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syndiotactic polystyrene synthesis characterization processing and applications

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  • SYNDIOTACTIC POLYSTYRENE

    • CONTENTS

    • PREFACE

    • CONTRIBUTORS

    • ABOUT THE EDITOR

    • PART I INTRODUCTION

      • 1. Historical Overview and Commercialization of Syndiotactic Polystyrene

        • 1.1 Discovery of Syndiotactic Polystyrene (SPS)

        • 1.2 Early Years of Development (1985–1989)

        • 1.3 Intense Development Years (1989–1996)

        • 1.4 Initial Commercial Launch Stage (1996–2001)

        • 1.5 Years 2001–2007

    • PART II PREPARATION OF SYNDIOTACTIC POLYSTYRENE

      • 2. Transition Metal Catalysts for Syndiotactic Polystyrene

        • 2.1 Introduction

        • 2.2 Transition Metal Compounds

          • 2.2.1 Metals

          • 2.2.2 Titanium Complexes

          • 2.2.3 Molecular Weight Control

          • 2.2.4 Supported and Heterogeneous Catalysts

        • 2.3 Summary

        • References

      • 3. Cocatalysts for the Syndiospecific Styrene Polymerization

        • 3.1 Introduction

        • 3.2 MAO

        • 3.3 Boron Compounds

        • 3.4 Other Chemicals

        • 3.5 Summary

        • References

      • 4. Mechanisms for Stereochemical Control in the Syndiotactic Polymerization of Styrene

        • 4.1 Introduction

        • 4.2 Insertion of the Growing Polymer Chain into the Double Bond of Styrene

        • 4.3 Stereochemistry of the Styrene Insertion

        • 4.4 Effects of Hydrogenation of the Catalyst

        • 4.5 Active Site Species

          • 4.5.1 Valence of Active Sites

          • 4.5.2 Number of Active Sites

          • 4.5.3 Structure of Active Sites

        • 4.6 Theoretical Analysis of the Catalyst

        • 4.7 Kinetic Analysis of Styrene Polymerization

        • 4.8 Conclusions

        • References

      • 5. Copolymerization of Ethylene with Styrene: Design of Efficient Transition Metal Complex Catalysts

        • 5.1 Introduction

        • 5.2 Ethylene/Styrene Copolymers: Microstructures, Thermal Properties, and Composition Analyses

        • 5.3 Ethylene/Styrene Copolymerization Using Transition Metal Complex–Cocatalyst Systems

          • 5.3.1 Half-Titanocenes, Cp´TiX(3)

          • 5.3.2 Linked (Constrained Geometry Type) Half-Titanocenes

          • 5.3.3 Modified Half-Titanocenes, C(p´)Ti(L)X(2)

          • 5.3.4 Non-Cp Titanium Complexes

          • 5.3.5 Metallocenes

          • 5.3.6 Others

        • 5.4 Summary and Outlook

        • References

      • 6. Structure and Properties of Tetrabenzo[a,c,g,i]fluorenyl-Based Titanium Catalysts

        • 6.1 Introduction

        • 6.2 The Tbf Ligand

        • 6.3 Tbf Lithium

          • 6.3.1 Synthesis and Characterization of Tbf Lithium

        • 6.4 Tbf Titanium(III) Derivatives

          • 6.4.1 Synthesis of Tbf Titanium(III) Chloride Complexes

          • 6.4.2 Reaction of TbfTi(III)Cl(2)(THF) (VIII) with Radicals

        • 6.5 Tbf Titanium(IV) Derivatives

          • 6.5.1 Synthesis of Tbf Titanium Monophenoxide Complexes

        • 6.6 Dynamic and Polymerization Behavior of Tetrabenzofluorenyl Titanium Complexes

          • 6.6.1 Styrene Polymerization

        • 6.7 Conclusions

        • References

      • 7. Rare-Earth Metal Complexes as Catalysts for Syndiospecific Styrene Polymerization

