| | Contents | |
| | | |
| |
| | Preface | V |
| | List of Contributors
Markus Gahleitner and John R. Severn | XIX |
| 1 | Designing Polymer Properties | 1 |
| 1.1 | Polyolefins | 1 |
| 1.2 | Levels and Scales of Polymer Structure and Modification | 2 |
| 1.2.1 | Chain Structure: Chemistry, Interaction, Regularity, and Disturbance | 2 |
| 1.2.1.1 | Chain Topology: SCB, LCB, and Special Structures | 4 |
| 1.2.1.1 | Molecular Weight Distribution (MWD) | 4 |
| 1.2.1.3 | Blends and Other Multiphase Structures | 5 |
| 1.2.2 | Semi-crystalline Polymers: From Lattices to Superstructures | 6 |
| 1.2.2.1 | Chain Structure and Crystallization Speed | 6 |
| 1.2.2.2 | Lamellar Thickness and Modulus | 7 |
| 1.2.2.3 | Nucleation and Polymorphism | 7 |
| 1.2.2.4 | Flow-induced Structures and Processing Effects | 8 |
| 1.2.3 | Multiphase Structures | 9 |
| 1.2.3.1 | General Concepts of Impact Modification | 9 |
| 1.2.3.2 | Multi-stage Copolymers (PP) | 9 |
| 1.2.3.3 | Polymer Blends and Reactive Modification | 9 |
| 1.2.3.4 | Compounds and (Nano)Composites | 10 |
| 1.2.4 | Property Optimization in Processing | 11 |
| 1.3 | Polymer Design: The Catalyst’s Point of View | 11 |
| 1.3.1 | Mechanisms and Kinetics: A “Tailors Toolbox” | 12 |
| 1.3.1.1 | Activation, Initiation, Propagation: On your Marks, Get Set, . . . Go!! | 12 |
| 1.3.1.2 | Chain Transfer | 15 |
| 1.3.1.3 | Insertion Control | 18 |
| 1.3.1.4 | Summary | 24 |
| 1.3.2 | Case Study 1: Development of Commercially Relevant Single-Site iPP Catalysts | 24 |
| 1.3.3 | Case Study 2: One Monomer, Many Microstructures | 28 |
| 1.3.3.1 | Propylene | 28 |
| 1.3.3.2 | Ethylene | 31 |
| 1.3.4 | Case Study 3: FI Catalysts; From Lazy to Hyperactive, and Beyond | 34 |
| 1.3.5 | Case Study 4: “Chain-shuttling” | 36 |
| 1.4 | Immobilizing “Single-site” Olefin Polymerization Catalysts: The Basic Problems | 38 |
| | Reference | 39 |
| 2 | Traditional Heterogeneous Catalysts | 43 |
| 2.1 | Ziegler–Natta Catalysts in Polyolefin Synthesis
John C. Chadwick, Thomas Garoff, and John R. Severn | 43 |
| 2.1.1 | Introduction | 43 |
| 2.1.2 | Ziegler–Natta Catalysts for Polypropylene | 44 |
| 2.1.2.1 | Third-Generation MgCl2-supported Catalysts | 44 |
| 2.1.2.2 | Fourth-Generation MgCl2-supported Catalysts | 46 |
| 2.1.2.3 | Fifth-Generation MgCl2-supported Catalysts | 47 |
| 2.1.2.4 | New Developments | 48 |
| 2.1.2.5 | Mechanistic Aspects | 48 |
| 2.1.3 | Ziegler Catalysts in Polyethylene | 52 |
| 2.1.3.1 | Ideal Catalysts | 52 |
| 2.1.3.2 | Ball-milled MgCl2-based Ziegler Catalysts | 52 |
| 2.1.3.3 | MgCl2-Titanium Catalysts on Silica | 53 |
| 2.1.3.4 | Precipitated and Supported MgCl2-based Catalysts | 54 |
| 2.1.3.5 | Spray-dried MgCl2-Titanium Catalysts | 54 |
| 2.1.3.6 | General Polymerization Behavior of the MgCl2-Titanium-based Ziegler Catalysts | 54 |
| 2.1.3.7 | Models for Chemical Composition Distribution and Comonomer Drift | 56 |
| 2.1.3.8 | Vanadium-based Ziegler Catalysts | 59 |
| 2.1.4 | Concluding Remarks | 59 |
