JP2004152776A - Solid polymer electrolyte, membrane electrode junction, and fuel cell - Google Patents

Solid polymer electrolyte, membrane electrode junction, and fuel cell Download PDF

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JP2004152776A
JP2004152776A JP2003422934A JP2003422934A JP2004152776A JP 2004152776 A JP2004152776 A JP 2004152776A JP 2003422934 A JP2003422934 A JP 2003422934A JP 2003422934 A JP2003422934 A JP 2003422934A JP 2004152776 A JP2004152776 A JP 2004152776A
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Toru Koyama
小山　　徹
Toshiyuki Kobayashi
稔幸 小林
Masashi Yamaga
賢史 山賀
Yuichi Kamo
友一 加茂
Kazuhisa Higashiyama
和寿 東山
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Hitachi Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a low cost and highly durable solid electrolyte having a deterioration resistance as same as or higher than that of fluoride solid polymer electrolytes, or sufficient for practical use. <P>SOLUTION: The electrolyte comprises a polyether ether sulfone having a sulfo alkyl group shown by general formula : -(CH<SB>2</SB>)n-SO<SB>3</SB>H bonded to the aromatic ring of the polyether ether sulfone. <P>COPYRIGHT: (C)2004,JPO

Description

本発明は燃料電池、水電解、ハロゲン化水素酸電解、食塩電解、酸素濃縮器、湿度センサ、ガスセンサ等に用いられる固体高分子電解質膜、電極触媒被覆溶液、上記膜と電極との接合体および燃料電池に関する。   The present invention is a fuel cell, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrator, humidity sensor, a solid polymer electrolyte membrane used for a gas sensor and the like, an electrode catalyst coating solution, a joined body of the membrane and the electrode and Related to fuel cells.

固体高分子電解質は、高分子鎖中にスルホン酸基等の固体高分子電解質基を有する固体高分子材料であり、特定のイオンと強固に結合したり、陽イオンまたは陰イオンを選択的に透過する性質を有していることから、粒子、繊維、あるいは膜状に成形し、電気透析、拡散透析、電池隔膜等の各種用途に利用されている。   A solid polymer electrolyte is a solid polymer material having a solid polymer electrolyte group such as a sulfonic acid group in the polymer chain, and is firmly bonded to a specific ion or selectively transmits a cation or an anion. Therefore, it is formed into particles, fibers, or membranes, and is used for various applications such as electrodialysis, diffusion dialysis, and battery diaphragm.

改質ガス燃料電池は、プロトン伝導性の固体高分子電解質膜の両面に一対の電極を設け、メタン、メタノール等、低分子の炭化水素を改質することにより得られる水素ガスを燃料ガスとして一方の電極（水素極）へ供給し、酸素ガスあるいは空気を酸化剤として他方の電極（酸素極）へ供給し、起電力を得るものである。また、水電解は、固体高分子電解質膜を用いて水を電気分解することにより水素と酸素を製造するものである。   A reformed gas fuel cell is provided with a pair of electrodes on both surfaces of a proton conductive solid polymer electrolyte membrane, and uses hydrogen gas obtained by reforming low molecular hydrocarbons such as methane and methanol as a fuel gas. To the other electrode (hydrogen electrode) and oxygen gas or air as an oxidant to the other electrode (oxygen electrode) to obtain an electromotive force. Water electrolysis is to produce hydrogen and oxygen by electrolyzing water using a solid polymer electrolyte membrane.

燃料電池や水電解等の固体高分子電解質膜として、ナフィオン（登録商標、デュポン社製）、Ａｃｉｐｌｅｘ（登録商標、旭化成工業株式会社製）、フレミオン（登録商標、旭硝子株式会社製）の商品名で知られる高いプロトン伝導性を有するパーフルオロスルホン酸固体高分子電解質膜に代表されるふっ素系固体高分子電解質膜が、化学的安定性に優れていることから使用されている。   Nafion (registered trademark, manufactured by DuPont), Aciplex (registered trademark, manufactured by Asahi Kasei Kogyo Co., Ltd.), and Flemion (registered trademark, manufactured by Asahi Glass Co., Ltd.) are used as solid polymer electrolyte membranes for fuel cells and water electrolysis. Fluorine-based solid polymer electrolyte membranes typified by known perfluorosulfonic acid solid polymer electrolyte membranes having high proton conductivity have been used because of their excellent chemical stability.

また、食塩電解は、固体高分子電解質膜を用いて塩化ナトリウム水溶液を電気分解することにより、水酸化ナトリウムと、塩素と水素を製造するものである。   Further, in the salt electrolysis, sodium hydroxide, chlorine and hydrogen are produced by electrolyzing an aqueous solution of sodium chloride using a solid polymer electrolyte membrane.

この場合、固体高分子電解質膜は塩素と高温，高濃度の水酸化ナトリウム水溶液に曝されるので、これらに対する耐性の乏しい炭化水素系固体高分子電解質膜を使用することができない。そのため、食塩電解用の固体高分子電解質膜には、一般に、塩素および高温，高濃度の水酸化ナトリウム水溶液に対して耐性があり、さらに、発生するイオンの逆拡散を防ぐために表面に部分的にカルボン酸基を導入したパーフルオロスルホン酸固体高分子電解質膜が用いられている。   In this case, since the solid polymer electrolyte membrane is exposed to chlorine and a high-temperature, high-concentration aqueous sodium hydroxide solution, it is not possible to use a hydrocarbon-based solid polymer electrolyte membrane having poor resistance to these. Therefore, the solid polymer electrolyte membrane for salt electrolysis is generally resistant to chlorine and high-temperature, high-concentration sodium hydroxide aqueous solution, and is partially coated on the surface to prevent back diffusion of generated ions. A perfluorosulfonic acid solid polymer electrolyte membrane into which a carboxylic acid group has been introduced is used.

ところで、パーフルオロスルホン酸固体高分子電解質膜に代表されるふっ素系固体高分子電解質は、Ｃ−Ｆ結合を有しているために化学的安定性が非常に大きく、上述の燃料電池用、水電解用、あるいは、食塩電解用の固体高分子電解質膜の他に、ハロゲン化水素酸電解用の固体高分子電解質膜としても用いられる。さらにはプロトン伝導性を利用して、湿度センサ、ガスセンサ、酸素濃縮器等にも広く応用されている。   By the way, a fluorine-based solid polymer electrolyte represented by a perfluorosulfonic acid solid polymer electrolyte membrane has a very high chemical stability due to having a C—F bond. In addition to the solid polymer electrolyte membrane for electrolysis or salt electrolysis, it is also used as a solid polymer electrolyte membrane for hydrohalic acid electrolysis. Furthermore, it is widely applied to humidity sensors, gas sensors, oxygen concentrators, and the like by utilizing proton conductivity.

しかし、ふっ素系固体高分子電解質は製造が困難で、非常に高価であると云う欠点がある。そのため、ふっ素系固体高分子電解質膜は、宇宙用あるいは軍用の固体高分子型燃料電池等の特殊な用途に用いられ、自動車用の低公害動力源としての固体高分子型燃料電池等の民生用への応用を困難なものとしていた。   However, fluorine-based solid polymer electrolytes have the drawback that they are difficult to produce and very expensive. For this reason, fluorine-based solid polymer electrolyte membranes are used for special applications such as solid polymer fuel cells for space or military use, and for civilian applications such as solid polymer fuel cells as low-pollution power sources for automobiles. It was difficult to apply to

安価な固体高分子電解質膜として特許文献１にはスルホン化ポリエーテルエーテルケトン、特許文献２、特許文献３にはスルホン化ポリエーテルスルホン、特許文献４にはスルホン化ポリエーテルエーテルスルホン、特許文献５にはスルホン化アクリロニトリル・ブタジエン・スチレンポリマ、特許文献６にはスルホン化ポリスルフィッド、特許文献７にはスルホン化ポリフェニレン等の芳香族炭化水素系固体高分子電解質膜が提案されている。   Patent Literature 1 discloses sulfonated polyetheretherketone, Patent Literatures 2 and 3 disclose sulfonated polyethersulfone, Patent Literature 4 discloses sulfonated polyetherethersulfone, and Patent Literature 5 as inexpensive solid polymer electrolyte membranes. Discloses a sulfonated acrylonitrile-butadiene-styrene polymer, Patent Document 6 proposes a sulfonated polysulfide, and Patent Document 7 proposes an aromatic hydrocarbon-based solid polymer electrolyte membrane such as sulfonated polyphenylene.

これらエンジニアプラスチックをスルホン化した芳香族炭化水素系固体高分子電解質膜は、ナフィオンに代表されるふっ素系固体高分子電解質膜と比較すると、製造が容易で低コストと云う利点がある。   Aromatic hydrocarbon-based solid polymer electrolyte membranes obtained by sulfonating these engineering plastics are advantageous in that they are easier to manufacture and lower in cost than fluorine-based solid polymer electrolyte membranes represented by Nafion.

特開平６−９３１１４号公報JP-A-6-93114

特開平９−２４５８１８号公報JP-A-9-245818 特開平１１−１１６６７９号公報JP-A-11-116679 特開平１１−６７２２４０号公報JP-A-11-672240 特表平１０−５０３７８８号公報Japanese Patent Publication No. Hei 10-503788 特表平１１−５１０１９８号公報Japanese Patent Publication No. 11-510198 特表平１１−５１５５５０４０号公報Japanese Patent Publication No. 11-5155040 特開２０００−１０６２０３号公報JP 2000-106203 A 特開平９−１０２３２２号公報JP-A-9-102322 特開平９−１０２３２２号公報JP-A-9-102322 米国特許第４，０１２，３０３号公報U.S. Pat.No. 4,012,303 米国特許第４，６０５，６８５号U.S. Pat. No. 4,605,685

しかし、その一方、スルホン化芳香族炭化水素系固体高分子電解質膜は劣化し易いと云う問題が残されていた。特許文献８によると、固体高分子電解質膜と酸素極の界面に形成された触媒層において生成した過酸化水素が、芳香族炭化水素骨格を酸化劣化させるため、芳香族炭化水素骨格を有する固体高分子電解質膜は劣化し易い。   However, on the other hand, there remains a problem that the sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane is easily deteriorated. According to Patent Document 8, hydrogen peroxide generated in a catalyst layer formed at the interface between a solid polymer electrolyte membrane and an oxygen electrode oxidizes and degrades an aromatic hydrocarbon skeleton. The molecular electrolyte membrane is easily deteriorated.

そこで、ふっ素系固体高分子電解質膜と同等以上の耐酸化劣化特性を有し、しかも低コストで製造可能な固体高分子電解質膜として、例えば、特許文献９には、炭化ふっ素系ビニルモノマと炭化水素系ビニルモノマとの共重合によって作られた主鎖と、スルホン酸基を有する炭化水素系側鎖とから構成される、スルホン酸型ポリスチレン−グラフト−エチレンテトラフルオロエチレン共重合体（ＥＴＦＥ）膜が提案されている。   Accordingly, as a solid polymer electrolyte membrane having oxidation resistance degradation properties equal to or higher than that of a fluorine-based solid polymer electrolyte membrane and capable of being manufactured at low cost, for example, Patent Document 9 discloses a fluorocarbon-based vinyl monomer and a hydrocarbon. Proposed a sulfonic acid type polystyrene-graft-ethylenetetrafluoroethylene copolymer (ETFE) membrane composed of a main chain formed by copolymerization with a vinyl monomer and a hydrocarbon side chain having a sulfonic acid group. Have been.

特許文献１０に開示されているスルホン酸型ポリスチレン−グラフト−ＥＴＦＥ膜は安価であり、燃料電池用の固体高分子電解質膜として十分な強度を有し、しかもスルホン酸基の導入量を増やすことによって導電率を向上させることが可能とされている。   The sulfonic acid type polystyrene-graft-ETFE membrane disclosed in Patent Document 10 is inexpensive, has sufficient strength as a solid polymer electrolyte membrane for a fuel cell, and can be obtained by increasing the amount of sulfonic acid groups introduced. It is possible to improve conductivity.

しかし、スルホン酸型ポリスチレン−グラフト−ＥＴＦＥ膜は、炭化ふっ素系ビニルモノマと炭化水素系ビニルモノマとの共重合によって作られた主鎖部分の耐酸化劣化特性は高いが、スルホン酸基を導入した側鎖部分は、酸化劣化を受け易い芳香族炭化水素系高分子である。従って、これを燃料電池に用いた場合には、膜全体の耐酸化劣化特性が不十分であり、耐久性に乏しいと云う問題がある。   However, the sulfonic acid type polystyrene-graft-ETFE membrane has a high oxidation resistance property of a main chain portion formed by copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer, but has a side chain into which a sulfonic acid group is introduced. The part is an aromatic hydrocarbon-based polymer that is susceptible to oxidative degradation. Accordingly, when this is used for a fuel cell, there is a problem that the oxidation resistance of the entire membrane is insufficient and the durability is poor.

また、特許文献１１及び特許文献１２には、炭化ふっ素系ビニルモノマと炭化水素系ビニルモノマとの共重合によって作られた膜に、α，β，β−トリフルオロスチレンをグラフト重合させ、これにスルホン酸基を導入して固体高分子電解質膜とした、スルホン酸型ポリ（トリフルオロスチレン）−グラフト−ＥＴＦＥ膜が提案されている。   Further, Patent Documents 11 and 12 disclose that α, β, β-trifluorostyrene is graft-polymerized on a film formed by copolymerization of a fluorocarbon vinyl monomer and a hydrocarbon vinyl monomer, and sulfonic acid is added thereto. A sulfonic acid type poly (trifluorostyrene) -graft-ETFE membrane has been proposed in which a group is introduced to form a solid polymer electrolyte membrane.

これは、前記のスルホン酸基を導入したポリスチレン側鎖部の化学的安定性が十分ではないとの認識を前提に、スチレンの代わりに、部分的にふっ素化したα，β，β−トリフルオロスチレンを用いたものである。しかし、側鎖部分の原料となるα，β，β−トリフルオロスチレンは、合成が困難なため、燃料電池用の固体高分子電解質膜として応用することを考えた場合には、前述のナフィオンの場合と同様にコストの問題がある。   This is based on the assumption that the chemical stability of the polystyrene side chain into which the sulfonic acid group is introduced is not sufficient, and instead of styrene, partially fluorinated α, β, β-trifluoro is used. It uses styrene. However, α, β, β-trifluorostyrene, which is a raw material for the side chain portion, is difficult to synthesize. Therefore, when considering application as a solid polymer electrolyte membrane for a fuel cell, the aforementioned Nafion is used. As in the case, there is a problem of cost.

また、α，β，β−トリフルオロスチレンは重合反応性が低いために、グラフト側鎖として導入できる量が少なく、得られる膜の導電率が低いと云う問題がある。   Further, since α, β, β-trifluorostyrene has low polymerization reactivity, there is a problem that the amount that can be introduced as a graft side chain is small, and the conductivity of the obtained film is low.

本発明の目的は、ふっ素系固体高分子電解質と同等以上、もしくは、実用上十分な耐劣化特性を有し、しかも低コストで製造可能な高耐久性固体高分子電解質を提供することにある。   It is an object of the present invention to provide a highly durable solid polymer electrolyte having a deterioration resistance characteristic equal to or higher than that of a fluorine-based solid polymer electrolyte, or sufficient for practical use, and which can be manufactured at low cost.

本発明者らは、固体高分子電解質膜の劣化メカニズムを詳細に検討した。その結果、芳香族環に直接スルホン酸基が結合している芳香族スルホン酸は水溶液中で芳香族環と硫酸との解離平衡状態にあり、硫酸濃度が低く温度が高くなるほど相対的に芳香族スルホン酸からスルホン酸基が脱離する傾向にあることが分った。   The present inventors have studied in detail the degradation mechanism of a solid polymer electrolyte membrane. As a result, the aromatic sulfonic acid in which the sulfonic acid group is directly bonded to the aromatic ring is in a dissociation equilibrium state between the aromatic ring and the sulfuric acid in the aqueous solution. It was found that the sulfonic acid groups tended to be eliminated from the sulfonic acid.

即ち、芳香族炭化水素系固体高分子電解質膜を用いた燃料電池の寿命低下は従来考えられていた膜自体の酸化劣化ではなく、燃料電池条件下においては硫酸濃度が低いため、芳香族環からスルホン酸基が脱離、イオン伝導度が低下する現象に起因することが分かった。   That is, the decrease in the service life of a fuel cell using an aromatic hydrocarbon-based solid polymer electrolyte membrane is not caused by oxidative deterioration of the membrane itself, which has been conventionally considered, but because the sulfuric acid concentration is low under fuel cell conditions, it is difficult to reduce the aromatic ring. It was found that the sulfonic acid group was eliminated and the ionic conductivity was reduced.

上記目的を解決するために本発明に係る高耐久性固体高分子電解質は、スルホン酸基の代わりに式〔１〕   In order to solve the above-mentioned object, a highly durable solid polymer electrolyte according to the present invention has a formula [1] instead of a sulfonic acid group.

Figure 2004152776
Figure 2004152776

（ｎは１〜６の整数）で示されるアルキレン基を介してスルホン酸基を導入したポリエーテルエーテルスルホンからなることを特徴とするもので、ふっ素系固体高分子電解質と同等以上、もしくは、実用上十分な耐久性を有し、しかも安価な高耐久性固体高分子電解質を得ることが可能となる。   (N is an integer of 1 to 6), characterized by comprising a polyetherethersulfone in which a sulfonic acid group is introduced via an alkylene group, which is equal to or more than a fluorine-based solid polymer electrolyte, or In addition, it is possible to obtain an inexpensive high-durability solid polymer electrolyte having sufficient durability.

また、同じイオン交換基当量重量ならばアルキル基を介してスルホン酸基を導入した固体高分子電解質のイオン導電率はスルホン酸基を導入した固体高分子電解質のイオン導電率より大きい利点がある。これはアルキレン基を介するスルホン酸基がアルキレン基を介さないスルホン酸基より運動し易いことと関係があるものと思われる。   If the ion exchange group equivalent weight is the same, the ionic conductivity of the solid polymer electrolyte in which a sulfonic acid group is introduced via an alkyl group has an advantage that the ionic conductivity of the solid polymer electrolyte in which a sulfonic acid group is introduced. This seems to be related to the fact that the sulfonic acid group via the alkylene group is more mobile than the sulfonic acid group not via the alkylene group.

上記化〔１〕のｎの数が３〜６のものは、ｎの数が１もしくは２のものよりもイオン伝導度が高くなり好ましい。この現象はｎの数が大きくなるとＳＯ３Ｈが動き易くなり、凝集構造、イオンチャンネル構造をとり易くなるためと考えられる。 The compound of the above formula [1] in which the number of n is 3 to 6 is preferable because the ionic conductivity is higher than that of the compound in which the number of n is 1 or 2. This phenomenon is considered to be because SO 3 H becomes easy to move as the number of n becomes large, and it becomes easy to take an aggregated structure and an ion channel structure.

本発明の特徴は、上記式〔１〕で示されるスルホアルキル基が結合しているポリエーテルエーテルスルホンを電解質に用いたことにある。   A feature of the present invention resides in that polyetherethersulfone having a sulfoalkyl group represented by the above formula [1] is used for the electrolyte.

本発明の特徴は、後記の式〔２〕〜式〔９〕で示されるアルキレン基を介してスルホン酸基が結合しているポリエーテルエーテルスルホンを電解質に用いることにある。   A feature of the present invention resides in that polyetherethersulfone having a sulfonic acid group bonded through an alkylene group represented by the following formulas [2] to [9] is used for the electrolyte.

また、本発明の他の特徴は、上述のスルホン酸がスルホン酸基当量重量で５３０〜９７０ｇ／当量であること。   Another feature of the present invention is that the above-mentioned sulfonic acid has a sulfonic acid group equivalent weight of 530 to 970 g / equivalent.

また、本発明の特徴は、上述した電解質を電解質膜へ適用したことにある。   A feature of the present invention resides in that the above-described electrolyte is applied to an electrolyte membrane.

また、本発明の他の特徴は、上述した固体高分子電解質を含む電極触媒被覆用溶液にある。   Another feature of the present invention resides in an electrode catalyst coating solution containing the above-mentioned solid polymer electrolyte.

また、本発明の他の特徴は、上述した固体高分子電解質膜と上記固体高分子電解質膜の両側に酸素極および水素極からなる一対の電極が配置された膜と電極との接合体である膜電極接合体にある。   Another feature of the present invention is a joined body of the solid polymer electrolyte membrane described above and a membrane in which a pair of electrodes including an oxygen electrode and a hydrogen electrode are arranged on both sides of the solid polymer electrolyte membrane. In the membrane electrode assembly.

また、本発明の特徴は、上述の電極触媒被覆用溶液によって覆われており、後述の式〔１〕〜式〔９〕のいずれかに示すアルキレン基を介してスルホン酸基が結合しているポリエーテルエーテルスルホンを用いた固体高分子電解質膜と、上記固体高分子電解質膜の両側に酸素極および水素極からなる一対の電極が配置された膜と電極との接合体とを含んで構成されている。   Further, a feature of the present invention is that the sulfonic acid group is covered by an alkylene group represented by any of the following formulas [1] to [9], which is covered with the above-mentioned electrode catalyst coating solution. A solid polymer electrolyte membrane using polyetherethersulfone, and a joined body of electrodes and a membrane in which a pair of electrodes including an oxygen electrode and a hydrogen electrode are arranged on both sides of the solid polymer electrolyte membrane ing.

また、本発明の特徴は、上述の電極触媒被覆用溶液は、ナフィオン（登録商標、デュポン社製パーフルオロスルホン酸固体高分子電解質溶液）である膜電極接合体にある。   A feature of the present invention lies in the membrane electrode assembly in which the above-mentioned solution for coating an electrode catalyst is Nafion (registered trademark, a perfluorosulfonic acid solid polymer electrolyte solution manufactured by DuPont).

さらに、本発明の特徴は、上述の固体高分子電解質膜と上記固体高分子電解質膜の両側に酸素極および水素極からなる一対の電極が配置された膜電極接合体と上記膜電極接合体の両面に配された一対の支持集電体と、上記支持集電体の外周に配置されたセパレータとを有する。   Further, the feature of the present invention is that the solid polymer electrolyte membrane and the membrane electrode assembly in which a pair of electrodes including an oxygen electrode and a hydrogen electrode are arranged on both sides of the solid polymer electrolyte membrane and the membrane electrode assembly It has a pair of support current collectors arranged on both sides, and a separator arranged on the outer periphery of the support current collector.

本発明に係るアルキレン基を介してスルホン酸基を導入したポリエーテルエーテルスルホンは、安価なエンジニアプラスチックを原料にし１乃至２工程で製造でき、原料が高価で５工程を経て製造されているパーフロロスルホン酸膜に代表されるふっ素系固体高分子電解質膜に比べ、そのコストは１／３０以下と安価である。   The polyetherethersulfone according to the present invention, in which a sulfonic acid group is introduced via an alkylene group, can be produced in one or two steps using inexpensive engineering plastic as a raw material. The cost is as low as 1/30 or less as compared with a fluorine-based solid polymer electrolyte membrane represented by a sulfonic acid membrane.

このように、芳香族環にアルキレン基を介してスルホン酸基を結合することにより、芳香族環に直接結合したスルホン酸基と異なり、イオン導電率も大きく、スルホン酸基が強酸，高温下で解離せず、実用上十分な高耐久性と、コストの低減を図ることができる。   As described above, by bonding a sulfonic acid group to an aromatic ring via an alkylene group, unlike the sulfonic acid group directly bonded to the aromatic ring, the ionic conductivity is large, and the sulfonic acid group is a strong acid under high temperature at high temperatures. Without practical dissociation, practically high durability and cost reduction can be achieved.

本発明のアルキレン基を介してスルホン酸基を導入したポリエーテルエーテルスルホン固体高分子電解質は式〔２〕に示すアルキレン基を介してスルホン酸基を導入したポリンエーテルエーテルスルホン固体高分子電解質であれば特に制限は無い。   The polyetherethersulfone solid polymer electrolyte having a sulfonic acid group introduced through an alkylene group of the present invention may be a polyetherethersulfone solid polymer electrolyte having a sulfonic acid group introduced through an alkylene group represented by the formula [2]. There are no particular restrictions.

Figure 2004152776
Figure 2004152776

（ｎは１〜６の整数、ｍ，ａ，ｂは０〜４の整数で全てが０にはならない。ｘは１〜３の整数、ｙは１〜５の整数。Ａｒは芳香族残基を表す）
具体例としては、式〔３〕〜式〔８〕に示すアルキル基を介してスルホン酸基を導入したポリエーテルエーテルスルホン固体高分子電解質が挙げられる。 (N is an integer of 1 to 6, m, a, and b are integers of 0 to 4 and are not all 0. x is an integer of 1 to 3, y is an integer of 1 to 5. Ar is an aromatic residue. Represents)
Specific examples include a polyetherethersulfone solid polymer electrolyte in which a sulfonic acid group is introduced via an alkyl group represented by the formulas [3] to [8].

Figure 2004152776
Figure 2004152776

（ｎは１〜６の整数、ａ，ｂ，ｃ，ｄは０〜４の整数であり、かつ、ｂ，ｃ，ｄが同時に０になることは無い。） (N is an integer of 1 to 6, a, b, c, and d are integers of 0 to 4, and b, c, and d do not become 0 at the same time.)

Figure 2004152776
Figure 2004152776

（ａ，ｂ，ｃ，ｄは０〜４の整数であり、かつａ，ｂ，ｃ，ｄが同時に０になることは無い。） (A, b, c, and d are integers from 0 to 4, and a, b, c, and d do not become 0 at the same time.)

Figure 2004152776
Figure 2004152776

（ａ，ｂ，ｃ，ｄは０〜４の整数であり、かつａ，ｂ，ｃ，ｄが同時に０になることは無い。） (A, b, c, and d are integers from 0 to 4, and a, b, c, and d do not become 0 at the same time.)

Figure 2004152776
Figure 2004152776

（ｎは１〜６の整数、ａ，ｂ，ｃは０〜４の整数であり、かつａ，ｂ，ｃが同時に０になることは無い。） (N is an integer of 1 to 6, a, b, and c are integers of 0 to 4, and a, b, and c do not become 0 at the same time.)

Figure 2004152776
Figure 2004152776

（ａ，ｂ，ｃは０〜４の整数であり、かつａ，ｂ，ｃが同時に０になることは無い。） (A, b, and c are integers from 0 to 4, and a, b, and c do not become 0 at the same time.)

Figure 2004152776
Figure 2004152776

（ａ，ｂ，ｃは０〜４の整数であり、かつａ，ｂ，ｃが同時に０になることは無い。） (A, b, and c are integers from 0 to 4, and a, b, and c do not become 0 at the same time.)

Figure 2004152776
Figure 2004152776

（ａ，ｂ，ｃ，ｄは０〜４の整数であり、かつａ，ｂ，ｃ，ｄが同時に０になることは無い。）
ポリエーテルエーテルスルホンあるいはそのポリマアロイにアルキレン基を介してスルホン酸基を導入する方法には、特に制限はないが、具体的な方法として例えば、Ｊ．Ａｍｅｒ．Ｃｈｅｍ．Ｓｏｃ．，７６，５３５７〜５３６０（１９５４）に記載されているような式（Ｉ）に示すスルトンを用いて芳香族環にアルキレン基を介してスルホン酸基を導入する方法がある。 (A, b, c, and d are integers from 0 to 4, and a, b, c, and d do not become 0 at the same time.)
The method for introducing a sulfonic acid group into the polyetherethersulfone or its polymer alloy via an alkylene group is not particularly limited. Amer. Chem. Soc. , 76, 5357-5360 (1954), a sulfonic acid group is introduced into an aromatic ring via an alkylene group using a sultone represented by the formula (I).

Figure 2004152776
Figure 2004152776

また、芳香族環の水素をリチウムに置換し、次いでジハロゲノアルカンでハロゲノアルキレン基に代え、アルキレン基を介してスルホン酸基に変換する方法やテトラメチレンハロゲニウムイオンを用いてハロゲノブチル基を導入し、ハロゲンをスルホン酸基に変換する方法などがある。   In addition, hydrogen of the aromatic ring is replaced with lithium, and then a halogenoalkylene group is substituted with a dihalogenoalkane, and a halogenobutyl group is introduced using a tetramethylene halogenium ion by converting to a sulfonic acid group via an alkylene group. Then, there is a method of converting a halogen into a sulfonic acid group.

Figure 2004152776
Figure 2004152776

アルキレン基を介してスルホン酸基を導入する反応はいずれも芳香族環に対する親電子反応であり、芳香族環の電子密度の高い本願の構造のポリエーテルエーテルスルホンは他のエンジニアリングプラスチックより比較的マイルドな条件で反応が起こり好ましい。   The reaction of introducing a sulfonic acid group via an alkylene group is an electrophilic reaction to an aromatic ring, and the polyetherethersulfone of the present structure having a high electron density of the aromatic ring is relatively milder than other engineering plastics. The reaction occurs under favorable conditions, which is preferable.

ポリエーテルエーテルスルホンにアルキレン基を介してスルホン酸基を導入する際に用いる方法には、特に制限はないが、コストの観点から合成工程が少ない方法、例えば、上記式（Ｉ）で表される方法が好ましい。   The method used for introducing a sulfonic acid group into the polyetherethersulfone via an alkylene group is not particularly limited, but a method having a small number of synthesis steps from the viewpoint of cost, for example, represented by the above formula (I) The method is preferred.

本発明で用いられる固体高分子電解質のイオン交換基当量重量は２５０〜２５００ｇ／当量のアルキレン基を介してスルホン酸基を導入したポリマである。好ましくは、イオン交換基当量重量は３００〜１５００ｇ／当量であり、さらに好ましくは５３０〜９７０ｇ／当量である。イオン交換基当量重量が２５００ｇ／当量を越えると出力性能が低下することがあり、２５０ｇ／当量より低いと該重合体の耐水性が低下し、それぞれ好ましくない。   The ion exchange group equivalent weight of the solid polymer electrolyte used in the present invention is a polymer in which a sulfonic acid group is introduced via an alkylene group of 250 to 2500 g / equivalent. Preferably, the ion exchange group equivalent weight is 300 to 1500 g / equivalent, and more preferably 530 to 970 g / equivalent. If the ion exchange group equivalent weight exceeds 2500 g / equivalent, the output performance may decrease, and if it is lower than 250 g / equivalent, the water resistance of the polymer decreases, which is not preferable.

