Syndiotactic Polystyrene: Synthesis, Characterization, Processing, and Applications

SYNDIOTACTIC POLYSTYRENE......Page 4
CONTENTS......Page 10
PREFACE......Page 20
CONTRIBUTORS......Page 24
ABOUT THE EDITOR......Page 28
PART I INTRODUCTION......Page 30
1.1 Discovery of Syndiotactic Polystyrene (SPS)......Page 32
1.2 Early Years of Development (1985–1989)......Page 34
1.3 Intense Development Years (1989–1996)......Page 35
1.4 Initial Commercial Launch Stage (1996–2001)......Page 41
1.5 Years 2001–2007......Page 42
PART II PREPARATION OF SYNDIOTACTIC POLYSTYRENE......Page 44
2.1 Introduction......Page 46
2.2.1 Metals......Page 47
2.2.2 Titanium Complexes......Page 48
2.2.3 Molecular Weight Control......Page 55
2.2.4 Supported and Heterogeneous Catalysts......Page 56
References......Page 58
3.2 MAO......Page 61
3.3 Boron Compounds......Page 65
3.4 Other Chemicals......Page 68
References......Page 69
4.2 Insertion of the Growing Polymer Chain into the Double Bond of Styrene......Page 71
4.3 Stereochemistry of the Styrene Insertion......Page 74
4.4 Effects of Hydrogenation of the Catalyst......Page 76
4.5.1 Valence of Active Sites......Page 77
4.5.2 Number of Active Sites......Page 81
4.5.3 Structure of Active Sites......Page 82
4.7 Kinetic Analysis of Styrene Polymerization......Page 83
4.8 Conclusions......Page 86
References......Page 87
5.1 Introduction......Page 89
5.2 Ethylene/Styrene Copolymers: Microstructures, Thermal Properties, and Composition Analyses......Page 90
5.3.1 Half-Titanocenes, Cp´TiX(3)......Page 93
5.3.2 Linked (Constrained Geometry Type) Half-Titanocenes......Page 94
5.3.3 Modified Half-Titanocenes, C(p´)Ti(L)X(2)......Page 100
5.3.4 Non-Cp Titanium Complexes......Page 108
5.3.5 Metallocenes......Page 112
5.3.6 Others......Page 114
5.4 Summary and Outlook......Page 115
References......Page 116
6.1 Introduction......Page 121
6.2 The Tbf Ligand......Page 123
6.3.1 Synthesis and Characterization of Tbf Lithium......Page 125
6.4.1 Synthesis of Tbf Titanium(III) Chloride Complexes......Page 127
6.4.2 Reaction of TbfTi(III)Cl(2)(THF) (VIII) with Radicals......Page 131
6.5 Tbf Titanium(IV) Derivatives......Page 134
6.5.1 Synthesis of Tbf Titanium Monophenoxide Complexes......Page 136
6.6 Dynamic and Polymerization Behavior of Tetrabenzofluorenyl Titanium Complexes......Page 146
6.6.1 Styrene Polymerization......Page 148
References......Page 149
7.1 Introduction......Page 154
7.2 Metallocene Catalysts......Page 155
7.3 Constrained Geometry Catalysts......Page 158
7.4 Half-Sandwich Catalysts......Page 159
7.5 Nonmetallocene Catalysts......Page 163
References......Page 165
8.1 Introduction......Page 169
8.2.1 Kinetic Profiles of Heterogeneous SPS Polymerization......Page 170
8.2.2 Liquid Slurry Polymerization with Heterogenized Cp*Ti(OCH(3))(3) Catalyst......Page 172
8.2.3 Modeling of Polymerization Kinetics......Page 174
8.2.4 Molecular Weight Distribution of SPS with Heterogeneous Catalysts......Page 176
8.3.1 Physical Transitions of Reaction Mixture During Polymerization......Page 178
8.3.2 Effect of Reaction Conditions on Polymer Morphology......Page 180
References......Page 182
PART III STRUCTURE AND FUNDAMENTAL PROPERTIES OF SYNDIOTACTIC POLYSTYRENE......Page 184
9.2 Polymorphic Behavior of SPS......Page 186
9.2.1 Crystallization from the Melt State......Page 188
9.2.2 Crystallization from the Glassy State......Page 189
9.2.3 Morphology Development in the Presence of Solvents......Page 192
9.3.1 Crystal Structure of the α Form......Page 193
9.3.2 Crystal Structure of the β Form......Page 197
9.3.3 Lamellar and Spherulitic Morphology of the Zigzag Forms......Page 199
9.4 Morphology of the Mesomorphic Phases......Page 202
9.5 Thermodynamic and Kinetics of Crystallization......Page 204
9.5.1 Thermodynamic and Kinetics of Crystallization......Page 206
9.6 Melting Behavior......Page 207
9.6.1 Equilibrium Melting Temperature of α and β Crystals......Page 209
9.6.2 Memory Effects......Page 211
9.7.1 Morphology of Injection Molded Samples......Page 212
9.7.2 Relation between Morphology Structure, Processing, and Properties......Page 213
References......Page 215
10.1 Introduction......Page 223
10.2 Co-Crystals......Page 224
10.2.1 Crystalline Structures......Page 225
10.2.2 Processing and Materials......Page 228
10.2.3 Characterization Studies......Page 231
10.2.4 Properties and Applications......Page 238
10.3 Nanoporous Crystalline Phases......Page 241
10.3.1 Crystalline Structures......Page 242
10.3.2 Processing and Materials......Page 244
10.3.3 Characterization Studies......Page 246
10.3.4 Applications......Page 248
10.4 Conclusions and Perspectives......Page 253
References......Page 254
11.1 Introduction......Page 267
11.2 Theoretical Background......Page 268
11.3 Equilibrium Melting Point of SPS......Page 269
