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.

• List of tables xiii List of figures xvPreface ix1 Introduction to Polymers of Propylene 11.1 Origins of Crystalline Polypropylene 11.2 Basic Description of Polypropylene 41.3 Types and Nomenclature of Polypropylene 91.4 Molecular Weight of Polypropylene 121.5 Transition Metal Catalysts for Propylene Polymerization 151.6 Questions 17References 182 Polymer Characterization 192.1 Introduction 192.2 Polymer Tacticity 242.3 Molecular Weight and Molecular Weight Distribution 362.4 Polymer Bulk Density 482.5 Particle Size Distribution and Morphology 502.6 Questions 54References 553 Ziegler-Natta Catalysts 593.1 A Brief History of Ziegler-Natta Catalysts 593.2 Definitions and Nomenclature 613.3 Characteristics of Ziegler-Natta Catalysts 633.4 Early Commercial Ziegler-Natta Catalysts 653.5 Supported Ziegler-Natta Catalysts 673.6 Prepolymerized Ziegler-Natta Catalysts 683.7 Mechanism of Ziegler-Natta Polymerization 693.8 Questions and Exercises 73References 734 Propylene Polymerization Catalysts 754.1 Introduction 754.2 Zero Generation Ziegler-Natta Catalysts 774.3 First Generation ZN Catalysts 794.4 Second Generation ZN Catalysts 824.5 Third Generation ZN Catalysts 844.6 Fourth Generation ZN Catalysts 864.7 Fifth Generation ZN Catalysts 894.8 ZN Catalysts for Atactic Polypropylene 924.9 Metallocenes and Other Single Site Catalysts 934.10 Cocatalysts for ZN Catalysts 944.11 Kinetics and ZN Catalyst Productivity 994.12 Concluding Remarks 1024.13 Questions 102References 1055 Aluminum Alkyls in Ziegler-Natta Catalysts 1115.1 Organometallic Compounds 1115.2. Characteristics of Aluminum Alkyls 1135.3 Production of Aluminum Alkyls 1225.4 Reducing Agent for the Transition Metal 1265.5 Alkylating Agent for Creation of Active Centers 1275.6 Scavenger of Catalyst Poisons 1285.7 Chain Transfer Agent 1295.8 Questions 129References 1306 Single Site Catalysts and Cocatalysts 1336.1 Introduction 1336.2 The Structures of Metallocenes and SSCs 1346.3 Non-Metallocene Polymerization Catalysts 1386.4 Cocatalysts for SSCs 1396.5 Supports for SSCs 1436.6 Characteristics of mPP 1456.7 Selected Applications of mPP Resins 1486.8 Metallocene Synthesis 1506.9 Syndiotactic Polypropylene 1526.10 Commercial Reality and Concluding Remarks 1546.11 Questions 155References 1567 Catalyst Manufacture 1637.1 Introduction 1637.2 Development of the Manufacturing Process 1637.3 Chemistry of Catalyst Manufacture 1647.4 Raw Materials Storage and Handling 1667.5 Catalyst Preparation 1677.6 Catalyst Drying 1697.7 Catalyst Packaging 1697.8 Recovery and Recycle of Spent Solvents 1707.9 Prepolymerization at the Catalyst Manufacturing Plant 1727.10 Plant Size 1727.11 Site Safety 1727.12 Quality Control and Specifications 1747.13 Diagram of a Hypothetical Plant 1747.14 Custom Manufacture 1767.15 Brief Consideration of Metallocene Catalyst Manufacture 1787.16 Concluding Remarks 1797.17 Questions 179References 1808 An Overview of Industrial Polypropylene Processes 1838.1 Introduction 1838.2 Slurry (Suspension) Processes 1888.3 Bulk ("Liquid Pool") Process 1898.4 "Loop Slurry" Process (Chevron Phillips Chemical) 1898.5 Gas Phase Processes 1908.6 Solution process 1948.7 Hybrid Processes 1948.8 Kinetics and Reactivity Ratios 1968.9 Emergency Stoppage of Polymerization 1988.10 Questions 199References 1999 Laboratory Catalyst Synthesis 2019.1 Introduction 2019.2 General Synthesis Requirements 2029.3 Equipment Requirements 2029.4 Synthesis