JP6731074B2 - 自己加湿性イオン交換複合膜およびその製造方法 - Google Patents
自己加湿性イオン交換複合膜およびその製造方法 Download PDFInfo
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Description
前記多孔性高分子支持体は電気紡糸膜または不織布であることを特徴とする。
前記疎水性薄膜コーティング層は、−CF2−、−CF3またはこれらの組合せである疎水性作用基を含むことを特徴とする。
Ar1は置換もしくは非置換の4価の炭素数6〜24のアリレン基および置換もしくは非置換の4価の炭素数4〜24の複素環基から選択される芳香族環基であり、
前記芳香族環基は、
単独で存在する;
2個以上が互いに縮合環を形成する;
2個以上が単一結合、O、S、CO、SO2、Si(CH3)2、(CH2)p(1≦P≦10)、(CF2)q(1≦q≦10)、C(CH3)2、C(CF3)2またはCO−NHで連結されており、
Ar2は置換もしくは非置換の2価の炭素数6〜24のアリレン基および置換もしくは非置換の2価の炭素数4〜24の複素環基から選択される芳香族環基であり、
前記芳香族環基は、
単独で存在する;
2個以上が互いに縮合環を形成する;
2個以上が単一結合、O、S、CO、SO2、Si(CH3)2、(CH2)p(1≦P≦10)、(CF2)q(1≦q≦10)、C(CH3)2、C(CF3)2またはCO−NHで連結されており、Qは単一結合;O、S、CO、SO2、Si(CH3)2、(CH2)p(1≦P≦10)、(CF2)q(1≦q≦10)、C(CH3)2、C(CF3)2、CO−NH、C(CH3)(CF3)、または置換もしくは非置換のフェニレン基であり、
x、yはそれぞれ繰り返し単位内のモル分率で、0.1≦x≦0.9、0.1≦y≦0.9、x+y=1である。)
X7、X8、X9、X10、X12、X13、X14、X15、X16、X17、X18、X19、X20、X21、X22、X24、X25、X26、X27、X28、X29、X30、X31、X32、X33、X34、X35、X36、X37、X39、X40、X41およびX42は互いに同じでも異なっていてもよく、スルフィド(S)、エーテル(O)またはスルホン(SO2)であり、X11、X23、X38はスルホン(SO2)であり、
T1、T2、T3、T4、T5、T6、T7、T8、T12、T13、T14、T15、T16、T17、T18、T19、T20、T21、T22、T23、T24、T25、T26、T27、T31、T32、T33、T34、T35、T36、T37、T38、T39、T40、T41、T42、T43、T44、T45、T46、T50、T51、T52、T53、T54、T55、T56およびT57は互いに同じでも異なっていてもよく、フルオロ(F)、ニトリル基(CN)またはスルホン酸基(SO3H)であり、
T9、T10、T28、T29、T48およびT49スルホン酸基(SO3H)であり、
T11、T30およびT47はニトリル基(CN)であり、
k1、k3、およびk5は互いに同じでも異なっていてもよく(親水性部分)、0.4〜0.6の範囲に含まれ、
k2、k4、およびk6はそれぞれ1−k1、1−k3、および1−k5であり(疎水性部分)、互いに同じでも異なっていてもよく、0.6〜0.4の範囲に含まれる。)
以下、本発明による実施例を添付図面に基づいて具体的に説明する。
下記の[化Ia]で表示されるスルホン化ポリアリレンエーテルスルホンを公知の方法で合成した。
多孔性高分子支持体として商業化したポリエチレンテレフタレート(PET)不織布を使い、前記PET不織布の表面に実施例1の[化Ia]で表示されるスルホン化ポリアリレンエーテルスルホン(BPSH60)イオン交換膜を形成し(PET RCM)、前記イオン交換膜(PET RCM)に対して実施例1と同じ条件の下で常圧プラズマ処理を20回繰り返し行うことによって目的物である自己加湿性イオン交換複合膜(P−PET RCM R20)を製造した。
Claims (12)
