Cover

Title Page

Copyright Page

Contents

Preface

1. Global Polyethylene Business Overview

1.1 Introduction

1.2 The Business of Polyethylene

1.3 Cyclical Nature of the Polyethylene Business

1.3.1 Global Feedstock Cost Variations

1.3.2 Change in Middle East Feedstock Cost Advantage

1.3.2.1. 2012 Capital Requirements for an Integrated Ethylene/Polyethylene Facility

1.4 Early History of Ethylene and Polyethylene Manufacturing

1.4.1 Discovery of Polyethylene

1.4.1.1 Branched High-Pressure Polyethylene

1.4.1.2 Linear Polyethylene

1.4.2 Linear Low-Pressure Polyethylene – High-Density Polyethylene

1.4.3 Manufacture of HDPE (1955–1975)

1.4.3.1 Phillips Catalyst Produced HDPE with Higher Product Demand

1.4.3.2 Phillips Catalyst Manufacturing Advantages

1.4.3.3 Second Generation Ziegler Catalysts

1.4.4 Single-Site Ethylene Polymerization Catalysts

1.4.5 Status of the Polyethylene Industry as of 2010

1.4.6 Global Demand for Polyethylene in 2010

1.4.7 Polyethylene Product Lifecycle

1.4.7.1 North American Polyethylene Market

1.4.8 Comparison of Other Global Polyethylene Markets with the North American Market

1.4.9 Growth of the Global Consumer Class

1.4.9.1 Quantitative Forecast for the Growth of the Global Middle Class

1.4.10 Global Economic Freedom

1.4.11 Future Economic Growth in India and China

1.4.12 Long-Term Global Polyethylene Capacity Expansion (2010–2050)

1.4.12.1 Location of New Ethylene/Polyethylene Capacity (2010–2050)

1.4.13 Ethylene Feedstock Costs

1.4.13.1 Manufacture of Ethylene

1.4.13.2 Crude Oil and Natural Gas Prices

1.4.14 Impact of the Shale Natural Gas Revolution on Global Polyethylene Business

1.4.15 Natural Gas Liquids

1.4.15.1 North American Natural Gas Supply

1.4.15.2 Globalization of Natural Gas

1.4.15.3 Status of Ethylene Costs as of 2010 and Future Trends

1.4.15.4 Additional Feedstock for Ethylene Production

1.4.15.5 U.S. Ethylene Forecast by Burns & McDonnell (2013)

1.4.15.6 Ethylene Based on New Feedstock

1.4.15.7 Methane/Methanol as Feedstock for Ethylene

1.4.15.8 Biomass as Feedstock

1.4.15.9 Governmental Policy and Regulation

1.4.16 Environmental Factors

1.4.16.1 Polyethylene Recycling – Waste-to-Energy

1.4.16.2 Biodegradation

1.4.17 Biobased Ethylene

References

2. Titanium-Based Ziegler Catalysts for the Production of Polyethylene

2.1 Introduction

2.2 Titanium-Based Catalyst Developments

2.2.1 Historical Developments

2.2.2 The Role of Professor G. Natta

2.2.3 Historical Controversy – Isotactic Polypropylene with Cr-Based Catalyst

2.3 Titanium-Based Catalysts for the Manufacture of Polyethylene

2.3.1 First Generation Ziegler Catalysts for the Manufacture of Polyethylene

2.3.2 Types of Metal Alkyls Investigated

2.3.3 Soluble Titanium-Based Complexes for Ethylene Polymerization (1955–1960)

2.3.4 Mechanism of Polymerization

2.4 Second Generation Ziegler Catalyst for the Manufacture of Polyethylene

2.4.1 Early History of Ti/Mg-Based Catalysts – Solvay & Cie Catalyst

2.4.1.1 Solvay & Cie Catalyst Details

2.4.2 Gas-Phase Fluidized-Bed Polymerization

2.4.3 Impact of High-Activity Mg/Ti Ziegler Catalysts on the Polyethylene Industry

2.4.4 Overview of Particle-Form Technology

2.4.4.1 Historical Introduction

2.4.5 Growth of the Polymer Particle

2.4.6 Catalyst Polymerization Kinetics and Polyethylene Particle Morphology

2.4.7 Magnesium-Containing Compounds that Provide High-Activity Ziegler Catalysts

2.4.8 Additional Preparation Methods for Catalyst Precursors

