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Including recent advances and historically important catalysts, this book overviews methods for developing and applying polymerization catalysts - dealing with polymerization catalysts that afford commercially acceptable high yields of polymer with respect to catalyst mass or productivity. * Contains the valuable data needed to reproduce syntheses or use the catalyst for new applications * Offers a guide to the design and synthesis of catalysts, and their applications in synthesis of polymers * Includes the information essential for choosing the appropriate reactions to maximize yield of…mehr
Including recent advances and historically important catalysts, this book overviews methods for developing and applying polymerization catalysts - dealing with polymerization catalysts that afford commercially acceptable high yields of polymer with respect to catalyst mass or productivity. * Contains the valuable data needed to reproduce syntheses or use the catalyst for new applications * Offers a guide to the design and synthesis of catalysts, and their applications in synthesis of polymers * Includes the information essential for choosing the appropriate reactions to maximize yield of polymer synthesized * Presents new chapters on vanadium catalysts, Ziegler catalysts, laboratory homopolymerization, and copolymerization
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Autorenporträt
RAY HOFF is a former research scientist in polymerization catalysts for B.F. Goodrich, Chemplex Company, and Quantum Chemical Corporation and was a member of the adjunct faculty at Roosevelt University in Schaumburg, Illinois.
Inhaltsangabe
Notes on Contributors xvii Preface xxix Acknowledgments xxxiii 1 Industrial Metal Alkyls and Their Use in Polyolefin Catalysts 1 Dennis B. Malpass 1.1 Introduction 1 1.2 Metal Alkyls in Ziegler-Natta Catalysts 2 1.3 Aluminum Alkyls 4 1.4 Manufacturers of Aluminum Alkyls 10 1.5 Pricing and Selection Criteria for Aluminum Alkyls 11 1.6 Methylaluminoxanes 13 1.7 Magnesium Alkyls 18 1.8 Organoboron Compounds 24 1.9 Organozinc Compounds 26 References 27 2 Porous Silica in Transition Metal Polymerization Catalysts 31 Thomas J. Pullukat and Robert E. Patterson 2.1 Introduction 31 2.2 Production of Silica Gel Catalysts 33 2.3 Influence of Silica Gel Properties and Polymerization Conditions on Catalyst Performance 36 2.4 Conclusions 52 References 53 3 Activator Supports for Metallocene and Related Catalysts 57 Ray Hoff 3.1 Introduction 57 3.2 Activator Support Studies 58 3.3 Activator Support Patents 60 3.4 Conclusion 62 References 64 4 Computational Modeling of Polymerization Catalysts 67 Monika Srebro Hooper and Artur Michalak 4.1 Introduction 67 4.2 Computational Modeling of Chemical Reactions 68 4.3 Modeling the Catalyst Properties and the Polymerization Processes 76 4.4 Concluding Remarks 116 Acknowledgment 117 References 117 5 Computational Studies of Chromium: Silica Catalysts 131 Zhen Liu and Boping Liu 5.1 Introduction 131 5.2 Mechanistic Proposals for Phillips Catalyst 132 5.3 Theoretical Study on Phillips Catalyst 137 5.4 The Limitation of the Current Computations and a Prospect for the Future 156 References 157 6 Laboratory Reactors and Procedures for Catalyst Evaluation 161 Rinaldo Schiffino 6.1 Introduction 161 6.2 Setup in the Fume Hood 162 6.3 Autoclave Reactors and Safety Relief Devices 163 6.4 Purification Methods 164 6.5 Modular Reactor System 165 6.6 Catalyst Addition 168 6.7 Temperature Control 170 6.8 Autoclave Reactor Setup 172 6.9 Copolymerization 173 6.10 Gas?-Phase Laboratory Reactors 175 References 176 7 Scale?