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Polyisoprene, December 1972

l Report No. 82

e POLYISOPRENE

by ROBERT L. MAGOVERN

and SARA L. SODER


0

December 197 2

l A private report by the

PROCESS ECONOMICS PROGRAM

I
STANFORD RESEARCH INSTITUTE MENLO PARK, CALIFORNIA
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Polyisoprene, December 1972

CONTENTS

1 INTRODUCTION. , . . . . . . . . . . . , . . . . . . . . . . 1

2 SUMMARY ..........................

General Aspects ......................


Polyisoprene Manufacture .................
Polyisoprene Latex Manufacture ..............
Technical Aspects .....................

3 INDUSTRY STATUS . . . . . , , . . , . . . . , . . . . . . . 13

4 CHEMISTRY ......................... 19
Lithium Catalysts ..................... 21
Mechanism ........................ 23
Initiation ....................... 24
Propagation ....................... 25
Termination ...................... 26
Effect of Solvent Composition .............. 27
Effect of Catalyst Concentration ............. 28
Effect of Monomer Conversion ............... 29
Rate of Polymerization .................. 31
Ziegler Catalysts ..................... 32

5 PROPERTIES AND APPLICATIONS ................ 41


Property-Structure Relationship .............. 44
Effect of Structure on Physical and Mechanical
Properties ....................... 44
Effect of Structure and Properties on Processing ..... 47
Viscosity-MolecularWeight Relationships ......... 48
"Minirnurnll
Molecular Weight ................ 48
Polyisoprene Unsaturation ................ 49
cis-trans Isomerization and Other Chemical Reactions ... 49
Compounding Ingredients ................. 50
Compounding and Processing ................. 51
CoralB Rubber ...................... 52
Cariflex@ IR ....................... 52
Natsy# ......................... 53
AmeripolB SN ....................... 56
Russian %KI1( Polyisoprene ................ 56
Product Design with Polyisoprene ............. 56
Injection Molding .................... 56
Oil-extended Polyisoprene ................. 58

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CONTENTS

5 (continued)

Polyisoprene Latex ..................... 60


trans-1,4 Polyisoprene ................... 62
Polyisoprene Copolymers, Popcorn Polymer, and Cyclized
Polyisoprene ....................... 64

6 REVIEW OF PROCESSES .................... 67


Ziegler-Type Catalysts ................... 68
Lithium Catalysts ..................... 70

7 POLYISOPRENE BY A ZIEGLER CATALYST ............. 159


Process Description .................... 159
Process Discussion .................... 175
Reactor Design Basis ................... 175
Polymer Purification and Recovery ............ 177
Monomer and Solvent Recovery ............... 178
Polymer Drying and Finishing ............... 178
Utilities ........................ 179
Cost Estimates ....................... 179
Capital Costs ...................... 179
Production Costs ..................... 180
Selling Price ...................... 181
Effect of Monomer Cost .................. 181

8 POLYISOPRENE BY A LITHIUM CATALYST . . , , , . , . . . . . . 187


Process Description . . . . . ............... 187
Process Discussion . . . .,. . ............... 203
Reactor Design Basis . . . . ............... 203
Polymer Recovery . . . , . . ............... 206
Monomer and Solvent Recovery ............... 206
Polymer Drying and Finishing ............... 206
Utilities . . . . . . . . . ............... 206
Cost Estimates . . . . . . . . ............... 211
Capital Costs . , , . . . . ............... 211
Production Costs . . , . . . ............... 211
Selling Price . . . . . . . ............... 212
Effect of Monomer Cost . . . ............... 212

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CONTENTS

9 POLYISOPRENE LATEX. .................... 217


Process Review ....................... 218
Process Description .................... 226
Process Discussion ..................... 232
Cost Estimates ....................... 234
Capital Costs ...................... 234
Production Costs ..................... 234
Selling Price ...................... 235

