Kinetics Of Ziegler Natta Polymerization

This book, aimed at academic and industrial scientists, presents the most advanced theory and methods of chemical kinetics. The theory is explained on the basis of the author's historical and logical view of traditional kinetics, beginning with van't Hoff and S. Arrhenius and progressing to the work of H. Eyring, E. Wigner and J. Horiuti. The theory has been applied to the understanding of Ziegler-Natta-Kaminsky catalysis, the results being supported by the author's own experimental studies. Organic chemists interested in finding new active catalysts will learn from this text how to understand the fundamental and practical kinetic method as relevant for catalyst research in industry and universities.

Coordination Polymerization contains the proceedings of a symposium sponsored by the American Chemical Society and held at the University of California-Los Angeles on April 3, 1974. The papers explore developments in coordination polymerization and cover topics ranging from stereoselection and stereoelection in a-olefin polymerization to heterogeneous Ziegler-Natta polymerization; transition metal alkyl polymerization catalysts; chain transfer in Ziegler-type polymerization of ethylene; and stereospecific polymerization of diolefins by h3-allylic coordination complexes. This book is comprised of 13 chapters and begins with a discussion on Karl Ziegler's major contributions to the chemistry of free radicals, organo-alkali metal compounds, many-membered rings, and organotransition metallic compounds. The next two chapters focus on the origin of steric control in the polymerization of a-olefins, with emphasis on steroselection and stereoelection as well as the influence of the chirality of the transition metal on the stereoregularity of the resulting polymer. The problem of counting active sites is then addressed, and results obtained with various methods are compared. The mechanisms of initiation, propagation, termination, and transfers in polymerizations by (p-C5H5)2 TiCl2 catalysts are also considered, along with polymerizations by allyl, benzyl, trimethylsilmethyl, and other derivatives of Ti and Zr. The last three chapters examine the kinetics of Ziegler-Natta polymerization; the Langmuir adsorption mechanism; supported Ziegler-Natta catalysts; factors that affect the stereoregularity of polymerization of propylene by supported catalysts; and polymerizations of diolefins to equibinary polymers by h3-allylic coordination complexes. This monograph will be of interest to chemists as well as polymer scientists and engineers.

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.

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.

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.

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.