なお、本発明のイオン交換基当量重量とは、導入されたアルキレン基を介するスルホン酸基単位当量あたりの該アルキレン基を介してスルホン酸基を導入したポリマの分子量を表し、値が小さいほどアルキレン基を介するスルホン酸基の導入度が大きいことを示す。イオン交換基当量重量は、１Ｈ−ＮＭＲスペクトロスコピー、元素分析、特公平１−５２８６６号明細書に記載の酸塩基滴定、非水酸塩基滴定（規定液はカリウムメトキシドのベンゼン・メタノール溶液）等により測定が可能である。 In addition, the ion exchange group equivalent weight of the present invention refers to the molecular weight of the polymer in which the sulfonic acid group is introduced through the alkylene group per unit equivalent of the sulfonic acid group through the introduced alkylene group. This indicates that the degree of introduction of the sulfonic acid group through the group is large. Ion-exchange group equivalent weight is determined by 1 H-NMR spectroscopy, elemental analysis, acid-base titration and non-hydroxy-base titration described in JP-B-1-52866 (the specified solution is a solution of potassium methoxide in benzene / methanol). The measurement can be performed by the method described above.

アルキレン基を介してスルホン酸基を導入した該固体高分子電解質のイオン交換基当量重量を２５０〜２５００ｇ／当量に制御する方法としては、芳香族炭化水素系高分子とスルホアルキル化剤の配合比、反応温度、反応時間、反応溶媒等を変化させることで、目的とするイオン交換基当量重量を有するアルキレン基を介してスルホン酸基を導入したポリマを得ることができる。   As a method for controlling the equivalent weight of the ion exchange group of the solid polymer electrolyte in which a sulfonic acid group is introduced via an alkylene group to 250 to 2500 g / equivalent, a compounding ratio of an aromatic hydrocarbon polymer and a sulfoalkylating agent is used. By changing the reaction temperature, reaction time, reaction solvent and the like, it is possible to obtain a polymer in which a sulfonic acid group is introduced via an alkylene group having a target ion exchange group equivalent weight.

本発明で用いられる固体高分子電解質を燃料電池用として使用する際には、通常膜の状態で使用される。アルキレン基を介してスルホン酸基を導入したポリマを膜へ転化する方法に特に制限はないが、溶液状態より製膜する方法（溶液キャスト法）あるいは溶融状態より製膜する方法（溶融プレス法もしくは溶融押し出し法）等が可能である。具体的には前者については、例えば、ポリマ溶液をガラス板上に流延塗布し、溶媒を除去することにより製膜する。   When the solid polymer electrolyte used in the present invention is used for a fuel cell, it is usually used in the form of a membrane. There is no particular limitation on the method of converting a polymer having a sulfonic acid group introduced through an alkylene group into a film, but a method of forming a film from a solution state (solution casting method) or a method of forming a film from a molten state (melt press method or (Melt extrusion method) and the like. Specifically, for the former, for example, a polymer solution is cast onto a glass plate and the solvent is removed to form a film.

製膜に用いる溶媒は、高分子を溶解し、その後に除去し得るものであれば特に制限はなく、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチルー２−ピロリドン、ジメチルスルホキシド等の非プロトン性極性溶媒、あるいはエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等のアルキレングリコールモノアルキルエーテル、ジクロロメタン、トリクロロエタン等のハロゲン系溶媒、ｉ−プロピルアルコール、ｔ−ブチルアルコール等のアルコールが好適に用いられる。   The solvent used for film formation is not particularly limited as long as it can dissolve the polymer and can be removed thereafter. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide Aprotic polar solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other alkylene glycol monoalkyl ethers; dichloromethane, trichloroethane and other halogenated solvents; i-propyl Alcohols such as alcohol and t-butyl alcohol are preferably used.

固体高分子電解質膜の厚みは、特に制限はないが１０〜２００μｍが好ましい。特に、３０〜１００μｍが好ましい。実用に耐える膜の強度を得るには１０μｍより厚い方が好ましく、膜抵抗の低減、つまり発電性能向上のためには２００μｍより薄い方が好ましい。溶液キャスト法の場合、膜厚は溶液濃度あるいは基板上への塗布厚により制御できる。溶融状態より製膜する場合、膜厚は溶融プレス法あるいは溶融押し出し法等で得た所定厚さのフィルムを、所定の倍率に延伸することで膜厚を制御できる。   The thickness of the solid polymer electrolyte membrane is not particularly limited, but is preferably from 10 to 200 μm. In particular, 30 to 100 μm is preferable. It is preferable that the thickness be larger than 10 μm to obtain the strength of the film that can withstand practical use, and it is preferable that the thickness be smaller than 200 μm to reduce the film resistance, that is, to improve the power generation performance. In the case of the solution casting method, the film thickness can be controlled by the solution concentration or the coating thickness on the substrate. When the film is formed from a molten state, the film thickness can be controlled by stretching a film having a predetermined thickness obtained by a melt press method or a melt extrusion method at a predetermined magnification.

また、本発明の固体高分子電解質を製造する際に、通常の高分子に使用される可塑剤、安定剤、離型剤等の添加剤を本発明の目的に反しない範囲内で使用することができる。   Further, when producing the solid polymer electrolyte of the present invention, additives such as a plasticizer, a stabilizer, and a release agent used for a normal polymer are used within a range not inconsistent with the object of the present invention. Can be.

燃料用電池として用いる際の膜電極接合体に使用される電極は、触媒金属の微粒子を担持した導電材により構成され、必要に応じて撥水剤や結着剤が含まれていてもよい。また、触媒を担持していない導電材と、必要に応じて含まれる撥水剤や結着剤とからなる層を、触媒層の外側に形成してもよい。   The electrode used for the membrane electrode assembly when used as a fuel cell is formed of a conductive material carrying fine particles of a catalyst metal, and may contain a water repellent or a binder as necessary. Further, a layer made of a conductive material not carrying a catalyst and a water repellent or a binder contained as necessary may be formed outside the catalyst layer.

この電極に使用される触媒金属としては、水素の酸化反応および酸素の還元反応を促進する金属であればいずれでもよく、例えば、白金、金、銀、パラジウム、イリジウム、ロジウム、ルテニウム、鉄、コバルト、ニッケル、クロム、タングステン、マンガン、バナジウム、あるいは、それらの合金が挙げられる。   The catalyst metal used for this electrode may be any metal that promotes the oxidation reaction of hydrogen and the reduction reaction of oxygen.For example, platinum, gold, silver, palladium, iridium, rhodium, ruthenium, iron, cobalt , Nickel, chromium, tungsten, manganese, vanadium, or alloys thereof.

これらの触媒の中で、特に、白金が多くの場合用いられる。なお、触媒となる金属の粒径は、通常は１０〜３００オングストロームである。これらの触媒はカーボン等の担体に付着させた方が触媒の使用量が少なくコスト的に有利である。触媒の担持量は電極が成形された状態で０．０１〜１０ｍｇ／ｃｍ２が好ましい。 Among these catalysts, in particular, platinum is often used. The particle size of the metal serving as a catalyst is usually from 10 to 300 Å. When these catalysts are attached to a carrier such as carbon, the amount of the catalyst used is small and the cost is advantageous. The supported amount of the catalyst is preferably 0.01 to 10 mg / cm 2 in a state where the electrode is formed.

導電材としては、電子導伝性物質であればいずれのものでも良く、例えば、各種金属や炭素材料などが挙げられる。   The conductive material may be any material as long as it is an electron conductive material, and examples thereof include various metals and carbon materials.

炭素材料としては、例えば、ファーネスブラック、チャンネルブラック、およびアセチレンブラック等のカーボンブラック、活性炭、黒鉛等が挙げられ、これらが単独あるいは混合して使用される。   Examples of the carbon material include carbon black such as furnace black, channel black, and acetylene black, activated carbon, and graphite. These may be used alone or in combination.

撥水剤としては、例えば、ふっ素化カーボン等が使用される。バインダーとしては本発明の電極触媒被覆用溶液をそのまま用いることが、接着性の観点から好ましいが、他の各種樹脂を用いても差し支えない。その場合は撥水性を有する含ふっ素樹脂が好ましく、特に、耐熱性，耐酸化性の優れたものがより好ましく、例えば、ポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロアルキルビニルエーテル共重合体、およびテトラフルオロエチレン−ヘキサフルオロプロピレン共重合体が挙げられる。   As the water repellent, for example, fluorinated carbon or the like is used. As the binder, the electrode catalyst coating solution of the present invention is preferably used as it is from the viewpoint of adhesiveness, but other various resins may be used. In that case, a fluorine-containing resin having water repellency is preferred, and those having excellent heat resistance and oxidation resistance are more preferred. For example, polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetra A fluoroethylene-hexafluoropropylene copolymer may be mentioned.

燃料用電池として用いる際の固体高分子電解質膜と電極接合法についても特に制限はなく、公知の方法を適用することが可能である。膜電極接合体の製法として、例えば、カーボンに担持させたＰｔ触媒紛をポリテトラフルオロエチレン懸濁液と混ぜ、カーボンペーパに塗布、熱処理して触媒層を形成する。次いで、固体高分子電解質膜と同一の固体高分子電解質溶液を触媒層に塗布し、固体高分子電解質膜とホットプレスで一体化する方法がある。   The method for bonding the solid polymer electrolyte membrane and the electrodes when used as a fuel cell is not particularly limited, and a known method can be applied. As a method for producing a membrane electrode assembly, for example, a Pt catalyst powder supported on carbon is mixed with a polytetrafluoroethylene suspension, applied to carbon paper, and heat-treated to form a catalyst layer. Next, there is a method in which the same solid polymer electrolyte solution as the solid polymer electrolyte membrane is applied to the catalyst layer, and integrated with the solid polymer electrolyte membrane by hot pressing.

この他、固体高分子電解質膜と同一の固体高分子電解質溶液を、予め、Ｐｔ触媒紛にコーテイングする方法、触媒ペーストを固体高分子電解質膜の方に塗布する方法、固体高分子電解質膜に電極を無電解めっきする方法、固体高分子電解質膜に白金族の金属錯イオンを吸着させた後、還元する方法等がある。   In addition, a method in which the same solid polymer electrolyte solution as the solid polymer electrolyte membrane is previously coated on the Pt catalyst powder, a method in which the catalyst paste is applied to the solid polymer electrolyte membrane, and an electrode in the solid polymer electrolyte membrane And a method in which platinum group metal complex ions are adsorbed on a solid polymer electrolyte membrane and then reduced.

固体高分子型燃料電池は、以上のように形成された固体高分子電解質膜と電極との接合体の両側に薄いカーボンペーパのパッキング材（支持集電体）を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）を配したものを単セルとし、この単セルの複数個を冷却板等を介して積層することにより構成される。燃料電池は、高い温度で作動させる方が、電極の触媒活性が上がり電極過電圧が減少するため望ましいが、固体高分子電解質膜は水分がないと機能しないため、水分管理が可能な温度で作動させる必要がある。燃料電池の作動温度の好ましい範囲は室温〜１００℃である。   In the polymer electrolyte fuel cell, a thin carbon paper packing material (supporting current collector) is brought into close contact with both sides of the joined body of the solid polymer electrolyte membrane and the electrode formed as described above, and the electrodes are formed from both sides. A single cell is provided with a conductive separator (bipolar plate) that also serves as a chamber separation and a gas supply passage to the electrode, and is formed by stacking a plurality of the single cells via a cooling plate or the like. You. It is desirable to operate the fuel cell at a high temperature because the catalytic activity of the electrode increases and the electrode overvoltage decreases, but since the solid polymer electrolyte membrane does not function without moisture, it is operated at a temperature at which moisture can be controlled. There is a need. A preferable range of the operating temperature of the fuel cell is from room temperature to 100 ° C.

以下実施例により本発明をさらに詳しく説明する。なお、各物性の測定条件は次の通りである。   Hereinafter, the present invention will be described in more detail with reference to Examples. In addition, the measurement conditions of each physical property are as follows.

（１） イオン交換基当量重量
測定しようとするアルキレン基を介してスルホン酸基を導入したポリマを密閉できるガラス容器中に精秤（ａ：グラム）し、そこに過剰量の塩化カルシウム水溶液を添加して一晩撹拌した。系内に発生した塩化水素を０．１Ｎの水酸化ナトリウム標準水溶液（ｆ：力価）で、指示薬にフェノールフタレインを用いて滴定（ｂ：ｍｌ）した。イオン交換基当量重量（ｇ／当量）は下式より求めた。
〔数１〕
イオン交換基当量重量＝（１０００×ａ）／（０．１×ｂ×ｆ）
（２） 燃料電池単セル出力性能評価
電極を接合した固体高分子電解質膜を評価セルに組込み、燃料電池出力性能を評価した。 (1) Equivalent weight of ion exchange group Equivalently weighed (a: gram) a polymer in which a sulfonic acid group was introduced via an alkylene group to be measured into a sealable glass container, and added an excess amount of calcium chloride aqueous solution thereto. And stirred overnight. Hydrogen chloride generated in the system was titrated (b: ml) with a 0.1 N sodium hydroxide standard aqueous solution (f: titer) using phenolphthalein as an indicator. The ion exchange group equivalent weight (g / equivalent) was determined by the following equation.
[Equation 1]
Ion exchange group equivalent weight = (1000 × a) / (0.1 × b × f)
(2) Evaluation of Single Cell Output Performance of Fuel Cell The solid polymer electrolyte membrane with the electrodes joined was incorporated into an evaluation cell, and the output performance of the fuel cell was evaluated.

反応ガスには、水素／酸素を用い、共に１気圧の圧力で２３℃の水バブラーを通して加湿した後、評価セルに供給した。ガス流量は水素６０ｍｌ／ｍｉｎ、酸素４０ｍｌ／ｍｉｎ、セル温度は７０℃とした。電池出力性能は、Ｈ２０１Ｂ充放電装置（北斗電工社製）により評価した。   Hydrogen / oxygen was used as a reaction gas, and both were humidified at a pressure of 1 atm through a water bubbler at 23 ° C., and then supplied to an evaluation cell. The gas flow rate was 60 ml / min of hydrogen, 40 ml / min of oxygen, and the cell temperature was 70 ° C. The battery output performance was evaluated using a H201B charge / discharge device (manufactured by Hokuto Denko).

〔実施例 １〕
（１） スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃、１０時間保持乾燥した６．００ｇ（０．０１５５ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と合成用脱水クロロホルム１５０ｍｌを入れ、６０℃で約１時間保持して溶解した。この溶液にプロパンスルトン２．８３ｇ（０．０２３２ｍｏｌ）を加えた。 [Example 1]
(1) Synthesis of sulfopropylated poly 1,4-biphenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. 6.00 g (0.0155 mol) of poly-1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 ) kept at 110 ° C. for 10 hours and dried. -4-C 6 H 4 -4-O-) n] and 150 ml of dehydrated chloroform for synthesis were added and dissolved at 60 ° C. for about 1 hour. To this solution, 2.83 g (0.0232 mol) of propane sultone was added.

次いで、撹拌しながら約３０分かけて無水塩化アルミニウム３．１０ｇ（０．０２３２ｍｏｌ）を加えた。無水塩化アルミニウムを添加した後、５０℃で１５時間加熱攪拌した。析出物を濾過し、クロロホルム１５０ｍｌで洗浄後、減圧乾燥した。得られた析出物を水２５０ｍｌに懸濁させ、ミキサーで細かく砕いて濾過した。これを４回繰り返した後、水で十分洗浄し、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。   Then, 3.10 g (0.0232 mol) of anhydrous aluminum chloride was added over about 30 minutes while stirring. After adding anhydrous aluminum chloride, the mixture was heated and stirred at 50 ° C. for 15 hours. The precipitate was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained precipitate was suspended in 250 ml of water, finely crushed with a mixer, and filtered. After repeating this four times, it was sufficiently washed with water, and the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure.

１Ｈ−ＮＭＲを測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍ、３．８ｐｐｍに認められた。このことからスルホプロピル基が導入されていることが確認された。得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉのスルホン酸当量重量は１１００ｇ／当量であった。 When 1 H-NMR was measured, a new peak based on a —CH 2 CH 2 CH 2 SO 3 H group was newly observed at 2.2 ppm and 3.8 ppm. This confirmed that the sulfopropyl group had been introduced. The sulfonic acid equivalent weight of the obtained sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte I was 1100 g / equivalent.

スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料として１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte I can be produced in one step using poly 1,4-biphenylene ether ether sulfone, which is a commercially available relatively inexpensive engineering plastic, as a raw material. The raw material is expensive, and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉは、１工程で製造できるため、後述の実施例１１、１２に示すように、２段階の工程を経て製造されるスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩや、スルホヘキサメチル化スルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩより低コストで合成でき、コスト的に有利である。   Since the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte I can be manufactured in one step, as shown in Examples 11 and 12 described below, the sulfomethylated poly It can be synthesized at a lower cost than 1,4-biphenylene ether ether sulfone solid polymer electrolyte VII or sulfohexamethylated sulfomethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte VIII, which is advantageous in cost.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して充分に水洗した後、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte I and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the equivalent weight of the ion-exchange group of the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte I was measured.

その結果、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉのイオン交換基当量重量は、初期と変わらず１１００ｇ／当量と、高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the equivalent weight of the ion-exchange group of the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte I was 1100 g / equivalent to the initial level, which was an expensive perfluorosulfonic acid solid polymer electrolyte (Nafion 117). ) Was stable.

一方、後述の比較例１の（１）に示すように、安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 1 below, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was 1200 g under the same heating hydrolysis conditions. / Equivalent, larger than the initial value of 650 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｉは、後述の比較例１の（１）に記載した安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte I is the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid high polymer described in Comparative Example 1 (1). Unlike molecular electrolyte II, it is as stable as expensive perfluorosulfonic acid solid polymer electrolyte (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた固体高分子電解質Ｉを５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開して風乾した後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜Ｉを作成した。得られた固体高分子電解質膜Ｉのイオン導電率は１Ｓ／ｃｍであった。 (2) Preparation of Solid Polymer Electrolyte Membrane A mixed solvent of N, N-dimethylformamide-cyclohexanone-methylethylketone (20: volume ratio) was prepared so that the solid polymer electrolyte I obtained in the above (1) had a concentration of 5% by weight. 80:25). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane I. The ionic conductivity of the obtained solid polymer electrolyte membrane I was 1 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に、前記固体高分子電解質膜Ｉとイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の固体高分子電解質膜Ｉのイオン導電率は、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The solid polymer electrolyte membrane I and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. The ionic conductivity of the solid polymer electrolyte membrane I after the holding was the same as that of the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、後述の比較例１の（２）に示すように、比較的安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩは、同一加温加水分解条件で破け、ぼろぼろになっていた。   On the other hand, as shown in (2) of Comparative Example 1 described later, the relatively inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II breaks and becomes ragged under the same heating and hydrolysis conditions. I was

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜Ｉは、後述の比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に、安定でコストと耐加水分解性（耐久性）が両立したものが得られた。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane I is different from the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II of Comparative Example 1 described below, As in the case of the expensive perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), a stable one having both cost and hydrolysis resistance (durability) was obtained.

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液Ｉ）を調整した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte were added at a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution I).

テフロン（登録商標）コーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液Ｉの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して溶媒を揮散させ、生じた固体を水洗した後、電極触媒被覆用溶液Ｉのイオン交換基当量重量を測定した。その結果、該溶液Ｉのイオン交換基当量重量は、初期と変わらず１１００ｇ／当量と、高価なパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   1.0 g of the electrode catalyst coating solution I and 20 ml of ion-exchanged water were placed in a Teflon (registered trademark) SUS sealed container and kept at 120 ° C. for 2 weeks. Then, after cooling, the solvent was volatilized and the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution I was measured. As a result, the equivalent weight of the ion exchange group of the solution I was 1100 g / equivalent as in the initial stage, and was stable as in the case of the expensive perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、後述の比較例１の（２）に示すように、電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (2) of Comparative Example 1 described below, the ion exchange group equivalent weight of the electrode catalyst coating solution II changes to 1200 g / equivalent under the same heating hydrolysis conditions, and the initial 650 g / equivalent of It became larger than the value, and the sulfonic acid group was eliminated.

即ち、安価な電極触媒被覆用溶液Ｉは、後述の比較例１の（２）に記載した安価な電極触媒被覆用溶液ＩＩと異なり、高価なパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に、安定でコストと耐加水分解性（耐久性）が両立したものを得ることができた。   That is, the inexpensive electrode catalyst coating solution I is different from the inexpensive electrode catalyst coating solution II described in (2) of Comparative Example 1 below, and the expensive perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution is used. In the same manner as in the above, a stable product having both cost and hydrolysis resistance (durability) was obtained.

前記電極触媒被覆用溶液Ｉを、前記（２）で得られた固体高分子電解質膜Ｉの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｉを作製した。 The electrode catalyst coating solution I is applied to both sides of the solid polymer electrolyte membrane I obtained in the above (2), and then dried to produce a membrane electrode assembly I having a platinum loading of 0.25 mg / cm 2. did.

後述の比較例１の（２）に記載した電極触媒被覆用溶液ＩＩを、前記（２）で得られた固体高分子電解質膜Ｉの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｉ'を作製した。 An electrode catalyst coating solution II described in (2) of Comparative Example 1 described below was applied to both sides of the solid polymer electrolyte membrane I obtained in (2), and then dried to carry a platinum loading of 0.25 mg. / Cm 2 of the membrane electrode assembly I ′.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質（ナフィオン１１７）の５重量％濃度のアルコール／水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調整した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜Ｉの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｉ''を作製した。 A 40% by weight platinum-supported carbon was mixed with a 5% by weight alcohol / water mixed solution of perfluorosulfonic acid solid polymer electrolyte (Nafion 117) at a weight ratio of platinum catalyst to solid polymer electrolyte of 2: 1. And then uniformly dispersed to prepare a paste (electrode catalyst coating solution). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane I obtained in the above (2), and then dried to produce a membrane electrode assembly I ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体Ｉとイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の膜電極接合体Ｉは高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly I and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. The membrane electrode assembly I after holding is the same as a high cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and a membrane electrode assembly produced using a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm as before.

テフロンコーテングのＳＵＳ製密閉容器に、得られた前記膜電極接合体Ｉ'とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の膜電極接合体Ｉ'は、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly I ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS, and kept at 120 ° C. for 2 weeks. Although the electrode was slightly peeled off from the membrane / electrode assembly I ′ after the holding, the membrane was firm and had a power generation ability.

テフロンコーテングのＳＵＳ製密閉容器に、得られた前記膜電極接合体Ｉ''とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の膜電極接合体Ｉ''は、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly I ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. Although the electrode was slightly peeled off from the membrane / electrode assembly I ″ after the holding, the membrane was firm and had a power generation capability.

一方、後述の比較例１の（３）に示したようにスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと、電極触媒被覆用溶液ＩＩを用いて作製した膜電極接合体ＩＩは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 1 to be described later, a membrane / electrode assembly prepared using a sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II and an electrode catalyst coating solution II In the case of II, the film was broken and ragged under the same heated hydrolysis conditions, and the electrode was peeled off.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体は、後述の比較例１の（３）に記したスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＩＩと異なり、高価なパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れたものを得ることができた。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly is a sulfonated poly 1,4-biphenylene ether ether sulfone solid described in (3) of Comparative Example 1 described later. Unlike the polymer electrolyte membrane electrode assembly II, it is as stable as the expensive perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and is excellent in both cost and hydrolysis resistance (durability). Was completed.

（４）燃料電池単セルの耐久性試験
前記膜電極接合体Ｉ，Ｉ'またはＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組込み、燃料電池出力性能を評価した。即ち、図１に示す固体高分子電解質膜１、酸素極２および水素極３からなる実施例１の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる固体高分子型燃料電池単セルを作製した。 (4) Durability test of single cell of fuel cell The membrane electrode assembly I, I 'or I''was immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated. That is, a thin carbon paper packing material (supporting current collector) 5 is applied to both electrodes of the membrane / electrode assembly 4 of Example 1 comprising the solid polymer electrolyte membrane 1, the oxygen electrode 2 and the hydrogen electrode 3 shown in FIG. A solid polymer electrolyte fuel cell unit cell comprising a conductive separator (bipolar plate) 6 which was in close contact with each other and served as a separator for the polar chamber and a gas supply passage to the electrode from both sides was produced.

前記固体高分子型燃料電池単セルを電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果を図２に示す。 The solid polymer fuel cell single cell was subjected to a long-term operation test at a current density of 300 mA / cm 2 . The result is shown in FIG.

図２中の１２，１３，１４はそれぞれ膜電極接合体Ｉ，Ｉ'およびＩ''を用いた燃料電池単セルの耐久性試験結果である。図２中の１５はパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   2, 12, 13 and 14 are the results of the durability test of the single fuel cell using the membrane electrode assemblies I, I ′ and I ″, respectively. Reference numeral 15 in FIG. 2 indicates a durability test result of a single fuel cell using a perfluorosulfonic acid (Nafion 117) membrane electrode assembly.

図中の１２は実施例１のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化を、１３は実施例１のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In the figure, reference numeral 12 denotes a polyetherethersulfone solid polymer electrolyte membrane of Example 1 having a sulfonic acid group bonded via an alkylene group, and a polyetherethersulfone solid polymer electrolyte having a sulfonic acid group bonded via an alkylene group. 13 shows the change over time of the output voltage of a fuel cell unit cell using the electrode catalyst coating solution, and 13 shows a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 1, 4 is a time-dependent change in output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte having acid groups directly bonded.

また、１４は実施例１のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、１５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、１６は比較例１のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   Reference numeral 14 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group of Example 1, and a solution for coating an electrode catalyst of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). With time, the output voltage of the fuel cell unit cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) was changed, and the sulfonic acid group of Comparative Example 1 was changed. The change over time of the output voltage of a fuel cell unit cell using a polyetherethersulfone solid polymer electrolyte membrane directly bonded to a polyetherethersulfone solid polymer electrolyte is there.

図２の１２および１４に示すように膜電極接合体Ｉ，Ｉ''を用いた燃料電池単セルの出力電圧は初期０．７０Ｖと、図２の１５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧より低いが、稼動時間５０００時間後でも初期と変わらないため、積層数を増やせば燃料電池として十分使える。   As shown in FIGS. 12 and 14, the output voltage of the single fuel cell using the membrane electrode assemblies I and I ″ is initially 0.70 V, and the perfluorosulfonic acid solid polymer electrolyte membrane of FIG. Although the output voltage is lower than the output voltage of a single cell of the fuel cell using (Nafion 117), it does not change from the initial state even after an operation time of 5000 hours.

一方、図２中の１６（後述に記載の比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖ、稼動時間６００時間後では出力が無くなった。このことからポリ１，４−ビフェニレンエーテルエーテルスルホンの芳香族環にアルキレン基を介してスルホン酸基を結合したポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜Ｉを用いた燃料電池単セルは、スルホン基と直接結合したポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩを用いた燃料電池単セルより耐久性に優れていることが明白である。   On the other hand, the output voltage of 16 (single fuel cell using the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II of Comparative Example 1 described later) in FIG. After 600 hours, there was no output. Therefore, a fuel cell unit cell using the poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane I in which a sulfonic acid group is bonded to the aromatic ring of poly 1,4-biphenylene ether ether sulfone via an alkylene group Is apparently superior in durability to a fuel cell unit cell using a poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II directly bonded to a sulfone group.

図２から分かるように膜電極接合体Ｉ，Ｉ''を用いた燃料電池単セルの耐久性は、膜電極接合体Ｉ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液Ｉは電極触媒被覆用溶液ＩＩより膜電極接合体の電極触媒被覆に適している。   As can be seen from FIG. 2, the durability of the single fuel cell using the membrane electrode assemblies I and I ″ is superior to the durability of the single fuel cell using the membrane electrode assembly I ′. That is, the electrode catalyst coating solution I is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔比較例 １〕
（１） スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃で１０時間保持乾燥した４．００ｇ（０．０１０３ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と脱水クロロホルム１００ｍｌ中を入れ、６０℃に約１時間保持して溶解した。この溶液に１．１６５ｇ（０．０１ｍｏｌ）のクロロスルホン酸を添加した１，１，２，２−テトラクロロエタン溶液５０ｍｌを約１０分間かけて加えた。 [Comparative Example 1]
(1) Synthesis of sulfonated poly 1,4-biphenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 4.00 g (0.0103 mol) of poly-1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 −) dried at 110 ° C. for 10 hours. 4-C 6 H 4 -4- O-) n ] and placed in a dehydrated chloroform 100 ml, was dissolved and held for about 1 hour to 60 ° C.. To this solution, 50 ml of a 1,1,2,2-tetrachloroethane solution to which 1.165 g (0.01 mol) of chlorosulfonic acid was added was added over about 10 minutes.

次いで、６０℃で４時間攪拌した。析出物を濾過し、クロロホルム１５０ｍｌで洗浄した。得られた析出物にメタノール２５０ｍｌを加え６０℃で溶解し、該溶液を６０℃で減圧乾燥した。   Then, the mixture was stirred at 60 ° C. for 4 hours. The precipitate was filtered and washed with 150 ml of chloroform. 250 ml of methanol was added to the obtained precipitate and dissolved at 60 ° C., and the solution was dried at 60 ° C. under reduced pressure.

得られたポリマーに水２５０ｍｌを加え、ミキサーで細かく砕き、濾過した。この操作を３回繰り返し、得られた水不溶性の微粉末を５酸化燐上で減圧下、９０℃で乾燥した。   250 ml of water was added to the obtained polymer, which was finely ground with a mixer and filtered. This operation was repeated three times, and the obtained water-insoluble fine powder was dried at 90 ° C. under reduced pressure over phosphorus pentoxide.

この微粉末は水に不溶、メタノールに可溶であった。１ＨＮＭＲを測定すると、原料のポリ１，４−ビフェニレンエーテルエーテルスルホン中のフェニル基の水素に基づく７．３〜８．０ｐｐｍの吸収が減少し、新たにＳＯ３Ｈ基に隣接するフェニル基の水素の基づく８．３ｐｐｍの吸収が認められた。このことからスルホン酸が導入されていることが確認された。得られたスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのスルホン酸当量重量は６５０ｇ／当量であった。 This fine powder was insoluble in water and soluble in methanol. When 1 HNMR was measured, the absorption of 7.3 to 8.0 ppm based on hydrogen of the phenyl group in the raw material poly 1,4-biphenylene ether ether sulfone was reduced, and the phenyl group adjacent to the SO 3 H group was newly added. An absorption of 8.3 ppm based on hydrogen was observed. This confirmed that sulfonic acid had been introduced. The sulfonic acid equivalent weight of the obtained sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte II was 650 g / equivalent.

テフロンコーテングのＳＵＳ製密閉容器に、前記スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩの１．０ｇと、イオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して十分に水洗した後、スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II and 20 ml of ion-exchanged water were put and kept at 120 ° C for 2 weeks. Then, after cooling and washing sufficiently with water, the ion exchange group equivalent weight of the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was measured.

その結果、スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのスルホン酸当量重量は１２００ｇ／当量と初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   As a result, the sulfonic acid equivalent weight of the sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte II was 1200 g / equivalent, which was larger than the initial value of 650 g / equivalent, and the sulfonic acid group was eliminated.

