Metalorganic Catalysts for Synthesis and Polymerization : Recent Results by Ziegler-Natta and Metallocene Investigations

45 years after the discovery of transition metals and organometallics as cocatalysts for the polymerization of olefins and for organic synthesis, these compounds have not lost their fascination. The birthday of Karl Ziegler, the great pioneer in this metalorganic catalysis, is now 100 years ago. Polyolefins and polydienes produced by Ziegler-Natta catalysis are the most important plastics and elastomers. New impulses for the polymerization of olefins have been brought about by highly active metallocenes and other single site catalysts. Just by changing the ligands of the organometallic compounds, the structure of the polymers produced can be tailored in a wide manner. In invited lectures and posters, relevant aspects of the metalorganic catalysts for synthesis and polymerization are discussed in this book. This includes mechanism and kinetics, stereochemistry, material properties, and industrial applications. Front Matter....Pages I-XIII Front Matter....Pages 1-1 Polyethylene: Polymer with Future....Pages 3-13 Polypropylene: 44 Years Young! The Challenge for the 21 st Century....Pages 14-29 Characterization of PP prepared with the latest metallocene and MgCl 2 -supported TiCl 4 catalyst systems....Pages 30-37 An Absolute Test of Rival Theories for MWDs in Heterogeneous Polymerization-MWDs during Quasi-Living Polymerization....Pages 38-49 Olefin Polymerization with Novel Type of Ziegler Catalysts....Pages 50-59 Kinetics and Mechanism of Ethylene Polymerization and Copolymerization Reactions with Heterogeneous Titanium-Based Ziegler-Natta Catalysts....Pages 60-75 New insight into propene polymerization promoted by heterogeneous Ziegler-Natta catalysts....Pages 76-88 Energy Distribution of Active Sites in Heterogeneous Ziegler-Natta Catalysts. Method of Study of Active Site Non-Uniformity....Pages 89-96 Ziegler-Natta and Metallocene Polymerisation of Olefins with Heterogeneous Catalysts....Pages 97-101 Front Matter....Pages 103-103 Formation, structure and mechanism of oligomeric methylaluminoxanes (MAO)....Pages 105-122 The Activation of Metal-Fluorine Bonds in Compounds of Group 4 by Aluminum Alkyls....Pages 123-127 A DFT quantum-chemical study of the structures and reactive sites of polymethylalumoxane....Pages 128-135 In situ FTIR spectroscopy shows no evidence of reaction between MAO and TMA....Pages 136-141 Alumoxanes alternative to MAO: Synthesis and characterization....Pages 142-149 Expanding the Scope of Metallocene Catalysis: Beyond Indenyl and Fluorenyl Derivatives....Pages 150-169 New C 1 -Symmetric Metallocenes for the Polymerization of Olefins....Pages 170-179 New Catalyst Concepts for the Polymerization of Ethylene with Metallocenes....Pages 180-191 Synthesis of Novel Complex with Bridged Bis(indenyl) Ligand and its Polymerization Behavior of Propylene....Pages 192-199 Linked Amido—Cyclopentadienyl Complexes of Group 3 and 4 Metals: The First “Post-Metallocenes”....Pages 200-211 Late Transition Metal Catalysts for Olefin Polymerization....Pages 212-219 Front Matter....Pages 221-221 Chain growth in zirconocene-catalyzed olefin polymerization - DFT studies on possible reaction paths and the influence of a second olefin ligand....Pages 223-235 Syndiotactic and Isotactic Specific Metailocene Catalysts with Hapto-flexible Cyclopentadienyl-Fluorenyl Ligand....Pages 236-247 Current Vitality of Ziegler’s Monumental Discovery of Zirconium Catalysis in Olefin Polymerization: Metallocene and Nonmetallocene Catalysts via Reductive Dimerization....Pages 248-263 Kinetic Features of Living Polymerization of Propene with the [ t -BuNSiMe 2 Flu]TiMe 2 /B(C 6 F 5 ) 3 Catalyst....Pages 264-273 Quantitative Structure-Activity Relationships for Unbridged Zirconocene Catalysts During Ethene Polymerization....Pages 274-282 Coexistence of Two Active Species in the Polymerization of 1-Hexene Catalyzed With Zirconocene / MAO