Development of Functionalized Polymers Using Bis(phenoxyimine)titanium and [alpha]-diimineNickel(II) Catalysts for the Production of New Polyolefin Architectures

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ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (671 download)

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Book Synopsis Development of Functionalized Polymers Using Bis(phenoxyimine)titanium and [alpha]-diimineNickel(II) Catalysts for the Production of New Polyolefin Architectures by : Amelia Marie Anderson

Download or read book Development of Functionalized Polymers Using Bis(phenoxyimine)titanium and [alpha]-diimineNickel(II) Catalysts for the Production of New Polyolefin Architectures written by Amelia Marie Anderson and published by . This book was released on 2010 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Decades of research in the area of metal-catalyzed olefin polymerization, since the initial discoveries by Ziegler and Natta in the 1950s, has lead to the development of a wide variety of transition metal catalysts as well as numerous polymer architectures. Although early work in the field focused on heterogeneous catalysis, Kaminsky's discovery of the scavenger/activator methylaluminoxane in 1980 facilitated a renaissance in the area of homogeneous catalysts. Today, many commercial polyolefin materials are still limited to linear homopolymers, random copolymers, or blends thereof. Therefore, our efforts have focused on the endfunctionalization and random incorporation of polar functional groups into polyolefins to produce polymers with improved properties and more complex architectures than traditional linear polymers. Initial work in this area focused on the development of well-defined long-chain branched polymers from end-functionalized polypropylene. Although many star polymers have been produced using anionic, cationic and radical methods, semicrystalline polypropylene materials with similar structures from coordinationinsertion polymerization were not known. Using a non-living bis(phenoxyimine)titanium catalyst, allyl-terminated syndiotactic polypropylene was produced and utilized in the production of alcohol-, azide- and amine-terminated polymers. These end-functionalized macromolecules were employed in the synthesis of a variety of well-defined branched polymers including star, miktoarm star and H- polymers. In an effort to produce branched polyolefin materials with high molecular weight, a norbornene-terminated polymer was synthesized from the allyl-terminated syndiotactic polypropylene. Using ring-opening metathesis polymerization, a number of high molecular weight polypropylene comb polymers were produced. All of the branched, syndiotactic polypropylene materials were analyzed further in an effort to related branching with observed polymer properties. To produce polyolefins with improved properties, a series of random copolymers derived from propylene and a polar, hydrogen bonding monomer were produced using Ni(II) [alpha]-diiminecatalysts. By varying the reaction temperature, hydrogen bonding polypropylene materials with a range of microstructures were produced. At high reaction temperatures, regioirregular, amorphous polypropylene was obtained, whereas, decreasing reaction temperature lead to highly regioregular, isotactic polypropylene. Utilizing the living nature of the Ni(II) [alpha]-diiminecatalysts, a series of triblock copolymers containing hydrogen bonding moieties in the midblock were also produced. The mechanical properties of all materials were investigated and generally observed to improve upon incorporation of small amounts (~1%) of the ureidopyrimidinone. For the branched and hydrogen bonding polymer reported herein, functionalization of polypropylene allowed for the synthesis of new polyolefin architectures.

New Polyolefin Architectures Through the Development of Living and Stereoselective Group IV Phenoxyketimine and Phenoxyamine Olefin Polymerization Catalysts

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Book Synopsis New Polyolefin Architectures Through the Development of Living and Stereoselective Group IV Phenoxyketimine and Phenoxyamine Olefin Polymerization Catalysts by : Joseph B Edson

