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Since the 1940s, since DuPont invented Teflon fluoropolymer has attracted interest of many scientists. As the fluorine-containing polymer having heat resistance and chemical resistance, refractive index and low surface energy of many advantages, which have a high-performance polymeric materials are widely used, such as high performance elastomers, high-performance surface active agents, high film coating, and fuel cells. The living / controlled radical polymerization method to the synthesis of fluorine-containing polymer, not only can precisely control the molecular weight and its distribution, and can design and prepare a fluorine-containing polymer complex structures, such as a block copolymer , graft copolymers, star copolymers, and the hyperbranched copolymer. In the past two decades, living / controlled radical polymerization has made significant progress, has found a stable nitroxide radical polymerization (NMP), atom transfer radical polymerization (ATRP) and reversible addition - fragmentation chain transfer (RAFT ) polymerization. These polymerization methods have been widely used for preparing a specific molecular weight, narrow molecular weight distribution, and the precise structure of a variety of different polymers. Although these methods have been used successfully fluorinated styrene, fluorinated side chain fluorinated acrylate monomers, but on a fluoroolefin (such as chlorotrifluoroethylene, hexafluoropropylene, etc.) of the active / controlled polymerization studies reported is very small. In this paper, we synthesized a variety of ATRP initiator and RAFT chain transfer agent, respectively, exploration and research of hexafluoropropylene and chlorotrifluoroethylene monomer living / controlled radical polymerization, and received some very meaningful experimental results. I. The synthesis of a xanthate as RAFT chain transfer agent, and chlorotrifluoroethylene and vinyl ether used in the RAFT polymerization. Polymerization at 70oC temperature. After NMR and gel permeation chromatography of the polymer structure, molecular weight and molecular weight distribution characterization, indicating that the polymerization reaction of the active / controllable. At the same time as the macromolecules of the polymer RAFT chain transfer agent, chain extender and hydrolysis by success was obtained an amphipathic fluorinated polymer. II. Xanthates with the same kind of RAFT chain transfer agent in the successful implementation of 75oC and chlorotrifluoroethylene RAFT polymerization of vinyl acetate. After NMR and gel permeation chromatography of the polymer structure, molecular weight and molecular weight distribution characterization, indicating that the polymerization reaction of the active / controllable. III. Polyphenylene ether was synthesized in a macromolecular chain transfer agent for the hexafluoropropylene and reversible addition - fragmentation chain transfer (RAFT) polymerization; 3,5 - dibromo was synthesized from 3,5-toluene - dibromo bromide such halogenated initiator, and for hexafluoropropylene atom transfer radical polymerization (ATRP), and the products were confirmed by 1H NMR analysis. IV. Cuprous bromide and 2,2 - bipyridine complex as catalyst, the successful implementation of hexafluoropropylene at room temperature dimerization.
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