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[资源] 【资源】Syndiotactic Polystyrene

Syndiotactic Polystyrene: Synthesis, Characterization, Processing, and Applications
by: Jürgen Schellenberg
en | Wiley

0470286881 9780470286883

Syndiotactic Polystyrene: Synthesis, Characterization, Processing, and Applications
By Jürgen Schellenberg

•Publisher: Wiley
•Number Of Pages: 484
•Publication Date: 2009-11-16
•ISBN-10 / ASIN: 0470286881
•ISBN-13 / EAN: 9780470286883

Product Description:

Syndiotactic Polystyrene (SPS), synthesized in a laboratory for the first time in 1985, has become commercialized in a very short time, with wide acceptance on the global plastics market. Written by leading experts from academia and industry from all over the world, Syndiotactic Polystyrene offers a comprehensive review of all aspects of SPS of interest to both science and industry, from preparation and properties to applications.

This essential reference to SPS covers:

•The preparation of syndiotactic polystyrene by half-metallocenes and other transition metal catalysts

•The structure and fundamental properties, especially morphology and crystallization and solution behavior

•The commercial process for SPS manufacturing

•Properties, processing, and applications of syndiotactic polystyrenes

•Polymers based on syndiotactic polystyrenes, for example, by functionalization and modification, and nanocomposites

Ideal for polymer chemists, physicists, plastics engineers, materials scientists, and all those dealing with plastics manufacturing and processing, this important resource provides the information one needs to compare, select, and integrate an appropriate materials solution for industrial use or research.

