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

ISBN-13: 9783642642920 / Angielski / Miękka / 2011 / 674 str.

Walter Kaminsky

Opis

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.

Spis treści

1. Heterogeneous Ziegler-Natta Catalysis.- Polyethylene: Polymer with Future.- Polypropylene: 44 Years Young! The Challenge for the 21st Century.- Characterization of PP Prepared with the Latest Metallocene and MgCl2-supported TiCl4 Catalyst Systems.- An Absolute Test of Rival Theories for MWDs in Heterogeneous Polymerization-MWDs during Quasi-Living Polymerization.- Olefin Polymerization with Novel Type of Ziegler Catalysts.- Kinetics and Mechanism of Ethylene Polymerization and Copolymerization Reactions with Heterogeneous Titanium-Based Ziegler-Natta Catalysts.- New Insight into Propene Polymerization Promoted by Heterogeneous Ziegler-Natta Catalysts.- Energy Distribution of Active Sites in Heterogeneous Ziegler-Natta Catalysts. Method of Study of Active Site Non-uniformity.- Ziegler-Natta and Metallocene Polymerisation of Olefins with Heterogeneous Catalysts.- 2. Homogeneous Catalysis, Synthesis and Polymerization.- Formation, Structure and Mechanism of Oligomeric Methylaluminoxanes(MAO).- The Activation of Metal-Fluorine Bonds in Compounds of Group 4 by Aluminum Alkyls.- A DFT Quantum-chemical Study of the Structures and Reactive Sites of Polymethylalumoxane.- In situ FTIR Spectroscopy Shows no Evidence of Reaction between MAO and TMA.- Alumoxanes alternative to MAO: Synthesis and characterization.- Expanding the Scope of Metallocene Catalysis: Beyond Indenyl and Fluorenyl Derivatives.- New C1-Symmetric Metallocenes for the Polymerization of Olefins.- New Catalyst Concepts for the Polymerization of Ethylene with Metallocenes.- Synthesis of Novel Complex with Bridged Bis(indenyl)Ligand and its Polymerization Behavior of Propylene.- Linked Amido-Cyclopentadienyl Complexes of Group 3 and 4 Metals: The First “Post-Metallocenes”.- Late Transition Metal Catalysts for Olefin Polymerization.- 3. Homogeneous Catalysis, Mechanism of Polymerization.- Chain Growth in Zirconocene-catalyzed Olefin Polymerization -DFT Studies on Possible Reaction Paths and the Influence of a Second Olefin Ligand.- Syndiotactic and Isotactic Specific Metallocene Catalysts with Hapto-flexible Cyclopentadienyl-Fluorenyl Ligand.- Current Vitality of Ziegler’s Monumental Discovery of Zirconium Catalysis in Olefin Polymerization: Metallocene and Nonmetallocene Catalysts via Reductive Dimerization.- Kinetic Features of Living Polymerization of Propene with the [t-BuNSiMe2Flu]TiMe2/B(C6F5)3 Catalyst.- Quantitative Structure-Activity Relationships for Unbridged Zirconocene Catalysts During Ethene Polymerization.- Coexistence of two Active Species in the Polymerization of 1-Hexene Catalyzed with Zirconocene/MAO Catalysts.- In-depth Investigation of Unsaturated Chain-end Groups: A Tool for Understanding Hydrogen Activation Mechanism in Zirconocene Catalysed Propene Polymerization.- 4. Supported Metallocene Catalysts.- Supported Metallocene Catalysts for Propene Polymerization.- 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.- 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.- Supported Metallocene Catalysts in Olefin Polymerization: Toward High Performances.- Zeolite Supported Metallocene Catalysts: Effect of Support Structure and Surface Groups on the Polymerization Process.- Preparation of Novel Supported Metallocene and their Olefin Polymerization Capabilities.- Development of Supported Single-site Catalysts and Produced Polyethylene.- Ethylene Polymerization with the Heterogeneous Single Site CpIndZrCl2 Catalyst.- The Impact of the Cocatalyst on the Polymerisation Behaviour of Supported Metallocenes.- Heterogenised MAO-free Metallocene Catalysts.- A New Supported Zirconocene Catalyst for Ethylene Polymerization.- 5. Polystyrene and Copolymers.- Syndiospecific Polymerization of Styrene.- Monocyclopentadienyl Titanium Catalyst.- The Effects of the Bridge Structure and the Ligand System of Zirconocene Catalysts on the Copolymerization of Styrene and Ethylene.- Branched Polyethenes Prepared via Olefin Copolymerization and Migratory Insertion.- Metallocene Catalyzed Alternating Copolymerization of Olefins.- Copolymer Microstructures of Ethylene Norbornene Copolymers Prepared with Homogeneous Metallocene Based Catalysts.- Studies on Properties of Metallocene Catalysed Copolymers of Ethylene and Linear, Non-conjugated Dienes.- Ethylene/?-Olefin Copolymerization with Dimethylsilyl-bis-(2-methyl-4-phenyl-indenyl)zirconium dichloride and Methylaluminoxane: Influences on Polymerization Activity and Molecular Weight.- 6. Functional Polyolefins and Polydienes.- The Role of the Cyclopentadienyl Ligand in Catalysts for 1,3-Diene Polymerization.- Catalytic Reaction Mechanisms and Structure-Reactivity Relationships in the Stereospecific Butadiene Polymerization.- Styrene and Conjugated Dienes Polymerization with Half Sandwich Titanocene Catalysts.- Half-Vanadocene Catalyst for Butadiene Polymerization.- Chemical Functionalization of Polypropylene with a V-based Living Polymerization Catalyst.- Copolymerization of Ethylene/?-Hydroxy ?-Olefins.- Stereospecific Polymerization of Methacrylates with Dimethylsilylene-bridged Zirconocene Catalysts.- Development of Catalytic Systems based on Lanthanoid Complexes for Olefin Polymerization.- 7. Polymer Characterization and Processes.- Initial 2,1-Insertions in Metallocene Polymerizations of Polypropylene.- Olefin Polymerization with DuPont’s VersipolTM Catalyst System.- Features of Cyclopentadienyl Metal Catalysts for Ethylene Copolymerization in Gas and Liquid Phase.- How to Avoid Gas-Liquid Mass Transfer Limitations During Polymerization of Olefins.- Ternary Metallocene Based Catalysts in High Temperature, High Pressure Polymerization.- Advanced in the Use of Stopped-flow Techniques for Olefin Polymerization.- Contributors.