        • 7.1 Introduction

        • 7.2 Metallocene Catalysts

        • 7.3 Constrained Geometry Catalysts

        • 7.4 Half-Sandwich Catalysts

        • 7.5 Nonmetallocene Catalysts

        • 7.6 Conclusion

        • References

      • 8. Syndiospecific Styrene Polymerization with Heterogenized Transition Metal Catalysts

        • 8.1 Introduction

        • 8.2 Kinetics of Syndiospecific Polymerization with Heterogeneous Metallocene Catalysts

          • 8.2.1 Kinetic Profiles of Heterogeneous SPS Polymerization

          • 8.2.2 Liquid Slurry Polymerization with Heterogenized Cp*Ti(OCH(3))(3) Catalyst

          • 8.2.3 Modeling of Polymerization Kinetics

          • 8.2.4 Molecular Weight Distribution of SPS with Heterogeneous Catalysts

        • 8.3 Nascent Morphology of Syndiotactic Polystyrene

          • 8.3.1 Physical Transitions of Reaction Mixture During Polymerization

          • 8.3.2 Effect of Reaction Conditions on Polymer Morphology

        • 8.4 Concluding Remarks

        • References

    • PART III STRUCTURE AND FUNDAMENTAL PROPERTIES OF SYNDIOTACTIC POLYSTYRENE

      • 9. Structure, Morphology, and Crystallization Behavior of Syndiotactic Polystyrene

        • 9.1 Introduction

        • 9.2 Polymorphic Behavior of SPS

          • 9.2.1 Crystallization from the Melt State

          • 9.2.2 Crystallization from the Glassy State

          • 9.2.3 Morphology Development in the Presence of Solvents

        • 9.3 Morphology of the Zigzag Forms

          • 9.3.1 Crystal Structure of the α Form

          • 9.3.2 Crystal Structure of the β Form

          • 9.3.3 Lamellar and Spherulitic Morphology of the Zigzag Forms

        • 9.4 Morphology of the Mesomorphic Phases

        • 9.5 Thermodynamic and Kinetics of Crystallization

          • 9.5.1 Thermodynamic and Kinetics of Crystallization

        • 9.6 Melting Behavior

          • 9.6.1 Equilibrium Melting Temperature of α and β Crystals

          • 9.6.2 Memory Effects

        • 9.7 Structure and Properties of the Crystallized Samples

          • 9.7.1 Morphology of Injection Molded Samples

          • 9.7.2 Relation between Morphology Structure, Processing, and Properties

        • References

      • 10. Preparation, Structure, Properties, and Applications of Co-Crystals and Nanoporous Crystalline Phases of Syndiotactic Polystyrene