APPENDIX A DESIGN AND COST BASIS ............... 239

APPENDIX B PHYSICAL DATA AND SPECIFICATIONS .......... 243

APPENDIX C PROCESSING AND COMPOUNDING OF SYNTHETIC


cis-1,4 POLYISOPRENE ................ 247

APPENDIX D SAFETY AND HANDLING ................ 265

CITED REFERENCES. ....................... 267

PATENT REFERENCES BYCOMPANY. ................. 327

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Polyisoprene, December 1972

ILLUSTRATIONS

4.1 Stereoregular Polyisoprene Structures . . . . . . . . . . 22


4.2 Polyisoprene by a Lithium Catalyst
Effect of Ethers on Microstructure . . . . . . . , . . . , 27

4.3 Polyisoprene by a Lithium Catalyst


Effect of Catalyst Concentration on Microstructure . . . . 28
4.4 Polyisoprene by a Lithium Catalyst
Effect of Catalyst Concentration on Inherent Viscosity . . 29
4.5 Polyisoprene by a Lithium Catalyst
Effect of Catalyst Concentration on Rate . , . . . . . . . 30
4.6 Polyisoprene by a Lithium Catalyst
Effect of Monomer Concentration on Rate
of Polymerization (Cyclohexane Solvent) . . . . . . . . . 32
4.7 Polyisoprene by a Lithium Catalyst
Monomer Conversion with Time , . , . . . . . . . . . . . . 33
4.8 Polyisoprene by a Ziegler Catalyst
Effect of Catalyst Composition on Microstructure . . . . . 35
4.9 Polyisoprene by a Ziegler Catalyst
Effect of Temperature on Inherent Viscosity . , . . . . . 36
7.1 Polyisoprene by a Ziegler Catalyst . . . . . . . , . , . . 163
7.2 Polyisoprene by a Ziegler Catalyst
Effect of Operating Level and Plant
Capacity on Production Cost , . . . , . , . . , . . . . , 186
8.1 Polyisoprene by a Lithium Catalyst . . . . . . , . . . . . 191
8.2 Polymerization of Isoprene by a Lithium Catalyst
Effect of Catalyst Concentration on Molecular Weight . . . 209
8.3 Polymerization of Isoprene by a Lithium Catalyst
Relationship between Catalyst Concentration and
Intrinsic Viscosity . . . . . . . . , . . . . . . . . . . 210
8.4 Polyisoprene by a Lithium Catalyst
Control of Molecular Weight . . . . . . , . . . . . . . . 210
8.5 Polyisoprene by a Lithium Catalyst
Effect of Operating Level and Plant
Capacity on Production Cost . . . . . . . . . . . . . . . 216

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ILLUSTRATIONS

9.1 Emulsifiability Diagram for Polyisoprene . . . . . . . , . 219


9.2 Solution Viscosity as Affected by Solids
Content and Polymer Intrinsic Viscosity
cis-1,4 Polyisoprene in Hexane . . . . . . . . . . . , . , 221
9.3 Process for Synthetic Rubber Latex . , . . . . , . . . . , 225
9.4 Polyisoprene Latex . . . . . . . . . . . . . . . . . . , . 229
9.5 Polyisoprene Latex
Effect of Emulsification Temperature
on Latex Particle Size . . . . . , . . . . . . . . . . . , 233
9.6 Polyisoprene Latex
Effect of Operating Level and Plant
Capacity on Production Cost . . . . . . . . , . . . . . , 238
Polyisoprene, December 1972

TABLES

2.1 Comparison of the Estimated Costs of Polyisoprene


Production Processes . . . . . . . . . . . . . . . . . . 6
2.2 Process Comparison for Polyisoprene Production . . . . . 10
3.1 Synthetic Rubber Production and Sales in the
United States . . . . , . . . . . . , . , . . . . , . . . 14
3.2 Estimated End Use Pattern of Polyisoprene in
the United States , . . , . . . . . . . . . . . , . . , . 15
3.3 Natural Rubber and Polyisoprene Consumption in
the United States . . . . . . . . . . . , . . . . . . . . 16
3.4 Major Rubbers Used in U.S. Tires . . . . . . . . . . . . 16
3.5 Polyisoprene Plant Capacities . . . . . . . . . . . . . . 17
4.1 Microstructure of Polyisoprene Catalyzed by
Alkali Metal and A'lkaliMetal Derivatives . . . . , . . . 24
4.2 Polymerization by a Lithium Catalyst
Effect of Conversion on Microstructure . . . . . , . . . 31

