Catalytic Polymerization Of Cycloolefins

This book covers the most important topics concerning cationic Ziegler-Natta and ring-opening metathesis polymerization of cycloolefins. The work describes the major pathways that cycloolefins can follow under the action of specific catalytic systems, essentially vinyl and ring-opening polymerization, both reaction types allowing the manufacture of distinct products with wide applicability in modern technologies. The comprehensive data available on this subject are logically and systematically selected and reviewed throughout 18 chapters, according to the basic catalytic processes involved, types of monomers and catalysts employed, reaction conditions and application fields. The modern trends in design of chiral metallocene catalysts, well-defined living metathesis catalysts, catalysts tolerant toward functionalities and water systems are highlighted. The book discusses in detail the relevant aspects of these processes including reaction thermodynamics, kinetics, mechanisms and stereochemistry and correlates the structure of produced polymers with their chemical and physical-mechanical properties. Related important topics include Ziegler-Natta polymerization of olefins and dienes, atom transfer radical polymerization of vinyl compounds, metathesis of olefins and acetylenes, acyclic diene metathesis reaction, carbonyl olefination reaction, metathesis polymerization of acetylenes, metathesis degradation of polymers and ring-opening polymerization of heterocycles. Special emphasis is laid upon the manufacture of commerical products, new polymers and copolymers of potential interest for industry and design and synthesis of speciality polymers with particular structures and architectures and desired properties. The book critically evaluates the most recent achievements reported in this field and outlines the modern trends on the research and application of the catalytic processes for cycloolefin polymerization. For the first time, comprehensive information about the published data on the subject up to now is provided for both academic and industrial researchers working in the areas of polymer chemistry, organic and organometallic chemistry, surface science and catalysis, petrochemistry and chemical engineering. This stimulating book offers an enlightening introduction and a quick documentation on the subject as well as a solid background in this field. Moreover, the work offers a wealth of useful information for specialists applying polymers in various scientific and industrial areas.

This book covers the proceedings of a symposium which was attended by researchers from all over the world who reported on and discussed recent advances in the field of catalytic polymerization of olefins. Over two decades have elapsed since the discovery of the Ziegler-Natta catalyst. Tremendous research effort has been aimed at improving this marvelous catalyst. In twenty-five years since the first publication, more than 15,000 papers and patents on the subject and on related subjects have appeared. This effort has yielded new generations of Ziegler-Natta catalysts with superior activity and stereospecificity. The complexities arising from the heterogeneity of the catalyst, however, have hindered understanding of the catalytic processes which take place on the catalyst surface. Nevertheless, many fundamental features of the catalyst system have now been clarified reasonably well. Recently a highly active homogeneous catalytic system has been developed, which is capable of catalyzing even isotactic polymerization of propene. There is no doubt that this finding will not only contribute to our understanding of the detailed mechanism of polymerization but also stimulate the development of various kinds of tailored polymers. Thus this subject will remain of paramount importance in the development of chemistry and polymer science for a long time to come.

The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and alkyne polymerization. The topics of the course were: mechanism of ROMP reactions/ new catalysts for ROMP/ new products by ROMP/ new catalysts for ADMET/ new products by ADMETI degradation of polymer by metathesis reactions/ alkyne polymerization and metathesis/ industrial application of metathesis reactions. The Advanced Study Institute was generously sponsored by the Scientific Affairs Division of NATO and the editor gratefully acknowledges this sponsorship. We also thank the Members of the Local Organizing Committee for their engagement on a successful NATO-AS!.

New synthetic techniques allow chemists to modify polymer microstructures more precisely than ever, making it possible to design materials that meet increasingly demanding performance requirements. Written and edited by experts in the field, Stereoselective Polymerization with Single-Site Catalysts reviews how the relative stereochemistry of

Since the last ASI in Turkey in Sept. 1995, the olefin metathesis has made remarkable strong developments with an incredible speed in various directions. New catalyst systems have been developed which have resulted in the synthesis of novel materials. Other fascinating developments have been the new catalysts for stereoselective metathesis and catalysts with considerable functional group tolerance. These new catalysts in addition to Ring Opening Metathesis Polymerisation (ROMP) and Acyclic Diene Metathesis (ADMET) are now powerful tools for Ring Closing Metathesis (RCM) and have found many applications in the synthesis of natural products. A lot of information has been established about all aspects of the olefin metathesis and there is a vast literature concerning the process, covering the initiators, mechanistic features and applications of this reaction in organic and polymer synthesis. The NATO ASI on rd th ROMP and Related Chemistry took place in Polanica-Zdroj, Poland during 3 to 15 Sept. 2000, to highlight the developments in this area and to discuss the prospects and visions for the year 2000 and beyond. The aims of the ASI were: to provide a platform for dissemination of knowledge; to promote communication between people who have a serious interest in this field of chemistry; to help establishing international scientific contacts and to provide an opportunity for the scientists with an appropriate scientific background to learn of recent developments in this field of science. There were 15 lecturers and 67 participants in this NATO ASI.

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.