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Catalytic Polymerization of Cycloolefins

Ionic, Ziegler-Natta and ring-opening metathesis polymerization

1st Edition - June 1, 2000

Authors: V. Dragutan, R. Streck

eBook ISBN:

9 7 8 - 0 - 0 8 - 0 5 2 8 6 2 - 5

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… Read more

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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.

Chapter headings and sub-headings: Introduction. General aspects. Definitions and reaction types. Scope and limitations. Cycloolefin Monomers. Types and Syntheses. Monomers for cationic polymerization. Monomers for anionic polymerization. Monomers for Ziegler-Natta polymerization. Monomers for ring-opening metathesis polymerization. Synthesis of cycloolefin monomers. Catalytic Systems. Cationic catalysts. Anionic catalysts. Ziegler-Natta catalysts. Ring-opening metathesis polymerization (ROMP) catalysts. Synthesis of catalysts for cycloolefin polymerization. Reaction Conditions. Monomer concentration. Catalyst concentration. Ratio of reactants. Premixing time of reaction components. Addition of reaction components. Reaction time. Reaction temperature. Reaction medium. Inhibitors. Activators. Reaction pressure. Effect of agitation. Cationic Polymerization of Cycloolefins. Cationic polymerization of monocyclic olefins. Cationic polymerization of bicyclic olefins. Cationic polymerization of polycyclic olefins. Anionic Polymerization of Cycloolefins. General aspects. Ziegler-Natta Polymerization of Cycloolefins. Polymerization of monocyclic olefins. Polymerization of bicyclic olefins. Polymerization of polycyclic olefins. Polymerization of functionalized cycloolefins. Ring-Opening Metathesis Polymerization of Cycloolefins. Ring-opening polymerization of monocyclic olefins. Ring-opening polymerization of bicyclic olefins. Ring-opening polymerization of polycyclic monomers. Polymerization of Functionalized Cycloolefins. General considerations. Four-membered ring monomers. Five-membered ring monomers. Six-membered ring monomers. Eight-membered ring monomers. Higher monocyclic olefins. Functionalized bicyclic olefins. Functionalized polycyclic olefins. Polymerization of Heterocyclic Olefins. Four-membered ring monomers. Five-membered ring monomers. Heteroatom-containing norbornenes and norbornadienes. Seven-membered ring monomers. High-membered ring monomers. Copolymerization Reactions of Cycloolefins. Introduction; reaction types. Cationic copolymerization of cycloolefins. Ziegler-Natta copolymerization of cycloolefins. Ring-opening metathesis copolymerization of cycloolefins. Structure and Properties of Poly(cycloolefin)s. Structure of poly(cycloolefin)s. Solution properties. Solid state properties. Thermodynamic Aspects of Cycloolefin Polymerization. Thermodynamic stability of cycloolefin monomers. Thermodynamic parameters of cycloolefin polymerization. Thermodynamic equilibrium in ring-opening metathesis polymerization. Reaction Kinetics. Kinetics of cationic polymerization. Kinetics of Ziegler-Natta polymerization. Kinetics of ring-opening metathesis polymerization. Aspects of Reaction Mechanism. Mechanism of cationic polymerization of cycloolefins. Mechanism of anionic polymerization of cycloolefins. Mechanism of Ziegler-Natta polymerization of cycloolefins. Mechanism of ring-opening metathesis polymerization of cycloolefins. Features of metallacarbene/metallacyclobutane mechanism. Stereochemistry of Cycloolefin Polymerization. Steric efffects in cationic polymerization. Steric configuration of vinyl polymers. Stereoselectivity in Ziegler-Natta polymerization. Steric configuration of polyalkenamers. Stereoselectivity in ring-opening metathesis polymerization. Tacticity of polyalkenamers. The nature of steric interactions in ROMP. Related Processes. Catalytic polymerization of olefins and dienes. Atom transfer radical polymerization of vinyl compounds. Metathesis reactions of olefins and acetylenes. Acyclic diene methatesis (ADMET) and acyclic diyne methatesis (ADIMET) polymerization. Carbonyl olefination reactions. Metathesis degradation of unsaturated polymers. Catalytic polymerization of acetylenes. Ring-opening polymerization of heterocycles. Miscellaneous processes. Practical Applications and Future Outlook. Commercial products. Products of interest for industry. Potential applications. Future outlook. Subject Index. References with all chapters.