsequent polymer coagulation makes bulk processes difficult to control. then suspension polymerization is especially suitable.

2. Although PVAs with a low DH are poor drop stabilizers in aqueous media. PVA often becomes grafted onto polymer that is formed inside the drops. O’Shima and Tanaka [22] suggested that the contact angle between dispersed liquid and inorganic solid is a crucial factor in determining whether an inorganic 217 . In some cases. Attempts have been made to measure the distribution of the stabilizer between the two phases and the interface [19].5. Water-miscible polymers are not expected to be good drop stabilizers when the continuous phase is nonaqueous (see Section 5.2 Stability and Size Control of Drops 5. But when the DH is less than 60%. it is well known that some particulate inorganic solids can also stabilize drops in suspension [20]. such as those formed in the manufacture of expandable polystyrene beads. Although organic substances are commonly used as drop stabilizers. and zinc phosphate) being used in the suspension polymerization of styrene [1]. such as gelatin and pectin. inorganic particles are able to stabilize relatively large drops. but that is a misnomer because not all the acetate groups are hydrolyzed. the development of drop stability may be slow [17]. small amounts of surfactants (such as sodium alkylsulfonates) are added to assist the dispersion of those solids. Drops retain their integrity even when agitation levels are reduced [18]. Partially hydrolyzed poly(vinyl acetate) (PVA). Polymeric stabilizers do not all act in the same way but steric effects are often important [16]. aluminium hydroxide. Inorganic stabilizers are advantageous when only low levels of contamination are required because they can sometimes be removed effectively from the final polymer particles.5). That may arise because rearrangement of stabilizer molecules on the drop surface is necessary. other solids are not stabilizers and may even be destabilizers. Munzer and Trommsdorff provide a detailed list of patented stabilizers [1]. This is especially important in the suspension polymerization of vinyl chloride. There are many reports of inorganic solids (such as calcium phosphate.3. a common stabilizer. Although transfer of stabilizer molecules from the continuous phase to the drop surfaces can sometimes be fast. These materials are sometimes called protective colloids. leading to the formation of a ‘‘skin’’ on the final particle surface. The effect of electrolytes can also be important [21]. drop sizes become sensitive to reduction in agitation intensity [18]. This is important because subsequent removal of the skin is not easy. and a wide range of synthetic polymers such as partially hydrolyzed poly(vinyl acetate)s. They include naturally occurring substances. is often called poly(vinyl alcohol). Modified natural products such as cellulose ether derivatives are also widely used.1 Stabilizer Types Many drop stabilizers in suspension polymerization are water-miscible polymers. they are still useful because they affect product morphology by influencing events inside the vinyl chloride drops (see Section 5. Although some inorganic solids are effective stabilizers for drops in suspension polymerization. PVA with a DH between 70% and 80% is a good stabilizer for drops in aqueous media. The extent of hydrolysis (DH) has significant effects on the behavior of the PVA.3). Also.

If some particles remain in the continuous phase. it is compatible with a wide range of experimental results. The fluids in agitated vessels are often turbulent. Although crowding theory does not explain all the observations. the dispersed phase can be broken into small drops when its surface is disrupted. have been suggested to explain the mechanism of drop stabilization by inorganic solids [21]. while those bigger than the mesh cannot pass through the meshes and are stopped from coalescing further. In that model. Two theories. In practical operation. 5. those which have a relatively small contact angle (such as carbon black) would tend to be destabilizers. If the turbulence in local regions can be regarded as isotropic. [23] used hydroxyapatite and calcium carbonate in the suspension polymerization of styrene. particles are not required to be permanently adsorbed on drop surfaces but they become effective when two drops come close together. Both theories are plausible but many workers believe that the stabilization is obtained mainly by a coverage effect. In the coverage theory. Solids that provide a relatively large contact angle (such as aluminium hydroxide) would be stabilizers in aqueous media. We. That disruption can be caused either by frictional forces (via viscous shear) or by inertial forces (via turbulence) [26]. In turbulent flow. it is suggested that dispersed inorganic solids cover the surfaces of monomer drops and form a layer which prevents drop coalescence. In contrast. When Wolters et al.218 5 Free-radical Polymerization: Suspension solid is a stabilizer or a destabilizer in suspension polymerization. The addition of surfactants often improves the dispersion action of the fine particles. Wang and Brooks [24] noticed that many of their stabilizing particles settled on the bottom of the vessel when stirring of a liquid–liquid dispersion ceased. In many cases it is not easy to measure contact angles. The ratio of the external disrupting force to the interfacial tension force is often expressed as the Weber number. a drop will break into smaller drops. random eddies are superimposed on the main flow.2. but it is possible to stabilize dispersions solely with mono-sized spherical colloidal particles [25]. When We exceeds a critical value. it is not feasible for the coverage theory to provide a description for every case of suspension polymerization in which an inorganic solid is used as a stabilizer. Eddy sizes are influenced by the location of the vessel walls and are . Also. finely divided inorganic solids which are dispersed in water form a screen. According to the screen theory. the adsorption equilibrium was found to be far on the side of desorption. the contact angle will probably vary with any given inorganic solid if different monomers are used.2 Drop Breakage Mechanisms In an agitated suspension. However. 27]. Wang and Brooks suggested a crowding theory which takes account of the dynamic effects of stabilizer particles [24]. screen theory and coverage theory. not all inorganic solids are adsorbed by the monomer drops. Dispersed monomer drops smaller than the mesh of the screen are free to move through the meshes. a criterion for the drop breakage mechanism can be developed [26. Drop deformation increases as We increases.

until it reaches the smallest ones. the Reynolds number (Re) is defined by Eq. when the kinetic energy reaches the small eddies. The macroscale of turbulence. However. e ¼ C3 N 3 D 2 d max ¼ C4 ðs=rc Þ ð5Þ 3=5 N 6=5 d max =D ¼ C4 ðWeÞ0:6 4=5 D ð6Þ ð7Þ In order to use this expression. (1)] for the length of the smallest eddy (h). that should be observed when turbulence is isotropic. (5) holds. This transfer is assumed to occur without energy dissipation. d32 (which is more readily determined). Here. where N is the impeller speed. Coulaloglou and Tavlarides [28]. and n is the kinematic viscosity of the dispersion. d max . by Eq. can then be related to a critical Weber number. d max . d g h and the viscous forces may be neglected in comparison with the inertial forces. In theories of local isotropy. (3). so that Eqs. Kuriyama et al.5.2 Stability and Size Control of Drops restricted by the impeller diameter [28]. D is the impeller diameter. Kolmogoroff [27] and Hinze [31] derived an expression for the maximum drop diameter. [30] suggested that local isotropy could exist when the Reynolds number is >10 4 . [34]. We crit . h ¼ n 3=4 e1=4 ð1Þ Rushton et al. Velocity fluctuations are determined by the local rate of energy dissipation per unit mass of fluid (e) and by the kinematic viscosity (n). We crit is given by Eq. Kinetic energy is transferred to smaller eddies in a sequential fashion. Kolmogorov [29]. Re ¼ ND 2 =n ¼ ND 2 r=m ð2Þ Pressure fluctuations can deform the drops and they may break if the inertial forces exceed the interfacial tension forces. A linear relationship between d32 and d max has been demonstrated by Sprow [33]. is then much larger than the microscale of turbulence. Here. it is dissipated as heat to overcome the viscous forces. (4). (2). L (approximately equal to the impeller diameter). (6) [32] and (7) follow. Thus. We crit ¼ rc u 2 ðdÞd=s ð3Þ The inertial forces are related to e. it is often necessary to relate d max (which is difficult to measure) to the Sauter mean diameter. it is assumed that the small eddies are statistically independent of each other. 219 . 5=3 We crit ¼ ðC1 rc e 2=3 d max Þ=s ð4Þ Rushton et al. derived an expression [Eq. [30] showed that Eq. and Zerfa and Brooks [35]. by dimensional reasoning.

Experimental expressions for f ðjÞ are reviewed by Yuan et al.4. as shown in Figure 5. Fig. and by Zerfa and Brooks [35].3 0. 5.1. (7). An expression with similar form is given by Borwankar et al. [15]. [5].01 0. If the surface coverage of the drops by the stabilizer exceeds a critical value then the dispersion can remain stable after agitation ceases [15].4 20 10 0 0 10 0. Reproduced by permission of Elsevier Science Ltd.0. Then. 35. Zerfa and Brooks found the relationship in Eq. In the suspension polymerization of vinyl chloride.06 20 )We . The extent of drop coalescence is reduced by addition of an appropriate drop stabilizer.1. 36–38].5 Free-radical Polymerization: Suspension 30 Volume fraction of dispersed phase 4 d 32 /D ( x 10 ) 220 0. When drop coalescence is significant. real suspension polymerizations are operated with a high volume fraction of dispersed phase. j. in suspension polymerization. From Ref. in the suspension polymerization of vinyl chloride. that is proportional to N 0:75 . The steady-state drop size distribution (DSD) can take some time to become established [18. in noncoalescing systems [28]. d32 =D ¼ 0:027ðþ3:06jÞWe0:6 ð9Þ Equation (9) applied when values of j ranged between 0. d min . That may not be a serious problem with nonreacting dispersions but. d32 was given by Eq. To allow for this.027(1 + 3. But. drop coalescence and breakage happen simultaneously and damping of the turbulent fluctuations may occur.6 30 4 ( x 10 ) Correlation of vinyl chloride drop size with volume fraction j and Weber number We.1 0. The latter workers showed that. the physical prop- . 0:58 d32 ¼ d max ð8Þ Equation (6) has been verified with a large number of liquid–liquid dispersions where the volume fraction of the dispersed phase is not high. (8).01 and 0. (9).2 0. Shinnar [32] showed that there will be a minimum drop size. a factor f ðjÞ is often introduced into Eq. It must be remembered that correlations between average drop sizes and We only apply at steady state. that is. unlike many laboratory studies.05 0.

it is not surprising that the many published studies on drop behavior in liquid–liquid suspensions lead to a variety of different results. In laminar flow. (10). Therefore. which ranges between 0 and 1. Correlations that are found in idealized laboratory studies only provide rough guides to events that occur in commercial reactors. Presumably. [41] found that drop breakage could occur via viscous shear when flow in the suspension was turbulent. depended on the ratio of phase viscosities (Eq. drop breakage can produce more than two new drops.5. Drop stabilizers influence turbulence near drop surfaces and non-Newtonian behavior leads to further complications. The form taken by f ðmd =mc Þ depends on the nature of the flow. the drop size was not able to respond to changes in md =mc that 221 . Taylor showed [40] that the extent of drop distortion. relatively small increases in md =mc are accompanied by large increases in We crit . We crit tends to an infinitely high value if md =mc > 4 so that drop breakage no longer occurs [42. Local flow in large stirred vessels is often ill defined. For simple shear a ¼ 0. Leng and Quarderer [39] found that d max depended on N 0:8 . sometimes described as a generalized Weber group [31].2 Stability and Size Control of Drops erties change with time so that the DSD can continue to change during the process [37]. before breakup. they also showed that d max depended on mc0:5 when drop breakage occurred by viscous shear. respectively). (11) and (12). where md and mc are the viscosities of the dispersed and the continuous phase. Chatzi and Kiparissides [44] suggested that the formation of a daughter drop is accompanied by the formation of a number of smaller satellite drops. see Figure 5. 43]. the Kolmogorov length would have been larger that that found when low-viscosity aqueous solutions are used. After the minimum is reached. Here. d max is given by Eqs. We crit (now equivalent to the critical capillary number Cacrit ) passes through a minimum as md =mc increases. 32] demonstrated that for locally isotropic flow where ðqu=qrÞ 2 ¼ e=n. With low a values. d max ¼ ðsnc1=2 =mc e 1=2 Þ f ðmd =mc Þ ð11Þ d max z ðsnc1=2 =mc ÞN 3=2 D1 f ðmd =mc Þ ð12Þ When viscosity-increasing agents were present in the continuous phase for the suspension copolymerization of styrene and divinylbenzene. stresses from viscous shear will be much larger than those from inertial effects. Also. Drop breakage is then the result of viscous shear [26]. When a ¼ 0. We crit ¼ mc ðqu=qrÞðd=sÞ ¼ f1 ðmd =mc Þ ð10Þ Shinnar and Church [26. When the diameter of the drops is less than the Kolmogorov length h. for the suspension polymerization of methyl methacrylate. By using data from the literature. a drop will break if the deformation variable. and for pure elongational (hyperbolic) flow a ¼ 1 [43]. exceeds a critical value [39].2. In that case. the contributions of rotational and elongational components can be expressed via the value of a parameter a. again. Jegat et al.

average drop size was found to be a linear function of interfacial tension. But with a high drop viscosity.6 A 1. would have occurred during polymerization.4 B 0 0 1 2 3 4 log10 (viscosity ratio) + 3 Fig. In liquid–liquid dispersions the drop size distributions (DSDs) depend on the breakage and on coalescence processes. The validity of the correlation was confirmed experimentally using a dispersed phase with a wide range of viscosity.5 Free-radical Polymerization: Suspension 1. fluids were used for those experiments. Although model. Borwankar et al. 42 and 43. Critical capillary number against log10 of viscosity ratio (md =mc ) for laminar flow. Data from Refs. as expected.3 Drop Coalescence The volume fraction of drops in commercial suspension polymerization reactors is usually high and drop coalescence cannot be ignored. [15] suggested that the relationship between d max and agitator speed may depend on agitator type. the results are relevant to suspension polymerization. [45] derived a correlation for drop breakup from a Voigt model to represent the elastic properties. They also concluded that the stabilizer does not effectively prevent the coalescence of drops with diameters larger than d max . when the initial drop viscosity was low. their elastic properties must be taken into account. When polymer-containing drops are broken. By comparing drop collisions in agitated . They showed that the influence of interfacial tension on drop breakage decreased as the dispersed-phase viscosity increased. when viscous shear was important. From experiments in which both drop breakage and coalescence occurred.2. However. [34] found that drop sizes reached a steady value within an hour.2 Ca crit 222 0. Konno et al. (A) a ¼ 0 (simple shear flow). nonreacting. The overall rate of drop coalescence is related to the collision frequency of the drops and to the coalescence efficiency. the drop size reduction continued for longer periods of time and the final drop size was higher. [47] found that the Sauter mean diameter increased as the polymer viscosity increased. In their study of drop coalescence in the suspension polymerization of styrene. Wang and Calabrese [46] carried out experiments with drops made from wellcharacterized model fluids.2. 5. (B) a ¼ 1 (hyperbolic flow). Kuriyama et al.8 0. Arai et al. 5.

especially when the drops have a high viscosity [55]. But. Considerable periods of time might be required for that to occur [18]. [37] in the suspension polymerization of methyl methacrylate. That was shown to be the case by Jahanzad et al. the physical properties of the drops change with monomer conversion. For some combinations of stabilizer type and stirrer speed. which takes account of viscosity effects. That model distinguishes between the impeller region and the remainder of the reactor. expressions can be obtained for the coalescence efficiency [50]. Both regions are assumed to be well mixed and CFD simulations predicted drop size distributions that were compatible with experimental results from nonpolymerizing model liquid–liquid dispersions. Expressions. Yang et al. and the average drop size increases. then coalescence may occur [26]. for coalescence and for collision rates are not easy to use because they often contain parameters that are difficult to quantify.5. in dilute agitated suspensions for which coalescence is negligible. the final particle size distribution (PSD) is quite different from the steady-state DSD that would be expected from nonpolymerizing drops. and to permit drainage of the continuous phase that is trapped between them. previous workers have developed expressions for collision rates between drops of different sizes [48. as the polymer content of the drops increases. the DSDs of polymerizing drops were broader than that of the DSDs in the corresponding nonpolymerizing monomer drops. is a result of fluctuations with a wavelength equal to the drop diameter. By taking account of these events. 49]. Maggioris et al. their successful use must allow for variations of turbulence intensity within the reactor. Consequently. If drops adhere for sufficient time to allow them to deform. [51] describe a two-compartment population balance model for an agitated suspension polymerization reactor.2. the DSD continues to change. 5. in the case of suspension polymerization. [50] constructed a model for drop breakage and coalescence. Alvarez et al. [46. If no chemical reaction occurs. exposed to a turbulent flow field. Then.4 Drop Size Distributions Even when expressions for drop breakage and coalescence rates are available. Fluctuations with wavelengths that are smaller or larger than the drop diameter do not lead to drop breakage. 53] showed that. [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.2 Stability and Size Control of Drops dispersions with molecular collisions in homogeneous fluids. the equilibrium drop size distribution broadened considerably as dispersed-phase viscosity increased. early increases in drop viscosity reduce the rates of breakage and coalescence before a steady-state DSD can be established. In a batch process. That model assumes that breakage of a drop. then the rates of drop breakage and drop coalescence eventually become equal and a stable DSD is obtained [54]. Calabrese et al. in the suspension polymerization of styrene. But the 223 . bimodal drop size distributions were predicted by the model and found in the experiments. There.

2. the DSD became similar to that expected when the stirrer speed was maintained at its lowest value.224 5 Free-radical Polymerization: Suspension 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. such as methyl methacrylate. [56]. a growth stage exists in which drop coalescence continues when drop breakage rates are low [50]. the rate of drop coalescence is affected by changes in drop viscosity. Similar results were obtained by Konno et al. although the diameters of most drops and particles ranged between 10 and 300 mm. and vinyl chloride. The polymers then precipitate inside the drops and their apparent viscosity does not increase substantially until appreciable conversions have been attained. Most of those smaller particles probably developed from satellite drops which are formed during the breakage process. When drop viscosity remains low. Therefore. was used. with a low degree of hydrolysis. because excess stabilizer reduced drop coalescence in both systems. a reduction in stirrer speed led to a broadening of the DSD. Clearly. There.3.4. thereby. or copolymers. coalescence events can depend on the nature of the drop stabilizer. as shown in Figure 5. 5. a second peak appeared in the particle size distribution. Low viscosities may be encountered when the polymers. If emulsion polymerization becomes prevalent. [37] also showed that. that had a high degree of hydrolysis. 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 induce some emulsion polymerization. The average diameter of particles that accounted for that second peak was about 1 mm. With smaller amounts of stabilizer. The existence of small satellite drops is compatible with the ideas of Chatzi and Kiparissides [44] and with the work of Sathyagal et al. any induced kinetic effects that alter the polymer molecular weight (and. change the viscosity) could influence the coalescence rate and the DSD. In batch reactors. When hydrolyzed poly(vinyl acetate) (PVA) is used as the drop stabilizer. The amount of stabilizer that is available to stabilize the drops is then reduced [57]. the ‘‘good’’ stabilizer protected the drops from coalescence. are immiscible with their monomers. Promoting chain transfer is one way for that to happen. Jahanzad et al.3 occur when drops have a uniform chemical composition. But when a ‘‘poor’’ PVA stabilizer. as shown in Figure 5. a reduction in stirrer speed had little effect on the DSD. The increase in average drop size can be substantial and continues until the identification point is reached when drop viscosity is too high to permit further drop coalescence. That is the case with the suspension polymerization of vinyl chloride. Zerfa and Brooks [18] showed that DSDs depended on stirrer speed. but sometimes it is necessary to add material to a . then a significant amount of the drop stabilizer will be adsorbed on the surfaces of the small particles. With ‘‘good’’ PVA stabilizers.2.5 Drop Mixing Most of the coalescence events described in Section 5. vinyl acetate. That can by important with monomers that are more water-soluble. [47].

2 Stability and Size Control of Drops Drop number 200 A 150 100 50 0 15 35 55 75 95 Drop diameter (microns) Drop number 200 B 150 100 50 0 15 35 55 75 95 Drop diameter (microns) Drop number 200 C 150 100 50 0 15 35 55 75 95 Drop diameter (microns) Fig. That can happen if control of copolymer composition is important. 18. (C) N reduced from 650 to 350 rpm. copolymer composition usually changes with overall conversion because monomers react at different rates [58]. Data from Ref.5% hydrolyzed. Change in drop size with stirrer speed with PVA 72.3. reactor in which a suspension already exists. (B) N ¼ 650 rpm (10. In batch operation.8 s1 ). This drift in copolymer composition may be limited by adding one of the mono- 225 . 5.5.8 s1 ). (A) N ¼ 350 rpm (5.

(C) N reduced from 650 to 350 rpm. Then.5 Free-radical Polymerization: Suspension Drop number 200 A 150 100 50 0 15 35 55 75 95 Drop diameter (microns) Drop number 200 B 150 100 50 0 15 35 55 75 95 Drop diameter (microns) 200 Drop number 226 150 C 100 50 0 15 35 55 75 95 115 Drop diameter (microns) Change in drop size with stirrer speed with PVA 55% hydrolyzed. 5. But. (B) N ¼ 650 rpm (10. Fig. when new dispersible material is added to an existing suspension. mers to the reactor incrementally (that is. by using a semi-batch procedure).8 s1 ).8 s1 ). new drops may form with a monomer composition that differs from that of . (A) N ¼ 350 rpm (5. Data from Ref. [18]. the new material and existing drops can remain segregated for a significant period of time.4.

5. a monomodal DSD is expected [60]. radical generator. from refluxed monomer. the drop size distribution became bimodal whereas. might not be helpful because there is the danger of stabilizing new drops with the ‘‘wrong’’ monomer composition that contain little. the initiator is often dispersed in the aqueous phase of a stabilized suspension. A special drop mixing problem arises with the suspension polymerization of vinyl chloride. Above that size. the mixing rate increased. Therefore. Then the subsequent mixing of monomer and initiator can be quite slow. the coalescence rate also increases. This nonuniformity in drop behavior affected the final polymer properties. The vapor is then condensed. in the absence of reflux. the drop mixing rate increases as the drop viscosity decreases. a high heat removal rate is usually necessary to maintain a constant reactor temperature. appeared to provide a mechanism for transfer of initiator (bis(4-t-butylcyclohexyl) peroxy dicarbonate) through the continuous phase. formed by simultaneous emulsion polymerization. The enthalpy of polymerization for most of the vinyl monomers that are used in suspension polymerization ranges between 30 and 90 kJ mol1 . at some stirrer speeds. the drop size distribution broadened. cooled. The presence of small particles. as a safety precaution. With high reflux rates. As the dispersed-phase viscosity increased. With the suspension polymerization of vinyl chloride. 62] showed that many monomer drops remained ‘‘uninitiated’’ when monomer in other drops had polymerized to a considerable extent. had limited access to the drop stabilizer (PVA) and were larger than the ‘‘old’’ drops. Drop mixing may become an issue when volatile monomers are used. It appears that there is a critical drop size which determines the coalescence efficiency. Zerfa and Brooks [61. Also. 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. Heat removal can be improved by allowing the monomer to vaporize. drops of returning monomer must gain access to initiator and drop stabilizer. the mixing rate is influenced noticeably by the drop size. addition of initiator via the aqueous phase promoted simultaneous emulsion polymerization and modified the PSD. The drops were composed of polystyrene solutions in styrene. If the polymerization process is to be maintained. as the drop size increases. This is difficult to achieve by heat transfer through the reactor walls in commercial operations because large reactors have a relatively small surface area to volume ratio. and returned to the reactor as a liquid. New drops. with the new monomer. Therefore. The new monomer cannot mix with existing drops (which contain the initiator and have adsorbed most of the drop stabilizer). That did not happen when initiator was dissolved in the monomer before it was dispersed: see Figure 5. Drop mixing rates were quantified by using dyed monomer 227 . or no. Hashim and Brooks [59] studied the addition of styrene to a suspension of stabilized drops.5. The initial drop viscosity affected the drop size and the rate of coalescence between drops. Adding extra drop stabilizer.2 Stability and Size Control of Drops the original drops. Zerfa and Brooks [60] found that monomer returning from a reflux condenser formed drops that acquired initiator without the need for coalescence with existing stabilized drops. Below the critical drop size.

5. 3. Inc. 60 min. PVA concentration ¼ 0. From Ref. 1.8 s1 ).228 5 Free-radical Polymerization: Suspension Effect of the method of initiator addition to vinyl chloride: (A) initiator predissolved in drop phase. 20 min.3 Events at High Monomer Conversion Suspension polymerization provides a practical method of achieving high monomer conversions. drops in the experiments. . 2. N ¼ 350 rpm (5. 5. Reproduced by permission of John Wiley & Sons. j ¼ 0:1. studies of polymerization and drop behavior that deal with events at low monomer conversion may not be applicable to suspension polymerization. 5 min. The mixing rate was found to depend on both the concentration of the PVA and the grade that was used [61].06%. (B) initiator predispersed in continuous phase. Therefore. 5. 62. Panels: Fig.

kd is the initiator decomposition rate coefficient and CI is the initiator concentration. Brooks et al.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). 229 . Although most workers agree that the chain termination reaction is diffusioncontrolled. In some cases.1 Breakage of Highly Viscous Drops In batch reactors drop breakage and coalescence are affected by the polymerization process because the viscosity of the polymerizing fluid often increases. 5. polymer volume fraction and polymer molecular weight. (13). CM is monomer concentration. meaningful experiments. in the presence of polymer.2). (14) applies. However. The classical expression for the rate of polymerization (R p ).3. R p ¼ k p CM ðR i =k t Þ 1=2 ð13Þ If radicals are generated by the thermal decomposition of an added initiator then. is Eq. The latter three entities are interrelated in complicated ways. Most academic investigations have been carried out in ‘‘idealized’’ conditions where the extent of monomer conversion is low. a phenomenon often described as a ‘‘gel effect’’. in a single-phase reaction. reliable quantitative relationships between the rate coefficients and measurable properties of the reaction medium are not generally available. where k p is the propagation rate coefficient. k p decreases also [64]. Radical diffusion can depend on solution viscosity.3 Events at High Monomer Conversion 5. both k p and k t diminish (even in isothermal conditions). R i is the initiation rate and k t is the termination rate coefficient [63]. The value of kd can often be determined independently but traditional steadystate experiments give values for k p =k t0:5 and do not provide separate values for k p and k t . at steady-state conditions. This restriction becomes a problem for reactor modeling because.5. At high polymer concentrations. Eq. which may relate them to the rate coefficients. R i ¼ 2f kd CI ð14Þ Chain termination is often diffusion-controlled and the value of k t diminishes substantially as the polymer concentration increases. showed that effects of viscosity changes on polymerization rate could be distinguished from the effects of polymer volume fraction [66]. the value of f may also depend on polymer content [67]. The reduction in k t leads to an increase in the polymerization rate. Many aspects of the interaction of drop behavior with the polymerization process have been discussed already (see Section 5. are not easy to devise [65]. where f is an efficiency factor.

Qin et al. as discussed previously (see Section 5.230 5 Free-radical Polymerization: Suspension Pulse laser techniques. In practice. Manipulation of polymer precipitation. The resulting fouling problems that occur in bulk polymerization are greatly reduced by using suspension polymerization.1. combined with accurate molecular weight measurement. indicating that chain entanglements are not necessary for a gel effect to occur [73]. a number of different models for the gel and glass effects gave an adequate description of isothermal time–conversion data over the entire conversion range for a single type and loading of initiator. up to high monomer conversion was satisfactory for isothermal conditions. bulk polymerization may be difficult to handle. inside the drops. Although most workers agree that k p is reduced at high monomer conversions. [72] showed that. the glass transition temperature of the polymer solution also increases and the drops can become glassy. Tefera et al. An increase in reaction temperature may become necessary in order to achieve complete monomer conversion. The match with experimental data. The monomer sequence in styrene–methyl methacrylate copolymers at high conversion have been found to differ from those observed at low conversion [77]. isothermal conditions are not always maintained in suspension polymerization and temperature increases can lead to a marked reduction in initiator concentration. [74] have suggested that diffusion control may not be the only reason for that to occur. [75] developed a three-stage model to account for the gel and glass effects. Achilias and Kiparissides [76] showed.3. for methyl methacrylate and styrene polymerizations. When a gel effect is observed. 69]. kinetic analysis can be difficult because k t becomes dependent on chain length [70] and the pseudo-steady state assumption may not be valid [71]. however. when a high monomer conversion is attained. It has been shown that autoacceleration in free radical polymerization can be observed even when low molecular weight polymer is being formed. The initiator efficiency. A suspension process may then be the only feasible way in which the copolymerization can be carried out [4]. Faldi et al. 5. This is one of the reasons for choosing a suspension process for PVC manufacture.5).3 Consequences of Polymer Precipitation Inside Drops Polymers that are insoluble in their monomers will precipitate during polymerization. Suspension processes also provide a means of investigating copolymerization kinetics at high conversion. have been used to determine independent values for k p but those techniques are only feasible in the absence of preformed polymer [68. during . that data for polymerization of those monomers were compatible with a model that did not require ‘‘break points’’ for the gel and glass effects. If crosslinking or copolymer precipitation occurs. But models that ignored the effect of polymer molecular weight on the diffusion of macro radicals failed to describe the time–conversion data if the concentration of the initiator varied. has been shown to depend on the size of the initiator radicals at high monomer conversion [76]. As the monomer conversion increases. The chain propagation reaction then becomes diffusion-controlled and the value of k p decreases significantly. f .

Some components of the drop stabilizers are chosen because they are miscible with the monomer and they can influence the agglomeration of primary particles [82]. The precipitating polymer aggregates to form unstable microdomains. Schematic representation of polymer formation inside vinyl chloride drops. and of the density difference between PVC and VCM. especially the porosity. unlike particles that form from polymers that are completely miscible with their monomers. The particle size. 5. and the degree of porosity of PVC grains depend on polymerization conditions.6. The primary particles grow by polymerization within them and by buildup of microdomains or domains on their surfaces. polymerization can influence the properties of the final product. PVC grains have a complicated morphology and they can be highly porous.3 Events at High Monomer Conversion Fig. These include the agitation in the reactor. see Figure 5. the PSD.6. 79]. Those components are sometimes called secondary suspending agents (SSAs). the type and concentration of suspend- 231 . which aggregate further to give domains. forming a separate polymer-rich phase inside the drops. At about 70% conversion the monomer-rich phase disappears and further polymerization occurs in the polymer-rich phase [80. Subsequent aggregation of domains results in the formation of primary particles. PVC starts to precipitate from the monomer phase when the conversion exceeds 0. Eventually multiple contacts lead to the formation of a continuous network of primary particles throughout the polymer particle/monomer droplet.5.1% conversion. the morphological characteristics. Structural changes that occur inside the drops of polymerizing vinyl chloride monomer (VCM) have been discussed by a number of authors [78. which in the case of PVC affects the ability of the polymer to take up plasticizers. The final polymer grains have irregular shapes. 81]. As a direct consequence of the process described above.

with PVA as the main stabilizer. such as sorbitan monolaurate. The primary suspending agent system is often based on PVA. the mean particle size of PVC resins increases quickly as the concentration of nonionic surfactant increases [82]. the suspending agents also affect the substructure and porosity of the particles.232 5 Free-radical Polymerization: Suspension ing agent(s). That improves the subsequent uptake of plasticizer and also promotes the removal of unreacted VCM at the end of polymerization. SSAs are regularly used in the production of suspension PVC to impart higher porosity to the PVC grains. are used as SSAs. PVC porosity increases if a high monomer reflux rate is used. at low monomer conversion. graft copolymers of PVA and PVC form a skin (or membrane) around the polymer particles [93]. 90–92]. using different reactor capacities. regardless of type. In some cases. surface roughness. the polymerization temperature. and particle shape were found to depend on the origin of the PVA [62]. Zerfa and Brooks [60] showed that. Span60. Porosity. and many correlations have been developed [83. The increase in the mean particle size of the final PVC is probably caused by increased coalescence of VCM/PVC droplets during the polymerization process. as a result of a lowering of water-drop interfacial tension by the SSA. PVA with a low degree of hydrolysis and nonionic surfactants. will become occupied by nonionic surfactant molecules. 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. Thus. 84]. and bulk density of the PVC produced. the monomer conversion. and they will be absorbed faster than PVA on the VCM/water interface. Wolf and Schuessler [85] concluded that the plasticizer absorption (which depends on porosity) of the resulting PVC was related to the surface activity of the suspending agent. Nonionic surfactants such as Span20. and the ratio of monomer to water. however. When nonionic surfactants. cold plasticizer absorption. such as Span85. the choice of suspending agent(s) affects the particle size distribution of the final polymer. Particle shape can also be influenced by the method . In the case of PVC. The mechanism by which such SSAs function is not entirely clear [80. As with the suspension polymerization of other monomers. have been used commercially as SSAs [89]. Ormondroyd [86] demonstrated the effect of PVA structure on the particle size. Part of the interface. The degree of agglomeration of primary particles increases with polymerization temperature and with conversion. [81] showed how HPMC structure and concentration influenced the particle properties of PVC. the secondary suspending agents. or a mixture of the two. substituted cellulose. Effects of agitation on the mean particle size of PVC resins have been studied by many researchers. Span60 and Span20. which would otherwise be occupied by PVA molecules. and Span85 have more affinity with VCM than the PVA has. Cheng [87] and Cheng and Langsam [88] used hydroxypropyl methylcellulose (HPMC) as a suspending agent and analyzed the influence of molecular weight and chemical structure of the cellulose on the particle morphology of the resulting PVC. The effects of agitation on PVC porosity have also received much attention [80]. Cebollada et al. A nonionic surfactant with a greater hydrophilelyophile balance (HLB) value is more effective in raising the particle size [82].

increased porosity may be the result of incomplete drop coalescence creating voids at the sites where droplets are not well contacted [82].CPA (g DOP/100g PVC) 5. Inc. High conversions of VCM are not always desirable because the porosity of PVC particles usually decreases linearly with monomer conversion. to promote crosslinking and phase sepa- 233 . A diene comonomer can be added to a monomer. This could be the consequence of an altering interfacial tension between the PVC-rich phase and the monomer. The porosity increases as the concentration of nonionic surfactant increases. When a nonionic surfactant is used as an SSA. The surface of primary particle aggregates becomes coarser as surfactant is added [82]. or in analytical instruments. The increase in porosity may be caused by a combination of increased coalescence of VCM/PVC droplets and the nonionic surfactant’s steric effect inside the droplets [82].7 [60. Reproduced by permission of John Wiley & Sons. In that case. 5. Effect of polymerization conversion on the cold plasticizer absorption (CPA) of PVC. with a low degree of hydrolysis. but in other cases particle porosity is induced to enhance access to functional groups within the polymer. 82]. 82.7. From Ref. as an SSA increased particle porosity in the suspension copolymerization of vinyl chloride and propylene [95]. PVC porosity decreases linearly with an increase of polymerization temperature [82].3 Events at High Monomer Conversion 100 90 80 70 60 50 40 30 20 0 20 40 60 80 100 Polymerisation conversion (%) Fig. The use of PVA. as shown in Figure 5. In vinyl chloride polymerization. That might be expected to decrease the contact deformation of the primary particles and increase the pore space. of initiator addition [62]. That is useful when polymer beads are required for use in ion-exchange columns. particle porosity facilitates the subsequent uptake of plasticizers. the SSA was more soluble in the organic phase than the primary stabilizer (a cellulose ether). and a surfactant with a lower HLB value is more effective in raising the porosity. the porosity of PVC increases as the concentration of nonionic surfactant increases. Bao et al. Nonionic surfactant with a lower HLB value (hence with a higher affinity for VCM and a higher solubility in VCM) is more effective in raising the product porosity. showed that particle morphology and PVC properties can be controlled by using blends of PVA suspending agents with differing degrees of hydrolysis [94]. in conjunction with PVA. When nonionic SSAs are used. Here.

5. Periodically formed vortices were con- . see Section 5. Oldshue et al.5. Basic expressions were modified to allow for evolving physical properties of the suspension. [51] and Vivaldo-Lima et al. However. [51] showed that it was feasible to estimate the volume ratio of the impeller and circulation regions. Reactor configurations other than conventional stirred tanks have been proposed for suspension polymerization. Fluid mixing was achieved by eddies that are generated when a fluid passes through a set of equally spaced. [100] showed that agitator type and vessel geometry have an important influence on internal liquid flow. Maggioris et al. This must be taken into account in the design of large vessels for suspension polymerization. These permit the prediction of drop size evolution in a suspension polymerization reactor with a high volume fraction of dispersed phase. In some cases. 5. but drop size changes can occur [103] and flow patterns may be complicated [104]. Although many industrial suspension polymerizations are described as ‘‘batch’’ processes. Tanaka et al.4 Reaction Engineering for Suspension Polymerization The discussion above (see Sections 5. they are not genuine batch operations because some material enters the reactor after polymerization has started. In both these situations.3) provides guidelines for the design of suspension polymerization processes on an industrial scale. Ni et al. can be used for suspension polymerization [102]. and the exchange flow rate of the two compartments at different agitation rates and continuous-phase viscosities. [105] used a loop reactor for the suspension polymerization of styrene. or ‘‘internal loops’’. unconverted monomer with low viscosity is being mixed with drops of higher viscosity. extrapolating from idealized small-scale studies to full-scale commercial operation is not straightforward. [101] devised two-compartment population balance models to account for the large spatial variations of the local turbulent kinetic energy.234 5 Free-radical Polymerization: Suspension ration inside the drops [96–99]. substantial reflux of monomers occurs and condensed monomer returns to the reactor continuously. They employed a double agitation method to control the transient droplet diameter distribution and the final particle size distribution. Maggioris et al. In others. Appropriate functional groups can be incorporated in the monomers.1 Dispersion Maintenance and Reactor Choice Many suspension polymerization processes employ stirred vessels. The complexities of these mixing processes have been discussed above. the ratio of turbulent dissipation rates.4. stationary. [106] developed an oscillatory baffled reactor for batch suspension polymerization of methyl methacrylate. Maintenance of uniform reactor conditions cannot be guaranteed inside large reactors and controlled heat transfer from reactors can be difficult.2. a semi-batch process is used to control product composition. orifice baffles that are located inside a tube. Draft tubes.2 and 5.

