Introduction to Industrial Polypropylene: Properties, Catalysts Processes Book

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