Introduction to Industrial Polyethylene E-Book

Dennis B. Malpass

• Herausgeber: John Wiley & Sons
• Kategorie: Fachliteratur
• Serie: Wiley-Scrivener
• Sprache: Englisch

Seitenzahl: 178

Veröffentlichungsjahr: 2010

Beschreibung

Demystifies the largest volume manmade synthetic polymer by distillingthe fundamentals of what polyethylene is, how it's made and processed,and what happens to it after its useful life is over. Endorsement for Introduction to Industrial Polyethylene "I found this to be a straightforward, easy-to-read, and useful introductory text on polyethylene, which will be helpful for chemists, engineers, and students who need to learn more about this complex topic. The author is a senior polyethylene specialist and I believe we can all benefit from his distillation of knowledge and insight to quickly grasp the key learnings." --R.E. King III; Ciba Corporation (part of the BASF group) Jargon used in industrial polyethylene technology can often be bewildering to newcomers. Introduction to Industrial Polyethylene educates readers on terminology commonly used in the industry and demystifies the chemistry of catalysts and cocatalysts employed in the manufacture of polyethylene. This concise primer reviews the history of polyethylene and introduces basic features and nomenclatures for this versatile polymer. Catalysts and cocatalysts crucial to the production of polyethylene are discussed in the first few chapters. Latter chapters provide an introduction to the processes used to manufacture polyethylene and discuss matters related to downstream applications of polyethylene such as rheology, additives, environmental issues, etc. Providing industrial chemists and engineers a valuable reference tool that covers fundamental features of polyethylene technology, Introduction to Industrial Polyethylene: * Identifies the fundamental types of polyethylene and how they differ. * Lists markets, key fabrication methods, and the major producers of polyethylene. * Provides biodegradable alternatives to polyethylene. * Describes the processes used in the manufacture of polyethylene. * Includes a thorough glossary, providing definitions of acronyms and abbreviations and also defines terms commonly used in discussions of production and properties of polyethylene. * Concludes with the future of industrial polyethylene.

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Library of Congress Cataloging-in-Publication Data:

ISBN 978-0-470-62598-9

Printed in the United States of America

10 9 8 7 6 5 4 3 2 1

Contents

Preface

List of Tables

List of Figures

Chapter 1    Introduction to Polymers of Ethylene

1.1  Genesis of Polyethylene

1.2  Basic Description of Polyethylene

1.3  Types and Nomenclature of Polyethylenes

1.4  Molecular Weight of Polyethylenes

1.5  Transition Metal Catalysts for Ethylene Polymerization

Chapter 2    Free Radical Polymerization of Ethylene

2.1  Introduction

2.2  Free Radical Polymerization of Ethylene

2.3  Organic Peroxide Initiators

Chapter 3    Ziegler-Natta Catalysts

3.1  A Brief History of Ziegler-Natta Catalysts

3.2  Definitions and Nomenclature

3.3  Characteristics of Ziegler-Natta Catalysts

3.4  Early Commercial Ziegler-Natta Catalysts

3.5  Supported Ziegler-Natta Catalysts

3.6  Prepolymerized Ziegler-Natta Catalysts

3.7  Mechanism of Ziegler-Natta Polymerization

Chapter 4    Metal Alkyls in Polyethylene Catalyst Systems

4.1  Introduction

4.2  Aluminum Alkyls in Ziegler-Natta Catalysts

4.2.1  Reducing Agent for the Transition Metal

4.2.2  Alkylating Agent for Creation of Active Centers

4.2.3  Scavenger of Catalyst Poisons

4.2.4  Chain Transfer Agent

4.3  Magnesium Alkyls in Ziegler-Natta Catalysts

4.3.1  R2Mg for Production of Supports

4.3.2  R2Mg as Reducing Agent

4.4  Lithium Alkyls

4.5  Organoboron Compounds

4.6  Zinc Alkyls

4.7  Safety and Handling of Metal Alkyls

Chapter 5    Chromium Catalysts

5.1  Chromium Catalysts Supported on Metal Oxides

5.2  Basic Chemistry of Phillips Catalysts

5.3  Generations of Phillips Catalysts

5.4  Union Carbide Chromium Catalysts

5.5  Mechanism of Polymerization with Supported Chromium Catalysts

Chapter 6    Single Site Catalysts

6.1  Introduction

6.2  Metallocene Single Site Catalysts

6.2.1  Non-metallocene Single Site Catalysts

6.3    Cocatalysts for Single Site Catalysts

6.3.1  Methylaluminoxanes

6.3.2  Arylboranes

6.3.3  Other Cocatalysts for Single Site Catalysts

6.4  Mechanism of Polymerization with Single Site Catalysts

Chapter 7    An Overview of Industrial Polyethylene Processes

7.1  Introduction

7.2  High Pressure Processes

7.2.1  Autoclave Process

7.2.2  Tubular Process

7.3  Slurry (Suspension) Process

7.4  Gas Phase Process

7.5  Solution Process

7.6  Combined Processes

Chapter 8    Downstream Aspects of Polyethylene

8.1  Introduction

8.2  Additives

8.3  Melt Processing

8.4  Markets

8.5  Environmental

Glossary

Trade Name Index

Index

Preface

Polyethylene is, by a wide margin, the largest volume synthetic polymer made by mankind. As of this writing, about 77 million metric tons are produced annually and the growth rate is expected to continue at about 5% per year into the foreseeable future. Within the three minutes or so it takes to read this preface, over 400 tons of polyethylene will have been manufactured. It is produced in various forms on 6 continents and its applications are ubiquitous in daily life, from the trash bag you placed on the curb this morning to Uncle Fred’s artificial hip.

