Polyolefins: 50 years after Ziegler and Natta II: Polyolefins by Metallocenes and Other Single-Site Catalysts (Advances in Polymer Science Book 258)

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Preface 6 Contents 8 Methylaluminoxane: Key Component for New Polymerization Catalysts 10 1 Introduction 11 2 Formation and Structure of MAO 13 3 New Polyolefins 18 3.1 Homopolymers 18 3.2 Copolymers 25 3.3 Polyolefin Nanocomposites 28 4 Outlook 32 References 34 Development of ansa-Metallocene Catalysts for Isotactic Olefin Polymerization 38 1 Introduction 39 2 Structural Variants of ansa-Metallocene Catalysts 39 3 Mechanisms of Catalyst Activation and Polymerization Catalysis 41 4 Industrial Use of ansa-Metallocene Catalysts 44 5 Concluding Remarks 48 References 49 Syndiotactic Polypropylene: Discovery, Development, and Industrialization via Bridged Metallocene Catalysts 52 1 Introduction 54 2 Bridged Cyclopentadienyl-Fluorenyl Metallocene Molecules 55 2.1 Molecular Structure of Isopropylidene(cyclopentadienyl-fluorenyl)MCl2 (M=Zr, Hf): Bonding and Symmetry 57 2.2 Crystal Structure of the Metallocenium-Monoalkyl Cation and the Structure of the Putative Active Site 58 2.3 Polymerization Behavior of 1/MAO and 2/MAO Catalyst Systems 60 2.4 Mechanism of Syndiospecific Polymerization 62 2.5 Syndiospecific Transition State Structure and Syndio-Insertion Catalytic Cycle 64 3 Structural Modifications to Enhance the Syndiospecific Catalytic Performance 67 3.1 Modification of the Bridge and Syndiotactic Polymer Molecular Weight 68 3.2 Bridge Size Modification: 1,2-Ethano-Bridge Versus 2,2-Propano-Bridge 69 3.3 Bridge Substituents and Syndiotactic Polypropylene Molecular Weight 74 3.4 Polymerization Behavior of Diphenylmethylidene(cyclopentadienyl-fluorenyl)MCl2/MAO: Methyl Versus Phenyl Substituent in the Bridge 74 4 Fluorenyl Substituents and Catalyst Enantioselectivity 79 4.1 Stereoregularity Improvement and Frontal Substituents 79 4.2 Computational Calculations: Determination and/or Prediction of Enantioselectivity of Syndiospecific Catalyst Systems 82 4.3 Importance of the Frontal Substituents 85 5 Stereorigidity of Bridged Metallocenes and Stereoselectivity of the Catalysts 90 5.1 Catalysts Stereorigidity and Site Epimerization 92 5.2 The Origin of Site Epimerization: Computational Investigation 93 5.3 Site Epimerization in the ``Absence ́ ́ of the Counter-Ion 93 5.4 Counter-Ion-Assisted Site Epimerization 94 6 Metallocene Molecular Symmetry and the Catalyst ́s Syndiotactic Specificity 98 6.1 Syndio- and Nonsyndiospecific Catalyst Systems with Cs Symmetric Metallocene Structures 99 6.2 Other Types of Cs Symmetric Metallocene Catalysts with Syndio- and Nonsyndiospecific Behavior 101 6.3 C1 Symmetric Structures: Syndio- and Nonsyndiospecific Catalyst Systems 102 6.4 Other C1 Symmetric but Syndiospecific Catalyst Systems 104 6.5 Industrial Production of Syndiotactic Polypropylene 105 6.6 Optimization of the Procedure for Synthesis of the Metallocene Molecule 106 6.7 Proper Choice of the Silica and MAO 106 6.8 Large-Scale Preparation of the Supported Metallocene Catalysts 107 6.9 Large-Scale Production of Syndiotactic Polypropylene 107 6.10 Processing of