Catalysis in Precision Polymerization


Book Description

This book provides a comprehensive survey of the entire field of catalysis in polymer synthesis covering the majority of essential aspects from basic organic, organometallic and bio-chemistry to industrial production. Particular emphasis is placed on "precision polymerization," where the catalyst plays a key role in the fabrication of innovative polymers. Precision polymerization enables the production of polymers with precisely controlled structures, molecular weight, distribution and stereochemistry, free from defects.




Polymer Design Enabled by Catalysis


Book Description

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.




Organic Catalysis for Polymerisation


Book Description

Organic Catalysis for Polymerisation has been edited by leading figures in the field and provides a holistic overview of the field.







Late Transition Metal Polymerization Catalysis


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.




Enzyme-Catalyzed Synthesis of Polymers


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Supramolecular Catalysis


Book Description

Supramolecular Catalysis Provides a timely and detailed overview of the expanding field of supramolecular catalysis The subdiscpline of supramolecular catalysis has expanded in recent years, benefiting from the development of homogeneous catalysis and supramolecular chemistry. Supramolecular catalysis allows chemists to design custom-tailored metal and organic catalysts by devising non-covalent interactions between the various components of the reaction. Edited by two world-renowned researchers, Supramolecular Catalysis: New Directions and Developments summarizes the most significant developments in the dynamic, interdisciplinary field. Contributions from an international panel of more than forty experts address a broad range of topics covering both organic and metal catalysts, including emergent catalysis by self-replicating molecules, switchable catalysis using allosteric effects, supramolecular helical catalysts, and transition metal catalysis in confined spaces. This authoritative and up-to-date volume: Covers ligand-ligand interactions, assembled multi-component catalysts, ligand-substrate interactions, and supramolecular organocatalysis and non-classical interactions Presents recent work on supramolecular catalysis in water, supramolecular allosteric catalysis, and catalysis promoted by discrete cages, capsules, and other confined environments Highlights current research trends and discusses the future of supramolecular catalysis Includes full references and numerous figures, tables, and color illustrations Supramolecular Catalysis: New Directions and Developments is essential reading for catalytic chemists, complex chemists, biochemists, polymer chemists, spectroscopists, and chemists working with organometallics.




Sequence-Controlled Polymers


Book Description

Edited by a leading authority in the field, the first book on this important and emerging topic provides an overview of the latest trends in sequence-controlled polymers. Following a brief introduction, the book goes on to discuss various synthetic approaches to sequence-controlled polymers, including template polymerization, genetic engineering and solid-phase chemistry. Moreover, monomer sequence regulation in classical polymerization techniques such as step-growth polymerization, living ionic polymerizations and controlled radical polymerizations are explained, before concluding with a look at the future for sequence-controlled polymers. With its unique coverage of this interdisciplinary field, the text will prove invaluable to polymer and environmental chemists, as well as biochemists and bioengineers.




Catalytic Polymerization of Cycloolefins


Book Description

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.




Catalysis by Polymers


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