Metal Catalysts In Olefin Polymerization

Polyolefin is a major industry that is important for our economy and impacts every aspect of our lives. The discovery of new transition metal-based catalysts is one of the driving forces for the further advancement of this field. Whereas the classical heterogeneous Ziegler-Natta catalysts and homogeneous early transition metal metallocene catalysts remain the workhorses of the polyolefin industry, in roughly the last decade, tremendous progress has been made in developing non-metallocene-based olefin polymerization catalysts. Particularly, the discovery of late transition metal-based olefin polymerization catalysts heralds a new era for this field. These late transition metal complexes not only exhibit high activities rivaling their early metal counterparts, but more importantly they offer unique properties for polymer architectural control and copolymerization with polar olefins. In this book, the most recent major breakthroughs in the development of new olefin polymerization catalysts, including early metal metallocene and non-metallocene complexes and late transition metal complexes, are discussed by leading experts. The authors highlight the most important discoveries in catalysts and their applications in designing new polyolefin-based functional materials.

More than 30 years after the discovery of transition metals and organometal lics as catalysts for olefin polymerization these catalysts did not have lost their fascination. Since 1953 when Karl Ziegler has discovered the catalytic polymerization of ethylene leading to plastically formable polymers which are mechanically stable up to temperatures of about 100°C, synthetic polymers and rubbers have made their way right into private houses. This discovery has been a main impetus for the fast growing production of plastics. The stereoselective poly merization of propylene and other long-chain a-olefins first detected by Giulio Natta leads to an even broadened field of applications. Another enforcing factor were the developments of Standard Oil of Indiana and Phillipps Petroleum Company who engaged in the polymerization of a-olefins supported molybdenum, cobalt and later on chromium catalysts which clearly indicates the wide variety of suitable systems. This kind of research acknowledged merit when in 1963 the Nobel prize of chemistry was awarded to Ziegler and Natta. Although to a great extent there is a technical application for these catalysts, up to now the nature of the active centres and many reaction mechanisms are not completely known.

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.

Polyolefin is a major industry that is important for our economy and impacts every aspect of our lives. The discovery of new transition metal-based catalysts is one of the driving forces for the further advancement of this field. Whereas the classical heterogeneous Ziegler-Natta catalysts and homogeneous early transition metal metallocene catalysts remain the workhorses of the polyolefin industry, in roughly the last decade, tremendous progress has been made in developing non-metallocene-based olefin polymerization catalysts. Particularly, the discovery of late transition metal-based olefin polymerization catalysts heralds a new era for this field. These late transition metal complexes not only exhibit high activities rivaling their early metal counterparts, but more importantly they offer unique properties for polymer architectural control and copolymerization with polar olefins. In this book, the most recent major breakthroughs in the development of new olefin polymerization catalysts, including early metal metallocene and non-metallocene complexes and late transition metal complexes, are discussed by leading experts. The authors highlight the most important discoveries in catalysts and their applications in designing new polyolefin-based functional materials.

This book highlights key advances that have occurred in the field of olefin conversion in recent years. The role of homogenous transition metal catalysts which contain an imine functionality is emphasized; their potential applications in the processing and upgrade of olefins to a wide variety of commodity products of very high industrial value is also explored. On the threshold of the fiftieth anniversary of the Noble Prize to Ziegler and Natta, this book gives a critical summary of the state of the art developments in the fascinating and rapidly developing field of the olefin polymerization, oligomerization, and co-polymerization catalysis.

"Catalysis is more art than science", probably all of you have heard and even used this expression. Whether it is true or not, it alludes to the experience that new catalysts are hard to find, and near impossible to predict. Hard work and a lifetime of experience is invaluable. However, a keen mind might give insight into where to search, but not necessarily about where to find the answers. Historically, "quantum leaps" have often arisen from serendipity - we all know the story about the nickel-contaminated reactor that triggered further research towards the first coordination catalyst for ethene polymerization. Taking advan tage of this event, Karl Ziegler became the first chemist to earn both a Nobel prize and a fortune for the same invention. A broken NMR tube helped Walter Kaminsky discover the effect of high concentrations of methylaluminoxanes as co catalysts for metallocenes. When air reacted with the concentrated trim ethyl aluminum solution, sufficient amounts of methylaluminoxanes were formed, and the lazy catalyst dormant in the NMR tube suddenly became sensationally active. Ziegler and Kaminsky were lucky and had the genius needed to take advantage of their luck.

This compilation provides advanced graduate students and researchers with a structured overview of olefin polymerization. Divided into eight chapters written by international experts, this book covers polymerization using various organotransition-metal catalysts, including early and late transition metal complexes, new trends in olefin oligomerization and related reactions. All authors address the historic and scientific backgrounds of the field as well as current research progress and potential for further research. The complete book is designed to present eight independent lectures and, because all authors are well versed in organometallic chemistry, each is based on a profound understanding of the reactions and structures of organotransition metal complexes. This book is an ideal accompaniment for researchers taking courses in olefin polymerization and also serves as a valuable resource for teachers and lecturers of chemistry when planning and researching material for advanced lecture courses.