Radial mixing of the fluid occurs but near plug-flow is obtained. reactor agitation influences the rate of heat transfer to. Complete mixing of the drops gave a molecular weight distribution which was narrower than that found in batch reactors. oscillation amplitude. in the suspension polymerization of vinyl acetate. and baffle spacing. When conventional stirred tanks are used. 5. An oscillatory baffled reactor can also be used for continuous-flow suspension polymerization. If flow through a back-mixed region occurs. A constant level of turbulence intensity in the reactor can lead to particle size distributions similar to those expected from a batch reactor. the surroundings and determines the quality of mixing. the drops will be subject to a distribution of residence times and the nature of the mixing for the dispersed phase is important. a two-phase dispersion. some continuous-flow processes have been proposed [107]. produced an increase in polymer molecular weight. the agitation must also be good enough to generate. the impeller diameter (D) and the clearance underneath the impeller (G) are related to the tank diameter (T) as follows:  HAT D A T=3  G A T=3  The use of baffles limits nonuniformity in the turbulence and restricts vortex formation. Baade et al. [108] and Taylor and Reichert [109] showed that complete segregation of drops.4 Reaction Engineering for Suspension Polymerization trolled by choosing appropriate values for oscillation frequency. With suspension polymerization reactors. When vertical baffles are close to the walls their width (B) is often given by:  B A T=10 235 . Ni et al. and to maintain.4. [110] describe the effect of superimposed oscillations on the main flow through a tube.2 Agitation and Heat Transfer in Suspensions In single-phase processes. Here.5. The final particle size distribution and polymer molecular weight were comparable with those of a product obtained from a conventional stirred tank reactor. and from. baffle diameter. the height of the total suspension (H). Vortices are undesirable because the centrifugal effect favors drop congregation 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). a ‘‘standard’’ reactor geometry may be adequate to promote convective heat transfer. Also. Use of flow reactors may affect the nature of the drop size distribution and the molecular weight distribution. the distribution of molecular weights became broader than that expected in a batch reactor. Although most industrial polymerization processes are batch or semi-batch operations.

the internal temperature of drops could be . heat transfer between polymerizing drops and the continuous phase is rapid and both phases have the same temperature. with different half-lives and activation energies. The feasibility of such an approach depends on the accuracy of the reactor model that is used. (6)–(7) (see Section 5. Then it may become possible to match the heat generation rate with the cooling capacity of the reactor jacket. in reality. They constructed a model that predicted a reduction in total reaction time for a given monomer conversion. could be used. it can be helpful to have a small gap between the outer baffle edge and the reactor wall. When most of the heat transfer occurs via a cooling jacket. reactor fouling is sometimes a problem. then some heat can be removed relatively quickly by monomer vaporization (as discussed above for vinyl chloride polymerization. Mejdell et al. and in that region the use of baffles increases the required power input. especially after the startup period in batch operation when a gel effect causes autoacceleration in the polymerization. Lazrak and Ricard [115] showed that.2. must be sufficient to create and to maintain the required drop size distribution. Drop breakage and drop coalescence may occur in different regions of the reactor [5].5). Heat removal from suspension polymerization reactors can be a problem. If the reactor cooling capacity is chosen to cope with heat generation rates in the later stages of batch operation. But. It is commonly assumed that. then the heat removal capacity of the reactor will not be fully utilized in the early stages of the polymerization. The required stirrer speed for the appropriate turbulence level can be estimated from Eqs. The necessary power input can be predicted from correlations between the power number and the Reynolds number [30]. If the monomers are volatile at the working pressure of the reactor. in suspension polymerization. However. Longeway and Witenhafer [113] suggested that the reactor could be operated at a higher temperature in the early stages. where the effective viscosity of the suspension may be unknown. to make full use of the cooling capacity. see Section 5.2). when autoacceleration occurs. special strategies may be necessary to manage the heat transfer. those correlations are usually developed for single-phase fluids and care must be taken when using them for suspensions. In such cases. with methyl methacrylate polymerization. [112] showed that the reaction rates predicted from models for the industrial suspension polymerization of vinyl chloride were subject to significant noise because the heat capacity of the suspension was large and the resolution of temperature measurements was limited. the turbulence will not be uniform. Pinto and Giudici [111] suggested that a mixture of initiators. That may reduce accumulation of coagulated solids at the wall–baffle junction.2. It should be remembered that the overall heat transfer coefficient for a jacketed reactor depends on the nature of the wall material. However. via the impeller. But the power input to the suspension. Some form of turbine impeller is often suitable for suspension polymerization when the apparent viscosity of the suspension is not very high. Transfer coefficients for stainless steel reactors are approximately double the coefficients found for glass-lined carbon steel reactors [114]. The Reynolds number in most large-scale suspension polymerization reactors is usually high enough to generate turbulent flow.236 5 Free-radical Polymerization: Suspension With suspension polymerization.

it not practical to use a stirrer speed. should help reactor designers to relate observations in laboratory experiments to events that occur on a large scale. and polymer molecular weight. In such cases. Sometimes those can be included in modifications to the Weber number correlations (see Section 5. Often.2. Temperature differences were large enough to cause changes to polymer quality. In the case of VCM polymerization. But. in a small reactor. such as the Weber number correlations (see Section 5.3 Scaleup Limitations with Suspension Polymerization Many aspects of scaleup (or scaledown) of suspension polymerization reactors are similar to those encountered with other polymerization processes. it is possible for the fluid in a large reactor to be fully turbulent but for the fluid in a small reactor to be in the transition region (between laminar and turbulent flow). In the case of VCM polymerization. A good estimate for the physical properties of the whole suspension is necessary in order to predict values for the Reynolds number. These concern parameters that control polymerization rate. then the rate of monomer reflux can depend on reactor size. then new scaleup criteria may become necessary. the maintenance of particle porosity is also an issue.4. there can be a serious difficulty in maintaining constant average turbulence intensities.5. When the suspension viscosity is high.4 Reaction Engineering for Suspension Polymerization higher than that of their surroundings when drop diameters exceeded 1 mm. [5] and by Leng and Quarderer [39]. this can result in particle porosity changing with reactor size (see Section 5. correlations between dimensionless entities. This arises because a high Reynolds number (Re ¼ ND 2 r=m) is easier to achieve in a large reactor than in a small reactor. An unbaffled spherical laboratory reactor will not behave in the same way as a large baffled cylindrical reactor. which is high enough to compensate for the relatively small value of D 2 .2). Some key relationships are discussed by Yuan et al. the drop breakage mechanism can change with reactor size.3). In principle. it is difficult to ensure similarity of conditions inside reactors with greatly differing sizes. In addition to the problem of matching turbulence homogeneity in reactors of different sizes. Consequently. product composition. 237 . even if fundamental requirements for drop breakage and drop coalescence are known (which is not always the case). special consideration must be given to maintaining the required drop/particle size distribution. If some heat transfer occurs via monomer evaporation. such as that required for a crossflow membrane [16] or a pulsed column [106]. especially when autoacceleration occurs.2). In the case of suspension polymerization. Scaleup criteria should allow for any variations of volumetric phase ratio that may occur. however. When drop formation depends on reactors with a special geometry. Scaleup is most likely to be successful when the reactors have a similar basic shape. it may not be possible to achieve the same time– temperature profile in a large reactor as is obtained with a small reactor. 5. Heat transfer rates per unit mass of suspension increase as reactor size decreases.3.

highly viscous drops can accumulate and coalesce at the bottom of the reactor. which can be dangerous when large amounts of monomer are being handled. inhibitors are often removed from the monomer before it is dispersed in the continuous phase. This arises because the heat of reaction is high and there is no effective steady state. Even when geometric similarity is maintained. In large-scale operation.4 Reactor Safety with Suspension Processes The potential for thermal runaway exists with most commercial free-radical polymerization processes that employ batch reactors. it may be difficult to reproduce exact laboratory proce- . largely because spontaneous free-radical generation occurs with that particular monomer as the temperature increases.4. it is important to allow for small changes that occur in the physical properties of the polymerizing fluid. In those cases the polymerizing drops may gradually sink during the process. If the suspension fails. the reactor is maintained at a positive pressure because a volatile blowing agent (for example. Disaster may be avoided if a pressure release device (for example. Otherwise. large overestimates of temperature rises are obtained [117]. In small-scale suspension polymerization. This was demonstrated by Nemeth and Thyrion [116] who showed that very sharp temperature rises could occur in the suspension polymerization of styrene. Consequently. but it is essential that the design. Such a potential risk arises with suspension polymerization of styrene in the production of pre-expanded beads. the inhibitor may not be removed. Even though styrene has a relatively high boiling point. of such a device do not permit excessive fouling by polymer deposits. 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.4.5 Component Addition during Polymerization Scaleup often involves more than an increase in reactor size. Regular reactor cleaning is important. If good mixing is not maintained. heat transfer from the coalesced drops is quickly reduced and the temperature of the polymerizing mass begins to rise. with all its inherent disadvantages. Although temperature control in suspension polymerization reactors is often better that that found in bulk polymerization.238 5 Free-radical Polymerization: Suspension 5. 5. When models are used to predict temperature rises in polymerization reactors. however. the possibility of thermal runaway cannot be ignored. and location. a bursting disk) functions well. when the drop viscosity is still relatively low). Its presence lowers the risk of premature polymerization. The subsequent increase in vapor pressure of the water can cause the total pressure to reach unsafe values. the particle size distribution obtained from the large reactor may differ from that in the small reactor because drop breakage can occur before significant amounts of polymer are formed (that is. pentane) must remain in the drop phase. The process then reverts to a bulk polymerization.

acylamide.5 ‘‘Inverse’’ Suspension Polymerization When a water-miscible polymer is to be made via a suspension process.1 Initiator Types The thermal decomposition of single-component initiators (such as inorganic persulfates) can be used to generate the free radicals in the aqueous drops. Here. often a hydrocarbon. but in 239 . 5. the DSD and final PSD may depend on the scale of operation. 5. the polymerization reaction occurs inside the monomercontaining drops. Conventional stirred reactors are usually used for inverse suspension polymerization and the drop size distribution can be fairly wide. because polymerization (and a change in drop properties) occurs during the drop creation process. 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 drop phase is often an aqueous monomer solution which contains a water-soluble initiator. and methacrylic acid.5. Ni et al. the initial dispersion of drop stabilizers and initiator may require different amounts of time with reactors of different sizes. Many scaleup criteria do not apply to transient events because they employ relationships that assume steady-state conditions. At startup conditions. Thus. These polymers are used in water treatment and as thickening agents for textile applications. The new material may include fresh monomer(s). occur in the drops. Physical changes. A more accurate expression is either ‘‘inverse microsuspension’’ or ‘‘inverse dispersion’’ polymerization. the continuous phase is a water-immiscible fluid.5 ‘‘Inverse’’ Suspension Polymerization dures when a large reactor is used. Beads of polysaccharides can also be made in inverse suspensions but.5. as with conventional suspension polymerization. rather than polymerization reactions. Consequently. the polymers are usually preformed before the suspension is created. or modifiers for polymer properties. In such circumstances the adjective ‘‘inverse’’ is often used to identify the process [118]. the time required to disperse added material may depend on reactor size. [119] found that good control of DSD and PSD could be achieved in the inverse-phase suspension polymerization of acrylamide by using an oscillatory baffled reactor. the surfaces of the small particles must be rendered hydrophobic. However. in those cases. The drop stabilizers are initially dispersed in the continuous (nonaqueous phase). 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. Inverse dispersion polymerization is used to make water-soluble polymers and copolymers from monomers such as acrylic acid. If particulate solids are used for drop stabilization. blowing agents.

Much of the new work on recipes and product properties is material-specific and will continue to appear in the patent literature. 5. The way in which the ingredients are brought together can affect the polymer properties. Redox reactions produce free radicals at relatively low temperatures. Improvements to existing processes need closer attention to ways in which reactors are operated. Otherwise. The polymerization kinetics can be complicated when redox systems are used and the mechanism of radical generation may depend on the specific reductant– oxidant pair that is chosen [121].5. which is advantageous when the polymerization is very fast at higher temperatures.8).240 5 Free-radical Polymerization: Suspension some cases a redox initiator system is used. the initial suspension has two types of aqueous drops which must become mixed before polymerization can begin. Therefore. The actual volumes and concentrations used for the two aqueous solutions affect the rate of viscosity increase in the drops and the polymerization rate [124]. 121]. These should include the following aspects. Often.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. 5. Therefore. polymerization would begin before the desired DSD was attained. This type of polymerization is not always strictly analogous to ‘‘simple’’ conventional suspension polymerization. The development of new processes requires further fundamental investigation. Liu and Brooks [123] used a freeze–fracture technique with electron microscopy to show how ‘‘large’’ reductant drops became mixed with ‘‘small’’ monomercontaining oxidant drops in the early stages of acrylic acid polymerization (Figure 5. drops of an aqueous solution of monomer and oxidant are initially dispersed in an oil and stabilized with an appropriate agent. and that a small amount of polymerization occurs in the oil phase [120]. In some circumstances. 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.6 Future Developments Future work on suspension polymerization will be concerned with new products and with new processes. Then aqueous reductant is added to start the reaction [122.6. improvements in the control of product quality may depend on developing better .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. 5.

That is especially important when the initiator and monomer are not premixed before entry to the reactor. a careful choice of drop stabilizer. From Ref.6 Future Developments Fig. Inverse dispersion polymerization of acrylic acid. 5. and possibly the use of solvents. reactor startup procedures. Reproduced by permission of Elsevier Science Ltd. That might be achieved by careful use of radical inhibitors which reduce initial polymerization rates (and associated viscosity increases) and allow the initial DSD to develop in a desired way. then drop segregation must be overcome. before they are put into the reactor. have 241 . may be helpful. Desirable changes in PSD may be obtained by exercising better control of drop viscosity in the initial drop formation stage. Here. which represent a small mass fraction of the drop phase. If late addition of some monomer is used to maintain constant composition at high conversions. That could be important because those emulsion particles. Radical inhibitors that dissolve preferentially in the continuous phase might also be used to eliminate the initial formation of emulsion particles.5.8. should not be made in an arbitrary way. Good control of copolymer composition will continue to be difficult when monomer reactivity ratios vary widely. Freeze–fracture SEM image of dispersion 2 min after adding aqueous reductant. The initial sequence in which the initiator and drop stabilizer are put into the reactor can affect copolymer composition and polymerization rates because inter-drop mixing can be restricted during polymerization. 123. The decision to remove (or not remove) radical inhibitors from monomers.

even when they are potentially important. continuous-flow reactors could offer other advantages.2 Maintaining Turbulence Uniformity in Batch Reactors Turbulence in conventional stirred vessels is far from uniform and prediction (or control) of DSD is difficult. 5.6. the use of new reactors. That is undesirable when the final particles are used directly (for example. in ion-exchange resins). New designs of oscillatory baffled reactors [106] may make such processes feasible on an industrial scale. restricted overall back-mixing. the drop formation and polymerization stages could be separated to give better control of the DSD.242 5 Free-radical Polymerization: Suspension a large surface area and they can distort the distribution of drop stabilizer during the initial drop development stage. with suspension polymerization. Then.4 Quantitative Allowance for the Effects of Changes in the Properties of the Continuous Phase In suspension polymerization. the final PSD is often very wide. In those cases. But when the volume fraction of drops is high. 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 conditions. and drop breakage via viscous shear becomes important. could be helpful. Maintenance . Consequently. a narrow PSD is often required. 5.6. or when a significant fraction of the drop stabilizer remains in the continuous phase. events that occur in that phase are sometimes neglected. the continuous phase is often regarded as ‘‘inert’’. If ‘‘near plug-flow’’ conditions could be attained. 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 final PSD. The overall Reynolds number is often high enough to ensure that drop breakage is via turbulence and that ‘‘conventional’’ Weber number correlations apply.3 Developing Viable Continuous-flow Processes Continuous-flow reactors are often developed to produce high tonnages with low reactor maintenance but. Also. such as the oscillatory baffled reactor. 5. and good heat transfer. the Kolmorgorov length may exceed the drop diameter. Here. the effective viscosity of the suspension becomes high. More work is required to determine the relationships between drop sizes and agitation conditions when the fluid flow is not fully turbulent. Thus. For a continuous-flow reactor to operate successfully the following conditions must be attained simultaneously: a suitable residence time (often a few hours). That will lead to a lower proportion of ‘‘off-specification’’ material. small regions of localized turbulence.6.

However. 5. the use of SSAs is often important. the location of those particles at the end of polymerization is important.Notation 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. C3 . Further systematic studies are required to determine the effect of the size and surface condition of the stabilizer particles on their ability to stabilize drops. Also. Prediction 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. it is necessary to determine what fraction of those stabilizers is inside drops of the dispersed phase and how they affect structure inside the particles. it may be advantageous to treat stabilizer particles so that they remain with the polymer product in order to confer some desirable property. The chances of all monomers being ‘‘insoluble’’ in the continuous phase are small. 5. will be important. Therefore the effects of monomer distribution between the phases. Notation B C1 . especially on the copolymer composition.6. to gain a better understanding of their role. Some of the theories do not always agree with experimental results.5 Further Study of the Role of Secondary Suspending Agents The porosity and structure of polymer particles are important for many product applications. In some cases. but our understanding of their action is far from complete. Then. C4 CI CM d d max d min d32 D baffle width [m] constants (dimensionless) initiator concentration [mol m3 ] monomer concentration [mol m3 ] drop diameter [m] maximum drop diameter [m] minimum drop diameter [m] Sauter mean diameter [m] impeller diameter [m] 243 . The importance of grafting of SSAs to the polymer should be clarified.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.6.

Trommsdorff. 35/36. Hamielec. 4 B. Appl. Rev. J. Kalfas. 717–732. E. 307–334. New York. T. Flatan. 121– 140. Langsam. Munzer. H. I. Makromol. Eng. 1984. C31(2/3). Ray. Chem. Bieringer. P. Schildknecht.. Makromol.. Sci. 1988. G. J. 939–965. 106. W. 24. Paint. Yuan. G. 58. Wood. Chem. 6 7 8 9 Rev. Cheng. Colloid Polym. Polym. 1991. 1990. C. J. 30. Sci. Chapter 5.. Phys. 541–544. 270. Polym. G. in Polymerization Processes. Brooks. Mater. Wiley.. Hagberg. Eng. Makromol. Reese. R. Symp. Polym. Warson. 3 H. 5 H. 1983. M. Ashady. E. E. A. Makromol. 215–299. Chem. Angew. 123. Skeist.. 1977. 1997. D. 614–621. Chem. Col. C. E. Vivaldo-Lima. Ind.244 5 Free-radical Polymerization: Suspension f G H kd kp kt N Re Ri Rp T We We crit efficiency factor (dimensionless) clearance underneath impeller [m] height of the total suspension [m] initiator decomposition rate coefficient [s1 ] propagation rate coefficient [m 3 mol1 s1 ] termination rate coefficient [m 3 mol1 s1 ] impeller speed [s1 ] Reynolds number (dimensionless) initiation rate [mol m3 s1 ] polymerization rate [mol m3 s1 ] tank diameter [m] Weber number (dimensionless) critical Weber number (dimensionless) Greek parameter to define flow (dimensionless) local energy dissipation rate per unit mass of fluid [m 2 s3 ] Kolmogorov length [m] viscosity [kg m1 s1 ] kinematic viscosity [m 2 s1 ] density [kg m3 ] interfacial tension [kg m2 ] volume fraction of dispersed phase (dimensionless) a e h m n r s j Subscripts c d continuous phase dispersed phase References 1 M. K. .. Ed.. 36. 1992. E. 1985. Sci. W. p. 2 H. 1285–1308.

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In a scenario of reduction of margins. A critical point is to know how these process variables affect the final properties of the product.1 has important eco1) The symbols used in this chapter are listed at the end of the text. branching. KGaA. which most often is water. Jose´ M. Giuseppe Storti. Leiza. and environmentally friendly way. 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 substitution of solvent-based system by waterborne products. the dispersion is called latex. textiles. and diagnostic tests and drug delivery systems [1–4]. molecular weight distribution (MWD).249 6 Emulsion Polymerization1 Jose´ C. the term microstructure is used in a broad sense. paints. and particle size distribution (PSD) of the dispersion) as a link between the reactor variables and the final properties (Figure 6. emulsion polymerization is used in the production of a wide range of specialty polymers. and public sensitivity to environmental issues. including aspects such as copolymer composition. Handbook of Polymer Reaction Engineering. Weinheim ISBN: 3-527-31014-2 .1 Introduction Emulsion polymerization leads to the production of a fine dispersion of a polymer in a continuous medium. Jose´ R. The implementation of the approach illustrated in Figure 6. Asua. emulsion polymer producers are forced to achieve efficient production of high-quality materials in a consistent. and Massimo Morbidelli 6. safe. gel fraction. crosslinking. J. impact modifiers for plastic matrices. and construction materials.1). under ‘‘Notation’’. binders for nonwoven fabrics. 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 microstructure (here. Emulsion polymers are ‘‘products-by-process’’ whose main properties are determined during polymerization. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. particle morphology. including adhesives. additives for paper. Edited by T. de la Cal. With a worldwide annual production in excess of 20 million tonnes. increasing competition. Meyer. Alessandro Butte`.

Polymer properties as a function of formulation and process type. On the other hand. the highest level of understanding being the development of predictive mathematical models. the needs/ opportunities of the market.11. efficient. optimization. The polymer is mainly made out of a mixture of ‘‘hard’’ monomers (leading to polymers with a high glass transition temperature. This involves a deep understanding of the emulsion polymerization process. In addition. First.250 6 Emulsion Polymerization Fig. Finally.1 presents a typical formulation for emulsion polymerization. should be translated in terms of the desired polymer microstructure. Crosslinking agents and chain-transfer agents (CTAs) are used to control the molecular weight distribution of the polymer. and consistent production requires accurate on-line monitoring. Last but not least. safe. for example. styrene) and ‘‘soft’’ monomers (low Tg. .4–6. the emulsion polymer reaction engineering is addressed in Sections 6. small amounts of functional monomers such as acrylic and methacrylic acids are included in the formulation as they provide some special characteristics. nomic implications and is scientifically challenging. and control. This requires quantitative microstructure/properties relationships. expressed as desired properties of the final product.8–6. Tg . for example.3. such as improved adhesion. This chapter is focused on the challenge of achieving the efficient.1. this polymer microstructure should be achieved in the reactor. 6. and consistent production of emulsion polymers of the desired microstructure.1 Description of the Process Table 6. 6. Sections 6. the main features of emulsion polymerization are discussed in Sections 6. safe. butyl acrylate) of low solubility in water. efficient methods for removal of residual monomer and volatile organic compounds (VOCs) should be developed to produce environmentally friendly products. On the one hand.2.2 Features of Emulsion Polymerization 6. In addition.7 are devoted to the understanding of the kinetics of the process.2 and 6.

6. The growth rate of the oligoradicals is generally modest because of the low concentration of monomer in the aqueous phase. the mixture of monomers is dispersed in water using emulsifiers.2 Features of Emulsion Polymerization Tab.2(a)). Typical formulation for emulsion polymerization. emulsion polymerization is carried out in stirred-tank reactors. The monomer droplets are stabilized by the surfactant adsorbed on their surface. Ingredient Content [wt. but in practice anionic surfactants. In a batch emulsion polymerization. When a water-soluble initiator such as potassium persulfate is added to the monomer dispersion. and redox. After adding some monomer units. In principle. AIBN) may also be used. Polymerization is commonly initiated by water-soluble initiators (both thermal. Because of the high concentration of monomer in the micelle. the oligoradicals become hydrophobic enough to be able to enter the micelles (entry into the monomer droplets is not likely because their total surface area is about three orders of magnitude smaller than that of the micelles).%] Monomer(s) styrene methyl methacrylate vinyl chloride vinyl acetate butadiene butyl acrylate 2-ethylhexyl acrylate Veova 10 ethylene (meth)acrylic acid crosslinking monomers Deionized water Initiators Emulsifiers Chain-transfer agents 50–55 45 0. although both batch and continuous operations are also used. they react with the monomer dissolved in the aqueous phase. in most formulations. tert-butyl hydroperoxide/ascorbic acid) although oil-soluble initiators (for example.5 0. 6. The available surfactant partitions between the surface of the monomer droplets and the aqueous phase. radicals are formed and as these radicals are too hydrophilic to enter the organic phases of the systems. nonionic surfactants.5–3 Typically. potassium persulfate. which commonly operate in a semicontinuous mode. The excess of surfactant forms micelles that are swollen with monomer (Figure 6. the amount of surfactant exceeds that needed to completely cover the monomer droplets and saturate the aqueous phase. for example. for example. and mixtures thereof account for the great majority of the systems used. any type of surfactant may be used.1. the oligoradical that has entered the micelle grows 251 . forming oligoradicals.

252 6 Emulsion Polymerization Fig. and upon reaching some critical length they become too hydrophobic and precipitate. The process of formation of polymer particles by entry of radicals into micelles is called heterogeneous nucleation [5]. monomer will diffuse into the new polymer particle. The emulsifier present in the system will adsorb onto the newly formed interface. The oligoradicals that do not enter into micelles will continue growing in the aqueous phase. Both homoge- . 6. thus stabilizing the polymer. Then. fast. Intervals in the batch emulsion polymerization.2. forming a polymer chain. The process of formation of polymer particles by precipitation of oligoradicals is called homogeneous nucleation [6]. The new species formed upon entry of a radical into a micelle is considered to be a polymer particle.

monomer droplets. the system is composed of monomer droplets and polymer particles (Figure 6. and hence monomer partitions between the different phases of the system according to the thermodynamic equilibrium.5 g/100 g of water) and heterogeneous nucleation is predominant for water-insoluble monomers (for example. and monomer swollen polymer particles coexist in the reactor (Figure 6.2(c)).5 g/100 g of water – and vinyl acetate – 2. stabilizing them [7–9].2(b)). Unless coagulation occurs. homogeneous nucleation is predominant for monomers of relatively high water solubility (for example. Conse- 253 . In Interval II. the number of particles remains constant during the rest of the process. After some time. In general. 10 17 –10 18 particles per liter are formed. all the micelles disappear. in the presence of monomer droplets. The stage of the batch emulsion polymerization in which particle nucleation occurs is called Interval I. At the end of Interval I. The number of micelles decreases because they become polymer particles upon entry of a radical and also because they are destroyed to provide surfactant to stabilize the increasing surface area of the growing polymer particles. the size of the particles increases and that of the monomer droplets decreases. Therefore. The mass-transfer rate of monomers with water solubility equal or greater than that of styrene (0. The monomer consumed by polymerization in the polymer particles is replaced by monomer that diffuses from the monomer droplets through the aqueous phase. 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. Therefore. the concentration of the monomer in the polymer particles reaches a maximum value. and hence monomer is consumed by polymerization inside the polymer particles. in the so-called mechanism of coagulative nucleation.1). It is worth mentioning that polymerization proceeds according to the same mechanisms as are discussed in Chapter 4 for free-radical polymerization in homogeneous systems. which typically occurs at a monomer conversion of about 5–10% (depending on the surfactant/monomer ratio).2 Features of Emulsion Polymerization neous and heterogeneous nucleation may be operative in a given system. As discussed below (see Section 6. It is arguable that the emulsifier molecules may diffuse fast enough to adsorb on the surface of these fast-growing particles.045 g/100 g of water) is substantially higher than the polymerization rate. During nucleation. Polymer particles compete efficiently for radicals. only limited formation of new particles may occur after this point because heterogeneous nucleation is not possible and there is no free surfactant available in the system to stabilize the particles formed by homogeneous nucleation. Therefore.045 g/100 g of water). styrene – 0. This is considered to be the end of the nucleation.6. Irrespective of the mechanism of particle nucleation (heterogeneous or homogeneous) the newly formed particles are very small and suffer a tremendous increase in surface area upon particle growth. methyl methacrylate – 1. The monomer that is consumed by polymerization in the polymer particles is replaced by monomer that diffuses from the monomer droplets through the aqueous phase.4. monomer swollen micelles. this saturation value arises from the energy (interfacial tension) needed to increase the surface area of the polymer particles upon swelling.

On the other hand. This marks the end of Interval II. The system will contain only monomer-swollen polymer particles if both monomer and surfactant are fed slowly (Figure 6. monomer concentration in the polymer particles decreases continuously. In general. the transition from Interval II to Interval III occurs at about 40% conversion for styrene and at about 15% conversion for vinyl acetate. the overall concentration of radicals is higher than in homogeneous (bulk and solution) free-radical polymerization. In a semicontinuous reactor in which monomers. This means that most monomer polymerizes in Interval III (Figure 6. Because of the polymerization and monomer transport. chain-transfer agents) with water solubility lower than that of the styrene from monomer droplets to polymer particles may be diffusionally limited. slow monomer feed and fast surfactant feed may lead to a system composed of polymer particles and micelles (Figure 6. Thus. the earlier the monomer droplets disappear.3(a)). Consequently. the compartmentalization of radicals among a huge number of polymer particles is likely to be the most distinctive feature of emulsion polymerization.3(b)). liable to suffer thermal runaways. Compared with bulk and solution polymerization. emulsion polymerization does not follow the sequence of events described above. and hence the lower the monomer conversion at the end of Interval II. the more water-soluble the monomer. the monomer concentration in the polymer particles is roughly constant during 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.3(c)). 6. 6.2(d)).2. a fast monomer feed and a low surfactant feed will lead to a system containing monomer droplets and polymer particles (Figure 6. leading to a higher polymerization rate. and water may be continuously fed into the reactor. In this interval.% solids) dispersion of tiny (80–500 nm in diameter) polymer particles called latex. In addition. This refers to the fact that the radicals are distributed among the different particles. the compartmentalization of radicals in a large number of particles results in a longer lifetime of the radicals. the higher the maximum swelling.254 6 Emulsion Polymerization quently. and after some time the monomer droplets disappear. The final product is a waterborne.3 Advantages of Emulsion Polymerization Free-radical polymerization is a very exothermic process. surfactant. and hence radicals in different particles cannot terminate between them. initiator.2 Radical Compartmentalization From a mechanistic point of view. the polymer particles grow in size.2. which leads to higher molecular weights. emulsion polymeriza- . Thus. concentrated (50–60 wt. The transport of reactants (monomers.

as water is used as the reaction medium.2 Features of Emulsion Polymerization Fig. Because of the compartmentalization of the radicals. Compared with solution polymerization.3. emulsion polymerization is environmentally friendly. because of its high heat capacity. This allows combination of high polymerization rates and good temperature control. In addition. emulsion polymerization overcomes the limita- 255 . the low viscosity of the system allows easy removal of both unreacted monomer and VOCs.6. 6. the water absorbs large amounts of heat with only a moderate increase in temperature. In addition. tion is advantageous because the low viscosity of the latex allows high heat removal rates. Species present in semicontinuous emulsion polymerization.

additives for paper. When the initiator is added to the system. leather treatment. catalytic chain-transfer agents. and diagnostic tests and drug delivery systems. . The available surfactant adsorbs on the large surface area of the droplets. and microemulsion polymerization. the size of the monomer droplets is substantially reduced (dd ¼ 50–1000 nm) by combining a suitable emulsifier and an efficient emulsification apparatus. agents for controlled radical polymerization) in the reaction loci.3 Alternative Polymerization Techniques Dispersed polymers are also achieved by inverse emulsion polymerization. In the last few years. anionic polymerization. encapsulation of inorganic solids. In miniemulsion polymerization [11]. production of hybrid polymer particles. catalytic polymerization. Inverse emulsion polymerization is used in the preparation of solventbased 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 organic solvent [10]. 6. dispersion polymerization.256 6 Emulsion Polymerization tions imposed by the kinetics of bulk and solution polymerization. miniemulsion polymerization in nonaqueous media. when needed (for example. plenty of new applications have been discovered. Droplet nucleation minimizes the diffusional limitations encountered in conventional emulsion polymerization and allows the incorporation of water-insoluble compounds (monomers. inorganic materials. miniemulsion polymerization. for rubber for tires) latexes are easy to process into dry polymer. which become polymer particles. can only be produced by emulsion polymerization. controlled radical polymerization in dispersed media. low-viscosity latexes. textiles and construction materials. and stabilizing the resulting monomer miniemulsion against diffusional degradation by using a costabilizer (hydrophobic. low molecular weight compound). In addition. Some valuable products with applications in paper coating. which give it water sensitivity. and hence no micelles are formed. and high polymerization rates and high molecular weights can be achieved simultaneously. the radicals enter the monomer droplets. impact modifiers for plastic matrices. step polymerization in aqueous dispersed media. stable operation in continuous polymerization reactors. catalysts. These applications include:           production of high-solids. polymers. The main disadvantage of emulsion polymerization is that the product contains emulsifier and residues of initiator. incorporation of hydrophobic monomers. binders for nonwoven fabrics.

whose stability is due to the very low interfacial tension achieved using appropriate emulsifiers. production of low molecular weight polymers in dispersed media. the initiator and the stabilizer (or stabilizer precursor) are dissolved in a solvent which is not a solvent for the polymer (Figure 6.4). forming unstable nuclei (Figure 6. the monomers. This leads to a higher number of polymer particles. 6. Microemulsions are thermodynamically stable and isotropic dispersions.4(c)). which results in a more compartmentalized system. Microemulsion polymerization [13] involves the polymerization of oil-in-water and water-in-oil monomer microemulsions.4(a)). In dispersion polymerization [12]. which are too large for emulsion polymerization and too small for suspension polymerization. Under these conditions the lifetime of the polymer chains increases. Particle nucleation occurs upon entry of a radical into a microemulsion droplet. The nuclei are stabilized by the stabilizer present in the system (Figure 6.6. Microemulsion polymerization allows the production of particles smaller than those obtained by emulsion polymerization. leading to ultra-high molecular weights. Because of the compartmentalization of the radicals among the polymer particles. the polymerization locus changes from the continuous to the dispersed phase. Nucleation ends when the number of stable polymer particles increases to a point at which all new nuclei are captured by the existing stable particles.4(b)). Dispersion polymerization allows the production of monodispersed micron-size particles.4.3 Alternative Polymerization Techniques Fig. 257 . 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. Polymerization starts in a homogeneous phase and the polymer is precipitated.   Dispersion polymerization. preparation of latexes with special particle morphology.

(3). ½Mi p . P2 ¼ 1  P1 ð4Þ In order to calculate the polymerization rate. . The lack of available values for the large number of parameters involved in this model makes it advisable to use simpler models. and monomer droplets) and polymerization may. where k p is the propagation rate constant [m 3 mol1 s1 ]. In this case. in principle. where kpji is the propagation rate constant of radicals with terminal unit j with monomer i [m 3 mol1 s1 ]. ! X n Np ðmol/m 3 sÞ kpji Pj ½Mi p ð3Þ Rp i ¼ N A V j P1 ¼ kp21 ½M1 p kp21 ½M1 p þ kp12 ½M2 p . n the average number of radicals per particle and NA Avogadro’s number. occur in any phase. ½Mp the concentration of monomer in the polymer particles [mol m3 ]. the concentration of the radicals in the monomer droplets is very low because the monomer droplets are not efficient at capturing the radicals formed in the aqueous phase.258 6 Emulsion Polymerization 6. n and Np should be available. On the other hand. where Np is the number of polymer particles in the reactor. However. (2). The polymerization in the polymer particles follows the same mechanisms as in bulk polymerization and the rate of polymerization per polymer particle Rpp is given by Eq. Rpp ¼ k p ½Mp n NA ðmol/particle sÞ ð1Þ The overall polymerization rate Rp takes into account the existence of many polymer particles in the system according to Eq. and hence the extent of the polymerization in the aqueous phase is in most cases negligible. aqueous phase. However. propagation depends on the nature of the monomer and on the last two units of the growing chain [14]. Rp ¼ k p ½Mp n Np NA V ðmol/m 3 sÞ ð2Þ Most emulsion polymerization processes involve several monomers. (4) [16]. in which polymerization is governed by the nature of the monomer and the terminal unit of the growing chain. and V the volume of the reactor.4 Kinetics of Emulsion Polymerization Conventional emulsion polymerization occurs in a three-phase system (polymer particles. there is considerable evidence that for many polymerization systems. (1). the polymerization rate Rpi of a given monomer is expressed as Eq. such as the terminal model [15]. and Pj the time-averaged probability of finding an active chain with ultimate unit of type j that for a two-monomer system is given by Eq. the concentrations of both monomer and radicals in the polymer particles are much higher than those in the aqueous phase (see below).

6.2) it can be seen that the higher the water solubility of the monomer. 259 .4. Except for poorly emulsified. The swelling equilibrium depends on the particle size. monomers are continuously fed into the reactor. at some point.6. the higher the equilibrium swelling.73 0. aqueous phase.4 Kinetics of Emulsion Polymerization 6. The monomer that is consumed by polymerization in the polymer particles is replaced by monomer that diffuses from the monomer droplets through the aqueous phase. there are no droplets and the monomer is mostly located in the polymer particles. and hence the concentrations of the monomers in the different phases are given by the thermodynamic equilibrium. the calculation of the concentrations of the monomers in the different phases involves the simultaneous solution of the thermodynamic equilibrium equations and the material balances. and polymer particles.6 0. From values of the maximum swelling for homopolymerization [17] (Table 6. p Monomer fM [a] Styrene n-Butyl methacrylate n-Butyl acrylate Methyl methacrylate Vinyl acetate Methyl acrylate 0. The limiting swelling of the polymer particles is due to the contribution of the surface energy to the total free energy of the system.85 [a] fp M ¼ volume fraction of monomer in the polymer particles. Under these circumstances.65 0. that is to say at high fractional conversions (polymer/monomer ratios close to 90:10 (by weight). The amount of monomer that can be absorbed in the polymer particles is limited and the excess of monomer forms droplets. For a multimonomer system. 19].85 0.1 Monomer Partitioning During Intervals I and II of a batch emulsion polymerization. monomers partition among monomer droplets. In semibatch processes. Several equilibrium equations may be used. the surface energy increases as particles swell and. the rate of mass-transfer is faster than the polymerization rate.6 0.2. The concentration of monomer in the polymer particles depends on the relative values of mass-transfer and polymerization rates. but for particle sizes common in emulsion polymerization this effect is negligible [18. those based on partition coefficients [20] and on the Tab. In Interval III. usually under starved conditions. this compensates for the decrease in the free energy due to the monomer–polymer mixing. Swelling equilibrium data for homopolymerization [17]. only the newly fed monomer droplets are present in the reactor and the lifetime of these droplets is short because the monomers diffuse through the aqueous phase to the polymer particles. highly water-insoluble monomers. Because of the interfacial tension. where they are consumed by polymerization.

where Ki is the partition coefficient of monomer i between phase j and the aqueous phase. 6.%) the use of the Morton–Flory–Huggins equation does not provide significant advantages over the use of partition coefficients. For a multimonomer system.5 illustrates the mechanisms controlling n. Vw the volume of the aqueous phase. (7). In the latj ter case. j fi the volume fraction of monomer i in phase j. droplets ð5Þ Material balances: fpp þ X p fi ¼ 1 i fww þ X fiw ¼ 1 i X fid ¼ 1 ð6Þ i p Vp fi þ Vd fid þ Vw fiw ¼ Vi Vw fww ¼ W Vp fpp ¼ Vpol Efficient methods for solving Eqs (5) and (6) are given elsewhere [19. In most emulsion polymerization systems. fww the volume fraction of water in the aqueous phase. and W are the volumes of monomer i. Vpol . Vd the volume of monomer droplets. 20]. and Vi . respectively. and it has been shown [22] that for solids contents typical of commercial latexes (> 50 wt. and water. fpp the volume fraction of polymer in the polymer particles. X nNn n¼ X Nn ð7Þ Figure 6. polymer. Equilibrium equations: j j Ki ¼ fi fiw j ¼ polymer particles. the system of algebraic equations (5) and (6) needs to be solved. the parameters of the Morton–Flory–Huggins are not usually available.2 Average Number of Radicals per Particle The average number of radicals per particle n is given by Eq.4. Vp the volume of polymer particles. radicals are produced in the aqueous phase from thermal or redox .260 6 Emulsion Polymerization Morton–Flory–Huggins equation [21] being the most commonly applied.

On the other hand. the radicals undergo the classical mecha- 261 . 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. but the radicals directly produced from inorganic initiators are too hydrophilic to be able to enter a hydrophobic phase. whereas the propagational model is a simpler approach applicable to many homopolymerizations. they must stay in the aqueous phase until they polymerize. 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. The rate of radical entry can 3 also be expressed as Eq. the radicals generated from radical desorption (see below) are hydrophobic and able to enter the polymer particles regardless of their length. Rate of entry ¼ ka ½Rw ðradicals/particle sÞ ð8Þ Equation (8) is a simplification because it assumes that all radicals are able to enter the polymer particles. these radicals are too hydrophilic and cannot directly enter the hydrophobic phases (polymer particles. There is some debate about the mechanism for radical entry. micelles). Therefore. the total area of the polymer particles is much larger than that of the monomer droplets. diffusional [23] and propagational [24]. initiators.6. 6. resulting in a low initiation efficiency. Once inside the polymer particles. Often. Processes controlling the average number of radicals per particle. The diffusional model is more general. In conventional emulsion polymerization. where ka is the entry rate coefficient [maqueous phase mol1 s1 ] and ½Rw the concentration of radicals in the aqueous phase [mol m3 aqueous phase ]. therefore most of the radicals are captured by the polymer particles. monomer droplets.4 Kinetics of Emulsion Polymerization Fig. (8).5.

(11). and hence the polymerization rate is higher. where kd is the rate coefficient for radical exit [Eq.262 6 Emulsion Polymerization nisms of free-radical polymerization: propagation. ½Mw the concentration of monomer in the aqueous phase. exit. the desorption rate is proportional to n but the re-entry of newly desorbed small radicals is proportional to n. Equation (10). m the partition coefficient of the small radicals between the polymer particles and the aqueous phase. (13). (9). (12)]. (11)] [25]. chain transfer. Chain-transfer reactions to monomers and chain-transfer agents lead to the formation of small and mobile radicals that can exit the polymer particle. Rate of Exit ¼ kd n ðradicals/particle sÞ ð10Þ   lNp gNA kd ¼ l ðs1 Þ 1 hm lNp þ k p ½Mw þ 2k tw ½Rw ð11Þ The rate of radical exit from particles with n radicals is the product of kdðnÞ and n [Eq. the term n=n takes account of the fact that in particles with n radicals. termination. in order to suffer a bimolecular termination reaction. Obviously. Because radical entry. 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). gives the rate of radical exit from a population of particles with an average number of radicals per particle n. The rate of termination in a particle with n radicals is given by Eq. Rate of Exit ¼ kdðnÞ n ðradicals/particle sÞ 0 1 n lN p A gNA @ n kdðnÞ ¼ l 1 lNp þ k p ½Mw þ 2k tw ½Rw hm ð12Þ ðs1 Þ ð13Þ In Eq. k tw the termination rate constant in the aqueous phase. (13). and kdðnÞ is given by Eq. and ½Rw the concentration of radicals in the aqueous phase. 2kt nðn  1Þ ¼ 2cnðn  1Þ Rate of Termination ¼ vp NA   radicals particle s ð9Þ 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 termination are stochastic events. the particle should contain two or more radicals. as radicals in different particles cannot terminate between them. l is an overall mass-transfer rate coefficient. Equation (14) gives the population balance of particles . particles have a different number of radicals and the number of radicals in a given particle varies stochastically with time. In Eq. and so on. Radical desorption leads to a decrease in the average number of radicals per particle.

