JP4194843B2 - プロトン伝導性高分子膜およびその製造方法 - Google Patents
プロトン伝導性高分子膜およびその製造方法 Download PDFInfo
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- JP4194843B2 JP4194843B2 JP2002563241A JP2002563241A JP4194843B2 JP 4194843 B2 JP4194843 B2 JP 4194843B2 JP 2002563241 A JP2002563241 A JP 2002563241A JP 2002563241 A JP2002563241 A JP 2002563241A JP 4194843 B2 JP4194843 B2 JP 4194843B2
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- polymer membrane
- proton
- conductive polymer
- membrane
- proton conductive
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- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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Description
芳香族単位の一部分にプロトン伝導性置換基を有する下記一般式(1)で表わされる繰り返し単位を構成成分とし、メタノールに対する室温での溶解度が0.01重量%未満およ びN−メチル−2−ピロリドンに対する5℃での溶解度が5重量%未満である高分子化合物からなるプロトン伝導性高分子膜に関する。
B.3官能フェニル単位(この場合、残った結合手の1つはスルフィド単位を介して他の高分子鎖と結合し、架橋分子構造をとる)、
C.前記B以外の架橋あるいは分岐単位(この場合、スルフィド単位以外の単位を介して他の高分子鎖と結合し、架橋分子構造をとる)。
さらには、一般式(1)において、Ar1が、式(2)〜(4)で表わされる2価の芳香族単位のいずれかであり、xが0で表わされる繰り返し単位を構成成分とする高分子化合物からなる高分子フィルムを、スルホン化剤と接触させることにより行なわれる。
(II):前記(I)記載の工程で得られた高分子化合物と可塑剤の混合物を高分子フィルム化する工程、
(III):前記(II)記載の工程で得られた高分子フィルムにプロトン伝導性置換基を導入する工程。
(式中、Ar1は2価の芳香族単位、xは0〜2の整数)
試験体を塩化ナトリウム飽和水溶液に浸漬し、ウォーターバス中で60℃、3時間反応させる。室温まで冷却したのち、サンプルをイオン交換水で充分に洗浄し、フェノールフタレイン溶液を指示薬として0.01N水酸化ナトリウム水溶液で滴定し、イオン交換容量を算出する。
イオン交換水中に保管した試験体(10mm×40mm)を取り出し、試験体表面の水を濾紙で拭き取る。電極間距離30mmで白金電極間に試験体を装着し、2極非密閉系のテフロン製セルに設置したのち、室温下で電圧0.2Vの条件で、交流インピーダンス法(周波数:42Hz〜5MHz)により、試験体の膜抵抗を測定し、プロトン伝導度を算出する。
島津製作所製FTIR8100を使用して、KBr錠剤試料を作製し、赤外吸収スペクトルを測定した。
室温(約25℃)の雰囲気下で、スクリュー管に所定試料を秤量し、試料濃度が0.01重量%になるようにメタノールを投入し、スターラーで攪拌した。溶解度は目視観察により、判断した。
5℃の雰囲気下で、スクリュー管に所定試料を秤量し、試料濃度が5重量%になるようにN−メチル−2−ピロリドンを投入し、スターラーで攪拌した。溶解度は目視観察により、判断した。
JIS K 7127の方法に準じて、所定試料の引張強度および破断伸びを測定した。
XPS分析装置(ファイ社製、Quantum2000)を用いて、X線強度 AIK
α/15kV・12.5W、X線ビーム径 100μmφ、パルスエネルギー 187.85eV(ワイド)・23.50eV(ナロー)の分析条件により、主鎖中のS種ピーク割合(Area%)を求めた。
ポリフェニレンサルファイドからなる高分子フィルム(商品名:トレリナ、東レ株式会社製、膜厚50μm)を使用した。
クロロスルホン酸量を0.232g、前記高分子フィルム量を0.1077gとした以外は、実施例1と同様にしてスルホン化ポリフェニレンサルファイドである本発明のプロトン伝導性高分子膜を得た(クロロスルホン酸量は、ポリフェニレンサルファイドの芳香族単位に対して2当量)。
高分子フィルムとして、シンジオタクチックポリスチレンフィルム(商品名:ザレック、出光石油化学株式会社製、膜厚:50μm)を使用した。
前記高分子フィルムとして、ポリエーテルエーテルケトンフィルム(商品名:スミライトFS−1100C、住友ベークライト株式会社製、膜厚:50μm)を使用した。
固体高分子形燃料電池用プロトン伝導性高分子膜として、パーフルオロカーボンスルホン酸膜(商品名:ナフィオン117、デュポン株式会社製、膜厚:175μm)を使用した。この膜のイオン交換容量は0.94ミリ当量/g、プロトン伝導度は9.5×10-2S/cmであった。評価結果を表1にまとめて示す。