4.3 Polyisoprene by a Ziegler Catalyst


Effect of Catalyst Concentration on Rate . . . . . . . . 37
5.1 Comparison of Polyisoprene and Natural
Rubber Properties . , . . . . . . . . . . . . . . . . . . 42
5.2 Gum and Tread Vulcanizate Properties of IR, NR,
SBR,andBR................. . . . . . . 43
5.3 Effect of Molecular Weight Distribution on
Processability of Linear cis Polyisoprenes . . , . . . . 47
5.4 Effect of Oil Level on Polyisoprene Properties , . , , . 59
5.5 Properties of IR, NR, and SBR Latices . . . . . . . . . . 60
6.1 Microstructures of Polyisoprene and Natural Rubber , . . 67
6.2 Polyisoprene
Patent Summary . , . , . . . . . . . . . . . . . . . . . 72
7.1 Polyisoprene by a Ziegler Catalyst
Major Process Equipment and Utilities Summary . . , . . . 163
7.2 Polyisoprene by a Ziegler Catalyst
Stream Flows . . . . . . . . . . . . . . . . . . . . . . 171

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TABLES

7.3 Polyisoprene by a Ziegler Catalyst


Effect on Catalysts of Adding Phenyl Ether , , . , . . . 176
7.4 Polyisoprene by a Ziegler Catalyst
Total Capital Investment . . . . . . . . . . . . . . . . 183
7.5 Polyisoprene by a Ziegler Catalyst
Production Costs . . . . . . . . . , . . . . . , . . , . 185
8.1 Polyisoprene by a Lithium Catalyst
Major Process Equipment and Utilities Summary . . . . . . 190
8.2 Polyisoprene by a Lithium Catalyst
Stream Flows . . . . . . . . . . . . . . . . , . , . . . 199
8.3 Lithium-Catalyzed Polymerization of Isoprene
Reaction Conditions . . . , . . . . . . . . . . . . . . . 207
8.4 Polyisoprene by a Lithium Catalyst
Total Capital Investment . . . . . . . . . . . . . . . , 213
8.5 Polyisoprene by a Lithium Catalyst
Production Costs . . . , . . . . . . , . . . . , . , . . 215
9.1 Polyisoprene Latex
Major Process Equipment and Utilities Summary . , . . , . 229
9.2 Polyisoprene Latex
Stream Flows . , . . . . . . . . . . . . . . . . . . . . 231
9.3 Polyisoprene Latex
Total Capital Investment . . . . . . . . . . . . , . . . 236
9.4 Polyisoprene Latex
Production Costs , . . . . . . . . . . . . . . . , . . , 237
B.l Specifications for Shell Isoprene Rubber . , . , . . . , 244
B.2 Properties of Raw Latex for Shell Isoprene Latex 700 . . 245
c.1 Suggested Mixing Procedures for Shell Isoprene
Rubber in Injection Molding . . . . , , , . . . . . . , . 249
c.2 NR, IR, and BR Tread Recipes and Physical Test
Data on Factory Extruded Treads . . . , . . . . , . . , . 250
c.3 Comparison of "SKI'Iand Natural Rubber , . . . , . . , . 252
c.4 Comparison of WSKIfl/SKD(BR)BAF Tread
Vulcanizates with NR, SBR, and BR . . , . . . . . . . . . 253

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TABLES

c.5 Representative Formulations of Natsyn and


Cariflex IR Nontire Products , . . . . . . . . . . . . . 254
C.6 Electrical Resistivity and Water Absorption
of NR and Shell IR Gum Stocks . . . . , . . . . . . . . . 256
c.7 Evaluation of Oil-Extended Natsyn 450 in Gum Stocks . . . 257
C.8 Evaluation of Oil-Extended Natsyn 450 in BAF
Black Stocks . . . . . . . . . . . . . . . . . . . . . . 259
c.9 Polyisoprene Latex Foam Formulations and Physical
Properties . . . . . . . . . . . , . . . . . . . . . . . 261
c.10 Formulations for Polyisoprene Latex Dipped Goods . . . . 262
c.11 Formulations for Miscellaneous Polyisoprene Latex
Products . . . . . . . . . . . . . . . . . . . . . . . . 263

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