Introduction to Industrial Polypropylene

The intent of this book is to provide chemists, engineers and students an introduction to the essentials of industrial polypropylene-what it is, how it's made and fabricated, the markets it serves and its environmental fate. Technical aspects are described in a straightforward way with minimal discussion of esoteric theory such that a person with even a modicum of training in chemistry should be able to grasp. The purpose is to show practical, down-to-earth interpretations of polypropylene technology. Specifically, the book elucidates; Ziegler-Natta catalysts Propylene polymerization catalysts Single Site catalysts and cocatalysts Polypropylene manufacturing and processing Catalysts synthesis in the laboratory\ Testing Various downstream aspects of industrial polypropylene such as biopolymers alternatives and additives.

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	p. xiii
List of Figures	p. xv
Preface	p. xix
Introduction to Polymers of Propylene	p. 1
Origins of Crystalline Polypropylene	p. 1
Basic Description of Polypropylene	p. 4
Types and Nomenclature of Polypropylene	p. 9
Molecular Weight of Polypropylene	p. 12
Transition Metal Catalysts for Propylene Polymerization	p. 15
Questions	p. 17
References	p. 18
Polymer Characterization	p. 19
Introduction	p. 19
Polymer Tacticity	p. 24
Introduction	p. 24
Measurement of Polymer Microtacticity by ¹³C NMR	p. 27
Total Isotactic Index	p. 30
Total Xylene Insolubles	p. 33
Molecular Weight and Molecular Weight Distribution	p. 36
Introduction	p. 36
Gel Permeation Chromatography	p. 37
Intrinsic Viscosity	p. 41
Melt Flow Rate	p. 45
Polymer Bulk Density	p. 48
Introduction	p. 48
Measurement Method	p. 50
Particle Size Distribution and Morphology	p. 50
Introduction	p. 50
Measurement Method	p. 52
Questions 54 References	p. 55
Ziegler-Natta Catalysts	p. 59
A Brief History of Ziegler-Natta Catalysts	p. 59
Definitions and Nomenclature	p. 61
Characteristics of Ziegler-Natta Catalysts	p. 63
Early Commercial Ziegler-Natta Catalysts	p. 65
Supported Ziegler-Natta Catalysts	p. 67
Prepolymerized Ziegler-Natta Catalysts	p. 68
Mechanism of Ziegler-Natta Polymerization	p. 69
Questions and Exercises	p. 73
References	p. 73
Propylene Polymerization Catalysts	p. 75
Introduction	p. 75
Zero Generation Ziegler-Natta Catalysts	p. 77
First Generation ZN Catalysts	p. 79
Second Generation ZN Catalysts	p. 82
Third Generation ZN Catalysts	p. 84
Fourth Generation ZN Catalysts	p. 86
Fifth Generation ZN Catalysts	p. 89
ZN Catalysts for Atactic Polypropylene	p. 92
Metallocenes and Other Single Site Catalysts	p. 93
Cocatalysts for ZN Catalysts	p. 94
Kinetics and ZN Catalyst Productivity	p. 99
Concluding Remarks	p. 102
Questions	p. 102
References	p. 105
Aluminum Alkyls in Ziegler-Natta Catalysts	p. 111
Organometalhc Compounds	p. 111
Characteristics of Aluminum Alkyls	p. 113
Basic Physical and Chemical Properties	p. 116
Hydride Content	p. 116
Other R₃Al Impurities	p. 116
Analysis of Aluminum Alkyls	p. 117
Impurities Resulting from Exposure to Minute Concentrations of Water and Oxygen	p. 118
Assays of Aluminum Alkyls	p. 118
Reactivity with Organic Substrates	p. 118
Reactivity with CO₂ and CO	p. 119
Distillation	p. 119
Association of Aluminum Alkyls	p. 119
Storage Stability	p. 120
Thermal Stability	p. 121
Production of Aluminum Alkyls	p. 122
Reducing Agent for the Transition Metal	p. 125
Alkylating Agent for Creation of Active Centers	p. 127
Scavenger of Catalyst Poisons	p. 128
