Note: 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.