（２） 固体高分子電解質膜の作製
前記（１）で得られたスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩを、５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４５μｍの固体高分子電解質膜ＩＩを作成した。得られた固体高分子電解質膜ＩＩのイオン導電率は３Ｓ／ｃｍであった。 (2) Preparation of Solid Polymer Electrolyte Membrane The sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II obtained in the above (1) was N, N-dimethyl so as to have a concentration of 5% by weight. It was dissolved in a mixed solvent of formamide-cyclohexanone-methylethylketone (volume ratio: 20:80:25). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a solid polymer electrolyte membrane II having a film thickness of 45 μm. The ionic conductivity of the obtained solid polymer electrolyte membrane II was 3 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に前記固体高分子電解質膜ＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、得られた固体高分子電解質膜ＩＩは破け、ぼろぼろになっていた。   The solid polymer electrolyte membrane II and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the obtained solid polymer electrolyte membrane II was broken and ragged.

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＩＩ）を調整した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution II).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＩＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させ、生じた固体を水洗後、電極触媒被覆用溶液ＩＩのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution II and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the mixture was cooled to evaporate the solvent, and the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution II was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution II changed to 1200 g / equivalent under the same heating hydrolysis conditions, became larger than the initial value of 650 g / equivalent, and the sulfonic acid group was eliminated. .

前記電極触媒被覆用溶液ＩＩを前記（２）で得られた固体高分子電解質膜ＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＩを作製した。 The solution II for coating the electrode catalyst was applied to both sides of the solid polymer electrolyte membrane II obtained in the above (2), and then dried to produce a membrane electrode assembly II having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＩＩの膜は破け、ぼろぼろになり、電極は剥がれていた。   The obtained membrane electrode assembly II and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane of the membrane / electrode assembly II was broken and ragged, and the electrode was peeled off.

（４） 燃料電池単セルの耐久性試験
比較例１の膜電極接合体ＩＩの両側に薄いカーボンペーパのパッキング材（支持集電体）を密着させ、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）からなる固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。 (4) Durability test of single cell of fuel cell A packing material (supporting current collector) of thin carbon paper is adhered to both sides of the membrane electrode assembly II of Comparative Example 1, and separation of the electrode chamber from both sides and gas to the electrode are performed. A single cell of a polymer electrolyte fuel cell composed of a conductive separator (bipolar plate) also serving as a supply passage was manufactured, and a long-term operation test was performed under a condition of a current density of 300 mA / cm 2 .

その結果、図２の１６に示すように出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力電圧が無くなった。   As a result, as shown at 16 in FIG. 2, the output voltage was initially 0.73 V and disappeared after 600 hours of operation.

〔実施例 ２〕
（１） スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃で１０時間保持乾燥した２２．６ｇ（０．０１５５ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と脱水１，１，２−トリクロロエタン１５０ｍｌを入れ、１１３℃で約１時間保持して溶解した。この溶液にプロパンスルトン２４．８ｇ（０．０１５５ｍｏｌ）を加えた。 [Example 2]
(1) Synthesis of sulfopropylated poly 1,4-biphenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. 22.6 g (0.0155 mol) of poly-1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 ) dried at 110 ° C. for 10 hours. -4-C 6 H 4 -4- O-) n ] and ml of dehydrated 1,1,2-trichloroethane 150 ml, were dissolved by holding for about 1 hour at 113 ° C.. To this solution, 24.8 g (0.0155 mol) of propane sultone was added.

次いで、撹拌しながら約３０分かけて無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加後、３０時間，１１３℃で攪拌した。析出したポリマーを濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥した。得られたポリマーを水２５０ｍｌに懸濁させ、ミキサーで細かく砕いた。得られた微粉砕物を濾過した。これを４回繰り返した。   Then, while stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride was added over about 30 minutes. After adding anhydrous aluminum chloride, the mixture was stirred at 113 ° C. for 30 hours. The precipitated polymer was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained polymer was suspended in 250 ml of water and crushed with a mixer. The obtained finely pulverized product was filtered. This was repeated four times.

水で十分洗浄後、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。１ＨＮＭＲを測定すると、新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍ、３．８ｐｐｍに認められた。このことからスルホプロピル基が導入されていることが確認された。得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩＩのスルホン酸当量重量は４３０ｇ／当量であった。 After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure. When 1 HNMR was measured, a new peak based on a —CH 2 CH 2 CH 2 SO 3 H group was found at 2.2 ppm and 3.8 ppm. This confirmed that the sulfopropyl group had been introduced. The sulfonic acid equivalent weight of the obtained sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte III was 430 g / equivalent.

スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩＩのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte III can be produced in one step using poly 1,4-biphenylene ether ether sulfone, which is a commercially available relatively inexpensive engineering plastic, as a raw material. The raw material is expensive, and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩＩの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して十分に水洗した後、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte III and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the ion exchange group equivalent weight of the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte III was measured.

その結果、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩＩのイオン交換基当量重量は、初期と変わらず４３０ｇ／当量と高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the equivalent weight of the ion-exchange group of the sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte III was 430 g / equivalent to the initial level, and the expensive perfluorosulfonic acid solid polymer electrolyte (Nafion 117) As stable as.

一方、比較例１の（１）に示したように、スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 1, the ion exchange group equivalent weight of the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was 1200 g / equivalent under the same heating hydrolysis conditions. The sulfonic acid group had been eliminated, and became larger than the initial value of 650 g / equivalent.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩＩは、比較例１の（１）に記載したスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に、安定でコストと耐加水分解性（耐久性）が両立したものが得られた。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte III is the same as the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II described in (1) of Comparative Example 1. Unlike the expensive perfluorosulfonic acid solid polymer electrolyte (Nafion 117), a stable one having both cost and hydrolysis resistance (durability) was obtained.

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を、５重量％の濃度になるようＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜ＩＩＩを作成した。得られた固体高分子電解質膜ＩＩＩのイオン導電率は５５Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane A mixed solvent of N, N-dimethylformamide-cyclohexanone-methylethylketone (20:80:25 by volume) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane III. The ionic conductivity of the obtained solid polymer electrolyte membrane III was 55 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に前記固体高分子電解質膜ＩＩＩと、イオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、そのイオン導電率は高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The solid polymer electrolyte membrane III and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity was the same as that of the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例１の（２）に示したように、スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩは、同一加温加水分解条件で破け、ぼろぼろになっていた。   On the other hand, as shown in (2) of Comparative Example 1, the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was broken and ragged under the same heating and hydrolysis conditions.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩＩは、比較例１の（２）に記載した安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane III is the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer described in (2) of Comparative Example 1. Unlike the electrolyte membrane II, it is as stable as the expensive perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＩＩＩ）を調整した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution III).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＩＩＩの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して溶媒を揮散させ、生じた固体を水洗後、電極触媒被覆用溶液ＩＩＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution III and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the solvent was volatilized by cooling, and the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution III was measured.

その結果、電極触媒被覆用溶液ＩＩＩのイオン交換基当量重量は、初期と変わらず４３０ｇ／当量と高価なパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution III was 430 g / equivalent to the initial stage, and was stable as in the case of the expensive perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例１の（２）に示したように、電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液ＩＩＩは、比較例１の（２）に記載した安価な電極触媒被覆用溶液ＩＩと異なり、高価なパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 1, the ion exchange group equivalent weight of the electrode catalyst coating solution II changes to 1200 g / equivalent under the same heating hydrolysis conditions, and the initial value of 650 g / equivalent value. It became larger and the sulfonic acid group was eliminated. That is, unlike the inexpensive electrode catalyst coating solution II described in (2) of Comparative Example 1, the inexpensive electrode catalyst coating solution III is similar to the expensive perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. It is excellent in both cost and hydrolysis resistance (durability).

前記電極触媒被覆用溶液ＩＩＩを、前記（２）で得られた固体高分子電解質膜ＩＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＩＩを作製した。 The electrode catalyst coating solution III was applied to both sides of the solid polymer electrolyte membrane III obtained in the above (2), and then dried to produce a membrane electrode assembly III having a platinum loading of 0.25 mg / cm 2 . .

比較例１の（２）に記載した電極触媒被覆用溶液ＩＩを、前記（２）で得られた固体高分子電解質膜ＩＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＩＩ'を作製した。 The solution II for electrode catalyst coating described in (2) of Comparative Example 1 was applied to both sides of the solid polymer electrolyte membrane III obtained in (2), and then dried to carry a platinum loading of 0.25 mg / cm 2. Was prepared.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調整した。   To a 40% by weight platinum-supported carbon, a 5% by weight alcohol-water mixed solution of a perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. The paste was uniformly dispersed to prepare a paste (solution for coating an electrode catalyst).

この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＩＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＩＩ''を作製した。 This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane III obtained in the above (2), and then dried to produce a membrane electrode assembly III ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＩＩと、イオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体ＩＩＩは、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に、初期と変わらず膜もしっかりしていた。   The obtained membrane electrode assembly III and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly III is similar to a membrane / electrode assembly manufactured using a high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm as before.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＩＩ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＩＩＩ'は電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The obtained membrane electrode assembly III ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly III ′ had a slightly peeled-off electrode, but had a firm membrane and a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＩＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＩＩＩ''は電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The obtained membrane electrode assembly III ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, although the electrode of the membrane electrode assembly III ″ was slightly peeled off, the membrane was firm and had a power generation ability.

一方、比較例１の（３）に示したように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜ＩＩと、電極触媒被覆用溶液ＩＩを用いて作製した膜電極接合体ＩＩは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体は、比較例１の（３）に記載した安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホンル固体高分子電解質膜電極接合体ＩＩとは異なり、高価なパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   On the other hand, as shown in (3) of Comparative Example 1, a relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane II and a membrane / electrode assembly II produced using an electrode catalyst coating solution II In the case of, under the same heating hydrolysis conditions, the membrane was broken and ragged, and the electrode was peeled off. That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly is the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone described in (3) of Comparative Example 1. Unlike the solid polymer electrolyte membrane electrode assembly II, it is as stable as the expensive perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and is excellent in both cost and hydrolysis resistance (durability).

（４） 燃料電池単セル出力性能評価
前記膜電極接合体ＩＩＩ、ＩＩＩ'およびＩＩＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組込み、燃料電池出力性能を評価した。 (4) Evaluation of fuel cell single cell output performance The membrane electrode assemblies III, III ′ and III ″ were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

図１に示す、固体高分子電解質膜１、酸素極２および水素極３からなる実施例２の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果を図３に示す。図３中の１７，１８，１９はそれぞれ膜電極接合体ＩＩＩ、ＩＩＩ'、ＩＩＩ''を用いた燃料電池単セルの耐久性試験結果である。 A thin carbon paper packing material (supporting current collector) 5 is tightly attached to both electrodes of the membrane electrode assembly 4 of Example 2 shown in FIG. 1 comprising the solid polymer electrolyte membrane 1, the oxygen electrode 2 and the hydrogen electrode 3. Then, a single cell of a polymer electrolyte fuel cell composed of a conductive separator (bipolar plate) 6 which also functions as an electrode separation chamber and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm 2. A long-term operation test was performed under the following conditions. The result is shown in FIG. 3, 17, 18 and 19 are the results of the durability test of the fuel cell single cells using the membrane electrode assemblies III, III ′ and III ″, respectively.

図３において、１７は実施例２のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、１８は実施例２のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 3, reference numeral 17 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 2, and a polyetherethersulfone solid polymer having a sulfonic acid group bonded through an alkylene group. The change over time of the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 18 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 2, 4 is a time-dependent change in output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte having acid groups directly bonded.

また、１９は実施例２のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、２０はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、２１は比較例２のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた、燃料電池単セルの出力電圧の経時変化である。   Reference numeral 19 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 2, and a solution for coating an electrode catalyst of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). With time, the output voltage of the fuel cell single cell using perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) was changed, and the sulfonic acid group of Comparative Example 2 was changed. Change over time of the output voltage of a single cell of a fuel cell using a polyetherethersulfone solid polymer electrolyte membrane directly bonded to the polymer and a solution for coating the electrode catalyst of the polyetherethersulfone solid polymer electrolyte directly bonded to the sulfonic acid group It is.

図３中の２０はパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   Reference numeral 20 in FIG. 3 indicates a durability test result of a single fuel cell using a perfluorosulfonic acid (Nafion 117) membrane electrode assembly.

図３の１７，１９に示すように膜電極接合体ＩＩＩ，ＩＩＩ''を用いた燃料電池単セルの出力電圧は初期０．８８Ｖで、稼動時間５０００時間後でほぼ初期の９４％に低下しているが、低下後の値はパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体を用いた燃料電池単セルの値とほぼ同等であり、燃料電池として十分使用できる。   As shown at 17 and 19 in FIG. 3, the output voltage of the fuel cell single cell using the membrane electrode assemblies III and III ″ is 0.88 V in the initial stage, and falls to almost 94% of the initial stage after 5000 hours of operation. However, the value after the decrease is almost the same as the value of a single cell of a fuel cell using a perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and can be sufficiently used as a fuel cell.

一方、図３中の２１（比較例２のスルホン化芳香族炭化水素固体高分子電解質ＩＩを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 21 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte II of Comparative Example 2) in FIG. 3 was initially 0.73 V, and the output disappeared after 600 hours of operation. Was.

このことから芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質ＩＩＩを用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質ＩＩを用いた燃料電池単セルより耐久性に優れていることが明白である。   Therefore, a fuel cell single cell using an aromatic hydrocarbon-based solid polymer electrolyte III in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the single cell of the fuel cell using the hydrocarbon-based solid polymer electrolyte II.

膜電極接合体ＩＩＩおよびＩＩＩ''を用いた燃料電池単セルの耐久性は膜電極接合体ＩＩＩ'を用いた燃料電池単セルの耐久性より優れている。   The durability of the fuel cell unit cell using the membrane electrode assemblies III and III ″ is superior to the durability of the fuel cell unit cell using the membrane electrode assembly III ′.

即ち、電極触媒被覆用溶液ＩＩＩは、比較例１の電極触媒被覆用溶液ＩＩより、膜電極接合体の電極触媒被覆に適している。また、実施例２および比較例２の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例２の燃料電池単セルの出力電圧が、比較例２の燃料電池単セルの出力電圧より大きい理由は、実施例２の膜電極接合体ＩＩＩの固体高分子電解質膜ＩＩＩおよび電極触媒被覆用溶液ＩＩＩのイオン導電率が、比較例２の膜電極接合体ＩＩの固体高分子電解質膜ＩＩおよび電極触媒被覆用溶液ＩＩのイオン導電率より高いからである。 That is, the electrode catalyst coating solution III is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II of Comparative Example 1. The amount of supported platinum of the membrane electrode assembly of Example 2 and Comparative Example 2 even though the same as 0.25 mg / cm 2, the output voltage of the fuel cell unit of Example 2, Comparative Example 2 The reason is that the ionic conductivity of the solid polymer electrolyte membrane III and the solution III for electrode catalyst coating of the membrane electrode assembly III of Example 2 is higher than the output voltage of the single cell of the fuel cell of Example 2. This is because the ionic conductivity of the solid polymer electrolyte membrane II and the ionic conductivity of the electrode catalyst coating solution II are higher.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 ３〕
（１） スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換後、乾燥した６．００ｇ（０．０１５５ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と、合成用脱水クロロホルム１５０ｍｌを入れ、６０℃で約１時間保持し溶解した。この溶液にプロパンスルトン５．６７ｇ（０．０４６４ｍｏｌ）を加えた。 [Example 3]
(1) Synthesis of sulfopropylated poly 1,4-biphenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 6.00 g (0.0155 mol) of dried poly 1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4-C 6 H 4 -4-O-) n] and 150 ml of dehydrated chloroform for synthesis were added and dissolved at 60 ° C. for about 1 hour. 5.67 g (0.0464 mol) of propane sultone was added to this solution.

次いで、撹拌しながら約３０分かけて無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加した後、６０℃で３０時間還流攪拌した。析出物を濾過し、クロロホルム１５０ｍｌで洗浄、減圧乾燥した。得られた析出物を水２５０ｍｌに懸濁させ、ミキサーで細かく砕いて濾過した。これを４回繰り返した。   Then, while stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride was added over about 30 minutes. After adding anhydrous aluminum chloride, the mixture was refluxed and stirred at 60 ° C. for 30 hours. The precipitate was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained precipitate was suspended in 250 ml of water, finely crushed with a mixer, and filtered. This was repeated four times.

水で十分洗浄した後、水不溶性の微粉砕物を減圧下、９０℃で乾燥し、１ＨＮＭＲを測定すると、新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍ、３．８ｐｐｍに認められた。 After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure, and 1 HNMR was measured. As a result, a new peak based on —CH 2 CH 2 CH 2 SO 3 H group was 2.2 ppm, It was found at 3.8 ppm.

このことからスルホプロピル基が導入されていることが確認された。得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＶのスルホン酸当量重量は９７０ｇ／当量であった。   This confirmed that the sulfopropyl group had been introduced. The sulfonic acid equivalent weight of the obtained sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte IV was 970 g / equivalent.

スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＶのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料に、１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ、１／５０以下と安価である。   The cost of the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte IV can be produced in one step using poly 1,4-biphenylene ether ether sulfone, which is a commercially available relatively inexpensive engineering plastic, as a raw material. The raw material is expensive and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) produced through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＶの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して充分に水洗した後、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＶのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfopropylated poly (1,4-biphenylene ether ether sulfone) solid polymer electrolyte IV and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the equivalent weight of the ion-exchange group of the sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte IV was measured.

該固体高分子電解質ＩＶのイオン交換基当量重量は、初期と変わらず９７０ｇ／当量と高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   The ion exchange group equivalent weight of the solid polymer electrolyte IV was 970 g / equivalent as in the initial stage, and was stable as in the case of the expensive perfluorosulfonic acid solid polymer electrolyte (Nafion 117).

一方、比較例１の安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＶは、比較例２のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II of Comparative Example 1 was changed to 1200 g / equivalent under the same heating hydrolysis conditions, and the initial weight was 650 g / equivalent. It became larger than the equivalent value, and the sulfonic acid group was eliminated. That is, unlike the sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte II of Comparative Example 2, the inexpensive sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte IV is different from perfluorosulfonic acid. Like the solid polymer electrolyte (Nafion 117), it is stable, and is excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた固体高分子電解質ＩＶを、５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開して風乾後、８０℃で真空乾燥し、膜厚２５μｍの固体高分子電解質膜ＩＶを作成した。該電解質膜ＩＶのイオン導電率は１０Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane The solid polymer electrolyte IV obtained in the above (1) was mixed with a mixed solvent of N, N-dimethylformamide-cyclohexanone-methylethylketone (volume ratio: 20) so as to have a concentration of 5% by weight. : 80:25). This solution was spread on a glass plate by spin coating, air-dried, and vacuum-dried at 80 ° C. to form a solid polymer electrolyte membrane IV having a thickness of 25 μm. The ionic conductivity of the electrolyte membrane IV was 10 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に前記固体高分子電解質膜ＩＶとイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の固体高分子電解質膜ＩＶのイオン導電率は、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The solid polymer electrolyte membrane IV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. The ionic conductivity of the solid polymer electrolyte membrane IV after the holding was the same as that of the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例１の（２）に示したように、比較的安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩは、同一加温加水分解条件で破け、ぼろぼろになっていた。   On the other hand, as shown in (2) of Comparative Example 1, the relatively inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was broken and ragged under the same heating and hydrolysis conditions. Was.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＶは、スルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   That is, the inexpensive sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane IV is different from the sulfonated poly1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II, and is different from the perfluorosulfonic acid solid polymer electrolyte membrane II. It is as stable as the molecular electrolyte membrane (Nafion 117), and has both excellent cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＩＶ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution IV).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＩＶの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して溶媒を揮散させ、生じた固体を水洗後、電極触媒被覆用溶液ＩＶのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution IV and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. After cooling, the solvent was volatilized, and the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution IV was measured.

その結果、電極触媒被覆用溶液ＩＶのイオン交換基当量重量は、初期と変わらず９７０ｇ／当量とパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution IV was 970 g / equivalent to the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例１の電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, the equivalent weight of the ion exchange group of the electrode catalyst coating solution II of Comparative Example 1 was changed to 1200 g / equivalent under the same heating hydrolysis conditions, became larger than the initial value of 650 g / equivalent, and the sulfonic acid group was removed. Was separated.

即ち、安価な電極触媒被覆用溶液ＩＶは、比較例１の電極触媒被覆用溶液ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   That is, unlike the electrode catalyst coating solution II of Comparative Example 1, the inexpensive electrode catalyst coating solution IV is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution, and has a low cost and hydrolysis resistance. (Durability) is excellent.

前記電極触媒被覆用溶液ＩＶを、前記（２）で得られた固体高分子電解質膜ＩＶの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＶを作製した。 The electrode catalyst coating solution IV was applied to both sides of the solid polymer electrolyte membrane IV obtained in the above (2), and then dried to prepare a membrane electrode assembly IV having a platinum loading of 0.25 mg / cm 2 . .

４０重量％の白金担持カーボンに、比較例１の電極触媒被覆用溶液ＩＩを前記（２）で得られた固体高分子電解質膜ＩＶの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＶ'を作製した。 The electrode catalyst coating solution II of Comparative Example 1 was applied to both sides of the solid polymer electrolyte membrane IV obtained in (2) above on 40% by weight of platinum-carrying carbon, and then dried to carry a platinum-carrying amount of 0.25 mg. / Cm 2 of the membrane electrode assembly IV ′.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質（ナフィオン１１７）の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＩＶの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＶ''を作製した。 A 40% by weight platinum-supported carbon was mixed with a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) in a 5% by weight alcohol-water mixed solution, and the weight ratio between the platinum catalyst and the solid polymer electrolyte was 2: 1. And the mixture was uniformly dispersed to prepare a paste (electrode catalyst coating solution). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane IV obtained in the above (2), and then dried to produce a membrane electrode assembly IV ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＶと、イオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の膜電極接合体ＩＶは、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly IV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. The membrane electrode assembly IV after the holding is composed of a high cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and a membrane electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Similarly, the film was firm as before.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＶ'とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。保持後の膜電極接合体ＩＶ'は、電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The obtained membrane electrode assembly IV ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. Although the electrode was slightly peeled off from the membrane electrode assembly IV ′ after the holding, the membrane was firm and had a power generation ability.

テフロンコーテングのＳＵＳ製密閉容器に、前記膜電極接合体ＩＶ''とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体ＩＶ''は、電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The membrane electrode assembly IV ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, in the membrane electrode assembly IV ″, the electrodes were slightly peeled off, but the membrane was firm and had a power generation ability.

一方、比較例１の（３）に示したように、比較的安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと、電極触媒被覆用溶液ＩＩを用いて作製した膜電極接合体ＩＩは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 1, a membrane made using a relatively inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II and an electrode catalyst coating solution II. In the electrode assembly II, the film was broken and ragged under the same heating and hydrolysis conditions, and the electrode was peeled off.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体は、比較例１の安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly is the same as the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly of Comparative Example 1. Unlike the isomer II, it is as stable as the perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and is excellent in both cost and hydrolysis resistance (durability).

（４） 燃料電池単セルの耐久性試験
前記膜電極接合体ＩＶ、ＩＶ'またはＩＶ''を、沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組込み、燃料電池出力性能を評価した。図１に示す固体高分子電解質膜１、酸素極２および水素極３からなる実施例３の膜電極接合体４の両電極に薄いカーボンペーパーのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図固体高分子型燃料電池単セルを作製した。 (4) Durability test of fuel cell single cell The membrane electrode assembly IV, IV ′ or IV ″ was immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated. A packing material (supporting current collector) 5 made of thin carbon paper is adhered to both electrodes of the membrane electrode assembly 4 of Example 3 including the solid polymer electrolyte membrane 1, the oxygen electrode 2 and the hydrogen electrode 3 shown in FIG. A solid polymer fuel cell unit cell comprising a conductive separator (bipolar plate) 6 which also functions as a polar chamber separation and a gas supply passage to the electrode from both sides was prepared.

前記固体高分子型燃料電池単セルを電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。図４に示すように２２，２３，２４はそれぞれ膜電極接合体ＩＶ、ＩＶ'およびＩＶ''を用いた燃料電池単セルの耐久性試験結果である。図４中の２５はパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。 The solid polymer fuel cell single cell was subjected to a long-term operation test at a current density of 300 mA / cm 2 . As shown in FIG. 4, 22, 23 and 24 are the results of the durability test of the single fuel cell using the membrane electrode assemblies IV, IV ′ and IV ″, respectively. Reference numeral 25 in FIG. 4 indicates a durability test result of a fuel cell single cell using a perfluorosulfonic acid (Nafion 117) membrane electrode assembly.

図４中の２２は実施例３のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、２３は実施例３のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 4, reference numeral 22 denotes a polyetherethersulfone solid polymer electrolyte membrane of Example 3 in which a sulfonic acid group is bonded via an alkylene group, and a polyetherethersulfone solid polymer in which a sulfonic acid group is bonded via an alkylene group. The change over time of the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 23 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 3, 4 is a time-dependent change of an output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which an acid group is directly bonded.

また、２４は実施例３のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、２５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、そして、２６は比較例３のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜とスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   Reference numeral 24 denotes a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 3, and a solution for coating an electrode catalyst of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Of the output voltage of the fuel cell unit cell, the change of the output voltage of the fuel cell unit cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) with time, and 26 the sulfone of Comparative Example 3. Time course of the output voltage of a single fuel cell using a polyetherethersulfone solid polymer electrolyte membrane with directly bonded acid groups and a polyetherethersulfone solid polymer electrolyte with directly bonded sulfonic acid groups as an electrode catalyst coating solution It is.

図４の２２および２４の出力電圧は初期０．７８Ｖで、稼動時間５０００時間後でも初期と変わらず、図４の２５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）ＩＶを用いた結果と同等であった。   The output voltage of 22 and 24 in FIG. 4 was initially 0.78 V, which was the same as the initial value even after an operation time of 5000 hours, and was the result of using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) IV of 25 in FIG. Was equivalent to

一方、図４中の２６（比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩを使用した燃料電池単セル）の出力電圧は、初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 26 (single fuel cell using the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II of Comparative Example 1) in FIG. No output after hours.

このことから、ポリ１，４−ビフェニレンエーテルエーテルスルホンの芳香族環に、アルキレン基を介してスルホン酸基を結合したポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＶを用いた燃料電池単セルは、スルホン基と直接結合したポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩを用いた燃料電池単セルより耐久性に優れていることが明白である。   From this, a fuel cell using the poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane IV in which a sulfonic acid group is bonded to the aromatic ring of poly-1,4-biphenylene ether ether sulfone via an alkylene group It is apparent that the unit cell has better durability than the unit cell of the fuel cell using the poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II directly bonded to the sulfone group.

また、膜電極接合体ＩＶおよびＩＶ''を用いた燃料電池単セルの耐久性は膜電極接合体ＩＶ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＩＶは、比較例１の電極触媒被覆用溶液ＩＩより膜電極接合体の電極触媒被覆に適している。   Further, the durability of the fuel cell unit cell using the membrane electrode assemblies IV and IV ″ is superior to the durability of the fuel cell unit cell using the membrane electrode assembly IV ′. That is, the electrode catalyst coating solution IV is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II of Comparative Example 1.

また、実施例３および比較例１の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例３の燃料電池単セルの出力電圧が比較例１の燃料電池単セルの出力電圧より大きい理由は、実施例３の膜電極接合体の固体高分子電解質膜ＩＶおよび電極触媒被覆用溶液ＩＶのイオン導電率が、比較例１の膜電極接合体の固体高分子電解質膜ＩＩおよび電極触媒被覆用溶液ＩＩのイオン導電率より高いからである。 Further, the output voltage of the fuel cell unit cell of Example 3 was lower than that of Comparative Example 1 even though the supported amount of platinum of the membrane electrode assemblies of Example 3 and Comparative Example 1 was the same as 0.25 mg / cm 2 . The reason is that the ionic conductivity of the solid polymer electrolyte membrane IV of the membrane electrode assembly of Example 3 and the solution IV for electrode catalyst coating is higher than that of the membrane electrode assembly of Comparative Example 1. This is because the ionic conductivity of the polymer electrolyte membrane II and the ionic conductivity of the electrode catalyst coating solution II are higher.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 ４〕
（１） スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
乾燥した６．００ｇ（０．０１５５ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と、脱水クロロホルム１５０ｍｌをオートクレーブに入れ、６０℃にて約１時間保持し溶解した。この溶液にプロパンスルトン５．６７ｇ（０．０４６４ｍｏｌ）を加えた。 [Example 4]
(1) Synthesis of sulfopropylated poly 1,4-biphenylene ether ether sulfone 6.00 g (0.0155 mol) of dried poly 1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C) and 6 H 4 -4-OC 6 H 4 -4-C 6 H 4 -4-O-) n ], ml of dehydrated chloroform 150ml autoclave was dissolved and held at 60 ° C. for about 1 hour. 5.67 g (0.0464 mol) of propane sultone was added to this solution.

次いで、撹拌しながら約３０分かけて無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加後、２０時間，１３０℃で攪拌した。析出したポリマを濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥し、該ポリマを水２５０ｍｌに懸濁させ、ミキサーで細かく砕いた。得られた微粉砕物を濾過した。これを４回繰り返した。   Then, while stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride was added over about 30 minutes. After adding anhydrous aluminum chloride, the mixture was stirred at 130 ° C. for 20 hours. The precipitated polymer was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The polymer was suspended in 250 ml of water and crushed with a mixer. The obtained finely pulverized product was filtered. This was repeated four times.

水で十分洗浄後、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。１ＨＮＭＲを測定すると、新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍ、３．８ｐｐｍに認められた。このことからスルホプロピル基が導入されていることが確認された。得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｖのスルホン酸当量重量は５３０ｇ／当量であった。 After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure. When 1 HNMR was measured, a new peak based on a —CH 2 CH 2 CH 2 SO 3 H group was found at 2.2 ppm and 3.8 ppm. This confirmed that the sulfopropyl group had been introduced. The sulfonic acid equivalent weight of the obtained sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte V was 530 g / equivalent.

スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｖのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte V can be produced in one step using poly 1,4-biphenylene ether ether sulfone, which is a commercially available relatively inexpensive engineering plastic, as a raw material. The raw material is expensive, and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｖの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して十分に水洗した後、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｖのイオン交換基当量重量を測定した。その結果、該固体高分子電解質Ｖのイオン交換基当量重量は、初期と変わらず５３０ｇ／当量と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte V and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and sufficiently washing with water, the ion exchange group equivalent weight of the sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte V was measured. As a result, the ion exchange group equivalent weight of the solid polymer electrolyte V was 530 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117).