Chain Transfer Agent	p. 129
Safety and Handling of Aluminum Alkyls	p. 129
Questions	p. 130
References	p. 131
Single Site Catalysts and Cocatalysts	p. 133
Introduction	p. 133
The Structures of Metallocenes and SSCs	p. 134
Non-Metallocene Polymerization Catalysts	p. 138
Cocatalysts for SSCs	p. 139
Aluminoxanes	p. 139
Organoboron Cocatalysts	p. 142
Activated Supports	p. 142
Supports for SSCs	p. 143
Characteristics of mPP	p. 145
Selected Applications of mPP Resins	p. 148
Medical Applications	p. 148
Thin Wall Food Containers	p. 149
High Clarity Bottles for Personal Care	p. 149
Waxes	p. 149
New Resins from Hybrid Catalysts to Make Polypropylene Alloys	p. 150
Metallocene Synthesis	p. 150
Syndiotactic Polypropylene	p. 153
Commercial Reality and Concluding Remarks	p. 154
Questions	p. 155
References	p. 156
Catalyst Manufacture	p. 163
Introduction	p. 163
Development of the Manufacturing Process	p. 163
Chemistry of Catalyst Manufacture	p. 164
Raw Materials Storage and Handling	p. 166
Catalyst Preparation	p. 167
Catalyst Drying	p. 169
Catalyst Packaging	p. 169
Recovery and Recycle of Spent Solvents	p. 170
Prepolymerization at the Catalyst Manufacturing Plant	p. 172
Plant Size	p. 172
Site Safety	p. 172
Quality Control and Specifications	p. 174
Diagram of a Hypothetical Plant	p. 174
Custom Manufacture	p. 176
Brief Consideration of Metallocene Catalyst Manufacture	p. 178
Concluding Remarks	p. 179
Questions	p. 179
References	p. 180
An Overview of Industrial Polypropylene Processes	p. 183
Introduction	p. 183
Slurry (Suspension) Processes	p. 188
Bulk ("Liquid Pool") Process	p. 189
"Loop Slurry" Process (Chevron Phillips Chemical)	p. 189
Gas Phase Processes	p. 190
Solution Process	p. 194
Hybrid Processes	p. 194
Kinetics and Reactivity Ratios	p. 196
Emergency Stoppage of Polymerization	p. 198
Questions	p. 199
References	p. 199
Laboratory Catalyst Synthesis	p. 201
Introduction	p. 201
General Synthesis Requirements	p. 202
Equipment Requirements	p. 202
Synthesis Schedule	p. 207
Handling TiCl₄	p. 208
Handling Diethylaluminum Chloride	p. 209
Spent Liquids	p. 209
Synthetic Procedure for Fourth Generation Supported Catalyst	p. 210
Introduction	p. 210
Procedure	p. 210
Synthetic Procedure for Second Generation Precipitated TiCl₃ Catalyst	p. 211
Introduction	p. 211
Procedure	p. 212
Catalyst Analysis	p. 213
Questions	p. 213
References	p. 214
Polymerization Catalyst Testing	p. 217
Introduction	p. 217
Facility Requirements	p. 219
The Autoclave	p. 221
Key Equipment Items	p. 224
Raw Materials	p. 225
Polymerization Conditions	p. 227
Autoclave Preparation	p. 228
Polymerization Test Procedure	p. 228
Reproducibility	p. 230
Testing Metallocene Catalysts	p. 231
Questions	p. 232
References	p. 233
Downstream Aspects of Polypropylene	p. 235
Introduction	p. 235
Additives	p. 236
Fabrication Methods	p. 242
Biopolymers	p. 244
Environmental	p. 248
Questions	p. 254
References	p. 255
Overview of Polypropylene Markets	p. 257
Introduction	p. 257
The Supply Chain for Polypropylene	p. 258
The Global Polypropylene Market	p. 260
Questions	p. 266
References	p. 266
The Future of Polypropylene	p. 269
Introduction	p. 269
Key Growth Markets for Polypropylene	p. 270
Polypropylene and Free Markets	p. 272
Questions	p. 277
References	p. 277
	p. 279
	p. 297
	p. 315
Index	p. 317
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Introduction to Industrial Polypropylene Properties, Catalysts Processes

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