Trifluorovinyl aryl ether (TFVE) functionalized silicotungstic acid has been copolymerized with other TFVE monomers, resulting in a water stable film. Polymerization occurs via thermally induced cyclo-polymerization, forming perfluorocyclobutyl groups. Perfluorocyclobutyl polymers have been shown to have several properties that are ideal for high temperature fuel cell operation including high Tg, high dielectric constant, and chemical stability [1]. Silicotungstic acid, an inorganic super acid, is able to retain tightly bound water and conduct protons above 100 °C [2]. Both the acid functional group and the backbone of this novel polymer are suitable for high temperature and low humidity proton exchange membrane fuel cell (PEMFC) operation. The disappearance of the IR peak at 1833 cm-1 and appearance at 961 cm-1 are indicative of depletion TFVE groups and the formation of perfluorocyclobutyl groups, respectively [3]. 19F NMR has also been used to confirm polymerization has occurred, by disappearance of peaks at -120, -127, and -134 ppm, corresponding to the three fluorines of the TFVE group [4]. Preliminary proton conductivity over 0.40 S/cm at 80 C and 95% RH has been achieved with an unoptimized membrane. [1] Babb, D. A.; Snelgrove, R. V.; Smith, D. W.; Mudrich, S. F., Novel Step-Growth Polymers from the Thermal [2π + 2π] Cyclopolymerization of Aryl Trifluorovinyl Ether Monomers. 1996, 624, 431-441. [2] Horan, J. L.; Lingutla, A.; Ren, H.; Kuo, M. C.; Sachdeva, S.; Yang, Y.; Seifert, S.; Greenlee, L. F.; Yandrasits, M. A.; Hamrock, S. J.; Frey, M. H.; Herring, A. M., Fast Proton Conduction Facilitated by Minimum Water in a Series of Divinylsilyl-11-silicotungstic. Acid-co-Butyl Acrylate-co-Hexanediol Diacrylate Polymers. Journal of Physical Chemistry C 2014, 118, 135-144. [3] Smith, D. W.; Babb, D. A., Perfluorocyclobutane aromatic polyethers. Synthesis and characterization of new siloxane-containing fluoropolymers. Macromolecules 1996, 29, 852-860. [4] Spraul, B. K.; Suresh, S.; Jin, J.; Smith, D. W., Jr., Synthesis and electronic factors in thermal cyclodimerization of functionalized aromatic trifluorovinyl ethers. J Am Chem Soc 2006, 128, 7055-64.

Synthesis and characterization of water stable, silicotungstic acid functionalized perfluorocyclobutyl polymer electrolyte

249th National Meeting (2015)

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