Schedule 2079.5 Handling TiCl4 2089.6 Handling Diethylaluminum Chloride 2099.7 Spent Liquids 2099.8 Synthetic Procedure for Fourth Generation Supported Catalyst 2109.9 Synthetic Procedure for Second Generation Precipitated TiCl3 Catalyst 2119.10 Catalyst Analysis 2139.11 Questions 213References 21410 Polymerization Catalyst Testing 21710.1 Introduction 21710.2 Facility Requirements 21910.3 The Autoclave 22110.4 Key Equipment Items 22410.5 Raw Materials 22510.6 Polymerization Conditions 22710.7 Autoclave Preparation 22810.8 Polymerization Test Procedure 22810.9 Reproducibility 23011 Downstream Aspects of Polypropylene 23511.1 Introduction 23511.2 Additives 23611.3 Fabrication Methods 24211.4 Biopolymers 24411.5 Environmental 24811.6 Questions 254References 25512 Overview of Polypropylene Markets 25712.1 Introduction 25712.2 The Supply Chain for Polypropylene 25812.3 The Global Polypropylene Market 26112.4 Questions 269References 26913 The Future of Polypropylene 27113.1 Introduction 27113.2 Key Growth Markets for Polypropylene 27213.3 Polypropylene and Free Markets 27413.4 Questions 278References 279Appendix A 281Appendix B 299Appendix C 317Index 000

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.

• List of tables xiii List of figures xvPreface ix1 Introduction to Polymers of Propylene 11.1 Origins of Crystalline Polypropylene 11.2 Basic Description of Polypropylene 41.3 Types and Nomenclature of Polypropylene 91.4 Molecular Weight of Polypropylene 121.5 Transition Metal Catalysts for Propylene Polymerization 151.6 Questions 17References 182 Polymer Characterization 192.1 Introduction 192.2 Polymer Tacticity 242.3 Molecular Weight and Molecular Weight Distribution 362.4 Polymer Bulk Density 482.5 Particle Size Distribution and Morphology 502.6 Questions 54References 553 Ziegler-Natta Catalysts 593.1 A Brief History of Ziegler-Natta Catalysts 593.2 Definitions and Nomenclature 613.3 Characteristics of Ziegler-Natta Catalysts 633.4 Early Commercial Ziegler-Natta Catalysts 653.5 Supported Ziegler-Natta Catalysts 673.6 Prepolymerized Ziegler-Natta Catalysts 683.7 Mechanism of Ziegler-Natta Polymerization 693.8 Questions and Exercises 73References 734 Propylene Polymerization Catalysts 754.1 Introduction 754.2 Zero Generation Ziegler-Natta Catalysts 774.3 First Generation ZN Catalysts 794.4 Second Generation ZN Catalysts 824.5 Third Generation ZN Catalysts 844.6 Fourth Generation ZN Catalysts 864.7 Fifth Generation ZN Catalysts 894.8 ZN Catalysts for Atactic Polypropylene 924.9 Metallocenes and Other Single Site Catalysts 934.10 Cocatalysts for ZN Catalysts 944.11 Kinetics and ZN Catalyst Productivity 994.12 Concluding Remarks 1024.13 Questions 102References 1055 Aluminum Alkyls in Ziegler-Natta Catalysts 1115.1 Organometallic Compounds 1115.2. Characteristics of Aluminum Alkyls 1135.3 Production of Aluminum Alkyls 1225.4 Reducing Agent for the Transition Metal 1265.5 Alkylating Agent for Creation of Active Centers 1275.6 Scavenger of Catalyst Poisons 1285.7 Chain Transfer Agent 1295.8 Questions 129References 1306 Single Site Catalysts and Cocatalysts 1336.1 Introduction 1336.2 The Structures of Metallocenes and SSCs 1346.3 Non-Metallocene Polymerization Catalysts 1386.4 Cocatalysts for SSCs 1396.5 Supports for SSCs 1436.6 Characteristics of mPP 1456.7 Selected Applications of mPP Resins 1486.8 Metallocene Synthesis 1506.9 Syndiotactic Polypropylene 1526.10 Commercial Reality and Concluding Remarks 1546.11 Questions 155References 1567 