Transition Metal Catalyzed Polymerizations

This volume contains the proceedings of the Second International Symposium on Transition Metal Catalyzed Polymerizations held in 1986. The papers provide a broad-based perspective covering recent scientific and technological advances in Ziegler-Natta and metathesis polymerization, including olefin, diene, and acetylene polymerization, and copolymerization. The emphasis on reaction kinetics of polymerizations in different reagent and catalyst environments makes this volume of interest to both academic and industrial researchers.

Including recent advances and historically important catalysts, this book overviews methods for developing and applying polymerization catalysts – dealing with polymerization catalysts that afford commercially acceptable high yields of polymer with respect to catalyst mass or productivity. • Contains the valuable data needed to reproduce syntheses or use the catalyst for new applications • Offers a guide to the design and synthesis of catalysts, and their applications in synthesis of polymers • Includes the information essential for choosing the appropriate reactions to maximize yield of polymer synthesized • Presents new chapters on vanadium catalysts, Ziegler catalysts, laboratory homopolymerization, and copolymerization

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.

At the start of the 1950s, Ziegler and Natta discovered that simple metallorganic catalysts are capable of transforming olefins into linear polymers with highly ordered structures. This pioneering discovery was recognized with a Nobel Prize in 1963. In the 80s and 90s, the development of molecular defined metallocenes led to a renaissance for non-polar polyolefin materials. Designer catalysts allowed a greater precision in defining properties of the material. The past 10 years have seen the discovery of new catalysts based on late transition metals, which allow the combination of polar monomers with non-polar olefins and thus lead to innovative materials. Here, the world's leading authors from industry and academia describe the latest developments in this fascinating field for the first time in such comprehensive detail. In so doing, they introduce readers systematically to the basic principles and show how these new catalysts can effectively be used for polymerization reactions. This makes the book an ideal and indispensable reference for specialists, advanced students, and scientists of various disciplines dealing with research into catalysts and materials science.

The proposed book focusses on metal mediated/catalyzed “controlled/living radical polymerization” (CRP/LRP) methods. It surveys a wide variety of catalyzed polymerization reactions, making it essentially a “one stop” review in the field. A significant contribution to polymer science is “metathesis polymerization” discovered by Grubbs and others. The book will cover various metathesis polymerization methods and implications in polymer industry.

A one-stop resource for understanding and applying polymerization catalysts An edited volume featuring contributions from leading researchers, the Handbook of Transition Metal Polymerization Catalysts covers the design and synthesis of catalysts, and their applications in synthesis of polymers. Dealing with those polymerization catalysts that afford commercially acceptable yields of polymer with respect to catalyst mass and promising newer catalysts, this practical reference provides polymer and organic chemists with a comprehensive overview of the known methods for developing and applying these important catalysts. With both recent advances and historically important catalysts, the subjects covered in this text include: Metal alkyls and other compounds that function as co-catalysts with a large number of catalysts The varieties of porous silica either necessary or valuable in certain catalyst formulations Catalyst scale-up and commercialization Copper catalysts for olefin polymerization Morphology control Along with the above topics, the Handbook of Transition Metal Polymerization Catalysts provides tables of valuable data to assist in reproducing a synthesis or applying the knowledge to a new problem. Polymerization reactivities, polymer properties, monomer and solvent purity requirements, molecular weights, distribution, and reactivity ratios are also covered. The Handbook of Transition Metal Polymerization Catalysts offers an excellent one-stop resource for understanding and applying polymerization catalysts.

Presents an up-to-date overview of the rapidly growing field of carbene transformations Carbene transformations have had an enormous impact on catalysis and organometallic chemistry. With the growth of transition metal-catalyzed carbene transformations in recent decades, carbene transformations are today an important compound class in organic synthesis as well as in the pharmaceutical and agrochemical industries. Edited by leading experts in the field, Transition Metal-Catalyzed Carbene Transformations is a thorough summary of the most recent advances in the rapidly expanding research area. This authoritative volume covers different reaction types such as ring forming reactions and rearrangement reactions, details their conditions and properties, and provides readers with accurate information on a wide range of carbene reactions. Twelve in-depth chapters address topics including carbene C-H bond insertion in alkane functionalization, the application of engineered enzymes in asymmetric carbene transfer, progress in transition-metal-catalyzed cross-coupling using carbene precursors, and more. Throughout the text, the authors highlight novel catalytic systems, transformations, and applications of transition-metal-catalyzed carbene transfer. Highlights the dynamic nature of the field of transition-metal-catalyzed carbene transformations Summarizes the catalytic radical approach for selective carbene cyclopropanation, high enantioselectivity in X-H insertions, and bio-inspired carbene transformations Introduces chiral N,N'-dioxide and chiral guanidine-based catalysts and different transformations with gold catalysis Discusses approaches in cycloaddition reactions with metal carbenes and polymerization with carbene transformations Outlines multicomponent reactions through gem-difunctionalization and transition-metal-catalyzed cross-coupling using carbene precursors Transition Metal-Catalyzed Carbene Transformations is essential reading for all chemists involved in organometallics, including organic and inorganic chemists, catalytic chemists, and chemists working in industry.