Eqs. [27]. (2) small particles (dp < 100 nm).6. n¼ C¼ 2ka ½Rw kd þ ðkd2 þ 4ka ½Rw CcÞ 0:5 2ð2ka ½Rw þ kd Þ 2ka ½Rw þ kd þ c ð16Þ ð17Þ Equations (16) and (17) should be solved together with Eq. A simpler and still accurate equation for n is Eq. (14) and (15) are converted into algebraic equations by making the left-hand sides equal to zero. 3 . 1. n can be easily calculated by means of Eq. 2. (3) a low rate of generation of radicals from the initiator. Because for Smith–Ewart Case 2 n is constant. Under these circumstances. monomers and CTAs) or these small molecules are highly water insoluble. the polymerization rate is directly proportional to the number of polymer particles. (16). and k tw the termination rate in the aqueous phase 3 1 1 s ]. the average number of radicals per particle is n ¼ 0:5. where f is the efficiency factor of the initiator radicals. [I] the concentration of the thermal initiator in the aqueous phase [mol m3 aqueous phase ]. This is known as Smith–Ewart Case 2 and corresponds to systems in which (1) there is no chain transfer to small molecules (that is. has been given in terms of Bessel functions [26]. and (2) the polymer particles are relatively small (typically dp < 200 nm). In systems in which the entry rate per particle is limited and the rate of radical desorption is relatively high (large kd ). [maqueous phase mol dNn ¼ ka ½Rw Nn1 þ kdðnþ1Þ ðn þ 1ÞNnþ1 þ cðn þ 2Þðn þ 1ÞNnþ2 dt  ðka ½Rw Nn þ kdðnÞ nNn þ cnðn  1ÞNn Þ n ¼ 0. it includes the concentration of radicals in the aqueous phase. under pseudo steady-state conditions. and hence the material balance for these radicals is needed from Eq. . but their use is not friendly. The exact solution for n. The solution of this system of algebraic equations includes the three limiting cases of the pioneering work of Smith and Ewart [28]. (15). This is known as Smith–Ewart Case 1 and corresponds to systems with (1) relatively water-soluble monomers or relatively water-soluble CTAs. When the exit rate of radicals is zero (kd ¼ 0) and the termination of the entering radical and that existing in the polymer particle is instantaneous. (17). 263 . Therefore. the pseudo steady-state assumption can be applied to the radicals in the polymer particles and in the aqueous phase.4 Kinetics of Emulsion Polymerization with n radicals. (15). (18). n f 0:5. with C defined in Eq. kI the rate coefficient for initiator decomposition [s1 ]. . and (4) a large number of particles. ð particles/sÞ Np Np d½Rw ¼ 2f kI ½I þ kd n  2k tw ½Rw2  ka ½Rw dt NA Vw NA Vw ð14Þ 3 ðmol/maqueous phase sÞ ð15Þ For most practical cases.

(20). nm is the aggregation number (average number of molecules of surfactant per micelle). and hence the polymerization rate is independent of the number of polymer particles if aqueous-phase termination is negligible. If termination in the aqueous phase is significant. Otherwise. the polymerization rate increases with the number of polymer particles. (22).4. (21). 6. and coagulative nucleation (Figure 6.4. n o 1=Np .1 1 dNp Nm ¼ R nuc ¼ kam ½Rw V dt V Nm ¼ ðSw  CMCVw ÞNA nm ð particles/m 3 sÞ ðmicellesÞ ð20Þ ð21Þ In Eq. homogeneous nucleation. the polymerization rate increases with Np .6). (21).3. n g 0:5 (Smith–Ewart Case 3) and n can be calculated as follows:   ka ½Rw 0:5 n¼ 2c ð19Þ For a given solids content under Smith–Ewart Case 3 kinetics. Therefore. Eq. Heterogeneous Nucleation The rate of formation of polymer particles by heterogeneous nucleation is expressed by Eq. the polymerization rate is independent of the number of polymer particles. CMC is the critical micellar concentration [mol m3 aqueous phase ] and hence CMC  Vw is the amount of surfactant dissolved in the aqueous phase. Sw can be calculated by means of the overall material balance for the surfactant. The rate of particle generation depends on the mechanism considered. 6. kam the rate coefficient for radical entry into the micelles. for a given solids content and if termination in the aqueous phase is negligible. high initiator concentrations or redox initiators. For large particles (dp > 200 nm).3 Number of Polymer Particles Particle nucleation may occur through heterogeneous nucleation.264 6 Emulsion Polymerization n¼ ka ½Rw 2ka ½Rw þ kd ð18Þ Under Smith–Ewart Case 1 conditions. and Sw [mol] is the amount of surfactant that is in the aqueous phase forming micelles and dissolved in such a phase. where R nuc is the nucleation rate. and slow termination rates (gel effect). where ST [mol] is the total . n is inversely proportional to the number of polymer particles. and Nm the number of micelles in the reactor given by Eq.

as [m 2 mol1 ] 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.6. 6. amount of surfactant in the reactor.6. Particle nucleation mechanisms in emulsion polymerization.4 Kinetics of Emulsion Polymerization Fig. (23). Sw ¼ ST  Ap ¼ Ap as 4:83Np0:33 ð22Þ Vpol fpp !0:66 ð23Þ 265 .

(26). where rv [m 3 s1 ] is the volumetric growth rate of one polymer particle. where z approaches unity as the water solubility of the monomer increases. 6.6th power dependence of Np with respect ST . Therefore. In this context.2 R nuc ¼ k p ½Mw ðR jcrit þ Micrit Þ V ð particles/m 3 sÞ ð26Þ R jcrit and Micrit are calculated from the balances of radicals of type R and M in the aqueous phase assuming that pseudo steady-state conditions apply [Eqs.       2f kI ½INA fpp 1z as ST z Np o Vw rv Vw 0:6 a z a 1 ð25Þ Homogeneous Nucleation In homogeneous nucleation. Actually. (24). the critical length of the oligoradicals formed from an inorganic water-soluble initiator such as potassium persulfate (that is. However. the rate of formation of particles by homogeneous nucleation. the solution of Eqs (20)–(23) leads to Eq.       2f kI ½INA fpp 0:4 as ST 0:6 Np o Vw rv Vw ð24Þ The fulfillment of this equation. obtaining Eq. one should be aware of the assumptions used in the derivation of Eq. respectively. is the rate of polymerization of oligoradicals of critical length as expressed by Eq. 30]. The water solubility of the oligoradicals depends on their composition. (27) and (28)]. when radical desorption is taken into account. R nuc . in particular the 0. Smith and Ewart [28] solved Eqs.266 6 Emulsion Polymerization Assuming no termination of radicals in the aqueous phase and that during nucleation n ¼ 0:5. jcritdþ1 d1 a2 R jcrit ¼ a1 Micrit ¼ kd nNp icrit a k p ½Mw 1 2f kI INA k p ½Mw ðradicalsÞ ðradicalsÞ ð27Þ ð28Þ . (24) for the dependence of the number of particles on surfactant and initiator concentrations. (20)–(23). and R jcrit and Micrit are the number of oligoradicals of critical length (with jcrit > icrit ) formed from the initiator and from desorbed radicals. one containing an inorganic fragment) will be longer than that of the oligoradicals formed from desorbed radicals that are much more hydrophobic. is often considered as a proof of the occurrence of micellar nucleation. (25) [29.3.4. particles are formed by precipitation of the growing oligoradicals once they exceed the critical length that makes them insoluble in water. where ½Mw is the concentration of monomer in the aqueous phase.

particle nucleation may be formed by both heterogeneous and homogeneous mechanisms.5 Molecular Weights In these equations. 6. k2 . 32]. a1 is the probability of propagation of radicals able to enter the polymer particles (generated from desorbed radicals. 35]. that they are captured by the existing polymer particles. and from the initiator. the species formed by entry of radicals into micelles and by self-precipitation of radicals are considered nonstable precursor particles. and k4 are adjustable parameters that depend on the type and amount of surfactant] [33].4 Npr2 dNpr Np ¼ kam ½Rw Nm þ k p ½Mw ðR jcrit þ Micrit Þ  k1 Npr  k2 dt V V  k4 Npr R nuc ¼ k3 V ð32Þ ð33Þ 6. Emulsion polymerization is a compartmentalized system in 267 .4. and that the rate of nucleation of mature particles is proportional to a k4 th power of the precursor concentration [Eqs. 6. the overall nucleation rate is given by Eq.3. where k1 . d is the critical length for entry of radicals generated from the initiator. k3 .4. (32) and (33).6. (31). The actual particles are formed by coagulation and polymerization growth. k p ½Mw a1 ¼ k p ½Mw þ 2k tw ½Rw þ ka a2 ¼ Np Nm þ kam NA Vw NA Vw k p ½Mw k p ½Mw þ 2k tw ½Rw ð29Þ ð30Þ Simultaneous Heterogeneous and Homogeneous Nucleation In systems including rather water-soluble monomers and surfactant concentrations high enough for micelles to be present.5 Molecular Weights The molecular weight distribution of the polymer has a profound effect on its final properties [34. These probabilities are given by Eqs.3 R nuc ¼ ½kam ½Rw Nm þ k p ½Mw ðR jcrit þ Micrit Þ   1 ð particles/m 3 sÞ V ð31Þ Coagulative Nucleation In this mechanism. with length smaller than d). In this case.3. A simplified model can be derived by considering that the precursor particles disappear by mutual coagulation. The detailed modeling of coagulative nucleation is rather complex [31. with lengths equal or greater than d) and a2 the probability of propagation of radicals generated from the initiator. (29) and (30).

for monofunctional monomers with a polymerization scheme that does not include chain transfer to polymer.5. (34) allows calculation of the whole molecular weight distribution. Instead. and hence the system may be considered to be formed by particles with no radicals and particles with one radical (zero–one system). (34). 3. Zero–One System (Smith–Ewart Cases 1 and 2) In a zero–one system. where R m is the total number of radicals of length m in particles N1 . . M ½Mp R m þ ka ½Rw R m dt m ¼ 1. and in Case 3 n g 0:5. 2. Mathematical models for the calculation of the molecular weight distribution of linear [36] and nonlinear [37–40] polymers are available. Furthermore. the average number of radicals is large and the kinetics is close to bulk polymerization. in Case 2 n ¼ 0:5. . In Cases 1 and 2.1. branched and crosslinked polymers are obtained when multifunctional monomers are included in the formulation and when chain transfer to polymer is operative. Thus. the number of radicals in a given particle varies with time. nk ¼ y X m¼1 m k Mm ð35Þ . The balance for inactive chains of length m in particles with one radical (N1 ) is given by Eq. . In addition. Therefore. the probability of having particles with more than one radical is almost negligible. the inactive polymer chains are formed in particles containing one radical by chain transfer to monomer and by instantaneous termination upon entry of one radical. On the other hand. However.5. linear polymers are obtained.268 6 Emulsion Polymerization which different particles may have a different number of radicals. the architecture of the polymer formed depends on both the formulation and the kinetics of the process. 6. the MWD depends on the number of radicals per particle. Smith and Ewart [28] distinguished three limiting cases: In Case 1 n f 0:5. ðmacromolecules/sÞ ð34Þ Integration of Eq. 6. this is computationally demanding and often the MWD is represented in terms of the moments of the distribution. the kth-order moment of the distribution being defined by Eq.1 Linear Polymers As discussed above. some simplified equations for the calculation of the molecular weights of linear polymers in the limiting cases of Smith and Ewart [28] will be presented. (35).1 dMm ¼ k tr. but a detailed discussion of this issue is out of the scope of the present chapter. 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. In Case 3.

M ½Mp R m  kd N1 dm¼1 þ k p ½Mp ðRm1  R m Þ dt  k tr. n0 Mw ¼ n2 PM n1 ð39Þ On some occasions. (36). it is interesting to know the average molecular weights produced at a given moment in the process. (34) and (35) yields Eq. (40). M ½Mp þ ka ½Rw Þ mk V ð36Þ The balance for active chains of length m in particles with one radical (N1 ) is obtained from Eq. (39). (38). where Ruk is the generation rate of the kth-order moment of the distribution of inactive chains and mk is the kthorder moment of the distribution of active chains. M ½Mp þ k p ½Mp  kd ÞN1 m 2 ¼ m1 1 þ ka ½Rw þ k tr.6. (37) by applying the pseudo steady-state assumption to the active chains [Eqs.  X dR m  ¼ ka ½Rw N0 þ k tr. Mni ¼ Rv1 PM . (41). (36). (38)]. Rv0 Mwi ¼ Rv2 PM Rv1 Combination of Eqs. These instantaneous average molecular weights can be calculated by means of Eqs. Mn ¼ n1 PM .5 Molecular Weights Combination of Eqs. where PM is the average molecular weight of the repeating unit in the polymer chain. ð40Þ 269 . Ruk ¼ ðk tr. (37). M ½Mp The cumulative number-(Mn ) and weight-(M w ) average molecular weights can be calculated from the moments of the MWD by means of Eqs. m0 ¼ m1 ¼ X R m ¼ N1 ¼ nNp ka ½Rw N0 þ ðk tr. and (40) yields Eqs. M ½Mp ! 2k p ½Mp ð38Þ ka ½Rw þ k tr. M ½Mp R m  ka ½Rw R m ¼ 0 ð37Þ The first moments of the distribution of active polymer chains can be calculated from Eq.

M ½Mp þ k p ½Mp  kd Þ m1 PM ¼ PM m0 ka ½Rw þ k tr. (19) and the molecular weight is mainly controlled by chain transfer and bimolecular termination. (43) and hence Eq. M ½Mp PM ð41Þ 2k p ½Mp m2 PM ¼ 1 þ PM A 2M ni m1 ka ½Rw þ k tr.2 . (44). ka ½Rw g k tr. k tr. This is a specific feature of emulsion polymerization that cannot be achieved in any homogeneous (bulk or solution) free-radical polymerization. and hence it is possible to increase both Rp and the molecular weights at the same time by conveniently adjusting the formulation to increase the number of polymer particles. For the Smith–Ewart Case 1. M ½Mp For the Smith–Ewart Case 2. increases with the number of polymer particles. the concentration of radicals in the polymer particles is given by Eq. from Eq. M ð45Þ Therefore the molecular weights are controlled by chain-transfer reactions and are independent of Np . The rate of generation of polymer of length m in particles with i radicals is given by Eq. M ½Mp and then Eq. as well as the polymerization rate. M ½Mp g ka ½Rw and then Eq.5. (46). 6. In this case.270 6 Emulsion Polymerization M ni ¼ A M wi ¼ ka ½Rw N0 þ ðk tr. Pseudo Bulk System (Smith–Ewart Case 3) For Smith–Ewart Case 3. M ni A kp PM k tr. (45) applies. (15) we obtain Eq. M ni A k p ½Mp ka ½Rw PM ð42Þ If radical termination in the aqueous phase is negligible. M ½Mp k p ½Mp ka ½Rw þ k tr. ka ½Rw ¼ 2f kI ½I M ni A NA Vw Np k p ½Mp Np PM 2f kI ½INA Vw ð43Þ ð44Þ Consequently the molecular weight. the number of radicals per particle is large and the kinetics approaches bulk polymerization. (42) holds.1.

5 Molecular Weights n1 X dMmi cc i ¼ k tr. 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. M ½Mp Np Np ð49Þ The instantaneous number and weight-average molecular weights are then given by Eqs. M ½Mp 0 Np V V Rn1 ¼ ð2cd þ 2cc Þ m 0 m1 m þ k tr. Rn0 ¼ ð2cd þ cc Þ m02 m þ k tr. M ½Mp 1 Np V V Rn2 ¼ ð2cd þ 2cc Þ m0m2 m2 m þ 2cc 1 þ k tr. M ½Mp m 0 k p ½Mp m 0 A m0 m ð2cd þ 2cc Þ þ k tr. M ½Mp Np m m m2 ð2cd þ 2cc Þ 0 2 þ 2cc 1 þ k tr. M ½Mp m1 Np ð50Þ 271 . M ½Mp ð2cd þ 2cc Þ 0 þ k tr. M ½Mp m 0 2k p ½Mp m1 A m0 m ð2cd þ 2cc Þ þ k tr. M ½Mp R m  2 Rm Np !1=2 X ka ½Rw Np2 R m ¼ nNp ¼ m0 ¼ 2cd þ 2cc ð47Þ ð48Þ m1 ¼ ka ½Rw Np þ k p ½Mp m 0 þ k tr. M ½Mp ð2cd þ 2cc Þ 0 þ k tr. M ½Mp Rmi þ 2cd ði  1ÞRmi þ ði  1Þ Rki Rmk dt iNi k¼1 ðmacromolecules/sÞ ð46Þ From Eq. Mni ¼ Mwi k p ½Mp PM m ð2cd þ cc Þ 0 þ k tr. (50). M ½Mp m 2 Np Np ¼ PM m 0 m1 ð2cd þ 2cc Þ þ k tr.6. M ½Mp R m dm¼1 þ kp ½Mp ðRm1  R m Þ dt X ðcc þ cd Þ Rm ¼ 0  k tr. M ½Mp Np Np m2 ¼ ka ½Rw Np þ k p ½Mp ð2m1 þ m 0 Þ þ k tr. (47). (48) and (49)]. M ½Mp 2 Np V Np V V X  dR m  ¼ ka ½Rw Np þ k tr. (46) the moments of the inactive chains can be calculated according to Eqs.

Crosslinking. large polymer networks (gel) are formed in some cases. and 3 M wi ¼ M ni 2 if bimolecular termination is only by combination: Because for a given polymer content cc and cd are proportional to Np . and it is even more complex in emul- . further polymerizing and modifying their structure. if chain-transfer reactions are predominant over bimolecular termination. M . and Gel Formation In contrast to linear polymers.272 6 Emulsion Polymerization If bimolecular termination is predominant. then the instantaneous average molecular weights reduce to Eqs. the molecular weight of the nonlinear polymers evolves throughout the whole process because they may become active and inactive several times during that process. and polydispersity is equal to 2. which. M ni ¼ k p ½Mp Np ð2cd þ cc Þm 0 PM  M wi     m cc m1 2cd þ cc cc 1þ ¼ 2þ PM A Mni PM m1 ðcd þ cc Þm 0 cd þ cc 2ðcd þ cc Þ ð51Þ Therefore: M wi ¼ 2Mni if bimolecular termination is only by disproportionation. 42]. the molecular weights are also independent of Np and depend only on the ratio k p =k tr. (51). 6. other properties such as the level of branching and crosslinking density are required to fully characterize the polymer. and besides the MWD of the polymer.5. The accurate calculation of the structure of these nonlinear polymers is not an easy task in homogeneous systems [41. In addition.2 Nonlinear Polymers: Branching. On the other hand. the molecular weights are independent of the number of particles. (52). Thus. the instantaneous molecular weights are given by Eqs. once they are formed. The microstructure of these nonlinear polymers is more complex than that of linear polymers. preserve their structure (molecular size) during the rest of the process. M ð52Þ M wi ¼ 2Mni For this case. inactive nonlinear chains formed earlier in the process may become active through either a chain-transfer reaction to polymer or a propagation to pendent double bonds. M ni ¼ kp PM k tr.

Hard core–soft shell particles are particularly useful for paints because they have a low minimum film formation temperature and are not sticky at higher temperatures. namely an H-shaped structure.6. PDBs may also be present if multifunctional monomers are used in the formulation. and b-scission at relatively high temperatures. produces short-chain branches (SCBs). combine the properties 273 . such as epoxy–acrylic polymer particles. particles formed by an elastic core and a hard shell are used as impact modifiers for polymer matrices. Nevertheless. polymer chains of increasing density of branching and crosslinking are formed and their molecular weight will rapidly increase. the predominant reaction linking polymer chains and leading to polymeric networks is the propagation to pendent double bonds of the multifunctional monomers. gel is formed if the following conditions are fulfilled: (1) a mechanism leading to LCBs is operative. The discussion of these approaches is outside the scope of this chapter. Terminal double bonds may be formed by chain transfer to monomer. or  polymerization of formulations including multifunctional monomers (often called crosslinkers). if multifunctional monomers are homopolymerized or copolymerized with vinylic monomers. so-called backbiting. gel is also formed. A crosslink point is a tetrafunctional unit that links two polymer chains. for example termination by combination or propagation to pendent double bonds.  In the free-radical polymerization of vinylic monomers. for example chain transfer to polymer. Hollow particles are efficient opacifiers. and hybrid polymer– polymer particles. Intermolecular chain transfer to polymer and propagation to PDBs produces long-chain branches (LCBs). Thus. and intramolecular chain transfer to polymer. and (2) a mechanism that links polymer chains is also operative.6 Particle Morphology Latexes made out of composite polymer particles. The mechanisms leading to tetrafunctional units are: intermolecular chain transfer to polymer followed by bimolecular termination by combination of branched radicals. leading to the formation of gel polymer.6 Particle Morphology sion polymerization. that is. 43–46]. termination by disproportionation. particles containing different phases. Chain transfer to polymer occurs through hydrogen abstraction either from the backbone or from a side group. some solutions have been reported [37–40. present definitive advantages in many applications. Obviously. or  propagation of a growing branched radical on a terminal or pendent double bond. 6. Branches are formed by chain transfer to polymer (either intermolecular or intramolecular) or by propagation to pendent double bonds (PDBs). because of the compartmentalized nature of the system. Under these circumstances. In this case.

As the concentration of the newly formed polymer chains increases. During this migration. and repulsive. Then. If the entering radicals are anchored to the surface of the polymer particle.274 6 Emulsion Polymerization Fig. the clusters migrate toward the equilibrium morphology.7. leading to the formation of clusters. bringing the clusters toward the center of the polymer particle. bringing the clusters toward the surface of the particle. The properties of these materials largely depend on the particle morphology. The motion of the clusters is ruled by the balance between the van der Waals attraction/repulsion forces and the resistance to flow that arises from the viscous drag. phase separation occurs. the new monomer is fed into the reactor and the conditions are adjusted so that polymerization occurs inside the existing polymer particles. The resulting system is not thermodynamically stable because of the high surface energy associated with the large polymer–polymer interfacial area. and (3) coagulation with other clusters. In order to minimize the free energy. the van der Waals forces between clusters and the aqueous phase may be either attractive. (2) diffusion of polymer into or from the cluster. On the other hand. The van der Waals forces between clusters are always attractive. The reactor is initially charged with previously formed latex (seed). Figure 6. Development of particle morphology. and therefore both the size and the number of clusters increase. the new polymer chains will be mainly located in the outer layer of the particle. The position at which each polymer chain is formed depends on the radical concentration profile inside the polymer particles.7 illustrates the processes occurring during formation of the particle morphology during seeded semicontinuous emulsion polymerization. 6. It is worth mentioning that the van der Waals forces are pro- . Polymerization occurs in the clusters as well as in the polymer matrix. the size of the clusters may vary because of (1) polymerization in the cluster. of the constituent polymers in a synergetic way.

termination mainly by bimolecular combination limits the chain lifetime to a small fraction of the entire process time. and to the mild reaction conditions required to run the polymerization.7 Living Polymerization in Emulsion portional to the interfacial tensions. Moreover. composition. thus increasing the product heterogeneity. the corresponding processes do not involve a large demand for organic solvents. On the other hand.1) is still an issue. With reference to the macromolecule structure (that is. degree of crosslinking.7 Living Polymerization in Emulsion Free-radical polymerization (FRP) is a widespread technique for preparing longchain polymers (see Chapter 4). as 275 . chain architecture.7. Its success is mainly due to the broad range of monomers that can be readily polymerized by this technique. average molecular weight. In fact. which grow uniformly during the whole reaction.1 Chemistry of LRP In conventional FRP. monomer sequences. Equilibrium morphologies may be attained if the internal viscosity of the particle is low. Moreover. changes in the operating conditions (such as monomer concentration and composition. as discussed in the preceding sections in this chapter. a novel process has recently been proposed with much greater potential in terms of control capacity: living radical polymerization (LRP). and if the polymers are very incompatible (high interfacial tensions resulting in high van der Waals forces). emulsion polymerization (and in general every polymerization reaction carried out using water as the continuous medium) has alleviated all the residual inconveniences of FRP. Metastable morphologies can be achieved by working under starved conditions (high internal viscosity of the particles) and promoting grafting reactions (low interfacial tensions). these changes are equally distributed among all the polymer chains. temperature. it depends on the polymer–polymer and polymer–water interfacial tensions [47]. The final morphology heavily depends on the kinetics of cluster migration [47–49]. viscosity. 6. By this specific process it becomes possible to obtain block copolymers by FRP.6. and chain-end functionalization). instead. careful control of the polymer microstructure (in the broad sense defined in Section 6. The equilibrium morphology is the one that minimizes the interfacial energy of the system. they easily achieve large monomer conversions. In a living polymerization. Therefore. and so on) affect the structure of the polymer chains produced at different stages of the process. 6. and they exhibit reduced problems of heat removal. polydispersity. filling the gap between the free-radical polymerization technique and other polymerization techniques such as living anionic or cationic polymerization. to its tolerance toward functional monomers. thus making the process intrinsically safer.

At the same time. indicated as RX. Finally. the initiation step is very fast compared to the process time and. FRP does not suffer the same limitations. On the other hand. 51]. Living polymerization is typically started by introducing into the system an ‘‘initiator’’ providing the capping species. living polymerization represents a route to the production of block copolymers by successive additions of monomers. However. generically indicated as X. The av- . However. each chain experiences a sequence of activation–deactivation steps and the instantaneous DP grown during the generic active step is given by the ratio between the rates of propagation and reversible termination (k p ½M=kt ½X. this control is instead restored by introducing an additional but reversible termination reaction with a ‘‘capping’’ species. The degree of polymerization. since the instantaneous DP is given by the ratio between the frequencies of propagation and termination (compare Chapter 4). very low temperatures. and over a wide temperature range [52. 53]. it does not work with several widely used monomers. If the rate of this new termination is so large as to be dominant with respect to that of the irreversible termination reactions and comparable with that of propagation. it is easily operated in the presence of impurities. Therefore. the polymer retains the ionic end groups till the end of the polymerization and the reaction is simply restarted by further addition of monomer. such as styrene. In other words. which generally suffer little or no termination. this kind of polymerization is often impractical from the industrial viewpoint. it is quite natural to attempt to establish living conditions in such a process. this would lead to the production of polymer chains with extremely high molecular weight. it is not practical to approach such conditions by simply reducing the radical concentration so as to minimize the rate of bimolecular termination (a second-order reaction with respect to radical concentration. polymer growth will be distributed all over the process. the propagation being a first order reaction). an approach clearly not possible in FRP. nearly all vinyl and vinylidene monomers. Besides the drawback of the corresponding reduction of the polymerization rate. It can be applied to a broad range of monomers. as previously pointed out. where ðMÞn indicates a polymer chain made of n monomer units. all the chains start growing almost simultaneously. thus. Using LRP. since the main requirements are high purity of all the reactants. DP. Moreover.276 6 Emulsion Polymerization the living chains are still able to restart propagating when the monomer is completely depleted. In this case. So far. such as residual inhibitor residues and traces of oxygen. increases linearly with monomer conversion and is inversely proportional to the initiator concentration. This initiator reactivates itself many times and adds some monomer units before going back to the so-called dormant state in the form R–ðMÞn –X. where kt indicates the rate constant of the reversible termination). In these processes. hence. Poisson-like distributions of the polymer chain length are obtained with final polydispersity values close to the ideal value of (1 þ 1/DP). and the use of solvents. which are always acting as polymer chain ends and. the only living processes industrially available are anionic and cationic polymerization [50. the living process can be regarded as the insertion of a well-defined number of monomer units between the groups R and X. defined a priori.

Among these. Despite these efforts. many different routes are known which use different persistent radicals [54–58].7.2 277 . The catalytic cycle is closed by back-transfer from the transition metal to the final adduct of the halogen. if the number of monomer units added per active period is small enough).1 kde Rn þ X S RnX kac ðaÞ Today. and in general LRP.6. if the number of active periods each chain experiences is large enough (that is. If the fraction of terminated chains remains negligible compared to the initial amount of initiator. and requires high operating temperatures (about 120–140 C). X (the nitroxide radical group). R n .1. leading to low polydispersity of the chain length distributions. This mechanism is based on the so-called atom-transfer radical addition reaction. to form dormant polymer chains.7. and the total number of polymer chains. It is clear that. M0 XT (where XT is the monomer conversion and M0 the initial amount of monomer). 61].1. Note that some irreversibly terminated chains are produced anyhow. More recent studies were aimed to reduce the operating temperature and to broaden the monomer applicability so as to enlarge the spectrum of block copolymers accessible by this technique [58]. accompanied by oxidation of the metal atom. this last value corresponds also to the concentration of the dormant chains in the system and the DP grows linearly with conversion (DP ¼ M0 XT =RX). But it is only in the 1990s with the work of Georges and co-workers [56. received the attention they deserved. if the radical produced can undergo a few propagation steps 6.7 Living Polymerization in Emulsion erage DP of the polymer is given by the ratio between the converted monomer. This living mechanism [Eq. TEMPO is by far the most widely used. Atom-transfer Radical Polymerization (ATRP) Atom-transfer radical polymerization (ATRP) was first reported by Kato et al. (a)] consists of the reversible combination of the growing radical chains. since these reactions are always taking place in competition with the activation/deactivation reactions. 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. [59] and by Wang et al. Moreover. RX. Different living mechanisms are available and the main ones are briefly enumerated in the following sections. and the so-called ‘‘persistent radical species’’. in 1995 [60. 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]. the polymer growth is distributed throughout the duration of the process and all the chains grow uniformly. the range of application remains quite limited. 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]. 57] that this novel polymerization technique. even though it suffers very limited applicability to monomers unlike styrene. R n X: 6.

the reaction can be summarized by Eq. which made this technique readily available for the production of several new block copolymers [62]. and the deep color typically imparted by this complex to the final polymer (if not removed) represent the major drawbacks of this process. the need for complex ligands to solubilize it. (meth)acrylamides. Ru-. MeðnÞ the metal with the corresponding oxidation state and Li the ligand. the exchange directly affects the radical concentration. the presence in the system of a metal. Pd-. (b). since the living reaction of Eq. (c). 6. The resulting reversible reaction is represented by Eq. where R n I indicates the generic dormant species with iodine.7. 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. kde R n þ X –Meðnþ1Þ =Li S R n X þ MeðnÞ =Li kac ðbÞ ATRP owes most of its success to its high compatibility with many different monomers.1. Even though the majority of the work has been done with copper as the transition metal. the initial concentration of the species carrying the iodine group (in the following simply called the ‘‘transfer agent’’) determines the final DP of the polymer. and Co-based systems [62]. (c) is not affecting the radical concentration. Actually. acrylates. Therefore. such as styrene. provided that the initiator concentration is small compared to that of the transfer agent. the main difference 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 final concentration of the chains terminated by bimolecular combination will be half of the initial concentration of initiator. In LRP by DT.3 kex Rn þ Rm I ! Rm þ RnI ðcÞ Therefore. Therefore. chlorine and bromine have been used successfully as the halogen atoms. As a matter of fact. and if this product is still able to undergo another transfer cycle. Ni-. and acrylonitrile. instead. Degenerative Transfer (DT) As mentioned above. but can also modify the reactivity of the metal toward both the activation and deactivation reactions. The initial amount of this species has to be properly selected. When an iodine atom is used as end group. this reaction can be used to produce the same exchange between active and dormant states as is found in NMP. Different ligands have been used to solubilize the copper atom and it has been noticed that they not only prepare the copper for the reaction. whereas iodine gives rise to side reactions [63]. Thus far. where X indicates the halogen atom. styrene ATRP has been carried out using Fe-. in both NMP and ATRP the exchange between the active and the dormant state is based on a reversible (although different) termination mechanism. this exchange is carried out by direct transfer of the o-end group between an active and a dormant chain. methacrylates.278 6 Emulsion Polymerization before participating in the back-transfer. .

6. and thus no control is actually achieved. the structure of which can be described as R–Y –CðZÞ ¼ Y. ðZÞYR n ! R m þ R n YCðZÞY R n þ R m YCðZÞY ! ðdÞ ðÞ kfrag Note that the best results have been reported when using a sulfur atom as the Y group [67–70]. not only because this is going to be one polymer chain end (the other end being occupied by the RAFT group).7 Living Polymerization in Emulsion Only a few papers have appeared in the literature dealing with LRP by DT [64– 66]. with polydispersity values as low as 1. forming the initial radical again. From Eq. it is in fact clear that in the first addition reaction an intermediate species is formed. and the applications are almost completely limited to the homopolymerization of styrene. the reaction can either go back.7. (d). and for the complete lack of control reported for other monomers [64–66]. or proceed forward with the transfer of the Y ¼ CðZÞ–Y moiety from the dormant to the active chain. care must be given to the correct choice of which monomer has to be polymerized first. In this case. Accordingly. the probability that the following fragmentation reaction proceeds backward or forward – depends mainly upon thermodynamic considerations.4. but mainly because it influences the initial reactivity of the RAFT agent. Better performances are difficult to obtain with styrene. The fate of such a species – that is.4 kadd ðþÞ kfrag  R m YC . which is now identified as the transfer species. mainly because of the limited transfer activity of the iodine atoms. it was possible to obtain good control of the final CLD. if the leaving group generates a radical that is too unstable compared to the polymer radical. Similar considerations apply in block polymerization of two monomers. (d). n-butyl acrylate). 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. indicating the good control of polymer growth). namely upon which.3–1. is of paramount importance. is the more stable. The process is started by introducing into the system a so-called RAFT agent. having the R group on one side and the polymer radical on the other.6. In other words. or leaving group. Moreover. the operating temperatures used to carry out this polymerization are usually close to those typical of conventional radical polymerization 279 . the process is also very effective for many other monomers. 68]. Even though the most satisfactory results have been obtained by RAFT polymerization of styrene (Figure 6. where the first block can be regarded as a special case of the R group. As shown in Eq. such as acrylates and methacrylates [67–70]. The correct choice of the R group. At this stage.1.8 shows an example of the application of RAFT to bulk styrene polymerization. the RAFT is always going to proceed backward. the polymer radical or the leaving-group radical. This is the main reason for the very poor results obtained when applying this process to the polymerization of acrylates (for example. Reversible Addition–Fragmentation Transfer (RAFT) Polymerization The RAFT process can be regarded as a special case of degenerative transfer.

Pd ¼ 1 when all chains are of the same length). right: evolution of molecular weight distribution as measured by GPC [71]. Once more. To minimize terminations. The homogeneity of chain lengths is the key factor in homopolymerization and it is usually expressed in terms of polydispersity ratio.280 6 Emulsion Polymerization Example of application of RAFT to bulk polymerization of styrene.7. [67–70]. in competition with ATRP. along with the wide range of compatible monomers. are both very fast and controlled .2 Polymerization of LRP in Homogeneous Systems As already pointed out. the final 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 low temperature. makes this mechanism one of the most promising techniques to be applied on an industrial scale for the production of new materials.8. from the product. It has been exhaustively demonstrated that. Fig. in spite of the fact that these bimolecular reactions. which confer to the final polymer a deep color ranging from yellow to red. as briefly reviewed below. For clarity. 6. The fraction of dead chains becomes even more important when the process is intended to produce block copolymers. a significant drawback is the need to remove the sulfur atoms. deactivation and termination. Pd (defined as the ratio between weight and number-average molecular weight. As previously pointed out. different strategies are effective for the different living mechanisms. let us start by discussing the application of NMP to a bulk system. 6. in which case terminated homopolymer chains represent a significant drawback with respect to the product quality. 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 termination. Left: degree of polymerization (DP) and polydispersity versus conversion.

and therefore the activation process can be approximated as a monomolecular process as in NMP. because of the nature of NMP. It can be easily verified that the concentration of the metal in the reduced form. that is. deactivation soon becomes the favored reaction path anyway. termination and deactivation. the same arguments presented above for NMP can be used. it is fundamental to keep the radical concentration as low as possible to ensure a final fraction of dead chains which is negligible with respect to the dormant polymer. where new radical chains can be created from dormant ones by activation. this mechanism does not require a radical initiator. (53) to evaluate the concentration of radicals for an NMP [72]. termination subtracts polymer chains from the activation/deactivation equilibrium and. In a bulk or solution polymerization. the two bimolecular termination reactions. an initiator is necessary to sustain the reaction and the concentration of radical chains is set by the equilibrium between initiation and bimolecular termination. start to operate. when the reaction starts. the persistent radical effect is totally absent and the kinetics of DT and RAFT is identical to that of a conventional nonliving system. thus shortening the active lifetime of the active radicals and their concentration. Albeit the living action in ATRP takes place by a different reaction mechanism. Accordingly. R ¼ ðRi =kt Þ 1=2 ð54Þ No matter which is the living mechanism under consideration. MeðnÞ [compare the corresponding reaction scheme. But. Fischer et al. Eq. (b)]. remains roughly constant during the whole process. let us first point out that. where ðRXÞ0 is the initial concentration of dormant chains. This is often referred to as the ‘‘persistent radical effect’’ [72. To explain this behavior. Accordingly. Thus. dormant chains start to activate. (54). trapping radicals (nitroxides) are accumulated. Given the nature of the living mechanism of these two systems.  R¼ kac ðRXÞ0 3kde kt t 1=3 ð53Þ This equation confirms that the radical concentration steadily decreases in time. building up a radical concentration. On the other hand. the well known formula in Eq. derived Eq. based on a transfer reaction.7 Living Polymerization in Emulsion by diffusion. degenerative transfer and RAFT are characterized by completely different kinetics when the polymerization is performed in a homogeneous system. At the same time. but also decreasing the final amount of irreversibly terminated chains. according to simple stoichiometric arguments. while deactivation simply produces a dormant chain again. where Ri represents the rate of radical generation.6. the final concentration of dead chains is a function of the radical concentration only: high polymerization rates correspond to high dead 281 . 73]. radical concentration is not affected by the living system. The ultimate effect of this accumulation of trapping radicals is that deactivation becomes faster and faster. holds in this case also.