CONTENTS
vii
PREFACE xvii
CONTRIBUTORS xxi
ABOUT THE EDITOR xxv
PART I INTRODUCTION 1
1. Historical Overview and Commercialization of Syndiotactic
Polystyrene 3
Michael Malanga, Osamu Isogai, Takeshi Yamada, Shigeo Iwasaki, and
Masahiko Kuramoto
1.1 Discovery of Syndiotactic Polystyrene (SPS) 3
1.2 Early Years of Development (1985.1989) 5
1.3 Intense Development Years (1989.1996) 6
1.4 Initial Commercial Launch Stage (1996.2001) 12
1.5 Years 2001.2007 13
PART II PREPARATION OF SYNDIOTACTIC POLYSTYRENE 15
2. Transition Metal Catalysts for Syndiotactic Polystyrene 17
Norio Tomotsu, Thomas H. Newman, Mizutomo Takeuchi,
Richard Campbell Jr., and Jurgen Schellenberg
2.1 Introduction 17
2.2 Transition Metal Compounds 18
2.2.1 Metals 18
2.2.2 Titanium Complexes 19
2.2.3 Molecular Weight Control 26
2.2.4 Supported and Heterogeneous Catalysts 27
2.3 Summary 29
References 29
viii CONTENTS
3. Cocatalysts for the Syndiospecifi c Styrene Polymerization 32
Norio Tomotsu, Hiroshi Maezawa, and Thomas H. Newman
3.1 Introduction 32
3.2 MAO 32
3.3 Boron Compounds 36
3.4 Other Chemicals 39
3.5 Summary 40
References 40
4. Mechanisms for Stereochemical Control in the Syndiotactic
Polymerization of Styrene 42
Norio Tomotsu, Thomas H. Newman, and Richard Campbell Jr.
4.1 Introduction 42
4.2 Insertion of the Growing Polymer Chain into the Double
Bond of Styrene 42
4.3 Stereochemistry of the Styrene Insertion 45
4.4 Effects of Hydrogenation of the Catalyst 47
4.5 Active Site Species 48
4.5.1 Valence of Active Sites 48
4.5.2 Number of Active Sites 52
4.5.3 Structure of Active Sites 53
4.6 Theoretical Analysis of the Catalyst 54
4.7 Kinetic Analysis of Styrene Polymerization 54
4.8 Conclusions 57
References 58
5. Copolymerization of Ethylene with Styrene: Design of Effi cient
Transition Metal Complex Catalysts 60
Kotohiro Nomura
5.1 Introduction 60
5.2 Ethylene/Styrene Copolymers: Microstructures, Thermal
Properties, and Composition Analyses 61
5.3 Ethylene/Styrene Copolymerization Using Transition Metal
Complex.Cocatalyst Systems 64
5.3.1 Half-Titanocenes, CpŒTiX3 64
5.3.2 Linked (Constrained Geometry Type)
Half-Titanocenes 65
5.3.3 Modifi ed Half-Titanocenes, CpŒTi(L)X2 71
CONTENTS ix
5.3.4 Non-Cp Titanium Complexes 79
5.3.5 Metallocenes 83
5.3.6 Others 85
5.4 Summary and Outlook 86
References 87
6. Structure and Properties of Tetrabenzo[a,c,g,i]fl uorenyl-Based
Titanium Catalysts 92
Rudiger Beckhaus, Kai Schroder, and Jurgen Schellenberg
6.1 Introduction 92
6.2 The Tbf Ligand 94
6.3 Tbf Lithium 96
6.3.1 Synthesis and Characterization of Tbf Lithium 96
6.4 Tbf Titanium(III) Derivatives 98
6.4.1 Synthesis of Tbf Titanium(III) Chloride
Complexes 98
6.4.2 Reaction of TbfTiIIICl2(THF) (VIII) with
Radicals 102
6.5 Tbf Titanium(IV) Derivatives 105
6.5.1 Synthesis of Tbf Titanium Monophenoxide
Complexes 107
6.6 Dynamic and Polymerization Behavior of
Tetrabenzofl uorenyl Titanium Complexes 117
6.6.1 Styrene Polymerization 119
6.7 Conclusions 120
References 120
7. Rare-Earth Metal Complexes as Catalysts for Syndiospecifi c
Styrene Polymerization 125
Klaus Beckerle and Jun Okuda
7.1 Introduction 125
7.2 Metallocene Catalysts 126
7.3 Constrained Geometry Catalysts 129
7.4 Half-Sandwich Catalysts 130
7.5 Nonmetallocene Catalysts 134
7.6 Conclusion 136
References 136
x CONTENTS
8. Syndiospecifi c Styrene Polymerization with Heterogenized
Transition Metal Catalysts 140
Kyu Yong Choi
8.1 Introduction 140
8.2 Kinetics of Syndiospecifi c Polymerization with
Heterogeneous Metallocene Catalysts 141
8.2.1 Kinetic Profi les of Heterogeneous SPS
Polymerization 141
8.2.2 Liquid Slurry Polymerization with Heterogenized
Cp*Ti(OCH3)3 Catalyst 143
8.2.3 Modeling of Polymerization Kinetics 145
8.2.4 Molecular Weight Distribution of SPS with
Heterogeneous Catalysts 147
8.3 Nascent Morphology of Syndiotactic Polystyrene 149
8.3.1 Physical Transitions of Reaction Mixture During
Polymerization 149
8.3.2 Effect of Reaction Conditions on Polymer
Morphology 151
8.4 Concluding Remarks 153
References 153
PART III STRUCTURE AND FUNDAMENTAL PROPERTIES
OF SYNDIOTACTIC POLYSTYRENE 155