Catalyst Manufacture 1637.1 Introduction 1637.2 Development of the Manufacturing Process 1637.3 Chemistry of Catalyst Manufacture 1647.4 Raw Materials Storage and Handling 1667.5 Catalyst Preparation 1677.6 Catalyst Drying 1697.7 Catalyst Packaging 1697.8 Recovery and Recycle of Spent Solvents 1707.9 Prepolymerization at the Catalyst Manufacturing Plant 1727.10 Plant Size 1727.11 Site Safety 1727.12 Quality Control and Specifications 1747.13 Diagram of a Hypothetical Plant 1747.14 Custom Manufacture 1767.15 Brief Consideration of Metallocene Catalyst Manufacture 1787.16 Concluding Remarks 1797.17 Questions 179References 1808 An Overview of Industrial Polypropylene Processes 1838.1 Introduction 1838.2 Slurry (Suspension) Processes 1888.3 Bulk ("Liquid Pool") Process 1898.4 "Loop Slurry" Process (Chevron Phillips Chemical) 1898.5 Gas Phase Processes 1908.6 Solution process 1948.7 Hybrid Processes 1948.8 Kinetics and Reactivity Ratios 1968.9 Emergency Stoppage of Polymerization 1988.10 Questions 199References 1999 Laboratory Catalyst Synthesis 2019.1 Introduction 2019.2 General Synthesis Requirements 2029.3 Equipment Requirements 2029.4 Synthesis Schedule 2079.5 Handling TiCl4 2089.6 Handling Diethylaluminum Chloride 2099.7 Spent Liquids 2099.8 Synthetic Procedure for Fourth Generation Supported Catalyst 2109.9 Synthetic Procedure for Second Generation Precipitated TiCl3 Catalyst 2119.10 Catalyst Analysis 2139.11 Questions 213References 21410 Polymerization Catalyst Testing 21710.1 Introduction 21710.2 Facility Requirements 21910.3 The Autoclave 22110.4 Key Equipment Items 22410.5 Raw Materials 22510.6 Polymerization Conditions 22710.7 Autoclave Preparation 22810.8 Polymerization Test Procedure 22810.9 Reproducibility 23011 Downstream Aspects of Polypropylene 23511.1 Introduction 23511.2 Additives 23611.3 Fabrication Methods 24211.4 Biopolymers 24411.5 Environmental 24811.6 Questions 254References 25512 Overview of Polypropylene Markets 25712.1 Introduction 25712.2 The Supply Chain for Polypropylene 25812.3 The Global Polypropylene Market 26112.4 Questions 269References 26913 The Future of Polypropylene 27113.1 Introduction 27113.2 Key Growth Markets for Polypropylene 27213.3 Polypropylene and Free Markets 27413.4 Questions 278References 279Appendix A 281Appendix B 299Appendix C 317Index 000

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.

• List of tables xiii List of figures xvPreface ix1 Introduction to Polymers of Propylene 11.1 Origins of Crystalline Polypropylene 11.2 Basic Description of Polypropylene 41.3 Types and Nomenclature of Polypropylene 91.4 Molecular Weight of Polypropylene 121.5 Transition Metal Catalysts for Propylene Polymerization 151.6 Questions 17References 182 Polymer Characterization 192.1 Introduction 192.2 Polymer Tacticity 242.3 Molecular Weight and Molecular Weight Distribution 362.4 Polymer Bulk Density 482.5 Particle Size Distribution and Morphology 502.6 Questions 54References 553 Ziegler-Natta Catalysts 593.1 A Brief History of Ziegler-Natta Catalysts 593.2 Definitions and Nomenclature 613.3 Characteristics of Ziegler-Natta Catalysts 633.4 Early Commercial Ziegler-Natta Catalysts 653.5 Supported Ziegler-Natta Catalysts 673.6 Prepolymerized Ziegler-Natta Catalysts 683.7 Mechanism of Ziegler-Natta Polymerization 693.8 Questions and Exercises 73References 734 Propylene Polymerization Catalysts 754.1 Introduction 754.2 Zero Generation Ziegler-Natta Catalysts 774.3 First Generation ZN Catalysts 794.4 