Introduction to Industrial Polypropylene Scrivener Publishing 100 Cummings Center, Suite 41J Beverly, MA 01915-6106

Introduction to Industrial Polypropylene Scrivener Publishing 100 Cummings Center, Suite 41J Beverly, MA 01915-6106 Publishers at Scrivener Martin Scrivener ([email protected]) Phillip Carmical ([email protected]) Introduction to Industrial Polypropylene Properties, Catalysts, Processes Dennis B. Malpass and Elliot I. Band Scrivener ©WILEY Copyright © 2012 by Scrivener Publishing LLC. All rights reserved. Co-published by John Wiley & Sons, Inc. Hoboken, New Jersey, and Scrivener Publishing LLC, Salem, Massachusetts. Published simultaneously in Canada. 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For general information on our other products and services or for technical support, please contact our Customer Care Department within the United States at (800) 762-2974, outside the United States at (317) 572-3993 or fax (317) 572-4002. Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in electronic formats. For more information about Wiley products, visit our web site at www.wiley.com. For more information about Scrivener products please visit www.scrivenerpublishing.com. Cover design by Russell Richardson with concept and figures supplied by Elliot Band Library of Congress Cataloging-in-Publication Data: ISBN 978-1-118-06276-0 Printed in the United States of America 10 987654321 This book is dedicated to the memory of Professor Jerome F. Eastham, Sr., who lived his life with courage and élan. He was a mentor, a scholar and a true Tennessee gentleman. The world is a poorer place without him. Jerome F Eastham, Sr was born September 22,1924 in Daytona Beach, FL. He grew up in Lake City, FL and completed high school in Hazard, KY. He served in the US infantry in World War II. After the war, he attended The University of Kentucky and graduated in 1948. He then attended graduate school at The University of California in Berkeley and received a PhD in organic chemistry. Following fellowships at the University of London and the University of Wisconsin, he accepted an assistant professorship in 1953 at The University of Tennessee in Knoxville. During his early years at UT, he became well known for his work in organic and organometallic chemistry. He was a dynamic instruc- tor and inspired many graduate students over his long tenure at UT. In the late 1960s, he made a bold decision to change careers and entered medical school to pursue an interest in neurochemistry. An author of this text (DBM) was privileged to be Prof Eastham's final graduate student in organometallic chemistry before Prof Eastham entered medical school. After obtaining his doctor of medicine in Memphis, Eastham returned to Knoxville where he became an attending physician in the Department of Internal Medicine at the UT Research Hospital. Synchronously (one of his favorite lecture words), he resumed teaching organic chemistry to new generations of students. He completed a career that spanned 39 years with the University of Tennessee and retired in 1995. He passed away on August 22, 2008. Contents List of Tables xiii List of Figures xv Preface xix 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 2.2.1 Introduction 24 2.2.2 Measurement of Polymer Microtacticity by 13C NMR 27 2.2.3 Total Isotactic Index 30 2.2.4 Total Xylene Insolubles 33 2.3 Molecular Weight and Molecular Weight Distribution 36 2.3.1 Introduction 36 2.3.2 Gel Permeation Chromatography 37 2.3.3 Intrinsic Viscosity 41 2.3.4 Melt Flow Rate 45 vn viii CONTENTS 2.4 Polymer Bulk Density 48 2.4.1 Introduction 48 2.4.2 Measurement Method 50 2.5 Particle Size Distribution and Morphology 50 2.5.1 Introduction 50 2.5.2 Measurement Method 52 2.6 Questions 54 References 55 4 Ziegler-NattPolyme a 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 PropylenPolyme e 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 CONTENTS ix 5.2 Characteristics of Aluminum Alkyls 113 5.2.1 Basic Physical and Chemical Properties 116 5.2.2 Hydride Content 116 5.2.3 Other R3A1 Impurities 116 5.2.4 Analysis of Aluminum Alkyls 117 5.2.5 Impurities Resulting from Exposure to Minute Concentrations of Water and Oxygen 118 5.2.6 Assays of Aluminum Alkyls 118 5.2.7 Reactivity with Organic Substrates 118 5.2.8 Reactivity with C02 and CO 119 5.2.9 Distillation 119 5.2.10 Association of Aluminum Alkyls 119 5.2.11 Storage Stability 120 5.2.12 Thermal Stability 121 5.3 Production of Aluminum Alkyls 122 5.4 Reducing Agent for the Transition Metal 125 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 Safety and Handling of Aluminum Alkyls 129 5.9 Questions 130 References 131 4 SinglPolymee 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 6.4.1 Aluminoxanes 139 6.4.2 Organoboron Cocatalysts 142 6.4.3 Activated Supports 142 6.5 Supports for SSCs 143 6.6 Characteristics of mPP 145 6.7 Selected Applications of mPP Resins 148 6.7.1 Medical Applications 148 6.7.2 Thin Wall Food Containers 149 6.7.3 High Clarity Bottles for Personal Care 149 x CONTENTS 6.7.4 Waxes 149 6.7.5 New Resins from Hybrid Catalysts to Make Polypropylene Alloys 150 6.8 Metallocene Synthesis 150 6.9 Syndiotactic Polypropylene 153 6.10 Commercial Reality and Concluding Remarks 154 6.11 Questions 155 References 156 4 CatalysPolymet 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 4 APolymen 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 CONTENTS 8.6 Solution Process 194 8.7 Hybrid Processes 194 8.8 Kinetics and Reactivity Ratios 196 8.9 Emergency Stoppage of Polymerization 198 8.10 Questions 199 References 199 4 LaboratorPolyme y 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

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