Recent Advances in Mechanistic and Synthetic Aspects of Polymerization

Due to their specific properties, polymers with well-defined structures have been receiving increasing attention over the last several years. Owing to the wide variability of their properties, these specialty polymers have been used in various areas from biomedical engineering to electronics or energy applications. The synthesis of such polymers necessi­ tates the use of new methods of polymerization which derived from an insight into the mechanism of polymerization reactions. A NATO Advanced Research Workshop on "Frontiers in Polymerization Catalysis and Polymer Synthesis" was held in BANDOl (FRANCE) in February 1987. Its aim was to assess the new polymerization methods, as well as the latest advances in the mechanisms of conventional polymerization reactions together with their applications to the synthesis of new macromolecular structures. The financial support from the NATO Scientific Affairs Division which covered the "lecturers' accomodation and travel expenses as well as the organization charges of this event gave it international scope. Several industrial companies participate at the meeting and contributed to it success. The organizors who are also editors of these proceedings, want to express their thanks to both NATO Scientific Affairs Division and the companies present at the meeting.

Inhalt

I- Group Transfer Polymerization.- Recent advances in the controlled synthesis of acrylic polymers by group transfer polymerization.- Kinetics of group transfer polymerization.- Group transfer polymerization of methyl methacrylate with basic catalysts.- The mechanism of nucleophilic activation at silicon.- Aldol GTP in controlled synthesis of vinyl alcohol polymers.- Report of discussions and recommendations.- II -Stability of Active Centers in Polymerization.- Controlled synthesis of various poly(alkyl methacrylates) by anionic techniques.- The anionic polymerization of alkyl acrylates:a challenge.- Stability of active centres in polymerization: methods of study of short-lived active centres.- Living cationic olefin polymerization.- Living and 'immmortal' polymerizations of epoxide with metalloporphyrin catalyst.- From anionic to Ziegler-Natta polymerization: application to the determination of the reactivity of Ziegler-Natta active centers.- Report of discussions and recommendations.- III - Catalysis of Polycondensation Reactions.- Novel polycondensation system for the synthesis of polyamides and polyesters.- Recent progress in the use of phase transfer catalysis for polycondensation reactions. Application to the preparation of polyethers, polycarbonates and polyesters.- Synthesis of polyaryletherketones.- Electrochemical reductive polycondensation of dibromoaromatic derivatives into poly (1,4-phenylene).- Polymerization of reactive telechelic oligomers. Formation of thermostable networks.- Report of discussions and recommendations.- IV - Polymerizations in Organised Medium.- Polymerization in inclusion compounds.- Radical polymerization along macromolecular templates.- Formation of polymers of ß-hydroxybutyric acid in bacterial cells and a comparison of the morphology of growth with the formation of polyethylene in the solid state.- Additional report.- Polymerized vesicles.- Polymerization of acrylamide in inverse emulsion.- Report of discussions and recommendations.- V - Carbenes and Polymerization.- Metal carbene complexes in polymer synthesis.- The role of carbene complexes in the Phillips olefin polymerization (surface compounds of transition metals, Part XXXI(1)).- Stereochemistry and intermediates in the ring-opening polymerization of norbornene and its derivatives.- Polymerization of alkynes initiated by stable metal carbene complexes.- Report of discussions and recommendations.- VI - Chiral Polymers.- Optically active vinyl polymers with backbone chirality.- Conformational optical activity in polymers.- Chiral thermotropic liquid crystalline polymers: an overview.- Atropisomeric polymers.- Report of discussions and recommendations.- VII - Polymerizations by Coordination Catalysts.- Some aspects of the polymerization of olefins with high activity heterogeneous catalysts.- Molecular weight distribution in Ziegler-Natta olefin polymerization.- Stereospecific polymerization of olefins with homogeneous catalysts.- The migratory catalyst : ?-olefin polymerization by 2, ?-linkage.- Nickel catalysts for ethylene homo- and copolymerization.- Pending questions in coordination polymerization of diolefins.- Report of discussions and recommendations.- List of Contributors.