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Development Of Late Transition Metal Insertion Polymerization Catalysts
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Book Synopsis Development of Late Transition Metal Insertion Polymerization Catalysts by : Tobias Friedberger
Download or read book Development of Late Transition Metal Insertion Polymerization Catalysts written by Tobias Friedberger and published by . This book was released on 2015 with total page 406 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Late Transition Metal Polymerization Catalysis by : Bernhard Rieger
Download or read book Late Transition Metal Polymerization Catalysis written by Bernhard Rieger and published by John Wiley & Sons. This book was released on 2006-03-06 with total page 345 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Metal Catalysts in Olefin Polymerization by : Zhibin Guan
Download or read book Metal Catalysts in Olefin Polymerization written by Zhibin Guan and published by Springer. This book was released on 2009-02-21 with total page 262 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Development of Late Transition Metal Catalysts for Olefin Polymerization by : Shingo Kikukawa
Download or read book Development of Late Transition Metal Catalysts for Olefin Polymerization written by Shingo Kikukawa and published by . This book was released on 2000 with total page 462 pages. Available in PDF, EPUB and Kindle. Book excerpt:
Book Synopsis Handbook of Transition Metal Polymerization Catalysts by : Ray Hoff
Download or read book Handbook of Transition Metal Polymerization Catalysts written by Ray Hoff and published by John Wiley & Sons. This book was released on 2010-09-16 with total page 599 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Alkene Polymerization Reactions with Transition Metal Catalysts by : Yury Kissin
Download or read book Alkene Polymerization Reactions with Transition Metal Catalysts written by Yury Kissin and published by Elsevier. This book was released on 2008-03-10 with total page 607 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Development of Late Transition Metal Catalysts and Advanced Polyolefins by : Nolan Evan Mitchell
Download or read book Development of Late Transition Metal Catalysts and Advanced Polyolefins written by Nolan Evan Mitchell and published by . This book was released on 2018 with total page 183 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Transition Metals and Organometallics as Catalysts for Olefin Polymerization by : Walter Kaminsky
Download or read book Transition Metals and Organometallics as Catalysts for Olefin Polymerization written by Walter Kaminsky and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 443 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Design of Nanoscale Polymeric Materials With Transition Metal Catalysis by :
Download or read book Design of Nanoscale Polymeric Materials With Transition Metal Catalysis written by and published by . This book was released on 2004 with total page 7 pages. Available in PDF, EPUB and Kindle. Book excerpt: The ARO grant provided partial support to the research efforts in PI's laboratory on development of highly efficient catalytic syntheses of polymeric materials having complex topologies and functionalities from simple commercial olefinic monomers. In the past three years, we have made significant progress in both developing new polymeric materials and designing new catalysts. Specifically, the following accomplishments were achieved in this laboratory: (1) successfully demonstrated a new strategy of one-pot synthesis of hyperbranched polymers via direct free radical polymerization of commercial divinyl monomers by using a cobalt chain transfer catalyst; (2) developed a highly efficient one-pot synthesis of amphiphilic dendritic molecular nanocarriers that can be used for drug delivery and scaffold for multivalent ligands; (3) developed new NAP based and bisazaferrocene ligands for late transition metal polymerization catalysts; and (4) developed a novel family of cyclophane-based late transition metal complexes that are highly active and stable catalysts for olefin polymerization.
Book Synopsis Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II by : Giuliano GIAMBASTIANI
Download or read book Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II written by Giuliano GIAMBASTIANI and published by Springer Science & Business Media. This book was released on 2011-05-19 with total page 272 pages. Available in PDF, EPUB and Kindle. Book excerpt: Olefin Upgrading Catalysis by Nitrogen-based Metal Complexes II: State-of-the-art and Perspectives provides a critical review of the state-of-the-art developments in industrially relevant processes connected to efficient and selective olefin upgrading. Specific attention is devoted to catalysts containing imine- and amine-based ligands. All the chapters in this book have been designed to provide a systematic account of the vast amount of information available for this type of catalyst as well as to highlight the factors that ultimately control the catalyst’s performance and productivity. A comprehensive panorama of catalyst precursors is presented, spanning from group 10 α-diimine complexes and iron and cobalt 2,6-bis(imino)pyridine derivatives, to vanadium, chromium, titanium, zirconium and lanthanide complexes supported by nitrogen-containing ligands. The authors of this collective work are currently involved in the development of imine-based catalysts for efficient and selective olefin upgrading and the majority of them have dedicated most of their scientific career to this important field. In writing this book, their major goal is to transfer as many ideas and experiences as possible to the global audience of scientists engaged in this area of research.