When a radical is formed and. It can be shown [72] that the time needed to obtain 90% conversion after proper tuning of the process parameters so as to obtain a defined fraction of dead chains.5 (Smith–Ewart Case 2). absorbs or enters a particle without radicals. It is again important to notice that in emulsion polymerization the rate of formation of dead chains by irreversible termination is regulated by the frequency of entry only. the particle goes back to a state without radicals until another entry takes place. t 90. while the transfer reaction rate independently controls the homogeneity of polymer growth. 6. Therefore. the fraction of dead chains in the system can be adjusted by tuning the frequency of entry properly.5) and. and thus the final quality of the polymer. while the polymerization rate is not affected.3) [72. the two radicals react with each other almost instantaneously to produce a dead chain. This particular kinetic condition is often referred to as a zero–one system (compare Section 6. 73].2–0.282 6 Emulsion Polymerization chain concentrations. this same radical goes on propagating until the particle experiences a second entry. While increased reaction temperatures and thus propagation rates generally should promote smaller dead chain contents [compare Eq (55)]. given the very small size of the particle and the diffusion-limited nature of the termination reaction. RAFT/DT: C ¼ 1). (55). under the assumption of negligible radical desorption. At this point.7.3 Kinetics of LRP in Heterogeneous Systems A possible way out of this problem comes from the application of LRP to segregated systems. while keeping under control the ratio between dormant and dead chains. in the case of styrenic copolymers this leads to limited improvements only. Kinetic behavior similar to that of a zero–one system is readily established with DT and RAFT as living mechanisms [74]. after a few propagation steps. the same kinetics as in a nonliving process is again operative. Let us focus on a system characterized by the presence of very small polymer particles and a water-soluble initiator. namely emulsion polymerization. where the factor C is different for the different living mechanisms (NMP/ATRP: C ¼ 4=3. since undesired side reactions negatively affecting the polymer quality (such as chain transfer and thermal initiation) become more and more important. Even if it can be shown that low polydispersity values can be achieved also at higher f values (> 0. Accordingly. f ¼ C kt ðln 10Þ 2 fkp2 ðRXÞ0 ð55Þ Using typical parameter values for styrene homopolymerization at 80 C. is given by Eq. . Thus. in principle it is possible to maintain the same high polymerization rates typical of emulsion systems. f. Since a transfer reaction is taking place in both cases. the corresponding average number of active chains per particle is equal to 0. these values cannot be accepted in copolymerization. reaction times of the order of magnitude of 100 h are needed to have f ¼ 0:05.

it is not possible to have one radical per particle for a significant time period. Note that the average time particles spend with zero and one radical is 1=fa and 1=fd . fc . In other words. is therefore as sketched in Figure 6. activation. i ¼ number of radicals per particle.6.5. Accordingly. the principle behind radical segregation cannot hold when NMP is active. Note that the living reactions are not involved at all. Referring once more to NMP for simplicity. the radicals recombine almost immediately. this average number of radicals can be readily estimated as fa =fd . the frequencies of activation and deactivation being fa ¼ kac ½RXp and fd ¼ kde ½Xp . 75]. i. and the average number of radicals per particle has a value much smaller than 0. thus canceling the advantages of operating in emulsion from a kinetic point of view [75]. respectively. Actually.9. the two transient radicals may terminate with each other and accumulate two persistent radicals in the particle. much smaller than 0.5. bimolecular termination. In other words. a second activation is more likely to take place instead of a deactivation. Expected kinetics for LRP in emulsion: (a) RAFT/DT.9(a). and deactivation. since two radicals are generated each time an activation reaction occurs in the particle. respectively. Accordingly.7 Living Polymerization in Emulsion Fig. each particle accumulates persistent radicals till the rate of the second activation becomes small enough (that is. is readily verified. it has been shown that the process kinetics approaches that of the corresponding bulk process. fde ¼ frequencies of radical entry. This reduction of the polymerization rate cannot be counteracted by increasing the rate of the activation reaction: when fa approaches fd . that typical of DT and RAFT in emulsion. thus increasing the frequency of deactivation. the probability of this event being equal to fa =ð fa þ fd Þ. Comparable propagation rates are not found when using NMP or ATRP [74. 283 . the average number of active chains per particle remains close to 0. 6.5. The corresponding time evolution of the number of active chains per particle. when fa f fd . fac . 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. r. An average value of active chains per particle. The corresponding sketch of the time evolution of the number of active chains per particle is shown in Figure 6.9(b). when fa f fd ). Note that. (b) NMP/ATRP.

can with difficulty be applied to ab-initio emulsion polymerization. even in this case. and thus polymerization in monomer droplets proceeds as in particles [78]. while nitroxides that are too hydrophilic lead to long induction periods. where it is possible to exploit the segregation typical of these systems. where the reaction actually takes place. Despite the initial rather unsuccessful efforts to conduct an NMP in emulsion. since the multiphase environment greatly complicates the global kinetics of the process. Unfortunately ATRP.7. this process turns out to be much more complicated than others (for example. albeit less versatile. the RAFT mechanism is better suited to emulsion polymerization. in systems like NMP and ATRP. and (2) the possible occurrence of some polymerization in the monomer droplets that 6. switching to nonionic ones did not bring substantial improvements. However. this process proved to give good results [76].284 6 Emulsion Polymerization 6. 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. Great care must be put into the choice of the nitroxide: the use of nitroxides that are too hydrophobic leads to uncontrolled reactions.7. However. performing a LRP by ab-initio emulsion polymerization is still the objective of major research efforts by many groups. miniemulsion) when applied to LRP. On the contrary.4. which is generally very hydrophobic. mainly because this process is generally simpler and more commercially established. Although this always happens to a small extent also in non-LRP.3. It has also been observed that polymerization in the monomer droplets plays a fundamental role. where it is initially stored.1 . than other emulsion processes. Micron-sized particles were often observed. which is more versatile than NMP. As shown earlier. The reasons for such behavior are always the same: (1) poor transport of very hydrophobic species from monomer droplets to particles. Earlier attempts failed just because anionic surfactants reacted with the metal [80].7. and (2) RX must be uniformly distributed among all the particles. Nonetheless. where submicron particles were obtained. becomes even more complicated [79]. with the exception of n-butyl methacrylate (BMA). inside the polymeric reaction locus demands fast material transport of this species out of the monomer droplets. mainly due to stability problems. segregation is not effective at enhancing the radical concentration in the polymer particles. which involves one more species (the metal–ligand complex). although rather susceptible to coagulation [81]. due to the large difference in radical concentrations (and therefore reaction rates) between monomer droplets and polymer particles. The need to have the RX species. across the water phase to the polymer particles. mainly due to the significant duration of LRP in water [77]. its application to ab-initio emulsion polymerization did not enjoy much success. the impact of this process is very limited.4 Application of LRP in Heterogeneous Systems Ab-initio Emulsion Polymerization Besides the kinetic considerations illustrated in Section 6. mainly because its chemistry.

a very effective way to operate an LRP in segregated systems is indeed miniemulsion. ATRP is also very effective when applied to miniemulsion systems.7. studies involving polymerization of acrylates have also appeared [87]. a fast buildup of nitroxides is often observed in this case. 85]. More subtle is the evidence of instabilities in the miniemulsion due to the kinetics of LRP. to destabilization [86]. care is needed in the choice of surfactant (nonionic) and ligand (not too water-soluble). which depresses the polymerization rate. further difficulties have been reported. Due to the improvements in nitroxide efficiency.4. such as incomplete droplet nucleation and colloidal stability problems [74. since they mainly move the polymerization into the water phase. 82. small monomer droplets are the primary locus of reaction and all the difficulties from interphase transfer vanish. Miniemulsion Polymerization Among different alternatives. since monomer and all the other hydrophobic species required to run an LRP are already in the main reaction locus. all show good control of the MWD and the aforementioned problem of slow polymerization rates [76]. but their surface activity is high enough to keep them away from the aqueous-phase chemistry. starting from the metal in the oxidized form. The poor results in terms of polydispersity are even worse because these RAFT agents remain anchored to the surface. which proved to give good control of polymer growth together with high polymerization rates. 6. Among them is the evidence of long induction times. where long chains are created from the beginning. eventually. since the original metal complex (such as Cu(I)) is rather sensitive to oxidation during miniemulsion formation by sonication [88]. A possible solution is represented by the removal of the excess of nitroxides. As for NMLP.6. some problems remain unsolved. even though they suffer from low activity in controlling the polymer growth.7 Living Polymerization in Emulsion makes these species even more insoluble [82]. although this can turn out to be an effective way to produce core–shell particles. Also. literature abounds with examples of styrene miniemulsion polymerizations by NMP. Finally.10 shows a typical result of a block copolymerization of MMA and styrene. Despite these difficulties. more water-soluble RAFT agents failed to solve the problem. that is. Still. A simple solution to this problem could come from the use of surface-active RAFT agents. However. This might lead to superswelling states of the droplets and. it proved effective to run a so-called ‘‘reverse ATRP’’. This has been shown to be easily solved by using oligomeric RAFT agents [74]. However. in LRP all the polymer chains are short initially. which has also given good results in styrene polymerization [87]. In contrast to conventional systems. Figure 6.2 285 . A notable exception is again the polymerization of BMA [83]. The best example of such a species is represented by xanthates [84]. Still. In this case. These are sufficiently water-soluble to diffuse fast across water. generally attributed to high desorption rates as a consequence of the initial exchange reaction to very short species. RAFT also has been successfully applied to miniemulsion polymerization with several monomers [82].

These drawbacks are: 6. semibatch. The batch operation can be used for small-scale production of homopolymers from monomers with a relatively low heat of polymerization. the operation mode. This reactor may operate in batch. Stirred-tank Reactors The stirred-tank reactor is the reactor most commonly used in emulsion polymerization.  Batch-to-batch variations due to irreproducible particle nucleation may jeopardize product consistency. considering the load.286 6 Emulsion Polymerization Fig. Productivity is low. or continuous mode. The use of seeded polymerization mitigates the problem.  . 6.  Because all of the monomer is initially charged into the reactor. unload. A batch reactor is a closed system in which time is the only independent variable. 6. and the control strategy play a key role in achieving an efficient.8.10. and cleaning times.1. the heat generation rate is high and the control of the reactor temperature is very difficult. the drawbacks associated with this type of operation limit its industrial use.8 Emulsion Polymerization Reactors Emulsion polymers are ‘‘products-by-process’’ whose microstructure and properties are determined during the polymerization. safe. and consistent production of high-quality emulsion polymers. Left: conversion profile. may be employed. the reactor type. Therefore.1 Reactor Types and Processes In principle. and combinations thereof. both stirred-tank reactors and tubular reactors. However.1  Control of the polymer properties is impracticable. right: evolution of molecular weight distribution as measured by GPC. 6. Example of application of RAFT to miniemulsion polymerization for the formation of poly(methyl methacrylate)b-polystyrene [74].8.

copolymer composition and molecular weight can be controlled by intermediate feeds of monomer or chain-transfer agents. CSTRs are liable to suffer intermittent nucleations [89. The same behavior describes the age of the particles in the reactor and hence the particle size distribution (PSD) at the exit. 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. The 6. The main characteristic of a continuous stirred tank reactor (CSTR) is the broad residence time distribution (RTD). in which polymer particles are formed in a smooth way [91]. Therefore. even though it is different from that of the feed. where reaction time is equivalent to the space time (t) in the tube. CSTRs in series are used for hightonnage productions such as styrene–butadiene rubber (SBR). which in turn leads to a narrower PSD. reactor plugging. particle morphology. the copolymer composition is quite constant.1. In addition.8. which is characterized by a decreasing exponential function.6. The broad RTD together with the problem of heat removal in large stirred tanks make it difficult to achieve high conversions in a single tank. which allows any polymer property to be tailored.2 287 . but are not well adapted to the production of specialties because of the difficulties associated with grade transitions. The main drawback of this operation mode is the relatively low productivity. and the rest of the formulation is fed in continuously over a period of time. On the other hand. as well as the composition and flow rates of the feeds. For this reactor type. grade transition between different polymer grades is instantaneous. it is not possible to obtain narrow monodisperse latexes using a single CSTR. including copolymer composition. a large portfolio of products can be produced with a single reactor. A continuous plug-flow reactor is somewhat similar to a batch stirred-tank reactor. A wide range of products are accessible using this technique.8 Emulsion Polymerization Reactors In semibatch operation. and wall fouling [92]. 90] that lead to multimodal PSDs. both temperature and polymer quality can be controlled. Tubular Reactors From a safety point of view. and particle size distribution. An important disadvantage of the tubular reactor is the inadequate mixing that can lead to phase separation. In addition. By varying the composition and amount of the initial charge. but the control of polymer properties is almost impracticable. both feed and effluent streams flow continuously. molecular weight distribution. Moreover. Most commercial emulsion products are manufactured in semibatch reactors. The main characteristic of this process is its great flexibility. Several modifications have been performed to improve radial mixing and minimize the associated problems. polymer architecture. An arrangement of multiple stirred tanks in series allows better heat removal and presents a narrower residence time distribution. but to date tubular reactors have not been widely utilized for industrial production. This may be alleviated by using a tubular reactor before the CSTR. In continuous operation mode. some fraction of the reactants (the initial charge) is charged into the reactor initially. which is being compensated by using larger reactors.

pulsed-flow reactors. commercial emulsion polymerization is mostly carried out in stirred-tank reactors or in reactors that have a similar macromixing behavior. The wicker-tube reactor consists of a coiled tube which meanders between solid. 104]. lowers the attractiveness of tubular reactors for commercial production. The boundaries of the vortices represent a barrier for axial mixing. wicker-tube reactors. The Couette–Taylor reactor consists of two concentric cylinders of which the outer one is fixed and jacketed. The continuous-loop reactor is probably the only tubular reactor used in commercial production of emulsion polymers [93. the residence time distribution is very close to that of a CSTR [98]. and high heat removal capacity are the main characteristics of these reactors [105–108]. Raschig rings. A continuous-loop reactor consists of a tubular loop that connects the inlet and the outlet of a recycle pump. and cleaning coagulum from these reactors will be very difficult. However. 100]. which reduces phase segregation and plugging. In this way. while radial mixing inside each vortex is good. Therefore the discussion will be limited to stirred-tank reactors. and Couette–Taylor flow reactors. Pulsed-flow reactors consist basically of a column in which a periodic external pulsation is provided. fixed. together with a lack of flexibility in controlling product properties. wall fouling. the reaction takes place in the annulus formed between the two cylinders. 94] and its use is limited to production of vinyl acetate homopolymers and copolymers (with ethylene and Veova 10) [95–97]. the loop recirculation rate is significantly greater than the feed rate.2 Reactor Equipment Despite the availability of different reactors. such as the loop reactor. The macromixing of such reactors is between that of plug-flow and well-mixed reactors.288 6 Emulsion Polymerization most important modified tubular reactors include loop reactors. The heat removal capacity is high and it is claimed that the multiple changes in flow direction allow the production of a polymer dispersion with a very low coagulum content [103. The introduction of sieved plates. cylindrical supports. Commonly. if the inner cylinder exceeds a certain speed the fluid inside the gap develops counter-rotating toroidal vortices. while the inner one rotates as a stirrer. This results in a substantial reduction in the reactor volume. The goal of the pulsed flow regime is to achieve highly effective mixing. Good radial mixing. For a specific configuration. Consequently the Couette–Taylor reactor may be modeled as a hydrodynamically formed train of continuous stirred tank reactors. 102]. Under these circumstances. The main disadvantage of this reactor is that highly mechanically stable formulations are required to prevent shear-induced coagulation at high recycling rates. and tube plugging [99.8. or baffles is reported to improve mixing [101. minimizing phase segregation. The mixing problems associated with tubular reactors. Its high heat-transfer area/reactor volume ratio allows efficient heat removal and hence high conversions in short residence times can be achieved. . these internal elements may be sources of coagulation. 6.

a lower agitation intensity is needed to avoid shear-induced coagulation. a certain amount of turbulence is required for emulsification and to avoid phase segregation. If neat monomer is fed in.1 and 1.1 289 . Radial-flow turbines produce a radial fluid motion from the impeller to the wall. The location of the addition point of the reactants is important. This requirement may be avoided by feeding a pre-emulsion. In emulsion polymerization. the agitation requirements in emulsion polymerization are often related to the operation mode. the mixing equipment must ensure that the tasks of emulsification and blending are performed well. Mixing For agitator selection it is critical to define correctly the mixing requirements. but incorrect definition of the agitator main task. and it must facilitate mass and heat transfer without causing coagulation [109]. The designs of axial-flow impellers are derived from three-blade propellers. high fluid circulation is needed in order to guarantee the macroscopic uniformity and to enhance mass and heat transfer. mixed-flow turbines with features of both radial and axial flow can be useful. which increases ionic strength and thus promotes coagulation. Axial flow impellers usually produce a fluid motion that is downward at the central axis of the vessel and upward in the wall region. Continuous operation requires mixing characteristics similar to those of the semibatch process. it is very important for mixing of the entering reactants to be instantaneous: this requires a high circulation flow rate. Stainless steel vessels with a height/diameter ratio between 1. In addition. with much of the energy dissipated by turbulence around the impeller. where the radial flow separates into an upper and a lower circulation loop. Moreover. In any case.2. The most common of these impellers is the 45 angled blade turbine. and the accumulation of emulsifiers. which leads to local nucleations and/or flocculations. to avoid monomer pools and other problems derived from the accumulation of initiators. Radial-flow turbines have flat blades or a disk with flat blades. which is directly related to shear rate and turbulence. 6. the most common cause of agitator failure is not miscalculation of the power or rotational speed. These reactors must be equipped for mixing and heat transfer. The power consumption of an impeller is the product of the pumping capacity (circulation flow rate) and the velocity head. Multiple impellers on the same shaft can also be employed. In practice. a high shear rate may cause coagulation. They are characterized by a relatively low flow/power ratio. They are designed to produce a high flow/power ratio with little turbulent loss. In semicontinuous operations. multiple impellers are normally used to ensure agitation as the level goes up. Later on. a certain amount of turbulence is required to facilitate dispersion. In emulsion polymerization.8 Emulsion Polymerization Reactors The stirred-tank reactors used for the production of emulsion polymers have sizes ranging from 5 to 50 m 3 . In batch operations.8. In this way. Depending on the type and size of the impeller.3:1 are usually employed. However. vigorous agitation is required in the initial stages to avoid monomer segregation and promote good phase dispersion. either the flow or the turbulence can be favored [110].6.

8. semibatch. can be found elsewhere [111]. and mixing time.9 Reaction Engineering Independently of the operation mode (batch. or continuous). In semibatch mode. extra cooling is provided by the cold feed. it is often not sufficient to operate with a simple cooling jacket and other devices must be incorporated in the design [112]: 6. external heat exchangers can be used also to cool the feedstreams in continuous and semicontinuous operations.  cooled baffles (the use of internal coils is not an option because they tend to increase fouling and coagulation).  reflux condensers.2  improved jacket design to increase turbulence. heat-transfer requirements are largely determined by the operation mode.  external loop heat exchangers for the reaction medium – in this case. Increasing the agitation speed to increase the internal heat-transfer coefficient is not an option because a high impeller speed can lead to coagulum formation. for the reactor as a whole. the heat generated can be easily controlled by the monomer feed rate. and hence the heat-transfer coefficient (dimpled. such as power consumption. particularly when the reactor temperature is high.290 6 Emulsion Polymerization Empirical correlations for the key aspects of mixing. . Heat Transfer Polymerization reactions are highly exothermic and the heat generated must be removed in order to control reactor temperature. In continuous mode. Both safety and product quality depend on the heat removal capacity of the reactor. and time is the only independent variable. 6. Batch is the most critical operation because high polymerization rates are achieved due to the high monomer concentration. half-pipe). The advances in computational fluid dynamics (CFD) combined with new techniques of measuring the local flow pattern are likely to transform the whole field. emulsification. the necessary balances for the reactor design may be made at macroscopic level – that is. For industrial reactors. liquid circulation. In commercial emulsion polymerization. Therefore. the heat removal rate from the reactor is often the factor limiting productivity. the continuous cold feed facilitates the control of the reactor temperature. In these reactors.2. In any case. in wellmixed stirred-tank reactors the properties do not vary significantly with the position in the reactor. a mechanically stable formulation is required.

(58)]. where XT can be gravimetric or molar depending on the units used for Polymeri and Monomeri (grams or moles.6. and for amounts of each polymerized monomer. dNi ¼ Fie  Fis þ ðRi ÞV dt ð56Þ where Ni [mol] is the total amount of compound i in the reactor. where V is constant in a continuous operation and Q s is the volumetric outlet flow rate.  Xi ¼ Polymeri Polymeri þ Monomeri  ð58Þ in the reactor When more than one monomer is polymerized. although in those cases units other than moles should be used. Equation (56) also applies to the number of polymer particles and of precursor particles and the moments of the molecular weight distribution. 2 3 Polymeri 5 X XT ¼ 4 X Polymeri þ Monomeri X ð59Þ in the reactor 291 . For batch processes. Fis [mol s1 ] the outlet molar flow rate of i. an overall conversion can be calculated from Eq. and for semicontinuous operation Fis ¼ 0. the density of the reaction medium does not change significantly. and emulsifier. Therefore. The advance of the polymerization is usually given in terms of the conversion Xi of monomer i [Eq. initiator.9. Fis ¼ Q s Ni V ð57Þ In emulsion polymerization. Here Polymeri and Monomeri are either in grams or in moles. the polymerization rate of monomer j is expressed as the rate of monomer consumption (Rpj ). and hence ðRMj Þ ¼ Rpj . For the continuous operation Fis can be calculated from Eq. water. the mass balance [Eq. and V [m 3 ] the reactor volume. (56)] for any species i results. Usually. (Ri ) [mol s1 m3 ] the net generation rate of i in the reactor.9 Reaction Engineering 6. (57). the volumetric inlet and outlet flow rates can be considered to be the same. Equation (56) applies for the particular combination of monomers. Fie [mol s1 ] the inlet molar flow rate of component i. respectively).1 Mass Balances Considering inlet and outlet streams in the reactor. The specific forms of the net generation rates are discussed below. Fie ¼ Fis ¼ 0. (59).

The instantaneous copolymer composition refers to the composition of the copolymer that is being formed at a given time.3 summarizes the expressions for the different reactors. (62). Rp1 y1i ¼ X Rpi ð60Þ The cumulative composition is the average composition of the copolymer formed up to a given time.2 Heat Balance Assuming that the energy balance for the reacting systems is essentially an enthalpy balance. Referred to monomer 1 this composition is given by Eq. 6. Usual conversion definitions. Rpi [mol m3 s1 ] is the polymerization rate of monomer i. The calculation of the monomer conversion depends on the operation mode. Npol1 y1cum ¼ X Npoli ð61Þ In continuous operations under steady-state conditions. where Npoli is the amount [mol] of monomer i polymerized. (60).292 6 Emulsion Polymerization Tab.9. respectively. this reduces to Eq. where Rpi is the polymerization rate of monomer i. y1i ¼ y1cum during the whole process. Table 6. as stated in Eq. 6. (61). where cpi and cpie [J mol1 K1 ] are the heat capacity of compound i in the reactor and under the entry conditions. In order to calculate the gravimetric conversions.[a] Conversion Fractional conversion of monomer i Overall fractional conversion Overall global conversion Batch Ni0  Ni Ni0 P ðNi0  Ni Þ P Ni0 Semicontinuous Ð Ni0 þ Fie dt  Ni Ð Ni0 þ Fie dt Ð P ðNi0 þ Fie dt  Ni Þ Ð P ðNi0 þ Fie dtÞ Ð P ðNi0 þ Fie dt  Ni Þ P NTi Continuous (steady state) Fie  Fis Fie P ðFie  Fis Þ P Fie [a] N i0 ¼ number of moles of monomer i at time zero. NTi ¼ the total amount of monomer i [mol] to be fed in a semicontinuous operation. it is necessary to multiply each term by the molecular weight of the corresponding monomer.3. (DHri ) [J mol1 ] .

Q loss [J s1 ] the heat losses to the surroundings (for example. If Twe A Tws then DTml A ðT  Tw Þ. external heat exchanger and reflux condenser). and physical properties of the fluid. (63). Equation (65) presents the usual form of these expressions [111]. the impeller speed. T [K] is the reactor temperature. Pr and Re are the Nusselt. Nu ¼ a Re b Pr c  j jw d ð65Þ Due to changes in the properties of the reaction media (for example.6. (64). where Nu. X Ni cpi X dT X ¼ Rpi ðDHri ÞV  Fie cpie ðT  Te Þ dt þ Q transfer þ Q loss þ Q stirring ð62Þ For heat removal through the cooling jacket Q transfer is given by Eq. cooling baffles. j and jw the viscosity of the reaction medium at the reactor and wall temperatures respectively. b. where Twe and Tws [K] are the inlet and outlet temperatures of the cooling fluid (normally water) in the jacket. Q stirring [J s1 ] the heat produced by the agitator. the heat-transfer area varies during the operation. DTml ¼ ðT  Twe Þ  ðT  Tws Þ ðT  Twe Þ ln ðT  Tws Þ ð64Þ The overall heat-transfer coefficient includes several resistances in series. viscosity) the overall heat-transfer coefficient changes during the process. Prandtl. through the reactor lid). Te [K] the temperature of the feeds. where U [J m2 s1 K1 ] is the overall heat-transfer coefficient.9 Reaction Engineering is the polymerization heat of monomer i under the reactor conditions. the reactor diameter. Q transfer ¼ UADTml ð63Þ DTml is given by Eq. 293 . A [m2 ] the total heattransfer area and DTml the logarithmic mean temperature difference between the cooling fluid and the reaction medium. and a. The internal heat-transfer coefficient is a function of several factors such as the impeller type and dimensions. and Reynolds numbers. In semicontinuous operation. but the internal resistance usually controls the heat-transfer rate (hi A U). Empirical correlations based on dimensionless groups can be used. and d are constants. and Q transfer [J s1 ] the heat removed through the heat removal devices (cooling jacket. c.

and stability of the latex. where the lefthand side accounts for the accumulation of particles in the reactor. the third for the formation and loss of particles of unswollen volume v due to particle growth. rv ðvÞ [mparticle metric growth rate of each particle of volume v.294 6 Emulsion Polymerization A practical method to determine the heat transferred in any cooling device is to measure the flow rate and the inlet and outlet temperatures of the cooling fluid. the number of particles with unswollen volumes between v1 and v2 is given by Eq. The units of nðvÞ are the polymer particles of unswollen volume v [mparticle number of particles per unit of unswollen volume of particle. which in turn influences heat removal rate.10. v 0 Þ the coagulation rate con- .1. (68). In Eq. (69) nðvÞ and ne ðvÞ are the reactor and inlet number density of polymer particles. V [m 3 ] the reactor volume. mixing. the first term on the right-hand side accounts for the entry of particles into the reactor. histograms are used when the PSD is determined by transmission electron microscopy. 6.6). Q s [m 3 s1 ] 3 s1 ] the voluis the volumetric flow rate. mass transfer. 114]. the mathematical analysis is simpler if the PSD is defined in terms of the number density of 3 ]. and often this depends on the method used to measure it. In addition. and the total number of particles by Eq. Thus.3 Polymer Particle Population Balance (Particle Size Distribution) Particle size distribution strongly affects rheology [115]. particle size distribution affects film formation and some application properties [116. the second for the exit of particles from the reactor. (67). kðv. Q transfer ¼ m_ w cpw ðTwe  Tws Þ ð66Þ Combination of Eqs.9. which are related by Eq. (66) where m_ w [kg s1 ] is the mass flow rate and cpw [J kg1 K1 ] the heat capacity. From this definition. the fourth for the loss of particles by coagulation with other particles and the fifth term accounts for the formation of particles of unswollen volume v by particle coagulation. However. This method. nðvÞ. 117]. On many occasions all of these aspects determine the scaleup and the feasibility of the operation. which is called reaction calorimetry (see Section 6. (62) and (63) or (66) allows the estimation of the polymerization rate from temperature measurements. There are several ways in which the PSD can be represented. Np ðv1 ! v2 Þ ¼ ð v2 nðvÞ dv ð67Þ v1 Np ¼ ðy nðvÞ dv ð68Þ 0 Equation (69) gives the macroscopic population balance for a CSTR. is a powerful noninvasive on-line monitoring technique and it has been extensively applied to polymerization reactors [113.

6. This table 295 . Unfortunately. However. (69) should be removed for batch reactors.9 Reaction Engineering stant for particles of volumes v and v 0 . and v0 the volume of particles formed by nucleation. (26).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 . at the projected manufacturing cost.4 Scaleup The main objective of scaleup is to reproduce the laboratory results in commercialscale reactors in such a way that the end-use polymer properties can be maintained. ð qnðvÞ Q s Qs qrv ðvÞnðvÞ nðvÞ y kðv. v 0 Þnðv 0 Þ dv 0 ne ðvÞ  nðvÞ  ¼  V V qt qv V v0 ð 1 vv0 þ kðv  v 0 . To achieve this goal. where R nuc is the nucleation rate given by Eqs. In theory. together with heat and mass transfer. as well as for semicontinuous reactors to which no particles are fed. (31). when several mechanisms are involved in the process. nðv0 Þ ¼ R nuc V rv ðv0 Þ ð70Þ The first and second terms on the right-hand side of Eq. The calculated values assume geometric similarity with a constant impeller/tank diameter ratio and a constant height/tank diameter ratio. In this way. v 0 Þnðv  v 0 Þnðv 0 Þ dv 0 2V v0 ð69Þ This equation is a partial-differential-integral equation and the nucleation term is best incorporated as a boundary condition at volume v0 as in Eq. (20). The flow into the vessel. Then. it is impossible to maintain all the dimensionless groups constant simultaneously. the design variables that affect these controlling mechanisms must be maintained constant from the smaller scale to the commercial equipment. it is very important to know which similarities to keep and which to sacrifice. 120].6. the coagulation terms may be neglected for stable formulations. and to the desired quality standards [121]. and (33). must be considered in emulsion polymerization reactors because all of these mechanisms can have a great influence on polymer properties and reactor behavior. (70) [118]. Equations (69) and (70) are conveniently solved by using orthogonal collocation [119. the mixing and heat-transfer parameters do not scale equally. In this case. this could be done by applying the principle of similarity by means of dimensionless groups characterizing the phenomena of interest. On the other hand. In Table 6. a successful scaleup takes place when the latex is produced on a large scale at planned rates. knowledge of the mechanisms that control the reactor behavior and the product properties is required [122].9.

05 1 0. 6. Intermediate pilot plant experiments are required in most cases to make a successful scaleup. Changes in viscosity during the process affect mixing.1 0.21 46. In addition.1 100 10 10 5 1 10 3 100 0. Nevertheless this scaleup criterion is impractical because it demands excessive impeller tip speeds and high power costs. It is often essential to maintain the same rate of heat transfer in the large-scale unit. and scaleup becomes more difficult.01 10 3 1 are as given in the Notation section. Monomer droplet and particle size. to compensate the negative effect in the heat-transfer rate when another scaleup criterion is selected. Parameter [a] Pilot scale (50 L) Plant scale of 50 m 3 (scaleup procedure) P (power) N (impeller rpm) Q (impeller flow) P=V (power/volume) q=V (heat transfer rate/volume) ND (tip speed) Q=Q S (impeller flow/feed rate) Q=H (impeller flow/head) Re (Reynolds number) 1 1 1 1 1 1 1 1 1 10 3 0. For this reason. changes in the formulation can be utilized to maintain dynamic similarity. coagulation and kinetics may be affected by mixing parameters.8 21.296 6 Emulsion Polymerization Tab.08 2.4.0001 0.21 215 1 0. shows. . With respect to mixing characteristics.1 0. the main objectives to be fulfilled are:  Safety: The reactor temperature must be kept under safe limits to avoid thermal runaways. 6. where mixing affects several polymer properties. Several scale factors during scaleup.1 0. but an adequate combination of several mixing parameters can be better to maintain product quality. This task is difficult in emulsion polymerization. additional cooling devices are necessary in most cases [123]. Computational fluid dynamics will probably transform scaleup in the near future. mass transfer between the different phases.1 0.21 10 1 10 100 0.01 10 0. it is very important to identify the parameters that have a major effect on the polymer properties. in different columns the change in selected parameters when one of them is held constant. The power per volume or the tip speed are the more usual scaleup criteria.1 100 0. In some cases.01 0. violation of environmental regulations both in the plant environment and in the finished products must be avoided.10 On-line Monitoring in Emulsion Polymerization Reactors In the production of dispersed polymers.5 [a] Units 10 8 10 10 4 10 5 1 100 10 1 10 3 100 0.

branching and crosslinking.1 On-line Sensor Selection One of the issues when monitoring an emulsion polymerization reactor is selection of the most appropriate technique [124. and particle size distribution. MWD.10. Reaction control strategies rely on both efficient monitoring techniques and state estimation and filtering techniques. In polymer latexes the properties that one would like to control during the polymerization include: monomer(s) conversion. copolymer composition. and near-infrared. fluorescence. and product quality.6. tensile strength. gel content. 6. and know-how required). maintenance. ultrasound. 126]. and other spectroscopic methods such as Raman. toughness. 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). it is necessary to develop suitable control strategies. PSD. Detailed reviews for on-line monitoring techniques for polymerization reactors are available [124–126]. mid-range infrared.  Product quality: The required quality is given by the end-use properties such as viscosity. but unfortunately no such technique is currently available. flexibility. production rate. The main idea behind this plot is the fact that the amount of information provided by the available techniques is different and furthermore. In order to implement the process conditions that lead to the required specifications of safety. Not all of these properties can be monitored on-line. elasticity. Polymer latexes are ‘‘products-by-process’’. refractive index. Other properties. the implementation of these techniques involves different degrees of difficulty (including here robustness in a harsh environment. Figure 6. such as molecular weight distribution of nonlinear polymers and particle morphology. For instance.11 can be used as a guide for the selection of a technique for monitoring monomer conversion and copolymer composition. particle morphology.10 On-line Monitoring in Emulsion Polymerization Reactors  Production rate: The goal is to maximize the production rate of the available reactors. monomer conversion and copolymer composition can be monitored on-line by means of densimetry. The ideal technique would be located in the upper left-hand corner. gas chromatography. calorimetry. although some can be made observable by combining available measurements and mathematical models. are currently neither measurable nor observable. scrub resistance. 297 . In this section the main focus is on the instrumentation available for monitoring emulsion polymerization reactors. and glosss. and therefore the required structural and morphological properties of the polymer that yield the adequate end-use properties are produced in the reactor. ultraviolet reflection.

11. as for latex GC. Although successful implementation of this technique for latexes with a high solids content has been reported [134].11 will be presented. a brief description of the monitoring techniques shown in Figure 6. 6.2 Densimetry This technique is based on the density change that occurs when monomer is converted to polymer. In the rest of Section 6.10. 136]. This difference. 133]. and finally examples of application for emulsion polymerization reactors will be given.1.1. Additional disadvantages of this monitoring technique include the time delays associated with the analysis itself when multicomponent copolymerizations are monitored. which is obviously a maximum in bulk polymerization. a sample of the reaction medium must be introduced in the thermostated measurement cell and the system is liable to suffer clogging.3 . the setup is liable to suffer clogging. 6.1. emphasizing the advantages and disadvantages of each one. the estimation of the monomer concentrations in the polymer particles requires that equilibrium between the latex and gas phase is attained.1 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. In addition. 6. The main disadvantage of on-line densimetry is that. This drawback can be partially alleviated by using capillary columns and modern gas chromatography equipment with reduced analysis time. A further dis6.298 6 Emulsion Polymerization Fig. Guideline chart for sensor selection. However.10. allows emulsion polymerizations of relatively high solids content to be accurately monitored [137]. Note also that formulation ingredients such as CTAs are not measurable by this means.10.10. which introduces an additional uncertainty to the measurements. Latex Gas Chromatography In this technique.1. the values of the equilibrium parameters are required. a latex sample from the reactor is first diluted and then injected into the GC to analyze unreacted monomers and CTAs [132.

6. and compressibility. and critical micellar concentration can also be measured [141]. An additional advantage is that a fiber-optic probe can be installed in an existing reactor within a short time without expensive modifications. This has been possible due to the recent development of fiber-optic probes. and MIR are absorption-based. and. Nevertheless. and the dynamic relaxation of the polymeric material [138. mid-infrared (MIR) and Raman spectroscopic techniques can be used for polymerization reaction monitoring. ultraviolet (UV). calibration is required to obtain accurate predictions of monomer conversion or other properties such as particle size because the theoretical models linking those characteristics to sound propagation velocity are not predictive. In principle.5 299 .4 Spectroscopic Techniques Since the mid-1990s. An advantage of densimetry in comparison to GC is that there is no delay in the measurement of density.10. 6. other latex properties such as particle size. the main advantages of this technique are that it is noninvasive in nature (although care should be taken with emitter–receiver transducers located inside the reactor). and hence partial conversions and copolymer compositions must be inferred using a model [129]. there are technical problems in measuring the attenuation at high solids and the presence of gas bubbles can make the measurements difficult. Furthermore. These can be divided between absorption. Ultrasound The principle of ultrasound relies on the propagation of the ultrasonic wave pressure. monomer solubilities. pressures. thermal losses. toxic environments. Sound propagation velocity is better suited to monitor emulsion polymerization reactors and it has been proven in systems with high conversion and high solids content [140–142]. The main disadvantage is that to exploit the information on the sound velocity and attenuation fully. Fluorescent. sound scattering in dispersed media. 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. which can be monitored almost continuously. viscosity. 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.10.1.10 On-line Monitoring in Emulsion Polymerization Reactors advantage of densimetry is that it provides only overall conversion measurements for copolymerization. which allow insitu measurements in remote and harsh environments (high temperatures. NIR. and so on). in addition to monomer conversion. 139]. the viscous losses within the particles and at the interface between the particle and the continuous phase. which are a function of the medium where the wave propagates and hence of the density. IR. infrared (IR). The measurable properties are the ultrasonic velocity and the attenuation of the wave. near-infrared (NIR).6.1.and emission-based techniques. there has been plenty of activity regarding the use of spectroscopic techniques for on-line evaluation of polymer properties [143–146]. it is fast and cheap.

 Low-cost fiber-optic technology can be used to monitor polymerization reactors remotely. in situ. water is absorbed in this region and it may hide bands that are important for further analysis. with high accuracy. In addition. Although NIR has been used to monitor emulsion polymerization reactions [147].  The penetration depth of the Raman signal is greater than for NIR and hence in emulsion polymerization interference by monomer droplets can be avoided. 148. Currently. . In addition. but to combinations of them. which makes IR not as suitable as other techniques for remote monitoring. Furthermore. transmission through fiber-optics is still relatively poor in the infrared region. the use of MIR spectroscopy to monitor emulsion polymerization reactors is scarce. 149]. The main disadvantage of NIR comes from the fact that in this region. Although conventional dispersive Raman spectroscopy (laser wavelengths between 500 and 700 nm) has not been successfully used to monitor polymerization reactions due to the tremendous effect of fluorescence on the spectra. Raman spectroscopy can be considered as the spectroscopic technique with the greater potential to monitor polymerization reactors. However. Furthermore. which have a low cost. Another difficulty of NIR is the short penetration depth of the NIR signal. This region is very rich in fundamental absorptions and hence the potential of this technique is high.300 6 Emulsion Polymerization IR is not well suited to monitor polymerizations in dispersed media because water gives a strong absorption. absorption bands are broad because they do correspond not to specific bonds or groups of molecules. Raman spectroscopy is an emission-based technique. and hence important bands are overlapped or hidden by that of the water. 1034 nm) or modern dispersive Raman equipments (laser wavelengths over 800 nm) overcome this difficulty. the detection of the minor compounds in polymerization formulations is not easy. The most important ones are:  Water is a weak scatterer and hence Raman is well suited to monitor polymerization in dispersed media. NIR spectroscopy corresponds to the spectral region 14000–4000 cm1 . The MIR spectral region is from 4000 to 400 cm1 . FT-Raman (laser wavelength in the NIR region. and especially emulsion polymerization reactors. The main advantages of NIR are that no sample preparation is required and that the NIR signal can be easily transmitted through fiber-optics made of silica. This makes the accurate quantitative analysis difficult. Raman spectroscopy presents several advantages over the absorption techniques (MIR and NIR). This makes it possible to follow.  It is very sensitive to CbC bonds. difficulties due both to broad bands associated with water absorption and to the effect of the particle size have been reported [141. the disappearance of monomer by polymerization. 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. the presence of big monomer droplets might cause inaccuracies in the quantitative analysis due to inhomogeneous sampling of the reactor by the NIR probe.

