Table of Contents

List of tables xiii List of figures xv Preface ix 1 Introduction to Polymers of Propylene 1 1.1 Origins of Crystalline Polypropylene 1 1.2 Basic Description of Polypropylene 4 1.3 Types and Nomenclature of Polypropylene 9 1.4 Molecular Weight of Polypropylene 12 1.5 Transition Metal Catalysts for Propylene Polymerization 15 1.6 Questions 17 References 18 2 Polymer Characterization 19 2.1 Introduction 19 2.2 Polymer Tacticity 24 2.3 Molecular Weight and Molecular Weight Distribution 36 2.4 Polymer Bulk Density 48 2.5 Particle Size Distribution and Morphology 50 2.6 Questions 54 References 55 3 Ziegler-Natta Catalysts 59 3.1 A Brief History of Ziegler-Natta Catalysts 59 3.2 Definitions and Nomenclature 61 3.3 Characteristics of Ziegler-Natta Catalysts 63 3.4 Early Commercial Ziegler-Natta Catalysts 65 3.5 Supported Ziegler-Natta Catalysts 67 3.6 Prepolymerized Ziegler-Natta Catalysts 68 3.7 Mechanism of Ziegler-Natta Polymerization 69 3.8 Questions and Exercises 73 References 73 4 Propylene Polymerization Catalysts 75 4.1 Introduction 75 4.2 Zero Generation Ziegler-Natta Catalysts 77 4.3 First Generation ZN Catalysts 79 4.4 Second Generation ZN Catalysts 82 4.5 Third Generation ZN Catalysts 84 4.6 Fourth Generation ZN Catalysts 86 4.7 Fifth Generation ZN Catalysts 89 4.8 ZN Catalysts for Atactic Polypropylene 92 4.9 Metallocenes and Other Single Site Catalysts 93 4.10 Cocatalysts for ZN Catalysts 94 4.11 Kinetics and ZN Catalyst Productivity 99 4.12 Concluding Remarks 102 4.13 Questions 102 References 105 5 Aluminum Alkyls in Ziegler-Natta Catalysts 111 5.1 Organometallic Compounds 111 5.2. Characteristics of Aluminum Alkyls 113 5.3 Production of Aluminum Alkyls 122 5.4 Reducing Agent for the Transition Metal 126 5.5 Alkylating Agent for Creation of Active Centers 127 5.6 Scavenger of Catalyst Poisons 128 5.7 Chain Transfer Agent 129 5.8 Questions 129 References 130 6 Single Site Catalysts and Cocatalysts 133 6.1 Introduction 133 6.2 The Structures of Metallocenes and SSCs 134 6.3 Non-Metallocene Polymerization Catalysts 138 6.4 Cocatalysts for SSCs 139 6.5 Supports for SSCs 143 6.6 Characteristics of mPP 145 6.7 Selected Applications of mPP Resins 148 6.8 Metallocene Synthesis 150 6.9 Syndiotactic Polypropylene 152 6.10 Commercial Reality and Concluding Remarks 154 6.11 Questions 155 References 156 7 Catalyst Manufacture 163 7.1 Introduction 163 7.2 Development of the Manufacturing Process 163 7.3 Chemistry of Catalyst Manufacture 164 7.4 Raw Materials Storage and Handling 166 7.5 Catalyst Preparation 167 7.6 Catalyst Drying 169 7.7 Catalyst Packaging 169 7.8 Recovery and Recycle of Spent Solvents 170 7.9 Prepolymerization at the Catalyst Manufacturing Plant 172 7.10 Plant Size 172 7.11 Site Safety 172 7.12 Quality Control and Specifications 174 7.13 Diagram of a Hypothetical Plant 174 7.14 Custom Manufacture 176 7.15 Brief Consideration of Metallocene Catalyst Manufacture 178 7.16 Concluding Remarks 179 7.17 Questions 179 References 180 8 An Overview of Industrial Polypropylene Processes 183 8.1 Introduction 183 8.2 Slurry (Suspension) Processes 188 8.3 Bulk ("Liquid Pool") Process 189 8.4 "Loop Slurry" Process (Chevron Phillips Chemical) 189 8.5 Gas Phase Processes 190 8.6 Solution process 194 8.7 Hybrid Processes 194 8.8 Kinetics and Reactivity Ratios 1968.9 Emergency Stoppage of Polymerization 1988.10 Questions 199References 199 9 Laboratory Catalyst Synthesis 201 9.1 Introduction 201 9.2 General Synthesis Requirements 202 9.3 Equipment Requirements 202 9.4 Synthesis Schedule 207 9.5 Handling TiCl4 208 9.6 Handling Diethylaluminum Chloride 209 9.7 Spent Liquids 209 9.8 Synthetic Procedure for Fourth Generation Supported Catalyst 210 9.9 Synthetic Procedure for Second Generation Precipitated TiCl3 Catalyst 211 9.10 Catalyst Analysis 213 9.11 Questions 213 References 214 10 Polymerization Catalyst Testing 217 10.1 Introduction 217 10.2 Facility Requirements 219 10.3 The Autoclave 221 10.4 Key Equipment Items 224 10.5 Raw Materials 225 10.6 Polymerization Conditions 227 10.7 Autoclave Preparation 228 10.8 Polymerization Test Procedure 228 10.9 Reproducibility 230 11 Downstream Aspects of Polypropylene 235 11.1 Introduction 235 11.2 Additives 236 11.3 Fabrication Methods 242 11.4 Biopolymers 244 11.5 Environmental 248 11.6 Questions 254 References 255 12 Overview of Polypropylene Markets 257 12.1 Introduction 257 12.2 The Supply Chain for Polypropylene 258 12.3 The Global Polypropylene Market 261 12.4 Questions 269 References 269 13 The Future of Polypropylene 271 13.1 Introduction 271 13.2 Key Growth Markets for Polypropylene 272 13.3 Polypropylene and Free Markets 274 13.4 Questions 278 References 279 Appendix A 281 Appendix B 299 Appendix C 317 Index 000

About the Author

Dennis B. Malpass received his PhD in organometallic chemistry from The University of Tennessee in 1970 and began his career with Texas Alkyls, Inc. (now AkzoNobel). His industrial career spanned thirty-three years working on synthesis, characterization, and applications of metal alkyls, especially aluminum alkyls in Ziegler-Natta polymerization of olefins. He has more than eighty patents and publications and now consults in the polyolefins industry. He also teaches organic chemistry and is an instructor for continuing education courses for SPE and ACS. In 2010 he authored Introduction to Industrial Polyethylene . Elliot I. Band received his PhD in inorganic chemistry from Cornell University in 1980. He has been in research and development with AkzoNobel and its predecessor companies for over thirty years. His tenure includes twenty years in Ziegler-Natta catalyst synthesis, manufacture, quality control, and technical support to polypropylene manufacturers in North and South America. He presently manages a group of chemists and engineers that develops new cationic, anionic, and nonionic surfactants for AkzoNobel. Elliot has thirty publications and more than twenty patents.