Download or read book New Polyolefin Architectures Through the Development of Living and Stereoselective Group IV Phenoxyketimine and Phenoxyamine Olefin Polymerization Catalysts written by Joseph B Edson and published by . This book was released on 2009 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Since the pioneering work by Ziegler and Natta in the 1950s on metalcatalyzed olefin polymerization, decades of research have led to the development of catalysts capable of furnishing a wide variety of polymers. Early work focused on heterogeneous catalysts, but the later development of homogeneous catalysts provided mechanistic insights that have allowed researchers to develop catalysts that provide access and control over specific polymer microstructures. The majority of commercial polyolefins has traditionally been limited to homopolymers, random copolymers, or blends thereof. In the past decade however, the development of olefin polymerization catalysts that are living have now allowed access to virtually a limitless number of new polyolefin architectures. Despite the fact that a living polymerization system is capable of producing only one polymer chain per metal center, the real advantage lies in the ability to synthesize well-defined block copolymers and identify new materials with promising properties. Our efforts have focused on C2-symmetric bis(phenoxyketimine) titanium dichloride complexes and C1-symmetric phenoxyamine zirconium and hafnium dibenzyl complexes supported by an sp3-C donor. We have shown that upon activation, these complexes can catalyze the living and isoselective polymerization of !-olefins. Using these, the synthesis of a number of new block copolymers featuring semicrystalline isotactic polypropylene segments and amorphous poly(ethylene-co-propylene) segments was accomplished. The resultant block copolymers displayed elastomeric behavior and excellent mechanical properties. We have further shown that catalysts derived from the C1-symmetric phenoxyamine zirconium and hafnium dibenzyl complexes are capable of the cyclopolymerization of 1,5-hexadiene. The resultant polymers were shown to have a previously unreported cis-isotactic microstructure.

Metal Catalysts in Olefin Polymerization

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Publisher : Springer Science & Business Media
ISBN 13 : 3540877509
Total Pages : 262 pages
Book Rating : 4.5/5 (48 download)

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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 Science & Business Media. This book was released on 2009-03-31 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.

Catalyst Design for Tailor-Made Polyolefins

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Publisher : Elsevier
ISBN 13 : 0080887538
Total Pages : 437 pages
Book Rating : 4.0/5 (88 download)

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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.

Handbook of Transition Metal Polymerization Catalysts

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Publisher : John Wiley & Sons
ISBN 13 : 1119242134
Total Pages : 696 pages
Book Rating : 4.1/5 (192 download)

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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 2018-05-08 with total page 696 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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

Catalytic Polymerization of Cycloolefins

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Publisher : Elsevier
ISBN 13 : 0080528627
Total Pages : 1293 pages
Book Rating : 4.0/5 (85 download)

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Book Synopsis Catalytic Polymerization of Cycloolefins by : V. Dragutan

Download or read book Catalytic Polymerization of Cycloolefins written by V. Dragutan and published by Elsevier. This book was released on 2000-06-26 with total page 1293 pages. Available in PDF, EPUB and Kindle. Book excerpt: 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.

Development of Late Transition Metal Insertion Polymerization Catalysts

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ISBN 13 : 9781321964240
Total Pages : 406 pages
Book Rating : 4.9/5 (642 download)

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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.

Beyond Metallocenes

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ISBN 13 :
Total Pages : 272 pages
Book Rating : 4.3/5 (91 download)

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Book Synopsis Beyond Metallocenes by : Abhimanyu O. Patil

Download or read book Beyond Metallocenes written by Abhimanyu O. Patil and published by . This book was released on 2003 with total page 272 pages. Available in PDF, EPUB and Kindle. Book excerpt: The past 15 years have witnessed tremendous advances in the design and use of organometallic complexes as precatalysts for olefin polymerization. Most recently, an intense search has been started in next-generation single-site catalysts. New approaches have been taken to ligand design. This research has yielded extraordinary results such as catalysts with activities as high or higher than those of conventional metallocenes, stereospecific and living polymerizations, and amazing new polymer structures such as highly-branched ethylene homopolymers. This volume presents some of the recent disclosures in this exciting and rapidly expanding field, featuring papers by some of the leading investigators.

Metal Complex Catalysts Supercritical Fluid Polymerization Supramolecular Architecture

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Publisher : Springer
ISBN 13 : 9783662147931
Total Pages : 207 pages
Book Rating : 4.1/5 (479 download)

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Book Synopsis Metal Complex Catalysts Supercritical Fluid Polymerization Supramolecular Architecture by :

Download or read book Metal Complex Catalysts Supercritical Fluid Polymerization Supramolecular Architecture written by and published by Springer. This book was released on 2013-10-03 with total page 207 pages. Available in PDF, EPUB and Kindle. Book excerpt: recent resultsinadvancedorganometallicchemistry.Firstofall,somerecentexamples of the previous reviews concerning the Ziegler-Natta polymerization are cited [1—10]. Then, relevant new reports are surveyed in a systematic fashion.

New Polyolefin Architectures Through the Development of Living and Stereoselective Nickel-based Catalysts

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ISBN 13 :
Total Pages : 700 pages
Book Rating : 4.:/5 (498 download)

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Book Synopsis New Polyolefin Architectures Through the Development of Living and Stereoselective Nickel-based Catalysts by : Jeffrey Michael Rose

Download or read book New Polyolefin Architectures Through the Development of Living and Stereoselective Nickel-based Catalysts written by Jeffrey Michael Rose and published by . This book was released on 2008 with total page 700 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Polymer Design Enabled by Catalysis

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ISBN 13 :
Total Pages : 0 pages
Book Rating : 4.:/5 (144 download)

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Book Synopsis Polymer Design Enabled by Catalysis by : Sean Gitter

Download or read book Polymer Design Enabled by Catalysis written by Sean Gitter and published by . This book was released on 2024 with total page 0 pages. Available in PDF, EPUB and Kindle. Book excerpt: Modern synthetic polymer chemistry is defined by control over macromolecular architecture. Among controlled polymerization schemes, ring-opening metathesis polymerization (ROMP) represents one of the most widely adopted strategies for precision polymer synthesis. Advances in metal-alkylidene initiator technologies have enabled access to polymers with unrivalled degrees of microstructural control via ROMP. Unfortunately, relying on stoichiometric amounts of organometallic initiators can be cost prohibitive and limit the utility of ROMP materials in metal-sensitive applications like biomedicine or electronics. Therefore, recent effort has been devoted to developing metal-free approaches to ROMP (MF-ROMP). The Boydston group has developed a strategy which relies on organic initiators and photoredox catalysts to achieve MF-ROMP. Despite precluding the deleterious metallic byproducts inherent to metal-mediated ROMP, MF-ROMP remains limited in comparison to metal-mediated approaches to ROMP. Outstanding challenges in MF-ROMP include achieving a high degree of control over polymer microstructure, the incorporation of functional (co)monomers in MF-ROMP materials, and conducting polymerizations in nonpolar media. My doctoral research has begun to address these challenges. First, I was part of a collaborative team that discovered an ion-pairing approach to stereoselectivity during MF-ROMP that affords materials with tunable alkene stereochemistry using simple to change reaction parameters. During a further investigation we discovered that ion-pairing can also be used to improve the molecular weight control of MF-ROMP. These findings directly led to the discovery that active esters are readily polymerizable under MF-ROMP conditions. Post-polymerization modification of these materials provided access to a diverse array of functionalized MF-ROMP polymers for the first time. Separately, I was also on a team that developed a method for the C-H functionalization and allylic amination of ROMP polynorbornenes (poly(NBEs)). Notably, our approach to C-H functionalization yielded materials with high and tunable degrees of amination without consuming or transposing the alkenes in the polymers' backbones. In combination these discoveries highlight the utility of catalysis to access polymeric architectures that are otherwise inaccessible.

New Methods in the Synthesis of Functionalized Polyolefins and Solar Cell Donor Materials

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Publisher :
ISBN 13 : 9781109367447
Total Pages : 320 pages
Book Rating : 4.3/5 (674 download)

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Book Synopsis New Methods in the Synthesis of Functionalized Polyolefins and Solar Cell Donor Materials by : Robert Charles Coffin

Download or read book New Methods in the Synthesis of Functionalized Polyolefins and Solar Cell Donor Materials written by Robert Charles Coffin and published by . This book was released on 2009 with total page 320 pages. Available in PDF, EPUB and Kindle. Book excerpt: Functionalized olefin block copolymers are a highly sought after class of materials with enormous potential. We demonstrate three methods of preparing these types of material starting from the alpha-iminocarboxamide Ni(II) catalyst system. First, by functionalizing the benzyl group of the Ni(II) catalyst with a free radical initiator, we prepare end-functionalized polyolefins. Subsequent controlled free radical polymerization is then used to prepare block copolymers of ethylene and styrene, and ethylene and n-butylacrylate. Second, by taking advantage of the quasi-living copolymerization behavior of the alpha-iminocarboxamide Ni(II) catalyst system, pseudo-tetrablock copolymers of ethylene and a functionalized comonomer are prepared. Third, we prepare a bimetallic catalyst system that is capable of polymerizing ethylene and a functionalized comonomer in an inside-out fashion yielding triblock-like copolymers. The mechanical properties of the latter two materials are examined to assess their potential as thermoplastic elastomers.