11.3.1 Evaluation of Spherulitic Growth Rate G......Page 273
11.4 Analyses of Spherulitic Growth Rate G......Page 277
11.5 Comparison Between SPS and IPS......Page 278
References......Page 279
PART IV COMMERCIAL PROCESSES FOR MANUFACTURING OF SYNDIOTACTIC POLYSTYRENE......Page 282
12.2 Monomer Purification Section......Page 284
12.4 Polymerization Section......Page 285
12.4.1 Continuous Stirred Tank Reactor Process......Page 286
12.4.3 Continuous Self-Cleaning Reactor Process......Page 287
12.6 Deactivating Section......Page 289
12.8 Blending Section......Page 291
12.9 Shipping Section......Page 292
References......Page 293
PART V PROPERTIES, PROCESSING, AND APPLICATIONS OF SYNDIOTACTIC POLYSTYRENE......Page 296
13.2 Rheological Properties of SPS......Page 298
13.3.1 Thermal Properties of SPS......Page 301
13.3.2 Mechanical Properties of SPS......Page 303
13.4.1 Properties of Uniaxially Oriented SPS......Page 310
13.4.2 Properties of Biaxially Oriented SPS (BoSPS)......Page 311
13.5.1 Electrical Properties of SPS......Page 315
13.5.2 Chemical Resistance of SPS......Page 316
References......Page 318
14.1 Introduction......Page 319
14.2.1 Introduction......Page 323
14.2.2 Compounding Equipment......Page 324
14.2.3 Compounding Process Conditions......Page 325
14.3.1 Introduction......Page 327
14.3.2 General Product Design......Page 328
14.3.4 Injection Mold Design......Page 330
14.3.5 Injection Mold Melt Delivery System (Runners and Gates)......Page 331
14.3.8 Shrinkage during the Cooling Phase......Page 333
14.3.9 Injection Molding Process Set-up......Page 335
14.3.10 Injection Molding Cycle......Page 337
14.3.11 Special Injection Molding Cycles......Page 339
14.4.2 Extrusion......Page 340
14.4.3 General Extruder Design......Page 341
14.4.4 Processing Parameters......Page 342
14.5.2 Cast Film Extrusion......Page 343
14.5.3 Thermoforming......Page 344
14.6 Fiber Spinning......Page 345
References......Page 348
15.1 Introduction......Page 350
15.2 The Performance Capabilities of SPS......Page 351
15.3 Connectors for Automotive and Electronic Applications......Page 358
15.4 Electronic Components: Plated and Non-Plated......Page 359
15.5 Industrial and Appliance Components......Page 360
References......Page 366
16.2 Composition of SPS/Nylon Blends......Page 367
16.3 Properties of SPS/Nylon Blends......Page 368
16.3.1 Mechanical Properties of SPS/Nylon Blends......Page 369
16.3.3 Moisture Absorption and Moisture Growth of SPS/Nylon Blends......Page 372
16.3.4 Dimensional Stability of SPS/Nylon Blends......Page 375
16.3.5 USCAR Performance of SPS/Nylon Blends......Page 376
16.4.1 SPS/Nylon Blend Under-the-hood Automotive Connectors......Page 378
16.4.2 SPS/Nylon Blend Carpet Fibers......Page 379
16.4.3 SPS/Nylon Blend Application Patents......Page 382
References......Page 384
17.1 Introduction......Page 389
17.3 Theoretical Background......Page 390
17.4 Tacticity Effect on Miscibility......Page 392
17.5 Properties of Blends of SPS and APS......Page 395
References......Page 399
18.1 Introduction......Page 400
18.2 Morphological Analyses of HISPS......Page 401
18.2.1 SAXS Profiles of HISPS in the Crystalline State......Page 403
18.2.2 Effect of Nucleators on Lamellar Orientation in HISPS......Page 404
18.3 Morphology of SPS/PPO Binary Blends......Page 405
18.3.1 Structural Analyses Using SAXS Technique......Page 406
18.3.2 Crystallization Kinetics of SPS/PPO Blends......Page 407
18.3.3 Influence of Blending PPO with Different Molecular Weights on the Morphology of HISPS......Page 409
18.4 Compatibilizer Effects......Page 411
18.4.1 Evaluation of Interaction Parameters......Page 412
18.4.2 Evaluation of Domain Size and Interfacial Thickness......Page 417
References......Page 422
PART VI POLYMERS BASED ON SYNDIOTACTIC POLYSTYRENES......Page 424
19.1 Introduction......Page 426
19.2.1 Copolymerization of Styrene and B-styrene......Page 427
19.2.2 Side-Chain Functionalized SPS Polymers......Page 431
19.2.3 SPS Graft Copolymers......Page 435
19.3 Functionalization of SPS via Borane Chain Transfer Agents......Page 438
19.3.1 SPS Containing a Terminal Functional Group......Page 439
19.3.2 SPS Block Copolymers......Page 441
References......Page 444
20.1 Introduction......Page 446
20.2 Polymer Nanocomposites and Microstructure......Page 447
20.3 Fabrication of Polymer Nanocomposites......Page 448
20.4 Characterization of Polymer Nanocomposites......Page 449
20.5 Preparation of SPS Nanocomposites......Page 450
20.5.1 Effect of Alkyl Chain Aggregation in Organoclay—Bilayer versus Monolayer Arrangement......Page 452
20.5.2 Improvement in the Thermal Stability of Organoclay......Page 453
20.6.1 Mechanical Properties......Page 454
20.6.3 Dynamic Rheological Properties......Page 455
20.7 Final Remarks......Page 456
References......Page 458
INDEX......Page 460