This book is primarily intended as an introductory text for chemists, engineers and students who wish to gain an understanding of the fundamentals of the commercially important polymers and copolymers of ethylene. The reader is assumed to have had a modicum of training in chemistry but little prior knowledge about polyethylene. I also intend it to be useful as a complement to courses on polymer chemistry. This book will answer essential questions such as:

What are the types of polyethylene and how do they differ?

What catalysts are used to produce polyethylene and how do they function?

What is the role of cocatalysts in polyethylene production?

What processes are used in the manufacture of polyethylene?

What is the fate of polyethylene after its useful life is over?

Jargon used in industrial polyethylene technology can be bewildering to newcomers. This text will educate readers on terminology in common use in the industry and demystify the chemistry of catalysts and cocatalysts employed in the manufacture of polyethylene. I have employed several techniques to make the text user friendly A thorough glossary is included in the appendix. The glossary not only provides definitions of acronyms and abbreviations, but also concisely defines terms commonly used in discussions of production and properties of polyethylene. An extensive index with liberal cross-referencing enables the reader to find a topic quickly.

Chapter 1 is used to review the history of polyethylene, to survey quintessential features and nomenclatures for this versatile polymer and to introduce transition metal catalysts (the most important catalysts for industrial polyethylene). Free radical polymerization of ethylene and organic peroxide initiators are discussed in Chapter 2. Also in Chapter 2, hazards of organic peroxides and high pressure processes are briefly addressed. Transition metal catalysts are essential to production of nearly three quarters of all polyethylene manufactured and are described in Chapters 3, 5 and 6. Metal alkyl cocatalysts used with transition metal catalysts and their potentially hazardous reactivity with air and water are reviewed in Chapter 4. Chapter 7 gives an overview of processes used in manufacture of polyethylene and contrasts the wide range of operating conditions characteristic of each process. Chapter 8 surveys downstream aspects of polyethylene (additives, rheology, environmental issues, etc.). However, topics in Chapter 8 are complex and extensive subjects unto themselves and detailed discussions are beyond the scope of an introductory text.

I must take this opportunity to express my appreciation to friends and associates who made constructive suggestions on the content of this book. Thanks to Drs. James C. Stevens and Rajen Patel (of The Dow Chemical Company in Freeport, TX) for their comments on the product descriptions and single-site catalysts. Dr. Roswell (Rick) E. King III (of Ciba, now part of BASF, in Tarrytown, NY) and Dr. Brian Goodall reviewed portions of the text and provided recommendations for improvement. Dr. Malcolm J. Kaus of ExxonMobil directed me to several outstanding literature discussions on catalyst and process technologies and kindly provided a reprint of a conference paper on the ExxonMobil high pressure process for polyethylene. Dr. James Strickler (of Albemarle Corporation in Baton Rouge, LA) helped with valuable suggestions about the chapter on metal alkyls. I am indebted to Drs. Balaji B. Singh and Clifford Lee of Chemical Marketing Resources, Inc. (Webster, TX) who shared information on markets and fabrication methods. Drs. Bill Beaulieu and Max McDaniel (of Chevron Phillips) reviewed information on “Phillips Catalysts” and instructed me on the intricacies of these mysterious catalysts. People mentioned above made suggestions that I found very helpful and tried to meld into the text. However, any residual errors are solely my responsibility. Finally,. I would like to thank my publisher Martin Scrivener for the invitation to write this book and for his help in getting it published.

In closing, I would be remiss if I did not acknowledge my former colleagues at Texas Alkyls, Inc. (now Akzo Nobel) with whom I toiled for more than 30 years producing and marketing the metal alkyls that are so crucial to the polyolefins industry. The experiences and knowledge acquired during those years contributed mightily to the foundations for this book. However, my former coworkers at Texas Alkyls shall remain anonymous, for the list would be far too long.

I hope the reader will find the text informative on the fundamental aspects of industrial polyethylene.

Dennis B. MalpassMarch 8, 2010

List of Tables

Chapter 1   Introduction to Polymers of Ethylene

Table 1.1   IUPAC names of selected polymers and copolymers of ethylene

Table 1.2   Classification of selected polyethylenes

Table 1.3   Polyethylene catalysts containing transition metals

Chapter 2   Free Radical Polymerization of Ethylene

Table 2.1   Key organic peroxide initiators for LDPE

Chapter 4   Metal Alkyls in Polyethylene Catalyst Systems

Table 4.1   Comparative cost of selected trialkylaluminum compounds

Chapter 5   Chromium Catalysts

Table 5.1   Generations of Phillips catalysts

Chapter 6   Single Site Catalysts

Table 6.1   Contrasting characteristics of single-site and Ziegler-Natta catalysts

Chapter 7   An Overview of Industrial Polyethylene Processes

Table 7.1   Features of key industrial polyethylene processes

Table 7.2   Typical operating features of autoclave processes for LDPE

Table 7.3   Typical operating features of tubular processes for LDPE

Table 7.4   Typical operating features of slurry/suspension processes for LLDPE and HDPE

Table 7.5   Typical operating features of gas phase processes for HDPE and LLDPE

Table 7.6   Typical operating features of solution processes for LLDPE and HDPE

Chapter 8   Downstream Aspects of Polyethylene

Table 8.1   Comparison of selected film properties of LDPE and LLDPE

Table 8.2   Top 10 global producers of polyethylene in 2006