実施例1同様のポリフェニレンサルファイドフィルム(商品名:トレリナ、東レ株式会社製、膜厚:50μm)を使用した。
実施例3で得られた前記スルホン化ポリフェニレンサルファイド膜に、加速電圧4.6MeV、照射線量60kGyの電子線を照射した。前記スルホン化ポリフェニレンサルファイド膜の特性を評価した。
電子線の照射線量を100kGyとした以外は、実施例4と同様にした。得られたスルホン化ポリフェニレンサルファイド膜は、膜形状を維持しており、この膜のイオン交換容量は1.45ミリ当量/g、室温でのプロトン伝導度は5.3×10-2S/cmであった。評価結果を表2にまとめて示す。
電子線の照射線量を300kGyとした以外は、実施例4と同様にした。得られたスルホン化ポリフェニレンサルファイド膜は、膜形状を維持しており、この膜のイオン交換容量は1.49ミリ当量/g、室温でのプロトン伝導度は5.2×10-2S/cmであった。前記評価結果を表2にまとめて示す。
電子線の照射線量を500kGyとした以外は、実施例4と同様にした。得られたスルホン化ポリフェニレンサルファイド膜は、膜形状を維持しており、この膜のイオン交換容量は1.57ミリ当量/g、室温でのプロトン伝導度は7.5×10-2S/cmであった。前記評価結果を表2にまとめて示す。
500mLのセパラブルフラスコ中で、15gの1,4−ポリフェニレンサルファイド(アルドリッチ製試薬、重量平均分子量:10000)を300mLのクロロスルホン酸に溶解させた。氷冷して、反応温度5℃で60分攪拌した。ついで、反応液を20℃にして、発煙硫酸(15%SO3)を100mLを滴下し、300分攪拌した。2kgの氷と600mLの硫酸(30重量%)の混合物中に、前記反応液を攪拌しながら添加した。沈殿物を煮沸したイオン交換水中で洗浄し、沈殿物をろ過により回収した。80℃で3時間乾燥し、スルホン酸基が導入されたポリフェニレンサルファイド(以下、スルホン化ポリフェニレンサルファイド)を得た。
高分子化合物として、ポリフェニレンサルファイド(商品名:DIC PPS FZ−2200−A5、大日本インキ化学工業株式会社製、以下PPSと表記)を使用した。また、可塑剤として、トリクレジルホスフェート(商品名:TCP、大八化学工業株式会社製、以下TCPと表記)を使用した。
TCPの添加量を10重量部とした以外は、実施例8と同様にした。得られたプロトン伝導性高分子膜は、膜形状を維持しており、この膜のイオン交換容量は1.70ミリ当量/g、室温でのプロトン伝導度は9.1×10-2S/cmであった。評価結果を表3、4に示す。
TCPの添加量を20重量部とした以外は、実施例8と同様にした。
TCPの添加量を30重量部とした以外は、実施例8と同様にした。得られたプロトン伝導性高分子膜は、膜形状を維持しており、この膜のイオン交換容量は1.56ミリ当量/g、室温でのプロトン伝導度は7.8×10-2S/cmであった。評価結果を表3、4に示す。
TCPの添加量を50重量部とした以外は、実施例8と同様にした。得られたプロトン伝導性高分子膜は、膜形状を維持しており、この膜のイオン交換容量は1.65ミリ当量/g、室温でのプロトン伝導度は8.2×10-2S/cmであった。評価結果を表3、4に示す。
TCPを添加しなかった以外は、実施例8と同様にした。
プロトン伝導性高分子膜として、デュポン社製ナフィオン115を使用した以外は、実施例8と同様にした。
実施例1と同様のポリフェニレンサルファイドからなる高分子フィルムを使用した。
つぎに、実施例14〜21で得られたスルホン化ポリフェニレンサルファイド膜に、加速電圧4.6MeV、照射線量500kGy、電流20mAの電子線を照射し、前記スルホン化ポリフェニレンサルファイド膜の特性を評価した。電子線を照射したのちのスルホン化ポリフェニレンサルファイド膜の膜特性と浸漬時間の関係を表6に示す。
高分子化合物として、ポリフェニレンサルファイド(商品名:FZ−2200−A5、大日本インキ化学工業株式会社製、以下PPSと表記)を使用した。また、可塑剤として、トリクレジルホスフェート(商品名:TCP、大八化学工業株式会社製、以下TCPと表記)を使用した。
Claims (20)
- さらに、可塑剤を含む前記高分子化合物からなる請求項1記載のプロトン伝導性高分子膜。
- 前記可塑剤が、リン酸エステル系化合物である請求項2記載のプロトン伝導性高分子膜。
- 前記リン酸エステル系化合物が、トリフェニルホスフェートおよびトリクレジルホスフェートからなる群から選択される少なくとも1種である請求項3記載のプロトン伝導性高分子膜。
- 前記一般式(1)において、Ar1が、前記式(2)〜(4)で表わされる2価の芳香族単位のいずれかであり、xが0である請求項1記載のプロトン伝導性高分子膜。
- 繰り返し単位の総量を基準にして、高分子化合物のスルフィド単位のうち、スルホキシドまたはスルホンに酸化されている量が、0〜10モル%である請求項1記載のプロトン伝導性高分子膜。
- γ線、電子線およびイオンビームからなる群から選択される少なくとも1種の放射線を照射した請求項1記載のプロトン伝導性高分子膜。