-Up of Catalyst Recipes to Commercial Production 177 Chung Ping Cheng 7.1 Introduction 177 7.2 Fundamental of Process Scale?-Up 178 7.3 Considerations in Scaling Up a Laboratory Recipe 180 7.4 A Modern Polymerization Catalyst Production Facility 182 7.5 Other Scale?-Up Considerations 187 References 187 8 Supported Titanium/Magnesium Ziegler Catalysts for the Production of Polyethylene 189 Yury V. Kissin, Thomas E. Nowlin, and Robert I. Mink 8.1 Introduction 189 8.2 Particle?-Form Technology 192 8.3 General Architecture and Preparation of Supported Catalysts 193 8.4 Nonuniformity of Active Centers in Supported Ziegler Catalysts 205 8.5 Kinetics and Mechanism of Ethylene Polymerization Reactions with Ziegler Catalysts 209 8.6 Kinetic Interpretation of Ethylene Polymerization Reactions 217 8.7 Active Centers in Ziegler Catalysts 221 References 224 9 Stereospecific ?-Olefin Polymerization with Heterogeneous Catalysts 229 John Severn and Robert L. Jones, JR 9.1 Introduction 229 9.2 Traditional Ziegler-Natta Catalyst Systems 241 9.3 Stereospecific Single Site Catalysts 266 9.4 Conclusion 295 References 296 10 Olefin Polymerization by Vanadium Complex Catalysts 313 Kotohiro Nomura and Xiaohua Hou 10.1 Introduction: Classical Ziegler?-Type Vanadium Catalyst Systems 313 10.2 Vanadium Complexes Designed for Olefin Coordination Insertion Polymerization 315 10.3 Outlook 332 References 333 11 MgCl2?-Supported Ti Catalysts for the Production of Morphology?-Controlled Polyethylene 339 Long Wu and Sieghard Wanke 11.1 Introduction 339 11.2 Preparation of Morphology?-Controlled MgCl2/TiCl4 Catalysts 342 11.3 Polymerization Processes 345 11.4 Effect of Prepolymerization on Activity Profiles and Prepolymer Properties 349 11.5 Polymerization Behavior 358 11.6 Summary and Conclusions 364 References 365 12 Product Morphology in Olefin Polymerization with Polymer?-Supported Metallocene Catalysts 369 Long Wu and Sieghard Wanke 12.1 Introduction 369 12.2 Preparation of Polymer?-Supported Metallocene Catalysts 371 12.3 Factors Affecting Morphology of Product Particles 379 12.4 Factors Affecting Product Morphology 389 12.5 Product Fines and Densities 394 12.6 Conclusions 396 References 396 13 A Review of the Phillips Chromium Catalyst for Ethylene Polymerization 401 Max P. McDaniel 13.1 Historical and Commercial Background 401 13.2 Catalyst Preparation 404 13.3 Control of Catalyst Activity 414 13.4 Control of Molecular Weight and MW Distribution 439 13.5 Control of Crystallinity 482 13.6 Control of Elasticity 509 13.7 Concluding Remarks 542 References 546 14 Silica?-Supported Silyl Chromate?-Based Ethylene Polymerization Catalysts 573 Kevin Cann 14.1 Introduction 573 14.2 Silyl Chromate Catalyst Development 573 14.3 Catalyst Structure 575 14.4 Polymerization Process 578 14.5 Product Characterization and Applications 579 14.6 Silica?-Supported Reduced Silyl Chromate Catalyst Advancements 582 Acknowledgements 588 References 588 15 Late Transition Metal Catalyzed Co?- and Terpolymerization of ?-Olefins with Carbon Monoxide: Synthesis and Modification 591 Timo M. J. Anselment, Manuela Zintl, Maria Leute, Rüdiger Nowack, and Bernhard Rieger 15.1 Introduction and Historical Overview 591 15.2 Polyketone Synthesis: General Concept and Mechanism 593 15.3 Influence of the Catalyst on the Polymer Structure in ?-Olefin/CO Copolymerization Reactions 599 15.4 Other Olefins for the Copolymerization with CO 610 15.5 Chemical Modification of Polyketones 616 References 618 16 Ethylene Polymerization and ?-Olefin Oligomerization Using Catalysts Derived from Phosphoranes and Ni(II) or Ni(0) Precursors 623 Scott Collins 16.1 Introduction 623 16.2 Starting Materials 626 References 629 17 Overview of Ring?