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Study on the synthesis of perfluorovinyl‐sulfonic functional monomer and its copolymerization with tetrafluoroethylene

机译:Study on the synthesis of perfluorovinyl‐sulfonic functional monomer and its copolymerization with tetrafluoroethylene

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AbstractTetrafiuoroethylene (TFE) and hexafluoropropylene (HFP) were subjected to reactions with freshly distilled sulfur trioxide to obtain 1‐fluorosulfonyldifluoro‐acetylfluoride (FSDFAF, yield 65–70) and pentafluoro‐2‐propenylfluorosulfate (PPFS, yield up to 50). A subsequent reaction of FSDFAF with PPFS under anhydrous conditions led to a preparation of 2‐(1‐pentafluoro‐2‐propenyloxy)tetrafluoroethanesulfonyl fluoride (PPOTESF, yield 40–41) whose structure was proved by both infrared (IR) spectroscopy and nuclear magnetic resonance (19F NMR). TFE was copolymerized with PPOTESF in bulk by using a free radical initiator of the hydrocarbon type at a temperature of 50°C. Various TFE/PPOTESF mole ratios were employed and the presence of sulfonyl fluoride (SO2F) functional groups in the copolymers was proven by IR spectroscopy. The copolymers were subjected to alkaline hydrolysis and the SO2F content was found not to exceed 0.70–0.80 mEq/g with polymer yields in the range of 11–31. The reactivity ratiosr1andr2related to TFE and PPOTESF, respectively, were determined by using the Fineman‐Ross method. A random distribution of PPOTESF units along the polymeric chain, consisting mainly of TFE fragments, was found to exist. The copolymers had melting temperatures 40–45°C lower than polytetrafluoroethylene and were thermally stable to 305

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