一方、比較例１の（１）に示したように、安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 1, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was 1200 g / Equivalent, and became larger than the initial value of 650 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質Ｖは、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte V is different from the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II of Comparative Example 1, and is different from perfluorosulfonic acid. Like the solid polymer electrolyte (Nafion 117), it is stable, and is excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜Ｖを作成した。得られた固体高分子電解質膜Ｖのイオン導電率は２０Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamido-cyclohexanone-methylethylketone mixed solvent (volume ratio 20:80:25) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a solid polymer electrolyte membrane V having a thickness of 25 μm. The ionic conductivity of the obtained solid polymer electrolyte membrane V was 20 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記固体高分子電解質膜Ｖとイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、そのイオン導電率は高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained solid polymer electrolyte membrane V and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity was the same as that of the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例１の（２）に示したように比較的安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩは、同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜Ｖは、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   On the other hand, as shown in (2) of Comparative Example 1, the relatively inexpensive sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte II was broken and ragged under the same heating and hydrolysis conditions. . That is, unlike the sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II of Comparative Example 1, the inexpensive sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane V was Like the sulfonic acid solid polymer electrolyte membrane (Nafion 117), it is stable, and has both excellent cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液Ｖ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution V).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液Ｖの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して溶媒を揮散させ、生じた固体を水洗後、電極触媒被覆用溶液Ｖのイオン交換基当量重量を測定した。該溶液Ｖのイオン交換基当量重量は、初期と変わらず５３０ｇ／当量と、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution V and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, the solvent was volatilized by cooling, the resulting solid was washed with water, and the ion exchange group equivalent weight of the electrode catalyst coating solution V was measured. The ion exchange group equivalent weight of the solution V was 530 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例１の（２）に示したように電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液Ｖは、比較例１の電極触媒被覆用溶液ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 1, the equivalent weight of the ion-exchange group of the solution II for electrode catalyst coating changes to 1200 g / equivalent under the same heating and hydrolysis conditions, and the initial equivalent value of 650 g / equivalent changes. It became larger and the sulfonic acid group was eliminated. That is, unlike the electrode catalyst coating solution II of Comparative Example 1, the inexpensive electrode catalyst coating solution V is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution, and has a low cost and hydrolysis resistance. (Durability) are both excellent.

前記電極触媒被覆用溶液Ｖを前記（２）で得られた固体高分子電解質膜Ｖの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｖを作製した。 The electrode catalyst coating solution V was applied to both sides of the solid polymer electrolyte membrane V obtained in the above (2), and then dried to prepare a membrane electrode assembly V having a platinum loading of 0.25 mg / cm 2 . .

比較例１の（２）に記載した電極触媒被覆用溶液ＩＩを、前記固体高分子電解質膜Ｖの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｖ'を作製した。 The solution II for electrode catalyst coating described in (2) of Comparative Example 1 was applied to both sides of the solid polymer electrolyte membrane V, dried, and dried to obtain a membrane electrode assembly V ′ having a platinum carrying amount of 0.25 mg / cm 2. Was prepared.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコール／水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜Ｖの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｖ''を作製した。 To a 40% by weight platinum-supported carbon, a 5% by weight alcohol / water mixed solution of perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. Then, the mixture was uniformly dispersed to prepare a paste (electrode catalyst coating solution). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane V obtained in the above (2), and then dried to produce a membrane electrode assembly V ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に、前記膜電極接合体Ｖとイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体Ｖは、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The membrane electrode assembly V and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly V is similar to the membrane-electrode assembly manufactured using the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm as before.

テフロンコーテングのＳＵＳ製密閉容器に前記膜電極接合体Ｖ'とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体Ｖ'は電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The membrane electrode assembly V 'and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C for 2 weeks. As a result, the electrode of the membrane electrode assembly V ′ was slightly peeled off, but the membrane was firm and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に前記膜電極接合体Ｖ''とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体Ｖ''は電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The membrane electrode assembly V ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly V ″ had a slightly peeled electrode but a firm membrane and a power generation capacity.

一方、比較例１の（３）に示したように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜ＩＩと、電極触媒被覆用溶液ＩＩを用いて作製した膜電極接合体ＩＩは同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体は、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   On the other hand, as shown in (3) of Comparative Example 1, a relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane II and a membrane / electrode assembly II produced using an electrode catalyst coating solution II The film was torn and ragged under the same heated hydrolysis conditions, and the electrode was peeled off. That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly is the same as the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly II of Comparative Example 1. Unlike the perfluorosulfonic acid (Nafion 117) membrane / electrode assembly, it is stable, and is excellent in both cost and hydrolysis resistance (durability).

（４） 燃料電池単セル出力性能評価
前記膜電極接合体Ｖ、Ｖ'およびＶ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。これらの膜電極接合体を評価セルに組込み、燃料電池出力性能を評価した。図５に膜電極接合体Ｖを組み込んだ燃料電池単セルの電流密度−電圧プロットを示す。 (4) Evaluation of fuel cell single cell output performance The membrane electrode assemblies V, V ′ and V ″ were immersed in boiling deionized water for 2 hours to absorb water. These membrane electrode assemblies were assembled in an evaluation cell, and the output performance of the fuel cell was evaluated. FIG. 5 shows a current density-voltage plot of a single fuel cell incorporating the membrane electrode assembly V.

電流密度１Ａ／ｃｍ２のとき出力電圧は０．７０Ｖで、電流密度３００ｍＡ／ｃｍ２のとき出力電圧は０．８０Ｖで、固体高分子型燃料電池単セルとして十分使用可能であった。 When the current density was 1 A / cm 2, the output voltage was 0.70 V, and when the current density was 300 mA / cm 2 , the output voltage was 0.80 V, which was sufficiently usable as a single cell of a polymer electrolyte fuel cell.

次いで、電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った結果を図６に示す。図６中の２７，２８，２９はそれぞれ膜電極接合体Ｖ、Ｖ'およびＶ''を用いた燃料電池単セルの耐久性試験結果である。図６中の３０はパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。 Next, FIG. 6 shows the results of a long-term operation test performed under the conditions of a current density of 300 mA / cm 2 . In FIG. 6, reference numerals 27, 28, and 29 denote durability test results of the fuel cell single cells using the membrane electrode assemblies V, V ′, and V ″, respectively. Reference numeral 30 in FIG. 6 indicates a durability test result of a single cell of a fuel cell using a perfluorosulfonic acid (Nafion 117) membrane electrode assembly.

図６中、２７は実施例４のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、２８は実施例４のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 6, reference numeral 27 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded via an alkylene group and a polyetherethersulfone solid polymer having a sulfonic acid group bonded via an alkylene group in Example 4. The change over time of the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 28 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 4, 4 is a time-dependent change of an output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which an acid group is directly bonded.

また、２９は実施例４のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、３０はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、そして、３１は比較例４のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   Reference numeral 29 denotes a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 4, and a solution for coating an electrode catalyst of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). With time, the output voltage of the fuel cell single cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) was changed, and 31 was the sulfone of Comparative Example 4. Time course of the output voltage of a fuel cell single cell using a polyetherethersulfone solid polymer electrolyte membrane with acid groups directly bonded and a solution of the polyetherethersulfone solid polymer electrolyte with directly bonded sulfonic acid groups for electrode catalyst coating It is a change.

図６の２７，２８の出力電圧は初期０．８０Ｖで、稼動時間５０００時間後でも初期とほとんど変わらず、図６の３０のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等であった。   The output voltage at 27 and 28 in FIG. 6 was initially 0.80 V, and was almost the same as the initial voltage even after 5000 hours of operation, and the result of using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 30 in FIG. Was equivalent to

一方、図６中の３１（比較例１のスルホン化芳香族炭化水素固体高分子電解質ＩＩを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 31 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte II of Comparative Example 1) in FIG. 6 was initially 0.73 V, and the output disappeared after 600 hours of operation. Was.

このことから芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質Ｖを用いた燃料電池単セルは、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質ＩＩを用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a single fuel cell using an aromatic hydrocarbon-based solid polymer electrolyte V in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group has an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the single cell of the fuel cell using the hydrocarbon-based solid polymer electrolyte II.

膜電極接合体ＶおよびＶ''を用いた燃料電池単セルの耐久性は、膜電極接合体Ｖ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液Ｖは電極触媒被覆用溶液ＩＩより、膜電極接合体の電極触媒被覆に適している。   The durability of a single fuel cell using the membrane electrode assemblies V and V ″ is superior to the durability of a single fuel cell using the membrane electrode assembly V ′. That is, the electrode catalyst coating solution V is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II.

また、実施例４および比較例１の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例４の燃料電池単セルの出力電圧が比較例１の燃料電池単セルの出力電圧より大きい理由は、実施例４の膜電極接合体Ｖの固体高分子電解質膜Ｖおよび電極触媒被覆用溶液Ｖのイオン導電率が、比較例１の膜電極接合体ＩＩの固体高分子電解質膜ＩＩおよび電極触媒被覆用溶液ＩＩのイオン導電率より高いからである。 Further, the output voltage of the single cell of the fuel cell of Example 4 was lower than that of Comparative Example 1 even though the supported amount of platinum of the membrane electrode assemblies of Example 4 and Comparative Example 1 was the same as 0.25 mg / cm 2 . The reason for the higher output voltage of the single cell of the fuel cell is that the ionic conductivity of the solid polymer electrolyte membrane V of the membrane electrode assembly V of Example 4 and the ionic conductivity of the electrode catalyst coating solution V are different from those of the membrane electrode assembly II of Comparative Example 1. Is higher than the ionic conductivity of the solid polymer electrolyte membrane II and the electrode catalyst coating solution II.

実施例３と４から分かるように、スルホン酸当量重量が５３０〜９７０ｇ／当量であるスルホアルキル化ポリ−エーテルエーテルスルホン固体電解質を用いた燃料電池単セルの初期の出力電圧は、パーフルオロスルホン酸（ナフィオン１１７）膜を用いた燃料電池単セルの出力電圧と同等以上であり、５０００時間稼動させても劣化せず特に好ましい。   As can be seen from Examples 3 and 4, the initial output voltage of a fuel cell unit cell using a sulfoalkylated poly-ether ether sulfone solid electrolyte having a sulfonic acid equivalent weight of 530 to 970 g / equivalent is determined by the perfluorosulfonic acid The output voltage is equal to or higher than the output voltage of a single cell of a fuel cell using a (Nafion 117) membrane, and is particularly preferable because it does not deteriorate even after operating for 5000 hours.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 ５〜９〕
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃で１０時間保持乾燥した６．００ｇ（０．０１５５ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と脱水溶媒１５０ｍｌを入れ、加熱溶解した。この溶液にプロパンスルトンを加えた。 [Examples 5 to 9]
The inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, and then dried at 110 ° C. for 10 hours by drying 6.00 g (0.0155 mol). poly 1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4-C 6 H 4 -4-O-) n ] and dehydration 150 ml of the solvent was added and dissolved by heating. To this solution was added propane sultone.

次いで、乳鉢で良くすりつぶした無水塩化アルミニウムを撹拌しながら約３０分かけて加えた。なお、プロパンスルトンと無水塩化アルミニウムの配合量を表１に記した。   Then, anhydrous aluminum chloride, well ground in a mortar, was added over about 30 minutes with stirring. The amounts of propane sultone and anhydrous aluminum chloride are shown in Table 1.

無水塩化アルミニウムを添加した後、表１記載の温度で表１記載の時間攪拌した。   After adding anhydrous aluminum chloride, the mixture was stirred at the temperature shown in Table 1 for the time shown in Table 1.

生じた沈澱を濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥した。得られた沈澱を水２５０ｍｌに懸濁させ、ミキサーで細かく砕き、濾過した。これを４回繰り返した。水で十分洗浄した後、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。１ＨＮＭＲを測定すると、新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づく２．２ｐｐｍ、３．８ｐｐｍが認められた。このことからスルホプロピル基が導入されていることが確認された。得られたスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質のスルホン酸当量重量の測定、固体高分子電解質、固体高分子電解質膜、電極触媒被覆溶液および固体高分子電解質膜電極接合体の耐水劣化特性、および、燃料電池単セルの評価を行った。その結果を表１に示す。 The resulting precipitate was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The resulting precipitate was suspended in 250 ml of water, crushed with a mixer and filtered. This was repeated four times. After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure. When 1 HNMR was measured, 2.2 ppm and 3.8 ppm based on the —CH 2 CH 2 CH 2 SO 3 H group were newly observed. This confirmed that the sulfopropyl group had been introduced. Measurement of sulfonic acid equivalent weight of the obtained sulfoalkylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte, solid polymer electrolyte, solid polymer electrolyte membrane, electrode catalyst coating solution and solid polymer electrolyte membrane electrode bonding The body was evaluated for water resistance and the fuel cell unit cells were evaluated. Table 1 shows the results.

Figure 2004152776
Figure 2004152776

スルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質のコストは、市販の安価なエンジニアプラスチックを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ、１／４０以下と安価である。   The cost of the sulfoalkylated poly (1,4-biphenylene ether ether sulfone) solid polymer electrolyte can be produced in one step from a commercially available inexpensive engineering plastic, so that the raw material is expensive and the perfluorosulfone produced through five steps Compared to the cost of the acid solid polymer electrolyte (Nafion 117), it is inexpensive at 1/40 or less.

実施例５〜９のスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質を、テフロンコーテングのＳＵＳ製密閉容器中イオン交換水中で１２０℃／２週間保持後のスルホン酸当量重量は、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＶと異なり、初期と変わらず、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   The sulfonic acid equivalent weight of the sulfoalkylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolytes of Examples 5 to 9 after being kept at 120 ° C. for 2 weeks in ion-exchanged water in a Teflon-coated closed container made of SUS is as follows: Unlike the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte IV of Comparative Example 1, the same as the initial stage, the same as perfluorosulfonic acid solid polymer electrolyte (Nafion 117) is stable, cost and hydrolysis resistant Excellent in durability (durability).

実施例５〜９のスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜を、テフロンコーテングのＳＵＳ製密閉容器中イオン交換水中で１２０℃／２週間保持した後の形態は、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜と異なり、初期と変わらず、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   The form after holding the sulfoalkylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membranes of Examples 5 to 9 in ion-exchanged water in a Teflon-coated closed vessel made of SUS at 120 ° C for 2 weeks is comparative. Unlike the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane of Example 1, the same as the initial stage, the same as the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), it is stable, cost and water resistant. Excellent in both decomposability (durability).

実施例５〜９の電極触媒被覆溶液を、テフロンコーテングのＳＵＳ製密閉容器中イオン交換水中で１２０℃／２週間保持した後のスルホン酸当量重量は、比較例１の電極触媒被覆溶液ＩＩと異なり、初期と変わらず、パーフルオロスルホン酸（ナフィオン１１７）電極被覆溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   The sulfonic acid equivalent weight after holding the electrode catalyst coating solutions of Examples 5 to 9 in ion-exchanged water at 120 ° C. for 2 weeks in a Teflon-coated closed vessel made of SUS is different from the electrode catalyst coating solution II of Comparative Example 1. As in the initial stage, it is stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode coating solution, and is excellent in both cost and hydrolysis resistance (durability).

実施例５〜９のスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体を、テフロンコーテングのＳＵＳ製密閉容器中イオン交換水と１２０℃に２週間加熱しても、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン膜電極接合体と異なり初期と変化せず、パーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   The sulfoalkylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assemblies of Examples 5 to 9 were heated to 120 ° C. with ion-exchanged water in a Teflon-coated closed vessel made of SUS for 2 weeks, Unlike the sulfonated poly 1,4-biphenylene ether ether sulfone membrane electrode assembly of Comparative Example 1, it does not change from the initial stage, and is stable and cost similar to the perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly. And excellent hydrolysis resistance (durability).

また、３００ｍＡ／ｃｍ２で５０００時間稼動後の実施例５〜９のスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜を用いた単電池セルの出力は、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜を用いた単電池セルと異なり、初期と変わらず、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた単電池セルと同様に安定でコストと耐加水分解性（耐久性）が両立し優れている。 In addition, the output of the single cell using the sulfoalkylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane of Examples 5 to 9 after operation at 300 mA / cm 2 for 5000 hours is the same as that of the sulfone of Comparative Example 1. Battery cell using a perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), unlike the single battery cell using a hydrogenated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane It is excellent in both cost and hydrolysis resistance (durability).

〔実施例 １０〕
（１） スルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換後、１１０℃で１０時間保持乾燥した６．００ｇ（０．０１５５ｍｏｌ）のポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕と脱水クロロホルム１５０ｍｌを入れ、６０℃にて約１時間保持して溶解した。この溶液にブタンスルトン６．２６ｇ（０．０４６４ｍｏｌ）を加えた。 [Example 10]
(1) Synthesis of sulfobutylated poly 1,4-biphenylene ether ether sulfone The inside of a 500 ml four-necked round-bottomed flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. 6.00 g (0.0155 mol) of poly-1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4) which was kept and dried at 10 ° C. for 10 hours. -C 6 H 4 -4-O-) n ] and ml of dehydrated chloroform 150 ml, was dissolved and held for about 1 hour at 60 ° C.. 6.26 g (0.0464 mol) of butane sultone was added to this solution.

次いで、乳鉢で良くすりつぶした無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を撹拌しながら約３０分かけて加えた。無水塩化アルミニウムを添加後、２０時間，６０℃で還流攪拌した。析出物を濾過し、クロロホルム１５０ｍｌで洗浄して減圧乾燥した。析出物を水２５０ｍｌに懸濁させ、ミキサーで細かく砕き、得た微粉砕物を濾過した。これを４回繰り返した。水で十分洗浄した後、水不溶性の微粉砕物を減圧下９０℃で乾燥した。１ＨＮＭＲを測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが１．６〜３．８ｐｐｍに認められた。このことからスルホブチル基が導入されていることが確認された。 Then, 6.19 g (0.0464 mol) of anhydrous aluminum chloride thoroughly ground in a mortar was added over about 30 minutes while stirring. After the addition of anhydrous aluminum chloride, the mixture was refluxed and stirred at 60 ° C. for 20 hours. The precipitate was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The precipitate was suspended in 250 ml of water, finely ground with a mixer, and the obtained finely pulverized product was filtered. This was repeated four times. After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure. When 1 HNMR was measured, a peak based on a —CH 2 CH 2 CH 2 CH 2 SO 3 H group was newly observed at 1.6 to 3.8 ppm. This confirmed that the sulfobutyl group had been introduced.

得られたスルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩのスルホン酸当量重量は６７０ｇ／当量であった。   The sulfonic acid equivalent weight of the obtained sulfobutylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI was 670 g / equivalent.

スルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfobutylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI can be produced in one step using poly 1,4-biphenylene ether ether sulfone, a commercially available relatively inexpensive engineering plastic, as a raw material. Is expensive and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

スルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩは、スルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩと同様に１工程で製造できるため、後述の実施例１１，１２に示したように、２段階の工程を経て製造されるスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質や、スルホヘキサメチル化スルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質より低コストで合成でき、コスト的に有利である。   Since the sulfobutylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI can be produced in one step similarly to the sulfopropylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI, the following Example 11 was used. , 12, a sulfomethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte produced through a two-step process, a sulfohexamethylated sulfomethylated poly-1,4-biphenylene ether ether sulfone solid It can be synthesized at lower cost than the polymer electrolyte, and is advantageous in cost.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して十分に水洗した後、スルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfobutylated poly1,4-biphenylene ether ether sulfone solid polymer electrolyte VI and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the equivalent weight of the ion-exchange group of the sulfobutylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI was measured.

その結果、スルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩのイオン交換基当量重量は初期と変わらず、６７０ｇ／当量と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the ion-exchange group equivalent weight of the sulfobutylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI was unchanged from the initial level, and was 670 g / equivalent, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Was stable.

一方、比較例１の（１）に示したように安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 1, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II was 1200 g / equivalent under the same heated hydrolysis conditions. And became larger than the initial value of 650 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩは、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   That is, the inexpensive sulfobutylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte VI is different from the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II of Comparative Example 1, and is different from perfluorosulfonic acid solid polymer electrolyte VI. It is as stable as the polymer electrolyte (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミドーシクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜ＶＩを作成した。得られた固体高分子電解質膜ＶＩのイオン導電率は２５Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamido-cyclohexanone-methylethylketone mixed solvent (volume ratio 20:80:25) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane VI. The ionic conductivity of the obtained solid polymer electrolyte membrane VI was 25 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に前記固体高分子電解質膜ＶＩとイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、該電解質膜ＶＩのイオン導電率は、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The solid polymer electrolyte membrane VI and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity of the electrolyte membrane VI was the same as that of the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例１の（２）に示したように比較的安価なスルホン化芳香族炭化水素系固体高分子電解質ＩＩは、同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩは、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩとは異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   On the other hand, as shown in (2) of Comparative Example 1, the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte II was broken and ragged under the same heating and hydrolysis conditions. That is, unlike the sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II of Comparative Example 1, the inexpensive sulfobutylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VI is different from perfluorosulfone. Like the acid solid polymer electrolyte membrane (Nafion 117), it is stable, excellent in both cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＶＩ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution VI).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＶＩの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃で２週間保持した。その後、冷却して溶媒を揮散させ、生じた固体を水洗後、電極触媒被覆用溶液ＶＩのイオン交換基当量重量を測定した。その結果、該溶液ＶＩのイオン交換基当量重量は初期と変わらず６７０ｇ／当量と、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution VI and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the mixture was cooled to evaporate the solvent, the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution VI was measured. As a result, the ion exchange group equivalent weight of the solution VI was 670 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例１の（２）に示したように電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液ＶＩは、比較例１の電極触媒被覆用溶液ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定でコストと耐加水分解性（耐久性）が両立し優れている。   On the other hand, as shown in (2) of Comparative Example 1, the equivalent weight of the ion-exchange group of the solution II for electrode catalyst coating changes to 1200 g / equivalent under the same heating and hydrolysis conditions, and the initial equivalent value of 650 g / equivalent changes. It became larger and the sulfonic acid group was eliminated. That is, the inexpensive electrode catalyst coating solution VI is different from the electrode catalyst coating solution II of Comparative Example 1 in that it is as stable, cost-effective and hydrolytically resistant as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. Durability).

前記電極触媒被覆用溶液ＶＩを前記（２）で得られた固体高分子電解質膜ＶＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩを作製した。 The electrode catalyst coating solution VI was applied to both sides of the solid polymer electrolyte membrane VI obtained in the above (2), and then dried to prepare a membrane electrode assembly VI having a platinum loading of 0.25 mg / cm 2 . .

比較例１の（２）に記載した電極触媒被覆用溶液ＩＩを前記（２）で得られた固体高分子電解質膜ＶＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩ'を作製した。 The electrode catalyst coating solution II described in (2) of Comparative Example 1 was applied to both sides of the solid polymer electrolyte membrane VI obtained in (2), and then dried to carry a platinum loading of 0.25 mg / cm 2. Was prepared.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコール／水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＶＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩ''を作製した。 To a 40% by weight platinum-supported carbon, a 5% by weight alcohol / water mixed solution of perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. Then, the mixture was uniformly dispersed to prepare a paste (electrode catalyst coating solution). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane VI obtained in the above (2), and then dried to produce a membrane electrode assembly VI ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＶＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩは、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly VI and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane electrode assembly VI is composed of a high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and a membrane electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Similarly, the film was firm as before.

テフロンコーテングのＳＵＳ製密閉容器に前記膜電極接合体ＶＩ'とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体ＶＩ'は電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The membrane electrode assembly VI ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, although the electrode was slightly peeled off in the membrane electrode assembly VI ′, the membrane was firm and had a power generation ability.

テフロンコーテングのＳＵＳ製密閉容器に前記膜電極接合体ＶＩ''とイオン交換水２０ｍｌを入れ、１２０℃で２週間保持した。その結果、膜電極接合体ＶＩ''は電極が若干剥がれていたが膜はしっかりしており、発電能力もあった。   The membrane electrode assembly VI ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the electrode of the membrane electrode assembly VI ″ was slightly peeled off, but the membrane was firm and had a power generation capability.

一方、比較例１の（３）に示したように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜ＩＩと、電極触媒被覆用溶液ＩＩを用いて作製した膜電極接合体ＩＩは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 1, a relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane II and a membrane / electrode assembly II produced using an electrode catalyst coating solution II In the case of, under the same heating hydrolysis conditions, the membrane was broken and ragged, and the electrode was peeled off.

即ち、安価なスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＶＩは、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＩＩとは異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立し優れている。   That is, the inexpensive sulfopropylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly VI is the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly of Comparative Example 1. Unlike II, it is as stable as the perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and is excellent in both cost and hydrolysis resistance (durability).

（４） 燃料電池単セル出力性能評価
前記膜電極接合体ＶＩ、ＶＩ'およびＶＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。これらの膜電極接合体を評価セルに組みこみ、燃料電池出力性能を評価した。図７に膜電極接合体ＶＩを組み込んだ燃料電池単セルの電流密度−電圧プロットを示す。 (4) Evaluation of fuel cell single cell output performance The membrane electrode assemblies VI, VI ′ and VI ″ were immersed in boiling deionized water for 2 hours to absorb water. These membrane electrode assemblies were assembled into an evaluation cell, and the output performance of the fuel cell was evaluated. FIG. 7 shows a current density-voltage plot of a single fuel cell incorporating the membrane electrode assembly VI.

電流密度１Ａ／ｃｍ２のとき出力電圧は０．７０Ｖで、電流密度３００ｍＡ／ｃｍ２のとき出力電圧は０．７９Ｖであり、固体高分子型燃料電池単セルとして十分使用可能であった。 When the current density was 1 A / cm 2, the output voltage was 0.70 V, and when the current density was 300 mA / cm 2 , the output voltage was 0.79 V. Thus, the cell was sufficiently usable as a single polymer electrolyte fuel cell.

実施例１０の膜電極接合体ＶＩ、ＶＩ'およびＶＩ''の両側に薄いカーボンペーパのパッキング材（支持集電体）を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）からなる固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果を図８に示す。 A thin carbon paper packing material (supporting current collector) is adhered to both sides of the membrane electrode assemblies VI, VI ′, and VI ″ of Example 10, and separation of the electrode chamber from both sides thereof and a gas supply passage to the electrode are performed. A single cell of a polymer electrolyte fuel cell composed of a conductive separator (bipolar plate) also serving as a role was manufactured, and a long-term operation test was performed under the conditions of a current density of 300 mA / cm 2 . FIG. 8 shows the result.

図８中の３２，３３，３４はそれぞれ膜電極接合体ＶＩ、ＶＩ'、ＶＩ''を用いた燃料電池単セルの耐久性試験結果である。図８中の３５はパーフルオロスルホン酸（ナフィオン１１７）膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 8, reference numerals 32, 33, and 34 denote durability test results of a single fuel cell using the membrane electrode assemblies VI, VI ', and VI' ', respectively. Reference numeral 35 in FIG. 8 indicates a durability test result of a single fuel cell using a perfluorosulfonic acid (Nafion 117) membrane electrode assembly.

図８中、３２は実施例１０のアルキレン基を介してスルホン酸基が結合したポリ−エーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリ−エーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、３３は実施例１０のアルキレン基を介してスルホン酸基が結合したポリ−エーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリ−エーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 8, reference numeral 32 denotes a poly-ether ether sulfone solid polymer electrolyte membrane having a sulfonic acid group bonded via an alkylene group in Example 10, and a poly-ether ether sulfone solid having a sulfonic acid group bonded via an alkylene group. Time-dependent change in output voltage of a fuel cell unit cell using a solution for coating an electrode catalyst of a polymer electrolyte, reference numeral 33 denotes a poly-ether ether sulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 10. And the change over time of the output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a poly-ether ether sulfone solid polymer electrolyte to which sulfonic acid groups are directly bonded.

また、３４は実施例１０のアルキレン基を介してスルホン酸基が結合したポリ−エーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、３５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、そして、３６は比較例１０のスルホン酸基が直接結合したポリ−エーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリ−エーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   Reference numeral 34 denotes a poly-ether ether sulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 10, and a solution for coating an electrode catalyst of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The change with time of the output voltage of the single cell of the fuel cell used, the change with 35 of the output voltage of the single cell of the fuel cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the 36 of Comparative Example 10 Output of a fuel cell single cell using a poly-ether ether sulfone solid polymer electrolyte membrane having sulfonic acid groups directly bonded and a solution for coating an electrode catalyst of a poly-ether ether sulfone solid polymer electrolyte having directly bonded sulfonic acid groups It is a change with time of the voltage.

図８の３２，３４の出力電圧は初期０．７９Ｖで、稼動時間５０００時間後でも初期と変わらず、図８の３５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等であった。   The output voltages of 32 and 34 in FIG. 8 were initially 0.79 V, which were the same as the initial values even after an operation time of 5000 hours. The results obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 35 in FIG. It was equivalent.

一方、図８中の３６（比較例１のスルホン化芳香族炭化水素固体高分子電解質ＩＩを使用した燃料電池単セル）の電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the voltage of 36 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte II of Comparative Example 1) in FIG. 8 was initially 0.73 V, and the output disappeared after 600 hours of operation. .

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質ＶＩを用いた燃料電池単セルは、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質ＩＩを用いた燃料電池単セルより耐久性に優れていることが明白である。   From this, the fuel cell single cell using the aromatic hydrocarbon-based solid polymer electrolyte VI in which a sulfonic acid group is bonded to the aromatic ring of the aromatic hydrocarbon via an alkylene group is not suitable for the fuel cell unit cell. It is evident that the fuel cell has higher durability than the single cell using the aromatic hydrocarbon-based solid polymer electrolyte II.

また、膜電極接合体ＶＩおよびＶＩ''を用いた燃料電池単セルの耐久性は膜電極接合体ＶＩ'を用いた燃料電池単セルの耐久性より優れている。   Further, the durability of the single fuel cell using the membrane electrode assemblies VI and VI ″ is superior to the durability of the single fuel cell using the membrane electrode assembly VI ′.

即ち、電極触媒被覆用溶液ＶＩは、電極触媒被覆用溶液ＩＩよりも膜電極接合体の電極触媒被覆に適している。   That is, the electrode catalyst coating solution VI is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II.

また、実施例１０および比較例１の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１０の燃料電池単セルの出力電圧が、比較例１の燃料電池単セルの出力電圧より大きい理由は、実施例１０の膜電極接合体の固体高分子電解質膜ＶＩおよび電極触媒被覆用溶液ＶＩのイオン導電率が、比較例１の膜電極接合体の固体高分子電解質膜ＩＩおよび電極触媒被覆用溶液ＩＩのイオン導電率より高いからである。 In addition, the output voltage of the single fuel cell of Example 10 was lower than that of Comparative Example 1 even though the supported amount of platinum of the membrane electrode assembly of Example 10 and Comparative Example 1 was the same as 0.25 mg / cm 2. The reason is that the ionic conductivity of the solid polymer electrolyte membrane VI and the solution VI for electrode catalyst coating of the membrane electrode assembly of Example 10 is larger than that of the membrane electrode assembly of Comparative Example 1. This is because the ionic conductivity of the solid polymer electrolyte membrane II and the ionic conductivity of the electrode catalyst coating solution II are higher.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、図１３に示す固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the unit cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell shown in FIG. 13, an output of 3 kW was shown.