-Opening Metathesis Polymerizations (ROMP) and Acyclic Diene Metathesis (ADMET) Polymerizations with Selected Ruthenium and Molybdenum Complexes 631 Robert T. Mathers 17.1 Introduction 631 17.2 Ruthenium Catalysts 634 17.3 Molybdenum Complexes 646 17.4 Summary 651 References 651 18 Copolymerization of Ethylene with Conjugated Dienes 661 Islem Belaid, Vincent Monteil, and Christophe Boisson 18.1 Introduction 661 18.2 Conventional Ziegler-Natta Catalysts 663 18.3 Group 4 Metallocene Systems 665 18.4 Group 4 Post?-metallocene Catalysts 670 18.5 Vanadium Bis(imino)pyridyl Catalysts 673 18.6 Group 8?-, 9?-, and 10?-Based Catalysts 674 18.7 Rare Earth Catalysts 675 18.8 Conclusion 686 References 687 Appendix A: Pyrophoricity of Metal Alkyls 693 Dennis B. Malpass Appendix B: Rheological Terms for Polymerization Catalyst Chemists 705 Gregory W. Kamykowski Index 711
Notes on Contributors xvii Preface xxix Acknowledgments xxxiii 1 Industrial Metal Alkyls and Their Use in Polyolefin Catalysts 1 Dennis B. Malpass 1.1 Introduction 1 1.2 Metal Alkyls in Ziegler-Natta Catalysts 2 1.3 Aluminum Alkyls 4 1.4 Manufacturers of Aluminum Alkyls 10 1.5 Pricing and Selection Criteria for Aluminum Alkyls 11 1.6 Methylaluminoxanes 13 1.7 Magnesium Alkyls 18 1.8 Organoboron Compounds 24 1.9 Organozinc Compounds 26 References 27 2 Porous Silica in Transition Metal Polymerization Catalysts 31 Thomas J. Pullukat and Robert E. Patterson 2.1 Introduction 31 2.2 Production of Silica Gel Catalysts 33 2.3 Influence of Silica Gel Properties and Polymerization Conditions on Catalyst Performance 36 2.4 Conclusions 52 References 53 3 Activator Supports for Metallocene and Related Catalysts 57 Ray Hoff 3.1 Introduction 57 3.2 Activator Support Studies 58 3.3 Activator Support Patents 60 3.4 Conclusion 62 References 64 4 Computational Modeling of Polymerization Catalysts 67 Monika Srebro Hooper and Artur Michalak 4.1 Introduction 67 4.2 Computational Modeling of Chemical Reactions 68 4.3 Modeling the Catalyst Properties and the Polymerization Processes 76 4.4 Concluding Remarks 116 Acknowledgment 117 References 117 5 Computational Studies of Chromium: Silica Catalysts 131 Zhen Liu and Boping Liu 5.1 Introduction 131 5.2 Mechanistic Proposals for Phillips Catalyst 132 5.3 Theoretical Study on Phillips Catalyst 137 5.4 The Limitation of the Current Computations and a Prospect for the Future 156 References 157 6 Laboratory Reactors and Procedures for Catalyst Evaluation 161 Rinaldo Schiffino 6.1 Introduction 161 6.2 Setup in the Fume Hood 162 6.3 Autoclave Reactors and Safety Relief Devices 163 6.4 Purification Methods 164 6.5 Modular Reactor System 165 6.6 Catalyst Addition 168 6.7 Temperature Control 170 6.8 Autoclave Reactor Setup 172 6.9 Copolymerization 173 6.10 Gas?-Phase Laboratory Reactors 175 References 176 7 Scale?-Up of Catalyst Recipes to Commercial Production 177 Chung Ping Cheng 7.1 Introduction 177 7.2 Fundamental of Process Scale?-Up 178 7.3 Considerations in Scaling Up a Laboratory Recipe 180 7.4 A Modern Polymerization Catalyst Production Facility 182 7.5 Other Scale?-Up Considerations 187 References 187 8 Supported Titanium/Magnesium Ziegler Catalysts for the Production of Polyethylene 189 Yury V. Kissin, Thomas E. Nowlin, and Robert I. Mink 8.1 Introduction 189 8.2 Particle?-Form Technology 192 8.3 General Architecture and Preparation of Supported Catalysts 193 8.4 Nonuniformity of Active Centers in Supported Ziegler Catalysts 205 8.5 Kinetics and Mechanism of Ethylene Polymerization Reactions with Ziegler Catalysts 209 8.6 Kinetic Interpretation of Ethylene Polymerization Reactions 217 8.7 Active Centers in Ziegler Catalysts 221 References 224 9 Stereospecific ?