| 2.2 | Chromium Polymerization Catalysts: Still Alive in Polyethylene Production
Hilkka Knuuttila and Arja Lehtinen | 60 |
| 2.2.1 | Introduction | 60 |
| 2.2.2 | The Chromium Catalyst System | 60 |
| 2.2.2.1 | Activation of the Chromium Catalyst | 62 |
| 2.2.3 | Polymerization Mechanism | 64 |
| 2.2.4 | Chromium Catalyst Performance | 67 |
| 2.2.4.1 | The Effect of Carrier Material and Calcination Temperature | 67 |
| 2.2.4.2 | Effect of Polymerization Temperature | 68 |
| 2.2.4.3 | Effect of Hydrogen/Hydrogen Sensitivity | 69 |
| 2.2.5 | Summary | 70 |
| | References | 72 |
| 3 | Polymer Particle Growth and Process Engineering Aspects
Michael Bartke | 79 |
| 3.1 | Heterogeneous Polymerization with Supported Catalysts versus Polymerization in Homogeneous Phase | 79 |
| 3.2 | Phenomena in Polymerization with Heterogeneous Catalysts | 80 |
| 3.2.1 | The Particle as Microreactor | 80 |
| 3.2.2 | Polymer Particle Growth and Morphology Development | 81 |
| 3.2.3 | Mass Transfer in Polymerizing Particles | 85 |
| 3.2.4 | Role of Catalyst Porosity | 86 |
| 3.2.5 | Particle Homogeneity/Videomicroscopy | 86 |
| 3.2.6 | Prepolymerization | 87 |
| 3.3 | Polymerization Processes and Reactors for Polymerization with Heterogeneous Catalysts | 88 |
| 3.3.1 | Slurry/Bulk Processes | 88 |
| 3.3.2 | Gas-Phase Polymerization | 89 |
| 3.3.3 | Cascaded Processes | 90 |
| 3.4 | Requirements for Polymerization Catalysts | 93 |
| | References | 93 |
| 4 | Methylaluminoxane (MAO), Silica and a Complex: The “Holy Trinity” of Supported Single-site Catalyst
John R. Severn | 95 |
| 4.1 | Introduction | 95 |
| 4.1.1 | Background | 95 |
| 4.1.2 | Commercial Catalysts | 96 |
| 4.1.3 | Polymer Particle Growth | 98 |
| 4.2 | Basic Ingredients | 100 |
| 4.2.1 | Silica Supports | 100 |
| 4.2.1.1 | Silica Synthesis | 100 |
| 4.2.1.2 | Thermal Modification | 103 |
| 4.2.2 | Methylaluminoxane | 105 |
| 4.2.2.1 | Synthesis of MAO | 105 |
| 4.2.2.2 | Characterization of MAO | 107 |
| 4.2.2.3 | MAO Interaction with a Precatalyst Complex | 109 |
| 4.2.2.4 | MAO Interaction with a Silica Surface | 110 |
| 4.3 | Catalyst Preparations | 113 |
| 4.3.1 | Illustrative Examples of Route C | 114 |
| 4.3.2 | Illustrative Examples of Route A | 115 |
| 4.3.3 | Illustrative Examples of Route B | 119 |
| 4.3.4 | A Summary of Catalyst Preparations | 122 |
| 4.4 | Pitfalls in the Generation of Single-Site Polymer Material | 122 |
| 4.4.1 | The Polymerization Experiment | 123 |
| 4.4.2 | Multiple Sites and Product Quality | 125 |
| 4.4.2.1 | Catalyst Homogeneity | 125 |
| 4.4.2.2 | Influencing the Coordination Sphere of the Active Sites | 129 |
| 4.4.2.3 | Mass Transport Limitations | 131 |
| 4.5 | Conclusions | 135 |
| | References | 135 |
| 5 | Perfluoroaryl Group 13 Activated Catalysts on Inorganic Oxides
Gregory G. Hlatky and Michael W. Lynch | 139 |
| 5.1 | Introduction | 139 |
| 5.2 | Supported Perfluoroarylborate Catalysts | 140 |