〔実施例 １１〕
（１） クロルメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、３６．１ｇのポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｏ−）ｎ〕、６０ｇ（２モル）のパラホルムアルデヒド、乾燥した５０ｍｌのニトロベンゼンを入れた。１００℃に保って撹拌しながら７３ｇの塩化水素ガスを吹き込んだ。吹き込み終了後、１５０℃で４時間保った。 [Example 11]
(1) Synthesis of chloromethylated poly-1,4-biphenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 36.1g of poly 1,4-biphenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4-O-) n ], 60 g (2 moles) Of paraformaldehyde and 50 ml of dried nitrobenzene. 73 g of hydrogen chloride gas was blown in while maintaining the temperature at 100 ° C. and stirring. After the completion of the blowing, the temperature was kept at 150 ° C. for 4 hours.

次いで、反応溶液を１リットルの脱イオン水にゆっくりと滴下することでクロルメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と、吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、８０℃で一晩減圧乾燥した。   Then, the reaction solution was slowly dropped into 1 liter of deionized water to precipitate chloromethylated poly 1,4-biphenylene ether ether sulfone, which was collected by filtration. The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 80 ° C. overnight.

（２） スルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換後、１０ｇの前記クロルメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン、乾燥した５０ｍｌのニトロベンゼン、３０ｇの硫酸ナトリウムを入れ、１００℃で５時間撹拌した。さらに、１０ｍｌのイオン交換水を加え、５時間撹拌した。 (2) Synthesis of sulfomethylated poly 1,4-biphenylene ether ether sulfone 10 g after replacing the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube with nitrogen. Of chloromethylated poly-1,4-biphenylene ether ether sulfone, 50 ml of dried nitrobenzene and 30 g of sodium sulfate were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 10 ml of ion-exchanged water was added, and the mixture was stirred for 5 hours.

次いで、反応溶液を１リットルの脱イオン水にゆっくりと滴下することでスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と、吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、１２０℃で一晩減圧乾燥した。   Then, the reaction solution was slowly dropped into 1 liter of deionized water to precipitate sulfomethylated poly-1,4-biphenylene ether ether sulfone, which was collected by filtration. The precipitated precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 120 ° C. overnight.

１ＨＮＭＲを測定すると新たに−ＣＨ２ＳＯ３Ｈ基に基づくピークが４．５ｐｐｍに認められ、スルホメチル基が導入されていることが確認された。得られたスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩのイオン交換基当量重量は６６０ｇ／当量であった。 When 1 HNMR was measured, a new peak based on —CH 2 SO 3 H group was observed at 4.5 ppm, confirming that a sulfomethyl group was introduced. The ion exchange group equivalent weight of the obtained sulfomethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte VII was 660 g / equivalent.

本製法で得られるスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩのコストは、市販の安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料に２工程で製造でき、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／３０以下と極めて安価である。   The cost of the sulfomethylated poly (1,4-biphenylene ether ether sulfone) solid polymer electrolyte VII obtained by this method can be produced in two steps using poly (1,4-biphenylene ether ether sulfone), a commercially available inexpensive engineering plastic, as a raw material. The raw material is expensive, and is extremely inexpensive at 1/30 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) produced through five steps.

テフロンコーテングのＳＵＳ製密閉容器に得られたスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩの１．０ｇと、イオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して十分に水洗した後、スルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩのイオン交換基当量重量を測定した。   1.0 g of the obtained sulfomethylated poly (1,4-biphenylene ether ether sulfone) solid polymer electrolyte VII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the ion exchange group equivalent weight of the sulfomethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VII was measured.

その結果、スルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩのイオン交換基当量重量は、初期と変わらず６６０ｇ／当量とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the ion-exchange group equivalent weight of the sulfomethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VII was 660 g / equivalent to the initial value, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). It was stable.

一方、比較例１の（１）に示したように、安価なスルホン化芳香族炭化水素固体高分子電解質ＩＩのイオン交換基当量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 1, the ion exchange group equivalent of the inexpensive sulfonated aromatic hydrocarbon solid polymer electrolyte II was changed to 1200 g / equivalent under the same heating and hydrolysis conditions. Was larger than the value of 650 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩは、安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホンＶＩＩ固体高分子電解質ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfomethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte VII is different from the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone VII solid polymer electrolyte II, and is different from the expensive perfluorosulfonic acid. Like the solid polymer electrolyte (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（３） 固体高分子電解質膜の作製
前記（２）で得られたスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩを、５重量％の濃度になるようにトリクロロエタン−ジクロロエタンの混合溶媒（１：１）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４２μｍのスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩを作成した。得られた固体高分子電解質膜ＶＩＩのイオン伝導度は７Ｓ／ｃｍであった。 (3) Preparation of solid polymer electrolyte membrane The sulfomethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VII obtained in the above (2) was mixed with trichloroethane-dichloroethane so as to have a concentration of 5% by weight. Dissolved in solvent (1: 1). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 42 μm-thick sulfomethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VII. The ionic conductivity of the obtained solid polymer electrolyte membrane VII was 7 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に前記スルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、固体高分子電解質膜ＶＩＩのイオン導電率は、高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The sulfomethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity of the solid polymer electrolyte membrane VII was the same as that of the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例１の（２）に示したように比較的安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩは、同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩは、安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 1, the relatively inexpensive sulfonated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte II was broken and ragged under the same heating and hydrolysis conditions. . That is, the inexpensive sulfomethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VII is different from the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II and is different from the expensive perfluorosulfone. Similar to the acid solid polymer electrolyte membrane (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（４） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（３）のトリクロロエタン−ジクロロエタンの混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＶＩＩ）を調製した。 (4) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The mixed solution of (3) trichloroethane and dichloroethane described above in 40% by weight of platinum-carrying carbon was used, and the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2%. : 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution VII).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＶＩＩの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液ＶＩＩのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＶＩＩのイオン交換基当量重量は、初期と変わらず６６０ｇ／当量とパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution VII and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and evaporating the solvent and washing the resulting solid, the ion exchange group equivalent weight of the electrode catalyst coating solution VII was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution VII was 660 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例１の（２）に示したように、電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (2) of Comparative Example 1, the ion exchange group equivalent weight of the electrode catalyst coating solution II changes to 1200 g / equivalent under the same heating hydrolysis conditions, and the initial value of 650 g / equivalent value. It became larger and the sulfonic acid group was eliminated.

即ち、安価な電極触媒被覆用溶液ＶＩＩは、比較例１の電極触媒被覆用溶液ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, unlike the electrode catalyst coating solution II of Comparative Example 1, the inexpensive electrode catalyst coating solution VII is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution, and has a low cost and hydrolysis resistance. (Durability) are both excellent.

前記電極触媒被覆用溶液ＶＩＩを前記（２）で得られた固体高分子電解質膜ＶＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩＩを作製した。 The electrode catalyst coating solution VII was applied to both sides of the solid polymer electrolyte membrane VII obtained in the above (2), and then dried to prepare a membrane electrode assembly VII having a platinum loading of 0.25 mg / cm 2 . .

比較例１の（２）に記した電極触媒被覆溶液ＩＩを前記（２）で得られた固体高分子電解質膜ＶＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩＩ'を作製した。４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコール−水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＶＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩＩ''を作製した。 The electrode catalyst coating solution II described in (2) of Comparative Example 1 was applied to both sides of the solid polymer electrolyte membrane VII obtained in (2), and then dried to obtain a platinum-supporting amount of 0.25 mg / cm 2 . A membrane electrode assembly VII 'was produced. To a 40% by weight of platinum-supported carbon, a 5% by weight alcohol-water mixed solution of perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. Then, the mixture was uniformly dispersed to prepare a paste (electrode catalyst coating solution). This solution for coating an electrode catalyst is applied to both sides of the solid polymer electrolyte membrane VII obtained in the above (2), and then dried to produce a membrane electrode assembly VII ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に、得られた前記膜電極接合体ＶＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩＩは高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly VII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly VII is similar to a membrane / electrode assembly manufactured using a high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). As in the early days, the film was firm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＶＩＩ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩＩ'は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly VII ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS, and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly VII 'had slightly peeled electrodes, but the membrane was firm and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＶＩＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩＩ''は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly VII ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly VII ″ had electrodes slightly peeled off, but the membrane was firm and had a power generation capability.

一方、比較例１の（３）に示したように比較的安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩと電極触媒被覆用溶液ＩＩを用いて作製した膜電極接合体ＩＩは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。即ち、安価なスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＶＩＩは、比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (3) of Comparative Example 1, a membrane-electrode junction formed using a relatively inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II and an electrode catalyst coating solution II. In the case of the body II, the membrane was broken and ragged under the same heating hydrolysis conditions, and the electrode was peeled off. That is, the inexpensive sulfomethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly VII is the same as the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly II of Comparative Example 1. Unlike the perfluorosulfonic acid (Nafion 117) membrane electrode assembly, it is stable, and is excellent in both cost and hydrolysis resistance (durability).

（５） 燃料電池単セル出力性能評価
前記膜電極接合体ＶＩＩ、ＶＩＩ'およびＶＩＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体ＶＩＩを評価セルに組み込み、燃料電池出力性能を評価した。得られた電流密度−出力電圧プロットを図９に示す。電流密度１Ａ／ｃｍ２のとき出力電圧は０．６５Ｖで、電流密度３００ｍＡ／ｃｍ２のとき出力電圧は０．７４Ｖで固体高分子型燃料電池単セルとして十分使用可能であった。 (5) Evaluation of Single Cell Output Performance of Fuel Cell The membrane electrode assemblies VII, VII ′ and VII ″ were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly VII was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated. FIG. 9 shows the obtained current density-output voltage plot. When the current density was 1 A / cm 2, the output voltage was 0.65 V, and when the current density was 300 mA / cm 2 , the output voltage was 0.74 V, which was sufficiently usable as a single cell of a polymer electrolyte fuel cell.

また、前記固体高分子型燃料電池単セルを電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果を図１０に示す。 A long-term operation test was performed on the single cell of the polymer electrolyte fuel cell under the condition of a current density of 300 mA / cm 2 . The result is shown in FIG.

図１０中の３７，３８，３９はそれぞれ固体高分子電解質膜電極接合体ＶＩＩ，ＶＩＩ'，ＶＩＩ''を用いた燃料電池単セルの耐久性試験結果である。図１０中の４０はパーフルオロスルホン酸（ナフィオン１１７固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   37, 38, and 39 in FIG. 10 are the results of the durability test of the single fuel cell using the solid polymer electrolyte membrane electrode assemblies VII, VII ′, and VII ″, respectively. In FIG. 10, reference numeral 40 denotes a durability test result of a fuel cell unit cell using a perfluorosulfonic acid (Nafion 117 solid polymer electrolyte membrane electrode assembly).

図１０中、３７は実施例１１のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、３８は実施例１１のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、３９は実施例１１のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、４０はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、４１は比較例１１のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 10, reference numeral 37 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 11, and a polyetherethersulfone solid polymer having a sulfonic acid group bonded through an alkylene group. The change over time of the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 38 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 11; Change with time of output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which an acid group is directly bonded. Reference numeral 39 denotes a sulfonic acid group bonded via an alkylene group in Example 11. Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte With time of the output voltage of a single cell of a fuel cell using the electrode catalyst coating solution of Naion 117), and 40 with time of the output voltage of a single cell of a fuel cell using a perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) Reference numeral 41 denotes a polyetherethersulfone solid polymer electrolyte membrane to which sulfonic acid groups were directly bonded, and a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which sulfonic acid groups were directly bonded. It is a change with time of the output voltage of a single fuel cell.

図１０の３７と３９の電圧はいずれも初期０．７４Ｖで、稼動時間５０００時間後でも初期と変わらず、図１０の４０のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等であった。   The voltage at 37 and 39 in FIG. 10 was initially 0.74 V, and was the same as the initial voltage even after the operation time of 5000 hours. The result of using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 40 in FIG. Was equivalent to

一方、図１０中の４１（比較例１のスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＩを使用した燃料電池単セル）の電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the voltage of 41 (single fuel cell using the sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane II of Comparative Example 1) in FIG. 10 was initially 0.73 V, and the operating time was 600 hours. Later the output was gone.

このことから芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   This suggests that a single fuel cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to the aromatic ring of an aromatic hydrocarbon via an alkylene group can be used to form an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the fuel cell has a higher durability than the single cell using the hydrogen-based solid polymer electrolyte.

膜電極接合体ＶＩＩおよびＶＩＩ''を用いた燃料電池単セルの耐久性は膜電極接合体ＶＩＩ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＶＩＩは、電極触媒被覆用溶液ＩＩより膜電極接合体の電極触媒被覆に適している。   The durability of a single fuel cell using the membrane electrode assemblies VII and VII ″ is superior to the durability of a single fuel cell using the membrane electrode assembly VII ′. That is, the electrode catalyst coating solution VII is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II.

また、実施例１１および比較例１の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１１の燃料電池単セルの出力電圧が比較例４の燃料電池単セルの出力電圧より大きい理由は、実施例１１の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が比較例１の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 Further, the output voltage of the single cell of the fuel cell of Example 11 was lower than that of Comparative Example 4 even though the supported platinum amount of the membrane electrode assemblies of Example 11 and Comparative Example 1 was the same as 0.25 mg / cm 2 . The reason why the output voltage is higher than the output voltage of the single cell of the fuel cell is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 11 and the ionic conductivity of the solution for coating the electrode catalyst are the solid polymer electrolyte of the membrane electrode assembly of Comparative Example 1. This is because it is higher than the ionic conductivity of the solution for coating the membrane and the electrode catalyst.

（６） 燃料電池の作製
前記（５）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (6) Production of Fuel Cell When the cell unit cell produced in the above (5) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 １２〕
（１） ブロモヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、３８．８ｇのポリ１，４−ビフェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕、乾燥した５０ｍｌのニトロベンゼンを入れた。これに６．５ｇのｎ−ブトキシリチウムを加え、室温に２時間保った。次いで、１００ｇの１，６−ジブロモヘキサンを加え、さらに１２時間撹拌した。反応溶液を１リットルの脱イオン水にゆっくりと滴下することでブロモヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンを析出させ、濾過回収した。 [Example 12]
(1) Synthesis of bromohexamethylated poly 1,4-biphenylene ether ether sulfone The inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. after, poly 1,4-biphenylene ether ether sulfone 38.8g [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4-C 6 H 4 -4-O- N), 50 ml of dried nitrobenzene were added. To this was added 6.5 g of n-butoxylithium and kept at room temperature for 2 hours. Next, 100 g of 1,6-dibromohexane was added, and the mixture was further stirred for 12 hours. The reaction solution was slowly dropped into 1 liter of deionized water to precipitate bromohexamethylated poly-1,4-biphenylene ether ether sulfone, which was collected by filtration.

析出した沈澱をミキサーによる脱イオン水洗浄と吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、１２０℃にて一晩減圧乾燥した。   The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 120 ° C. overnight.

（２） スルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１０ｇの前記ブロモヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン、乾燥した５０ｍｌのニトロベンゼン、３０ｇの硫酸ナトリウムを入れ、１００℃にて５時間撹拌した。さらに、１０ｍｌのイオン交換水を加え、５時間撹拌した。 (2) Synthesis of sulfohexamethylated poly 1,4-biphenylene ether ether sulfone The inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. Thereafter, 10 g of the above bromohexamethylated poly 1,4-biphenylene ether ether sulfone, 50 ml of dried nitrobenzene, and 30 g of sodium sulfate were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 10 ml of ion-exchanged water was added, and the mixture was stirred for 5 hours.

次いで、反応溶液を１リットルの脱イオン水にゆっくりと滴下することでスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホンを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、１２０℃にて一晩減圧乾燥した。１ＨＮＭＲを測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが１．３〜３．８ｐｐｍに認められた。このことから得られたスルホヘキサメチル基が導入されていることが確認された。スルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩのイオン交換基当量重量は６７０ｇ／当量であった。 Next, the reaction solution was slowly dropped into 1 liter of deionized water to precipitate sulfohexamethylated poly-1,4-biphenylene ether ether sulfone, which was collected by filtration. The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 120 ° C. overnight. When 1 HNMR was measured, a peak based on a —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 SO 3 H group was newly observed at 1.3 to 3.8 ppm. From this, it was confirmed that the obtained sulfohexamethyl group was introduced. The ion exchange group equivalent weight of the sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VIII was 670 g / equivalent.

本製法で得られるスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩのコストは、市販の安価なエンジニアプラスチックであるポリ１，４−ビフェニレンエーテルエーテルスルホンを原料に２工程で製造できるために、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／３０以下と安価である。   The cost of the sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VIII obtained by the present method can be obtained in two steps using poly-1,4-biphenylene ether ether sulfone, a commercially available inexpensive engineering plastic, as a raw material. Since it can be produced, the raw material is expensive, and is less than 1/30 of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) produced through five steps.

テフロンコーテングのＳＵＳ製密閉容器に得られたスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩの１．０ｇとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して十分に水洗した後、スルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩのイオン交換基当量重量を測定した。   1.0 g of the obtained sulfohexamethylated poly (1,4-biphenylene ether ether sulfone) solid polymer electrolyte VIII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. Then, after cooling and washing with water sufficiently, the ion exchange group equivalent weight of the sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VIII was measured.

その結果、スルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩのイオン交換基当量重量は初期と変わらず６７０ｇ／当量とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the equivalent weight of the ion-exchange group of the sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte VIII was unchanged from the initial value, and was 670 g / equivalent, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Was stable.

一方、比較例１の（１）に示したように安価なスルホン化芳香族炭化水素固体高分子電解質ＩＩのイオン交換基当量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価なスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＶＩＩＩは、安価なスルホン化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質ＩＩと異なり、高価なパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (1) of Comparative Example 1, the ion-exchange group equivalent of the inexpensive sulfonated aromatic hydrocarbon solid polymer electrolyte II changed to 1200 g / equivalent under the same heating and hydrolysis conditions. It became larger than the value of 650 g / equivalent, and the sulfonic acid group was eliminated. That is, the inexpensive sulfohexamethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte VIII is different from the inexpensive sulfonated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte II and is expensive perfluorosulfone. Like the acid solid polymer electrolyte (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（３） 固体高分子電解質膜の作製
前記（２）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。 (3) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamide-cyclohexanone-methylethylketone mixed solvent (volume ratio 20:80:25) was prepared so that the product obtained in the above (2) had a concentration of 5% by weight. ).

この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４２μｍのスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩＩを作成した。得られたスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩＩのイオン導電率は３５Ｓ／ｃｍであった。   The solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to prepare a 42 μm-thick sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VIII. . The ionic conductivity of the obtained sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VIII was 35 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記スルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、得られた固体高分子電解質膜ＶＩＩＩのイオン導電率は、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VIII obtained in a Teflon-coated closed container made of SUS and 20 ml of ion-exchanged water were kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity of the obtained solid polymer electrolyte membrane VIII was the same as that of the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例１の（２）に示したように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質ＩＩは同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体高分子電解質膜ＶＩＩＩは、スルホン化芳香族炭化水素系固体高分子電解質膜ＩＩと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 1, the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte II was broken and ragged under the same heating and hydrolysis conditions. That is, unlike the sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane II, the inexpensive sulfohexamethylated poly 1,4-biphenylene ether ether sulfone solid polymer electrolyte membrane VIII is different from the perfluorosulfonic acid solid polymer electrolyte membrane. It is stable as (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（４） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（３）のトリクロロエタン−ジクロロエタンの混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＶＩＩＩ）を調製した。 (4) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The mixed solution of (3) trichloroethane and dichloroethane described above in 40% by weight of platinum-carrying carbon was used, and the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2%. : 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution VIII).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＶＩＩＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液ＶＩＩＩのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＶＩＩＩのイオン交換基当量重量は初期と変わらず６７０ｇ／当量とパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution VIII and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and evaporating the solvent to evaporate the solid, the solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution VIII was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution VIII was 670 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例１の（２）に示したように電極触媒被覆用溶液ＩＩのイオン交換基当量重量は、同一加温加水分解条件で１２００ｇ／当量と変化し、初期の６５０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液ＶＩＩＩは、比較例１の電極触媒被覆用溶液ＩＩと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 1, the equivalent weight of the ion-exchange group of the solution II for electrode catalyst coating changes to 1200 g / equivalent under the same heating and hydrolysis conditions, and the initial equivalent value of 650 g / equivalent changes. It became larger and the sulfonic acid group was eliminated. That is, the inexpensive electrocatalyst coating solution VIII is different from the electrocatalyst coating solution II of Comparative Example 1 in that it is as stable, cost-effective and hydrolytically resistant as perfluorosulfonic acid (Nafion 117) electrocatalyst coating solution. Durability).

前記電極触媒被覆用溶液ＶＩＩＩを前記（３）で得られた固体高分子電解質膜の両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩＩＩを作製した。比較例１の（２）に記載した電極触媒被覆用溶液ＩＩを前記（２）で得られた固体高分子電解質膜ＶＩＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩＩＩ'を作製した。 The electrode catalyst coating solution VIII was applied to both sides of the solid polymer electrolyte membrane obtained in the above (3), and then dried to prepare a membrane electrode assembly VIII having a platinum loading of 0.25 mg / cm 2 . The solution II for electrode catalyst coating described in (2) of Comparative Example 1 was applied to both sides of the solid polymer electrolyte membrane VIII obtained in (2), and then dried to carry a platinum loading of 0.25 mg / cm 2. Was prepared.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＶＩＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＶＩＩＩ''を作製した。 To a 40% by weight platinum-supported carbon, a 5% by weight alcohol-water mixed solution of a perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. And uniformly dispersed to prepare a paste (solution for coating an electrode catalyst). This solution for coating an electrode catalyst is applied to both sides of the solid polymer electrolyte membrane VIII obtained in the above (2), and then dried to produce a membrane electrode assembly VIII ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＶＩＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩＩＩは、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly VIII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly VIII was similar to the membrane / electrode assembly produced using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm, as it was.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＶＩＩＩ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩＩＩ'は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly VIII ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly VIII ′ had a slightly peeled electrode but a firm membrane, and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＶＩＩＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＶＩＩＩ''は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly VIII ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly VIII ″ had electrodes slightly peeled off, but the membrane was firm and had a power generation capability.

（５） 燃料電池単セル出力性能評価
前記膜電極接合体ＶＩＩＩ、ＶＩＩＩ'およびＶＩＩＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組みこみ、燃料電池出力性能を評価した。 (5) Evaluation of Single Cell Output Performance of Fuel Cell The membrane electrode assemblies VIII, VIII ′ and VIII ″ were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

前記膜電極接合体ＶＩＩＩを用いた燃料電池単セルの電流密度−電圧プロットを図１１に示す。電流密度１Ａ／ｃｍ２のとき出力電圧は０．６９Ｖで、電流密度３００ｍＡ／ｃｍ２のとき出力電圧は０．８３Ｖで固体高分子型燃料電池単セルとして十分使用可能であった。 FIG. 11 shows a current density-voltage plot of a single cell of the fuel cell using the membrane electrode assembly VIII. When the current density was 1 A / cm 2, the output voltage was 0.69 V, and when the current density was 300 mA / cm 2 , the output voltage was 0.83 V, which was sufficiently usable as a single cell of a polymer electrolyte fuel cell.

また、前記固体高分子型燃料電池単セルを電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果を図１２に示す。 A long-term operation test was performed on the single cell of the polymer electrolyte fuel cell under the condition of a current density of 300 mA / cm 2 . FIG. 12 shows the result.

図１２中の４２，４３，４４はそれぞれ固体高分子電解質膜電極接合体ＶＩＩＩ，ＶＩＩＩ'およびＶＩＩＩ''を用いた燃料電池単セルの耐久性試験結果である。図１２中の４５はパーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   Reference numerals 42, 43, and 44 in FIG. 12 indicate the durability test results of the fuel cell single cells using the solid polymer electrolyte membrane electrode assemblies VIII, VIII ', and VIII' ', respectively. Numeral 45 in FIG. 12 indicates a durability test result of a fuel cell single cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１２中、４２は実施例１２のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、４３は実施例１２のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、４４は実施例１２のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、４５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、４６は比較例１２のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   12, reference numeral 42 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 12, and a polyetherethersulfone solid polymer having a sulfonic acid group bonded through an alkylene group. 43 shows the change over time of the output voltage of a single cell of a fuel cell using the solution for coating the electrode catalyst of the electrolyte, 43 denotes a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 12; Time-dependent change in output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which acid groups are directly bonded. Reference numeral 44 denotes a sulfonic acid group bonded via an alkylene group in Example 12. Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte Over time of the output voltage of a fuel cell single cell using the electrode catalyst coating solution of Zion 117), and 45 the time course of the output voltage of a fuel cell single cell using a perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117). Change 46 used the polyetherethersulfone solid polymer electrolyte membrane of Comparative Example 12 having sulfonic acid groups directly bonded, and the solution for coating the electrode catalyst of the polyetherethersulfone solid polymer electrolyte having sulfonic acid groups directly bonded. It is a change with time of the output voltage of a single fuel cell.

図１２の４２および４４から分かるように、本発明の固体高分子電解質膜電極接合体ＶＩＩＩおよびＶＩＩＩ''を用いた単電池セルの電圧は初期０．８３Ｖで、稼動時間５０００時間後でも初期と変わらず、図１２の４５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変化しなかった。   As can be seen from 42 and 44 in FIG. 12, the voltage of the unit cell using the solid polymer electrolyte membrane electrode assemblies VIII and VIII ″ of the present invention was initially 0.83 V, and the voltage was the same even after 5000 hours of operation. There was no change from the initial stage, which was equivalent to the result obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 45 in FIG.

一方、図１２中の４６（比較例１のスルホン化芳香族炭化水素固体高分子電解質を使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 46 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte of Comparative Example 1) in FIG. 12 was initially 0.73 V, and the output was lost after 600 hours of operation. .

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

膜電極接合体ＶＩＩＩおよびＶＩＩＩ''を用いた燃料電池単セルの耐久性は膜電極接合体ＶＩＩＩ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＶＩＩＩは、電極触媒被覆用溶液ＩＩより膜電極接合体の電極触媒被覆に適している。   The durability of the single fuel cell using the membrane electrode assemblies VIII and VIII ″ is superior to the durability of the single fuel cell using the membrane electrode assembly VIII ′. That is, the electrode catalyst coating solution VIII is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution II.

また、実施例１２および比較例１の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１２の燃料電池単セルの出力電圧が比較例１の燃料電池単セルの出力電圧より大きい理由は、実施例１２の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が、比較例１の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 Further, the output voltage of the fuel cell unit cell of Example 12 was lower than that of Comparative Example 1 even though the supported amount of platinum of the membrane electrode assemblies of Example 12 and Comparative Example 1 was the same as 0.25 mg / cm 2 . The reason for the higher output voltage of the single cell of the fuel cell is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 12 and the ionic conductivity of the solution for coating the electrode catalyst are different from those of the membrane electrode assembly of Comparative Example 1. This is because it is higher than the ionic conductivity of the electrolyte membrane and the solution for coating the electrode catalyst.

実施例１１，９，１０，１２の（１）および（２）から分かるように、前記式〔３〕で表されるアルキレン基のｎの数が１，３，４，６のスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体電解質のイオン交換基当量重量（ｇ／当量）は、それぞれ６６０，６８０，６７０，６７０と殆ど同じである。それに対応する固体高分子電解質膜のイオン伝導度Ｓ／ｃｍはそれぞれ７，１５，２５，３５である。即ち、スルホアルキル化芳香族炭化水素固体電解質のｎの数が大きいほどイオン伝導度が大きく、プロトンの伝達性が大きくなり固体高分子型燃料電池として優れている。   As can be seen from (1) and (2) in Examples 11, 9, 10, and 12, the sulfoalkylated polyalkylene group represented by the formula [3] wherein n is 1, 3, 4, 6 The ion exchange group equivalent weight (g / equivalent) of the 1,4-biphenylene ether ether sulfone solid electrolyte is almost the same as 660, 680, 670, and 670, respectively. The corresponding ion conductivity S / cm of the solid polymer electrolyte membrane is 7, 15, 25, and 35, respectively. That is, the larger the number n of the sulfoalkylated aromatic hydrocarbon solid electrolyte, the higher the ionic conductivity and the greater the proton transferability, which is excellent as a polymer electrolyte fuel cell.

一方、コストの観点からスルホンとの１段反応により合成できるスルホプロピル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体電解質と、スルホブチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体電解質が、２段階反応によって合成されるスルホヘキサメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体電解質やスルホメチル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体電解質より有利である。イオン伝導度とコストとの両立の観点からｎの数は３〜４が好ましい。   On the other hand, a sulfopropylated poly 1,4-biphenylene ether ether sulfone solid electrolyte that can be synthesized by a one-step reaction with a sulfone from a cost viewpoint and a sulfobutylated poly 1,4-biphenylene ether ether sulfone solid electrolyte can be synthesized by a two-step reaction. It is more advantageous than the synthesized sulfohexamethylated poly-1,4-biphenylene ether ether sulfone solid electrolyte or the sulfomethylated poly-1,4-biphenylene ether ether sulfone solid electrolyte. The number n is preferably 3 to 4 from the viewpoint of achieving a balance between ion conductivity and cost.

（６） 燃料電池の作製
前記（５）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (6) Production of Fuel Cell When the cell unit cell produced in the above (5) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 １３〕
（１） スルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃において１０時間保持乾燥した４．８４ｇ（０．０１５５ｍｏｌ）のポリ１，４−フェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｏ−）ｎ〕と脱水クロロホルム１５０ｍｌを入れ、６０℃にて約１時間保持して溶解した。この溶液にプロパンスルトン５．６７ｇ（０．０４６４ｍｏｌ）を加えた。 [Example 13]
(1) Synthesis of sulfopropylated poly 1,4-phenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. 4.84 g (0.0155 mol) of poly-1,4-phenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 ) dried at 110 ° C. for 10 hours. -4-O-) n] and 150 ml of dehydrated chloroform were added and dissolved at 60 ° C. for about 1 hour. 5.67 g (0.0464 mol) of propane sultone was added to this solution.

次いで、撹拌しながら約３０分かけて乳鉢で良くすりつぶした無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加した後、３０時間６０℃で還流攪拌した。析出したポリマーを濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥した。得られたポリマーを水２５０ｍｌに懸濁させ、ミキサーで細かく砕き、得られた微粉砕物を濾過した。これを４回繰り返し、水で十分洗浄した後、水不溶性の微粉砕物を減圧下，９０℃で乾燥した。   Then, with stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride thoroughly ground in a mortar was added over about 30 minutes. After addition of anhydrous aluminum chloride, the mixture was refluxed and stirred at 60 ° C. for 30 hours. The precipitated polymer was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained polymer was suspended in 250 ml of water, finely ground with a mixer, and the obtained finely pulverized product was filtered. This was repeated four times, and after sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure.