- a)下記の[化2]で表示される繰り返し単位を有する架橋構造のポリアリレンエーテルスルホン共重合体からなる多孔性高分子支持体;
b)前記支持体の表面に形成された芳香族炭化水素系高分子イオン交換膜;および
c)前記イオン交換膜の表面にナノクラックのモーフォロジーパターンを有する疎水性薄膜コーティング層;を含む、自己加湿性イオン交換複合膜。
- 前記多孔性高分子支持体は電気紡糸膜または不織布であることを特徴とする、請求項1に記載の自己加湿性イオン交換複合膜。
- 前記芳香族炭化水素系高分子は、ポリベンズイミダゾール系、ポリベンゾオキサゾール系、ポリイミド系、ポリエーテルイミド系、ポリフェニレンスルフィド系、ポリスルホン系、ポリエーテルスルホン系、ポリエーテルケトン系、ポリエーテルエーテルケトン系、ポリフェニルキノキサリン系、およびこれらの共重合体、ならびにこれらの組合せからなる群から選択されることを特徴とする、請求項1に記載の自己加湿性イオン交換複合膜。
- 前記芳香族炭化水素系高分子イオン交換膜は下記の[化3]で表現される第1繰り返し単位および下記[化4]で表現される第2繰り返し単位を含む芳香族炭化水素系高分子と;
下記の[化5]、[化6]または[化7]で表現される芳香族炭化水素系高分子と;のうち一方または両方を含むことを特徴とする、請求項1に記載の自己加湿性イオン交換複合膜。
T1、T2、T3、T4、T5、T6、T7、T8、T12、T13、T14、T15、T16、T17、T18、T19、T20、T21、T22、T23、T24、T25、T26、T27、T31、T32、T33、T34、T35、T36、T37、T38、T39、T40、T41、T42、T43、T44、T45、T46、T50、T51、T52、T53、T54、T55、T56およびT57は互いに同じでも異なっていてもよく、フルオロ(F)、ニトリル基(CN)またはスルホン酸基(SO3H)であり、
T9、T10、T28、T29、T48およびT49スルホン酸基(SO3H)であり、
T11、T30およびT47はニトリル基(CN)であり、
k1、k3、およびk5は互いに同じでも異なっていてもよく(親水性部分)、0.4〜0.6の範囲に含まれ、
k2、k4、およびk6はそれぞれ1−k1、1−k3、および1−k5であり(疎水性部分)、互いに同じでも異なっていてもよく、0.6〜0.4の範囲に含まれる。)
- 前記疎水性薄膜コーティング層は、−CF2−、−CF3またはこれらの組合せである疎水性作用基を含むことを特徴とする、請求項1に記載の自己加湿性イオン交換複合膜。
- 前記疎水性薄膜コーティング層は、厚さが10〜1000nmであることを特徴とする、請求項1に記載の自己加湿性イオン交換複合膜。
- I)下記の[化2]で表示される繰り返し単位を有する架橋構造のポリアリレンエーテルスルホン共重合体からなる多孔性高分子支持体を得る段階;
II)前記支持体の表面に芳香族炭化水素系高分子をコートしてイオン交換膜を形成する段階;および
III)前記イオン交換膜を常圧プラズマで3〜40回繰り返し処理する段階;を含む、自己加湿性イオン交換複合膜の製造方法。
- 前記コーティングは、多孔性高分子支持体を芳香族炭化水素系高分子溶液に浸漬することを特徴とする、請求項7に記載の自己加湿性イオン交換複合膜の製造方法。
- 前記常圧プラズマ処理工程は、アルゴンガス、窒素ガス、酸素ガス、ヘリウムガスおよびこれらの組合せから選択される第1ガス;および炭化水素ガス、フッ化炭素ガスおよびこれらの組合せから選択される第2ガスを吹き入れながら行うことを特徴とする、請求項7に記載の自己加湿性イオン交換複合膜の製造方法。
- 前記炭化水素ガスはCH4ガスまたはC2H2ガスであることを特徴とする、請求項9に記載の自己加湿性イオン交換複合膜の製造方法。
- 前記フッ化炭素ガスは、C4F8ガス、CF4ガスまたはこれらの組合せであることを特徴とする、請求項9に記載の自己加湿性イオン交換複合膜の製造方法。
- 請求項1〜6のいずれか一項に記載の自己加湿性イオン交換複合膜を含む、燃料電池。
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