Catalysts....Pages 283-293 In-depth Investigation of Unsaturated Chain-end Groups: a Tool for Understanding Hydrogen Activation Mechanism in Zirconocene Catalysed Propene Polymerization....Pages 294-303 Front Matter....Pages 305-305 Supported Metallocene Catalysts for Propene Polymerization....Pages 307-320 Influence of the particle size of silica support on the kinetics and the resulting polymer properties at the polypropylene polymerization with heterogeneous metallocene catalysts; Part I: experimental studies and kinetic analysis....Pages 321-332 Influence of the Particle Size of Silica Support on the Kinetics and the Resulting Polymer Properties at the Polypropylene Polymerization with Heterogeneous Metallocene Catalysts; Part II: Development of a Model as Well as a Mathematical Simulation....Pages 333-346 Supported Metallocene Catalysts in Olefin Polymerization: Toward High Performances....Pages 347-357 Zeolite Supported Metallocene Catalysts: Effect of Support Structure and Surface Groups on the Polymerization Process....Pages 358-367 Preparation of Novel Supported Metallocene and their Olefin Polymerization Capabilities....Pages 368-380 Development of Supported Single-Site Catalysts and Produced Polyethylene....Pages 381-396 Ethylene Polymerization with the Heterogeneous Single Site CpIndZrCl 2 Catalyst....Pages 397-405 The Impact of the Cocatalyst on the Polymerisation Behaviour of Supported Metallocenes....Pages 406-412 Heterogenised MAO-free Metallocene Catalysts....Pages 413-425 A New Supported Zirconocene Catalyst for Ethylene Polymerization....Pages 426-431 Front Matter....Pages 433-433 Syndiospecific Polymerization of Styrene....Pages 435-445 Monocyclopentadienyl Titanium Catalyst....Pages 446-464 Front Matter....Pages 433-433 The effects of the bridge structure and the ligand system of zirconocene catalysts on the copolymerization of styrene and ethylene....Pages 465-468 Branched Polyethenes Prepared via Olefin Copolymerization and Migratory Insertion....Pages 473-484 Metallocene Catalyzed Alternating Copolymerization of Olefins....Pages 485-492 Copolymer Microstructures of Ethylene Norbornene Copolymers Prepared with Homogeneous Metallocene Based Catalysts....Pages 493-501 Studies on Properties of Metallocene Catalysed Copolymers of Ethylene and Linear, Non-conjugated Dienes....Pages 502-508 Ethylene/α-Olefin Copolymerization with Dimethylsilyl-bis(2-methyl-4-phenyl-indenyl) zirconium dichloride and Methylaluminoxane: Influences on Polymerization Activity and Molecular Weight....Pages 509-515 Front Matter....Pages 517-517 The Role of the Cyclopentadienyl Ligand in Catalysts for 1,3-Diene Polymerization....Pages 519-530 Catalytic Reaction Mechanisms and Structure-Reactivity Relationships in the Stereospecific Butadiene Polymerization....Pages 531-546 Styrene and Conjugated Dienes Polymerization with Half Sandwich Titanocene Catalysts....Pages 548-557 Half-Vanadocene Catalyst for Butadiene Polymerization....Pages 558-565 Chemical Functionalization of Polypropylene with a V-based Living Polymerization Catalyst....Pages 566-575 Copolymerization of Ethylene/ω-Hydroxy α-Olefins....Pages 576-583 Stereospecific Polymerization of Methacrylates with Dimethylsilylene-bridged Zirconocene Catalysts....Pages 583-589 Development of Catalytic Systems Based on Lanthanoïd Complexes for Olefin Polymerization....Pages 590-597 Front Matter....Pages 599-599 Initial 2,1-Insertions in Metallocene Polymerizations of Polypropylene....Pages 601-615 Olefin Polymerization with DuPont’s VersipolTM Catalyst System....Pages 616-628 Features of Cyclopentadienyl Metal Catalysts for Ethylene Copoly-Merization in Gas and Liquid Phase....Pages 629-642 How to Avoid Gas-Liquid Mass Transfer Limitations during Polymerization of Olefins....Pages 643-650 Ternary Metallocene Based Catalysts in High Temperature, High Pressure Polymerization....Pages 651-658 Advances in the Use of Stopped-flow Techniques for Olefin Polymerization....Pages 658-669 Back Matter....Pages 671-674