Alkene Polymerization Reactions With Transition Metal Catalysts
During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:\ 1. The list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely renewed affording an unprecedented degree of control over the polymer structure.\ 2. Research devoted to metallocene and other soluble transition-metal catalysis has vastly expanded and has shifted toward complexes of...
Search in google:
During the past 30 years, the field of alkene polymerization over transition metal catalysts underwent several major changes:1. The list of commercial heterogeneous Ziegler-Natta catalysts for the synthesis of polyethylene and stereoregular polyolefins was completely renewed affording an unprecedented degree of control over the polymer structure.2. Research devoted to metallocene and other soluble transition-metal catalysis has vastly expanded and has shifted toward complexes of transition metals with multidentate ligands.3. Recent developments in gel permeation chromatography, temperature-rising fractionation, and crystallization fractionation provided the first reliable information about differences between various active centers in transition-metal catalysts.4. A rapid development of high-resolution 13C NMR spectroscopy resulted in greatly expanded understanding of the chemical and steric features of polyolefins and alkene copolymers. These developments require a new review of all aspects of alkene polymerization reactions with transition-metal catalysts. The first chapter in the book is an introductory text for researchers who are entering the field. It describes the basic principles of polymerization reactions with transition-metal catalysts, the types of catalysts, and commercially manufactured polyolefins. The next chapter addresses the principal issue of alkene polymerization catalysis: the existence of catalyst systems with single and multiple types of active centers. The subsequent chapters are devoted to chemistry and stereochemistry of elemental reaction steps, structures of catalyst precursors and reactions leading to the formation of active centers, kinetics of polymerization reactions, and their mechanisms.The book describes the latest commercial polymerization catalysts for the synthesis of polyethylenes and polypropylene The book provides a detailed description of the multi-center nature of commercial Ziegler-Natta catalysts. The book devotes specialized chapters to the most important aspects of transition metal polymerization catalysts: the reactions leading to the formation of active centers, the chemistry and stereochemistry of elemental polymerization steps, reaction kinetics, and the polymerization mechanism. The book contains an introductory chapter for researchers who are entering the field of polymerization catalysis. It describes the basic principles of polymerization reactions with transition-metal catalysts and the types of commercially manufactured polyolefins and copolymers The book contains over 2000 references, the most recent up to end of 2006.
Preface viiAbbreviations and Definitions xiThe Beginner's Course: General Description of Transition Metal Catalysts and Catalytic Polymerization Reactions 1Classifications of Transition Metal Catalysts 2Composition and Structure of Ziegler-Natta Catalysts 6Metallocene Catalysts 11Homogeneous Catalysts Containing Non-Metallocene Complexes of Early- and Late-Period Transition Metals 14Chromium Oxide Catalysts 15Main Features of Alkene Polymerization Reactions 17Classes of Polymers Produced with Transition Metal Catalysts 28Single-Center and Multi-Center Polymerization Catalysis 35Definition of Single Type of Active Center 36Molecular Weight Distribution of Polymers Produced with Single-Center Catalysts 37Structural Uniformity of Polymers and Copolymers Produced with Single-Center Catalysts 46Examples of Polymers and Copolymers Produced with Single-Center Catalysts 63Examples of Polymers and Copolymers Produced with Multi-Center Catalysts 65Chemistry and Stereochemistry of Polymerization and Copolymerization Reactions with Transition Metal Catalysts 85Chemistry and Stereochemistry of Polymerization Reactions 86Heterogeneous Titanium- and Vanadium-Based Ziegler-Natta Catalysts 98Metallocene Catalysts 124Homogeneous Catalysts Based on Early-Period Transition Metals 166Homogeneous Catalysts Based on Late-Period Transition Metals 176Chromium-Based Catalysts 183Stereoselective and Stereoelective Polymerization Reactions of Branched 1-Alkenes 184Copolymerization Reactions of Alkenes 190Synthesis, Chemical Composition, and Structure of Transition Metal Components and Cocatalysts in Catalyst Systems for Alkene Polymerization 207Early Solid Catalysts 209Supported Catalysts for Homopolymerization and Copolymerization of Ethylene 211Supported Ziegler-Natta Catalysts for Polymerization of Propylene and Higher 1-Alkenes 224Chemical Composition of Solid Components and Cocatalyst Mixtures of Ti-Based Ziegler-Natta Catalyst Systems 236Reactions Leading to Formation of Active Centers in Ziegler-Natta Catalysts 243Metallocene Catalysts 253Non-Metallocene Homogeneous Catalysts 270Supported Homogeneous Catalysts 277Bicomponent Catalysts 284Catalysts for Stereospecific Polymerization of Styrenes 287Kinetics of Alkene Polymerization Reactions with Transition Metal Catalysts 291Two Aspects of Polymerization Kinetics 292Role of Diffusion in Alkene Polymerization Reactions 295Formal Kinetic Description of Alkene Polymerization Reactions with Transition Metal Catalysts 299Polymerization Reactions with Metallocene Catalysts 310Polymerization Reactions with Non-Metallocene Homogeneous Catalysts 334Synthesis of Alkene Block-Copolymers 343Polymerization Reactions with Solid and Supported Ziegler-Natta Catalysts 349Polymerization Reactions with Pseudo-Homogeneous Catalysts 412Polymerization Reactions with Chromium Oxide Catalysts 413Active Centers in Transition Metal Catalysts and Mechanisms of Polymerization Reactions 419Catalysts Derived from Metallocene Complexes 420Non-Metallocene Homogeneous Catalysts 476Active Centers in Heterogeneous Ziegler-Natta Catalysts 486Active Centers in Chromium Oxide Catalysts 515References 523Subject Index 571\\
