Acknowledgmentsxi Preface xiii Nomenclature xvii 1 Introduction to Polyolefins 1 1.1 Introduction 1 1.2 Polyethylene Resins 4 1.3 Polypropylene Resins 10 Further Reading 13 2 Polyolefin Microstructural Characterization 15 2.1 Introduction 15 2.2 Molecular Weight Distribution 17 2.2.1 Size Exclusion Chromatography 17 2.
2.2 Field Flow Fractionation 27 2.3 Chemical Composition Distribution 29 2.3.1 Crystallizability-Based Techniques 29 2.3.2 High-Performance Liquid Chromatography 40 2.4 Cross-Fractionation Techniques 43 2.
5 Long-Chain Branching 46 Further Reading 51 3 Polymerization Catalysis and Mechanism 53 3.1 Introduction 53 3.2 Catalyst Types 56 3.2.1 Ziegler-Natta Catalysts 56 3.2.2 Phillips Catalysts 61 3.2.
3 Metallocenes 62 3.2.4 Late Transition Metal Catalysts 67 3.3 Supporting Single-Site Catalysts 70 3.4 Polymerization Mechanism with Coordination Catalysts 76 Further Reading 86 4 Polyolefin Reactors and Processes 87 4.1 Introduction 87 4.2 Reactor Configurations and Design 89 4.2.
1 Gas-Phase Reactors 90 4.2.1.1 Fluidized Bed Gas-Phase Reactors 91 4.2.1.2 Vertical Stirred Bed Reactor 97 4.2.
1.3 Horizontal Stirred Gas-Phase Reactor 99 4.2.1.4 Multizone Circulating Reactor 102 4.2.2 Slurry-Phase Reactors 104 4.2.
2.1 Autoclaves 105 4.2.2.2 Slurry Loop Reactors 106 4.2.3 Solution Reactors 107 4.2.
4 Summary of Reactor Types for Olefin Polymerization 108 4.3 Olefin Polymerization Processes 109 4.3.1 Polyethylene Manufacturing Processes 112 4.3.1.1 Slurry (Inert Diluent) Processes 112 4.3.
1.2 Gas-Phase Processes 115 4.3.1.3 Mixed-Phase Processes 118 4.3.1.4 Solution Processes 119 4.
3.2 Polypropylene Manufacturing Processes 121 4.3.2.1 Slurry (Inert Diluent) Processes 122 4.3.2.2 Gas-Phase Processes 122 4.
3.2.3 Mixed-Phase Processes 125 4.4 Conclusion 128 References 128 Further Reading 129 5 Polymerization Kinetics 131 5.1 Introduction 131 5.2 Fundamental Model for Polymerization Kinetics 134 5.2.1 Single-Site Catalysts 134 5.
2.1.1 Homopolymerization 134 5.2.1.2 Copolymerization 145 5.2.2 Multiple-Site Catalysts 149 5.
2.3 Temperature Dependence of Kinetic Constants 152 5.2.4 Number of Moles of Active Sites 154 5.3 Nonstandard Polymerization Kinetics Models 156 5.3.1 Polymerization Orders Greater than One 156 5.3.
2 Hydrogen Effect on the Polymerization Rate 161 5.3.3 Comonomer Effect on the Polymerization Rate 173 5.3.4 Negative Polymerization Orders with Late Transition Metal Catalysts 179 5.4 Vapor-Liquid-Solid Equilibrium Considerations 181 Further Reading 184 6 Polyolefin Microstructural Modeling 187 6.1 Introduction 187 6.2 Instantaneous Distributions 188 6.
2.1 Molecular Weight Distribution 188 6.2.1.1 Single-Site Catalysts 188 6.2.1.2 Multiple-Site Catalysts 199 6.
2.2 Chemical Composition Distribution 212 6.2.2.1 Single-Site Catalysts 212 6.2.2.2 Multiple-Site Catalysts 222 6.
2.3 Comonomer Sequence Length Distribution 232 6.2.4 Long-Chain Branching Distribution 237 6.2.5 Polypropylene: Regio- and Stereoregularity 250 6.3 Monte Carlo Simulation 251 6.3.
1 Steady-State Monte Carlo Models 252 6.3.2 Dynamic Monte Carlo Models 262 Further Reading 268 7 Particle Growth and Single Particle Modeling 271 7.1 Introduction 271 7.2 Particle Fragmentation and Growth 274 7.2.1 The Fragmentation Step 275 7.2.
2 Particle Growth 284 7.3 Single Particle Models 286 7.3.1 Particle Mass and Energy Balances: the Multigrain Model (MGM) 287 7.3.2 The Polymer Flow Model (PFM) 292 7.3.3 An Analysis of Particle Growth with the MGM/PFM Approach 295 7.
3.4 Convection in the Particles - High Mass Transfer Rates at Short Times 301 7.4 Limitations of the PFM/MGM Approach: Particle Morphology 304 References 307 Further Reading 307 8 Developing Models for Industrial Reactors 311 8.1 Introduction 311 References 321 Further Reading 322 Index 325.