        • 10.1 Introduction

        • 10.2 Co-Crystals

          • 10.2.1 Crystalline Structures

          • 10.2.2 Processing and Materials

          • 10.2.3 Characterization Studies

          • 10.2.4 Properties and Applications

        • 10.3 Nanoporous Crystalline Phases

          • 10.3.1 Crystalline Structures

          • 10.3.2 Processing and Materials

          • 10.3.3 Characterization Studies

          • 10.3.4 Applications

        • 10.4 Conclusions and Perspectives

        • 10.5 Acknowledgments

        • References

      • 11. Crystallization Thermodynamics and Kinetics of Syndiotactic Polystyrene

        • 11.1 Introduction

        • 11.2 Theoretical Background

        • 11.3 Equilibrium Melting Point of SPS

          • 11.3.1 Evaluation of Spherulitic Growth Rate G

        • 11.4 Analyses of Spherulitic Growth Rate G

        • 11.5 Comparison Between SPS and IPS

        • References

    • PART IV COMMERCIAL PROCESSES FOR MANUFACTURING OF SYNDIOTACTIC POLYSTYRENE

      • 12. Processes for the Production of Syndiotactic Polystyrene

        • 12.1 Introduction

        • 12.2 Monomer Purification Section

        • 12.3 Catalyst Section

        • 12.4 Polymerization Section

          • 12.4.1 Continuous Stirred Tank Reactor Process

          • 12.4.2 Continuous Fluidized Bed Reactor Process

          • 12.4.3 Continuous Self-Cleaning Reactor Process

        • 12.5 Styrene Stripping Section

        • 12.6 Deactivating Section

        • 12.7 Pelletizing Section

        • 12.8 Blending Section

        • 12.9 Shipping Section

        • References

    • PART V PROPERTIES, PROCESSING, AND APPLICATIONS OF SYNDIOTACTIC POLYSTYRENE

      • 13. Properties of Syndiotactic Polystyrene

        • 13.1 Introduction

        • 13.2 Rheological Properties of SPS

        • 13.3 Basic Physical Mechanical Properties of SPS

          • 13.3.1 Thermal Properties of SPS

          • 13.3.2 Mechanical Properties of SPS

        • 13.4 Orientation of SPS and Properties of Oriented SPS

          • 13.4.1 Properties of Uniaxially Oriented SPS

          • 13.4.2 Properties of Biaxially Oriented SPS (BoSPS)

        • 13.5 Other Important Properties of SPS

          • 13.5.1 Electrical Properties of SPS

          • 13.5.2 Chemical Resistance of SPS

        • References

      • 14. Melt Processing of Syndiotactic Polystyrene

        • 14.1 Introduction

        • 14.2 Compounding

          • 14.2.1 Introduction

          • 14.2.2 Compounding Equipment

          • 14.2.3 Compounding Process Conditions

        • 14.3 Injection Molding

          • 14.3.1 Introduction

          • 14.3.2 General Product Design

          • 14.3.3 Thin Wall Product Designs

          • 14.3.4 Injection Mold Design

          • 14.3.5 Injection Mold Melt Delivery System (Runners and Gates)

          • 14.3.6 Venting

          • 14.3.7 Injection Molding Cooling Cycle and Crystallinity

          • 14.3.8 Shrinkage during the Cooling Phase

          • 14.3.9 Injection Molding Process Set-up

          • 14.3.10 Injection Molding Cycle

          • 14.3.11 Special Injection Molding Cycles

        • 14.4 Sheet and Film Extrusion

          • 14.4.1 Introduction

          • 14.4.2 Extrusion

          • 14.4.3 General Extruder Design

          • 14.4.4 Processing Parameters

          • 14.4.5 Material Drying

        • 14.5 Film Processing and Fabrication

          • 14.5.1 Introduction

          • 14.5.2 Cast Film Extrusion

          • 14.5.3 Thermoforming

        • 14.6 Fiber Spinning

        • References

      • 15. Applications of Syndiotactic Polystyrene

        • 15.1 Introduction

        • 15.2 The Performance Capabilities of SPS

        • 15.3 Connectors for Automotive and Electronic Applications

        • 15.4 Electronic Components: Plated and Non-Plated

        • 15.5 Industrial and Appliance Components

        • References

      • 16. Blends of Syndiotactic Polystyrene with Polyamide

        • 16.1 Introduction

        • 16.2 Composition of SPS/Nylon Blends

          • 16.2.1 Polyamides Used in SPS/Nylon Blends

          • 16.2.2 SPS/Nylon Blend Formulations

          • 16.2.3 SPS/Nylon Blend Composition Patents

          • 16.2.4 SPS/Nylon Blend Compositions Described in Technical Journals

        • 16.3 Properties of SPS/Nylon Blends

          • 16.3.1 Mechanical Properties of SPS/Nylon Blends

          • 16.3.2 Rheology of SPS/Nylon Blends

          • 16.3.3 Moisture Absorption and Moisture Growth of SPS/Nylon Blends

          • 16.3.4 Dimensional Stability of SPS/Nylon Blends

          • 16.3.5 USCAR Performance of SPS/Nylon Blends

          • 16.3.6 Environmental Stress Crack Resistance of SPS/Nylon Blends

        • 16.4 Applications of SPS/Nylon Blends

          • 16.4.1 SPS/Nylon Blend Under-the-hood Automotive Connectors

          • 16.4.2 SPS/Nylon Blend Carpet Fibers

          • 16.4.3 SPS/Nylon Blend Application Patents

        • References

      • 17. Blends of Syndiotactic Polystyrene with Polystyrenes

        • 17.1 Introduction

        • 17.2 SANS Measurements

        • 17.3 Theoretical Background

        • 17.4 Tacticity Effect on Miscibility

        • 17.5 Properties of Blends of SPS and APS

        • References

      • 18. Compatibilizers for Impact-Modified Syndiotactic Polystyrene

        • 18.1 Introduction

        • 18.2 Morphological Analyses of HISPS

          • 18.2.1 SAXS Profiles of HISPS in the Crystalline State

          • 18.2.2 Effect of Nucleators on Lamellar Orientation in HISPS

        • 18.3 Morphology of SPS/PPO Binary Blends

          • 18.3.1 Structural Analyses Using SAXS Technique

          • 18.3.2 Crystallization Kinetics of SPS/PPO Blends

          • 18.3.3 Influence of Blending PPO with Different Molecular Weights on the Morphology of HISPS

        • 18.4 Compatibilizer Effects

          • 18.4.1 Evaluation of Interaction Parameters

          • 18.4.2 Evaluation of Domain Size and Interfacial Thickness

        • References

    • PART VI POLYMERS BASED ON SYNDIOTACTIC POLYSTYRENES

      • 19. Functionalization and Block/Graft Reactions of Syndiotactic Polystyrene Using Borane Comonomers and Chain Transfer Agents

        • 19.1 Introduction

        • 19.2 Functionalization of SPS via Borane Comonomers

          • 19.2.1 Copolymerization of Styrene and B-styrene

          • 19.2.2 Side-Chain Functionalized SPS Polymers

          • 19.2.3 SPS Graft Copolymers

        • 19.3 Functionalization of SPS via Borane Chain Transfer Agents

          • 19.3.1 SPS Containing a Terminal Functional Group

          • 19.3.2 SPS Block Copolymers

        • 19.4 Summary

        • 19.5 Acknowledgment

        • References

      • 20. Nanocomposites Based on Syndiotactic Polystyrene

        • 20.1 Introduction

        • 20.2 Polymer Nanocomposites and Microstructure

        • 20.3 Fabrication of Polymer Nanocomposites

        • 20.4 Characterization of Polymer Nanocomposites

        • 20.5 Preparation of SPS Nanocomposites

          • 20.5.1 Effect of Alkyl Chain Aggregation in Organoclay—Bilayer versus Monolayer Arrangement