Book Synopsis Catalyst Design for Tailor-Made Polyolefins by : M. Terano
Download or read book Catalyst Design for Tailor-Made Polyolefins written by M. Terano and published by Elsevier. This book was released on 1994-11-01 with total page 437 pages. Available in PDF, EPUB and Kindle. Book excerpt: Recent development of olefin polymerization catalysts has caused marked changes in both industrial and academic research. Industrial use of homogeneous metallocene catalysts has already begun in the fields of high density polyethylene and syndiotactic polypropylene. Moreover, important data have been obtained from academic investigations which have proved useful for understanding conventional heterogeneous Ziegler-Natta catalysts. From the industrial viewpoint, however, heterogeneous high-yield catalysts seem to be more important. The present volume contains invited lectures and contributed papers. The following topics are covered: (1) Heterogeneous Catalysts, (2) Metallocene Catalysts and (3) New Trends in the Polyolefin Industry.
Book Synopsis Alkene Polymerization Reactions with Transition Metal Catalysts by : Y. V. Kissin
Download or read book Alkene Polymerization Reactions with Transition Metal Catalysts written by Y. V. Kissin and published by Elsevier Science & Technology. This book was released on 2008 with total page 592 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Polymerization of Ethylene with Supported Early and Late Transition Metal Catalysts by : Yiyoung Choi
Download or read book Polymerization of Ethylene with Supported Early and Late Transition Metal Catalysts written by Yiyoung Choi and published by . This book was released on 2011 with total page 158 pages. Available in PDF, EPUB and Kindle. Book excerpt: Single-site catalysts revolutionized the polyolefin manufacturing industry and research with their ability to make polymers with uniform microstructural properties. Several of these catalysts are currently used commercially to produce commodity and differentiated-commodity resins. The key to their rapid success and industrial implementation resides in the fact that they can be used without major modifications in the polymerization reactors that previously used heterogeneous Ziegler-Natta and Phillips catalysts. Since most of these industrial processes use slurry or gas-phase reactors, soluble single-site catalysts must be supported on adequate carriers that ensure not only high activity, but also the formation of polymer particles with the proper morphology and bulk densities. Metallocene catalysts have been supported on a variety of carriers, but supporting late transition metal catalysts has not been investigated in detail, despite their very interesting properties such as tolerance to polar comonomers and impurities, activity in the absence of MAO, and the formation of short chain branches by the chain walking mechanism. The research work of this PhD thesis intends to fill this gap, by developing supported late transition metal catalysts with high catalyst activities towards ethylene polymerization and good polymer particle morphology.
Book Synopsis Transition Metal Catalyzed Polymerizations by : Roderic P. Quirk
Download or read book Transition Metal Catalyzed Polymerizations written by Roderic P. Quirk and published by CUP Archive. This book was released on 1988 with total page 888 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Metalorganic Catalysts for Synthesis and Polymerization by : Walter Kaminsky
Download or read book Metalorganic Catalysts for Synthesis and Polymerization written by Walter Kaminsky and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 674 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Download or read book Ziegler Catalysts written by Gerhard Fink and published by Springer Science & Business Media. This book was released on 2012-12-06 with total page 509 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.
Book Synopsis Transition Metal Catalyzed Polymerizations by : Roderic P. Quirk
Download or read book Transition Metal Catalyzed Polymerizations written by Roderic P. Quirk and published by Taylor & Francis. This book was released on 1983 with total page 478 pages. Available in PDF, EPUB and Kindle. Book excerpt:
