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Author: Shingo Kikukawa
Publisher:
ISBN:
Category : Metal catalysts
Languages : en
Pages : 462
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Book Description
Author: Shingo Kikukawa
Publisher:
ISBN:
Category : Metal catalysts
Languages : en
Pages : 462
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Book Description
Author: Zhibin Guan
Publisher: Springer Science & Business Media
ISBN: 3540877509
Category : Science
Languages : en
Pages : 262
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Book Description
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.
Author: Nolan Evan Mitchell
Publisher:
ISBN:
Category : Alkenes
Languages : en
Pages : 183
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Book Description
This dissertation describes advances made within the Long Research Group to design single-site catalysts for olefin polymerizations, and for the synthesis of thermally cross-linkable polyolefins. We have 1) designed thermally robust Ni-based catalysts for ethylene polymerization, 2) expanded this thermal stability enhancement strategy to Co-based catalysts, and 3) developed thermally cross-linkable polyethylene that is facilitated by the rearrangement of a co-monomer. Catalysts employing late transition metals have been heavily studied for olefin polymerizations but their implementation in industry remains limited due to a variety of drawbacks. One specific limitation is the general thermal instability of these catalysts at temperatures commonly used for industrial polymerizations. We will herein demonstrate that the precatalyst bis[(2,6-dibenzhydryl-4-methylimino)acenaphthene] nickel(II) dibromide can be used to dramatically enhance the thermal stability of this family of Ni-based catalysts. This precatalyst proved to be thermally robust for ethylene polymerizations at temperatures as high as 90 °C and showing living polymerization behavior at temperatures as high as 75 °C. This bulky ligand was further expanded to sterically demanding Fe- and Co-based olefin polymerization catalysts bearing 2,6-bis(biphenylmethyl)-4-methylaniline substituted bis(imino)pyridine ligands were synthesized and evaluated for ethylene polymerization. Tthe extreme ligand bulk mitigated detectable chain-transfer to aluminum and associative chain-transfer events. These bulky Co catalysts display great thermal stability up to 80 °C and show enhanced thermal stability at 90 °C. These observations are attributed to the extreme steric demand by which the ligand mitigates catalyst transfer, deactivation, and decomposition. Lastly, materials that are accessible using catalysts currently employed in Industry. Industrial methods to cross-linked polyethylene are polymer irradiation and the incorporation of peroxides. These methods suffer from lack of control over cross-link bond formation and can result in a tacky polymer. We developed a thermally cross-linkable polyethylene that utilizes benzocyclobutene as a co-monomer. After polymerization, non-cross-linked films were formed and cross-linked by increasing the temperature to promote the thermal rearrangement of benzocyclobutene. These co-monomers can undergo cycloaddition with other activated benzocyclobutene co-monomers leading to covalently linked polyethylene chains. It will be demonstrated that cross-linking at temperatures above 200 °C yield cross-linked PEX films that show up to 82 % gel percent content.
Author: Tobias Friedberger
Publisher:
ISBN: 9781321964240
Category :
Languages : en
Pages : 406
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Book Description
Polyolefins are the number one commercially produced polymeric material by volume, and find ubiquitous uses as plastics, elastomers, and fibers. They are produced from gaseous olefins such as ethylene and propylene by the action of a transition metal catalyst. Despite tremendous academic and industrial efforts and successes in catalyst development over the past decades, the copolymerization of polar functionalized olefins with sufficiently high activities still remains a largely unsolved issue. Late transition metal catalysts were shown to be more suitable for this kind of polymerization reaction due to their generally lower oxophilic character. The main goal of this thesis was the development of novel late transition olefin polymerization catalysts based on ruthenium and palladium. Prior to this work, only few active olefin polymerization Ru-catalysts were reported. Several series of complexes based on ruthenium were synthesized, characterized and investigated for olefin polymerization. Ru(II)-complexes of the type RuCl2(N,N,N)L with facially coordinating nitrogen donor ligands (N,N,N = trispyridyl-, trispyrazoyl-, trisimidazoyl-methane derivatives) were found to be inactive towards ethylene polymerization. Employing bisanionic disulfonate phosphines as ligands gave Ru-complexes that produced linear, high-molecular weight polyethylene in the presence of an aluminum-alkyl based cocatalyst. Increasing the electrophilicity of the complex, by decreasing the donor strength of the ligand and using higher oxidation state Ru(IV)-complexes, the polymerization activity could be increased, and one of the highest activities for any Ru-based catalyst was observed. Polar additives such as acetone fully inhibited even the most electron-rich catalysts and copolymerization reactions yielded no polymer. In a different approach to solve the same problem, Pd-diimine complexes were modified with pendant olefin and boronate groups. Pd-diimine complexes can facilitate the copolymerization of ethylene with acrylates, and interactions of the pendant Lewis acid group with the functional, Lewis basic comonomer was anticipated to increase catalyst activity. However, no effect of a pendant pinacol boronate was observed on the incorporation ratio of methyl acrylate in room temperature copolymerizations. The ability of the pendant olefin to coordinate to cationic Pd-species resulted in hemilabile effects. Increased catalyst stability at the cost of decreased activities was found in comparison with unfunctionalized ligands.
Author: Bernhard Rieger
Publisher: John Wiley & Sons
ISBN: 3527605266
Category : Technology & Engineering
Languages : en
Pages : 345
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Book Description
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.
Author: Walter Kaminsky
Publisher: Springer Science & Business Media
ISBN: 3642832768
Category : Science
Languages : en
Pages : 443
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Book Description
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.
Author: Ray Hoff
Publisher: John Wiley & Sons
ISBN: 0470504420
Category : Technology & Engineering
Languages : en
Pages : 599
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Book Description
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.
Author: Giuliano Giambastiani
Publisher: Springer Science & Business Media
ISBN: 9048138159
Category : Science
Languages : en
Pages : 296
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Book Description
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.
Author: Yury Kissin
Publisher: Elsevier
ISBN: 0080557996
Category : Technology & Engineering
Languages : en
Pages : 607
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Book Description
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 copolymersThe book contains over 2000 references, the most recent up to end of 2006.
Author: T. Keii
Publisher: Elsevier
ISBN: 0080887546
Category : Technology & Engineering
Languages : en
Pages : 597
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Book Description
Recent development of a new generation of Ziegler-Natta Catalysts using either magnesium dichloride as carrier or methylaluminoxane as cocatalyst has markedly stimulated the research activity in the field of olefin polymerization. These discoveries have not only yielded economical processes for polyolefin production but also opened the way to a new generation of novel polymers. Moreover, the nature of active species is being clarified well by the effort to simplify catalyst systems. The present volume includes 38 papers from the 31 lectures and 18 posters presented at the symposium on `Recent Developments in Olefin Polymerization Catalysts', which covered the following topics: Overview of super-active homogeneous and heterogeneous catalysts, kinetic profile of olefin polymerization including copolymerization, characterization of catalysts and polymers, methods for the determination of active center concentration, role of Lewis bases on the catalysts isospecificity, polymerization mechanisms, and synthetic pathways for functionalized polyolefins. The contents are well balanced between fundamental research and application as well as between homogeneous and heterogeneous catalyst systems.