2.4.8.1 Reduction of TiCl4 with Organomagnesium Compounds

2.5 Catalysts Prepared on Silica

2.5.1 Physical Impregnation of a Soluble Mg/Ti Precursor into the Silica Pores

2.5.2 Chemical Impregnation of Silica

2.6 Characterization of Catalysts Prepared with Calcined Silica, Dibutylmagnesium or Triethylaluminum and TiCl4

2.6.1 Spray-Drying Techniques

2.6.2 Ball-Milling Techniques

2.6.3 Characterization of High-Activity Ti/Mg-based Ziegler Catalyst Precursors

2.6.4 Additional Electron Donor Complexes

2.6.5 Catalysts Based on Magnesium Diethoxide and TiCl4

2.6.6 Spherical Magnesium-Supported Catalyst Particles

2.6.7 Catalysts Prepared with Grignard Reagent/TiCl4 with and without Silica

2.6.8 Polyethylene Structure

2.6.9 Characterization of Reactivity Ratios in Multi-site Mg/Ti Catalysts

2.7 Kinetic Mechanism in the Multi-site Mg/Ti High-Activity Catalysts

2.7.1 Introduction

2.7.2 Multi-center Sites

References

Appendix 2.1

3. Chromium-Based Catalysts

3.1 Part I – The Phillips Catalyst

3.1.1 Early History of the Phillips Catalyst

3.1.2 Preparation of the Phillips Catalyst

3.1.3 Unique Features of the Phillips Catalyst

3.1.3.1 Control of Polyethylene Molecular Weight

3.1.3.2 Initiation of Polymerization at the Active Center

3.1.3.3 Possible Initiation Steps for Cr-Based Catalyst

3.1.4 Characterization of Polyethylene Produced with the Phillips Catalyst

3.1.5 Improvements to the Phillips Catalyst

3.1.6 Review Articles for the Phillips Catalyst

3.2 Part II – Chromium-Based Catalysts Developed by Union Carbide

3.2.1 Bis(triphenylsilyl)chromate Catalyst

3.2.2 Chromocene-Based Catalyst

3.2.3 Hydrogen Response of the Chromocene-Based Catalyst

3.2.4 Eff ect of Silica Dehydration Temperature on the Chromocene-Based Catalyst

3.2.5 Bis(indenyl) and Bis(fluorenyl) Chromium(II) Catalysts Supported on Silica

3.2.6 Organochromium Compounds for Ethylene Polymerization Based on (Me)5CpCr(III) Alkyls

3.2.7 Organochromium Complexes with Nitrogen-Containing Ligands for Ethylene Polymerization

3.2.8 Catalysts for Ethylene Polymerization with In-Situ Formation of 1-Hexene

3.3 Next Generation Chromium-Based Ethylene Polymerization Catalysts for Commercial Operations

References

4. Single-Site Catalysts Based on Titanium or Zirconium for the Production of Polyethylene

4.1 Overview of Single-Site Catalysts

4.1.1 Expanded Polyethylene Product Mix

4.1.2 Types of Single-Site Catalysts

4.2 Polyethylene Structure Attained with a Single-Site Catalyst

4.2.1 Product Attributes of Polyethylene Manufactured with Single-Site Catalysts

4.2.2 Processing Disadvantage of Polyethylene Manufactured with Single-Site Catalysts

4.3 Historical Background

4.3.1 First Single-Site Catalyst Technology – Canadian Patent 849081

4.3.2 Discovery of Highly Active Metallocene/Methylalumoxane Catalysts

4.3.2.1 Early Publications of Kaminsky

4.3.2.2 Kinetic Parameters of the Homogeneous Cp2ZrCl2/MAO Catalyst

4.3.3 Alkylalumoxanes – Preparation, Structure and Role in Single-Site Technology

4.3.3.1 Background

4.3.3.2 Preparation

4.3.4 Structure of Alumoxanes

4.3.4.1 Role of Methylalumoxane in Single-Site Catalysts

4.3.4.2 Supporting Evidence for Cationic Active Site for Ethylene Polymerization

4.3.5 Additional Methods for Activating Metallocene Single-Site Catalysts

4.3.6 Characterization Methods that Identify Polyethylene with a Homogeneous Branching Distribution Obtained with Single-Site Catalysts