Syndiotactic Polypropylene Polymers 108 7 Properties of Syndiotactic Polypropylene Polymers 108 7.1 Polymorphism of Syndiotactic Polypropylene 108 7.2 Thermal Properties and the Origin of Multiple Melting Behavior of s-PP 111 7.3 Syndiotactic Polypropylene: Physical and Mechanical Properties 112 7.4 Syndiotactic Polypropylene: Processing and Rheology 113 7.5 Market Applications 114 7.5.1 Injection Molding 114 7.5.2 Injection Blow Molding 115 7.5.3 Films 115 7.5.4 Fibers 115 7.5.5 Additive, s-PP/i-PP Blends 116 8 Experimental Details [187, 188] 116 8.1 Synthesis of Bridged, Cyclopentadienyl-Fluorenyl Zirconocenes. 116 9 Outlook 118 References 119 Polyolefins with Cyclic Comonomers 126 1 Introduction 127 2 Copolymers with Monocyclic Olefins 129 3 Ethene-Norbornene Copolymers 132 4 Propene-Norbornene Copolymers 137 5 Copolymerization with Functionalized Norbornenes 140 6 Other Cycloolefin Copolymers 144 7 Conclusions 146 References 147 Trialkylaluminum-Free Modified Methylaluminoxane as a Cocatalyst for Living Polymerization of Olefins 151 1 Introduction 152 2 Living Polymerization of Propene with a Chelating Diamidodimethyltitanium 153 2.1 Activation with dMMAO 153 2.2 Activation with SiO2-Supported dMMAO 155 3 Living Polymerization of Propene with ansa-Dimethysilylene(fluorenyl)(amido)-dimethyltitanium Activated with dMMAO 157 3.1 Effect of Solvents 157 3.2 Substituent Effects of Fluorenyl Ligand 159 3.3 Synthesis of Stereo-Block PP 160 4 Living Polymerization of Norbornene with ansa-Dimethysilylene(fluorenyl)(amido)-dimethyltitanium Activated with dMMAO 161 4.1 Homopolymerization of Norbornene 161 4.2 Random Copolymerization of Norbornene and 1-Alkene 162 4.3 Block Copolymerization of Norbornene and 1-Alkene 165 5 Conclusion 167 References 167 Novel Polyethylenes via Late Transition Metal Complex Pre-catalysts 170 1 The Characteristic Features of LT-PE 172 2 Variations in Iron and Cobalt Complex Pre-catalysts 173 3 The Nickel Complex Pre-catalysts 180 References 183 Functional Polyolefins Through Polymerizations by Using Bis(indenyl) Zirconium Catalysts 186 1 Introduction 189 2 Copolymerization Behavior of Bis(indenyl) Metallocenes 191 2.1 Effect of Heteroatoms in the Ligand Framework 195 2.2 Copolymerization Behavior of Siloxy-Substituted Bis(indenyl) Zirconium Dichlorides 196 2.3 Chain Termination 197 2.3.1 Effect of Hydrogen 199 3 Long-Chain Branched Polyethylenes Formed In Situ 201 3.1 LCB Mechanism 201 3.2 LCB Analytics 202 3.3 Influence of the Catalyst and Polymerization Conditions on LCB 205 3.3.1 Catalyst Structure 205 3.3.2 Effect of Ethylene Concentration 206 3.3.3 Hydrogen Concentration 208 3.3.4 Effect of Comonomer 208 3.4 Structure Considerations of the LCB 212 3.4.1 LCB Dependence on the Polymerization Process 215 4 Polymerization of Functional Comonomers with Olefins by Using Bridged Bis(indenyl) Catalysts 217 4.1 Polymerization of Strongly Interacting Comonomers 217 4.1.1 Copolymerization Behavior of Oxygen-Functional Alkenes 219 4.1.2 Copolymerization Behavior of Nitrogen-Functional Alkenes 220 4.1.3 Properties of Functionalized Copolymers 222 4.2 Polymerization of Weakly Interacting Comonomers 226 5 Functional Copolymers as Compatibilizers