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Effect of crosslinkers on the preparation and properties of ETFE-based radiation-grafted polymer electrolyte membranes

放射線グラフト法によるETFE基材とした電解質膜の合成と特性に及ぼす架橋剤の効果

Chen, J.; 浅野 雅春; 八巻 徹也; 吉田 勝

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

スチレンの誘導体であるメチルスチレン(MeSt)の$$gamma$$線グラフト重合反応及び得られた膜の特性に及ぼす架橋剤の影響について検討した。架橋剤として、ジビニルベンゼン(DVB),ビスビニルフェニルエタン(BVPE),トリアリルシアヌレート(TAC)を用いた。グラフト重合反応性は、DVBの場合、3%までグラフト率の急激な上昇が見られたが、その後濃度が高くなるに従い、急激に低下した。また、BVPEでは、40%までグラフト率の上昇が確認できた。TACの場合、グラフト率は40%まで変化しなかった。得られた架橋剤導入電解質膜の耐酸化性試験の結果、スルホン酸基の脱離は架橋剤の導入により、抑制されることがわかった。その抑制効果は、架橋剤の種類により異なり、TAC, BVPE, DVBの順に大きくなった。

This study concerns a comparative study of three crosslinkers, divinylbenzene (DVB), 1,2-bis(p,p-vinylphenyl)ethane (BVPE) and triallyl cyanurate (TAC) crosslinked poly(ethylene-co-tetrafluoroethylene) (ETFE)-based radiation-grafted membranes, which were prepared by radiation grafting of p-methylstyrene (MeSt) onto ETFE films and subsequent sulfonation. The effect of the different types and contents of the crosslinkers on the grafting and sulfonation, and the properties such as water uptake, proton conductivity and thermal/chemical stability of the resulting polymer electrolyte membranes was investigated in detail. Introducing crosslink structure into the radiation-grafted membranes leads to a decrease in proton conductivity due to the decrease in water uptake. The thermal stability of the crosslinked radiation-grafted membranes is also somewhat lower than that of the noncrosslinked one. However, the crosslinked radiation-grafted membranes show significantly higher chemical stability characterized in the 3% H$$_{2}$$O$$_{2}$$ at 50$$^{circ}$$C. Among the three crosslinkers, the DVB shows a most pronounced efficiency on the crosslinking of the radiation-grafted membranes, while the TAC has no significant influence; the BVPE is a mild and effective crosslinker, showing the moderate influence between the DVB and TAC crosslinkers.

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パーセンタイル:77.46

分野:Polymer Science

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