4.3.7 Control of Polymer Molecular Weight

4.4 Single-Site Catalyst Based on (BuCp)2ZrCl2/MAO and Silica for the Gas-Phase Manufacture of Polyethylene

4.5 Activation of the Metallocenes Cp2ZrCl2 or (BuCp)2ZrCl2 by Solid Acid Supports

4.5.1 Activation of Bridged Metallocenes by Solid Acid Supports

4.6 Dow Chemical Company Constrained Geometry Single-Site Catalysts (CGC)

4.6.1 Cocatalyst Activation of Constrained Geometry Catalyst

4.6.2 Processability of Polyethylene Manufactured with Dow’s CGC System

4.7 Novel Ethylene Copolymers Based on Single-Site Catalysts

4.8 Non-Metallocene Single-Site Catalysts

4.8.1 LyondellBasell Petrochemical

4.9 New Ethylene Copolymers Based on Single-Site Catalysts

4.9.1 Ethylene/Norbornene

4.9.2 Ethylene/Styrene Copolymers Using Nova Chemicals Catalyst

4.10 Compatible Metallocene/Ziegler Catalyst System

4.11 Next Generation Catalysts

References

Appendix 4.1

5. Commercial Manufacture of Polyethylene

5.1 Introduction

5.1.1 First Manufacturing Facility

5.1.2 Early Documentation of Manufacturing Processes

5.2 Commercial Process Methods

5.3 Global Polyethylene Consumption

5.4 High-Pressure Polyethylene Manufacturing Process

5.4.1 Historical Summary

5.4.2 Details of the Discovery of the High-Pressure Process

5.4.3 Developments during World War II (1940–1945)

5.4.4 Post World War II Developments (1945–1956)

5.4.5 Rapid Growth Period – Demand Exceeded Supply

5.4.6 Polyethylene Growth (1952–1960)

5.4.6.1 Polyethylene Product Attributes that Resulted in Rapid Growth

5.4.6.1.3 Property Comparison

5.4.6.1.4 Pipe Applications

5.4.7 Worldwide High-Pressure LDPE Capacity Increases (1980–2010)

5.4.8 Future of High-Pressure Manufacturing Process

5.5 Free-Radical Polymerization Mechanism for High-Pressure Polyethylene

5.5.1 Initiation Step

5.5.2 Propagation Step

5.5.3 Termination Step

5.6 Organic Peroxides as Free-Radical Source for Initiation Process

5.6.1 Types of Organic Peroxides

5.7 Structure of High-Pressure LDPE

5.7.1 General Features

5.7.2 Ethylene at High Pressures

5.7.3 Autoclave Reactor

5.7.4 Characterization of Short-Chain Branching (SCB) in LDPE

5.7.4.1 Structural Differences between LDPE and LLDPE

5.8 Low-Pressure Process

5.8.1 Early History

5.8.2 Particle-Form Technology for Low-Pressure Process

5.8.2.1 Historical Background

5.8.2.3 Solution Mode Operation

5.8.2.4 Slurry Polymerization Mode

5.8.2.5 Pilot Plant Designs for Particle-Form Reactors – Development History

5.8.2.6 Phillips Pilot PlantVertical Pipe-Loop Reactor Design

5.8.2.7 Operation of the Phillips Pilot Plant Pipe-Loop Reactor

5.8.3 First Ziegler Catalyst Commercial Process

5.8.4 Chevron-Phillips Slurry Loop Process Status as of 2010

5.8.4.1 Reactor Scale

5.8.5 Reactor Start-Up

5.8.6 Product Transitions

5.8.7 Reactor Fouling

5.8.8 New Vertical Loop Reactor Design

5.9 Gas-Phase Process

5.9.1 Historical Introduction

5.9.2 BASF Early Gas-Phase Reactor

5.9.3 Horizontal Gas-Phase Process

5.9.4 Union Carbide Gas-Phase Reactor

5.9.4.1 Gas Distribution Plate

5.9.5 Gas-Phase Univation Process (2012)

5.9.6 Fluidized-Bed Gas-Phase Operation Overview

5.9.6.1 Ethylene Partial Pressure

5.9.6.2 Catalyst Feed Rate

5.9.6.3 Product Discharge

5.9.6.4 Condensing Agent

5.9.6.5 Reactor Start-Up/Product Transitions

5.9.6.6 Reactor Fouling

5.9.6.7 Catalyst Requirements for Gas-Phase Fluid-bed Reactor

5.10 Gas-Phase Process Licensors

5.10.1 Background

5.10.2 Gas-Phase Process Company History

5.10.3 Reactor Size and Configuration

5.10.4 Gas Phase and Slurry Loop in Series

5.11 Solution Process

5.11.1 Historical Introduction

5.12 DuPont Sclair Process

5.12.1 Background

5.13 Solution Process (2012)

5.13.1 Overview

5.13.2 Bimodal MWD in Solution Reactors

5.13.3 Dowlex Solution Process

References