| 5.3 | Supported Perfluoroarylborane and Perfluoroarylalane Catalysts | 144 |
| 5.4 | Conclusions | 148 |
| | References | 148 |
| 6 | Catalysts Supported on Magnesium Chloride
John C. Chadwick | 151 |
| 6.1 | Introduction | 151 |
| 6.2 | Magnesium Chloride as Activator | 151 |
| 6.3 | Magnesium Chloride/Methylaluminoxane | 152 |
| 6.4 | Magnesium Chloride/Borate | 155 |
| 6.5 | Magnesium Chloride/Aluminum Alkyl | 157 |
| 6.5.1 | Early-Transition Metal Complexes | 157 |
| 6.5.2 | Late-Transition Metal Complexes | 162 |
| 6.6 | Conclusions | 166 |
| | References | 167 |
| 7 | Metallocene Activation by Solid Acids
Max P. McDaniel, Michael D. Jensen, Kumindini Jayaratne, Kathy S. Collins,Elizabeth A. Benham, Neal D. McDaniel, P. K. Das, Joel L. Martin, Qing Yang, Mathew G. Thorn, and Albert P. Masino | 171 |
| 7.1 | Introduction | 171 |
| 7.2 | Experimental | 172 |
| 7.2.1 | Solid Acid Preparation | 172 |
| 7.2.2 | Polymerization | 173 |
| 7.2.3 | Acidity Measurements | 174 |
| 7.3 | Results and Discussion | 174 |
| 7.3.1 | Simple Oxides | 174 |
| 7.3.2 | Silica with Added Anion | 175 |
| 7.3.2.1 | Fluoride Treatment | 176 |
| 7.3.2.2 | Chloride Treatment | 176 |
| 7.3.2.3 | Sulfate Treatment | 177 |
| 7.3.2.4 | Anions Containing a Lewis Acid Metal | 177 |
| 7.3.3 | Alumina with Added Anion | 178 |
| 7.3.3.1 | Fluoride Treatment | 179 |
| 7.3.3.2 | Chloride Treatment | 181 |
| 7.3.3.3 | Bromide Treatment | 182 |
| 7.3.3.4 | Phosphate Treatment | 182 |
| 7.3.3.5 | Triflate Treatment | 183 |
| 7.3.3.6 | Sulfate Treatment | 183 |
| 7.3.4 | Silica–Alumina with Added Anions | 185 |
| 7.3.4.1 | Fluoride Treatment | 186 |
| 7.3.4.2 | Triflic Acid Treatment | 188 |
| 7.3.4.3 | Treatment with Other Anions | 189 |
| 7.3.5 | Other Mixed Oxides with Added Anion | 190 |
| 7.3.6 | Combining Multiple Anions or Lewis Acidic Metals | 190 |
| 7.4 | Metallocene Choice | 192 |
| 7.5 | Participation by Aluminum Alkyl | 193 |
| 7.6 | Brønsted versus Lewis Acidity | 194 |
| 7.7 | Polymer Molecular Weight Distribution | 196 |
| 7.8 | Leaching of the Metallocene | 198 |
| 7.9 | Characterization of Active Sites | 199 |
| 7.9.1 | Adsorption of Pyridine | 199 |
| 7.9.2 | Adsorption of Metallocene | 200 |
| 7.9.3 | Adsorption of Ether | 203 |
| 7.9.4 | Adsorption of Carbon Monoxide | 205 |
| 7.9.5 | Adsorption of Water Vapor | 205 |
| 7.10 | Clay as an Activator | 206 |
| 7.11 | Zeolites as Metallocene Activators | 208 |
| 7.12 | Conclusions | 209 |
| | References | 210 |
| 8 | Supported Multicomponent Single-Site  -Olefin Polymerization Catalysts
Nic Friederichs, Nourdin Ghalit, and Wei Xu | 211 |
| 8.1 | Introduction | 211 |
| 8.2 | Supported Catalysts for Concurrent Tandem Oligomerization/Copolymerization | 212 |
| 8.3 | Concurrent Tandem Catalysis for Increased Levels of Long-Chain Branching (LCB) | 215 |
| 8.4 | Supported Multicomponent Catalysts for Bimodal/Multimodal MMD Polyethylene | 218 |
| 8.4.1 | Mixed Ziegler or Phillips and Single-Site Polymerization Catalysts | 220 |