New Group Four Complexes and Their Use as Homogeneous Polymerization Catalysts for the Production of Polyolefins

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Publisher :
ISBN 13 :
Total Pages : 386 pages
Book Rating : 4.:/5 (487 download)

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Book Synopsis New Group Four Complexes and Their Use as Homogeneous Polymerization Catalysts for the Production of Polyolefins by : John J. Esteb

Download or read book New Group Four Complexes and Their Use as Homogeneous Polymerization Catalysts for the Production of Polyolefins written by John J. Esteb and published by . This book was released on 2001 with total page 386 pages. Available in PDF, EPUB and Kindle. Book excerpt:

Structural Synergism in Functionalized Polymers: New Catalysts for Transacylation Reactions of Derivatives of Carboxylic and Phosphoric Acids

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ISBN 13 :
Total Pages : 6 pages
Book Rating : 4.:/5 (227 download)

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Book Synopsis Structural Synergism in Functionalized Polymers: New Catalysts for Transacylation Reactions of Derivatives of Carboxylic and Phosphoric Acids by :

Download or read book Structural Synergism in Functionalized Polymers: New Catalysts for Transacylation Reactions of Derivatives of Carboxylic and Phosphoric Acids written by and published by . This book was released on 1991 with total page 6 pages. Available in PDF, EPUB and Kindle. Book excerpt: This project has focused on the development of new highly-efficient, selective catalysts for widely-used commercial and biological reactions of carboxylic and phosphoric acids and their derivatives. The first phase of the project included the design and synthesis of linear, water-soluble polymers that are expected to self-organize in aqueous solution to form lipophilic substrate- binding domains adjacent to catalytic sites effective in transacylation reactions. The second phase of this work has dealt with the continuing evaluation of synthetic catalysts and the development of new methods for detailed structural characterization of these polymeric materials. Prof. R.G. Cooks (Purdue University, West Lafayette, IN) has been a key collaborator in this effort. The ultimate aim of this phase of the investigation is to ascertain the limits of substrate-selectivity for linear, synthetic polymeric catalysts.

Alkene Polymerization Reactions with Transition Metal Catalysts

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Publisher : Elsevier Science & Technology
ISBN 13 : 9781435628755
Total Pages : 592 pages
Book Rating : 4.6/5 (287 download)

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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.

Catalyst Development and Synthetic Methods for Tuning Polyethylene Microstructure

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ISBN 13 :
Total Pages : 250 pages
Book Rating : 4.:/5 (124 download)

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Book Synopsis Catalyst Development and Synthetic Methods for Tuning Polyethylene Microstructure by : Omar Padilla Velez