- 前記放射線の照射線量が、10〜1000kGyである請求項1記載のプロトン伝導性高分子膜。
- イオン交換容量が、0.5〜8ミリ当量/gである請求項1記載のプロトン伝導性高分子膜。
- 室温におけるプロトン伝導度が、1.0×10-2S/cm以上である請求項1記載のプロトン伝導性高分子膜。
- 前記プロトン伝導性高分子膜の厚みが、5〜200μmである請求項1記載のプロトン伝導性高分子膜。
- 請求項1記載のプロトン伝導性高分子膜からなる燃料電池用膜。
- 請求項1記載のプロトン伝導性高分子膜を用いた固体高分子形燃料電池。
- 前記スルホン化剤が、クロロスルホン酸、三酸化硫黄−トリエチルホスフェート、濃硫酸、発煙硫酸、トリメチルシリルクロロサルフェートからなる群から選択される少なくとも1種である請求項15記載のプロトン伝導性高分子膜の製造方法。
- 前記スルホン化剤の量が、高分子化合物の芳香族単位に対して、0.5〜10当量の範囲であることを特徴とする請求項15記載のプロトン伝導性高分子膜の製造方法。
- 前記スルホン化剤を溶媒存在下で高分子膜と接触させることを特徴とする請求項15記載のプロトン伝導性高分子膜の製造方法。
- 前記スルホン化剤および溶媒からなる混合溶液中のスルホン化剤の濃度が、0.1〜10重量%であることを特徴とする請求項15記載のプロトン伝導性高分子膜の製造方法。
- 前記溶媒が、1,1,2,2−テトラクロロエタン、1,1,1,2−テトラクロロエタン、1,1,1−トリクロロエタン、1,2−ジクロロエタン、トリクロロエチレン、テトラクロロエチレン、ジクロロメタンおよびクロロホルムから選択された少なくとも1種であることを特徴とする請求項15記載のプロトン伝導性高分子膜の製造方法。
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JP2001234606 | 2001-08-02 | ||
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JP2001328596 | 2001-10-26 | ||
JP2001328596 | 2001-10-26 | ||
PCT/JP2002/000875 WO2002062896A1 (fr) | 2001-02-05 | 2002-02-04 | Film polymere conducteur protonique et son procede de production |
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EP (1) | EP1380619A4 (ja) |
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KR (1) | KR20030072619A (ja) |
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JP4794170B2 (ja) * | 2002-09-20 | 2011-10-19 | 株式会社カネカ | プロトン伝導性高分子膜、それを用いた膜−電極接合体およびこれらを用いた燃料電池 |
CN1711612B (zh) * | 2002-11-18 | 2010-05-26 | 索尼株式会社 | 质子导体、单离子导体、其制造方法、及电解质电容器 |
WO2004102717A1 (ja) * | 2003-05-16 | 2004-11-25 | Gs Yuasa Corporation | 液体燃料形燃料電池とその燃料 |
US20070148518A1 (en) * | 2003-12-25 | 2007-06-28 | Sumitomo Chemical Company, Limited | Polymer electrolyte and use thereof |
JP2005203195A (ja) * | 2004-01-14 | 2005-07-28 | Hitachi Cable Ltd | 燃料電池用電解質膜及びその製造方法、燃料電池及びその製造方法、固体高分子膜電極アセンブリ |
JP4959924B2 (ja) * | 2004-03-16 | 2012-06-27 | 株式会社カネカ | プロトン伝導性高分子膜およびその製造方法並びにそれを使用した固体高分子形燃料電池 |
US7601449B2 (en) * | 2005-02-08 | 2009-10-13 | Gm Global Technology Operations, Inc. | Sulfonated poly(phenylene sulfide) films as polyelectrolyte membranes |
US8178224B2 (en) | 2005-02-08 | 2012-05-15 | GM Global Technology Operations LLC | Sulfonated polyelectrolyte membranes containing perfluorosulfonate ionomers |
