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Preparation of polymer electrolyte membranes consisting of alkyl sulfonic acid for a fuel cell using radiation grafting and subsequent substitution/elimination reactions

グラフト重合と置換/脱離反応を利用したアルキルスルホン酸を有する高分子電解質膜の合成

高橋 周一*; 小此木 裕行*; 萩原 時男*; 前川 康成

Takahashi, Shuichi*; Okonogi, Hiroyuki*; Hagiwara, Tokio*; Maekawa, Yasunari

燃料電池用電解質膜の高温作動時の耐久性向上を目的に、アルキルスルホン酸をグラフト鎖に有する電解質膜の合成を試みた。ETFEにアクリル酸メチル(MA)をグラフト重合後、クロロスルホン酸とジオキサンの当量錯体で処理することで、副反応なしにスルホン化が進行し、低含水率で高いイオン伝導性を示す電解質膜が合成できた。得られた電解質膜の重量及び滴定法による定量分析より、スルホン化と同時に脱カルボン酸も起こる置換/脱離反応が進行し、アルキルスルホン酸30%とアルキルカルボン酸70%の共重合グラフト鎖を有するグラフト型電解質膜であることが確認できた。

Polymer electrolyte membranes (PEM) consisting of alkylsulfonic acid were successfully synthesized by radiation-induced graft polymerization of methyl acrylate (MA) into a poly(ethylene-co-tetrafluoroethylene) (ETFE) film, followed by sulfonation at an $$alpha$$-carbonyl carbon of the MA units in the grafting chain using an equimolar complex of chlorosulfonic acid and dioxane (ClSO$$_{3}$$H-Complex). The ion exchange capacity and ion conductivity of the MA-grafted PEM were controlled in the respective ranges of 0.54-1.47 mmol/g and 0.014-0.14 S/cm by changing the grafting degree. It has been confirmed by titrimetric and gravimetric analyses of sulfonic and carboxylic acids in the film that the sulfonation reaction is accompanied with decarboxylation of the MA units equimolar to the substituted sulfonic acids (substitution of carboxylic acid with sulfonic acid), that the sulfonation degree was about 30%.

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パーセンタイル:72.11

分野:Engineering, Chemical

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