          • 20.5.2 Improvement in the Thermal Stability of Organoclay

        • 20.6 Properties of SPS Nanocomposites

          • 20.6.1 Mechanical Properties

          • 20.6.2 Crystallization Behavior

          • 20.6.3 Dynamic Rheological Properties

        • 20.7 Final Remarks

        • References

    • INDEX

Nội dung

[...]... Structure, Properties, and Applications of Co-Crystals and Nanoporous Crystalline Phases of Syndiotactic Polystyrene xi 173 175 177 178 180 182 183 183 184 186 194 Gaetano Guerra, Alexandra Romina Albunia, and Concetta D’Aniello 10.1 10.2 Introduction Co-Crystals 10.2.1 Crystalline Structures 10.2.2 Processing and Materials 10.2.3 Characterization Studies 10.2.4 Properties and Applications 10.3 Nanoporous... such as toner resins, and on polyethylene and polyethylene blends After a research stay at the Dow Chemical Company, Midland, MI, USA in 1997/1998, he continued to work on syndiotactic polystyrene (SPS) research at Dow Central Germany/Schkopau accompanied by the start-up and operation of the first commercial SPS plant worldwide, and later on worked on polypropylene and expandable polystyrene R&D too Jürgen... Crystalline Phases 10.3.1 Crystalline Structures 10.3.2 Processing and Materials 10.3.3 Characterization Studies 10.3.4 Applications 10.4 Conclusions and Perspectives 10.5 Acknowledgments References 11 Crystallization Thermodynamics and Kinetics of Syndiotactic Polystyrene 194 195 196 199 202 209 212 213 215 217 219 224 225 225 238 Tomoaki Takebe and Komei Yamasaki 11.1 11.2 11.3 Introduction Theoretical... 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 13.2 13.3 13.4 Introduction Rheological Properties of SPS Basic Physical Mechanical Properties of SPS 13.3.1 Thermal Properties of SPS 13.3.2 Mechanical Properties of SPS Orientation of SPS and Properties of... of Syndiotactic Polystyrene 8.3.1 Physical Transitions of Reaction Mixture During Polymerization 8.3.2 Effect of Reaction Conditions on Polymer Morphology 8.4 Concluding Remarks References PART III STRUCTURE AND FUNDAMENTAL PROPERTIES OF SYNDIOTACTIC POLYSTYRENE 9 Structure, Morphology, and Crystallization Behavior of Syndiotactic Polystyrene 140 141 141 143 145 147 149 149 151 153 153 155 157 Andrea... Size and Interfacial Thickness References 371 372 374 375 376 377 378 380 382 383 388 393 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 19.2 19.3 Introduction Functionalization of SPS via Borane Comonomers 19.2.1 Copolymerization of Styrene and. .. Kai Schröder, and Jürgen Schellenberg 6.1 6.2 6.3 Introduction The Tbf Ligand Tbf Lithium 6.3.1 Synthesis and Characterization of Tbf Lithium 6.4 Tbf Titanium(III) Derivatives 6.4.1 Synthesis of Tbf Titanium(III) Chloride Complexes 6.4.2 Reaction of TbfTiIIICl2(THF) (VIII) with Radicals 6.5 Tbf Titanium(IV) Derivatives 6.5.1 Synthesis of Tbf Titanium Monophenoxide Complexes 6.6 Dynamic and Polymerization... discusses the rheological, mechanical, and other properties of this polymer PREFACE xix (Chapter 13) and continues with melt processing, including injection molding, extrusion, films, and fibers (Chapter 14) Chapter 15 goes on to describe applications of SPS polymers themselves, followed by a discussion of blends with polyamides in Chapter 16 and with conventional polystyrenes in Chapter 17 Compatibilizers... Introduction 15.2 The Performance Capabilities of SPS 15.3 Connectors for Automotive and Electronic Applications 15.4 Electronic Components: Plated and Non-Plated 15.5 Industrial and Appliance Components References 16 Blends of Syndiotactic Polystyrene with Polyamide 321 322 329 330 331 337 338 Kevin Nichols, Akihiko Okada, and Hiroki Fukui 16.1 16.2 Introduction Composition of SPS/Nylon Blends 16.2.1 Polyamides... Mesomorphic Phases Thermodynamic and Kinetics of Crystallization 9.5.1 Thermodynamic and Kinetics of Crystallization 9.6 Melting Behavior 9.6.1 Equilibrium Melting Temperature of α and β Crystals 9.6.2 Memory Effects 9.7 Structure and Properties of the Crystallized Samples 9.7.1 Morphology of Injection Molded Samples 9.7.2 Relation between Morphology Structure, Processing, and Properties References 10 . Data: Schellenberg, Jürgen. Syndiotactic polystyrene : synthesis, characterization, processing, and applications / Jürgen Schellenberg. p. cm. Includes index. ISBN 978-0-470-28688-3 (cloth) 1. Polystyrene. . III STRUCTURE AND FUNDAMENTAL PROPERTIES OF SYNDIOTACTIC POLYSTYRENE 155 9. Structure, Morphology, and Crystallization Behavior of Syndiotactic Polystyrene 157 Andrea Sorrentino and Vittoria. 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

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