9. Structure, Morphology, and Crystallization Behavior of
Syndiotactic Polystyrene 157
Andrea Sorrentino and Vittoria Vittoria
9.1 Introduction 157
9.2 Polymorphic Behavior of SPS 157
9.2.1 Crystallization from the Melt State 159
9.2.2 Crystallization from the Glassy State 160
9.2.3 Morphology Development in the Presence of
Solvents 163
9.3 Morphology of the Zigzag Forms 164
9.3.1 Crystal Structure of the ƒ¿ Form 164
9.3.2 Crystal Structure of the ƒÀ Form 168
9.3.3 Lamellar and Spherulitic Morphology of the
Zigzag Forms 170
CONTENTS xi
9.4 Morphology of the Mesomorphic Phases 173
9.5 Thermodynamic and Kinetics of Crystallization 175
9.5.1 Thermodynamic and Kinetics of Crystallization 177
9.6 Melting Behavior 178
9.6.1 Equilibrium Melting Temperature of ƒ¿ and ƒÀ
Crystals 180
9.6.2 Memory Effects 182
9.7 Structure and Properties of the Crystallized Samples 183
9.7.1 Morphology of Injection Molded Samples 183
9.7.2 Relation between Morphology Structure,
Processing, and Properties 184
References 186
10. Preparation, Structure, Properties, and Applications of Co-Crystals
and Nanoporous Crystalline Phases of Syndiotactic Polystyrene 194
Gaetano Guerra, Alexandra Romina Albunia, and Concetta DfAniello
10.1 Introduction 194
10.2 Co-Crystals 195
10.2.1 Crystalline Structures 196
10.2.2 Processing and Materials 199
10.2.3 Characterization Studies 202
10.2.4 Properties and Applications 209
10.3 Nanoporous Crystalline Phases 212
10.3.1 Crystalline Structures 213
10.3.2 Processing and Materials 215
10.3.3 Characterization Studies 217
10.3.4 Applications 219
10.4 Conclusions and Perspectives 224
10.5 Acknowledgments 225
References 225
11. Crystallization Thermodynamics and Kinetics of Syndiotactic
Polystyrene 238
Tomoaki Takebe and Komei Yamasaki
11.1 Introduction 238
11.2 Theoretical Background 239
11.3 Equilibrium Melting Point of SPS 240
11.3.1 Evaluation of Spherulitic Growth Rate G 244
xii CONTENTS
11.4 Analyses of Spherulitic Growth Rate G 248
11.5 Comparison Between SPS and IPS 249
References 250
PART IV COMMERCIAL PROCESSES FOR MANUFACTURING
OF SYNDIOTACTIC POLYSTYRENE 253
12. Processes for the Production of Syndiotactic Polystyrene 255
Masao Aida, David Habermann, Hans-Joachim Leder,and
Jurgen Schellenberg
12.1 Introduction 255
12.2 Monomer Purifi cation Section 255
12.3 Catalyst Section 256
12.4 Polymerization Section 256
12.4.1 Continuous Stirred Tank Reactor Process 257
12.4.2 Continuous Fluidized Bed Reactor Process 258
12.4.3 Continuous Self-Cleaning Reactor Process 258
12.5 Styrene Stripping Section 260
12.6 Deactivating Section 260
12.7 Pelletizing Section 262
12.8 Blending Section 262
12.9 Shipping Section 263
References 264
PART V PROPERTIES, PROCESSING, AND APPLICATIONS
OF SYNDIOTACTIC POLYSTYRENE 267
13. Properties of Syndiotactic Polystyrene 269
Tomoaki Takebe, Komei Yamasaki, Keisuke Funaki, and Michael Malanga
13.1 Introduction 269
13.2 Rheological Properties of SPS 269
13.3 Basic Physical Mechanical Properties of SPS 272
13.3.1 Thermal Properties of SPS 272
13.3.2 Mechanical Properties of SPS 274
13.4 Orientation of SPS and Properties of Oriented SPS 281
13.4.1 Properties of Uniaxially Oriented SPS 281
13.4.2 Properties of Biaxially Oriented SPS (BoSPS) 282
CONTENTS xiii
13.5 Other Important Properties of SPS 286
13.5.1 Electrical Properties of SPS 286
13.5.2 Chemical Resistance of SPS 287
References 289
14. Melt Processing of Syndiotactic Polystyrene 290
David Bank, Kevin Nichols, Harold Fowler, Jason Reese,and
Gerry Billovits
14.1 Introduction 290
14.2 Compounding 294
14.2.1 Introduction 294
14.2.2 Compounding Equipment 295
14.2.3 Compounding Process Conditions 296
14.3 Injection Molding 298
14.3.1 Introduction 298
14.3.2 General Product Design 299
14.3.3 Thin Wall Product Designs 301
14.3.4 Injection Mold Design 301
14.3.5 Injection Mold Melt Delivery System (Runners
and Gates) 302
14.3.6 Venting 304
14.3.7 Injection Molding Cooling Cycle and
Crystallinity 304
14.3.8 Shrinkage during the Cooling Phase 304
14.3.9 Injection Molding Process Set-up 306
14.3.10 Injection Molding Cycle 308