１ＨＮＭＲを測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍ、３．８ｐｐｍに認められた。このことからスルホプロピル基が導入されていることが確認された。 When 1 HNMR was measured, a new peak based on a —CH 2 CH 2 CH 2 SO 3 H group was newly observed at 2.2 ppm and 3.8 ppm. This confirmed that the sulfopropyl group had been introduced.

得られたスルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＩＸのスルホン酸当量重量は６７０ｇ／当量であった。   The sulfonic acid equivalent weight of the obtained sulfopropylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte IX was 670 g / equivalent.

スルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＩＸのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−フェニレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfopropylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte IX can be produced in one step using poly 1,4-phenylene ether ether sulfone, which is a commercially available relatively inexpensive engineering plastic, as a raw material. The raw material is expensive, and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＩＸの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して十分に水洗した後スルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＩＸのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfopropylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte IX and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the equivalent weight of the ion-exchange group of the sulfopropylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte IX was measured.

その結果、スルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＩＸのイオン交換基当量重量は、初期と変わらず６７０ｇ／当量とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the equivalent weight of the ion-exchange group of the sulfopropylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte IX was 670 g / equivalent to the initial value, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Was stable.

一方、後述の比較例２の（１）に示すように、安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘのイオン交換基当量重量は、同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価なスルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＩＸは、後述の比較例２のスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in Comparative Example 2 (1) below, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was 1250 g under the same heating hydrolysis conditions. / Equivalent, larger than the initial value of 660 g / equivalent, and the sulfonic acid group was eliminated. That is, the inexpensive sulfopropylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte IX is different from the sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X of Comparative Example 2 described later, Like the sulfonic acid solid polymer electrolyte (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜ＩＸを作成した。得られた固体高分子電解質膜ＩＸのイオン導電率は１５Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamide-cyclohexanone-methylethylketone mixed solvent (20:80:25 by volume) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane IX. The ionic conductivity of the obtained solid polymer electrolyte membrane IX was 15 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記固体高分子電解質膜ＩＸとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、得られた固体高分子電解質膜ＩＸのイオン導電率は、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained solid polymer electrolyte membrane IX and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity of the obtained solid polymer electrolyte membrane IX was not changed from the initial state similarly to the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、後述の比較例２の（２）に示すように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質Ｘは、同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホプロピル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＩＸは、後述の比較例２の（２）に記載した安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホンＸ固体高分子電解質膜Ｘと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 2 described later, the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte X was broken and ragged under the same heating and hydrolysis conditions. That is, the inexpensive sulfopropylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane IX is the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone X described in (2) of Comparative Example 2 described later. Unlike the solid polymer electrolyte membrane X, it is as stable as the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＩＸ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte were added at a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution IX).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＩＸの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗後、電極触媒被覆用溶液ＩＸのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＩＸのイオン交換基当量重量は初期と変わらず６７０ｇ／当量と、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution IX and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the solid formed by cooling and evaporating the solvent was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution IX was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution IX was 670 g / equivalent from the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、後述の比較例２の（２）に示すように、電極触媒被覆用溶液Ｘのイオン交換基当量重量は同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液ＩＸは、後述の比較例２の（２）に記載した安価な電極触媒被覆用溶液Ｘと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 2 described later, the ion exchange group equivalent weight of the solution X for electrode catalyst coating changes to 1250 g / equivalent under the same heating hydrolysis conditions, and the initial value of 660 g / equivalent value. It became larger and the sulfonic acid group was eliminated. That is, the inexpensive electrode catalyst coating solution IX is different from the inexpensive electrode catalyst coating solution X described in (2) of Comparative Example 2 below, and is the same as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. It is excellent in both cost and hydrolysis resistance (durability).

前記電極触媒被覆用溶液ＩＸを前記（２）で得られた固体高分子電解質膜ＩＸの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＸを作製した。 The electrode catalyst coating solution IX was applied to both sides of the solid polymer electrolyte membrane IX obtained in the above (2), and then dried to prepare a membrane electrode assembly IX having a platinum loading of 0.25 mg / cm 2 . .

後述の比較例２の（２）に記載した電極触媒被覆用溶液Ｘを、前記（２）で得られた固体高分子電解質膜ＩＸの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＸ'を作製した。 The solution X for coating an electrode catalyst described in (2) of Comparative Example 2 described below was applied to both sides of the solid polymer electrolyte membrane IX obtained in (2), and dried to obtain a platinum loading of 0.25 mg / cm 2 of a membrane electrode assembly IX ′ was produced.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＩＸの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＩＸ''を作製した。 To a 40% by weight platinum-supported carbon, a 5% by weight alcohol-water mixed solution of a perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. And uniformly dispersed to prepare a paste (solution for coating an electrode catalyst). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane IX obtained in the above (2), and then dried to produce a membrane electrode assembly IX ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＸとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＩＸは、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly IX and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane electrode assembly IX has the same initial and membrane properties as the membrane electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm, as it was.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＸとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＩＸは、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly IX and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, in the membrane electrode assembly IX, although the electrodes were slightly peeled off, the membrane was firm and had a power generation ability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＩＸとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＩＸ'は、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly IX and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly IX ′ had some electrodes peeled off, but the membrane was firm and had a power generation capability.

一方、後述の比較例２の（３）に示すように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜Ｘと電極触媒被覆用溶液Ｘを用いて作製した膜電極接合体Ｘは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 2 described below, a membrane electrode assembly X prepared using a relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane X and a solution X for coating an electrode catalyst. In the case of, under the same heating hydrolysis conditions, the membrane was broken and ragged, and the electrode was peeled off.

即ち、安価なスルホプロピルポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＩＸは、後述の比較例２の（３）に記載した安価なスルホン化芳香族炭化水素系固体高分子電解質膜電極接合体Ｘとは異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfopropyl poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly IX is an inexpensive sulfonated aromatic hydrocarbon-based solid polymer described in (3) of Comparative Example 2 described later. Unlike the electrolyte membrane electrode assembly X, it is excellent in stability, cost, and hydrolysis resistance (durability) at the same time as the perfluorosulfonic acid (Nafion 117) membrane electrode assembly.

（４） 燃料電池単セルの耐久性試験
前記膜電極接合体ＩＸ、ＩＸ'およびＩＸ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組みこみ、燃料電池出力性能を評価した。 (4) Durability test of fuel cell single cell The membrane electrode assemblies IX, IX 'and IX''were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

即ち、固体高分子電解質膜１、酸素極２および水素極３からなる実施例１３の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図１に示す固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２条件で、長期劣化試験を行った。その結果を図１３に示す。 That is, a thin carbon paper packing material (supporting current collector) 5 is brought into close contact with both electrodes of the membrane electrode assembly 4 of Example 13 including the solid polymer electrolyte membrane 1, the oxygen electrode 2, and the hydrogen electrode 3, A single cell of a polymer electrolyte fuel cell shown in FIG. 1 comprising a conductive separator (bipolar plate) 6 which also functions as an electrode compartment separation and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm. A long-term deterioration test was performed under two conditions. The result is shown in FIG.

図１３中の４７，４８，４９は、それぞれ固体高分子電解質膜電極接合体ＩＸ、ＩＸ'およびＩＸ''を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 13, 47, 48, and 49 indicate the durability test results of the single fuel cell using the solid polymer electrolyte membrane electrode assemblies IX, IX ', and IX' ', respectively.

図１３中の５０はパーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   Reference numeral 50 in FIG. 13 indicates a durability test result of a fuel cell single cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１３中、４７は実施例１３のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、４８は実施例１３のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、４９は実施例１３のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、５０はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、５１は比較例１３のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 13, reference numeral 47 denotes a polyetherethersulfone solid polymer electrolyte membrane of Example 13 in which a sulfonic acid group is bonded via an alkylene group, and a polyetherethersulfone solid polymer in which a sulfonic acid group is bonded via an alkylene group. The change over time of the output voltage of a single cell of a fuel cell using the solution for coating the electrode catalyst of the electrolyte, 48 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 13, Change with time of the output voltage of a fuel cell single cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which acid groups are directly bonded, 49 is a sulfonic acid group bonded via an alkylene group in Example 13. Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte Over time of the output voltage of a single cell of a fuel cell using the electrode catalyst coating solution of Zion 117), and 50 is the change over time of the output voltage of a single cell of a fuel cell using a perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117). Reference numeral 51 denotes a polyetherethersulfone solid polymer electrolyte membrane to which sulfonic acid groups were directly bonded and a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which sulfonic acid groups were directly bonded in Comparative Example 13. It is a change with time of the output voltage of a single fuel cell.

図１３の４７および４９から分かるように、本発明の固体高分子電解質膜電極接合体ＩＸおよびＩＸ''を用いた単電池セルの電圧は初期０．７９Ｖで、稼動時間５０００時間後でも初期と変わらず、図１３の５０のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変化しなかった。   As can be seen from 47 and 49 in FIG. 13, the voltage of the unit cell using the solid polymer electrolyte membrane electrode assemblies IX and IX ″ of the present invention was 0.79 V in the initial stage, There was no change from the initial stage, which was equivalent to the result obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 50 in FIG.

一方、図１３中の５１（後述の比較例２のスルホン化芳香族炭化水素固体高分子電解質Ｘを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 51 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte X of Comparative Example 2 described later) in FIG. 13 was initially 0.73 V, and was output after 600 hours of operation time. Is gone.

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

膜電極接合体ＩＸおよびＩＸ''を用いた燃料電池単セルの耐久性は、膜電極接合体ＩＸ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＩＸは電極触媒被覆用溶液Ｘより膜電極接合体の電極触媒被覆に適している。   The durability of a single fuel cell using the membrane electrode assemblies IX and IX ″ is superior to the durability of a single fuel cell using the membrane electrode assembly IX ′. That is, the electrode catalyst coating solution IX is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution X.

また、実施例１３および比較例２の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１３の燃料電池単セルの出力電圧が比較例２の燃料電池単セルの出力電圧より大きい理由は、実施例１３の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が、比較例２の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 The amount of supported platinum of the membrane electrode assembly of Example 13 and Comparative Example 2 even though the same as 0.25 mg / cm 2, the output voltage of the fuel cell unit of Example 13 is Comparative Example 2 The reason for the higher output voltage of the single cell of the fuel cell is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 13 and the ionic conductivity of the solution for coating the electrode catalyst were different from those of the membrane electrode assembly of Comparative Example 2. This is because it is higher than the ionic conductivity of the electrolyte membrane and the solution for coating the electrode catalyst.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔比較例 ２〕
（１） スルホン化ポリ１，４−フェニレンエーテルエーテルスルホンの合成 撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃において１０時間保持乾燥した３．２２ｇ（０．０１０３ｍｏｌ）のポリ１，４−フェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｏ−）ｎ〕とクロロホルム１００ｍｌ中を入れ、６０℃に約１時間保持して溶解した。 [Comparative Example 2]
(1) Synthesis of sulfonated poly 1,4-phenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 3.22 g (0.0103 mol) of poly-1,4-phenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 −) dried at 110 ° C. for 10 hours. 4-O-) n] and chloroform in 100 ml, and dissolved at 60 ° C. for about 1 hour.

この溶液にクロロスルホン酸１．１６５ｇ（０．０１ｍｏｌ）を１，１，２，２−テトラクロロエタン５０ｍｌに溶かした溶液を約１０分間かけて加えた。次いで、６０℃で４時間攪拌した。析出物を濾過し、クロロホルム１５０ｍｌで洗浄した。得られた析出物にメタノール２５０ｍｌを加え６０℃で溶解した。溶液を６０℃で減圧乾燥した。得られたポリマーに水２５０ｍｌを加え、ミキサーで細かく砕き、濾過した。この操作を３回繰り返した。   To this solution, a solution of 1.165 g (0.01 mol) of chlorosulfonic acid dissolved in 50 ml of 1,1,2,2-tetrachloroethane was added over about 10 minutes. Then, the mixture was stirred at 60 ° C. for 4 hours. The precipitate was filtered and washed with 150 ml of chloroform. 250 ml of methanol was added to the obtained precipitate and dissolved at 60 ° C. The solution was dried at 60 ° C. under reduced pressure. 250 ml of water was added to the obtained polymer, which was finely ground with a mixer and filtered. This operation was repeated three times.

得られた水不溶性の微粉末を五酸化燐上で減圧下，９０℃で乾燥した。この微粉末は、水に不溶、メタノールに可溶であった。   The obtained water-insoluble fine powder was dried at 90 ° C. under reduced pressure over phosphorus pentoxide. This fine powder was insoluble in water and soluble in methanol.

１ＨＮＭＲを測定すると原料のポリ１，４−フェニレンエーテルエーテルスルホン中のフェニル基の水素に基づく７．３〜８．０ｐｐｍの吸収が減少し、新たにＳＯ３Ｈ基に隣接するフェニル基の水素の基づく８．３ｐｐｍの吸収が認められた。このことからスルホン酸が導入されていることが確認された。得られたスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘのスルホン酸当量重量は６６０ｇ／当量であった。 When 1 HNMR is measured, the absorption of 7.3 to 8.0 ppm based on the hydrogen of the phenyl group in the raw material poly 1,4-phenylene ether ether sulfone decreases, and the hydrogen of the phenyl group adjacent to the SO 3 H group is newly added. Of 8.3 ppm based on the above. This confirmed that sulfonic acid had been introduced. The sulfonic acid equivalent weight of the obtained sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was 660 g / equivalent.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記スルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘの１．０ｇとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して充分に水洗したのちスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘのイオン交換基当量重量を測定した。その結果、スルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘのスルホン酸当量重量は１２５０ｇ／当量と初期の６６
（２） 固体高分子電解質膜の作製
前記（１）で得られたスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘを、５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４５μｍの固体高分子電解質膜Ｘを作成した。得られた固体高分子電解質膜Ｘのイオン導電率は８Ｓ／ｃｍであった。 1.0 g of the obtained sulfonated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte X and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS, and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the ion exchange group equivalent weight of the sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was measured. As a result, the sulfonic acid equivalent weight of the sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was 1250 g / equivalent to the initial 66%.
(2) Preparation of Solid Polymer Electrolyte Membrane The sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X obtained in the above (1) was N, N-dimethyl so as to have a concentration of 5% by weight. It was dissolved in a mixed solvent of formamide-cyclohexanone-methylethylketone (volume ratio: 20:80:25). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a solid polymer electrolyte membrane X having a film thickness of 45 μm. The ionic conductivity of the obtained solid polymer electrolyte membrane X was 8 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記固体高分子電解質膜Ｘとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、固体高分子電解質膜Ｘは破け、ぼろぼろになっていた。   The obtained solid polymer electrolyte membrane X and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the solid polymer electrolyte membrane X was broken and ragged.

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液Ｘ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution X).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液Ｘの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液Ｘのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液Ｘのイオン交換基当量重量は１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution X and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the solid produced by cooling and evaporating the solvent was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution X was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution X was changed to 1250 g / equivalent, became larger than the initial value of 660 g / equivalent, and the sulfonic acid group was eliminated.

前記電極触媒被覆用溶液Ｘを前記（２）で得られた固体高分子電解質膜Ｘの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体Ｘを作製した。 The electrode catalyst coating solution X was applied to both sides of the solid polymer electrolyte membrane X obtained in the above (2), and then dried to produce a membrane electrode assembly X having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体Ｘとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体Ｘの膜は破け、ぼろぼろになり、電極は剥がれていた。   The obtained membrane electrode assembly X and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane of the membrane electrode assembly X was broken and ragged, and the electrode was peeled off.

（４） 燃料電池単セルの耐久性試験
比較例２の膜電極接合体Ｘの両側に薄いカーボンペーパのパッキング材（支持集電体）を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）からなる固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果、図１３の５１に示すように出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力電圧が無くなった。 (4) Durability test of single cell of fuel cell A packing material (supporting current collector) made of thin carbon paper is adhered to both sides of the membrane electrode assembly X of Comparative Example 2, and separation of the electrode chamber from both sides is performed. A single cell of a polymer electrolyte fuel cell composed of a conductive separator (bipolar plate) also serving as a gas supply passage was manufactured, and a long-term operation test was performed under a condition of a current density of 300 mA / cm 2 . As a result, as shown at 51 in FIG. 13, the output voltage was initially 0.73 V and disappeared after 600 hours of operation.

〔実施例 １４〕
（１） スルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃において１０時間保持乾燥した４．８４ｇ（０．０１５５ｍｏｌ）のポリ１，４−フェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｏ−）ｎ〕と脱水クロロホルム１５０ｍｌを入れ、６０℃にて約１時間保持して溶解した。この溶液にブタンスルトン６．２６ｇ（０．０４６４ｍｏｌ）を加えた。次いで、撹拌しながら約３０分かけて乳鉢で良くすりつぶした無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加した後、３０時間６０℃で還流攪拌した。析出したポリマーを濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥した。得られたポリマーを水２５０ｍｌに懸濁させ、ミキサーで細かく砕き、得られた微粉砕物を濾過した。これを４回繰り返した。水で十分洗浄した後、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。 [Example 14]
(1) Synthesis of sulfobutylated poly 1,4-phenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 4.84 g (0.0155 mol) of poly-1,4-phenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 −) dried at 110 ° C. for 10 hours and dried. 4-O-) n] and 150 ml of dehydrated chloroform were added and dissolved at 60 ° C. for about 1 hour. 6.26 g (0.0464 mol) of butane sultone was added to this solution. Then, with stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride thoroughly ground in a mortar was added over about 30 minutes. After addition of anhydrous aluminum chloride, the mixture was refluxed and stirred at 60 ° C. for 30 hours. The precipitated polymer was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained polymer was suspended in 250 ml of water, finely ground with a mixer, and the obtained finely pulverized product was filtered. This was repeated four times. After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure.

１ＨＮＭＲを測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが１．３〜３．８ｐｐｍに認められた。このことからスルホブチル基が導入されていることが確認された。得られたスルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩのスルホン酸当量重量は６５０ｇ／当量であった。 When 1 HNMR was measured, a new peak based on a —CH 2 CH 2 CH 2 CH 2 SO 3 H group was newly observed at 1.3 to 3.8 ppm. This confirmed that the sulfobutyl group had been introduced. The sulfonic acid equivalent weight of the obtained sulfobutylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XI was 650 g / equivalent.

スルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，４−フェニレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfobutylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte XI can be produced in one step using poly 1,4-phenylene ether ether sulfone which is a commercially available relatively inexpensive engineering plastic. Is expensive and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して十分に水洗した後スルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfobutylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XI and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the equivalent weight of the ion-exchange group of the sulfobutylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XI was measured.

その結果、スルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩのイオン交換基当量重量は初期と変わらず６５０ｇ／当量と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the equivalent weight of the ion-exchange group of the sulfobutylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XI was 650 g / equivalent, unchanged from the initial level, and was similar to that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). It was stable.

一方、比較例２の（１）に示すように、安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘのイオン交換基当量重量は同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 2, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was 1250 g / equivalent under the same heating and hydrolysis conditions. It changed and became larger than the initial value of 660 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩは、比較例２の（１）に記載した安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘとは異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、低コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfobutylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte XI is the same as the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X described in (1) of Comparative Example 2. Unlike the perfluorosulfonic acid solid polymer electrolyte (Nafion 117), it is stable and has both low cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜ＸＩを作成した。得られた固体高分子電解質膜ＸＩのイオン導電率は２５Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamide-cyclohexanone-methylethylketone mixed solvent (20:80:25 by volume) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane XI. The ionic conductivity of the obtained solid polymer electrolyte membrane XI was 25 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記固体高分子電解質膜ＸＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、得られた固体高分子電解質膜ＸＩのイオン導電率は、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained solid polymer electrolyte membrane XI and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity of the obtained solid polymer electrolyte membrane XI was not different from the initial state similarly to the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例２の比較的安価なスルホン化芳香族炭化水素系固体高分子電解質Ｘは同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホブチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩは、比較例２のスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜Ｘと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte X of Comparative Example 2 was broken and ragged under the same heating and hydrolysis conditions. That is, unlike the sulfonated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane X of Comparative Example 2, the inexpensive sulfobutylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane X is different from perfluorosulfone. Similar to the acid solid polymer electrolyte membrane (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＸＩ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution XI).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＸＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液ＸＩのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＸＩのイオン交換基当量重量は初期と変わらず６５０ｇ／当量とパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution XI and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and evaporating the solvent, the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution XI was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution XI was 650 g / equivalent from the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例２の（２）に示すように、電極触媒被覆用溶液Ｘのイオン交換基当量重量は、同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液ＸＩは、比較例２の電極触媒被覆用溶液Ｘと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 2, the equivalent weight of the ion exchange group of the solution X for electrode catalyst coating changes to 1250 g / equivalent under the same heating hydrolysis conditions, and is higher than the initial value of 660 g / equivalent. It became larger and the sulfonic acid group was eliminated. That is, unlike the electrode catalyst coating solution X of Comparative Example 2, the inexpensive electrode catalyst coating solution XI is as stable, cost-effective and hydrolysis-resistant as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. Durability).

前記電極触媒被覆用溶液ＸＩを前記（２）で得られた固体高分子電解質膜ＸＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩを作製した。 After applying the electrode catalyst coating solution XI to both sides of the solid polymer electrolyte membrane XI obtained in the above (2), it was dried to produce a membrane electrode assembly XI having a platinum loading of 0.25 mg / cm 2 . .

比較例２の電極触媒被覆用溶液Ｘを前記（２）で得られた固体高分子電解質膜ＸＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩ'を作製した。 The electrode catalyst coating solution X of Comparative Example 2 was applied to both sides of the solid polymer electrolyte membrane XI obtained in the above (2), then dried and the membrane electrode assembly XI having a platinum loading of 0.25 mg / cm 2. 'Was made.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコール−水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＸＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩ''を作製した。 To a 40% by weight of platinum-supported carbon, a 5% by weight alcohol-water mixed solution of perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. Then, the mixture was uniformly dispersed to prepare a paste (electrode catalyst coating solution). This solution for coating an electrode catalyst is applied to both sides of the solid polymer electrolyte membrane XI obtained in the above (2), and then dried to produce a membrane electrode assembly XI ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩは、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly XI and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane electrode assembly XI has the same initial and membrane properties as the membrane electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm, as it was.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩ'は、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XI ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XI ′ had some electrodes peeled off, but the membrane was firm and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩ''は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XI ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the electrode of the membrane electrode assembly XI ″ was slightly peeled off, but the membrane was firm and had a power generation capability.

一方、比較例２の（３）に示すように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜Ｘと、電極触媒被覆用溶液Ｘを用いて作製した膜電極接合体Ｘは同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。即ち、安価なスルホブチルポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＸＩは、比較例２のスルホン化芳香族炭化水素系固体高分子電解質膜電極接合体Ｘと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (3) of Comparative Example 2, the membrane electrode assembly X manufactured using the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane X and the electrode catalyst coating solution X was Under the same heating hydrolysis conditions, the membrane was broken and ragged, and the electrode was peeled off. That is, the inexpensive sulfobutyl poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly XI differs from the sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane electrode assembly X of Comparative Example 2 in that Similar to the fluorosulfonic acid (Nafion 117) membrane electrode assembly, it is stable and excellent in both cost and hydrolysis resistance (durability).

（４） 燃料電池単セルの耐久性試験
前記膜電極接合体ＸＩ、ＸＩ'およびＸＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組み込み、燃料電池出力性能を評価した。 (4) Durability test of fuel cell single cell The membrane electrode assemblies XI, XI ′ and XI ″ were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

即ち、固体高分子電解質膜１、酸素極２および水素極３からなる実施例１４の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図１に示す固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長期劣化試験を行った。その結果を図１４に示す。 That is, a thin carbon paper packing material (supporting current collector) 5 is brought into close contact with both electrodes of the membrane electrode assembly 4 of Example 14 including the solid polymer electrolyte membrane 1, the oxygen electrode 2, and the hydrogen electrode 3, A single cell of a polymer electrolyte fuel cell shown in FIG. 1 comprising a conductive separator (bipolar plate) 6 which also functions as an electrode compartment separation and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm. A long-term deterioration test was performed under the conditions of 2 . FIG. 14 shows the result.

図１４中の５２，５３，５４は、それぞれ固体高分子電解質膜電極接合体ＸＩ、ＸＩ'およびＸＩ''を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 14, reference numerals 52, 53, and 54 denote durability test results of the fuel cell single cells using the solid polymer electrolyte membrane electrode assemblies XI, XI ′, and XI ″, respectively.

図１４中の５５は、パーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   Numeral 55 in FIG. 14 indicates a durability test result of a fuel cell single cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１４中、５２は実施例１４のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、５３は実施例１４のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、５４は実施例１４のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、５５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、５６は比較例１４のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 14, reference numeral 52 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded via an alkylene group in Example 14, and a polyetherethersulfone solid polymer having a sulfonic acid group bonded via an alkylene group. The change over time in the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 53 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 14, Change with time of the output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which acid groups are directly bonded. Reference numeral 54 denotes a sulfonic acid group bonded via an alkylene group in Example 14. Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte Over time of the output voltage of a fuel cell single cell using the electrode catalyst coating solution of Naion 117), and 55 the time over time of the output voltage of a fuel cell single cell using a perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117). Variation 56 used the polyetherethersulfone solid polymer electrolyte membrane of Comparative Example 14 in which sulfonic acid groups were directly bonded, and the electrode catalyst coating solution of the polyetherethersulfone solid polymer electrolyte in which sulfonic acid groups were directly bonded. It is a change with time of the output voltage of a single fuel cell.

図１４の５２および５４から分かるように、本発明の固体高分子電解質膜電極接合体ＸＩおよびＸＩ''を用いた単電池セルの電圧は初期０．７９Ｖで、稼動時間５０００時間後でも初期と変わらず、図１４の５５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変化しなかった。   As can be seen from 52 and 54 in FIG. 14, the voltage of the single battery cell using the solid polymer electrolyte membrane electrode assemblies XI and XI ″ of the present invention was initially 0.79 V, and the voltage was the same even after the operation time of 5000 hours. There was no change from the initial stage, which was equivalent to the result obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 55 in FIG.

一方、図１４中の５６（比較例２のスルホン化芳香族炭化水素固体高分子電解質Ｘを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 56 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte X of Comparative Example 2) in FIG. 14 was initially 0.73 V, and the output disappeared after 600 hours of operation. Was.

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

本発明の膜電極接合体ＸＩを用いた燃料電池単セルの耐久性は、膜電極接合体ＸＩ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＸＩは、電極触媒被覆用溶液Ｘより膜電極接合体の電極触媒被覆に適している。   The durability of the fuel cell unit cell using the membrane electrode assembly XI of the present invention is superior to the durability of the fuel cell unit cell using the membrane electrode assembly XI ′. That is, the electrode catalyst coating solution XI is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution X.

また、実施例１４および比較例２の膜電極接合体の白金担持量０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１４の燃料電池単セルの出力電圧が比較例２の燃料電池単セルの出力電圧より大きい理由は、実施例１４の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が、比較例２の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 Further, the output voltage of the single cell of the fuel cell of Example 14 was the same as that of the fuel cell of Comparative Example 2 even though the platinum carrying amount of the membrane electrode assembly of Example 14 and Comparative Example 2 was the same as 0.25 mg / cm 2. The reason for the higher output voltage of the single battery cell is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 14 and the ionic conductivity of the solution for coating the electrode catalyst are different from those of the solid polymer electrolyte of the membrane electrode assembly of Comparative Example 2. This is because it is higher than the ionic conductivity of the solution for coating the membrane and the electrode catalyst.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 １５〕
（１） クロルメチル化ポリ１，４−フェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、３６．１ｇのポリ１，４−フェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｏ−）ｎ〕、６０ｇ（２ｍｏｌ）のパラホルムアルデヒドと、乾燥した５０ｍｌのニトロベンゼンを入れた。１００℃に保って撹拌しながら７３ｇの塩化水素ガスを吹き込んだ。吹き込み終了後、１５０℃に４時間保った。 [Example 15]
(1) Synthesis of chloromethylated poly-1,4-phenylene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 36.1g of poly 1,4-phenylene ether ether sulfone [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4-O-) n ], 60 g of (2 mol) Paraformaldehyde and 50 ml of dried nitrobenzene were charged. 73 g of hydrogen chloride gas was blown in while maintaining the temperature at 100 ° C. and stirring. After the completion of the blowing, the temperature was kept at 150 ° C. for 4 hours.

次いで、反応溶液を１リットルの脱イオン水にゆっくりと滴下することでクロルメチル化ポリ１，４−フェニレンエーテルエーテルスルホンを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、８０℃にて一晩減圧乾燥した。   Then, the reaction solution was slowly dropped into 1 liter of deionized water to precipitate chloromethylated poly-1,4-phenylene ether ether sulfone, and the solution was collected by filtration. The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 80 ° C. overnight.

（２） スルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１０ｇの前記クロルメチル化ポリ１，４−フェニレンエーテルエーテルスルホン、乾燥した５０ｍｌのニトロベンゼン、３０ｇの硫酸ナトリウムを入れ、１００℃にて５時間撹拌した。さらに、１０ｍｌのイオン交換水を加え、５時間撹拌した。 (2) Synthesis of sulfomethylated poly 1,4-phenylene ether ether sulfone
After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, 10 g of the chloromethylated poly 1,4-phenylene ether ether sulfone was dried. 50 ml of the obtained nitrobenzene and 30 g of sodium sulfate were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 10 ml of ion-exchanged water was added, and the mixture was stirred for 5 hours.

次いで、反応溶液を１リットルの脱イオン水にゆっくりと滴下することでスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホンＸＩＩを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、１２０℃にて一晩減圧乾燥した。   Then, the reaction solution was slowly dropped into 1 liter of deionized water to precipitate sulfomethylated poly-1,4-phenylene ether ether sulfone XII, which was collected by filtration. The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 120 ° C. overnight.

１ＨＮＭＲを測定すると新たに−ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍに認められた。得られたスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩのイオン交換基当量重量は６５０ｇ／当量であった。 When 1 HNMR was measured, a new peak based on a —CH 2 SO 3 H group was newly observed at 2.2 ppm. The obtained sulfomethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XII had an ion exchange group equivalent weight of 650 g / equivalent.

本製法で得られるスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩのコストは、市販の安価なエンジニアプラスチックであるポリ１，４−フェニレンエーテルエーテルスルホンを原料に２工程で製造でき、５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／３０以下と安価である。   The cost of the sulfomethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XII obtained by this method can be produced in two steps using poly-1,4-phenylene ether ether sulfone, a commercially available inexpensive engineering plastic, as a raw material. The cost is as low as 1/30 or less of the cost of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

テフロンコーテングのＳＵＳ製密閉容器に得られたスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩの１．０ｇとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して十分に水洗した後スルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩのイオン交換基当量重量を測定した。   1.0 g of the obtained sulfomethylated poly (1,4-phenylene ether ether sulfone) solid polymer electrolyte XII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. After cooling and washing with water, the equivalent weight of the ion-exchange group of the sulfomethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XII was measured.

