Handbook of Transition Metal Polymerization Catalysts

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.

• Notes on Contributors xviiPreface xxixAcknowledgments xxxiii1 Industrial Metal Alkyls and Their Use in Polyolefin Catalysts 1Dennis B. Malpass1.1 Introduction 11.2 Metal Alkyls in Ziegler–Natta Catalysts 21.3 Aluminum Alkyls 41.4 Manufacturers of Aluminum Alkyls 101.5 Pricing and Selection Criteria for Aluminum Alkyls 111.6 Methylaluminoxanes 131.7 Magnesium Alkyls 181.8 Organoboron Compounds 241.9 Organozinc Compounds 26References 272 Porous Silica in Transition Metal Polymerization Catalysts 31Thomas J. Pullukat and Robert E. Patterson2.1 Introduction 312.2 Production of Silica Gel Catalysts 332.3 Influence of Silica Gel Properties and Polymerization Conditions on Catalyst Performance 362.4 Conclusions 52References 533 Activator Supports for Metallocene and Related Catalysts 57Ray Hoff3.1 Introduction 573.2 Activator Support Studies 583.3 Activator Support Patents 603.4 Conclusion 62References 644 Computational Modeling of Polymerization Catalysts 67Monika Srebro Hooper and Artur Michalak4.1 Introduction 674.2 Computational Modeling of Chemical Reactions 684.3 Modeling the Catalyst Properties and the Polymerization Processes 764.4 Concluding Remarks 116Acknowledgment 117References 1175 Computational Studies of Chromium: Silica Catalysts 131Zhen Liu and Boping Liu5.1 Introduction 1315.2 Mechanistic Proposals for Phillips Catalyst 1325.3 Theoretical Study on Phillips Catalyst 1375.4 The Limitation of the Current Computations and a Prospect for the Future 156References 1576 Laboratory Reactors and Procedures for Catalyst Evaluation 161Rinaldo Schiffino6.1 Introduction 1616.2 Setup in the Fume Hood 1626.3 Autoclave Reactors and Safety Relief Devices 1636.4 Purification Methods 1646.5 Modular Reactor System 1656.6 Catalyst Addition 1686.7 Temperature Control 1706.8 Autoclave Reactor Setup 1726.9 Copolymerization 1736.10 Gas-Phase Laboratory Reactors 175References 1767 Scale-Up of Catalyst Recipes to Commercial Production 177Chung Ping Cheng7.1 Introduction 1777.2 Fundamental of Process Scale-Up 1787.3 Considerations in Scaling Up a Laboratory Recipe 1807.4 A Modern Polymerization Catalyst Production Facility 1827.5 Other Scale-Up Considerations 187References 1878 Supported Titanium/Magnesium Ziegler Catalysts for the Production of Polyethylene 189Yury V. Kissin, Thomas E. Nowlin, and Robert I. Mink8.1 Introduction 1898.2 Particle-Form Technology 1928.3 General Architecture and Preparation of Supported Catalysts 1938.4 Nonuniformity of Active Centers in Supported Ziegler Catalysts 2058.5 Kinetics and Mechanism of Ethylene Polymerization Reactions with Ziegler Catalysts 2098.6 Kinetic Interpretation of Ethylene Polymerization Reactions 2178.7 Active Centers in Ziegler Catalysts 221References 2249 Stereospecific α-Olefin Polymerization with Heterogeneous Catalysts 229John Severn and Robert L. Jones, JR9.1 Introduction 2299.2 Traditional Ziegler–Natta Catalyst Systems 2419.3 Stereospecific Single Site Catalysts 2669.4 Conclusion 295References 29610 Olefin Polymerization by Vanadium Complex Catalysts 313Kotohiro Nomura and Xiaohua Hou10.1 Introduction: Classical Ziegler-Type Vanadium Catalyst Systems 31310.2 Vanadium Complexes Designed for Olefin Coordination Insertion Polymerization 31510.3 Outlook 332References 33311 MgCl2-Supported Ti Catalysts for the Production of Morphology-Controlled Polyethylene 339Long Wu and Sieghard Wanke11.1 Introduction 33911.2 Preparation of Morphology-Controlled MgCl2/TiCl4 Catalysts 34211.3 Polymerization Processes 34511.4 Effect of Prepolymerization on Activity Profiles and Prepolymer Properties 34911.5 Polymerization Behavior 35811.6 Summary and Conclusions 364References 36512 Product Morphology in Olefin Polymerization with Polymer-Supported Metallocene Catalysts 369Long Wu and Sieghard Wanke12.1 Introduction 36912.2 Preparation of Polymer-Supported Metallocene Catalysts 37112.3 Factors Affecting Morphology of Product Particles 37912.4 Factors Affecting Product Morphology 38912.5 Product Fines and Densities 39412.6 Conclusions 396References 39613 A Review of the Phillips Chromium Catalyst for Ethylene Polymerization 401Max P. McDaniel13.1 Historical and Commercial Background 40113.2 Catalyst Preparation 40413.3 Control of Catalyst Activity 41413.4 Control of Molecular Weight and MW Distribution 43913.5 Control of Crystallinity 48213.6 Control of Elasticity 50913.7 Concluding Remarks 542References 54614 Silica-Supported Silyl Chromate-Based Ethylene Polymerization Catalysts 573Kevin Cann14.1 Introduction 57314.2 Silyl Chromate Catalyst Development 57314.3 Catalyst Structure 57514.4 Polymerization Process 57814.5 Product Characterization and Applications 57914.6 Silica-Supported Reduced Silyl Chromate Catalyst Advancements 582Acknowledgements 588References 58815 Late Transition Metal Catalyzed Co- and Terpolymerization of α-Olefins with Carbon Monoxide: Synthesis and Modification 591Timo M. J. Anselment, Manuela Zintl, Maria Leute, Rüdiger Nowack, and Bernhard Rieger15.1 Introduction and Historical Overview 59115.2 Polyketone Synthesis: General Concept and Mechanism 59315.3 Influence of the Catalyst on the Polymer Structure in α-Olefin/CO Copolymerization Reactions 59915.4 Other Olefins for the Copolymerization with CO 61015.5 Chemical Modification of Polyketones 616References 61816 Ethylene Polymerization and α-Olefin Oligomerization Using Catalysts Derived from Phosphoranes and Ni(II) or Ni(0) Precursors 623Scott Collins16.1 Introduction 62316.2 Starting Materials 626References 62917 Overview of Ring-Opening Metathesis Polymerizations (ROMP) and Acyclic Diene Metathesis (ADMET) Polymerizations with Selected Ruthenium and Molybdenum Complexes 631Robert T. Mathers17.1 Introduction 63117.2 Ruthenium Catalysts 63417.3 Molybdenum Complexes 64617.4 Summary 651References 65118 Copolymerization of Ethylene with Conjugated Dienes 661Islem Belaid, Vincent Monteil, and Christophe Boisson18.1 Introduction 66118.2 ConventionalZiegler–Natta Catalysts 66318.3 Group4 Metallocene Systems 66518.4 Group 4 Post-metallocene Catalysts 67018.5 Vanadium Bis(imino)pyridyl Catalysts 67318.6 Group 8-, 9-, and 10-Based Catalysts 67418.7 Rare Earth Catalysts 67518.8 Conclusion 686References 687Appendix A: Pyrophoricity of Metal Alkyls 693Dennis B. MalpassAppendix B: Rheological Terms for Polymerization Catalyst Chemists 705Gregory W. KamykowskiIndex 711