DE102005010411A1 (de) * | 2005-03-07 | 2006-09-14 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Sulfonierte Poly(arylene) als hydrolytisch und thermo-oxidativ stabile Polymere |
FR2883292B1 (fr) * | 2005-03-16 | 2008-01-04 | Inst Nat Polytech Grenoble | Extrusion de polymeres ioniques a groupements ioniques acides |
FR2883293B1 (fr) | 2005-03-16 | 2007-05-25 | Inst Nat Polytech Grenoble | Extrusion de polymeres ioniques a groupements ioniques alcalins |
US7455722B2 (en) * | 2005-07-26 | 2008-11-25 | Honda Motor Co., Ltd | Ion irradiated electrolyte membrane, anode, and/or cathode |
FR2893624B1 (fr) * | 2005-11-22 | 2010-05-21 | Inst Nat Polytech Grenoble | Preparation de films constitues par un polymere ayant des groupes ioniques |
JP5225976B2 (ja) * | 2007-03-15 | 2013-07-03 | 三菱樹脂株式会社 | 熱収縮性部材に用いる樹脂組成物、該樹脂組成物からなる熱収縮性チューブ、及び該チューブで被覆された部材 |
JP5484477B2 (ja) * | 2008-10-24 | 2014-05-07 | ナノシス・インク. | 界面層を有する膜電極複合体 |
WO2010048407A1 (en) | 2008-10-24 | 2010-04-29 | Nanosys, Inc. | Electrochemical catalysts for fuel cells |
US20150021180A1 (en) * | 2012-08-01 | 2015-01-22 | National Institute For Materials Science | Highly proton-conductive polymer film, method for producing same, and humidity sensor |
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US4110265A (en) * | 1977-03-01 | 1978-08-29 | Ionics Inc. | Ion exchange membranes based upon polyphenylene sulfide |
GB8331195D0 (en) * | 1983-11-23 | 1983-12-29 | Ici Plc | Membranes |
JPS60255110A (ja) * | 1984-05-30 | 1985-12-16 | Nitto Electric Ind Co Ltd | スルホン化ポリスルホン半透膜及びその製造方法 |
JPH06211992A (ja) * | 1993-01-16 | 1994-08-02 | Sumitomo Electric Ind Ltd | 架橋ポリフェニレンスルフィド樹脂成形物及びその製造方法 |
WO1997005191A1 (de) * | 1995-07-27 | 1997-02-13 | Hoechst Research & Technology Deutschland Gmbh & Co. Kg | Polymerelektrolyte und verfahren zu deren herstellung |
JP3861367B2 (ja) * | 1996-04-18 | 2006-12-20 | 住友化学株式会社 | 高分子電解質、その製造方法およびそれを使用してなる燃料電池 |
JPH10239523A (ja) * | 1997-02-26 | 1998-09-11 | Sekisui Chem Co Ltd | 位相差フィルムの製造方法 |
CA2300934C (en) * | 1997-08-29 | 2008-08-26 | Foster-Miller, Inc. | Composite solid polymer electrolyte membranes |
JP4337175B2 (ja) * | 1998-07-06 | 2009-09-30 | 東レ株式会社 | 高分子電解質およびイオン交換体 |
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JPWO2002062896A1 (ja) | 2004-06-10 |
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