Second Generation ZN Catalysts 824.5 Third Generation ZN Catalysts 844.6 Fourth Generation ZN Catalysts 864.7 Fifth Generation ZN Catalysts 894.8 ZN Catalysts for Atactic Polypropylene 924.9 Metallocenes and Other Single Site Catalysts 934.10 Cocatalysts for ZN Catalysts 944.11 Kinetics and ZN Catalyst Productivity 994.12 Concluding Remarks 1024.13 Questions 102References 1055 Aluminum Alkyls in Ziegler-Natta Catalysts 1115.1 Organometallic Compounds 1115.2. Characteristics of Aluminum Alkyls 1135.3 Production of Aluminum Alkyls 1225.4 Reducing Agent for the Transition Metal 1265.5 Alkylating Agent for Creation of Active Centers 1275.6 Scavenger of Catalyst Poisons 1285.7 Chain Transfer Agent 1295.8 Questions 129References 1306 Single Site Catalysts and Cocatalysts 1336.1 Introduction 1336.2 The Structures of Metallocenes and SSCs 1346.3 Non-Metallocene Polymerization Catalysts 1386.4 Cocatalysts for SSCs 1396.5 Supports for SSCs 1436.6 Characteristics of mPP 1456.7 Selected Applications of mPP Resins 1486.8 Metallocene Synthesis 1506.9 Syndiotactic Polypropylene 1526.10 Commercial Reality and Concluding Remarks 1546.11 Questions 155References 1567 Catalyst Manufacture 1637.1 Introduction 1637.2 Development of the Manufacturing Process 1637.3 Chemistry of Catalyst Manufacture 1647.4 Raw Materials Storage and Handling 1667.5 Catalyst Preparation 1677.6 Catalyst Drying 1697.7 Catalyst Packaging 1697.8 Recovery and Recycle of Spent Solvents 1707.9 Prepolymerization at the Catalyst Manufacturing Plant 1727.10 Plant Size 1727.11 Site Safety 1727.12 Quality Control and Specifications 1747.13 Diagram of a Hypothetical Plant 1747.14 Custom Manufacture 1767.15 Brief Consideration of Metallocene Catalyst Manufacture 1787.16 Concluding Remarks 1797.17 Questions 179References 1808 An Overview of Industrial Polypropylene Processes 1838.1 Introduction 1838.2 Slurry (Suspension) Processes 1888.3 Bulk ("Liquid Pool") Process 1898.4 "Loop Slurry" Process (Chevron Phillips Chemical) 1898.5 Gas Phase Processes 1908.6 Solution process 1948.7 Hybrid Processes 1948.8 Kinetics and Reactivity Ratios 1968.9 Emergency Stoppage of Polymerization 1988.10 Questions 199References 1999 Laboratory Catalyst Synthesis 2019.1 Introduction 2019.2 General Synthesis Requirements 2029.3 Equipment Requirements 2029.4 Synthesis Schedule 2079.5 Handling TiCl4 2089.6 Handling Diethylaluminum Chloride 2099.7 Spent Liquids 2099.8 Synthetic Procedure for Fourth Generation Supported Catalyst 2109.9 Synthetic Procedure for Second Generation Precipitated TiCl3 Catalyst 2119.10 Catalyst Analysis 2139.11 Questions 213References 21410 Polymerization Catalyst Testing 21710.1 Introduction 21710.2 Facility Requirements 21910.3 The Autoclave 22110.4 Key Equipment Items 22410.5 Raw Materials 22510.6 Polymerization Conditions 22710.7 Autoclave Preparation 22810.8 Polymerization Test Procedure 22810.9 Reproducibility 23011 Downstream Aspects of Polypropylene 23511.1 Introduction 23511.2 Additives 23611.3 Fabrication Methods 24211.4 Biopolymers 24411.5 Environmental 24811.6 Questions 254References 25512 Overview of Polypropylene Markets 25712.1 Introduction 25712.2 The Supply Chain for Polypropylene 25812.3 The Global Polypropylene Market 26112.4 Questions 269References 26913 The Future of Polypropylene 27113.1 Introduction 27113.2 Key Growth Markets for Polypropylene 27213.3 Polypropylene and Free Markets 27413.4 Questions 278References 279Appendix A 281Appendix B 299Appendix C 317Index 000