in Polyolefin Blends and Composites 231 5.1 Functionalized Polyethylenes as Compatibilizers for Polyethylene/Polyamide Blends 232 5.2 Weakly Interacting Compatibilizers in Polyolefin Composites 233 6 Outlook 234 References 234 Functional Polyolefins: Synthesis and Energy Storage Applications 240 1 Introduction 241 2 New Functionalization Approach 243 2.1 Polyolefins with Side Chain Functional Groups 244 2.2 Polyolefins with a Chain-End Functional Group 258 3 Polyolefin Block and Graft Copolymers 269 4 Functional PP Capacitors for Energy Storage 274 5 Conclusions 280 References 282 Polyolefin Nanocomposites and Hybrid Catalysts 286 1 Introduction 287 2 Polyolefin Nanocomposites and Catalysis 288 2.1 Polymerization Filling and In situ Nanocomposites 290 2.2 Polyolefin Carbon Hybrid Materials 295 2.3 ``All Polyolefin ́ ́ Composites and Hybrid Catalysts 301 3 Summary, Conclusions, and Outlook 305 References 307 Polyolefin/Layered Silicate Nanocomposites Prepared by In Situ Polymerization 317 1 Introduction 318 2 Structure and Properties of Layered Silicates 320 3 Clay Surface Modifications 321 3.1 Organic Modification of the Clay 321 3.2 Thermal Treatment of the Clay 323 3.3 Treatment of Clay with Alkylaluminum Compounds 323 4 Nanocomposite Structures 323 5 Techniques Used for the Characterization of Nanocomposites 325 6 Methods of Nanocomposite Preparation 327 6.1 Polyolefin/Clay Nanocomposites by In Situ Polymerization of Olefins with a Coordination Catalyst 329 6.1.1 Clay as Polymer Filler 329 6.1.2 Clay as Catalyst or Cocatalyst Support 330 6.1.3 Clay Acts as a Cocatalyst for Coordination Polymerization 333 7 Outlook 339 References 339 Iron Catalyst in the Preparation of Polyolefin Composites 346 1 Introduction 347 1.1 Polyolefins: Polymerization and Properties 347 2 Ethylene Polymerization with Iron Catalysts 349 2.1 Combination of Aluminum Alkyls and Bis(iminoaryl)-pyridyl Iron Dichloride 349 2.2 Polyethylenes from Iron Catalysts 352 2.3 Kinetics of Polyolefin Formation 353 2.4 Ethylene Polymerization with Supported BIP FeCl2 356 2.5 Nanocomposites by BIP FeCl2 Catalysis 360 3 Summary, Conclusions, Outlook 363 References 363 Index 368 Front Matter....Pages i-viii Methylaluminoxane: Key Component for New Polymerization Catalysts....Pages 1-28 Development of ansa -Metallocene Catalysts for Isotactic Olefin Polymerization....Pages 29-42 Syndiotactic Polypropylene: Discovery, Development, and Industrialization via Bridged Metallocene Catalysts....Pages 43-116 Polyolefins with Cyclic Comonomers....Pages 117-141 Trialkylaluminum-Free Modified Methylaluminoxane as a Cocatalyst for Living Polymerization of Olefins....Pages 143-161 Novel Polyethylenes via Late Transition Metal Complex Pre-catalysts....Pages 163-178 Functional Polyolefins Through Polymerizations by Using Bis(indenyl) Zirconium Catalysts....Pages 179-232 Functional Polyolefins: Synthesis and Energy Storage Applications....Pages 233-278 Polyolefin Nanocomposites and Hybrid Catalysts....Pages 279-309 Polyolefin/Layered Silicate Nanocomposites Prepared by In Situ Polymerization....Pages 311-339 Iron Catalyst in the Preparation of Polyolefin Composites....Pages 341-362 Back Matter....Pages 363-366