6 Fabrication of Polyethylene

6.1 Introduction

6.1.1 Fabrication Business

6.1.2 Terms and Definitions Important in Polyethylene Fabrication

6.1.3 Development of Melt Index Instrument

6.1.4 Polyethyene Product Space for the Fabrication of Finished Products

6.2 Early History of Polyethylene Fabrication (1940–1953)

6.2.1 Post World War II

6.3 Stabilization of Polyethylene

6.3.1 Introduction

6.3.2 Thermal Oxidation Mechanism (1920–1960)

6.3.3 Polyethylene Melt Processing

6.3.3.1 Scission

6.3.3.2 Crosslinking

6.3.3.3 Temperature Dependence of Crosslinking and Scission

6.4 Historical Overview of Some Common Polyethylene Additives

6.4.1 Polyethylene Additives (1935–1955)

6.4.1.1 Carbon Black

6.4.1.2 Antioxidants

6.4.1.3 Flame Retardants

6.4.1.4 Lubricants

6.4.1.5 Anti-Static Agents

6.4.1.6 Calcium Carbonate as Filler

6.5 Examples of Additives Presently Used in the Polyethylene Industry (2012)

6.5.1 Antioxidants

6.5.2 Secondary Antioxidants

6.5.3 UV-Light Stabilizers

6.5.4 Mineral Fillers/Reinforcing Agents

6.5.5 Lubricants

6.5.6 Blowing Agents

6.5.7 Flame Retardants

6.5.8 Antiblock Agents

6.6 Rheological Properties of Polyethylene

6.7 Fabrication of Film

6.7.1 Introduction

6.8 Blown Film Extrusion

6.8.1 Description of Blown Film Extrusion

6.8.2 History of Polyethylene Rapid Growth in Film Applications

6.8.2.1 Cost

6.8.2.2 Shelf-Life

6.8.3 Blown Film Apparatus

6.8.4 Multilayer Films

6.8.5 Low-Density Polyethylene Films

6.8.6 LLDPE with a Broad MWD

6.8.7 Blown Film Process for HMW-HDPE Film

6.8.8 High-Stalk Extrusion

6.8.9 Cast Film Line

6.8.10 Pipe Applications

6.9 Fabrication of Polyethylene with Molding Methods

6.9.1 Blow Molding

6.9.1.1 Brief History of Blow Molding (ca. 1850–1960)

6.9.1.2 Environmental Stress Crack Resistance

6.9.1.3 Types of Blow Molding Machines

6.9.1.4 Method to Decrease Die Swell

6.9.1.5 Milk Bottle Resin

6.9.2 Injection Molding

6.9.2.1 Introduction

6.9.2.2 Polyethylene Shrinkage

6.9.2.3 New Product Applications

6.9.2.4 History of Injection Molding Process

6.9.2.5 Some Aspects of the Machine Design

6.9.2.6 Mold Design

6.10 Rotational Molding

6.10.1 Background History

6.11 Thermoforming

6.11.1 Thin- and Thick-Gauge Thermoforming

6.11.2 Grades of Polyethylene for Thermoforming

References

7. Experimental Methods for Polyethylene Research Program

7.1 Introduction

7.1.1 High Throughput Laboratory Equipment

7.2 Experimental Process

7.2.1 Catalyst Preparation

7.2.1.1 Some Catalyst Preparation Operation Guidelines

7.2.2 Catalyst Evaluation Process

7.2.3 Catalyst Performance Characteristics

7.3 Important Considerations for Laboratory Slurry (Suspension) Polymerization Reactors

7.3.1 Background Information

7.3.2 Basic Laboratory Polymerization Reactor Design

7.3.3 Polymerization Rate/Total Polymer Yield

7.3.4 Isolation of Polyethylene Product

7.3.5 Steady-State Polymerization Conditions

7.3.5.1 Determination of Steady-State Conditions During Polymerization

7.3.5.2 Operation Guidelines for a Slurry Polymerization Reactor under Steady-State Condition

7.3.6 Polymer Characterization

7.3.6.1 Laboratory Characterization Equipment

7.3.6.2 Melt Index and Density Data

7.3.6.3 Infrared Method

7.3.6.4 Differential Scanning Calorimetry

7.3.6.5 Gel Permeation Chromatography

7.3.6.6 Temperature Rising Elution Fractionation

7.3.6.7 CRYSTAF Method

7.3.6.8 Carbon-13 Nuclear Magnetic Resonance

7.3.7 Catalyst Process Attributes

7.3.7.1 Catalyst Activity (g PE/g cat) and Polymerization Kinetics

7.3.7.2 Reactivity with Higher 1-Olefins such as 1-Butene, 1-Hexene and 1-Octene

7.3.8 Additional Features of Commercial Catalysts

7.4 Polymerization Reactor Design for High-Throughput Methods

7.5 Polymer Characterization

7.6 Process Models

References

Index

EULA