その結果、スルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩのイオン交換基当量重量は、初期と変わらず６５０ｇ／当量とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the ion-exchange group equivalent weight of the sulfomethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XII was 650 g / equivalent to the initial value, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). It was stable.

一方、比較例２の（１）に示すように、安価なスルホン化芳香族炭化水素固体高分子電解質Ｘのイオン交換基当量は、同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価なスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩは、スルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (1) of Comparative Example 2, the ion-exchange group equivalent of the inexpensive sulfonated aromatic hydrocarbon solid polymer electrolyte X changed to 1250 g / equivalent under the same heating and hydrolysis conditions. It became larger than the value of 660 g / equivalent, and the sulfonic acid group was eliminated. That is, unlike the sulfonated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte X, the inexpensive sulfomethylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte XII is different from the perfluorosulfonic acid solid polymer electrolyte ( Like Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（３） 固体高分子電解質膜の作製
前記（２）で得られたスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩを５重量％の濃度になるようにトリクロロエタン−ジクロロエタンの混合溶媒（１：１）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４２μｍのスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩを作成した。得られた固体高分子電解質膜ＸＩＩのイオン伝導度は５Ｓ／ｃｍであった。 (3) Preparation of Solid Polymer Electrolyte Membrane A mixed solvent of trichloroethane-dichloroethane so that the sulfomethylated poly1,4-phenylene ether ether sulfone solid polymer electrolyte XII obtained in the above (2) has a concentration of 5% by weight. (1: 1). This solution was spread on a glass plate by spin coating, air-dried, and vacuum-dried at 80 ° C. to prepare a 42 μm-thick sulfomethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XII. The ionic conductivity of the obtained solid polymer electrolyte membrane XII was 5 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に前記スルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、固体高分子電解質膜ＸＩＩのイオン導電率は、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The sulfomethylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C for 2 weeks. As a result, the ionic conductivity of the solid polymer electrolyte membrane XII was the same as that of the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例２の（２）に示すように、比較的安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘは、同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩは、安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜Ｘと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 2, the relatively inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was broken and ragged under the same heating and hydrolysis conditions. . That is, the inexpensive sulfomethylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XII is different from the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane X in that the perfluorosulfonic acid solid As with the polymer electrolyte membrane (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（４） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（３）のトリクロロエタン−ジクロロエタンの混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＸＩＩ）を調製した。 (4) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The mixed solution of (3) trichloroethane and dichloroethane described above in 40% by weight of platinum-carrying carbon was used, and the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2%. : 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution XII).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＸＩＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液ＸＩＩのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＸＩＩのイオン交換基当量重量は、初期と変わらず６５０ｇ／当量とパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the solution XII for electrode catalyst coating and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and evaporating the solvent, the solid produced was washed with water and then the ion exchange group equivalent weight of the electrode catalyst coating solution XII was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution XII was 650 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例２の（２）に示すように、電極触媒被覆用溶液Ｘのイオン交換基当量重量は、同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。即ち、安価な電極触媒被覆用溶液ＸＩＩは、比較例２の（２）に記載した安価な電極触媒被覆用溶液Ｘと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 2, the equivalent weight of the ion exchange group of the solution X for electrode catalyst coating changes to 1250 g / equivalent under the same heating hydrolysis conditions, and is higher than the initial value of 660 g / equivalent. It became larger and the sulfonic acid group was eliminated. That is, unlike the inexpensive electrode catalyst coating solution X described in (2) of Comparative Example 2, the inexpensive electrode catalyst coating solution XII is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. It is excellent in both cost and hydrolysis resistance (durability).

前記電極触媒被覆用溶液ＸＩＩを前記（２）で得られた固体高分子電解質膜ＸＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＩを作製した。 The electrode catalyst coating solution XII was applied to both sides of the solid polymer electrolyte membrane XII obtained in the above (2), and then dried to prepare a membrane electrode assembly XII having a platinum loading of 0.25 mg / cm 2 . .

比較例２の（２）に記載した電極触媒被覆用溶液Ｘを、前記（２）で得られた固体高分子電解質膜ＸＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＩ'を作製した。 The solution X for electrode catalyst coating described in (2) of Comparative Example 2 was applied to both sides of the solid polymer electrolyte membrane XII obtained in (2), and then dried to carry a platinum loading of 0.25 mg / cm. Thus, a membrane electrode assembly XII ′ of No. 2 was prepared.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質（ナフィオン１１７）の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＸＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＩ''を作製した。 A 40% by weight platinum-supported carbon was mixed with a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) in a 5% by weight alcohol-water mixed solution, and the weight ratio between the platinum catalyst and the solid polymer electrolyte was 2: 1. And the mixture was uniformly dispersed to prepare a paste (electrode catalyst coating solution). This solution for coating an electrode catalyst is applied to both sides of the solid polymer electrolyte membrane XII obtained in the above (2), and then dried to produce a membrane electrode assembly XII ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＩは，パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly XII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XII is similar to the membrane / electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm, as it was.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＩ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＩ'は、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XII ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XII ′ had a slightly peeled electrode but a firm membrane, and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＩ''は、電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XII ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XII ″ had a slightly peeled electrode but a firm membrane, and had a power generation capability.

一方、比較例２の（３）に示すように、比較的安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜Ｘと、電極触媒被覆用溶液Ｘを用いて作製した膜電極接合体Ｘは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 2, a relatively inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane X and a membrane electrode prepared using an electrode catalyst coating solution X were used. In the conjugate X, the film was broken and ragged under the same heating and hydrolysis conditions, and the electrode was peeled off.

即ち、安価なスルホメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＸＩＩは、比較例２のスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜電極接合体Ｘと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfomethylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly XII is the same as the sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane electrode assembly X of Comparative Example 2. Unlike the perfluorosulfonic acid (Nafion 117) membrane electrode assembly, it is stable, and is excellent in both cost and hydrolysis resistance (durability).

（４） 燃料電池単セルの耐久性試験
前記膜電極接合体ＸＩＩ、ＸＩＩ'およびＸＩＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組み込み、燃料電池出力性能を評価した。 (4) Durability test of fuel cell single cell The membrane electrode assemblies XII, XII 'and XII''were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

即ち、固体高分子電解質膜１，酸素極２および水素極３からなる実施例１５の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図１に示す固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長期劣化試験を行った。その結果を図１５に示す。 That is, a thin carbon paper packing material (supporting current collector) 5 is brought into close contact with both electrodes of the membrane electrode assembly 4 of Example 15 including the solid polymer electrolyte membrane 1, the oxygen electrode 2, and the hydrogen electrode 3, A single cell of a polymer electrolyte fuel cell shown in FIG. 1 comprising a conductive separator (bipolar plate) 6 which also functions as an electrode compartment separation and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm. A long-term deterioration test was performed under the conditions of 2 . The result is shown in FIG.

図１５中の５７，５８，５９はそれぞれ固体高分子電解質膜電極接合体ＸＩＩ，ＸＩＩ'およびＸＩＩ''を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 15, reference numerals 57, 58, and 59 denote durability test results of a single fuel cell using the solid polymer electrolyte membrane electrode assemblies XII, XII ', and XII' ', respectively.

図１５中の６０はパーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   Reference numeral 60 in FIG. 15 indicates a durability test result of a fuel cell unit cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１５中、５７は実施例１５のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、５８は実施例１５のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 15, reference numeral 57 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 15, and a polyetherethersulfone solid polymer having a sulfonic acid group bonded through an alkylene group. The change over time in the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 58 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 15, 4 is a time-dependent change in output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte having acid groups directly bonded.

また、５９は実施例１５のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、６０はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、６１は比較例１５のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   Reference numeral 59 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group of Example 15, and a solution for coating an electrode catalyst of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117). With time, the output voltage of the fuel cell unit cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) was changed, and the sulfonic acid group of Comparative Example 15 was changed. The change over time of the output voltage of a fuel cell unit cell using a polyetherethersulfone solid polymer electrolyte membrane directly bonded to a polyetherethersulfone solid polymer electrolyte is there.

図１５の５７および５９から分かるように、本発明の固体高分子電解質膜電極接合体ＸＩＩおよびＸＩＩ''を用いた単電池セルの電圧は初期０．７４Ｖで、稼動時間５０００時間後でも初期と変わらず、図１５の６０のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変わらなかった。   As can be seen from 57 and 59 in FIG. 15, the voltage of the single cell using the solid polymer electrolyte membrane electrode assemblies XII and XII ″ of the present invention was 0.74 V in the initial stage, and the voltage was the same even after 5000 hours of operation. There was no change, and the result was the same as the initial value, which was equivalent to the result obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 60 in FIG.

一方、図１５中の６１（比較例２のスルホン化芳香族炭化水素固体高分子電解質膜Ｘを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 61 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte membrane X of Comparative Example 2) in FIG. 15 was initially 0.73 V, and was output after 600 hours of operation time. Lost.

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

本発明の膜電極接合体ＸＩＩを用いた燃料電池単セルの耐久性は、膜電極接合体ＸＩＩ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＸＩＩは、電極触媒被覆用溶液Ｘより膜電極接合体の電極触媒被覆に適している。   The durability of a fuel cell unit cell using the membrane electrode assembly XII of the present invention is superior to the durability of a fuel cell unit cell using the membrane electrode assembly XII '. That is, the electrode catalyst coating solution XII is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution X.

また、実施例１５および比較例２の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１５の燃料電池単セルの出力電圧が比較例２の燃料電池単セルの出力電圧より大きい理由は、実施例１５の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が、比較例２の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 The amount of supported platinum of the membrane electrode assembly of Example 15 and Comparative Example 2 even though the same as 0.25 mg / cm 2, the output voltage of the fuel cell unit is Comparative Example 2 Example 15 The reason for this is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 15 and the ionic conductivity of the solution for coating the electrode catalyst was higher than that of the membrane electrode assembly of Comparative Example 2. This is because it is higher than the ionic conductivity of the electrolyte membrane and the solution for coating the electrode catalyst.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔実施例 １６〕
（１） ブロモヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、３８．８ｇのポリ１，４−フェニレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−４−ＯＣ６Ｈ４−４−Ｃ６Ｈ４−４−Ｏ−）ｎ〕、乾燥した５０ｍｌのニトロベンゼンを入れた。これに６．５ｇのｎ−ブトキシリチウムを加え、室温に２時間保った。次いで、１００ｇの１，６−ジブロモヘキサンを加え、さらに１２時間撹拌した。 [Example 16]
(1) Synthesis of bromohexamethylated poly-1,4-phenylene ether ether sulfone The inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. after, poly 1,4-phenylene ether ether sulfone 38.8g [(-C 6 H 4 -4-SO 2 C 6 H 4 -4-OC 6 H 4 -4-C 6 H 4 -4-O- N), 50 ml of dried nitrobenzene were added. To this was added 6.5 g of n-butoxylithium and kept at room temperature for 2 hours. Next, 100 g of 1,6-dibromohexane was added, and the mixture was further stirred for 12 hours.

反応溶液を１リットルの脱イオン水にゆっくりと滴下することでブロモヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホンを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、１２０℃にて一晩減圧乾燥した。   The reaction solution was slowly dropped into 1 liter of deionized water to precipitate bromohexamethylated poly-1,4-phenylene ether ether sulfone, which was collected by filtration. The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 120 ° C. overnight.

（２） スルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１０ｇの前記ブロモヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン、乾燥した５０ｍｌのニトロベンゼン、３０ｇの硫酸ナトリウムを入れ、１００℃にて５時間撹拌した。さらに、１０ｍｌのイオン交換水を加え、５時間撹拌した。 (2) Synthesis of sulfohexamethylated poly 1,4-phenylene ether ether sulfone The inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. Thereafter, 10 g of the bromohexamethylated poly 1,4-phenylene ether ether sulfone, 50 ml of dried nitrobenzene, and 30 g of sodium sulfate were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 10 ml of ion-exchanged water was added, and the mixture was stirred for 5 hours.

次いで、反応溶液を１リットルの脱イオン水にゆっくりと滴下することでスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホンを析出させ、濾過回収した。析出した沈澱をミキサーによる脱イオン水洗浄と吸引濾過による回収操作を、濾液が中性になるまで繰り返した後、１２０℃にて一晩減圧乾燥した。   Next, the reaction solution was slowly dropped into 1 liter of deionized water to precipitate sulfohexamethylated poly-1,4-phenylene ether ether sulfone, which was collected by filtration. The deposited precipitate was repeatedly washed with deionized water using a mixer and collected by suction filtration until the filtrate became neutral, and then dried under reduced pressure at 120 ° C. overnight.

１ＨＮＭＲを測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが１．３〜４．６ｐｐｍに認められた。このことからスルホヘキサメチル基が導入されていることが確認された。得られたスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩＩのイオン交換基当量重量は６６０ｇ／当量であった。 When 1 HNMR was measured, a peak based on a —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 SO 3 H group was newly observed at 1.3 to 4.6 ppm. This confirmed that the sulfohexamethyl group had been introduced. The ion exchange group equivalent weight of the obtained sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XIII was 660 g / equivalent.

本製法で得られるスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩＩのコストは、市販の安価なエンジニアプラスチックであるポリ１，４−フェニレンエーテルエーテルスルホンを原料に２工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／３０以下と安価である。   The cost of the sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XIII obtained by this method can be obtained in two steps using poly-1,4-phenylene ether ether sulfone which is a commercially available inexpensive engineering plastic as a raw material. Since it can be produced, the raw material is expensive and is less than 1/30 of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) produced through five steps.

テフロンコーテングのＳＵＳ製密閉容器に得られたスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩＩの１．０ｇとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して充分に水洗したのちスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩＩのイオン交換基当量重量を測定した。   1.0 g of the obtained sulfohexamethylated poly (1,4-phenylene ether ether sulfone) solid polymer electrolyte XIII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. Then, after cooling and washing sufficiently with water, the ion exchange group equivalent weight of the sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XIII was measured.

その結果、スルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩＩのイオン交換基当量重量は、初期と変わらず６６０ｇ／当量とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the ion-exchange group equivalent weight of the sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte XIII was 660 g / equivalent to the initial value, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Similarly stable.

一方、比較例２の（１）に示すように、安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘのイオン交換基当量は、同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 2, the ion exchange group equivalent of the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was 1250 g / equivalent under the same heated hydrolysis conditions. It changed and became larger than the initial value of 660 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質ＸＩＩＩは、安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   That is, unlike the inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X, the inexpensive sulfohexamethylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X Similar to the polymer electrolyte (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（３） 固体高分子電解質膜の作製
前記（２）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４２μｍのスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩＩを作成した。得られたスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩＩのイオン導電率は４０Ｓ／ｃｍであった。 (3) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamide-cyclohexanone-methylethylketone mixed solvent (volume ratio 20:80:25) was prepared so that the product obtained in the above (2) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to prepare a 42 μm-thick sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XIII. . The ionic conductivity of the obtained sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XIII was 40 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記スルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、得られた固体高分子電解質膜ＸＩＩＩのイオン導電率は、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained sulfohexamethylated poly-1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XIII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity of the obtained solid polymer electrolyte membrane XIII was the same as that of the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例２の（２）示すように、比較的安価なスルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘは同一加温加水分解条件で破け、ぼろぼろになっていた。   On the other hand, as shown in (2) of Comparative Example 2, the relatively inexpensive sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X was broken and ragged under the same heating and hydrolysis conditions.

即ち、安価なスルホヘキサメチル化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＩＩは、スルホン化ポリ１，４−フェニレンエーテルエーテルスルホン固体高分子電解質Ｘと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   That is, unlike the sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X, the inexpensive sulfohexamethylated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte membrane XIII is different from the sulfonated poly 1,4-phenylene ether ether sulfone solid polymer electrolyte X. As with the molecular electrolyte membrane (Nafion 117), it is stable and excellent in both cost and hydrolysis resistance (durability).

（４） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（３）のトリクロロエタン−ジクロロエタンの混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＸＩＩＩ）を調製した。 (4) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The mixed solution of (3) trichloroethane and dichloroethane described above in 40% by weight of platinum-carrying carbon was used, and the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2%. : 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution XIII).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＸＩＩＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液ＸＩＩＩのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＸＩＩＩのイオン交換基当量重量は、初期と変わらず６６０ｇ／当量とパーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution XIII and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and evaporating the solvent, the resulting solid was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution XIII was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution XIII was 660 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例２の（２）に示すように、電極触媒被覆用溶液Ｘのイオン交換基当量重量は同一加温加水分解条件で１２５０ｇ／当量と変化し、初期の６６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (2) of Comparative Example 2, the ion exchange group equivalent weight of the electrode catalyst coating solution X changes to 1250 g / equivalent under the same heating hydrolysis conditions, and is larger than the initial value of 660 g / equivalent. The sulfonic acid group was eliminated.

即ち、安価な電極触媒被覆用溶液ＸＩＩＩは、比較例２の（２）に記載した安価な電極触媒被覆用溶液Ｘと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定でコストと耐加水分解性（耐久性）が両立して優れている。   That is, unlike the inexpensive electrode catalyst coating solution X described in (2) of Comparative Example 2, the inexpensive electrode catalyst coating solution XIII is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. It is excellent in both cost and hydrolysis resistance (durability).

前記電極触媒被覆用溶液ＸＩＩＩを前記（３）で得られた固体高分子電解質膜ＸＩＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＩＩを作製した。 The electrode catalyst coating solution XIII was applied to both sides of the solid polymer electrolyte membrane XIII obtained in the above (3), and then dried to prepare a membrane electrode assembly XIII having a platinum loading of 0.25 mg / cm 2 . .

比較例２の（２）に記載した電極触媒被覆用溶液Ｘを前記（２）で得られた固体高分子電解質膜ＸＩＩＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＩＩ'を作製した。 The electrode catalyst coating solution X described in (2) of Comparative Example 2 was applied to both sides of the solid polymer electrolyte membrane XIII obtained in (2), and then dried to carry a platinum loading of 0.25 mg / cm 2. Was prepared.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質（ナフィオン１１７）の５重量％濃度のアルコール−水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調製した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＸＩＩＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＩＩ''を作製した。 A 40 wt% platinum-supported carbon was mixed with a 5 wt% alcohol-water mixed solution of perfluorosulfonic acid solid polymer electrolyte (Nafion 117) at a weight ratio of platinum catalyst to solid polymer electrolyte of 2: 1. And then uniformly dispersed to prepare a paste (electrode catalyst coating solution). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane XIII obtained in the above (2), and then dried to produce a membrane electrode assembly XIII ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＩＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＩＩは、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly XIII and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XIII has the same initial state as the membrane / electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm, as it was.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＩＩ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＩＩ'は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XIII ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XIII ′ had a slightly peeled electrode but a firm membrane, and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＩＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＩＩ''は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XIII ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XIII ″ had electrodes slightly peeled off, but the membrane was firm and had a power generation capability.

（４） 燃料電池単セルの耐久性試験
前記膜電極接合体ＸＩＩＩ、ＸＩＩＩ'およびＸＩＩＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組み込み、燃料電池出力性能を評価した。即ち、固体高分子電解質膜１、酸素極２および水素極３からなる実施例１６の膜電極接合体４の両電極に薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図１に示す固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長期劣化試験を行った。その結果を図１６に示す。 (4) Durability test of fuel cell unit cells The membrane electrode assemblies XIII, XIII ′ and XIII ″ were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated. That is, a thin carbon paper packing material (supporting current collector) 5 was brought into close contact with both electrodes of the membrane electrode assembly 4 of Example 16 comprising the solid polymer electrolyte membrane 1, the oxygen electrode 2 and the hydrogen electrode 3, A single cell of a solid polymer electrolyte fuel cell shown in FIG. 1 comprising a conductive separator (bipolar plate) 6 which also functions as an electrode separation chamber and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm 2. A long-term deterioration test was performed under the following conditions. FIG. 16 shows the result.

図１６中の６２，６３，６４はそれぞれ本発明の固体高分子電解質膜電極接合体ＸＩＩＩ、ＸＩＩＩ'およびＸＩＩＩ''を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 16, reference numerals 62, 63, and 64 denote durability test results of a single fuel cell using the solid polymer electrolyte membrane electrode assemblies XIII, XIII ′, and XIII ″ of the present invention, respectively.

図１６中の６５はパーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 16, reference numeral 65 denotes a durability test result of a fuel cell unit cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１６中、６２は実施例１６のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、６３は実施例１６のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、６４は実施例１６のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、６５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、６６は比較例１６のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 16, reference numeral 62 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded via an alkylene group and a polyetherethersulfone solid polymer having a sulfonic acid group bonded via an alkylene group in Example 16. The change over time of the output voltage of the fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 63 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 16, Change with time of the output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which acid groups are directly bonded, 64 is a sulfonic acid group bonded via an alkylene group in Example 16 Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte (naf On-time change of the output voltage of the fuel cell single cell using the electrode catalyst coating solution (on 117), 65 indicates the time-dependent change of the output voltage of the fuel cell single cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117). Reference numeral 66 denotes a polyetherethersulfone solid polymer electrolyte membrane directly bonded with sulfonic acid groups of Comparative Example 16 and an electrode catalyst coating solution of a polyetherethersulfone solid polymer electrolyte directly bonded with sulfonic acid groups. It is a change with time of the output voltage of a single fuel cell.

図１６の６２および６４から分かるように、本発明の固体高分子電解質膜電極接合体ＸＩＩＩおよびＸＩＩＩ'を用いた単電池セルの電圧は初期０．８３Ｖで、稼動時間５０００時間後でも初期と変わらず、図１６の６５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変わらなかった。   As can be seen from 62 and 64 in FIG. 16, the voltage of the unit cell using the solid polymer electrolyte membrane electrode assemblies XIII and XIII ′ of the present invention was initially 0.83 V, which was the same as the initial voltage even after 5000 hours of operation. However, the results were the same as those obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 65 in FIG.

一方、図１６中の６６（比較例２のスルホン化芳香族炭化水素固体高分子電解質Ｘを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 66 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte X of Comparative Example 2) in FIG. 16 was initially 0.73 V, and there was no output after 600 hours of operation time. Was.

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

本発明の膜電極接合体ＸＩＩＩを用いた燃料電池単セルの耐久性は、膜電極接合体ＸＩＩＩ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＸＩＩＩは電極触媒被覆用溶液Ｘより膜電極接合体の電極触媒被覆に適している。   The durability of the fuel cell unit cell using the membrane electrode assembly XIII of the present invention is superior to the durability of the fuel cell unit cell using the membrane electrode assembly XIII '. That is, the electrode catalyst coating solution XIII is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution X.

また、実施例１６および比較例２の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１６の燃料電池単セルの出力電圧が比較例２の燃料電池単セルの出力電圧より大きい理由は、実施例１６の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が比較例２の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 The amount of supported platinum of the membrane electrode assembly of Example 16 and Comparative Example 2 even though the same as 0.25 mg / cm 2, the output voltage of the fuel cell unit of Example 16 of Comparative Example 2 The reason for the higher output voltage of the single cell of the fuel cell is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 16 and the ionic conductivity of the solution for coating the electrode catalyst are the solid polymer electrolyte of the membrane electrode assembly of Comparative Example 2. This is because it is higher than the ionic conductivity of the solution for coating the membrane and the electrode catalyst.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

実施例１５，１３，１４，１６から分かるようにｎの数が１、３、４、６のスルホアルキル化ポリ１，４−フェニレンエーテルエーテルスルホン固体電解質のイオン交換基当量重量（ｇ／当量）は、それぞれ６５０，６７０，６５０，６６０と殆ど同じである。それに対応する固体高分子電解質膜のイオン伝導度Ｓ／ｃｍはそれぞれ５，１５，２５，４０である。   As can be seen from Examples 15, 13, 14, and 16, the ion-exchange group equivalent weight (g / equivalent) of the sulfoalkylated poly-1,4-phenylene ether ether sulfone solid electrolyte in which the number n is 1, 3, 4, or 6 Are almost the same as 650, 670, 650, and 660, respectively. The corresponding ion conductivity S / cm of the solid polymer electrolyte membrane is 5, 15, 25, and 40, respectively.

即ち、スルホアルキル化芳香族炭化水素固体電解質のｎの数が大きいほどイオン伝導度が大きく、プロトンの伝達性が大きくなり固体高分子型燃料電池として優れている。   That is, the larger the number n of the sulfoalkylated aromatic hydrocarbon solid electrolyte, the higher the ionic conductivity and the greater the proton transferability, which is excellent as a polymer electrolyte fuel cell.

一方、コストの観点からスルホンとの１段反応により合成できるスルホプロピル化芳香族炭化水素系固体高分子電解質とスルホブチル化芳香族炭化水素系高分子固体電解質が、２段階反応によって合成されるスルホヘキサメチル化芳香族炭化水素系高分子固体電解質やスルホメチル化芳香族炭化水素系高分子固体電解質より有利である。   On the other hand, from the viewpoint of cost, a sulfopropylated aromatic hydrocarbon-based solid polymer electrolyte and a sulfobutylated aromatic hydrocarbon-based polymer solid electrolyte which can be synthesized by a one-step reaction with a sulfone are obtained by a sulfohexa synthesized by a two-step reaction It is more advantageous than a methylated aromatic hydrocarbon-based polymer solid electrolyte or a sulfomethylated aromatic hydrocarbon-based polymer solid electrolyte.

即ち、イオン伝導度とコストとの両立の観点からｎの数は３〜４が好ましい。   That is, the number n is preferably 3 to 4 from the viewpoint of achieving both ion conductivity and cost.

〔実施例 １７〕
（１） スルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃において１０時間保持乾燥した６．０８ｇ（０．０１５５ｍｏｌ）のポリ１，５−ナフタレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−１−ＯＣ１０Ｈ６−５−Ｏ−）ｎ〕と、脱水クロロホルム１５０ｍｌを入れ、６０℃にて約１時間保持して溶解した。この溶液にプロパンスルトン５．６７ｇ（０．０４６４ｍｏｌ）を加えた。次いで、撹拌しながら約３０分かけて乳鉢で良くすりつぶした無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加した後、３０時間，６０℃で還流攪拌した。 [Example 17]
(1) Synthesis of sulfopropylated poly 1,6-naphthalene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen. , poly 1,5-naphthalene ether sulfone 6.08g was 10 hour hold dried at 110 ℃ (0.0155mol) [(-C 6 H 4 -4-SO 2 C 6 H 4 -1-OC 10 H 6 -5-O-) n] and 150 ml of dehydrated chloroform were added and dissolved at 60 ° C. for about 1 hour. 5.67 g (0.0464 mol) of propane sultone was added to this solution. Then, with stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride thoroughly ground in a mortar was added over about 30 minutes. After adding anhydrous aluminum chloride, the mixture was refluxed and stirred at 60 ° C. for 30 hours.

析出したポリマーを濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥した。得られたポリマーを水２５０ｍｌに懸濁させ、ミキサーで細かく砕いた。得られた微粉砕物を濾過した。これを４回繰り返した。水で十分洗浄した後、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。   The precipitated polymer was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained polymer was suspended in 250 ml of water and crushed with a mixer. The obtained finely pulverized product was filtered. This was repeated four times. After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure.

１ＨＮＭＲ解析を測定すると新たに−ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが２．２ｐｐｍ、３．８ｐｐｍに認められた。このことからスルホプロピル基が導入されていることが確認された。 When 1 HNMR analysis was measured, a new peak based on a —CH 2 CH 2 CH 2 SO 3 H group was newly observed at 2.2 ppm and 3.8 ppm. This confirmed that the sulfopropyl group had been introduced.

得られたスルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＩＶのスルホン酸当量重量は７７０ｇ／当量であった。   The sulfonic acid equivalent weight of the obtained sulfopropylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XIV was 770 g / equivalent.

スルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＩＶのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，６−ナフタレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べ１／５０以下と安価である。   The cost of the sulfopropylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XIV can be produced in one step using poly 1,6-naphthalene ether ether sulfone, which is a commercially available relatively inexpensive engineering plastic, as a raw material. The raw material is expensive, and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) manufactured through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＩＶの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して十分に水洗した後、スルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＩＶのイオン交換基当量重量を測定した。その結果、スルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＩＶのイオン交換基当量重量は、初期と変わらず７７０ｇ／当量とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfopropylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XIV and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Then, after cooling and washing with water sufficiently, the ion exchange group equivalent weight of the sulfopropylated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XIV was measured. As a result, the ion-exchange group equivalent weight of the sulfopropylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XIV was 770 g / equivalent to the initial value, which was the same as that of the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). Was stable.

一方、後述の比較例３の（１）に示すように、安価なスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶのイオン交換基当量重量は、同一加温加水分解条件で１３００ｇ／当量と変化し、初期の７６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 3 below, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XV was 1300 g under the same heating hydrolysis conditions. / Equivalent, larger than the initial value of 760 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＩＶは、後述の比較例３の（１）に記載した安価なスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfopropylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XIV is the inexpensive sulfonated poly 1,6-naphthalene ether ether sulfone solid high polymer described in Comparative Example 3 (1). Unlike the molecular electrolyte XV, it is as stable as the perfluorosulfonic acid solid polymer electrolyte (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜ＸＩＶを作成した。得られた固体高分子電解質膜ＸＩＶのイオン導電率は１５Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamide-cyclohexanone-methylethylketone mixed solvent (20:80:25 by volume) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane XIV. The ionic conductivity of the obtained solid polymer electrolyte membrane XIV was 15 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に、得られた前記固体高分子電解質膜ＸＩＶとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、イオン導電率はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained solid polymer electrolyte membrane XIV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity was the same as that of the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) as in the initial stage, and the membrane was firm.

一方、後述の比較例３の（２）に示すように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質ＸＶは、同一加温加水分解条件で破け、ぼろぼろになっていた。   On the other hand, as shown in (2) of Comparative Example 3 described later, the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte XV was broken and ragged under the same heating and hydrolysis conditions.

即ち、安価なスルホプロピル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＶは、後述の比較例３の（２）に記載した安価なスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質膜ＸＩＶと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfopropylated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte membrane XIV is the inexpensive sulfonated poly 1,6-naphthalene ether ether sulfone solid described in (2) of Comparative Example 3 described later. Unlike the polymer electrolyte membrane XIV, it is as stable as the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＸＩＶ）を調整した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution XIV).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＸＩＶの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗した後、電極触媒被覆用溶液ＸＩＶのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the solution XIV for electrode catalyst coating and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the solid formed by cooling and evaporating the solvent was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution XIV was measured.

