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Forty years after Ziegler's discovery of the "Aufbaureaktion" and low-pressure ethene polymerization, transition metal catalyzed olefin and diolefin polymerization continues to represent one of the most active and exciting areas. Since the 1980s, outstanding scientific innovations and process improvements have revolutionized polyolefin technology and greatly simplified polymerization processes. Well-defined catalyst systems are now at hand and facilitate the understanding of basic reaction mechanisms and correlations between catalyst structures, polymer microstructures, and polymer properties. This book reviews some of the modern approaches in organometallic chemistry, Ziegler-Natta catalysis, polymerization processes, design of novel materials, and the modelling in catalyst and process development.
Ziegler-Natta Catalysts and Polymerizations reviews the general aspects of Ziegler-Natta catalysts and polymerizations of olefins, dienes, and many other types of monomers. Topics covered include the physical state of the polymer during polymerization; modification of Ziegler-Natta catalysts by third components; and termination of polymer chain growth. The oxidation state of catalysts and active centers is also discussed, along with copolymerizations and block polymerizations. This book is comprised of 23 chapters and begins with an overview of Ziegler-Natta catalysts and polymerizations, their historical origins, scientific and commercial importance, and major advances in polymer science. The next chapter focuses on definitions and stereochemistry of Ziegler-Natta catalysts, together with analytical methods used to identify and quantitatively measure their structures. Some of the polymers produced commercially with Ziegler-Natta catalysts are considered. The discussion then turns to mechanisms for initiating and propagating olefins; mechanisms for stereochemical control of conjugated and nonconjugated dienes; and the basic kinetic parameters that characterize Ziegler-Natta polymerizations. This monograph is written especially for chemistry and engineering graduate students and for industrial chemists, engineers, and managers who may become involved in a Ziegler-Natta problem.
In spite of the vast number of patents and publications mainly issued duringthelastdecade, acomprehensivereviewthatcoversthescienti?caswell as the patent literature has been missing until now. In this volume we try to review the available literature by two independent approaches to Nd and Ln-catalyzed diene polymerizations. In the?rst part of thevolume, whichisentitled"Neodymium-Based Ziegler/NattaCatalystsand their Application in Diene Polymerization", a polymer chemist's view is given with strong emphasis on Nd-based catalyst systems. Also technological and industrialaspectsofNd-catalyzeddienepolymerizationsareaddressed. Inthe secondpartofthevolume, whichisentitled"Rare-EarthMetalsandAluminum Getting Close in Ziegler-type Organometallics", a more organometallic p- spective isgivenandLn-based catalystsystems areaddressed
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.
The discoveries of organometallic catalysts for olefin polymerization by Karl Ziegler and that of stereoregular olefin polymers by Giulio Natta are probably the two most important achievements in the areas of catalysis and polymer chemistry in the second half of this century. They led to the development of a new branch of chemical industry, and to a large volume production of high-density and linear low-density polyethylene, isotactic polypropylene, ethylene-propylene rubbers, isotactic poly I-butene, and poly-4-methyl-l-pentene. These discoveries merited the Nobel prize, which was awarded to K. Ziegler and G. Natta in 1963. The initial works of Ziegler and Natta were followed by an "explosion" of scientific papers and patents covering all aspects of polymerization chemistry, catalyst synthesis, and polymerization kinetics as well as the structural, chemical, physical, and technological characteristics of stereo regular polyolefins, polydienes, and olefin copolymers. It is sufficient to say that in the twenty-five years after the first publications more than 15,000 papers and patents appeared on subjects related to the area. . The development brought about the establishment of several prominent groups of scientists occupied with the study of olefin polymerization. The most important of these were scientific schools in Italy, Germany, England, the United States, Japan, the Soviet Union, Czechoslovakia, and Venezuela. In addition, many major chemical and petrochemical corporations throughout the world established labora tories devoted to the development of the technology of catalyst synthesis and olefin polymerization.
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.
With an enormous velocity, olefin polymerization has expanded to one of the most significant fields in polymers since the first industrial use about 50 years ago. In 2005, 100 million tons of polyolefins were produced - the biggest part was catalyzed by metallorganic compounds. The Hamburg Macromolecular Symposium 2005 with the title "Olefin Polymerization" involved topics such as new catalysts and cocatalysts, kinetics, mechanism and polymer reaction engineering, synthesis of special polymers, and characterization of polyolefins. The conference combined scientists from different disciplines to discuss latest research results of polymers and to offer each other the possibility of cooperation. This is reflected in this volume, which contains invited lectures and selected posters presented at the symposium.
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
Forty years after Ziegler's discovery of the "Aufbaureaktion" and low-pressure ethene polymerization, transition metal catalyzed olefin and diolefin polymerization continues to represent one of the most active and exciting areas. Since the 1980s, outstanding scientific innovations and process improvements have revolutionized polyolefin technology and greatly simplified polymerization processes. Well-defined catalyst systems are now at hand and facilitate the understanding of basic reaction mechanisms and correlations between catalyst structures, polymer microstructures, and polymer properties. This book reviews some of the modern approaches in organometallic chemistry, Ziegler-Natta catalysis, polymerization processes, design of novel materials, and the modelling in catalyst and process development.