Download or read book Catalyst Development and Synthetic Methods for Tuning Polyethylene Microstructure written by Omar Padilla Velez and published by . This book was released on 2020 with total page 250 pages. Available in PDF, EPUB and Kindle. Book excerpt: Plastics are a crucial technology that have enabled the advancement of modern society. Major aspects of daily life involve in one way or another the use of polymeric materials, like the use of underground pipes for water transport or containers to preserve food. Today, plastics are mostly applied for packaging of consumer goods. Polyolefins, like polyethylene and polypropylene, have prospered as packing materials due to their lightweight, stability and inexpensive production. Single-use consumer habits has promoted an excessive production of polyolefins. As a result, the accumulation of highly durable materials is a growing problem and an environmental threat. Chapter one reviews current and emerging copolymer technologies used for the compatibilization of recycled polyolefin blends. These materials can be reused in place of newly manufactures resins of comparable value and performance. Chapter two discusses the synthesis, characterization, and application of a Ni(II) a-diimine catalyst for the production of polyethylene block copolymers. This type of complex can produce both linear and branched polyethylene via a chain-walking polymerization. In addition, the Ni catalyst exhibits living behavior allowing for the synthesis of well-defined polyethylene block copolymers. The ability of the block copolymer to compatibilize an immiscible HDPE/LDPE blend is also discussed. Chapter three focuses on the design and study of a Pd(II) a-diimine complex for the synthesis of linear polyethylene from renewable olefin feedstocks. The use of a Pd center with rapid chain-walking and a large a-diimine ligand, that promotes 2,1-insertion, results in the selective chain-straightening polymerization of light a-olefins. The copolymerization of functionalized a-olefins to produce high-value polyethylene type materials is reported. Chapter four discusses the development of temporally controlled initiation in the living polymerization of ethylene. The method allows for tuning the molecular weight of linear polyethylene as well as the shape and breadth of its molecular weight distribution. The effects of the molecular weight distribution shape and breadth on the tensile and rheological properties of the polymers are also studied.

Anionic Synthesis of Well-defined Functionalized and Star-branched Polymers

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Publisher :
ISBN 13 :
Total Pages : 210 pages
Book Rating : 4.:/5 (911 download)

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Book Synopsis Anionic Synthesis of Well-defined Functionalized and Star-branched Polymers by : Manuela Ocampo

Download or read book Anionic Synthesis of Well-defined Functionalized and Star-branched Polymers written by Manuela Ocampo and published by . This book was released on 2007 with total page 210 pages. Available in PDF, EPUB and Kindle. Book excerpt: Novel methods for the synthesis of chain-end and in-chain functionalized polymers, as well as star polymers, were developed using anionic polymerization techniques. A new mechanism for the reaction of polymeric organolithium compounds with thiiranes has been found. The reaction of poly(styryl)lithium and poly(butadienyl)lithium with propylene sulfide and ethylene sulfide was investigated in hydrocarbon solution for the preparation of thiol-functional polymers. It was found by MALDI-TOF mass spectral analysis of the reaction products that the reaction proceeded by attack of the anion on the methylene carbon atom of the thiirane ring followed by ring opening to form the thiol-functionalized polymer. The reaction of poly(styryl)lithium with trimethylene sulfide did not produce the corresponding thiol-functionalized polymer; the resulting methyl-terminated polymer was formed by attack of the anion on the sulfur atom followed by ring opening to form a primary carbanion. A new method for synthesis of alkoxysilyl-functionalized polymers was developed. Using a general functionalization methodology based on the hydrosilation of vinyltrimethoxysilane with [omega]-silyl hydride-functionalized polystyrene, alkoxysilyl-functionalized polystyrene was obtained in high yield (83 %). The main side product was vinylsilane-functionalized polymer. A small amount of dimer (approximately 2 %) was formed from the hydrosilation reaction of silyl hydride-functionalized polymer and vinylsilane-functionalized polymer. Star polymers with an average number of 6.8 arms were obtained by reacting poly(styryl)lithium with 6.6 equivalents of vinyldimethylchlorosilane in benzene at 30 °C. It was found that, in benzene at 30 °C, vinyldimethylchlorosilane is an efficient linking agent for the preparation of well-defined star-branched polymers. In contrast, the reaction of poly(styryl)lithium with 5 equivalents of vinyldimethylchlorosilane in THF at -78 °C produced vinylsilane-functionalized polymer in high yield (> 93 %). Poly(styryl)lithium was reacted with 2.5 equivalents of vinyldimethylethoxysilane; reaction occurred exclusively by the addition of the living anion to the vinyl group. In-chain, dihydroxyl-functionalized polystyrene was prepared by reaction of poly(styryl)lithium and 1,3-butadiene diepoxide. The hydroxyl functionalities were activated with potassium naphthalenide. Addition of ethylene oxide monomer yielded the corresponding heteroarm polystyrene/poly(ethylene oxide) stars. Two commercially available triepoxides, N,N-diglycidyl-4-glycidyloxyaniline and Tactix 742, were used to prepare the corresponding 3-armed stars in high yield.