10 On-line Monitoring in Emulsion Polymerization Reactors a) Weight Fraction MMA 0.01 0 0 0.2 0. Chemometric (partial least squares.12 shows an example of monitoring a semibatch emulsion polymerization of MMA/BA of high solids content (55 wt.03 0. Evolution of (a) MMA.8 1 Conversion b) Weight Fraction BA 0. (b) BA. 6.2 0. Figure 6. On-line monitoring of a seeded semibatch emulsion copolymerization of MMA/BA.12.05 0. PLS) analysis was neces- 301 .04 0.8 1 Conversion Fig.%) by means of on-line FT-Raman spectroscopy [150]. It should be pointed out that this monomer system was challenging because the chemical structures of the monomers are very similar.002 0.003 0.6 0.4 0. and hence most of the bands overlap.004 0.02 0.005 0.6.4 0.006 0.001 0 0 0.6 0.

easiest. .10. in some cases nonlinear calibration techniques are necessary because PLS.2 0.6 Emulsion Polymerization c) Solids Content (%) 302 60 50 40 30 20 10 0 0. Reaction Calorimetry Reaction calorimetry is probably the cheapest. 6. Q r is the heat generation rate due to polymerization. Reaction calorimetry is based on the energy balance in the reactor. Q feed is the sensible heat genera- .12. and it is industrially applicable [151. The technique is noninvasive (basically.6 0. may not be sufficient if the degree of nonlinearity between the spectra and the properties of interest is significant. Consequently. Furthermore.8 1 Conversion Fig. due to the large enthalpy of polymerization of most monomers. The main drawback is that only overall polymerization rates can be obtained. (71). g.4 0. only temperature sensors are required). gravimetry and gas chromatography. a multivariate linear calibration. and most robust monitoring technique for polymerization reactors. given by Eq.1. (c) solids content.6 X Ni cpi dT ¼ Q r þ Q feed þ Q transfer þ Q loss þ Q stirring dt ð71Þ where the term on the left-hand side is the heat accumulated in the reactor. It yields continuous information on the heat released by polymerization and hence it is also very useful for safety issues. FT-Raman. sary to quantitatively determine the concentrations of monomers and the solids content. the determination of the individual rates requires estimation techniques [114. 6. 153–155]. 152].

m w cpw dTws ¼ UAðTws  TÞ þ m_ w cpw ðTwe  Tws Þ dt ð73Þ Heat-balance calorimetry allows the simultaneous estimation of U and Q r . Q transfer is calculated from the measurements of the reactor (T) and jacket (Tw ) temperatures by applying Eq. In heat-balance calorimetry. The amount of free monomer and the copolymer composition in emulsion polymerization reactors can be inferred from measurement of the heat of reaction. m_ w the mass flow rate of cooling fluid in the jacket.10 On-line Monitoring in Emulsion Polymerization Reactors tion rate due to the feeding of reagents into the reactor. Q transfer ¼ UAðT  Tw Þ ð72Þ The implementation of heat-flow calorimetry requires knowledge of the evolution of U. In heat-flow calorimetry. The advantage of this approach is that a-priori information of the overall heat-transfer coefficient is not necessary and hence it is more robust and reliable than heat-flow calorimetry. (73). because the oscillating signal is strongly attenuated as the reactor size increases. Twe the inlet jacket temperature and Tws the outlet jacket temperature.6. (71) and (72) are coupled with the energy balance in the jacket to produce Eq. Q r . This is the weakest point of this technique. The oscillation of the jacket and reactor temperatures can be achieved in different ways. The analysis of the oscillatory temperature signals allows calculatation of the UA term and Q r simultaneously [156. The generation rate of the heat of reaction. where U is the overall heat-transfer coefficient and A the heat-transfer area. can be calculated from the other terms. In emulsion polymerization reactors. This approach can only be applied to small reactors (< 20 L) with high flow rates of the cooling fluid. but perhaps the most practical one is by imposing a sinusoidal oscillation in the set-point of the reactor temperature. (72). and this is the case in industrial reactors. the largest of these terms is Q transfer . Oscillation calorimetry also allows simultaneous determination of the heat of reaction and the overall heat-transfer coefficient from temperature measurements of the reactor and the jacket. This is done by taking advantage of the different dynamics of heat transfer (fast) and heat of the reaction (slow) when an oscillation of either the reactor or jacket temperature is created artificially. Q r 303 . eqs. cpw its specific heat capacity. provided that Twe  Tws could be accurately measured. where m w is the mass of cooling fluid in the jacket. respectively. and Q loss and Q stirring represent the rate of heat losses and of heating due to stirring. heat-balance calorimetry is best suited for large-scale industrial reactors because a significant difference between the jacket inlet and outlet temperatures is necessary. 157]. provided that these can be calculated with sufficient accuracy. Therefore. Q transfer is the heat flow across the reactor wall. The higher reactor time-constants make the estimation of Q r and UA very uncertain [158].

2 VAc 0. the estimation of the terpolymer composition from calorimetric measurements is compared with NMR and GC measurements for a VAc/MMA/BA emulsion terpolymerization [159].0 ________ Terpolymer Composition 304 Calorimetry Full Points GC 0.4 MMA 0.6 Emulsion Polymerization a) 350 Free Monomer (g) Gravimetry 300 Chromatography Calorimetry 250 200 150 100 50 0 0 50 100 150 200 250 300 350 Time (min) b) 1.8 1.4 0. In Figure 6.0 0.0 Conversion Fig.8 Open Points NMR 0. 6. Figure 6.13.6 0. On-line monitoring of emulsion polymerization reactor by means of calorimetric measurements: (a) free monomer in VAc/BA/AA semibatch emulsion polymerization.6 BA 0.13(a) shows the evolution of the free monomer concentration as inferred from on-line reaction calorimetry compared with the off-line measurement (gravimetry and gas chromatography) for a VAc/BA/AA high solids content semibatch emulsion polymerization. . 128].13(b).2 0.0 0. [127. (b) terpolymer composition in the VAc/MMA/BA semibatch emulsion polymerization.

Once the desired molecular and morphological properties of the latex are established. Therefore.14). Closed-loop control strategy for optimal control of composition and MWD in emulsion polymerization reactors. and consistent production of high-quality materials. peel. 305 . In order to reduce this time-consuming methodology semiempirical approaches can be used. x are state variables of the polymerization reactor.11 Control of Emulsion Polymerization Reactors The objective of reactor control is to achieve an efficient.11 Control of Emulsion Polymerization Reactors 6. one would like to know the microstructure that will yield a given set of end-use properties (see Figure 6. the current industrial practice is a trial and error methodology. tack. 6. brightness.14. ymeas are properties that are monitored on-line. 161].1). 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. However. drawability. in practice. and shear resistances. which are the variables that can be controlled in the reactor. This can be achieved by inverting the model using appropriate techniques of optimization or neural networks [160. The development of first-principle structure–properties relationships is very challenging as the basis is not yet well established.14. and u are the manipulated variables of the process (basically flow rates of monomers and chain-transfer agents). safe. a closed-loop control strategy can be implemented. A typical closed-loop control strategy used to control copolymer composition and molecular weight distribution is shown in Figure 6. weatherability. Fig. 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. 161]. this relationship only provides a way to estimate the end-use properties from a given microstructural property (MWD in the example). The quality of the emulsion polymers is given by its end-use properties such as mechanical strength. Thus. and elastic modulus. In the control scheme. y are measurable properties of the polymer latex. impact strength.6. These end-use properties depend on the molecular and morphological properties of the latex.

Min ð 1 ½M p 0 1 dXT Rp  ð74Þ The minimization of Eq. X ni .306 6 Emulsion Polymerization The closed-loop control strategy requires calculation of the set-point. the objective function to be minimized is as expressed in 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 final MWD. (76). This comonomer ratio can be calculated from the Mayo–Lewis equation. These profiles can be calculated by means of an optimization algorithm. In order to calculate the X ni values that should be produced at each value of XT . (77). a brief description of the calculation of the optimal trajectories for copolymer composition and the MWD control is presented. (75). 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. where XTf is the final overall conversion. Eq. 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 desired copolymer composition and MWD in the minimum process time. ½M1 p ½M2 p ¼ ð2y1i  1Þ G fð2y1i  1Þ 2  4r1 ð y1i  1Þ y1i r2 g 1=2 2r1 ð y1i  1Þ ð75Þ 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. Wj ðnÞ is the instantaneous MWD . (74). When chain transfer to a CTA is the main termination event. that is. according to Eq. where r1 and r2 are the reactivity ratios and y1i is the instantaneous composition referred to monomer 1. This opens the possibility of decomposing the desired final MWD in a series of instantaneous MWDs to be produced at different stages of the reaction [130]. each of those MWDs can be characterized by the number-average chain length. X ni ¼ k p1 ½M1 p þ k p2 ½M2 p ktr. CTA ½CTAp ð76Þ Therefore the problem reduces to calculating the sequence of the values of X ni that provide the desired final MWD. X nij is the instantaneous number-average chain length produced in the conversion increment j. the trajectories or profiles of the state variables as a function of a measured variable (overall conversion). To achieve this goal. In what follows. the final MWD is discretized as in Eq. the polymer chains do not suffer any modification once they are formed. where Rp is the polymerization rate and XT is the overall conversion.

where Wcd ðnÞ and Wc ðnÞ are the desired and the calculated MWDs. and the maximum temperature and pressure that may be reached during a polymerization 307 . with polydispersity index equal or greater than 2 can be prepared by this method.% based on monomer) used in industrial practice. A priori any MWD. 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. Wcd ðnÞ. MWDs containing very low molecular weights may require the use of amounts of CTA that exceed the maximum allowable quantities (usually lower than 1 wt. On the other hand. 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. Strictly speaking. so the maximum amounts of the monomer that can be present in the reactor should be limited for safety reasons. In practice.6. The risk parameters are the onset temperature. and k is the number of increments into which XTf is divided. For a given number of conversion increments. (78). (79)]. the required values of X nij can be calculated by minimizing the Eq. this is very close to the molecular weight obtained without CTA. Wc ðnÞ k k 1 X DXT X n n ¼ Wj ðnÞDXTj ¼ exp  XTf j¼1 XTf j¼1 X nij X nij ! ð77Þ Note that in the discretization the most probable distribution is used because. (78) provides the values of X nij to be produced at different DXT [Eq. Therefore. if chain transfer to CTAs is the main termination event. X ni o ½M1 p þ ½M2 p ½CTAp ¼ f ðXT Þ ð79Þ Equations (75) and (79) are used as the constraints in the optimization algorithm to produce a copolymer of constant instantaneous composition Y1i and a given MWD. X ½Wcd ðnÞ  Wc ðnÞ 2 Min X ni ð78Þ n This is a nonlinear optimization in which the number of values of n should be greater than the number of conversion increments.11 Control of Emulsion Polymerization Reactors produced in the conversion increment j. The minimization of Eq. the instantaneously formed polymer obeys this distribution (polydispersity index ¼ 2). the adiabatic temperature increase. Wcd ðnÞ. Constraint 2: Safety considerations Polymerizations are exothermic processes that can cause runaways.

A typical result obtained in an adiabatic calorimeter for an emulsion polymerization reaction is shown in Figure 6. adiabatic calorimeters of low thermal inertia (phi-factor.15.17. the onset of the adiabatic reaction and the maximum temperature achieved can be determined. DT.308 6 Emulsion Polymerization process under adiabatic conditions. and furthermore to develop optimal control strategies under safe conditions. The particle size of the seed and the initiator/monomer ratio were the same in all the experiments. This criterion depends on the sensitivity of the equipment and is used as a reference to calculate the adiabatic temperature increase. respectively. Therefore. where Ni and cpi are the amount and the heat capacity. F. DT. is calculated for the experiments carried out in the adiabatic calorimeters by subtracting the Tonset from the maximum temperature achieved. and pressure (the latter not shown) increase upon increasing the monomer content. The plot. From the evolution of the temperature. adiabatic temperature increases under these conditions can be easily calculated. less than 15%) are used. particle size. which is based on the data displayed in Figure 6. particle size. X DT ¼ i MiTOT ðDHri Þ X Ni cpi ð80Þ i The adiabatic temperature increase. of each reagent i present in the reaction medium. solids content and initiator/monomer ratio are of paramount importance to establish the safe regions of operation of an emulsion polymerization reactor. DT ¼ Tmax  Tonset ð81Þ Thus. Figure 6. The plot shows that the onset temperature decreases as the monomer concentration in the polymer particles increases. MiTOT . and the heat capacity of the reaction medium according to Eq. which depends on the total amount of monomer in the formulation. To assess risk parameters. the heat of polymerization (DHri ).16. DT. is defined as the temperature at which the self-heating rate is equal to a given arbitrary onset criterion. is constructed assuming that the polymerization will be carried out at . the dependence of the risk parameters on process variables such as the monomer concentration in the polymer particles. An example of the safety limits for the VAc/BA/AA emulsion polymerization system is shown in Figure 6. The analysis can be extended for other process variables such as solids content.16 shows the evolution of the risk parameters as a function of the polymer/monomer ratio for the emulsion polymerization of VAc/BA/AA (78.5:3) as obtained in a VSP2 reactor (Fauske & Associates). Tmax . The evolution of the pressure provides an indication of the maximum pressure reached. Tmax . (80). Tonset . The onset temperature of the polymerization reaction. and initiator/monomer ratios.5:18.

Tlimit . final solids content ¼ 50 wt. Note that this temperature must be calculated on the basis of the maximum pressure that the reactor can withstand. The graph shows that the region of polymer/monomer ratio below 3:1 (concentration of monomer in the polymer particles higher than ½Mp ¼ 2:90 mol L1 ) will not be safe.5 1 0.15.%.5 2 1.%. initiator/monomer ratio ¼ 0.002 wt.5 3 2. seed particle size ¼ 156 nm. is 100 C. (b) pressure during emulsion polymerization of VAc/BA/AA (78. 6. and is also a function of the process variables. 80 C (Twork ) and that the maximum temperature allowed to run the process.6. Time evolution of (a) temperature.5 0 50 100 150 time (min) Fig. there is a risk of exceeding the Tlimit tempera- 309 .5:18. In other words. if higher monomer concentrations are used in the process and the cooling system fails.5:3) with initial monomer/polymer ratio ¼ 50:50.11 Control of Emulsion Polymerization Reactors a) 120 T (°C) 100 80 60 40 20 0 50 100 150 200 250 300 200 250 300 time (min) b) P (atm) 4 3.

Polymerization temperature ¼ 80 C. 140 Temperature (°C) 310 T 120 work + ∆T T limit 100 80 T work 60 SAFE REGION 40 ∆T 20 0 0 2 DANGER 4 6 8 Polym er / M onom er [M ] p Fig. maximum temperature allowed for the process ¼ 100 C.16. 6.17. Safety regions for a VAc/BA/AA emulsion polymerization. 6. Evolution of the risk parameters as a function of the polymer/monomer ratio for a VAc/BA/AA emulsion polymerization of high solids content. 10 .6 Emulsion Polymerization Temperature (°C) 140 120 Tonset ∆T 100 Tmax 80 60 40 20 0 0 2 4 6 8 10 Polymer/Monomer Fig.

6. (85)–(87)].14) reduces to tracking these profiles. d½M1f þ M1pol  b0 dXT ð82Þ d½M2f þ M2pol  b0 dXT ð83Þ d½CTA f þ CTA pol  b0 dXT ð84Þ 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. Constraint 3: Nonremoval of monomer and CTA The monomers and CTA already charged in the reactor cannot be removed (Eqs. Above the limit polymer/ mononor ¼ 3 (½Mp < 2:90 mol L1 ) the process can be operated safely because in none of the cases does the [Twork þ DT] operating line exceed the limit of the safe operation temperature. on-line measurements of the overall conversion and of the free amount of monomers and CTA are necessary. M2TOT . the implementation of the closed-loop strategy (Figure 6. A number of nonlinear controllers have been reported in the literature for this purpose: nonlinear model predictive controllers (NMPCs) [162]. respectively). 311 . and most robust option from an industrial perspective. These profiles are independent of the kinetics of the process and can be regarded as master curves.11 Control of Emulsion Polymerization Reactors ture (Twork þ DT > Tlimit ) and the runaway will take place. cheapest. M1f þ M1pol a M1TOT ð85Þ M2f þ M2pol a M2TOT ð86Þ CTA f þ CTA pol a CTATOT ð87Þ The optimization provides the amounts of monomers and CTAs in the reactor at any overall conversion. and CTATOT . nonlinear geometric controllers (NGCs) [163]. (82)–(84). Once the trajectories of the amounts of monomers and CTAs as a function of the conversion are calculated. respectively [Eqs. where the subscripts f and pol stand for free and polymerized amounts. M1TOT . Reaction calorimetry plus state estimation is probably the easiest. At each sampling time a nonlinear controller calculates the values of the manipulated variables u (flow rates of monomer and CTA) that must be added during the sampling interval to ensure tracking of the master trajectories and hence to produce the desired polymer. To do so. and internal model controllers (IMCs) [164] being the ones that have gained more attention in the specialized literature.

n-butyl acrylate.19 presents a comparison between the desired and obtained copolymer composition and MWD during the controlled experiment. and tert-dodecyl mercaptan (TDM) to produce the copolymer with the properties mentioned. Figure 6.2 0.5 0.6 Emulsion Polymerization 0.% of the polymer in each peak) of different polydispersities were sought: Mw1 ¼ 1:05  10 6 and PI1 ¼ 2:5 and Mw2 ¼ 1:15  10 5 and PI2 ¼ 3.19 [165]. An example of the performance of an on-line control strategy like the one depicted above is shown in Figures 6.003 0 0 0. Figure 6.18.6 0.18 and 6. Moreover. A copolymer with constant composition.012 CTA 0.009 1 0. the amount of TDM required was low since the mode with the high molecular weight was prepared first. during the production of the first 50% of the polymer.015 2 Butyl acrylate Styrene 1.18 presents the optimal profiles of styrene.006 0. at 50% conversion. Notation A Ap as c cc total heat-transfer area [m 2 ] total surface area of the polymer particles [m 2 ] saturated surface of the polymer particles covered by 1 mol of surfactant [m 2 mol1 ] overall termination rate coefficient in the polymer particles [Eq.8 1 Total amount of CTA (mol/L) Total amounts of monomers (mol/L) 312 0 Overall Conversion Optimal trajectories for the amount of monomer and CTA to produce S/n-BA ¼ 50:50 copolymer with a bimodal MWD. styrene/n-butyl acrylate (S/BA) ¼ 50:50 and a bimodal MWD with two peaks (50 wt. (9)] [s1 ] rate coefficient for bimolecular termination by combination [s1 ] . Fig. a sudden addition of TDM was required to start producing the low molecular-weight mode. It can be seen that to maintain the comonomer ratio the required amount of n-BA was always greater than that of styrene.5 0.4 0. 6.

Notation a) Copolymer Composition 1.8 0.0 w Experimental results of the on-line controlled emulsion polymerization of S/n-BA: (a) cumulative copolymer composition.0 3.96 0.19.8 1.6 X=0.3 X=0.0 Overall Conversion b) Desired w df/dlog(M ) 0.2 0. cd CMC cpi cpie cpw ½CTAp CTA f rate coefficient for bimolecular termination by disproportionation [s1 ] critical micellar concentration [mol m3 ] heat capacity of compound i in the reactor [J mol1 K1 ] heat capacity of compound i under the entry conditions [J mol1 K1 ] heat capacity of the cooling fluid [J kg1 K1 ] concentration of CTA in polymer particle [mol m3 ] free amount of CTA in the reactor [mol] 313 .6 0.2 0.5 4.4 0.0 4.0 0.0 3.2 0.4 X=0.18 0.0 log (M ) 6.0 0.5 X=0.0 0. Fig.0 5.5 5. 6. (b) MWD produced at different conversions.5 6.5 7.6 0.1 0.60 0.4 0.77 0.47 X=0.

v 0 Þ ka kac kadd kam kd kd ðnÞ kde kex ðÞ kfrag ðþÞ kfrag kI kp k pi kpji kt kt ktr. M k tw amount of CTA polymerized [mol] total amount of CTA in the formulation [mol] impeller diameter [m] diameter of the monomer droplets [nm] diameter of the polymer particles [nm] efficiency factor of the initiator radicals frequency of activation in living polymerization [s1 ] frequency of bimolecular termination [s1 ] frequency of deactivation in living polymerization [s1 ] inlet molar flow rate of component i [mol s1 ] outlet molar flow rate of component i [mol s1 ] velocity head [J kg1 ] internal heat-transfer coefficient [J m2 s1 K1 ] polymerization heat of monomer i under the reactor conditions [J mol1 ] amount of initiator [mol] concentration of initiator in the aqueous phase [mol m3 ] critical length of the oligoradicals formed from desorbed radicals critical length of the oligoradicals formed from initiator partition coefficient of monomer i between the phase j and the aqueous phase. backward reaction [s1 ] fragmentation rate coefficient in RAFT. CTA k tr. forward reaction [s1 ] rate coefficient for initiator decomposition [s1 ] propagation rate constant [m 3 mol1 s1 ] average propagation rate constant of monomer i in copolymerization [m 3 mol1 s1 ] propagation rate constant of radicals with terminal unit j with monomer i [m 3 mol1 s1 ] termination rate coefficient in the polymer particles [m 3 mol1 s1 ] reversible termination rate coefficient in living polymerization [m 3 mol1 s1 ] average chain transfer to CTA rate constant in copolymerization [m 3 mol1 s1 ] chain transfer to monomer rate coefficient [m 3 mol1 s1 ] termination rate coefficient in the aqueous phase [m 3 mol1 s1 ] . coagulation rate constant for particles of volumes v and v 0 [m 3 particle1 s1 ] entry rate coefficient [m 3 mol1 s1 ] activation rate coefficient in NMP or ATRP [s1 or m 3 mol1 s1 ] addition rate coefficient in RAFT [m 3 mol1 s1 ] rate coefficient for radical entry into the micelles [m 3 mol1 s1 ] rate coefficient for radical exit [s1 ] rate coefficient of radical exit from particles with n radicals [s1 ] deactivation rate coefficient in NMP or ATRP [m 3 mol1 s1 ] exchange rate coefficient in DT [m 3 mol1 s1 ] fragmentation rate coefficient in RAFT.314 6 Emulsion Polymerization CTA pol CTATOT D dd dp f fac fc fde Fie Fis H hi (DHri Þ I [I] icrit jcrit j Ki kðv.

Notation m Micrit Mif Mipol ½Mi p MiTOT Mm Mmi Mn Mni ½Mp mw m_ w Mw Mwi ½Mw N n n NA nðvÞ ne ðvÞ Ni Ni0 nm Nm Nn Np Npoli Npr NTi Nu P Pj PM Pr q Q Q feed Q loss Qr partition coefficient of small radicals between polymer particles and the aqueous phase [Eq. (11)] number of oligoradicals of critical length formed from desorbed radicals amount of free monomer i in the reactor [mol] amount of monomer i polymerized [mol] concentration of monomer i in the polymer particles [mol m3 ] total amount of monomer i in the formulation [mol] number of inactive chains of length m number of inactive chains of length m in particles with i radicals cumulative number-average molecular weight instantaneous number-average molecular weight monomer concentration in the polymer particles [mol/m 3 ] mass of the cooling fluid in the jacket [Kg] mass flow rate of the cooling fluid [Kg/s] cumulative weight-average molecular weight instantaneous weight-average molecular weight monomer concentration in the aqueous phase [mol/m 3 ] impeller rpm number of radicals in a particle average number of radicals per particle Avogadro’s number number of polymer particles per unit of unswollen volume of particle [particles m3 particle ] inlet number density of polymer particles [particles m3 particle ] total amount of compound i in the reactor [mol] moles of monomer i in the reactor at time zero [mol] aggregation number of surfactant [molecules/micelle] number of micelles number of polymer particles with n radicals number of polymer particles moles of monomer i polymerized [mol] number of precursor particles total amount of monomer i to be feed in a semicontinuous operation [mol] Nusselt dimensionless number impeller power consumption [J s1 ] time-averaged probability of finding an active chain with ultimate unit of type j average molecular weight of the repeating unit in the polymer chain Prandtl dimensionless number heat transfer rate [J s1 ] impeller flow [m 3 s1 ] sensible heat generation rate due to feeding into the reactor [J s1 ] rate of heat losses to the surroundings [J s1 ] heat generation rate by polymerization reaction [J s1 ] 315 .

316 6 Emulsion Polymerization Qs Q stirring Q transfer Re Ri ri R jcrit Rm Rmi R nuc Rp Rpi Rpp RX rv rv ðvÞ Rnk ½Rw ST Sw t T DT Te Tg Tlim Tmax DTml Tonset Tw Twe Tws U V Vi Vd Vw Vp vp Vpol W Wc ðnÞ Wcd ðnÞ volumetric flow rate [m 3 s1 ] rate of heat production by the agitator [J s1 ] heat removal rate [J s1 ] Reynolds dimensionless number net generation rate of component i [mol m3 s1 ] reactivity ratio of monomer i number of oligoradicals of critical length formed from initiator number of radicals of length m number of radicals of length m in particles with i radicals nucleation rate of polymer particles [particles m3 s1 ] overall polymerization rate [mol m3 s1 ] polymerization rate of monomer i [mol m3 s1 ] polymerization rate per polymer particle [mol particles1 s1 ] amount of the ‘‘capping’’ species in controlled polymerization [mol] volumetric growth rate of one polymer particle [m 3 s1 ] volumetric growth rate of a particle of volume v [m 3 s1 ] generation rate of the kth moment of the distribution of inactive chains concentration of radicals in the aqueous phase [mol m3 ] total amount of surfactant in the reactor [mol] amount of surfactant in the aqueous phase [mol] reaction time [s] reactor temperature [K] adiabatic temperature increase temperature of the feed [K] glass transition temperature [K] maximum temperature achievable for a safe operation [K] maximum temperature obtained during an adiabatic polymerization reaction [K] logarithmic mean temperature difference temperature at which the polymerization start under adiabatic conditions [K] jacket temperature [K] inlet temperature of the cooling fluid in the jacket [K] outlet temperature of the cooling fluid in the jacket [K] overall heat-transfer coefficient [J m2 s1 K1 ] reactor volume [m 3 ] volume of monomer i [m 3 ] volume of the droplet phase [m 3 ] volume of the aqueous phase [m 3 ] volume of the polymer particles [m 3 ] volume of a swollen polymer particle [m 3 ] volume of polymer [m 3 ] volume of water [m 3 ] cumulative weight MWD desired cumulative MWD .

UK. 69. Am. Warson. Polymer Dispersions and Their Industrial Applications. (17) viscosity of the reaction medium at the wall temperature [kg m1 s1 ] References 1 J. 1997. (11)] [m2 ] overall mass-transfer rate coefficient [m 3 s1 ] kth-order moment of the distribution of active chains kth-order moment of the distribution of inactive chains frequency of radical entry [s1 ] space time [s] viscosity of the reaction medium at the reactor temperature [kg m1 s1 ] fraction of the heat of reaction used to heat the reactor walls volume fraction of monomer in the polymer particles volume fraction of monomer i in phase j volume fraction of polymer in the polymer particles volume fraction of water in the aqueous phase parameter of Eq. (11)] [mol m5 ] critical length for entry of radicals generated from the initiator consumption rate of small radicals generated by chain transfer [Eq. 2 P. Harkins. Finch. Chem. K. A. Soc. 3 H.. 1947. D. 1428–1444. Chichester. Asua (Ed. John Wiley. Takamura (Eds. Emulsion Polymerization and Emulsion Polymers.References Wj ðnÞ [X] Xi X ni X nij XT XTf DXTj y1cum y1i instantaneous weight MWD of the polymer formed at conversion increment j concentration of ‘‘living agent’’ in controlled polymerization [mol m3 ] conversion of monomer i instantaneous number-average chain length instantaneous number-average chain length of the polymer formed in conversion increment j overall conversion final overall conversion jth overall conversion increment cumulative copolymer composition referred to monomer 1 instantaneous copolymer composition referred to monomer 1 Greek a1 a2 g d h l mk nk r t j F P fM j fi P fp fww C jw parameter of Eq. (29) parameter of Eq. Polymeric Dispersions: Principles and Applications. 4 D. Dordrecht.). Weinheim. Chichester. 5 W. El-Aasser (Eds. 3 vols. 317 . Germany. 2001. M. Urban. 1997. Wiley-VCH. J. 2002. A. C. UK. John Wiley. (30) generation rate of small radicals by chain transfer [Eq. S. Kluwer Academic Press. Lovell.). M.). Applications of Synthetic Resin Latices.

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The first difference is that free-radical polymerization is monomer-based. in radical polymerization it is sufficient 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. under ‘‘Notation’’. Edited by T. all active radical centers from one monomer are identical. Furthermore. It will deal mainly with those polymer reaction engineering aspects which are relevant for designing processes and products.. which just forms the tail of that growing chain. 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. After the formation of an active center (radical. 7. or cationic species).1 Introduction There are several recent monographs [1–7] on anionic and cationic polymerization covering various mechanistic.-M  . anionic. Like free-radical polymerization ionic polymerization is also a chain polyaddition. so here just some fundamental issues which are relevant for reaction engineering will be discussed. from a kinetic point of view there are two major differences between radical and ionic polymerization. KGaA. Weinheim ISBN: 3-527-31014-2 . As it cannot cover the entire subject. Handbook of Polymer Reaction Engineering.323 7 Ionic Polymerization1 Klaus-Dieter Hungenberg This chapter will deal with ionic chain growth polymerization for monomers which are of some industrial importance. So. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. the systems dealt with are chosen as examples of the most important features of ionic polymerization. monomer molecules are added to this active center to form long-chain molecules. However. and they are hardly in1) The symbols used in this chapter are listed at the end of the text. the reactivity of this growing chain in all reactions is determined by the nature of the monomer irrespective of the nature of the initiating radical. J. kinetic and preparative aspects. Meyer. from a practical point of view.

These facts make ionic polymerizations difficult to access for kinetic modeling from a practical point of view in an industrial environment. there are no such system-immanent termination reactions between species carrying the kinetic chain and. but because of their ionic nature there usually exists a complex chemical equilibrium between different species. In cationic polymerization. which irreversibly terminate the kinetic chain. and the presence of other salts. This equilibrium [Eq. þ X @@Pnþ X þ M ! @@Pnþ1 ð1Þ or þ @@Pn Y þ þ M ! @@P nþ1 Y ð2Þ So the kinetic scheme and parameters not only depend on M. ionic polymerization is site-based: that is. In contrast. at least. In free-radical polymerization. . the nature of the active center strongly depends on the nature of the initiator. such as in the elimination of LiH or NaH during anionic polymerization of styrene or butadiene [10–13]. the collapse of ion pairs to covalent species. the influences of penultimate units [8] or solvents [9] are quite small. covalent polarized bonds. (3)] between free ions.324 7 Ionic Polymerization fluenced by the nature of the surroundings. and between associated and non-associated species. or they are even slower. is a true termination reaction. the active centers are not uniform as in free-radical polymerization. There is another important difference between free-radical and ionic polymerization. Y þ $ X d Y dþ $ 1=n ðXYÞn ð3Þ All these species can in principle participate in all the reactions with different rate coefficients. they often occur on a similar time scale to initiation and propagation. are elimination reactions where the eliminated species is not able to re-initiate the polymerization. (1) or (2)]. but they may differ considerably according to the initiator used. In ionic systems. Examples of such reactions. the bimolecular disproportionation and combination between two radicals. contact ion pairs. solvent-separated ion pairs. even if the initiator has a unique structure. there are system-immanent. Furthermore. Propagation is by monomer insertion at an ion pair [Eq. nor by the solvent nor by penultimate units of the chain. Because these termination reactions are very fast (k t ¼ 10 7 –10 9 M1 s1 ) compared to propagation (k p ¼ 10 0 –10 3 M1 s1 ) and radical formation by initiator decomposition (kd ¼ 103 –101 s1 ) the pseudo-steady-state hypothesis can be applied. if there are reactions which terminate the active species. in general. the solvent itself. unavoidable termination reactions. as well as the concentration of these species strongly depend on the polarity or solvating power of the solvent system. where the counter ion comes from the initiator system. as in reaction (4) where the CaF bond is too strong for the ion pair to be reformed again. X þ Y þ $ X ==Y þ $ X .

The active center itself is preserved.2 Anionic Polymerization @@CH2 Cþ HPh þ PF 6 ! @@CH2 CHPhaF þ PF5 ð4Þ Many other similar eliminations are not true termination reactions.. but are transfer reactions..-Pn þ M ! . (6)–(8)]. Another difference between free-radical and ionic polymerization that must also be kept in mind is economic rather than scientific. Thus. the active center may be preserved throughout the reaction. by proper choice of the reaction conditions. but transfer reactions to other molecules such as monomers. so that the kinetic chain length and the length of the individual chain are the same and increase linearly with conversion. The most important systems are those for the anionic polymerization of diene rubbers [14– 325 . SO3 H ! @@CH2 aCðCH3 ÞbCH2 þ H2 SO4 ð5Þ So. polymers. when the eliminated species can re-initiate a new chain. and initiators are more expensive. but in most cases the requirement for purity of monomers and solvents in ionic polymerization is much higher. Living polymerization in its pure form is defined not only by the absence of any termination reaction destroying the active center. so ionic polymerization is chosen only if the monomers do not polymerize by a radical pathway.-P1  propagation ð6Þ transfer ð7Þ re-initiation ð8Þ So.7. of running as a living polymerization.-Pn þ T ! .. or if ionic polymerization offers other advantages. The conversion kinetics is only changed by transfer reactions if the re-initiation is much slower than the propagation step. but also by the absence of any transfer reaction. but they do not change the concentration of active centers. @@CH2 aCþ ðCH3 Þ2 .-Pn þ T T  þ M ! . such as access to molecular structures like block copolymers or specially designed molecular weight distributions. but a new chain is started...2 Anionic Polymerization Anionic polymerization involves a wide variety of reactions leading to high molecular weight molecules with the participation of an anionic species. and so on may stop the individual chain and initiate a new growing chain [Eqs. solvent.-Pnþ1 . especially in many cationic systems. transfer reactions change the molecular weight of the polymer. as in reaction (5). Most of the monomers can be polymerized by radical or ionic mechanisms (see Table 7.1). 7. ionic polymerization offers the possibility. the growth of the individual chains may be terminated by transfer reactions.  . However.

resulting in a so-called ‘‘living’’ polymerization.). Generally. Association Behavior/Kinetics There are numerous publications [1. ketones Type of initiation Radical Cationic Anionic þ   þ þ þ þ þ þ þ  þ þ   þ þ þ þ      þ þ þ þ þ   þ þ   þ þ þ    þ 16]. Here especially. 25.1 .3. 6] dealing with the equilibrium of Eq.1. methacrylamide Vinyl ethers N-Vinylcarbazole N-Vinylpyrrolidone Aldehydes. styrenic polymers. a-methylstyrene. the vinyl content increases with the fraction of free ions. 5. methacrylonitrile Acrylamide.2. and so on has gained scientific and industrial importance:  These monomers may be polymerized under such conditions that termination and transfer reactions are absent. (3) from the right to the left (see Table 7. So the microstructure of dienes strongly depends on the counter ion (see Table 7. (3) between free ions as one extreme possibility for the structure of the initiating and/ 7. 7.  The microstructure of the polydienes so produced can be varied over a wide range. lactones.3-Dienes Styrene. methacrylates Acrylonitrile. polymers from ethylene oxide and propylene oxide are important as base materials for polyurethanes [22–24].1-Dialkyl olefins 1. a-methylstyrene Halogenated olefins Vinyl esters Acrylates. which are capable of shifting the equilibrium in Eq. Monomers with different initiation mechanisms. or lactams. 7.2. An attempt to rationalize the influence of polar additives on the microstructure is given in Ref.2.1 Anionic Polymerization of Hydrocarbon Monomers – Living Polymerization There are two main reasons why anionic polymerization of hydrocarbon monomers such as styrene.326 7 Ionic Polymerization Tab.1. butadiene. and block copolymers of styrene and dienes [17–21] as well as the ring-opening polymerization of cyclic ethers. Monomers Ethylene a-Olefins 1. isoprene.) and the solvent or the presence of additives.

4 [ %] 1. Alkali metal cis-1. depending on the structure of P (monomer or initiator). where n gives the association number.2 Anionic Polymerization Tab. In particular.2 [ %] Diethyl ether Diethyl ether THF THF THF Diglyme Diglyme Diglyme 10:1 5:1 6:1 3:1 1:1 4:1 2:1 1:1 16 10 43 25 17 87 85 78 327 .4). For example. 7.2 [ %] Li Na K Rb Cs 35 10 15 7 6 52 25 40 31 35 13 65 45 62 59 or polymerizing species. 28] for the overall propagation rate coefficient k p  K 1=2 of the equilibrium system from monomeric and dimeric polystyryllithium in benzene and cyclohexane. solvent.7. 7. 200 M1 s1 for the ion pair [26]. and the rates for the same reaction may differ by several orders of magnitude depending on the species involved. are still under debate. and temperature (see Table 7. K ass ðPaLiÞn !  nPaLi ð9Þ Tab. which generally is between 2 and 6. All these species may participate in the polymerization. one of the most important industrial systems. Vinyl content of polybutadienes produced in hydrocarbon solvent with butyllithium as initiator with different additives (from [28a]). and the determination of the kinetic scheme and parameters. Microstructure of polybutadienes produced in hydrocarbon solvent with different counter ions (from [25a]). and aggregation of more or less covalently bonded species as the other extreme.4 [ %] trans-1.024 M0:5 s1 are reported [27.2.3. the propagation rate coefficient for anionic polymerization of styrene in THF at 25 C is 8  10 4 M1 s1 for the free ion. the association behavior is formulated as in Eq. (9). the question of association in lithium-based polymerization in nonpolar solvents. and values of 0.0155 and 0. Additive Molar ratio additive/lithium 1. In general.

(11). 1. pp.328 7 Ionic Polymerization Tab. With the assumption that association is high and the concentration of the monomeric species is low.8 4 4 1. when one is trying to set up a realistic mechanistic process model.  ½PaLi ¼ K ass ½PaLi0 n 1=n ð10Þ Assuming that the associated species are not reactive. 20. 16. where PaLi is either the initiating lithium alkyl or the propagating species. Extensive discussions on this subject are summarized in Refs. the reaction rates for initiation and propagation are given by Eq. Here. 138. but in every case of ionic polymerization. 7. Association number for different Li organyls. 6.   K ass 1=n 1=n 1=n r ¼ k½PaLi½M ¼ k ½PaLi0 ½M ¼ kobs ½PaLi0 ½M n ð11Þ This correlation of the association number with the reciprocal of the reaction order may be too simple. 5.4.3 2–3. where k is either ki or k p. (10).3 6 2–2. Therefore the anionic polymerization of hydrocarbon monomers in hydrocarbon solvents. and 29–33.1 4 4 2 2 1 2 2 2 2 2 2–4 2–4. which is one of the best-investigated anionic .[a] Li alkyl Solvent n n-BuLi benzene cyclohexane THF cyclohexane benzene THF benzene hexane cyclohexane benzene THF benzene cyclohexane hexane benzene hexane cyclohexane cyclohexane benzene hexane 6–6. or at least they are much less reactive than the non-associated one. just an overview of the various interpretations is given without trying to judge which is the right one. the concentration of the monomeric species is given by Eq.7 2 sec-BuLi t-BuLi Menthyl-Li Benzyl-Li Poly(styryl)-Li Poly(isoprenyl)-Li Poly(butadienyl)-Li [a] Compilation of data given in Ref. 6. similar questions must be answered.

extrapolating the association behavior from low to higher temperatures may cause errors.2 Anionic Polymerization systems. 35 this problem is addressed for the cross-association of styryland butadienyllithium.00001 0. 6). (10) is only valid if the concentration of non-associated species is low. the concentration of non-associated PaLi is given by Eq. Bywater discussed [42. Furthermore. 41].01 0. One reason for the debate is the high sensitivity of ionic systems to impurities. 7. which are at considerably higher temperatures (60– 100 C). for n ¼ 2 in the case of styrene.004 1/T / 1/K Fig. So. s ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi  K ass K ass 2 K ass ð12Þ þ þ ½PaLi0 ½PaLi ¼  4 4 2 Figure 7. Nevertheless. 329 . In addition it must be stated that Eq.7.1 0. there are some reports on the separate determination of K ass . cross-aggregation between initiating and propagating species is likely to occur and must be considered. dimers.1. Otherwise the equilibrium of Eq.0035 0.00000001 0. There are a number of recent publications reporting much higher association numbers of up to 100 and more [36–39]. (9) must be considered a priori: for example. is used here as an example to point out which aspects may become important for reactor and process layout. When the fraction a of non-associated polystyryllithium is calculated with the ˙ 10000000 1000 -1 K ass / M kp / M s 10 10 -1 10000 0.0025 0. [44–47]. 43] the difficulties in separating K ass and k p .1 gives the temperature dependence of K ass and k p for styrene from Ref. Association equilibrium constant K ass and propagation rate constant k p as f ðTÞ [44]. However. 44. which may cause experimental errors leading to various interpretations of the data. which are under discussion [40.1 in Ref.001 0. as well as intermediate equilibria between hexamers.003 0. 47. which however are contradictory. most of the data are from investigations at rather low temperatures (< 30 C) compared to industrial conditions. (12). In Ref. for dienes various orders are reported with differences between fractional reaction order and degree of aggregation (see Table 7. and monomers. from a mechanistic point of view also there are arguments that this simple correlation does not seem to be a general rule. For styrene with t-butyllithium initiation is reported to be independent of monomer concentration [34]. With the exception of those in Ref. tetramers.

4:5  10 8 2:6  10 9 2:9  10 11 5:2  10 8 5:1  10 7 6:8  10 8 60. In Ref.01 0.3 64. (12). simplification in Eq.001 M.3 56. Fig. þ. ˚ kOp. 0 [MC0:5 sC1 ] Ea [kJ molC1 ] Solvent Temperature [ C] Ref. So. Broken lines: exact solution according to Eq.000001 0.0001 M.6 none none cyclohexane benzene toluene toluene 20–50 4–21 30–50 10–30 20–50 30–60 49 50 51 27 52 53 .6 60.001 0. In Ref. 0. full lines: approximate solution according to Eq. 10 an attempt is made to describe the propagation over a wider tem- Literature values for propagation rate coefficient kp0 ¼ k p ðK=2Þ 0:5 for Li-initiated styrene polymerization in hydrocarbon solvents.9 63. (10). for industrial temperatures the fraction of associated species may be rather low and a first-order kinetic law with respect to lithium concentration may result [10.01 1 Fraction a of non-associated species as a function of K ass for dimerization for various polystyryllithium concentrations (b. Figure 7. 0. even when considering the same solvent and a rather limited temperature range of 4–60 C. 48 data for styrene and butadiene are given up to 70 C assuming n ¼ 2 for styrene and n ¼ 2 or 4 for butadiene. (11) with n ¼ 2.0 78.2 shows that there may be considerable deviations for values of K ass ¼ 105 M and higher.3 it can be seen that there are deviations of one order of magnitude between the results of different authors. More difficulties will arise when extrapolating to higher temperatures and tackling the problem of temperature dependence of the association behavior.7 Ionic Polymerization 10 1 α 330 0. Tab. 7. 7.2. From Figure 7.0001 Kass / M 0. 33].1 0. Table 7.01 M). 0.5.5 gives some examples of the temperature dependence of the propagation rate coefficient for Li-initiated styrene polymerization according to Eq. (10) and the correct solution in Eq. (12). .

This somewhat extensive discussion on the association behavior of lithiuminitiated polymerization. perature range. initiation and propagation [(Eqs.0031 0.2 Anionic Polymerization 1 acc. 6. 55].1. (12). 7. 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. to [53] acc.3.0035 0.2 331 .0032 0. with k p ¼ 1  10 11 e7900=T M1 s1 and K ¼ 3:2  10 38 e27600=T M according to Eq.0033 0. and careful checking of literature kinetic data is strongly recommended before they are used for reactor layout. shows the difficulties in kinetic modeling of ionic polymerization. to [52] 0. the best-investigated ionic system.0034 1/T / K -1 0. to [49] acc. from 10 C up to 100 C. irreversible termination and transfer reactions being absent. to [50] acc.001 0.0001 0. There is still an ongoing debate on the exact definition of living polymerization [5.2. Contrary to free-radical polymerization. Comparison of literature values for propagation rate coefficient kp0 ¼ k p ðK=2Þ 0:5 for lithum-initiated styrene polymerization in hydrocarbon solvents. the existence of all possible different species must be considered for every system under investigation. which collapses to a simple firstorder kinetic with respect to initiator above 40 C. 7.01 1/2 kp K / M s -1 -1 0. (13) and (14)] are the only reactions.0037 Fig. to [51] acc.1 0. Molecular Weight Distribution of Living Polymers The living nature of the anionic polymerization of hydrocarbon monomers has been revealed by Szwarc [54.003 0.0036 0. 55–57]. to [27] acc. There is no judgment on the quality of the various results.7. but this overview can serve as an example for the difficulties in ionic polymerization kinetics in general.

even if they do not participate in a propagation reaction. From the reactions in Eqs. (21)– (23). but they are in equilibrium with the active non-associated species on a much shorter time scale than the overall reaction. the associated species discussed above can also be called living. the set of differential equations (15)– (20) can be derived. (13) and (14). so monomer conversion and the kinetic chain length are given by Eqs. but if it is known quantitatively it can be considered by making the rate coefficients a function of [PaLi].332 7 Ionic Polymerization I þ M ! P1 initiation ð13Þ  P1 þ M ! Piþ1 propagation ð14Þ In the sense of this definition. ½M ¼ ½M0 ek p ½I 0 t ð21Þ ½M0  ½M ½M0  ½M0 ekP ½I 0 t ½M0 ¼ ¼ xM ½I 0 ½I 0 ½I 0 ð22Þ ½Pi  ¼ ½I 0 ð23Þ n¼ with y X i¼1 . in the following discussion the association is not considered explicitly. For simplicity.  d½I  ¼ k i ½I ½M dt ð15Þ  y X d½M ¼ k i ½I ½M þ k p ½M ½Pi  ¼ RP dt i¼1 ð16Þ  d½P1  ¼ k i ½I ½M þ k p ½P1 ½M dt ð17Þ  d½Pi  ¼ k p ½Pi1 ½M þ k p ½Pi ½M dt ð18Þ y X ½Pi  ¼ ½I 0  ½I  ð19Þ i½Pi  ¼ ½M0  ½M ð20Þ i¼1 y X i¼1 For fast initiation (k i g k p ). all initiator is transferred to growing chains immediately.

2 Anionic Polymerization The resulting frequency distribution hðiÞ of chain lengths i can be derived by solving the system of differential equations sequentially starting with ½P1 t¼0 ¼ ½I 0 and the definition of the kinetic chain length given above [Eq. (23) becomes invalid and must be replaced by Eq. meaning if the initiation rate coefficient is in the order of k p or even less. with R ¼ r  1. (26)–(28). but must be found numerically. Pn ¼ ½M0  ½M ¼1þn ½I 0 Pw ¼ 1 þ n þ D¼ ð26Þ n A 1 þ Pn 1þn ð27Þ Pw A1 Pn ð28Þ If.and weight-average degrees of polymerization and the polydispersity for this Poisson distribution are given by Eqs.7. From Eqs. k i g k p does not hold. (15) and (16). (29) with r ¼ k p =k i > 1. The averages of this distribution are given by Eqs. hðiÞ ¼ ½Ni  ¼ y X ½Ni  i¼1  i y r qu X uj e R j! j¼i rð1  eu=R Þ ð30Þ 333 . wðiÞ ¼ nði1Þ en ði  1Þ!ðn þ 1Þ ð25Þ The average number. there is no immediate conversion of initiator to growing chains and the simplification of Eq. (25). The frequency and weight distributions of the socalled Gold distribution are given by Eqs. 58 and 59. (32) and (33). ½Pi  ½Pi  nði1Þ en ¼ hðiÞ ¼ X ¼ ði  1Þ! ½Pi  ½I 0 ð24Þ The weight distribution is given by Eq. (19). The solution for this general case is given in Refs. however. ½M  ½M0 ¼ ð1  rÞð½I   ½I 0 Þ þ r½I 0 ln ½I  ½I 0 ð29Þ The variation of M and I with time cannot be solved analytically in this case. the variation of monomer conversion as a function of initiator conversion is given by Eq. (24)]. (30) and (31). q ¼ r=R and u ¼ ðr  1Þ lnð½I 0 =½I Þ.

If chain initiation is delayed for some chains (k i < k p ). the Gold distribution for (k i < k p .01 0 0 50 100 150 i Fig. with the peak maximum at 2½M0 =½I 0 .7 Ionic Polymerization wðiÞ ¼     y i½Ni  r i ru=ðr1Þ X uj ru u=R e Þ þ ¼ ð1  rÞð1  e y X r1 R j! j¼i i½Ni  ð31Þ i¼1 ð1  rÞð1  eu=ðr1Þ Þ þ Pn ¼ ru r1 ð32Þ ð1  eu=ðr1Þ Þ ru 1  ru þ 2ru þ ð2r  1Þðr  1Þð1  eu=ðr1Þ Þ r  1 r  1 Pw ¼ ru ð1  rÞð1  eu=ðr1Þ Þ þ r1 ð33Þ A Poisson distribution will also result when using bifunctional initiators [60]. Pw ¼ 64.4 gives a comparison of the Poisson distribution for n ¼ 50 (k i > k p ). hðiÞ ¼ p i1 ð1  pÞ (34) The width of the distributions reflects the sharpness of the initiation reaction. just reflecting some statistics of monomer addition.04 h(i) 334 0. 64. and 52. and the Schulz–Flory or most probable distribution resulting from step growth polymerization or free-radical polymerization with termination by disproportionation. 7. Figure 7. with k i > k p all chains start at the same time and the distribution is very narrow. Pw ¼ 102. Comparison of various distributions for Pn ¼ 51: Schulz–Flory distribution with p ¼ 0:98. 200 . the distribution is skewed and will become narrower if reac- 0.4.03 Gold 0.05 Poisson 0. r ¼ k p =k i ¼ 100). and Poisson distribution for n ¼ 50.02 Schulz-Flory 0. This most probable distribution is given by Eq. Gold distribution with r ¼ k p =k i ¼ 100. The corresponding weightaverages are 102. where p is the conversion of end groups in step growth polymerizations or polycondensation or the probability of propagation in chain growth polymerization. u ¼ 86:513.06 0. (34).

For laminar plug flow reactors [75. the value which is usually assumed to be typical for living polymerization and used as a criterion for ‘‘livingness’’. The monomer may be consumed before initiator conversion is complete. ½I0 ¼ 0:101 M. Besides the reactivity ratio r. can also have an impact on broadening the molecular weight distribution [61–73]. In ideal plug flow reactors under steady-state conditions.2 0. The MWD resulting from semi-batch operations of a stirred tank reactor with monomer feed under various conditions is treated in Refs. if radial diffusion of the monomer occurs from the inner tube to the walls. Fig.and weight-averages at xM ¼ 1 are 31 and 34 for r ¼ 10.3 xM D 0.4 0. because of the possibility of very long chains growing near the reactor walls. ½M0 ¼ 3 M.6 0. 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 flow reactor [74. 75]. (32).4 1. The broadest distribution is the most probable distribution if. The long-term stability of laminar flow tubular reactors is questioned [76].1 0. where the residence time approaches infinity. Slow initiation has some important consequences.5.8 1. and (33).2 Anionic Polymerization 1. but there are also a number of publications dealing with other reactors. there is no initiation but only chain propagation. and 51 and 64 for r ¼ 100. depending on ½M0 =½I 0 and conversion. 77–82. the steady-state concentrations of monomer and initiator can be derived from the monomer and initiator mass bal- 335 .7. the polydispersity may be considerably higher than 1. 7. as in step growth polymerization. which are shown in Figure 7. 76] some broadening of the distribution is observed. and for fast initiation the MWD is a Poisson distribution. Number.2 1 0 0 0.2 0.6 1. tion proceeds and more chains will be initiated and propagate. In a homogeneous continuous stirred tank reactor (HCSTR).8 1 xI Polydispersity D and monomer conversion xM as a function of initiator conversion xI for r ¼ 10 (full lines) and r ¼ 100 (broken lines) according to Eqs. Moreover. This may be important when using functionalization techniques or synthesizing block copolymers.4 1 0. (29). The MWD discussion up to now has concerned batch reactors. active and dormant species – which may have different reactivities in propagation reactions. the equilibrium between different species – associated and non-associated ones or free ions and ion pairs.5.

neglecting volume changes. and vin. This results in a Schulz–Flory distribution [83] [Eqs. The influence of termination. up to a value approaching that of a batch reactor for high conversions or long mean residence times. M are the volume feed flows of initiator and monomer. growing to very long molecules. Side Reactions Pure living polymerization of hydrocarbon monomers usually occurs at low temperatures. (34) with the propagation probability given by Eq. At higher temperatures. I . which must be solved simultaneously. I ½I f t ½I  ¼ V k i ½Mt þ 1 ð36Þ In a CSTR.3 . 86.  j1 1=t kP ½M hð jÞ ¼ kP ½Mt þ 1=t kP ½M þ 1=t  wð jÞ ¼ j 1=t kP ½Mt þ 1=t 2  ð37Þ j1 kP ½M kP ½M þ 1=t ð38Þ Pn ¼ 1 þ kP ½Mt ð39Þ Pw ¼ 1 þ 2kP ½Mt ð40Þ Equation (37) is equivalent to Eq. M ½Mf t V ½M ¼ k i ½I  þ kP k i ½M 2 ½I t 2 þ ½M ð35Þ vin. where side reactions are not important. ½Mf and ½I f are the feed concentrations. chain transfer.1. two side reactions do become important. 7. vin.2. the narrow Poisson distribution resulting from the chemistry is superimposed by the broad residence time distribution of the HCSTR – chains can leave the reactor after seconds of growth as very short chains. and longchain branching in batch and CSTR reactors is described in Refs. however.336 7 Ionic Polymerization ance. 31. (41). (37)–(40)]. (35) and (36). but there are also chains which reside in the reactor for very long time. p¼ kP ½M kP ½M þ 1=t ð41Þ 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. V is the reactor volume. 84 and 85. vin. where t is the mean residence time and [M] is the steady state-monomer concentration. by Eqs. 6. elimination of LiH and transfer to compounds with an acidic hydrogen [5. 87].

and for the influence of polar additives [104]. k tt ¼ 1:0  10 10 expð11798=TÞ s1 for s-BuLi and k tt ¼ 9:5  10 10 expð13407=TÞ s1 for n-BuLi can be evaluated. which is unable to propagate (see Scheme 7. the LiH elimination is followed by proton transfer to another polystyryllithium [93]. this elimination also depends on the reaction system. 89]. Polybutadienyllithium is somewhat more stable than polystyryllithium (k tt ¼ 6:7  105 s1 versus 1:9  104 s1 at 93 C [13]). resulting in an allylic anion. because the number of active chain ends PsH . For polystyryllithium. ethyl benzene and so on (Scheme 7. 103] and toluene. 99–101]. but rather similar values were obtained (k tt ¼ 2:4  10 6 eð8459=TÞ ).2). Bu Li Bu k tt + LiH i i + Li Bu + + PsLi i Scheme 7.1. Quantitative data for LiH elimination are given in Refs. and from polydienyllithium to alkenes [102. and in ethereal solvents proton abstraction or ether cleavage may occur [92]. The same holds for polystyrylsodium [94]. 95 the influence of THF was investigated. In Ref.1). 89. with first-order decomposition half-lives of 1–6 h at 87–98 C [88. The other class of important side reactions is transfer to compounds with acidic hydrogen atoms. Some quantitative data have been given for chain transfer from polystyryllithium to aromatic solvents [10.7. 91].2 Anionic Polymerization 337 There have been some investigations on the stability of alkyllithium derivatives and of growing chains. There is usually no effect on the polymerization rate. linear alkyllithiums are more stable than branched ones. As with all rate coefficients of ionic polymerization. 47. 33.and polystyryllithium are less stable. From Ref. Growing chains such as polydienyl. that is to say the half-life for the active chains is much higher (hours) than the half-life for propagation (seconds) at temperatures of 80 C and higher. 13 (k tt ¼ 295  e5280=T s1 ) and 10 (k tt ¼ 3:92  10 6 eð8700=TÞ ). but contrary to styrene. such as toluene. Generally. - Bu i Termination in anionic polymerization of styrene. It must be noted that these termination reactions are much slower than propagation. 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. the side reactions here may cause coupled and branched polymers [95–98].

either as statistical copolymers or block copolymers.338 7 Ionic Polymerization Bu Li Li Bu + k tr i + i Li Li + kp 1 Scheme 7.2. 33 and 99 it is pointed out that the presence of transfer reactions may be advantageous. 120]. This issue has seldom been addressed [35. which was developed originally for free-radical polymerization. The effect of side reactions. in Refs. This difference becomes important when considering the dependence of copolymer composition on conversion. 7. but the chain length of the macromolecules. the molecular weight. 66 and 105–119. for homopolymerzation of styrene in a CSTR. and this is the lifetime of the growing chain. But in spite of this complex association behavior. is maintained. or spontaneous termination and transfer to monomer or impurities. Transfer to ethylbenzene in anionic polymerization of styrene. However. on the molecular weight distribution are dealt with in Refs. From a kinetic point of view the association behavior discussed above becomes even more complex because of the possible cross-association between the different growing chain ends. The presence of transfer reactions limits the production of block copolymers by sequential addition of monomers to the living chains. is reduced. (42)] with two copolymerization parameters. such as termination by monomer.4 F1 ¼ r1 f12 þ f1 f2 þ 2f1 f2 þ r2 f22 r1 f12 ð42Þ However. Copolymerization The most important copolymers are those from styrene and butadiene. for example. in most cases the simple Mayo terminal model [Eq. Equation (42) gives the copolymer composition or mole fraction F1 of monomer M1 in the polymer as a function of mole fraction f1 in the monomer . they generally result in some broadening of the distribution.2. because they reduce the amount of initiator necessary to get the desired molecular weight. there is one important difference between free-radical and living anionic polymerization.1. that is. is in many cases sufficient to describe anionic copolymerization also. impurities.

This difference in composition from chain to chain is called first-order chemical heterogeneity. kBB ¼ 0:084. and where new chains are initiated throughout the overall reaction time by decomposition of radical initiators such as peroxides or azo compounds. however. every chain will see all the changes in monomer feed composition. as in living polymerization. The severity of the chemical heterogeneity strongly depends on the copolymerization parameters. Increasing conversion First-order chemical heterogeneity I-BBBBBSBB I-BBBBBSBB I-SBSBSSBS I-BBBBBSBB I-SBSBSSBS I-SSSSBSSS Second-order chemical heterogeneity R-BBBBBSBB-Li R-BBBBBSBBSBSBSSBS-Li R-BBBBBSBBSBSBSSBSSSSSSSSS-Li Scheme 7. Because of the different reactivity of the monomers. one between different chains. for one pair of monomers.3.2 Anionic Polymerization feed for incremental conversion. This is known as second-order chemical heterogeneity. the resulting overall 339 . Chemical heterogeneity with increasing conversion for free-radical (first-order) and living polymerization (second-order). These extreme values have a very drastic effect on the shift not only in composition but also in rates. usually f1 and consequently F1 change with increasing conversion. all chains start at the same time and live throughout the polymerization. where the lifetime of the growing polymer chain is in the order of seconds or less. are shown in Scheme 7. which may depend somewhat on temperature. compared to hours for the overall polymerization reaction. kBS ¼ 0:0066 M1 s1 ). In free-radical polymerization there is just one pair of parameters. kSB ¼ 110. The differences between these two kinds of heterogeneities.6). and consequently the composition will change along the chain and not from chain to chain. If. those chains which are initiated at different times or levels of conversion will differ in their composition.7.3. In free-radical polymerization. but those which are initiated at the same time will have the same composition. Taking the absolute rate coefficients given by Ohlinger [35] for Li-initiated copolymerization of butadiene and styrene at 20 C in toluene (kSS ¼ 0:45. the other within different fractions of one chain. whereas in ionic polymerization these parameters for every pair of monomers strongly depend on the counter ion and solvent polarity (see Table 7.

7. 6.2 12. Fig.2 0.1 7 0.1 11 0.04 0. during copolymerization nearly all the butadiene is consumed at a lower rate than in homopolymerization before styrene is incorporated to any appreciable extent.4 xS = 0. 35.8 xS = 0 xS = 0. 7.004 0.3 4 1.7 [a] Examples taken from Ref.4 11. The interesting feature is that even though the homopolymerization of styrene is faster than that of butadiene.65 0.025 0.035 0.04 5.[a] ˚ T [ C] Solvent r1 r2 25 20 30 50 30 78 0 25 25 bulk toluene benzene cyclohexane heptane THF THF THF diethyl ether 0.6.6 xS = 0. Simulation of overall conversion with data from Ref.6 and 7.6. 247ff. p.2 0 0 5000 10000 15000 20000 t/s Batch copolymerization of styrene and butadiene with n-butyllithium (1 g) at 20 C in toluene (10 kg) with various styrene feed fractions xS (20 mol monomer overall).5 0.9 10 15. Copolymerization parameters for Li-initiated copolymerization of styrene (¼ M1 ) and butadiene (¼ M2 ). 1 xS = 1 0. and after the butadiene is consumed the overall polymerization rate becomes that of pure styrene.3 0. 7.35 conversion 340 0.7 Ionic Polymerization Tab. conversion versus time curves are given in Figures 7. 25000 30000 .

6 one can see that a similar but reverse situation is valid in polar solvents. Thus. there is a block of nearly pure butadiene with some isolated styrene units. From Table 7.7. Overall. This combination is responsible for nearly all chain ends existing as butadienyllithium ends. The reason is that kSB has a high value and kBS has a low value. in a batch copolymerization. there will be a very fast addition of butadiene to regenerate butadienyllithium ends. here styrene is consumed first and then butadiene. Batch copolymerization of styrene and butadiene with n-butyllithium (1 g) at 20 C in toluene (10 kg) with various styrene feed fractions xS (20 moles monomer overall). there are two important tasks in tailoring polymers: one concerns their chemical distribution and the other the molecular weight distribution.35 0. 7.4 x S = 0. therefore. but again a copolymer with nearly pure blocks of homopolymer will result.8 x S = 0.5 0.6 xS inpolymer x S = 0. Simulation of mole fraction of styrene in copolymer with data from Ref.5 341 . followed by a rather short block where styrene and butadiene are incorporated at almost the same rates – a so-called tapered block. 7.2 Anionic Polymerization 0. If one of the occasional propagation reactions by addition of styrene gives a styryllithium chain end. which predominantly propagate by addition of butadiene (kBB > kBS ).3).2. Incorporation of styrene will increase only when nearly all the butadiene is consumed.2 0 0 5000 10000 15000 20000 25000 30000 t/s Fig. followed by a final block of nearly pure styrene (see Scheme 7. Tailor-made Polymers by Living Polymerization – Optimization Anionic living polymerization offers a unique opportunity for tailor-made polymers because all the chains and their living ends are accessible throughout the course of the reaction.7.65 0. In general.1. very few styrene units are incorporated into the chains during the first part of the reaction and they exist as isolated units. 35.

and homogeneous copolymers with the comonomer units randomly distributed along the chain.4.S k tt k p .4. is described in Ref. where the reactors are operated in an isokinetic way.t-Li Scheme 7. These are obviously the ratios for transfer and termination at higher temperatures. 121–127]. there are several possibilities. 129] initiators (see Scheme 7. In principle. Dead chains SSSSBBB + SSSSBBBSSSS Pathway to SBS tri-block copolymer and possible side products.5 and Eq. 130.i +lS R-So-Bup -Sr ––Li + R-Buq-Ss-Li + R-S . Bu + m Bu R-So-Bup-L -L + R-Li -Li + R-Buq-Li k Bu S k p .342 7 Ionic Polymerization The structure of copolymers in terms of composition or sequence length distribution may vary between two extremes – copolymers with a very high level of chemical heterogeneity within each chain. where the route from a monofunctional initiator to a three-block copolymer is shown as an example). From Figure 7. Reactivity ratios i for side reactions R-Li ki k p. block copolymers are accessible by sequential addition of monomers to either monofunctional or bifunctional [128.i SSSSBBBBB + BBBBB k tr k p . (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. One is . The optimal production of tri-block copolymers in a series of CSTRs.S +nS SSSSSS R-So-L -Li + R-Li -L k S Bu k p . but also the ratios for initiation and the cross-propagation reactions. The various pathways to block copolymers are described in a number of reviews and monographs [6. To produce a copolymer with a more random structure in spite of the extreme values of the copolymerization parameters. and so the yield of tri-block copolymers is reduced. The amount of undesired byproducts – homopolymers or di-block copolymers – depends on the reactivity ratios relative to propagation given in the scheme.

157–159] in a CSTR or a series of CSTRs. and the low content of residual styrene and oligomers in the final polymer [145–147]. 138] and oscillating feeds to homogeneous CSTRs offer the possibility of a wide range of MWDs [139–144]. but heat removal is by a countercurrent nitrogen stream. where there is no shift in composition. ½M1 0  ½M1  ¼ ½M2 0  ½M2  ½M1  þ1 ½M2  ½M2  þ1 r2 ½M1  r1 ð43Þ A third possibility is model-based feed control [133]. the requirements for purity of the reagents. Semi-batch operation with a programmed initiator feed [137. Optimized reactor operations for broadened or bimodal distributions in a tubular reactor are described in Refs. increase the costs for feed preparation compared to free-radical processes.2 Anionic Polymerization to use small amounts of polar additives such as THF. These rubbers are generally produced in aliphatic solvents [6. can be varied by the addition of polar compounds (see Table 7. The vinyl content. often with activated aluminum. 7. alkoxides. solvents. Industrial Aspects – Production of Living Polymers In general. The other important task is to tailor the molecular weight distribution of the polymer. Another obvious method is to polymerize in a continuous stirred tank reactor. Necessary distillations and/or adsorption towers. 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. The main reason for this interest is the high rate of polymerization which can be achieved compared to free-radical polymerization. 33 and 156. Anionic polymerization of styrene has attracted much attention during recent years and several publications and patents have been published on this issue. 152. and especially for this task the ‘‘livingness’’ in anionic polymerization is advantageous [134]. where butadiene is fed to a mixture of styrene and butadiene in such a way that a certain monomer ratio is maintained. Some are using recirculated loop reactors [148–151] or single-pass tubular reactors [75. For the steady state.7. which is usually about 10% in aliphatic solvents. 135 and 136. to bring the extreme r-values nearer to unity. and so on as modifiers [131. (43)].6 343 . ethers. 132]. A spray tower [155] has a similar residence time distribution. One problem seems to be fouling or gel formation in regions of the reactor where the flow of living chains is limited [76]. 153]. which may be segmented [154]. and monomers are much higher in anionic polymerization than in free-radical polymerization.3) over a wide range. which in many cases are operated in an adiabatic or at least non-isothermal mode.7).1.2. the copolymerization equation can be written as a function of feed (index 0) and reactor concentrations [Eq. The latter is mainly used as the rubber component in the production of HIPS (high impact polystyrene). Boiling CSTRs are described in Refs. There are several concepts for an anionic process.

However. or in a solution process using lithium initiators (S-SBR). 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.344 7 Ionic Polymerization Tab. 170] to control the comonomer distribution.2. cyanoacrylates (iii). 160–166] as well as (semi-) batch processes (167.5.or bifunctional initiators) [172–175]. almost no industrial applications have H H H CH3 H CN H COOR H COOR H COOR i ii iii H H H H H CN H COR iv Scheme 7. 168) with a controlled feed of butadiene [133. and on the sharpness of the transition between the various blocks. v Monomers with heteroatoms for anionic polymerization. These sequences depend on the functionality of the initiator (mono. . Another reason for apportioning the monomer feed is the limited heat removal capacity of the reactor. Catalyst cis-1.5). 7. There are continuous processes [157. 7. a free-radical polymerization. methacrylates (ii). 169] to maintain a constant monomer ratio. which however gives crosslinked polymers. Microstructure of polybutadienes produced in hydrocarbon solvent with different catalyst systems. 158. Randomizers are often used [131.4 [ %] 1.4 [ %] trans-1. and vinyl aldehydes or ketones (v) (see Scheme 7.2 [ %] Nd Co Ni Ti Li 98 96 96 93 36 1 2 3 3 52 1 2 1 4 12 Copolymers from styrene and butadiene (SBRs) with a more or less random comonomer distribution are produced either in an emulsion polymerization process (cold or hot E-SBR).7. 177]. nitriles (iv).2 Anionic Polymerization of Vinyl Monomers Containing Heteroatoms The possibilities of living polymerization described above have always attracted researchers toward extending this technique to other vinyl monomers such as acrylates (i). on the use of coupling agents [176.

A + H CH3 H COOMe A CH2 O ð44Þ OMe H3C The most important side reaction is the attack at the ester group. The t-butyl group is reported to prevent side reactions. especially the polymerization temperature. (47)].7. In general.or intramolecular [Eqs. (45). which can be polymerized by very weak bases such as water or skin proteins and which are used as superglues. the kinetic formalism for the heteroatom-containing monomers is the same as that described in Section 345 . H A + CH2 C COOR CH2 C + AH ð47Þ COOR 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. The propagating center in the anionic polymerization of (meth)acrylates is the ester enolate anion. (45) and (46)]. (45) is usually not reactive enough to initiate another chain. (44).2 Anionic Polymerization been developed up to now for this group of monomers. which can be inter. which make them hardly accessible in industrial applications. The reason for this deficiency in application is the presence of side reactions. this vinyl ketone is rapidly incorporated into the chain. which can only be suppressed by proper selection of the structure of the monomer itself and the reaction conditions. The alkoxide from reactions such as Eq. and a relatively unreactive dormant end group is produced. 5 and 7. These side reactions can be suppressed to some extent at temperatures below 0 C. An interesting example of the application of these monomers are the cyanoacrylates. Generally. H CH3 H COOMe CH3 H + R CH3 CH3 OMe O H3C O O ð45Þ CH3 CH2 OMe O MeO Me COR H CH3 CH2 + O O H3C + HC O 3 O OMe OMe ð46Þ Another side reaction is the enolization of acrylate polymer chains [Eq. Some overviews can be found in Refs. which is formed according to Eq.

and there is just the release of ring strain to make chain growth of cyclic monomers an exothermic reaction. 178 and 179. for example. (50).2. lactones and lactides.2. the anionic polymerization of (meth)acrylate monomers has not yet gained industrial importance. They cannot all be covered here. lactams. After completion of the polymerization. but there are a number of monographs and reviews on this subject [181–185]. but side reactions are more important. In polymerization via double bonds the driving force for chain growth is the energy difference between one double and two single bonds. Amines such as tri-n-butyl amine are used as initiators.2.2. Some recent developments in the polymerization of these monomers have been described in Refs. aðaCH2 aOaÞn CH2 aOH ! aðaCH2 aOaÞn1 CH2 aOH þ CH2 O ð49Þ 7. epoxides. for example by esterification with acetic anhydride to prevent the unzipping reaction of Eq. and cyclosiloxanes.346 7 Ionic Polymerization 7. However. It is polymerized [180] via its carbon–oxygen double bond to give polyacetal homopolymer or polyoxymethylene [Eq. nCH2 O ! ðaCH2 aOaÞn ð48Þ The polymerization is a precipitation polymerization from gaseous formaldehyde in an inert solvent such as cyclohexane at fairly low temperatures to prevent depolymerization reactions. The only monomer with some industrial importance is formaldehyde. (49). DGP ¼ DHP  TDSP (50) . cyclic carbonates. The Gibbs free energy of polymerization DGP is given in Eq. (48)]. cyclic sulfides. monomers with heteroatoms at the double bond can also be polymerized via an anionic mechanism. In ring-opening polymerization the number and nature of the bonds remain the same. it is necessary to stabilize the hydroxyl end groups. The polymer precipitates in the dispersing agent as powder. 7. which in most cases is high enough to overcome the loss in entropy when going from monomers to polymers.3 Anionic Polymerization of Monomers Containing Hetero Double Bonds Besides monomers containing carbon–carbon double bonds. many of them can be polymerized by an anionic as well as by a cationic mechanism. which can be polymerized by ring-opening reactions. and these papers also cover the relevant mechanistic literature.4 Anionic Polymerization via Ring Opening There are a number of heterocyclic monomers.

the changes for entropy and enthalpy are both negative (see Table 7. Standard thermodynamic parameters for some cyclic monomers for anionic polymerization [182].8. kp ½Piþ1  1 ¼ A kd ½Pi ½Me ½Me KP ¼ ð51Þ ln½Me ¼ ðDHP  TDSP Þ=RT ð52Þ For monomer concentrations below this equilibrium concentration.7. c – condensed.58 O O O O N H 1:16  102 O 2:2  103 O [a] State of monomer (first letter) and polymer (second letter): g – gaseous. the reversibility of the propagation must be taken seriously into account. there exists a limiting temperature TC above which polymerization is thermodynamically forbidden.8 it can be seen that for most of the cyclic monomers. 7.8).6 6 ss 22. (51) and the equilibrium monomer concentration ½Me in Eq.2 Anionic Polymerization The equilibrium constant KP for the chain growth step Pi þ M ! Piþ1 is defined in Eq.9 41. s – solution. TC is given by Eq. It has been shown [186] that.4 74 3  1011 5 ss 14 13. DHP DHP0 ¼ 0 DSP DSP þ R ln½M TC ¼ ð53Þ From Table 7. Monomer O O Atoms in ring States [a] DHp0 [kJ molC1 ] DSp0 [ J molC1 KC1 ] [M]e [M] 3 gc 140 174 4  1016 4 lc 82. even for a living polymerization without any termination or transfer re- Tab.1 7 lc 13. (53). As for most polymers.8 4. (52). where the standard state refers to unit concentration.6 O O P O OMe O N H 1.1 27. 347 . l – liquid.5 1:6  102 6 lc 7. no polymerization occurs.

First. Intramolecular chain transfer will lead to macrocycles. there are two further side reactions which are inherent to the system – inter. Instead it will add much faster to the Nacyllactam activator. formed from the monomer. but a scrambling of the molecular weight distribution will occur. As the cyclic monomer and the linear polymer chain consist of the same bonds. is added (Scheme 7. The chain propagation consists of the same sequence of elementary reactions. The equilibrium concentration according to the Jacobsen– Stockmayer theory [187] of these non-strained macrocycles of size n is given by Eq. but this step is rather slow. (54). In principle. This activated anionic polymerization is living in the sense that the number of active centers is preserved.7).and intramolecular transfer in ring-opening polymerization. this anion could add to another lactam molecule. inter. X X X X X Chain growth.6). but the inevitable intermolecular chain transfer to poly- . the limiting molecular weight distribution is not a Poisson distribution but a most probable distribution with D ¼ 2. leading to the most probable MWD as a limiting distribution. 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. 189] is usually via a so-called activated anionic mechanism with a two-component catalyst system from a strong base and an N-acyllactam.6. A subsequent proton transfer gives the active N-acyllactam end group and the lactamate anion is regenerated. 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 348 X kinter X X X X X X kintra + X + X X X X X kp X Scheme 7. which also can participate in propagation reactions. ½Mn e ¼ kp ðnÞ A n5=2 k p ðnÞ ð54Þ The anionic polymerization of lactams [188.7 Ionic Polymerization action but where the propagation step is reversible. By intermolecular chain transfer there is no change in Pn . because the number of chains remains the same.and intramolecular chain transfer to polymer (Scheme 7. there is H-abstraction from the monomer to give the lactamate anion.

191]. particularly. are performed below the melting temperature. are used in a wide range of mo- O . polyoxyalkylenes. Polymers from oxiranes. The polymerization of ethylene oxide was one of the first living polymerizations [196]. no large-scale process is known [190. O O N O n N O + H O N O H O N O NH N O + N n Activated anionic mechanism for ring-opening polymerization of lactams. The latter processes. 193]. so the equilibrium monomer (and oligomer) concentration is much lower (1–3%) compared to the hydrolytic polymerization (10–12%). whereas the anionic polymerization is complete within minutes.7. which takes several hours. here the transamidation. together with the propagation–depropagation of the cyclic monomer and macrocycles.2 Anionic Polymerization 349 initiation H O N R R O N O B O N O + + N O + N N O R H O N R O O N O O H O N N N O O N + O propagation O H O N * N O + N O * O H O N N n O H O N N n Scheme 7. even below the melting point of the polymer. in direct polymerization to fibers [194] and in casting and RIM processes [195]. will broaden the molecular weight distribution [189]. The anionic polymerization of caprolactam is described in melt in extruders [192. However. mer. where a monomer extraction step is necessary. This polymerization has attracted much attention because it is very fast compared to the hydrolytic polymerization of e-caprolactam.7.

The resulting water must be removed to ensure maximum conversion to the potassium alkoxide. OH OH OH + KOH HO OH O K HO OK + + + OK OK + + + + OK O K + + + + H2O initiatior formation + OH HO OK O O O OK O O + OK O O + OK O copolymerization EO / PO + + R R OK + H2O + OH R O O K HO + R R nO K + + O Termination H2 O mOH O R n OH + O mO K + chain transfer Scheme 7. The most important ones are rather low molecular weight polymers. often from multifunctional alcohols. are used as initiators. the differences are generally those between primary and secondary hydroxyl groups. 24]. Chains with alkoxide end groups can undergo chain transfer reaction with hydroxyl-terminated chains. This proton exchange.8. which may also happen with multifunctional initiator molecules. Remaining water will terminate growing chains.8 is a general reaction scheme for the copolymerization of ethylene oxide and propylene oxide with multifunctional alcohols as initiators. Anionic ring-opening copolymerization of ethylene and propylene oxide. . Scheme 7. so the equilibrium constant for the proton exchange is around unity. Usually potassium alkoxides. which are used either as nonionic surfactants [197] or as raw materials for polyurethanes [23. forming hydroxyl end groups. is the fastest reaction in this scheme. The acidity of the participating species is rather similar. They are formed in a separate step starting from the respective alcohol and potassium hydroxide.7 Ionic Polymerization 350 lecular weights and applications [22–24].

3 Cationic Polymerization This equilibrium between active and non-active chains is very fast. 199. and 181–183.3. In a second step. There is a detailed discussion on the mechanistic features in Refs. A recursive formula for a more complex distribution assuming different reactivities for each addition of ethylene oxide is given in Ref. homopolymers and random copolymers are accessible. is the isomerization of propylene oxide to allyl alcohol [210. showing the higher reactivity of ethylene oxide.1). but the most important polymers from an industrial point of view are homo. There are a number of recent publications on the kinetics and copolymerization kinetics of ethylene and propylene oxide initiated with several alcohols and KOH [203–209]. One important side reaction. By this process. For the case where the first addition is different from the subsequent ones. 7. it has been shown that normally the chain length dependence of the propagation rate coefficient is not important. with the exception of the first unit [200.3 Cationic Polymerization There are many monomers that can be polymerized via a cationic mechanism (see Table 7. monomers are fed into the reactor. 213] of ethoxylation and propoxylation is usually a semi-batch process. 201]. 212. Catalyst is removed by addition of acids and subsequent crystallization and filtration of precipitated salts.3. 1–5. Block copolymers are produced by successive feeds of the respective monomers. However. The reactivity of vinyl monomers in cati- 351 . The copolymerization parameters are generally in the ranges of rE ¼ 2–4.15–0.7. so in general a Poisson distribution will result. tetrahydrofuran. 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.and copolymers from isobutene and from some heterocyclic monomers such as trioxane. An optional fourth step is the removal of volatile compounds by distillation. 211]. 7. 7. either the Gold distribution [58] in Eq. Both distributions can be used to describe ethoxylation reactions [202]. rP ¼ 0. and epoxides.1 Cationic Polymerization of Vinyl Monomers Cationic polymerization of vinyl monomers is by electrophilic addition of the monomer to a growing carbenium ion. leading to an unsaturated end group (1) which may affect polyurethane production. R O CH2CH CH2 1 The industrial process [23. which may occur at higher temperatures. The starter alcohol and KOH are mixed and water is removed by distillation. (30) or a distribution given by Weibull [198] can be used.

For isobutene. if there are no other side reactions such as transfer or irreversible termination. k ass þM H3 CaCHA !  H3 CaCHþ A !  þM R k ion D ¼ Pw =Pn ¼ 1 þ ½I 0 k p =kass a a kp R H2C ð56Þ ð57Þ Bimodal distributions may result. AlX3/RX. (58)]. values of 1:5  10 8 M1 s1 are reported at 0 and 78 C [215].352 7 Ionic Polymerization onic polymerization follows the electron-donating ability of the substituents at the double bond. These may lead to branched polymers. As discussed for anionic polymerization. there is an equilibrium between active ions or ion pairs and inactive covalent species. Electron-donating substituents increase the nucleophilicity of the double bond in the addition reaction and stabilize the resulting carbenium ion. triflic acid. 190. A very comprehensive review is given in Ref. to transfer agents and solvent as well as Friedel–Crafts alkylation of aromatic rings. Covalent species are not active in propagation. where the ionization constant is rather low (105 M1 in the isobutene/BCl3 system). The dynamics of this equilibrium strongly affects the width of the molecular weight distribution. The general order of reactivity in cationic polymerization is given in Eq. but it has been pointed out (Ref. For the sequence of reactions [Eq. which has been addressed [216] for a tubular reactor. (56)] the polydispersity of the distribution is given by Eq. 2.or copolymerization. (57) [217]. For such high rate coefficients the polymerization may become diffusion-controlled. propagation rate coefficients in cationic polymerization are very large. with the double bond in either the endo or exo position. However. and so on) or Lewis acids together with a co-initiator such as BF3/H2 O. (55). if monomers like styrene are polymerized. pp. Me H2C CH N CH H2C CH H2C Me H2C CH H2C Me OR ð55Þ OMe Initiation is by either strong protonic acids (perchloric acid. . Proton transfer yields unsaturated chains [Eq. 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. 205) that the reactivity differences between the various species – carbenium ions and ion pairs – are not very great. In general. In cationic polymerization of alkenes. 214. for cationic polymerization also several different species may be involved in propagation. if free ions and ion pairs have the same reactivity but different lifetimes [218]. if the double bonds are accessible to homo.

water content. initiator. 222. The smaller epoxides. the molecular weight of the polymer decreases with temperature. are not polymerized cationically. p. rather narrow distributions. The problem of living or non-living cationic polymerization of alkenes is addressed in Refs. even for transfer constants up to 5  104 the system exhibits the behavior of a living system. and temperature. such as a linear increase of molecular weight with conversion. The most important polymers from cationic ring-opening polymerization are polyoxyalkylenes with one or four CH2 groups produced by the polymerization of trioxane and tetrahydrofuran. 157. and 223.7. Volatiles are removed in twin-screw extruders. It is shown that. 219 and 220. 220 and 221. Homopolymers and rubbers are also produced in the Exxon slurry process in methyl chloride at 95 C. 181–185 and 225– 227. and so on. The ethylene evaporates during polymerization and the polymer is scraped from the belt. The molecular weight is controlled by monomer purity. 7.3. Polyisobutene homopolymers comprise a wide range of polymers with molecular weights from a few thousand grams per mole up to 10 6 g mol1 . Tabulated transfer coefficients may be taken from Refs. ethylene and propylene oxide. because of the existence of side reactions leading to dioxane or 353 . depending on the molecular weight. though able to polymerize by a cationic and anionic mechanism. High molecular weight homopolymers are produced in the continuous BASF belt process at 100 C in boiling ethylene to remove the heat of polymerization. 224] from isobutene involve isobutene homopolymers and butene rubbers. 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. 683ff.2 Cationic Ring-opening Polymerization Monographs and reviews of this subject can be found in Refs. The polymerization rate is controlled by initiator feed and cooling is with liquid ethylene and/or propylene. Medium and low molecular weight polymers are produced in solution processes in light hydrocarbons in CSTR reactors or in recirculating tubular (loop) reactors. 3. and butene rubbers are copolymers of isobutene with 1–3 mol% of isoprene. Commercial polymers [2. The polymer slurry is withdrawn from the top of the reactor and worked up downstream.3 Cationic Polymerization * + C * A + + C A + + n ð58Þ n * n As proton transfer usually has the higher activation energy. Copolymerization parameters for cationic polymerization can be found in Refs.

˚ Monomer Counter ion Solvent T [ C] Propagating species k p [MC1 sC1 ] THF CF3 SO 3 CCl4 25 CH2 Cl2 25 CH3 NO2 25 ionic covalent ionic covalent ionic covalent covalent ionic covalent ionic 4  102 6  105 3:1  102 1:7  104 2:4  102 5  104 1:4  104 4  104 1:9  103 1:8  105 Oxepane CF3 SO 3 H3 NO2 25 Oxazoline CH3 C6 H4 O CD3 CN 40 . Propagation rate coefficients for some monomers for ionic and covalent species [2]. especially for THF. and so on. W or V. Initiation can be by strong protonic acids such as perchloric acid and fluorosulfonic acid. which is present to some extent in the monomer even after purification. 182. SBF5 . 229]. In complete thermodynamic equilibrium. Covalent species may reversibly result from association with counter ions  such as CF3 SO 3 or ClO4 .9.9). but their respective contribution usually cannot be distinguished because of the high exchange rates between the two. the equilibrium monomer concentration for the five. 7. inter. the conversion should be given by the equilibrium monomer concentration and the molecular weight distribution should be the most probable one with D ¼ 2. In contrast to these smaller homologs. but their reactivity is much less than that of the ionic species (see Table 7. for example BX3 .8). + R O 2 Ions and ion pairs are both active in propagation.354 7 Ionic Polymerization dioxolane [228]. THF and trioxane can only be polymerized by a cationic mechanism [23. oxonium salts like triethyloxonium (Et3 Oþ . Lewis acids usually need a co-initiator. Hetero polyacids of the general formula Hn Xm Mtz Oy with X ¼ P or Si and Mt ¼ Mo. A detailed discussion on the kinetics of propagation for THF is given in Ref. The active chain end is usually an oxiranium ion (2). They may participate in propagation reactions. As already discussed (see Section 7. which is responsible for scrambling of the molecular Tab.6). and Lewis acids. A ¼ BF4 or SbCl6 ).4). have gained more and more importance. Because of the low energy gain from ring strain. which in many cases is water. because of the intermolecular chain transfer.and six-membered rings such as THF and trioxane during polymerization is rather high (see Figure 7. PF5 .and intramolecular transfer reactions to polymer are of great importance with regard to the molecular weight distribution (Scheme 7.2.

7.5 ln[M] 2 1. as for THF. yielding the desired linear and narrow product [233]. the concentration of which should be proportional to n 5=2 [Eq.3dioxolane.3-dioxolane and siloxanes [230. the polymerization can be stopped at low conversions.003 0. and consequently conversion and kinetic chain length. in spite of these transfer reactions. if. transfer rates for trioxane to polymer are extremely fast. for THF it has been shown [232] that. Depending on reactivity ratios in propagation and transfer.0032 0. from 355 . Equilibrium THF concentration during polymerization according to Ref. However. 231]. (59)]: that is. This can be seen from the observation that during copolymerization of trioxane with 1.5 1 0. Chain growth. may have reached their equilibrium faster than the other equilibrium reactions. weight distribution. 252. ethylene oxide. However. if ring formation is reversible and all equilibrium conditions are fulfilled. even after monomer conversion has reached the equilibrium concentration.8.0034 0.5 0 0. One would therefore expect longer sequences of these comonomers. the system is not yet in equilibrium with respect to macrocycles and transfer reactions may still proceed.3 Cationic Polymerization 2. (54)]. 7.0028 0. +O + O + O O + O + O ð59Þ So. it has been shown.0036 1/T / 1/K Fig. linear polymers with a narrow molecular weight distribution can be formed by kinetic control. the transfer rate coefficient to polymer is rather small. 234–236]. Examples of this ideal equilibrium between linear and cyclic polymers are found for 1. Intramolecular chain transfer will give macrocycles. In contrast. there is still a buildup of cyclic monomers [Eq. and similar comonomers. the comonomer is nearly completely consumed at an early stage of reaction [229.

356 7 Ionic Polymerization NMR and stability studies. Thus formaldehyde should be considered as a comonomer [236. Most processes are run below the melting temperature of the polymer (164–167 C) in precipitating agents or in bulk. and the size of the macrocycles is determined by the size of the crystalline lamellae [240]. depending on the desired molecular weight. 238]. Other acidic catalysts such as zeolites or acid montmorillonite clay are also described [245–247]. The cationic copolymerization of trioxane with ethylene oxide. Cationic polymerization of poly-THF may be batch-wise or continuous [23. unzipping then starts from neutral but unstable end groups such as aOH or aCHO or from statistical chain scission. Cationic polymerization of trioxane is usually a precipitation polymerization leading to crystalline polymers. and a then stable copolymer will result. which may lead to more stable end groups. Newer processes use solid catalysts like zirconium oxide together with acetic anhydride to form poly-THF with two acetate end groups. 7. which will be accumulated until its equilibrium concentration and pressure is reached. and similar monomers. The polymerization–depolymerization equilibrium is not between the growing chain and the originally propagating monomer. for example BF3 . and the same holds for the intramolecular chain transfer leading to cyclic polymer [239. but to formaldehyde [Eq. which are not able to depolymerize. which are usually polymerized anionically from formaldehyde (see Section 7. Molecular weight is controlled by the catalyst concentration and monomer purity. This is either because of . dioxepane. 250]. 244] using strong protonic acids in a temperature range of 30 to 60 C. There are several industrial processes for poly-THF and polyoxymethylene. 242]. This is attributed to the fact that intermolecular chain transfer (transacetalization). trioxane. 1. which later are hydrolyzed to give the dihydroxy polymer. proceeds on a time scale similar to propagation.3-dioxolane. but it may also occur under thermal stress with the neutralized polymer. Unzipping will stop at comonomer units such as those from ethylene oxide. In many cases. (60)] [241. but there are also some descriptions of melt processes [251]. and suchlike is initiated either with strong protonic acids or Lewis acids. it is much faster than free-radical polymerization or polycondensation. and also by chain transfer agents such as methylal [248]. and are carried out in kneaders or double-screw reactors [249.3) will not be stable unless unstable end groups are transformed to stable ones. Homopolymers. contrary to THF polymerization.2. 240]. that the comonomers are randomly distributed along the chains [237. 243]. þ RaOCH2 aOCH2 aOCH2 aOaCHþ 2 T RaOCH2 aOCH2 aOaCH2 þ CH2 O ð60Þ This unzipping depolymerization occurs during polymerization.4 Conclusion Ionic polymerization offers several advantages.

it offers more control over the structure of the resulting polymer by changing the reactivity of the active center when using different counter ions. and so in general they must be determined again for every change in the system. LiH elimination [s1 ] rate coefficient for chain propagation [M1 s1 ] for monomer B added to chain ending with A rate coefficient of association rate coefficient of ionization. and copolymerization parameters may be varied over a wide range. 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. complexing agents. or for the production of polymer structures which are otherwise not accessible. because of its site-based nature. Notation D fi Fi hðiÞ i ½I f kt k tt kAB kass k ion kp kd ki K K ass [M] ½Meq polydispersity index mole fraction of monomer i in the monomer mixture mole fraction of monomer i in polymer chains being formed frequency distribution of chain length degree of polymerization initiator feed concentration rate coefficient for termination [M1 s1 ] rate coefficient for thermal termination. dissociation rate coefficient for chain propagation [M1 s1 ] rate coefficient for decomposition [s1 ] rate coefficient for chain initiation [M1 s1 ] equilibrium constant. The high sensitivity to impurities necessitates much more effort to purify monomers and solvents. ionic polymerization is used for monomers which cannot be polymerized by free radicals. Furthermore. So a wide range of structural isomers can be obtained. This may prevent the wider employment of ionic polymerization. the kinetic scheme and parameters of every system are different. this site-based nature of ionic polymerization also has some disadvantages. Generally. resulting in structures ranging from block copolymers to random copolymers from the same pair of monomers. general equilibrium constant of association monomer concentration [M] equilibrium monomer concentration 357 . However. or salts as additives. especially in the case of cationic polymerization. for example in living anionic polymerization compared to free-radical polymerization. solvents. for example. or because of the high stationary concentration of active centers. which is not possible by free-radical polymerization.Notation very high rate coefficients for propagation. from a kinetic and modeling point of view.

with active center) transfer agent ( .-. n-)Bu CSTR HCSTR M. M  T. r2 r Rp R T TC v_ in.(t-.(tert. with active center) tetrahydrofuran growing polymer chain with lithium counter ion polystyrene molecule ending with hydrogen molecular weight distribution polymer chain with degree of polymerization i high-impact polystyrene nuclear magnetic resonance reaction injection molding styrene–butadiene rubber segregated continuous stirred tank reactor . T  THF PaLi PsH MWD Pi HIPS NMR RIM SBR SCSTR sec. M wðiÞ xM xI monomer feed concentration number-average molecular weight [g mol1 ] weight-average molecular weight [g mol1 ] concentration of polymer chains with degree of polymerization i association number or ring size number average degree of polymerization weight average degree of polymerization copolymerization parameters according to the terminal model ratio of k p =k i for living polymerization rate of propagation [M s1 ] gas constant temperature ceiling temperature initiator feed flow [L s1 ] monomer feed flow [Ls1 ] mass distribution of chain length monomer conversion initiator conversion Greek DGp DHp DSp t n Gibbs free energy of polymerization enthalpy of polymerization entropy of polymerization residence time average kinetic chain length Acronyms s. I v_ in.. n-)butyl continuous stirred tank reactor homogeneous continuous stirred tank reactor monomer molecule ( .358 7 Ionic Polymerization ½Mf Mn Mw ½Ni  n Pn Pw r1 .

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tubular reactors. and a very wide range of applications. it can be said with confidence that the degree of sophistication of polyolefin manufacturing and characterization techniques has 1) The symbols used in this chapter are listed at the end of the text. films. There are many different types of catalysts for olefin polymerization and they can be used to synthesize polymer chains with very different microstructures and properties. synthetic fabrics.1 Polyolefin Properties and Applications 8. Industrial catalysts for olefin polymerization are mainly heterogeneous. fluidized-bed reactors – making them a prime choice for polymer reaction engineering studies. automobile parts and accessories. Edited by T. Keurentjes Copyright 8 2005 WILEY-VCH Verlag GmbH & Co. Despite the fact that polyolefins use comparatively simple monomers and have been around for many years. KGaA.365 8 Coordination Polymerization1 Joa˜o B. containers. Weinheim ISBN: 3-527-31014-2 . J. Handbook of Polymer Reaction Engineering. but dramatically so for polyolefins. It is true for any polymer. and higher a-olefins – are connected to form the polymer chains. under ‘‘Notation’’. It may seem surprising that polymers composed only of carbon and hydrogen atoms can be so flexible. the monomers can be either liquid (as in the case of propylene and higher a-olefins) or dissolved in an inert diluent. They are found in products as diverse as prosthetic implants. Polymerization may take place in either gas or liquid phases. but some processes also use soluble catalysts. gas pipelines. Soares and Leonardo C. P. Polyolefins are produced in practically all types of reactor configurations – autoclaves. Simon 8. For liquid-phase reactors. propylene. loop reactors. and toys. reduced environmental impact. but the versatility of polyolefins can be easily explained by the way the monomer molecules – ethylene. Meyer.1 Introduction Polyolefins are among the most important commodity plastics today due to their low production costs.1. that chain microstructure is the key to understanding their physical properties.

1. 180–290 C) or tubular reactors (1500–3500 atm. 140–180 C). Polyethylene microstructures. When produced as a homopolymer. Because of backbiting and chain transfer to polymer reactions. 8.0.88 . Figure 8. (Free-radical polyolefins are not the main topic of this chapter and will be described only in contrast with polyolefins made with coordination catalysts.) The oldest type of commercial polyolefin is low-density polyethylene (LDPE) made by free-radical polymerization.915-0.96-0.94 g/cm3 / 0. In this chapter.915–0. Low-density polyethylene is used predominantly for making films because of its limp feel. the long-chain branches give excellent processability and high melt tension to LDPE. Low-density polyethylene is made using supercritical ethylene under severe polymerization conditions in autoclaves (1500–2000 atm. and toughness. LDPE has both shortand long-chain branches. we will introduce the reader to this fascinating field of polymer reaction engineering by giving an overview of the different scientific and technological aspects related to olefin polymerization with coordination catalysts. Additionally. 8. HDPE has no short-chain branches.366 8 Coordination Polymerization no equal among other synthetic polymers. transparency.935 g cm3 – and affect several other mechanical and rheological properties.915-0.935 g/cm3 0.1 compares the molecular structures of some polyethylene resins made by coordination and free-radical polymerization.2 Types of Polyolefins and Their Properties Polyethylenes are the commercial polyolefins with the highest tonnage.912 g/cm3 Fig. High-density polyethylene (HDPE) was first made with Ziegler–Natta catalysts.1. These branches decrease the crystallinity and density of the polymer – typically in the range 0.97 g/cm3 . HDPE 0. but a H H H H H H H H H H H H H H C C C C C C C C C C C C C C H H H H H H H H H H H H H H LDPE LLDPE / VLDPE 0.

and shares the market with LDPE. down to 0. Since HDPE has few or no short-chain branches. toughness. While freeradical polymerization can only produce atactic polypropylene.1 Polyolefin Properties and Applications very small amount of a-olefin comonomer can be copolymerized with ethylene to form short-chain branches that decrease its density.2.94 g cm3 . as illustrated in Figure 8. Polypropylene microstructures and some metallocene catalysts used in their synthesis. but syndiotactic polypropylene and some stereoblock elastomeric polypropylenes made with metallocene catalysts have attracted some interest lately [1–3].8. and temperature resistance. the density. or 1-octene) with densities in the range 0. crystallinity. Ziegler–Natta catalysts can make highly isotactic polypropylene.915–0. The chain regularity of isotactic polypropylene is responsible for its high melting temperature and crystallinity. Linear low-density polyethylene is used predominantly in films. Olefins are commonly polymerized in a single reactor or in two or more reactors in series.88 g cm3 . 1-hexene. As a consequence. Typically. the density of HDPE resins is in the range from 0. 8.97 g cm3 . and rigidity of LLDPE are lower than for HDPE. Metallocene catalysts can produce several types of polypropylenes with other stereosequences.2 for some representative catalysts. Products with even lower densities. it has much greater rigidity than LDPE and can be used in structural applications.96 to 0. Isotactic polypropylene is by far the leader among the commercial stereoisomers of polypropylene. Copolymerization of ethylene with increasing amounts of a-olefins disrupts the order of the linear polyethylene chains by introducing short-chain branches. 367 . Single reactors are used when a polyolefin with more uniform composition is required. are sometimes called very low-density polyethylene (VLDPE) but are chemically identical to LLDPE. while reactors in series are employed for the commercial produc- atactic Cp2ZrCl2 isotactic Et(Ind)2ZrCl2 syndiotactic iPr(Flu)(Cp)HfCl2 isotacticstereoblock (NMCp)2ZrCl2 isotacticatacticstereoblock Et(Me4Cp)(Ind)TiCl2 hemi-isotactic iPr(Cp)(Ind)ZrCl2 Fig. Polypropylene is the second most important commercial polyolefin. Linear low-density polyethylene (LLDPE) is a copolymer of ethylene and a-olefins (generally 1-butene. making it ideal for injection molding and extrusion applications due to its excellent rigidity.

w. as illustrated in Figure 8. Propylene is fed to the first reactor. A series of reactors allows for significant flexibility during polymerization. the low molecular weight chains are also the ones that contain the highest a-olefin fraction. .368 8 Coordination Polymerization rubber domains propene + ethene PC PC propene catalyst + diluent product TC TC c. Coordination catalysts are also used to make elastomers. notably ethylene– propylene–diene (EPDM) rubbers [6]. homopolymer matrix Fig. c. The amorphous copolymer fraction is responsible for increasing the impact strength of the homopolymer matrix formed in the first reactor.3. In this case.w.4 shows some typical examples of dienes used for the manufacture of EPDM rubbers. High-impact propylene/ethylene copolymers are the most typical example of this polymerization technique.3. homogeneous catalysts are preferred to heterogeneous ones because they generally produce polymers with a more uniform distribution of crystallinity. It will be shown later that when ethylene and a-olefins are copolymerized with a heterogeneous Ziegler–Natta catalyst in a single reactor. One way of overcoming this problem is to produce a high molecular weight copolymer in the first 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. 8. 5]. The unreacted double bonds of the dienes are used during rubber crosslinking reactions. producing isotactic polypropylene particles. A mixture of propylene and ethylene is fed to the second reactor to make a propylene–ethylene amorphous copolymer phase which is dispersed within the isotactic polypropylene particles already formed. For pipe applications this is undesirable because it decreases the environmental stress cracking resistance of the polymer [4. Process for the production of high-impact polypropylene. tion of homopolymers and copolymers with more elaborate microstructural distributions. since each reactor can be kept in different polymerization conditions to make a polymer that can be considered a blend of two or more components (reactor blends). Another important example of polyolefins produced with reactors in series comprises HDPE resins for pipe applications. Figure 8.

These two techniques provide similar information on the chemical composition distribution of polyolefins and can be used interchangeably in the vast majority of cases. In Crystaf. Since gel permeation chromatography is a very well-established technique it will not be discussed here. A similar statement can be made for polypropylene and other polyolefin resins that are made with prochiral monomers: resins with high stereoregularity and regioregularity have higher crystallizabilities than atactic resins. determining the microstructure of polyolefins can be considered the first and most important step toward the understanding of their properties. Several publications provide additional discussions on the GPC technique [7–9]. The chemical composition distribution of polyolefins is measured (indirectly) by either temperature rising elution fractionation (Tref ) or crystallization analysis fractionation (Crystaf ). This information is used to generate a Crystaf profile relating crystallization temperatures to the fraction of polymer that crystallizes at those 369 . the way these atoms are connected – in other words. Both methods are based on the fact that the crystallizability of HDPE and LLDPE depends strongly on the fraction of a-olefin comonomer incorporated into the polymer chains.CH3 dicyclopentadiene Fig. Chains with fewer a-olefin units crystallize at higher temperatures.CH3 CH2 = CH . Different dienes used for the production of EPDM.CH2 . 8.1. chemical composition. and stereoregularity. 8.1 Polyolefin Properties and Applications 5-ethylidene-2-norbornene 1. that is. polyolefin chains are crystallized from a dilute solution by slowly lowering the solution temperature. the microstructure of a polyolefin – determines their properties. chains with an increased aolefin fraction have a decreased crystallizability.4.3 The Importance of Proper Microstructural Determination and Control in Polyolefins Since polyolefins are composed of only carbon and hydrogen atoms.4-hexadiene CH . while chains with a higher a-olefin fraction crystallize at lower temperatures. High-temperature gel permeation chromatography (GPC) is the standard technique for measuring the molecular weight distribution of polyolefins.CH = CH . Therefore. the microstructure of a polyolefin is defined by its distributions of molecular weight. long-chain branching. At the most elementary level.8.

is used to transform the Tref curve into the chemical composition distribution.6. but involves one additional step. Fig. it suffices to say that the chemical composition distribution of LLDPE made with heterogeneous Ziegler–Natta catalysts is generally bimodal or multimodal. as will . similar to the Crystaf calibration curve. Temperature rising elution fractionation operates in a similar way to Crystaf. as illustrated in Figure 8. 11].5.8 Coordination Polymerization Differential Crystaf Profile Cumulative Crystaf Profile Crystaf vessel dw/dTc 370 w Tc Tc Tc Chemical Composition Distribution w Calibration Curve Tc α-olefin fraction α-olefin fraction Estimation of the chemical composition distribution of a polyolefin using a Crystaf profile and a calibration curve. For our purposes in this chapter. while the other site type makes polymer with a much higher a-olefin content. as illustrated in Figure 8. 10.5. The presence of two or more active sites on heterogeneous Ziegler–Natta catalysts is also confirmed by the fact that they produce polyolefins 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. More details of the Tref and Crystaf analytical procedures can be obtained from many recent publications [7. temperatures. A Tref calibration curve. when the chains crystallized during the crystallization period described above are eluted from the Tref column to generate the Tref profile. The Crystaf profile is then converted into the chemical composition distribution by means of a calibration curve relating the fraction of a-olefin in the copolymer to the crystallization temperature. 8. This clearly indicates that heterogeneous Ziegler–Natta catalysts have at least two – but probably more – distinct active-site types with different reactivity ratios for a-olefin incorporation: one site type produces polymer with a low a-olefin content.

The average a-olefin fraction for these polymers is constant and independent of molecular weight. some catalysts will also produce polypropylene with a distribution of stereoregularities that can be traced back to the presence of multiple active-site types with distinct stereochemical control characteristics [13]. be discussed in more detail below. which confirms that they are made by a single-site catalyst [14]. in fact. considered the ‘‘fingerprint’’ of these resins. the chains with the lower a-olefin fractions are also the ones with the higher molecular weight averages. as depicted in Figure 8. An equally important contribution of metallocene catalysts to polyolefin synthesis is the ability to produce polyethylene and polypropylene with long-chain branches. In this way. In addition. the ability to make polyolefins with narrow microstructural distributions. In addition. several homogeneous Ziegler–Natta and metallocene catalysts make HDPE.1 Polyolefin Properties and Applications Weight fraction Easier to crystallize More difficult to crystallize Mol % α-olefin comonomer Crystallization temperature Chemical composition distribution of a polyolefin made with a heterogeneous Ziegler–Natta catalyst. due to the low levels of long-chain branches generally present in these resins. the distributions of molecular weight and chemical composition of polyolefins made with heterogeneous Ziegler–Natta catalysts are always coupled and are. 8. these measurements are 371 . Fig.8.6.7 [12]. is one of the main reasons why metallocene catalysts have had such an impact on the polyolefin manufacturing industry since the 1980s. In fact. 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 polyolefin industry [15]. with polydispersities higher than 2. The molecular weight distribution of polypropylene made with heterogeneous Ziegler–Natta catalysts is also broad. The only absolute way of measuring long-chain branches in polyolefins is by carbon-13 nuclear magnetic resonance ( 13 C NMR) but. LLDPE. and polypropylene with narrow distribution of chemical composition and molecular weight with the theoretical polydispersity of 2. On the other hand. and consequently with a much better control of polymer microstructures and properties.

02 6x104 0. very often subject to significant experimental error. Fig.2 Catalysts for Olefin Polymerization The class of catalysts we currently call Ziegler–Natta was first used by Ziegler in 1953 to polymerize ethylene at low pressure. although the market share of metallocene resins is increasing due to the enhanced .7. More recently. Most industrial processes today still use heterogeneous Ziegler–Natta catalysts.00 4x104 0 2 4 6 8 10 x. These catalyst systems are able to make polyolefins in very high yields and with a degree of microstructural control not possible to achieve using conventional Ziegler–Natta catalysts.) 372 8x104 0. Long-chain branch formation with polyolefins will be discussed in detail below in Section 8.06 2x105 0. Many other catalysts capable of polymerizing olefins have become available since the original Ziegler–Natta catalyst based on crystalline titanium chloride was introduced. the discovery of soluble metallocene/aluminoxane catalysts opened the doors to a new revolution in the production of polyolefins.3. this field has grown incessantly.04 105 Mw Normalized response (a.8 Coordination Polymerization 0. since then.u. with the development of improved catalysts and new industrial processes. and further developed by Natta in 1954 to produce isotactic polypropylene.4. very good evidence of the presence of long-chain branches can be found by studying the rheological response of these resins. Nonetheless. Both Ziegler and Natta were awarded the Nobel Prize in chemistry in 1963. 8. mole % butene Average weight-average molecular weight of ethylene– 1-butene copolymers made with a heterogeneous Ziegler–Natta catalyst as a function of average 1-butene content [11a]. 8.

3. and moisture. Br) AlR3 = alkylaluminum cocatalyst R = alkyl group (methyl. These impurities are electron donors. sulfur and nitrogen compounds. late transition metal catalysts may have a variety of ligands containing heteroatoms. Common activators are based on organoaluminum or organoborane compounds [16].8. 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. Figure 8. directly bonded to the transition metal. therefore. nitrogen.2 Catalysts for Olefin Polymerization properties of polyolefins made with these catalysts and the fact that polymerization processes that were originally designed to use Ziegler–Natta catalysts can be converted. The activator alkylates the pre-catalyst complex to form the active sites and stabilizes the resulting cationic active site.8. such as oxygen. Because the activator works as a Lewis acid (electron acceptor). sometimes it is stable even to moisture and oxygen.8 shows a simplified chemical equation for the activation mechanism and the corresponding equation used for modeling in the Section 8. Catalyst activation by reaction of a pre-catalyst and a cocatalyst. that poison the cationic active site. coordination catalysts include any complex of transition metals and organic ligands: Phillips catalysts are heterogeneous. or catalyst precursor. chromium-based complexes that are not classified as Ziegler–Natta catalysts. a transition metal surrounded by ligands. ethyl) Fig. to operate with metallocenes – the so called ‘‘dropin’’ technology. Ni. 8. metallocenes are complexes of a transition metal – in most cases an early transition metal – and cyclopentadienyl or cyclopentadienylderivative ligands. with minimal changes. or oxygen. such as phosphorus. it is also used to scavenge polar impurities from the reactor. In most cases the active site is produced by the activation of a complex called a pre-catalyst. The pre-catalyst is commonly stable and easy to handle. The active site in coordination catalysts for olefin polymerization is. The catalytic properties depend on the fine tuning between the transition metal and the ligands in terms of geometry and electronic character. L X A X L L R A L AlR3 C Al AlR2X2 C* A = transition metal center (Ti. …) L = ligands X = halogen (Cl. Zr. 373 . Although traditional heterogeneous and homogeneous Ziegler–Natta catalysts are commonly used as the standard example of coordination polymerization.

another olefin monomer can coordinate to the vacant site. Due to the cationic nature of the active sites. while the last two types produce saturated chain ends. Polymerization with coordination catalysts proceeds via two main steps: monomer coordination to the active site. Before insertion.10). Differently from free-radical polymerization. The type of termination reaction determines the chemical group bound to the active site and the terminal chemical group in the polymer chain. 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]. Figure 8. transfer by b-methyl elimination. Reaction of the active site with polar impurities deactivates the catalyst.9. and transfer to chain-transfer agent – commonly hydrogen – or other small molecules. depending on the design of the ligands bonded to the transition metal. nM P*1+n Monomer coordination and insertion. as illustrated in Figure 8. After the olefin is inserted into the growing polymer chain. transfer to cocatalyst. and monomer insertion into the growing polymer chain.and stereoselective. coordination polymerization can be regio. or atactic (Figure 8. the double bond in the olefin monomer coordinates to the coordination vacancy of the transition metal. Regioselectivity determines the sequence of 1–2 or 2–1 insertions while stereoselectivity determines whether the polymer is isotactic. Several chain-transfer mechanisms are operative in coordination polymerization: transfer by b-hydride elimination. Different rates of coordination and insertion of comonomers determine the final chemical composition of the copolymer chain. transfer to monomer. nucleophilic groups with a lone pair of elec- . 8. there is a competition between the comonomers to coordinate to the active sites and to be inserted into the growing polymer chains. The first three types produce unsaturated chain ends.11 illustrates these five transfer mechanisms.9.374 8 Coordination Polymerization L R A L L R A L L A L R C* P*1 M L A L ( L A L n ) Pol n R P*1 Fig. In the case of copolymerization. Insertion of a prochiral a-olefin such as propylene creates a chiral carbon bonded to the active site. syndiotactic.

or sulfur) can coordinate irreversibly with the active site.2 Catalysts for Olefin Polymerization Regioselectivity 1. nitrogen. The formation of latent states is difficult to probe and the mechanisms are generally not well understood. The term ‘‘latent state’’ can be used to describe certain catalytic intermediates that reduce the catalyst activity. Bimolecular catalyst deactivation happens when two active sites form a stable complex that is inactive for monomer polymerization.10.and stereoselectivity in coordination polymerization. Regio. This type of bimolecular intermediate is favored at high catalyst concentrations and is reversible [18]. 8.1-insertion Pol L A L L A L 2 1 1 2 Pol Stereoselectivity Pol L A L L A L Pol Pol L A L L A L Pol Fig.8.2-insertion Pol L A L L A L 2 1 2 Pol 1 2. Figure 8.12 shows chemical equations for this catalyst deactivation mechanism. 375 . causing irreversible catalyst deactivation. trons (generally substances containing oxygen.

L A L R AlR3 L L R A A L R L 2 Cd Catalyst deactivation by bimolecular reactions. L R A L 2 C* Fig. 8.11. P*A Al Pol D Al Chain termination mechanisms.12. AlR2 Pol .376 8 Coordination Polymerization chain transfer by β-hydride elimination L A L L H A L L H A L Pol Pol Pol P*H P*r Dr chain transfer by β-methyl elimination L A L CH3 L A L Pol P* P*r L CH3 A L Pol Pol Dr chain transfer to hydrogen L A L Pol P*r L H A 2 L H2 P*H H2 H L A L Pol Pol Dr chain transfer to monomer L A L L A L Pol P*r P *r M L A L Pol Dr chain transfer to cocatalyst L A L Pol P*r Fig. 8.

In general. Unfortunately. to express the catalyst activity in units of kgpolymer (mol catalyst h molmonomer )1 . way is to express catalyst activity as the mass of polymer made by one mole of catalyst per unit of time. Since the measured polymerization rate does not necessarily have a first-order dependence on monomer concentration.8. Since polymerization rate is proportional to monomer concentration. The catalytic cycle is a convenient graphical way to describe the central role played by the active site in the mechanism of polymerization. play a vital role in the catalyst mechanism because they affect the rate constants of each of these steps. Figure 8. In addition. such as temperature and monomer concentration. it may be expressed in several ways in the literature. which very often makes it difficult to compare experimental results from different research groups. A common. 377 . Another commonly used parameter when accessing catalyst activity is the turnover frequency.13 shows a catalyst cycle for olefin polymerization with coordination catalysts. A better way is to normalize the catalyst activity with respect to the moles of monomer present in the reactor. one should be very careful when extrapolating these average catalyst activities to different polymerization times. it is advisable that the complete plot of catalyst activity as a function of polymerization time be available for the proper quantification of polymerization kinetics with coordination catalysts. Changes in the polymerization reactor conditions. but it is certainly preferable to the first one. since coordination catalysts generally deactivate during polymerization.13. 8. for instance kgpolymer (mol catalyst h)1 . that is. this value of the catalyst activity cannot be used for different monomer concentrations. Such profiles are illustrated in Figure 8. this form may also be oversimplified. Catalytic cycle for polymerization. Catalytic activity is a measurement of how fast the monomer can be polymerized. in time1 units.14 for characteristic polymerization cases. but not recommended. which stands for the time necessary for one monomer insertion to take place. Changes in the nature of the active site will affect the catalytic mechanism and consequently the activity and the selectivity of the polymerization.2 Catalysts for Olefin Polymerization Dr H2 C Dr M AlR3 C* Dr P*r P*H P*H M P*Me M M M Fig.

20]. Two major advances in heterogeneous Ziegler–Natta catalysts were the use of supports and internal donors. and Vanadium Catalysts The low-pressure ethylene polymerization catalyst introduced by Ziegler was TiCl4 /AlR3 .1 Ziegler–Natta. Polyethylene made with Phillips catalysts . TiCl3 /AlR3 . Phillips catalysts are used in both gas-phase and slurry processes.2. and consequently decrease the load of transition metal in the final polymer. Fig. increase catalytic activity by many times. The active sites for polymerization are located at the surface and edges of the crystalline structure of titanium chloride. A catalyst for stereospecific polymerization of propylene.14. Phillips. The catalyst does not require addition of chemical activators before the polymerization. Inert supports such as magnesium chloride can improve the morphology of the final polymer particle in the reactor. First-generation Ziegler–Natta catalysts consisted of particulate titanium chloride crystals. for instance) [21. The evolution of heterogeneous Ziegler–Natta catalysts is a truly fascinating story that has been reported in detail in many references [19. 8. Internal donors help to control the selectivity of the catalyst by blocking certain sites and therefore are necessary to control polymer structure. where R is commonly an alkyl group such as methyl or ethyl. 22]. A mixture of chromium oxide and silicon oxide (CrO3/SiO2 ) is used to create the active sites. Differences of atomic arrangements around the titanium atoms on the titanium chloride surface affect the chemical properties and consequently the activity and the selectivity of the polymerization catalyst. The true structure of the Phillips catalyst is not well understood. since the active site is produced prior to the polymerization by thermal activation at high temperatures (600 C. Phillips catalysts are based on Cr(IV) supported on silica and alumina.8 Coordination Polymerization polymerization rate 378 Decay type Build-up type polymerization time Polymerization kinetics with coordination catalysts showing different deactivation rates. 8. was disclosed by Natta shortly after Ziegler’s discovery.

The symmetry imposed by ligands around the active site determines the geometry for monomer coordination and insertion. AlEt3 ) are not able to activate metallocene catalysts very well.2 Metallocene Catalysts Metallocene catalysts have structures similar to ferrocene (Cp2 Fe). Metallocenes are soluble and therefore can be used as homogeneous catalysts.8. polymerization time. 8. and chemical structure of the ligand can affect the activity and selectivity of the catalyst.2. geometry. The nature of the transition metal and the structure of the ligand have a large effect on catalyst behavior. 379 .15) is a well studied example of a metallocene catalyst for olefin polymerization. but they can also be supported on inert carriers such as silica. A large variety of metallocene catalysts can be obtained by altering the simple structure of Cp2 ZrCl2 . 8. where the transition metal lies between two cyclopentadienyl (Cp) rings. and consequently the relative orientation of catalyst and growing polymer chain. The catalyst is produced by activating a mixture of VCl3 and VCl4 with AlR3 (alkylaluminum) compounds. hydrogen is not an effective chain-transfer agent and generally decreases catalyst activity. The use of bulky activators. and magnesium chloride.2 Catalysts for Olefin Polymerization has a very broad molecular weight distribution. Even though metallocenes can be activated with these cocatalysts. among other inorganic and organic supports. 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 currently experiencing in polyolefin manufacture [25]. Interestingly. Cp2 ZrCl2 . they generally deactivate very fast. The shape. with polydispersities ranging from 12 to 24. and used as heterogeneous catalysts [24]. and consequently have no commercial interest. Other bulky Lewis acids such as trispentafluorophenylborane (B(C6 F5 )3 ) are also very good cocatalysts for metallocenes. Changes in the composition of the solvent. Cl Structure of a typical metallocene catalyst. Vanadium catalysts are used to manufacture ethylene–propylene–diene rubbers.15. which is a widely known complex with a ‘‘sandwich’’ structure. The cocatalysts commonly used with Ziegler–Natta catalysts (AlEt2 Cl. such as methylaluminoxane (MAO). The possibility of variations in the chemical Cl Zr Fig. Vanadium catalysts are very sensitive to reaction conditions [23]. In fact. is necessary to produce highly active metallocene catalysts. alumina. Cp2 ZrCl2 (Figure 8. and temperature can affect catalyst activity and selectivity.

8. for instance oscillating between configurations that produce atactic and isotactic polypropylene blocks. 2. this orientation is determined by the active site. especially if substitutions of ligands with heteroatoms are considered. 26]. The size and the type of the bridge connecting the cyclopentadienyl rings affect the opening on the opposite side of the transition metal. certain ligands can change the orientation during the growth of a polymer chain. This effect is called the ‘‘biting angle’’.16. By the proper choice of polymerization conditions it is possible to produce polypropylenes that have chains varying from mainly atactic through block atactic–isotactic to mainly isotactic configurations [28]. In the former. Since the stereochemical control of most metallocenes is of the enantiomorphic type. Furthermore. Fig. There are two mechanisms to explain control of stereoregularity: chain-end or enantiomorphic site control. 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. In the latter. as determined by the arrangements between the transition metal and its ligands [27]. and consequently the relative rates of the elementary steps in the polymerization mechanism. The literature on metallocene catalysts is very rich – one may even say opulent – and thousands of metallocene catalyst structures have been documented since the early 1980s [1. as elegantly illustrated in Figure 8. A practical and very interesting example is the control of tacticity in polypropylene. . The appropriate selection of ligand structure has a major effect on the selectivity of the polymerization mechanism. the orientation of the growing polymer chain determines the orientation of the monomer during insertion. substitutions and/or presence of bridging groups on the cyclopentadienyl rings creates an endless set of possible structures.16.380 8 Coordination Polymerization X X M X M X X M X C2v Cs (meso) C2 (racemic) (atactic PP) (atactic PP) (isotactic PP) Ex: Cp2ZrCl2 Et(Ind)2ZrCl2 X M X Ex: Et(Ind)2ZrCl2 X M X Cs C1 (syndiotactic PP) (no unequivocal prediction) Ex: iPr(Flu)(Cp)HfCl2 Ex: (Flu)(MeCp)ZrCl2 Symmetry requirements for the production of polypropylenes with different stereoregularities.

3 Late Transition Metal Catalysts This family of coordination catalysts is characterized by having a transition metal from groups 8. More importantly. Another important class of metallocene catalysts.3. As for metallocenes. these catalysts can form polyolefins containing long-chain branches via a mechanism that is analogous to the copolymerization of long a-olefins. The catalyst can be used in homogeneous solution or supported in inert carriers such as silica. 8. as will be described in Section 8. the ‘‘half-sandwich’’ metallocenes (Figure 8. The active site can be generated by activation of a metal halide complex such as (diimine)NiCl2 with organoaluminum compounds such as (CH3 )3 Al or MAO.17) have a more open structure because only one cyclopentadienyl ring is coordinated to the transition metal. These catalysts have a well defined structure and in homogeneous systems can behave as single-site catalysts.2. 8. 9. or 10.4. This feature is very attractive for modifying the chemical composition of polyolefins by copolymerization with vinyl alcohols. or other vinyl polar comonomers. 381 . Late transition metal catalysts are very active and produce high molecular weight polyethylene. such as dyeability. adhesion. The tolerance toward polar comonomers is attributed to the electronic configuration of the central metal and its interaction with its ligands.17. and compatibility with other polar polymers. A great advantage of some polymerization catalysts based on late transition metals is that the active sites are more tolerant to polar comonomers (and impurities) than the early transition metals used with metallocenes.8. the active species are cationic. A few polar functional groups can significantly increase the hydrophilicity of polyolefins and enhance several of their properties. acrylates.2 Catalysts for Olefin Polymerization CH3 H3C CH3 H3C H3C Si H3C CH3 N H3C Fig. Catalysts with open structures have very high reactivity ratios toward the incorporation of longer a-olefins and are used for the production of ethylene/1-octene copolymers [29]. CH3 Ti C CH3 CH3 A half-sandwich metallocene.