| 8.4.2 | Mixed Single-Site Catalysts | 223 |
| 8.4.3 | Challenges in Operating Dual Catalysts for Bimodal Polyethylene in a Single Reactor | 226 |
| 8.5 | Multicomponent Catalysts for Polypropylene | 229 |
| 8.6 | Multicomponent Catalysts for Block Copolymers | 231 |
| 8.7 | Conclusions | 231 |
| | References | 232 |
| 9 | Tethering Olefin Polymerization Catalysts and Cocatalysts to Inorganic Oxides
Jason C. Hicks and Christopher W. Jones | 239 |
| 9.1 | Introduction | 239 |
| 9.2 | Surface-Tethered Precatalysts | 240 |
| 9.2.1 | Surface-Tethered Metallocene Precatalysts | 240 |
| 9.2.2 | Surface-Tethered Constrained-Geometry Precatalysts | 246 |
| 9.2.3 | Tethering Late Transition Metal Precatalysts | 250 |
| 9.3 | Tethering Cocatalysts | 253 |
| 9.4 | Molecular Models | 255 |
| 9.5 | Conclusions | 258 |
| | References | 259 |
| 10 | Polymerization with the Single-Site Catalyst Confined within the Nanospace of Mesoporous Materials or Clays
Young Soo Ko and Seong Ihl Woo | 261 |
| 10.1 | Introduction | 261 |
| 10.2 | Single-Site Catalyst Confined within the Nanopores of Mesoporous Materials | 263 |
| 10.2.1 | Ethylene Polymerization | 263 |
| 10.2.1.1 | Extrusion Polymerization within the Pore | 263 |
| 10.2.1.2 | Al-MCM-41 | 264 |
| 10.2.1.3 | Shape-Selective Polymerization in the Nanopore | 267 |
| 10.2.1.4 | The Effect of Pore Diameter on Polymerization | 268 |
| 10.2.1.5 | Tethering of Single-Site Catalyst within the Nanopore of MCM-41 | 269 |
| 10.2.1.6 | In-situ Synthesis of CGC on the Surface of SBA-15 | 269 |
| 10.2.2 | Propylene Polymerization | 270 |
| 10.3 | Single-Site Catalyst Confined within the Nanogalleries of Mineral Clays | 271 |
| 10.4 | Summary | 274 |
| | References | 275 |
| 11 | Polymeric Supported Catalysts
Markus Klapper and Gerhard Fink | 277 |
| 11.1 | Introduction | 277 |
| 11.2 | Polysiloxanes | 278 |
| 11.2.1 | Supported Precatalysts | 278 |
| 11.2.2 | Supported Cocatalysts | 281 |
| 11.3 | Polystyrene | 283 |
| 11.3.1 | Metallocene Functionalized Linear Polystyrene | 283 |
| 11.3.2 | Metallocene Inside Polystyrene Resins | 284 |
| 11.3.3 | Metallocene Supported on Polystyrene Nanoparticles | 286 |
| 11.4 | Dendrimers | 292 |
| 11.5 | Polyolefins | 294 |
| 11.6 | Carbon Nanotubes | 295 |
| | References | 301 |
| 12 | Self-immobilizing Catalysts for Olefin Polymerization
Helmut G. Alt and Christian Görl | 305 |
| 12.1 | General Aspects: Why Heterogenize Homogeneous Olefin Polymerization Catalysts | 305 |
| 12.2 | A New Approach: Self-immobilizing Catalysts – Let the Catalyst Produce its own Support | 306 |
| 12.3 | Self-immobilizing Metallocene Catalysts | 307 |
| 12.3.1 | Preparation of Various Alkenyl Functionalized Metallocene Complexes | 307 |
| 12.3.2 | Metallacyclic Metallocene Complexes | 309 |
| 12.4 | Self-immobilizing Half-Sandwich Complexes | 314 |
| 12.5 | Self-immobilizing Non-Metallocene Transition Metal Complexes | 318 |
| 12.6 | Self-immobilizing Cocatalysts | 321 |
| | References | 322 |
| | Index | 327 |