-Olefin Polymerization with Heterogeneous Catalysts 229 John Severn and Robert L. Jones, JR 9.1 Introduction 229 9.2 Traditional Ziegler-Natta Catalyst Systems 241 9.3 Stereospecific Single Site Catalysts 266 9.4 Conclusion 295 References 296 10 Olefin Polymerization by Vanadium Complex Catalysts 313 Kotohiro Nomura and Xiaohua Hou 10.1 Introduction: Classical Ziegler?-Type Vanadium Catalyst Systems 313 10.2 Vanadium Complexes Designed for Olefin Coordination Insertion Polymerization 315 10.3 Outlook 332 References 333 11 MgCl2?-Supported Ti Catalysts for the Production of Morphology?-Controlled Polyethylene 339 Long Wu and Sieghard Wanke 11.1 Introduction 339 11.2 Preparation of Morphology?-Controlled MgCl2/TiCl4 Catalysts 342 11.3 Polymerization Processes 345 11.4 Effect of Prepolymerization on Activity Profiles and Prepolymer Properties 349 11.5 Polymerization Behavior 358 11.6 Summary and Conclusions 364 References 365 12 Product Morphology in Olefin Polymerization with Polymer?-Supported Metallocene Catalysts 369 Long Wu and Sieghard Wanke 12.1 Introduction 369 12.2 Preparation of Polymer?-Supported Metallocene Catalysts 371 12.3 Factors Affecting Morphology of Product Particles 379 12.4 Factors Affecting Product Morphology 389 12.5 Product Fines and Densities 394 12.6 Conclusions 396 References 396 13 A Review of the Phillips Chromium Catalyst for Ethylene Polymerization 401 Max P. McDaniel 13.1 Historical and Commercial Background 401 13.2 Catalyst Preparation 404 13.3 Control of Catalyst Activity 414 13.4 Control of Molecular Weight and MW Distribution 439 13.5 Control of Crystallinity 482 13.6 Control of Elasticity 509 13.7 Concluding Remarks 542 References 546 14 Silica?-Supported Silyl Chromate?-Based Ethylene Polymerization Catalysts 573 Kevin Cann 14.1 Introduction 573 14.2 Silyl Chromate Catalyst Development 573 14.3 Catalyst Structure 575 14.4 Polymerization Process 578 14.5 Product Characterization and Applications 579 14.6 Silica?-Supported Reduced Silyl Chromate Catalyst Advancements 582 Acknowledgements 588 References 588 15 Late Transition Metal Catalyzed Co?- and Terpolymerization of ?-Olefins with Carbon Monoxide: Synthesis and Modification 591 Timo M. J. Anselment, Manuela Zintl, Maria Leute, Rüdiger Nowack, and Bernhard Rieger 15.1 Introduction and Historical Overview 591 15.2 Polyketone Synthesis: General Concept and Mechanism 593 15.3 Influence of the Catalyst on the Polymer Structure in ?-Olefin/CO Copolymerization Reactions 599 15.4 Other Olefins for the Copolymerization with CO 610 15.5 Chemical Modification of Polyketones 616 References 618 16 Ethylene Polymerization and ?-Olefin Oligomerization Using Catalysts Derived from Phosphoranes and Ni(II) or Ni(0) Precursors 623 Scott Collins 16.1 Introduction 623 16.2 Starting Materials 626 References 629 17 Overview of Ring?-Opening Metathesis Polymerizations (ROMP) and Acyclic Diene Metathesis (ADMET) Polymerizations with Selected Ruthenium and Molybdenum Complexes 631 Robert T. Mathers 17.1 Introduction 631 17.2 Ruthenium Catalysts 634 17.3 Molybdenum Complexes 646 17.4 Summary 651 References 651 18 Copolymerization of Ethylene with Conjugated Dienes 661 Islem Belaid, Vincent Monteil, and Christophe Boisson 18.1 Introduction 661 18.2 Conventional Ziegler-Natta Catalysts 663 18.3 Group 4 Metallocene Systems 665 18.4 Group 4 Post?-metallocene Catalysts 670 18.5 Vanadium Bis(imino)pyridyl Catalysts 673 18.6 Group 8?-, 9?-, and 10?-Based Catalysts 674 18.7 Rare Earth Catalysts 675 18.8 Conclusion 686 References 687 Appendix A: Pyrophoricity of Metal Alkyls 693 Dennis B. Malpass Appendix B: Rheological Terms for Polymerization Catalyst Chemists 705 Gregory W. Kamykowski Index 711
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