Preparation and characterization of chemically stable polymer electrolyte membranes by radiation-induced graft copolymerization of four monomers into ETFE films

放射線グラフト重合による四元系グラフト電解質膜の合成と特性

Chen, J.; 浅野 雅春; 八巻 徹也; 吉田 勝

Chen, J.; Asano, Masaharu; Yamaki, Tetsuya; Yoshida, Masaru

高性能の電解質膜を得るために、スチレンに代わるモノマーとして、スチレンの誘導体であるメチルスチレン(MeSt)及びt-ブチルスチレン(tBuSt)さらに架橋剤として、電解質膜に導入した時に柔軟性の付与が期待できるビスビニルフェニルエタン(BVPE)と高密度の架橋構造の付与が期待できるジビニルベンゼン(DVB)を組合せた新規な電解質膜を放射線グラフト重合法により合成した。得られた四元系MeSt/tBuSt/DVB/BVPE(40/40/2.5/17.5wt%)電解質膜の耐久性加速試験(60C,3%過酸化水素水溶液中)の結果、スルホン酸基の脱離時間が300時間に達した。また、メタノール透過性ではナフィオンに比べて、四元系電解質膜は1/6まで抑制できることがわかった。

To develop a highly chemically stable polymer electrolyte membrane for application in a direct methanol fuel cell (DMFC), four styrene derivative monomers, m,p-methylstyrene (MeSt), p-tert-butylstyrene (tBuSt), divinylbenzene (DVB) and bis(p,p-vinyl phenyl) ethane (BVPE) were graft copolymerized into poly(ethylene-co-tetrafluoroethylene) (ETFE) films followed by sulfonation and hydrolysis. The latter two monomers were used as crosslinkers. The graft copolymerization was carried out by the -ray preirradiation method. The influence of the preirradiation dose and the grafting kinetics were investigated in detail. Sulfonation of the grafted ETFE films was performed in a chlorosulfonic acid solution, by which the sulfonation ratio reached about 90%. The newly obtained membrane possesses significantly higher chemical stability than the traditional styrene/DVB-grafted membrane and six times lower methanol permeability compared to the Nafion 112 membrane. Therefore, this study reveals the possibility of the developed inexpensive four monomers-grafted membranes, which could provide an attractive alternative as a substitute for the expensive Nafion membranes for DMFC applications.