14.3.11 Special Injection Molding Cycles 310
14.4 Sheet and Film Extrusion 311
14.4.1 Introduction 311
14.4.2 Extrusion 311
14.4.3 General Extruder Design 312
14.4.4 Processing Parameters 313
14.4.5 Material Drying 314
14.5 Film Processing and Fabrication 314
14.5.1 Introduction 314
14.5.2 Cast Film Extrusion 314
14.5.3 Thermoforming 315
14.6 Fiber Spinning 316
References 319
xiv CONTENTS
15. Applications of Syndiotactic Polystyrene 321
Tom Fiola, Akihiko Okada, Masami Mihara, and Kevin Nichols
15.1 Introduction 321
15.2 The Performance Capabilities of SPS 322
15.3 Connectors for Automotive and Electronic Applications 329
15.4 Electronic Components: Plated and Non-Plated 330
15.5 Industrial and Appliance Components 331
References 337
16. Blends of Syndiotactic Polystyrene with Polyamide 338
Kevin Nichols, Akihiko Okada, and Hiroki Fukui
16.1 Introduction 338
16.2 Composition of SPS/Nylon Blends 338
16.2.1 Polyamides Used in SPS/Nylon Blends 339
16.2.2 SPS/Nylon Blend Formulations 339
16.2.3 SPS/Nylon Blend Composition Patents 339
16.2.4 SPS/Nylon Blend Compositions Described in
Technical Journals 339
16.3 Properties of SPS/Nylon Blends 339
16.3.1 Mechanical Properties of SPS/Nylon Blends 340
16.3.2 Rheology of SPS/Nylon Blends 343
16.3.3 Moisture Absorption and Moisture Growth of
SPS/Nylon Blends 343
16.3.4 Dimensional Stability of SPS/Nylon Blends 346
16.3.5 USCAR Performance of SPS/Nylon Blends 347
16.3.6 Environmental Stress Crack Resistance of
SPS/Nylon Blends 349
16.4 Applications of SPS/Nylon Blends 349
16.4.1 SPS/Nylon Blend Under-the-hood Automotive
Connectors 349
16.4.2 SPS/Nylon Blend Carpet Fibers 350
16.4.3 SPS/Nylon Blend Application Patents 353
References 355
17. Blends of Syndiotactic Polystyrene with Polystyrenes 360
Tomoaki Takebe, Komei Yamasaki, Akihiko Okada, and
Takuma Aoyama
17.1 Introduction 360
17.2 SANS Measurements 361
CONTENTS xv
17.3 Theoretical Background 361
17.4 Tacticity Effect on Miscibility 363
17.5 Properties of Blends of SPS and APS 366
References 370
18. Compatibilizers for Impact-Modifi ed Syndiotactic Polystyrene 371
Tomoaki Takebe, Akihiko Okada, and Nobuyuki Sato
18.1 Introduction 371
18.2 Morphological Analyses of HISPS 372
18.2.1 SAXS Profi les of HISPS in the Crystalline State 374
18.2.2 Effect of Nucleators on Lamellar Orientation
in HISPS 375
18.3 Morphology of SPS/PPO Binary Blends 376
18.3.1 Structural Analyses Using SAXS Technique 377
18.3.2 Crystallization Kinetics of SPS/PPO Blends 378
18.3.3 Infl uence of Blending PPO with Different
Molecular Weights on the Morphology of HISPS 380
18.4 Compatibilizer Effects 382
18.4.1 Evaluation of Interaction Parameters 383
18.4.2 Evaluation of Domain Size and Interfacial
Thickness 388
References 393
PART VI POLYMERS BASED ON SYNDIOTACTIC
POLYSTYRENES 395
19. Functionalization and Block/Graft Reactions of Syndiotactic
Polystyrene Using Borane Comonomers and Chain Transfer
Agents 397
T. C. Mike Chung
19.1 Introduction 397
19.2 Functionalization of SPS via Borane Comonomers 398
19.2.1 Copolymerization of Styrene and B-styrene 398
19.2.2 Side-Chain Functionalized SPS Polymers 402
19.2.3 SPS Graft Copolymers 406
19.3 Functionalization of SPS via Borane Chain Transfer
Agents 409
19.3.1 SPS Containing a Terminal Functional Group 410
19.3.2 SPS Block Copolymers 412
xvi CONTENTS
19.4 Summary 415
19.5 Acknowledgment 415
References 415
20. Nanocomposites Based on Syndiotactic Polystyrene 417
O Ok Park and Mun Ho Kim
20.1 Introduction 417
20.2 Polymer Nanocomposites and Microstructure 418
20.3 Fabrication of Polymer Nanocomposites 419
20.4 Characterization of Polymer Nanocomposites 420
20.5 Preparation of SPS Nanocomposites 421
20.5.1 Effect of Alkyl Chain Aggregation in
Organoclay.Bilayer versus Monolayer
Arrangement 423
20.5.2 Improvement in the Thermal Stability of
Organoclay 424
20.6 Properties of SPS Nanocomposites 425
20.6.1 Mechanical Properties 425
20.6.2 Crystallization Behavior 426
20.6.3 Dynamic Rheological Properties 426
20.7 Final Remarks 427
References 429
INDEX 431
Preface
xvii

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