At low temperatures polymerization of a-olefins with certain diimine–NiCl2 catalysts behave as a living polymerization: that is. By choice of appropriate polymerization conditions.382 8 Coordination Polymerization Forward Chain Walking P Forward Chain Walking P A Chain Walking followed by Insertion Monomer Insertion P P Backward Chain Walking A A A A P Ethyl Branch Insertion A = metal active center P = polymer chain Fig. it is possible to produce branched polyethylene from pure ethylene without addition of comonomers. Chain walking mechanism. 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. as indicated in Figure 8. The molecular weight of polyethylene made with some late transition metal catalysts based on iron can be very high (> 1 000 000 g mol1 ) [30]. The chain walking mechanism involves simultaneous isomerization and polymerization steps.18. Increasing the polymerization temperature or decreasing the monomer concentration favors chain walking and increases the number of short-chain branches. 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]. . ethylene can be used to make polyethylene with properties varying from very low density (highly branched) to high density (few or no branches).18. 8. The number of branches produced by the chain walking mechanism can be controlled by varying the polymerization temperature and monomer concentration. Branches from methyl to hexyl or longer are produced during ethylene polymerization. the number-average molecular weight increases linearly with polymerization time and the polydispersity index (PDI) is approximately 1. Isomerization reactions cause the active site to move along the growing polymer chain without terminating chain growth. although methyl branches are predominant [31]. With the appropriate choice of ligands and reactor conditions. A short-chain branch is created when monomer insertion takes place after the active site has moved away from the chain end.

the initiator fragment moves away from the growing chain and therefore can influence chain growth and termination during only the first few monomer insertion steps. this makes the determination of general tables of polymerization rate constants and activation energies for coordination polymerization virtually impossible. are also responsible for the remarkable flexibility of coordination catalysts. while all heterogeneous Ziegler–Natta and Phillips catalysts have more than one site type. The mechanisms of free-radical and coordination polymerization are contrasted in Figure 8. it creates a significant challenge for model parameter estimation. Since the nature of the active sites is a rather complex (and unfortunately poorly understood) function of polymerization conditions such as temperature.1 383 . rate constants for coordination polymerization depend not only on the monomer type but also on the nature of the active sites present during polymerization. In contrast. independently of the type of initiator used during polymerization. that is to say those that make it difficult to predict the behavior of coordination polymerization a priori.2.8. In free-radical polymerization.3.2 Polymerization Kinetics with Single-site Catalysts Homopolymerization Several metallocene. 8. Consequently. As we will see. the values of the polymerization kinetic parameters depend mainly on the monomer type. presence and concentration of catalyst modifiers. The mechanism for coordination 8. electrical and steric effects around the active site affect polymerization kinetics as much as does the monomer type. since polymers with completely different 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. and homogeneous Ziegler–Natta catalysts behave as single-site catalysts. the same phenomena. among other factors. in coordination polymerization chain growth and termination take place by insertion of the monomer or chain-transfer agent into a metal–carbon bond.3. and solvent type.19.1 Comparison between Coordination and Free-radical Polymerization One of the main differences 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. catalyst/cocatalyst ratio and type. In this way. as proposed by the Cossee mechanism. thus permitting the creation of tables of rate constants and activation energies as a function of monomer type. late transition metal.3 Polymerization Kinetics and Mechanism with Coordination Catalysts 8.3. while the latter is almost exclusively regulated by monomer type. On the other hand.3 Polymerization Kinetics and Mechanism with Coordination Catalysts 8. Consequently. even though this may not constitute a problem for establishing an operative mechanism for coordination polymerization.

Comparison of the monomer propagation step in free-radical and coordination polymerization. under certain polymerization conditions. We will discuss the mechanism of long-chain branch formation with coordination catalysts in Section 8. but it can be as high as 1000:1 or more for metallocene catalysts. about the kinetics of catalyst activation for coordination polymerization. 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. it has been shown that the cocatalyst is required to reduce and alkylate the active site. Even though this terminology is more rigorous. Some catalysts. to form the active site C  [Eq. 8. No bimolecular termination reactions – termination by combination or disproportionation – as observed in free-radical polymerization take place with coordination catalysts.CH2 Ti CH2 CH2 Fig. which is generally present in great excess. Al. (In some references.) The cocatalyst/catalyst molar ratio is commonly 5:1–20:1 for heterogeneous Ziegler–Natta catalysts. catalyst initiation with monomer. Qualitatively. . from a quantitative point of view. and poisoning and deactivation [32]. we will adopt the looser terminology by which the transition metal compound is called the catalyst. C. (1)]. chain propagation. may polymerize dead polymer chains containing terminal vinyl unsaturations.384 8 Coordination Polymerization Free-radical polymerization is monomer-based: R* + M RM* RM* + M RMM* ••• R(M)n* + M R(M)n+1* Coordination polymerization is site-based: CH2 . even before reaction with the cocatalyst.4. leading to the formation of chains with long-chain branches. Coordination catalysts must be activated via reaction with a cocatalyst. polymerization can be divided into five main classes of reaction: catalyst activation with the cocatalyst. and cocatalyst or activator.3. Little is known.19. chain transfer. This reaction is generally assumed to proceed very quickly and to be first order with respect to catalyst.

ki C  þ M ! P1 ð2Þ A subsequent monomer propagation reaction with a growing polymer of chain length r. (3)]. The most important transfer reactions in coordination polymerization are: (1) bhydride elimination. On the other hand. Since in practice these constants are very difficult (if not impossible) to estimate independently. k p . M. and (4) transfer to cocatalyst. CH . k tH Pr þ H2 ! CH þ Dr ð7Þ 385 . (2)]. from the subsequent monomer propagation steps. (6)]. kp Pr þ M ! Prþ1 ð3Þ In general. (3) transfer to monomer. Pr . b-Hydride elimination is a first-order reaction in which the hydrogen atom attached to the b-carbon in the living chain is abstracted by the active center. (2)]. k tbCH3  þ D¼ Pr  ! CCH r 3 ð6Þ Chain-transfer agents are commonly used to control the molecular weight of the polymer. (4)]. vinyl-terminated chains are produced when b-methyl-transfer reactions take place [Eq. (7)]. (2) transfer to chain-transfer agent. the first monomer insertion step is considered to have a different reaction rate constant. By far the most common chain-transfer agent used in olefin polymerization is hydrogen [Eq. D¼ r [Eq. similarly to that of [Eq. b-hydride transfer will produce a dead polymer chain with a vinylidine chain end. For polypropylene polymerization. it is ready to polymerize the monomer. and a dead polymer chain containing a terminal vinyl unsaturation.3 Polymerization Kinetics and Mechanism with Coordination Catalysts ka C þ Al ! C  ð1Þ After the catalyst is activated by reaction with the cocatalyst. k tb Pr ! CH þ D¼ r ð4Þ The metal hydride center is available for polymerization and will undergo an initiation reaction in the presence of monomer [Eq. k i . (5)]. forming a metal hydride center. forming a living polymer chain P1 of length 1 [Eq. increases its length to r þ 1 [Eq.8. often the simplifying assumption k i G k iH is adopted. most kinetic models make the reasonable simplifying assumption that k i G k p . k iH CH þ M ! P1 ð5Þ The independent estimation of k i and k iH can be very involved.

(10) and (11)]. and a metal hydride active site that can be initiated with monomer according to Eq. (CH3 )3 Al. If the cocatalyst is trimethylaluminum. single-site catalysts can be represented with a single set of the elementary reactions described by Eqs. In other words. this elementary step produces a methylatedactive center. Al ð9Þ Coordination catalysts are very sensitive to polar impurities and may also be deactivated due to mono. Dr . Cd .or bimolecular mechanisms. I. which can also be initialized by the monomer in a subsequent step: k tAl  Pr þ Al ! CCH3 þ Dr. monomolecular and bimolecular deactivation reactions have been described with the simple kinetic schemes described by Eqs. single-site catalysts will produce linear . From a polymer microstructure point of view. Even though these elementary reactions are not very well understood from a quantitative point of view. but have been successful in describing several olefin polymerization processes with Ziegler–Natta and metallocene catalysts. kdI Pr þ I ! Cd þ Dr kdI C  þ I ! Cd ð10Þ ð11Þ Likewise. and a dead polymer chain have been modeled with the very simple equations [Eqs. From the point of view of catalyst structure. leading to the formation of a deactivated site. kd Pr ! Cd þ Dr  kd C ! Cd  kd 2C ! 2Cd ð12Þ ð13Þ ð14Þ These deactivation equations are not easy to prove. single-site catalysts are those where all active sites are represented by the same chemical species and have the same polymerization kinetic parameters. The term ‘‘single-site catalyst’’ has a very precise meaning in coordination polymerization. (8)]. k tM Pr þ M ! P1 þ D¼ r ð8Þ Finally. Transfer to monomer also occurs during olefin polymerization. (9)]. (12)–(14). (5). Reactions with polar impurities. leading to a vinyl-terminated chain for the case of polyethylene (and a vinylidine-terminated chain for the case of polypropylene) [Eq.386 8 Coordination Polymerization Chain transfer to hydrogen leads to the production of a dead chain with a saturated chain end. we will show next some simple reaction mechanisms proposed to describe them. (1)–(14) or any other equivalent set of polymerization mechanism equations. the cocatalyst may also act as a chain-transfer agent [Eq.

If these conditions change throughout the polymerization. It is only when the polymerization is operated at steady state that the instantaneous properties of the polymer will be equal the accumulated ones.4 0. (1)–(14).8. Therefore. as quantified by Eqs. even though polymer made with a single-site coordination catalyst has a polydispersity of 2 instantaneously. In fact. 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. Polymers made by a mechanism where the chain can either grow by propagation or terminate by transfer reactions. as indicated in Figure 8. so will the instantaneous property under examination. since this may lead to significant misunderstanding of catalyst behavior.20 for the case of decreasing chain-transfer agent concentration as a function of polymerization time.5 2 2. (15)].2 1 0.8 w (r ) time 0.3 Polymerization Kinetics and Mechanism with Coordination Catalysts polymers that have a theoretical polydispersity of 2 instantaneously.5 4 4. the second condition is the consequence of the first. 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.5 3 log r Fig. The qualification ‘‘instantaneously’’ used above should not be taken lightly. follow Flory’s most probable chain length distribution [33] [Eq.5 387 .20. These two conditions are not independent.2 0 1 1. 3. An instantaneous property refers to the property of the polymer made at a given instant in time under a set of invariant polymerization conditions.4 chain transfer agent time 1.6 0. wðrÞ ¼   r r exp  rn2 rn ð15Þ 1. 8.

the instantaneous value of F A can be calculated using the molar fraction of monomer A in the reactor. (20) [35]. particularly for studies of polymerization kinetics. 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 affect these reactions. from a polymer microstructure point of view. 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. is described by Stockmayer’s distribution [Eqs. the instantaneous bivariate chain length and chemical composition distribution. except for the fact that the polymerization rate constants now depend on the monomer and the chain end type. AA . F A . FA ¼ ðrA  1Þ fA2 þ fA ðrA þ rB  2Þ fA2 þ 2ð1  rB Þ fA þ rB ð20Þ . yÞ ¼ rA ¼ k p. BB k p. In the terminal model. (19). higher-order models such as the penultimate and pen-penultimate models have not found widespread use in coordination polymerization. Copolymerization The polymerization model most commonly adopted for olefin copolymerization is the terminal model. BA y ¼ FA  FA ð16Þ ð17Þ ð18Þ ð19Þ As indicated in Eq. fA . Besides the fact that it is logically expected. k p. An accepted form of the terminal model for the binary copolymerization of olefins is shown in Table 8. with the added complexity that more polymerization rate constants are required. Eq. Copolymerization models are similar to homopolymerization models.1. and the reactivity ratios rA and rB by the Mayo–Lewis equation.2.388 8 Coordination Polymerization In Eq. a coordination catalyst is considered to have only one site type if it produces polymer with a chain length distribution that follows Eq. As usual.2. AB rB ¼ k p. Notice that. there is also significant experimental evidence supporting the terminal model for olefin polymerization. Therefore. wðrÞ is the weight distribution of chains of length r and rn is the number-average chain length of the polymer population. only the last monomer molecule added to the chain end influences polymerization and transfer rates. the mechanism is essentially the same as the one described in Section 8. (15) instantaneously. y is the deviation from the average molar fraction of monomer type A in the copolymer.2    rffiffiffiffiffiffiffiffi r r r ry 2 exp  exp  rn2 rn 2pk 2k qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi k ¼ FA ð1  FA Þ 1  4FA ð1  FA Þð1  rA rB Þ wðr. (15).3. For the case of linear binary copolymers. (16)–(19)] [34].3. 8. yÞ. On the other hand.1 for homopolymerization. wðr.

A k t. B ! Cd þ Dr. All other symbols are the same as those used for homopolymerization. 389 . A þ D¼ r. A þ H2 ! CH þ Dr. A ! Cd þ Dr. A k p. B þ D¼ r. 8. A þ B ! Prþ1. A þ B ! P1. B Monomolecular deactivation Pr. instantaneously.  rffiffiffiffiffiffiffiffi     r r r ry 2 r r exp  exp  dy ¼ 2 exp  wðrÞ ¼ 2 rn 2pk rn rn 2k y rn ðy ð21Þ Therefore. B k p. A k tb. A kd. A k i. BA Pr.3 Polymerization Kinetics and Mechanism with Coordination Catalysts Tab. AB Pr. A k p. BB Pr. BB Pr. A k t. AA k tb. B Propagation Pr. B b-Hydride elimination Pr. B k i. B þ Al ! CCH3 þ Dr. A k tH. B Transfer to hydrogen Pr. The attentive reader may have noticed that Stockmayer’s distribution is an extension of Flory’s distribution for the case of copolymers. A kdI. Stockmayer’s distribution is the consequence of adopting the binary copolymerization mechanism described in Table 8. A þ D¼ r. B Pr.8. A þ I ! Cd þ Dr. A ! CH þ D¼ r. but the reaction rate constants indicate the type of chain end and reacting monomer with the generic nomenclature k i. B þ D¼ r. A k p. A [a] A and B represent the two monomer types. A þ A ! Prþ1. B Pr. AA kAl. the chain length distributions of linear binary (or multicomponent) copolymers also follow Flory’s most probable distribution and have. A þ A ! P1. B Transfer to cocatalyst  Pr.[a] ka Activation C þ A ! C Initiation C  þ A ! P1. B þ H2 ! CH þ Dr. In fact. B Transfer to monomer Pr.1. B k t. (21). A kdI. A þ Al ! CCH3 þ Dr. B þ B ! P1. upon integration in the interval y a y a y. B þ A ! Prþ1. BA Pr. B þ B ! Prþ1. Stockmayer’s distribution reduces to Flory’s distribution as demonstrated by Eq. (1)–(14). B C  þ B ! P1. B þ A ! P1. B  Pr. B ! CH þ D¼ r. a polydispersity of 2. B þ I ! Cd þ Dr. j where i is the chain end type and j represents the monomer type. A k tH. Al kAl. AB Pr. A k t. Al Deactivation with impurities Pr. A kd. Terminal model for binary copolymerization of olefins.1. In the same way that Flory’s distribution is the necessary outcome of adopting the homopolymerization model described by Eqs. B Pr. B Pr.

04 -0. Distribution parameters: rn ¼ 1000.007 0.23 shows that the chemical composition dis- 0.002 0. the chemical composition distribution is best apprehended by plotting Eq.02 0 0. in the interval 0 a r a y: wð yÞ ¼ ðy 0    rffiffiffiffiffiffiffiffi r r r ry 2 3 dr ¼ rffiffiffiffiffi exp  exp  5=2 rn2 rn 2pk 2k 2k y 2 rn 4 1þ rn 2k ð22Þ It is difficult to overestimate the explanatory power contained in these few simple expressions.01 0. Equation (16) teaches us that longer polymer chains also have narrow chemical composition distributions. as illustrated in Figure 8. as would be expected since chains with infinite length should all have exactly the same average copolymer composition. as described by Stockmayer’s bivariate distribution.06 -0. an expression for the chemical composition distribution alone can be obtained by integrating Eq. Equation (16) also shows that the tendency to form comonomer blocks (rA rB ! y) will necessarily broaden the chemical composition distribution of copolymers.08 -0.004 0.y ) 390 0.003 0.001 0 -0. 8. that is. while the tendency toward monomer alternation (rA rB ! 1) will narrow the chemical composition distribution and in the limit make all chains have the composition F A ¼ 0:5.21.06 0.08 0.1 .21. (16) over all chain lengths. This result simply reflects the fact that statistical deviations from the average copolymer composition become less likely as the chain increases in length.008 0.009 r = 250 r = 500 r = 1000 0. 0. Chemical composition distribution for several chain lengths.1 -0. as illustrated in Figure 8. (22) as a function of the lumped parameter rn =k. FA ¼ 0:5.005 0. Figure 8.22.04 0. rA rB ¼ 1.8 Coordination Polymerization Similarly. In fact.006 w (r .02 y Fig.

40 rn /κ = 1000 rn /κ = 2000 rn /κ = 4000 35 30 w( y) 25 20 15 10 5 0 -0.8.08 0.025 0.08 -0.035 r1r2 = 0.02 0. Fig.06 0.005 0 -0.23.08 0. 8.06 -0.01 r1r2 = 1.04 -0.1 -0. (22).1 391 .0 r1r2 = 5 0.04 -0.3 Polymerization Kinetics and Mechanism with Coordination Catalysts 0. Chemical composition distribution for the same chain length and varying rA rB .02 0 0. Distribution parameters: rn ¼ 1000.03 w (r .22. as described by Stockmayer’s bivariate distribution.08 -0. FA ¼ 0:5.1 y Fig.06 -0.1 -0. 8.02 0.02 y Chemical composition distribution as a function of the lumped parameter rn =k in Eq. y ) 0. 0. r ¼ 1000.06 0.04 0.01 0.02 0 0.04 0.015 0.

for the sake of simplicity they will not be further considered in this chapter. with different polymerization kinetic parameters assigned to each site type. Therefore. the polymerization mechanism may be extended to include site transformation steps. those with a distinct number-average chain length. several of the catalysts used industrially for polyolefin manufacturing have in fact two or more active-site types. where D could be a catalyst modifier such as an electron donor. (23).3. C1 þ D $ C2 ð23Þ Since these additional site transformation steps may affect the relative ratio of site types present in the reactor but do not influence the general polymerization behavior with multiple-site catalysts. The simplest way to visualize this phenomenon is to assume that every different site type on a multiplesite catalyst produces polymers that follow a distinct Flory’s distribution: that is. m i [Eq. the width of the instantaneous chemical composition distribution of binary copolymers made by coordination polymerization is a function of a single lumped parameter rn =k and. 8. for instance. reflecting the fact that polymers with shorter number-average chain lengths and a tendency to form blocks (see Eq. 37]. may behave like multiple-site catalysts even if they behaved as single-site catalysts in solution polymerization. In addition. such as the one described with the reversible reaction in Eq. (17): k increases when rA rB increases) have broader chemical composition distributions. rn. .392 8 Coordination Polymerization tribution becomes broader as the value of rn =k decreases. depends only on the number-average chain length and reactivity ratio product rA rB . In this way.1 for copolymerization. The kinetics of polymerization with multiple-site catalysts is generally considered to be the same as with single-site catalysts. where sites of one type may change into sites of another type. as described by Eqs. the chain length distribution for the whole polymer is a combination of distinct Flory’s distributions weighted by the mass fraction of polymer made on each site type. several metallocene catalysts. (24)]. In some cases. In conclusion. It is usually straightforward to detect the presence of multiple-site types on a coordination catalyst because these catalysts will produce polymer with polydispersity higher than 2 even under invariant polymerization conditions. i [38].3 Polymerization Kinetics with Multiple-site Catalysts All heterogeneous Ziegler–Natta and Phillips catalysts have two or more active-site types and many soluble Ziegler–Natta and metallocene catalysts may also show multiple-site behavior [36. when supported on organic and inorganic carriers. (1)–(14) for homopolymerization and in Table 8. for a given copolymer composition.

2 i   r exp  rn. rn. It is important to remember that the use of Eq. 2 ¼ 1000. 8. i ð24Þ The graphical representation of Eq. m1 ¼ 0:3.5 3 3.1 0 1 1. rn ¼ rw ¼ 2 n X mi !1 r i¼1 n. See Figure 8. Eqs. (24) for a coordination catalyst having three distinct site types is shown in Figure 8. used to describe single-site catalysts. i n X i¼1 m i rn.5 log r Fig. rn. (25) and (26).6 0. Flory’s distribution is the logical consequence of the mechanism adopted for coordination polymerization.24.3 0.8 0. (24) is a direct consequence of assuming that the mechanism of polymerization for multiple-site catalysts is described with the same set of equations. Distribution parameters: rn.5 0. (1)–(14).9 0.24.4 0.7 w (r ) 0. 3 ¼ 2000. the instantaneous number. i ð25Þ ð26Þ 393 . In other words.5 4 4.2 0. m2 ¼ 0:3. Chain length distribution of a polymer made with a coordination catalyst containing three different active-site types. For polymers made with multiple-site catalysts.5 2 2. 1 ¼ 500. m3 ¼ 0:4.3 Polymerization Kinetics and Mechanism with Coordination Catalysts 1 0.8.25 for the corresponding chemical composition distribution. wðrÞ ¼ n X mi i¼1 r rn.and weight-average chain lengths are given by Eqs.

ðrn =kÞ3 ¼ 8000.8 0. Chemical composition distribution of polymer made with a coordination catalyst containing three different active-site types. the distribution of polymer made with a multiple-site catalyst becomes Eq. i rn i¼1 ! n X mi ! r i¼1 n. (28) of a polyolefin made with a catalyst having three distinct active-site types. (27). whose chain length distribution has already been presented in Figure 8.94 0. 3 ¼ 0:93. ðrn =kÞ2 ¼ 4000. wð yÞ ¼ n X 3 m i sffiffiffiffiffiffiffiffiffiffiffiffiffi  ffi   5=2 k y 2 rn i¼1 1þ i 4 2 rn i 2 k i ð28Þ Figure 8. FA.88 0. Notice the characteristic bimodal distribution of ethylene/a-olefin copolymers made with het- . as described by Eq.24.24 for the corresponding chain length distribution.9 0.84 0. 8. See Figure 8. n X rw PDI ¼ ¼ 2 m i rn.25 shows the chemical composition distribution obtained with Eq. m1 ¼ 0:3. Therefore. (28). FA. the bivariate molecular weight and chemical composition distributions of binary copolymers made with multiple-site catalysts can be described as a weighted superposition of Stockmayer’s distributions [39]. m2 ¼ 0:3. i ð27Þ Similarly. which is always greater than or equal to 2. 2 ¼ 0:90. Distribution parameters: ðrn =kÞ1 ¼ 2000.8 Coordination Polymerization 25 20 w (fraction of ethylene) 394 15 10 5 0 0.92 0. 1 ¼ 0:88. (22).82 0. m3 ¼ 0:4. the polydispersity index of a polymer made with a catalyst having n site types is given by Eq. FA.98 1 fraction of ethylene Fig. If we consider only the chemical composition component of the distribution.25.96 0.86 0.

41]. ðr1 r2 Þ1 ¼ ðr1 r2 Þ2 ¼ ðr1 r2 Þ3 ¼ 1. 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. rn. m1 ¼ 0:3. FA. We have already seen that dead polyethylene chains with terminal unsaturations will be formed by 395 . rn. Bivariate distribution of chain length and chemical composition of a polymer made with a coordination catalyst containing three different active-site types. 3 ¼ 2000. The references at the end of the chapter give more information on this topic [40.26.27) [15]. Distribution parameters: rn. FA. The multiplicity of active sites on heterogeneous Ziegler–Natta and Phillips catalysts is a truly complex phenomenon and other explanations proposed to describe the observed broad chain length and chemical composition distributions have also been proposed.3 Polymerization Kinetics and Mechanism with Coordination Catalysts Fig.w (r. 8. 3 ¼ 0:93. m3 ¼ 0:4. 2 ¼ 0:90. which can very often be seen as a limitation of heterogeneous Ziegler–Natta catalysts. 1 ¼ 500. 1 ¼ 0:88. since low molecular weight chains with high aolefin fractions are easily extracted from the polymer particles and may cause reactor fouling. In this mechanism.4 Long-chain Branch Formation The mechanism of long-chain branch (LCB) formation with coordination polymerization catalysts is terminal branching. y) 8. These two figures illustrate a very important aspect of olefin polymerization with heterogeneous Ziegler–Natta catalysts. 2 ¼ 1000. This seems to be a universal property of heterogeneous Ziegler–Natta catalysts and is dramatically illustrated in Figure 8. m2 ¼ 0:3. erogeneous Ziegler–Natta catalysts. but most rely on similar approaches to the one described herein. Much research has been done to overcome this phenomenon. the fact that the sites that make polymer chains with higher number-average chain lengths also have a lower reactivity ratio toward comonomer incorporation. 8.26 for the bivariate distribution of chain length and chemical composition of a model polymer.3. a high extractable content in films – a serious limitation for food and medical applications – and odor problems during processing. FA.

while the subscripts r and s are their respective chain lengths. catalysts that have a high reactivity ratio toward a-olefin incorporation can also form polymers with high LCB contents. to the polymerization reactor. wðr. respectively. The polymerization mechanism described by Eqs. Mechanism of long-chain branch formation with coordination catalysts.1= Fig. in which the parameter t is given by Eq.27. when a linear growing chain (i ¼ 0) reacts with a linear macromonomer ( j ¼ 0). i þ D¼ s.4 Pr. b-hydride elimination and transfer to monomer reactions. heterogeneous Ziegler–Natta catalysts make only linear polyolefins. as expected. they are frequently called macromonomers. Eq. wðr. Since these chains can be reincorporated into the growing polymer chains via LCB-formation reactions. In contrast. kLCB Pr. Similar equations are easily developed for copolymerization. Therefore. iþjþ1 ð29Þ In Eq. j ! Prþs. to include long-chain branch formation.8 Coordination Polymerization Pr+s. Macromonomers can be made in situ via b-hydride elimination and transfer to monomer reactions or they can be added. iÞ is given by Eq. the subscripts i and j indicate the number of LCBs per chain. 8. The weight distribution of chain length for polymer populations containing i LCBs per chain. long-chain branch formation can be seen as a copolymerization reaction with a very long a-olefin and. (1)–(14) for homopolymerization needs to be augmented by only one additional equation. (29). Several metallocene catalysts and some homogeneous Ziegler–Natta catalysts are effective in forming polymer chains with LCBs. as described by Eqs. (4) and (8).2 CH 2 Zr = B 2 Zr CH  B = 396 Ds. (31). In this way. (30) [42]. a chain with one LCB is formed (i þ j þ 1 ¼ 1). as an additional comonomer type. (29). iÞ ¼ t¼ 1 r 2iþ1 t 2iþ2 expðtrÞ ð2i þ 1Þ! rate of chain transfer þ rate of LCB formation rate of propagation ð30Þ ð31Þ .

00015 4 LCB 5 LCB 0.00025 1 LCB 0. An analytical solution for the instantaneous chain length distribution for the whole polymer produced in a CSTR is also available [Eq. (15). and Eq. (34). given by Eq. Figure 8.8. Therefore. As expected.28 shows the chain length distribution for several polymer populations with increasing numbers of LCBs per chain. and Y is the concentration of growing polymer chains in the reactor. in the absence of LCB formation.00005 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 r Chain length distributions of the several polymer populations of branched polyolefins made with a single-site coordination catalyst (1=t ¼ 1000). s is the reciprocal of the average reactor residence time.00035 0. 44].28. 8.0001 0. y ) 0. The function I1 is the modified Bessel function of the first kind of order 1. t ¼ 1=rn . Eq. measured with respect to the total concentration of polymer.0003 w (r .0004 Linear 0. wðrÞ ¼ I1 ðxÞ ¼  pffiffiffi  ð1  aÞt expðrtÞ rt a pffiffiffi I1 2 1þa ð1 þ aÞ a y X ðx=2Þ 12k k!Gðk þ 2Þ k¼0 ð32Þ ð33Þ The parameter a is defined by Eq. (30) reduces to Flory’s most probable distribution. (33). Fig.0002 2 LCB 3 LCB 0.3 Polymerization Kinetics and Mechanism with Coordination Catalysts 0. where f ¼ is the molar fraction of macromonomer in the reactor. (32)] [15]. the chain length average increases with an increasing number of LCBs per chain. 397 . kLCB is the rate constant for LCB formation. Bessel functions are easily found in mathematical tables and are readily available is most scientific software applications [43.

all the factors determining LCB formation with a coordination catalyst. All chains are linear when a ¼ 0 since this implies that either f ¼ ¼ 0 (without macromonomers.5 0 0 5000 10000 15000 20000 25000 30000 35000 40000 r Fig.8 Coordination Polymerization 0.00015 0.0001 α = 0. in a very elegant way. Both cases imply that no macromonomers are accumulated in the reactor. (32) captures. kLCB Y ! y. On the other hand.0003 α = 0.00035 0.29 shows how the chain length distribution of the whole polymer is affected by the value of the parameter a. Eq. a condition obeyed only when all dead polymer chains in the reactor contain terminal unsaturations. notice that a belongs to the interval [0. LCB formation is maximal when a ¼ 1.00005 α = 0. Overall chain length distribution for branched polyolefins made with a single-site coordination catalyst (1=t ¼ 1000). by Eq. no LCBs can be formed) or s=ðkLCB YÞ ! y. s ! 0. The parameter a can also be related to the number of LCBs per chain for the whole polymer. a¼ f¼ 1 þ s=ðkLCB YÞ ð34Þ Figure 8.0002 w (r ) 398 0. Therefore. f ¼ ¼ 1.1 0. (35). 1]. or the rate of LCB formation is infinite. B. The latter condition is obeyed when either s ! y (that is.3 0.29.00025 0. and the residence time in the reactor is infinite. B¼ a 1a ð35Þ . 8. the reactor residence time tends to zero) or kLCB Y ¼ 0. First.

with values of B rarely exceeding unity. (36)–(38). for sparsely branched polymers. (40)] of Stockmayer’s distribution can be derived for binary copolymers containing LCBs formed by terminal branching [45]. Since most long-chain-branched polyolefins made with coordination catalysts are only sparsely branched. Similarly. but the number of more highly branched species increases as a ! 1. wðr. most of the chains are linear. a window into their chain architecture and can be very useful in understanding the constitution of these complex polymers.30.8. Chain length averages and polydispersity index for the whole polymer can also be related to the parameters a or B via Eqs. iÞ ¼ rffiffiffiffiffiffiffiffi   1 r ry 2 r 2iþ1 t 2iþ2 expðrtÞ exp  ð2i þ 1Þ! 2pk 2k ð40Þ These equations give a very accurate portrait of the chain microstructure of these polyolefins. They are. such as heterogeneous Ziegler–Natta and Phillips catalysts. as illustrated in Figure 8. typically silica. m i .4 Single Particle Models – Mass. y. by Eq.and Heat-transfer Resistances Notice that the average number of LCBs per chain can vary from 0 when a ¼ 0 to infinity when a ¼ 1. in fact. (39).4 Single Particle Models – Mass. 8. the upper limit of the paramter a should be considered only as a theoretical possibility never to be reached in practical situations. Many metallocene catalysts have also been supported on inorganic carriers.and Heat-transfer Resistances Most commercial processes for the manufacture of polyolefins use solid catalysts. an extension [Eq. mi ¼ ð2iÞ! a i ð1  aÞð2i þ 1Þ i!ði þ 1Þ! ð1 þ aÞ 2iþ2 ð39Þ Notice that. It is also interesting to calculate the mass fraction of polymer populations containing i LCBs per chain. 1 r n ¼ ð1 þ 2BÞ t ð36Þ 2 r w ¼ ð1 þ 2BÞð1 þ BÞ t ð37Þ PDI ¼ 2ð1 þ BÞ ð38Þ These equations demonstrate that the polydispersity index of long-chain-branched polyolefins is always greater than 2 and that the chain length averages increase with an increasing number of LCBs per chain. for industrial 399 .

(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. interparticle and intraparticle massand heat-transfer resistances may become a limiting step in heterogeneous olefin polymerization processes. When a fresh catalyst particle is first fed to the reactor it is evidently free of polymer. use [24]. as illustrated in . forming an expanding polymer particle composed of polymer chains surrounding catalyst fragments.2 0.3 0.31 are possible: (1) the polymer phase clogs the catalyst pores and inhibits any additional polymerization from happening. generating fines.2 α = 0. This leads to the so-called ‘‘replication phenomenon’’. as is usual with most heterogeneous catalysts. much catalyst research is behind the design of catalyst particles that can be properly fragmented to form uniform polymer particles. 8.5 0. At this point.30.8 0.9 α = 0.4 α = 0.7 0.5 5 i (LCB/chain) Fig.8 Coordination Polymerization 1 α = 0.5 2 2. As in any solid-catalyzed reaction. as a function of the parameter a. but its pores quickly become filled with polymer molecules formed as monomer diffuses from the bulk phase in the reactor to the surface of the active sites on the catalyst pores. Effective heterogeneous catalysts for olefin polymerization are highly porous. The last alternative is the only one that has industrial interest.6 mi 400 0.1 0 0 0.4 0.05 α = 0. (2) the structure of the catalyst is not strong enough to resist the expansion forces of the fast-forming polymer chains and ‘‘explodes’’ in several smaller particles.5 4 4. the three alternatives illustrated in Figure 8. Mass fraction of chains with i LCB per chain. Olefin polymerization with heterogeneous catalysts has several very distinct characteristics that should be discussed from a qualitative point of view before a more quantitative treatment is presented.1 0.5 3 3.8 0.5 1 1. whereby the size distribution of the catalyst particles is neatly replicated by the size distribution of the polymer particles exiting the reactor.

32. This picture of particle fragmentation and growth has been captured in its most important details by the multigrain model [36.4 Single Particle Models – Mass.and Heat-transfer Resistances catalyst particle with pores clogged with polymer catalyst fragmentation and formation of fines desired expanding catalyst-polymer particle Fig. Catalyst pre-polymerization in 401 . the references at the end of the chapter provide more details on this subject [46–50]. 8. but has also been used extensively to describe metallocene and late transition metals catalysts supported on inorganic carriers. Figure 8. this should not be seen as a limitation of the multigrain model for most industrial applications. Notice that the multigrain model does not deal directly with the initial seconds of particle fragmentation. the secondary particle expands as a function of polymerization time and activity.31.8. Proper replication of the catalyst particles is essential for stable reactor operation and also for the handling of the polymer particles in post-reactor processes. As polymer grows around the primary particles. The multigrain model is illustrated in Figure 8. Since many industrial catalysts are in fact pre-polymerized in milder conditions in a separate reactor before being fed to the polymerization reactor.33. It is considered to be formed by the agglomeration of several nonporous primary particles having polymerization active sites on their surfaces. Reactor residence time distribution in CSTRs may have an important effect on the replication phenomenon. Particle growth and fragmentation for polymerization with heterogeneous coordination catalysts. In the multigrain model. 51–60] which was originally developed to describe the crystalline structures of TiCl3 and TiCl4 /MgCl2 Ziegler–Natta catalysts. The secondary particle is the porous catalyst particle itself that is fed to the reactor. and the macroparticle or secondary particle. when the catalyst pores are being filled with polymer chains that start to fragment the catalyst particles. the polymer particle is divided into two levels of mass-transfer resistances: the microparticles or primary particles.

The multigrain model. Fig. 8.32. since the amount of polymer made during this very short initial stage is unlikely to have a marked influence on the overall properties of the Secondary Particle or Macroparticle Primary Particle or Microparticle Catalyst fragment Fig. 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 polymerization reactors. Several older and some more recent simulation studies deal with these initial instants of polymerization.8 Coordination Polymerization Polymerization Catalyst Polymer Cumulative % 402 Particle size Replication phenomenon for polymerization with heterogeneous coordination catalysts. These initial particle-fragmentation models are more interesting for prepolymerization studies.33. Growing polymer shell . but they are beyond the scope of this chapter. 8.

Equation (41) is subjected to the following boundary conditions given by Eqs. 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 difficulties in getting a good estimate for Deff . tÞ ¼ 0 qrs Deff qMs ðrs ¼ Rs . may be set to zero for a monomer-free catalyst condition. Finally. namely symmetry at the center of the particle and stationary convective mass transfer through the mass-transfer boundary layer surrounding the particle. ks is the mass-transfer coefficient in the external film surrounding the secondary particle.4 Single Particle Models – Mass. (43) and (44). A 2001 review covers some of these alternative models [36]. It is also common to assume a pseudo-steady- 403 . t. where Ms is the monomer concentration in the secondary particle as a function of polymerization time. qMs ðrs ¼ 0. where Db is the monomer bulk diffusivity in the reaction medium. Deff ¼ eDb t ð42Þ Finally. respectively. the polymerization is assumed to take place only at the surface of the primary particles. this term couples the models for the primary and secondary particles. respectively.   qMs 1 q qMs ¼ 2 Deff rs2  RVp rs qrs qt qrs ð41Þ The effective diffusivity in the secondary particle. (41). The multigrain model equation for spherical secondary particles is the classic diffusion-reaction equation in a sphere. Eq. (45). Deff . Ms0 .and Heat-transfer Resistances polymer produced in the reactor.8. Eq. can be estimated using the conventional expression for effective diffusivity in porous heterogeneous catalysts. tÞ ¼ ks ðMb  Ms Þ qrs Ms ðrs . but this generally leads to stiff differential equations that may be very hard to solve. RpV is the average volumetric rate of polymerization in the secondary particle at a given radial position. rs . Equations (43) and (44) are the classic boundary conditions for heterogeneously catalyzed chemical reactions. and Mb is the monomer concentration in the bulk phase. and e and t are the void fraction and tortuosity of the polymer particle. in the multigrain model. Since. the initial condition is given by Eq. t ¼ 0Þ ¼ Ms0 ð43Þ ð44Þ ð45Þ The initial concentration in the secondary particle. and radial position. (42). where Rs is the radius of the secondary particle.

where C  is the concentration of active sites at the surface of the catalyst fragment. tÞ ¼ pR 3c R pc 3 qrp Mp ðrp ¼ R p . (51). Meq . Meq ¼ Ms KMP ð50Þ The polymerization rate at the surface of the catalyst fragment is given by Eq. (41). the reaction term appears as one of the two required boundary conditions [Eq. Dp ¼ Da wi ð47Þ Notice that Eq. As can be very well imagined. (49) imposes the condition that the concentration at the surface of the primary particle equals the equilibrium concentration of monomer absorbed onto the polymer phase. Equation (48) states that the rate of monomer diffusion at the surface of the catalyst fragment. Equation (47) has been suggested to estimate the effective diffusivity of monomer in the primary particle. . between the two phases is known. Spherical primary particles are modeled with a similar equation [Eq.   qMp 1 q 2 qMp Dp rp ¼ 2 rp qrp qt qrp ð46Þ In Eq.404 8 Coordination Polymerization state concentration at t ¼ 0 to obtain the initial condition for Eq. where Da is the diffusivity of monomer in amorphous polymer and w and i are correction factors to account for the decrease in diffusivity due to chain crystallinity and immobilization of the polymer amorphous phase due to the crystallites. Because the multigrain model assumes that polymerization takes place at the surface of the catalyst fragment embedded within the primary particle. 4pR 2c Dp qMp 4 ðrp ¼ R c . and Eq. the subscript p refers to values in the primary particles. KMP . (46) does not contain a polymerization reaction term. R c . equals the rate of monomer consumption due to polymerization at rate of Rpc . (48)]. Unless one is interested in the monomer profiles for the very first seconds of polymerization. these parameters are also hard to determine and Dp is generally used as an adjustable parameter in the model. tÞ ¼ Meq a Ms ð48Þ ð49Þ The equilibrium concentration of monomer in polymer can be related by Eq. this approximation generally leads to a system of partial differential equations that is simpler to integrate. (46). (46)]. (50) to the monomer concentration in the secondary particle at a given radial position and time if a partition coefficient.

and heattransfer effects become less prevalent. Temperature profiles in the primary and secondary particles according to the multigrain model. t ¼ 0Þ ¼ Ts0   qTp qTp 1 q ¼ 2 ke rp2 rp qrp qt qrp 4 2 qTp 4pRc ke ðrp ¼ R p . 51–60]. it can be said with confidence 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. a pseudo-steady-state approximation may be adopted to reduce the stiffness of the system of differential equations for short polymeriza