その結果、電極触媒被覆用溶液ＸＩＶのイオン交換基当量重量は、初期と変わらず７６０ｇ／当量と、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution XIV was 760 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、後述の比較例３の（２）に示すように、電極触媒被覆用溶液ＸＶのイオン交換基当量重量は、同一加温加水分解条件で１３００ｇ／当量と変化し、初期の７６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (2) of Comparative Example 3 to be described later, the ion exchange group equivalent weight of the electrode catalyst coating solution XV changes to 1300 g / equivalent under the same heating hydrolysis conditions, and the initial 760 g / equivalent amount. It became larger than the value, and the sulfonic acid group was eliminated.

即ち、安価な電極触媒被覆用溶液ＸＩＶは、比較例３の（２）に記載した安価な電極触媒被覆用溶液ＸＶと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive electrode catalyst coating solution XIV is different from the inexpensive electrode catalyst coating solution XV described in (2) of Comparative Example 3, and is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. It is excellent in both cost and hydrolysis resistance (durability).

前記電極触媒被覆用溶液ＸＩＶを前記（２）で得られた固体高分子電解質膜ＸＩＶの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＶを作製した。 The solution XIV for coating the electrode catalyst was applied to both sides of the solid polymer electrolyte membrane XIV obtained in the above (2), and then dried to prepare a membrane electrode assembly XIV having a platinum loading of 0.25 mg / cm 2 . .

後述の比較例３の（２）に記載した電極触媒被覆用溶液ＸＶを前記（２）で得られた固体高分子電解質膜ＸＩＶの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＶ'を作製した。 The electrode catalyst coating solution XV described in (2) of Comparative Example 3 described below was applied to both sides of the solid polymer electrolyte membrane XIV obtained in (2), and then dried to obtain a platinum loading of 0.25 mg / cm 2 of a membrane electrode assembly XIV ′ was produced.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調整した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＸＩＶの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＩＶ''を作製した。 To a 40% by weight platinum-supported carbon, a 5% by weight alcohol-water mixed solution of a perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. The paste was uniformly dispersed to prepare a paste (solution for coating an electrode catalyst). This electrode catalyst coating solution was applied to both sides of the solid polymer electrolyte membrane XIV obtained in the above (2), and then dried to produce a membrane electrode assembly XIV ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＶとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＶは、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly XIV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XIV was similar to the membrane / electrode assembly manufactured using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117) in the initial stage. The film was firm, as it was.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＶ'とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＶ'は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XIV ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly XIV 'had slightly peeled electrodes, but the membrane was firm and had power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＩＶ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＩＶ''は電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XIV ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly XIV ″ had electrodes slightly peeled off, but the membrane was firm and had a power generation capability.

一方、後述の比較例３の（３）に示すように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜ＸＶと、電極触媒被覆用溶液ＸＶを用いて作製した膜電極接合体ＸＶは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 3 described later, a membrane electrode assembly produced using a relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane XV and an electrode catalyst coating solution XV In the case of XV, the membrane was broken and ragged under the same heating hydrolysis conditions, and the electrode was peeled off.

即ち、安価なスルホプロピルポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＸＩＶは、後述の比較例３の（３）に記載した安価なスルホン化芳香族炭化水素系固体高分子電解質膜電極接合体ＸＶと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfopropyl poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte membrane electrode assembly XIV is an inexpensive sulfonated aromatic hydrocarbon-based solid polymer described in (3) of Comparative Example 3 described later. Unlike the electrolyte membrane electrode assembly XV, it is as stable as the perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and is excellent in terms of both cost and hydrolysis resistance (durability).

（４） 燃料電池単セルの耐久性試験
前記膜電極接合体ＸＩＶ、ＸＩＶ'およびＸＩＶ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組みこみ、燃料電池出力性能を評価した。 (4) Durability test of fuel cell single cell The membrane electrode assemblies XIV, XIV 'and XIV''were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

即ち、固体高分子電解質膜１，酸素極２および水素極３からなる実施例１の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図１に示す固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長期劣化試験を行った。その結果を図１７に示す。 That is, a thin carbon paper packing material (supporting current collector) 5 is brought into close contact with both electrodes of the membrane electrode assembly 4 of the first embodiment including the solid polymer electrolyte membrane 1, the oxygen electrode 2, and the hydrogen electrode 3, A single cell of a polymer electrolyte fuel cell shown in FIG. 1 comprising a conductive separator (bipolar plate) 6 which also functions as an electrode compartment separation and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm. A long-term deterioration test was performed under the conditions of 2 . FIG. 17 shows the result.

図１７中の６７，６８，６９は、それぞれ本発明の固体高分子電解質膜電極接合体ＸＩＶ，ＸＩＶ'およびＸＩＶ''を用いた燃料電池単セルの耐久性試験結果である。   In FIG. 17, 67, 68, and 69 indicate the results of the durability test of the single fuel cell using the solid polymer electrolyte membrane electrode assemblies XIV, XIV ′, and XIV ″, respectively.

図１７中の７０はパーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   Reference numeral 70 in FIG. 17 indicates a durability test result of a fuel cell unit cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１７中、６７は実施例１７のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、アルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、６８は実施例１７のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、６９は実施例１７のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、７０はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、７１は比較例１７のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 17, reference numeral 67 denotes a polyetherethersulfone solid polymer electrolyte membrane having a sulfonic acid group bonded through an alkylene group in Example 17, and a polyetherethersulfone solid polymer having a sulfonic acid group bonded through an alkylene group. The change over time of the output voltage of a fuel cell single cell using the solution for coating the electrode catalyst of the electrolyte, 68 is a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 17, Change with time of the output voltage of a single cell of a fuel cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which acid groups are directly bonded. Reference numeral 69 denotes a sulfonic acid group bonded via an alkylene group in Example 17. Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte Of the output voltage of the fuel cell unit cell using the solution for coating the electrode catalyst of Zion 117), and 70 is the change over time of the output voltage of the fuel cell unit cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117). The reference numeral 71 denotes the polyetherethersulfone solid polymer electrolyte membrane of Comparative Example 17 having sulfonic acid groups directly bonded thereto, and the electrode catalyst coating solution of the polyetherethersulfone solid polymer electrolyte having sulfonic acid groups directly bonded thereto. It is a change with time of the output voltage of a single fuel cell.

図１７の６７および６９から分かるように、本発明の固体高分子電解質膜電極接合体ＸＩＶおよびＸＩＶ''を用いた単電池セルの電圧は初期０．７６Ｖで、稼動時間５０００時間後でも初期と変わらず、図１７の７０のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変化しなかった。   As can be seen from FIGS. 67 and 69, the voltage of the unit cell using the solid polymer electrolyte membrane electrode assemblies XIV and XIV ″ of the present invention was 0.76 V at the initial stage, There was no change from the initial stage, which was equivalent to the result obtained by using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) of 70 in FIG.

一方、図１７中の７１（後述の比較例３のスルホン化芳香族炭化水素固体高分子電解質ＸＶを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 71 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte XV of Comparative Example 3 to be described later) in FIG. 17 is initially 0.73 V, and is output after 600 hours of operation time. Is gone.

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

本発明の膜電極接合体ＸＩＶを用いた燃料電池単セルの耐久性は、膜電極接合体ＸＩＶ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＸＩＶは、電極触媒被覆用溶液ＸＶより膜電極接合体の電極触媒被覆に適している。   The durability of a fuel cell unit cell using the membrane electrode assembly XIV of the present invention is superior to the durability of a fuel cell unit cell using the membrane electrode assembly XIV '. That is, the electrode catalyst coating solution XIV is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution XV.

また、実施例１７および比較例３の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１７の燃料電池単セルの出力電圧が比較例３の燃料電池単セルの出力電圧より大きい理由は、実施例１７の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が、比較例３の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。
燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 Further, the output voltage of the fuel cell unit cell of Example 17 was lower than that of Comparative Example 3 even though the supported amount of platinum of the membrane electrode assemblies of Example 17 and Comparative Example 3 was the same as 0.25 mg / cm 2 . The reason why the output voltage is higher than that of the single cell of the fuel cell is that the ionic conductivity of the solid polymer electrolyte membrane of the membrane electrode assembly of Example 17 and the ionic conductivity of the solution for coating the electrode catalyst is higher than that of the membrane electrode assembly of Comparative Example 3. This is because it is higher than the ionic conductivity of the electrolyte membrane and the solution for coating the electrode catalyst.
Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

〔比較例 ３〕
（１）スルホン化ポリ１，６−ナフタレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃において１０時間保持乾燥した３．２２ｇ（０．０１０３ｍｏｌ）のポリ１，６−ナフタレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−１−ＯＣ１０Ｈ６−５−Ｏ−）ｎ〕と、クロロホルム１００ｍｌを入れ、６０℃に約１時間保持して溶解した。この溶液にクロロスルホン酸１．１６５ｇ（０．０１ｍｏｌ）を１，１，２，２−テトラクロロエタン５０ｍｌに溶かした溶液を約１０分間かけて加えた。 [Comparative Example 3]
(1) Synthesis of sulfonated poly 1,6-naphthalene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, poly 1,6-naphthalene ether sulfone 10 hour hold dried 3.22g at 110 ℃ (0.0103mol) [(-C 6 H 4 -4-SO 2 C 6 H 4 -1-OC 10 H 6 - 5-O-) n] and 100 ml of chloroform, and dissolved at 60 ° C. for about 1 hour. To this solution, a solution of 1.165 g (0.01 mol) of chlorosulfonic acid dissolved in 50 ml of 1,1,2,2-tetrachloroethane was added over about 10 minutes.

次いで、６０℃で４時間攪拌し、析出物を濾過して、クロロホルム１５０ｍｌで洗浄した。得られた析出物にメタノール２５０ｍｌを加え６０℃で溶解した。溶液を６０℃で減圧乾燥した。得られたポリマーに水２５０ｍｌを加え、ミキサーで細かく砕き、濾過した。この操作を３回繰り返した。   Next, the mixture was stirred at 60 ° C. for 4 hours, and the precipitate was filtered and washed with 150 ml of chloroform. 250 ml of methanol was added to the obtained precipitate and dissolved at 60 ° C. The solution was dried at 60 ° C. under reduced pressure. 250 ml of water was added to the obtained polymer, which was finely ground with a mixer and filtered. This operation was repeated three times.

得られた水不溶性の微粉末を五酸化燐上で減圧下、９０℃で乾燥した。この微粉末は、水に不溶、メタノールに可溶であった。   The obtained water-insoluble fine powder was dried at 90 ° C. under reduced pressure over phosphorus pentoxide. This fine powder was insoluble in water and soluble in methanol.

１ＨＮＭＲを測定すると、原料のポリ１，６−ナフタレンエーテルエーテルスルホン中のナフタレン環、ベンゼン環の水素に基づく７．３〜８．０ｐｐｍの吸収が減少し、新たにＳＯ３Ｈ基に隣接するフェニル基の水素の基づく８．３ｐｐｍの吸収が認められた。このことからスルホン酸が導入されていることが確認された。得られたスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶのスルホン酸当量重量は７６０ｇ／当量であった。 When 1 HNMR is measured, the absorption of 7.3 to 8.0 ppm based on hydrogen of the naphthalene ring and benzene ring in the raw material poly 1,6-naphthalene ether ether sulfone decreases, and the absorption is newly adjacent to the SO 3 H group. An absorption of 8.3 ppm based on hydrogen of the phenyl group was observed. This confirmed that sulfonic acid had been introduced. The sulfonic acid equivalent weight of the obtained sulfonated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XV was 760 g / equivalent.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記スルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶの１．０ｇとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その後、冷却して十分に水洗した後、スルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶのイオン交換基当量重量を測定した。その結果、スルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶのスルホン酸当量重量は１３００ｇ／当量と初期の７６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   1.0 g of the obtained sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C for 2 weeks. Then, after cooling and washing sufficiently with water, the ion exchange group equivalent weight of the sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XV was measured. As a result, the sulfonic acid equivalent weight of the sulfonated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XV was 1300 g / equivalent, which was larger than the initial value of 760 g / equivalent, and the sulfonic acid group had been eliminated.

（２） 固体高分子電解質膜の作製
前記（１）で得られたスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶを、５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚４５μｍの固体高分子電解質膜ＸＶを作成した。得られた固体高分子電解質膜ＸＩＶのイオン導電率は８Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane The sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XV obtained in the above (1) was N, N-dimethyl so as to have a concentration of 5% by weight. It was dissolved in a mixed solvent of formamide-cyclohexanone-methylethylketone (volume ratio: 20:80:25). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a solid polymer electrolyte membrane XV having a thickness of 45 μm. The ionic conductivity of the obtained solid polymer electrolyte membrane XIV was 8 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記固体高分子電解質膜ＸＩＶとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、固体高分子電解質膜ＸＶは破け、ぼろぼろになっていた。   The obtained solid polymer electrolyte membrane XIV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the solid polymer electrolyte membrane XV was broken and ragged.

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＸＶ）を調製した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte were added at a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution XV).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＸＶの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗後、電極触媒被覆用溶液ＸＶのイオン交換基当量重量を測定した。その結果、電極触媒被覆用溶液ＸＶのイオン交換基当量重量は、同一加温加水分解条件で１３００ｇ／当量と変化し、初期の７６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution XV and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the solid formed by cooling and evaporating the solvent was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution XV was measured. As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution XV changed to 1300 g / equivalent under the same heated hydrolysis conditions, became larger than the initial value of 760 g / equivalent, and the sulfonic acid group was eliminated. .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＶとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＶの膜は破け、ぼろぼろになり、電極は剥がれていた。   The obtained membrane electrode assembly XV and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane of the membrane / electrode assembly XV was broken and ragged, and the electrode was peeled off.

（４） 燃料電池単セルの耐久性試験
比較例３の膜電極接合体ＸＶの両側に薄いカーボンペーパのパッキング材（支持集電体）を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）からなる固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長時間稼動試験を行った。その結果、図１７の７１に示すように出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力電圧が無くなった。 (4) Durability test of fuel cell unit cell A packing material (supporting current collector) made of thin carbon paper is adhered to both sides of the membrane electrode assembly XV of Comparative Example 3, and the separation of the electrode chamber from both sides is performed. A single cell of a polymer electrolyte fuel cell composed of a conductive separator (bipolar plate) also serving as a gas supply passage was manufactured, and a long-term operation test was performed under a condition of a current density of 300 mA / cm 2 . As a result, as shown at 71 in FIG. 17, the output voltage was initially 0.73 V and disappeared after 600 hours of operation.

〔実施例 １８〕
（１） スルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホンの合成
撹拌機、温度計、塩化カルシウム管を接続した還流冷却器を付けた５００ｍｌの四つ口丸底フラスコの内部を窒素置換した後、１１０℃において１０時間保持乾燥した６．０８ｇ（０．０１５５ｍｏｌ）のポリ１，５−ナフタレンエーテルエーテルスルホン〔（−Ｃ６Ｈ４−４−ＳＯ２Ｃ６Ｈ４−１−ＯＣ１０Ｈ６−５−Ｏ−）ｎ〕と、脱水クロロホルム１５０ｍｌを入れ、６０℃にて約１時間保持して溶解した。この溶液にブタンスルトン６．２６ｇ（０．０４６４ｍｏｌ）を加えた。 [Example 18]
(1) Synthesis of sulfobutylated poly 1,6-naphthalene ether ether sulfone After the inside of a 500 ml four-necked round bottom flask equipped with a stirrer, a thermometer, and a reflux condenser connected to a calcium chloride tube was purged with nitrogen, poly 1,5-naphthalene ether sulfone 10 hour hold dried 6.08g at 110 ℃ (0.0155mol) [(-C 6 H 4 -4-SO 2 C 6 H 4 -1-OC 10 H 6 - 5-O-) n] and 150 ml of dehydrated chloroform were added and dissolved at 60 ° C. for about 1 hour. 6.26 g (0.0464 mol) of butane sultone was added to this solution.

次いで、撹拌しながら約３０分かけて乳鉢で良くすりつぶした無水塩化アルミニウム６．１９ｇ（０．０４６４ｍｏｌ）を加えた。無水塩化アルミニウムを添加した後、３０時間，６０℃で還流攪拌した。析出したポリマーを濾過し、クロロホルム１５０ｍｌで洗浄し、減圧乾燥した。得られたポリマーを水２５０ｍｌに懸濁させ、ミキサーで細かく砕き、得られた微粉砕物を濾過した。これを４回繰り返した。水で十分洗浄した後、水不溶性の微粉砕物を減圧下、９０℃で乾燥した。   Then, with stirring, 6.19 g (0.0464 mol) of anhydrous aluminum chloride thoroughly ground in a mortar was added over about 30 minutes. After adding anhydrous aluminum chloride, the mixture was refluxed and stirred at 60 ° C. for 30 hours. The precipitated polymer was filtered, washed with 150 ml of chloroform, and dried under reduced pressure. The obtained polymer was suspended in 250 ml of water, finely ground with a mixer, and the obtained finely pulverized product was filtered. This was repeated four times. After sufficiently washing with water, the water-insoluble finely pulverized product was dried at 90 ° C. under reduced pressure.

１ＨＮＭＲ解析を測定すると−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＳＯ３Ｈ基に基づくピークが新たに２．２ｐｐｍ、３．８ｐｐｍに認められた。このことからスルホプロピル基が導入されていることが確認された。得られたスルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶＩのスルホン酸当量重量は７７０ｇ／当量であった。 When the 1 HNMR analysis was measured, a peak based on a —CH 2 CH 2 CH 2 CH 2 SO 3 H group was newly observed at 2.2 ppm and 3.8 ppm. This confirmed that the sulfopropyl group had been introduced. The sulfonic acid equivalent weight of the obtained sulfobutylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XVI was 770 g / equivalent.

スルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶＩのコストは、市販の比較的安価なエンジニアプラスチックであるポリ１，６−ナフタレンエーテルエーテルスルホンを原料に１工程で製造できるため、原料が高価で５工程を経て製造されるパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）のコストに比べて１／５０以下と安価である。   The cost of the sulfobutylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XVI can be produced in one step using poly 1,6-naphthalene ether ether sulfone, a commercially available relatively inexpensive engineering plastic, as a raw material. Is expensive and is 1/50 or less of the cost of a perfluorosulfonic acid solid polymer electrolyte (Nafion 117) produced through five steps.

テフロンコーテングのＳＵＳ製密閉容器に、得られたスルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶＩの１．０ｇと、イオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して十分に水洗した後スルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the obtained sulfobutylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XVI and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the mixture was cooled and sufficiently washed with water, and the equivalent weight of the ion-exchange group of the sulfobutylated poly-1,6-naphthalene ether ether sulfone solid polymer electrolyte XVI was measured.

その結果、スルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶＩのイオン交換基当量重量は、初期と変わらず７５０ｇ／当量と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定であった。   As a result, the equivalent weight of the ion-exchange group of the sulfobutylated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XVI was 750 g / eq. Was stable.

一方、比較例３の（１）に示すように、安価なスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶのイオン交換基当量重量は、同一加温加水分解条件で１３００ｇ／当量と変化し、初期の７６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (1) of Comparative Example 3, the equivalent weight of the ion-exchange group of the inexpensive sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XV was 1300 g / equivalent under the same heating hydrolysis conditions. And became larger than the initial value of 760 g / equivalent, and the sulfonic acid group was eliminated.

即ち、安価なスルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶＩは、比較例３の（１）に記載した安価なスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質ＸＶと異なり、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfobutylated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XVI is the inexpensive sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte XV described in (1) of Comparative Example 3. Unlike the perfluorosulfonic acid solid polymer electrolyte (Nafion 117), it is stable, and is excellent in both cost and hydrolysis resistance (durability).

（２） 固体高分子電解質膜の作製
前記（１）で得られた生成物を５重量％の濃度になるようにＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶媒（体積比２０：８０：２５）に溶解した。この溶液をスピンコートによりガラス板上に展開し、風乾した後、８０℃で真空乾燥して膜厚２５μｍの固体高分子電解質膜ＸＶＩを作成した。得られた固体高分子電解質膜ＸＶＩのイオン導電率は２５Ｓ／ｃｍであった。 (2) Preparation of solid polymer electrolyte membrane An N, N-dimethylformamide-cyclohexanone-methylethylketone mixed solvent (20:80:25 by volume) was prepared so that the product obtained in the above (1) had a concentration of 5% by weight. ). This solution was spread on a glass plate by spin coating, air-dried, and then vacuum-dried at 80 ° C. to form a 25 μm-thick solid polymer electrolyte membrane XVI. The ionic conductivity of the obtained solid polymer electrolyte membrane XVI was 25 S / cm.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記固体高分子電解質膜ＸＶＩとイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、そのイオン導電率は、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に初期と変わらず、膜もしっかりしていた。   The obtained solid polymer electrolyte membrane XVI and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the ionic conductivity was the same as that of the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and the membrane was firm.

一方、比較例３の（２）に示すように、比較的安価なスルホン化芳香族炭化水素系固体高分子電解質ＸＶは、同一加温加水分解条件で破け、ぼろぼろになっていた。即ち、安価なスルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質膜ＸＶＩは、比較例３の（２）に記載した安価なスルホン化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質膜ＸＶと異なり、パーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   On the other hand, as shown in (2) of Comparative Example 3, the relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte XV was broken and ragged under the same heating and hydrolysis conditions. That is, the inexpensive sulfobutylated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte membrane XVI is the inexpensive sulfonated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte described in (2) of Comparative Example 3. Unlike the membrane XV, the membrane is stable as in the case of the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117), and is excellent in both cost and hydrolysis resistance (durability).

（３） 電極触媒被覆用溶液および膜電極接合体の作製
４０重量％の白金担持カーボンに、前記（２）の５重量％濃度のＮ，Ｎ−ジメチルホルムアミド−シクロヘキサノン−メチルエチルケトン混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液ＸＶＩ）を調整した。 (3) Preparation of Electrode Catalyst Coating Solution and Membrane Electrode Assembly The above-mentioned mixed solution of N, N-dimethylformamide-cyclohexanone-methylethylketone (5% by weight) of (2) above was mixed with 40% by weight of platinum-supported carbon, And a solid polymer electrolyte in a weight ratio of 2: 1 and uniformly dispersed to prepare a paste (electrode catalyst coating solution XVI).

テフロンコーテングのＳＵＳ製密閉容器に、前記電極触媒被覆用溶液ＸＶＩの１．０ｇとイオン交換水２０ｍｌを入れて１２０℃に２週間保持した。その後、冷却して溶媒を揮散させて生じた固体を水洗後、電極触媒被覆用溶液ＸＶＩのイオン交換基当量重量を測定した。   In a Teflon-coated closed container made of SUS, 1.0 g of the electrode catalyst coating solution XVI and 20 ml of ion-exchanged water were put and kept at 120 ° C. for 2 weeks. Thereafter, the solid formed by cooling and evaporating the solvent was washed with water, and then the ion exchange group equivalent weight of the electrode catalyst coating solution XVI was measured.

その結果、電極触媒被覆用溶液ＸＶＩのイオン交換基当量重量は、初期と変わらず７５０ｇ／当量と、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定であった。   As a result, the ion exchange group equivalent weight of the electrode catalyst coating solution XVI was 750 g / equivalent as in the initial stage, and was stable as in the case of the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution.

一方、比較例３の（２）に示したように電極触媒被覆用溶液ＸＶのイオン交換基当量重量は、同一加温加水分解条件で１３００ｇ／当量と変化し、初期の７６０ｇ／当量の値より大きくなり、スルホン酸基が脱離していた。   On the other hand, as shown in (2) of Comparative Example 3, the ion exchange group equivalent weight of the electrode catalyst coating solution XV changes to 1300 g / equivalent under the same heating hydrolysis conditions, and is higher than the initial value of 760 g / equivalent. It became larger and the sulfonic acid group was eliminated.

即ち、安価な電極触媒被覆用溶液ＸＶＩは、比較例３の（２）に記載した安価な電極触媒被覆用溶液ＸＶと異なり、パーフルオロスルホン酸（ナフィオン１１７）電極触媒被覆用溶液と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, unlike the inexpensive electrode catalyst coating solution XV described in (2) of Comparative Example 3, the inexpensive electrode catalyst coating solution XVI is as stable as the perfluorosulfonic acid (Nafion 117) electrode catalyst coating solution. It is excellent in both cost and hydrolysis resistance (durability).

前記電極触媒被覆用溶液ＸＶＩを前記（２）で得られた固体高分子電解質膜ＸＶＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＶＩを作製した。 The electrode catalyst coating solution XVI was applied to both sides of the solid polymer electrolyte membrane XVI obtained in the above (2), and then dried to produce a membrane electrode assembly XVI having a platinum loading of 0.25 mg / cm 2 . .

比較例３の（２）に記載した電極触媒被覆用溶液ＸＶを前記（２）で得られた固体高分子電解質膜ＸＶＩの両側に塗布した後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＶＩ'を作製した。 The electrode catalyst coating solution XV described in (2) of Comparative Example 3 was applied to both sides of the solid polymer electrolyte membrane XVI obtained in (2), and then dried to carry a platinum carrying amount of 0.25 mg / cm 2. Was produced.

４０重量％の白金担持カーボンに、パーフロロスルホン酸固体高分子電解質の５重量％濃度のアルコールー水混合溶液を、白金触媒と固体高分子電解質との重量比が２：１となるように添加し、均一に分散させてペースト（電極触媒被覆用溶液）を調整した。この電極触媒被覆用溶液を前記（２）で得られた固体高分子電解質膜ＸＶＩの両側に塗布後、乾燥して白金担持量０．２５ｍｇ／ｃｍ２の膜電極接合体ＸＶＩ''を作製した。 To a 40% by weight platinum-supported carbon, a 5% by weight alcohol-water mixed solution of a perfluorosulfonic acid solid polymer electrolyte was added so that the weight ratio of the platinum catalyst to the solid polymer electrolyte was 2: 1. The paste was uniformly dispersed to prepare a paste (solution for coating an electrode catalyst). This solution for coating an electrode catalyst is applied to both sides of the solid polymer electrolyte membrane XVI obtained in the above (2), and then dried to prepare a membrane electrode assembly XVI ″ having a platinum loading of 0.25 mg / cm 2 . .

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＶＩと，イオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＶＩは，高コストのパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）とパーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）を用いて作製した膜電極接合体と同様に初期と変わらず、膜もしっかりしていた。   The obtained membrane electrode assembly XVI and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly XVI is similar to the membrane-electrode assembly manufactured using the high-cost perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117) and the perfluorosulfonic acid solid polymer electrolyte (Nafion 117). The film was firm as before.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＶＩ'と，イオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＶＩ'は，電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XVI ′ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane / electrode assembly XVI ′ had a slightly peeled electrode but a firm membrane, and had a power generation capability.

テフロンコーテングのＳＵＳ製密閉容器に得られた前記膜電極接合体ＸＶＩ''とイオン交換水２０ｍｌを入れ、１２０℃に２週間保持した。その結果、膜電極接合体ＸＶＩ''は，電極が若干剥がれていたが膜はしっかりしており、発電能力はあった。   The obtained membrane electrode assembly XVI ″ and 20 ml of ion-exchanged water were placed in a Teflon-coated closed container made of SUS and kept at 120 ° C. for 2 weeks. As a result, the membrane-electrode assembly XVI ″ had electrodes slightly peeled off, but the membrane was firm and had a power generation capability.

一方、比較例３の（３）に示したように比較的安価なスルホン化芳香族炭化水素系固体高分子電解質膜ＸＶと、電極触媒被覆用溶液ＸＶを用いて作製した膜電極接合体ＸＶは、同一加温加水分解条件で膜は破け、ぼろぼろになり、電極は剥がれていた。   On the other hand, as shown in (3) of Comparative Example 3, a relatively inexpensive sulfonated aromatic hydrocarbon-based solid polymer electrolyte membrane XV and a membrane electrode assembly XV produced using the electrode catalyst coating solution XV are: Under the same heated hydrolysis conditions, the membrane was broken and ragged, and the electrode was peeled off.

即ち、安価なスルホブチル化ポリ１，６−ナフタレンエーテルエーテルスルホン固体高分子電解質膜電極接合体ＸＶＩは、後述の比較例３の（３）に記載した安価なスルホン化芳香族炭化水素系固体高分子電解質膜電極接合体ＸＶと異なり、パーフルオロスルホン酸（ナフィオン１１７）膜電極接合体と同様に安定で、コストと耐加水分解性（耐久性）が両立して優れている。   That is, the inexpensive sulfobutylated poly 1,6-naphthalene ether ether sulfone solid polymer electrolyte membrane electrode assembly XVI is an inexpensive sulfonated aromatic hydrocarbon-based solid polymer described in (3) of Comparative Example 3 described later. Unlike the electrolyte membrane electrode assembly XV, it is as stable as the perfluorosulfonic acid (Nafion 117) membrane electrode assembly, and is excellent in terms of both cost and hydrolysis resistance (durability).

（４）燃料電池単セルの耐久性試験
前記膜電極接合体ＸＶＩ、ＸＶＩ'およびＸＶＩ''を沸騰した脱イオン水中に２時間浸漬することにより吸水させた。得られた膜電極接合体を評価セルに組みこみ、燃料電池出力性能を評価した。 (4) Durability Test of Single Cell of Fuel Cell The membrane electrode assemblies XVI, XVI ′ and XVI ″ were immersed in boiling deionized water for 2 hours to absorb water. The obtained membrane electrode assembly was assembled in an evaluation cell, and the output performance of the fuel cell was evaluated.

即ち、固体高分子電解質膜１、酸素極２および水素極３からなる実施例１８の膜電極接合体４の両電極に、薄いカーボンペーパのパッキング材（支持集電体）５を密着させて、その両側から極室分離と電極へのガス供給通路の役割を兼ねた導電性のセパレータ（バイポーラプレート）６からなる図１に示す固体高分子型燃料電池単セルを作製し、電流密度３００ｍＡ／ｃｍ２の条件で長期劣化試験を行った。その結果を図１８に示す。 That is, a thin carbon paper packing material (supporting current collector) 5 is brought into close contact with both electrodes of the membrane electrode assembly 4 of Example 18, which includes the solid polymer electrolyte membrane 1, the oxygen electrode 2, and the hydrogen electrode 3, A single cell of a polymer electrolyte fuel cell shown in FIG. 1 comprising a conductive separator (bipolar plate) 6 which also functions as an electrode compartment separation and a gas supply passage to the electrode from both sides was prepared, and the current density was 300 mA / cm. A long-term deterioration test was performed under the conditions of 2 . FIG. 18 shows the result.

図１８中の７２、７３、７４はそれぞれ本願発明の固体高分子電解質膜電極接合体ＸＶＩ、ＸＶＩ'、ＸＶＩ''を用いた燃料電池単セルの耐久性試験結果である。図１８中の７３はパーフルオロスルホン酸（ナフィオン１１７）固体高分子電解質膜電極接合体を用いた燃料電池単セルの耐久性試験結果である。   18, 72, 73, and 74 are the results of the durability test of the single fuel cell using the solid polymer electrolyte membrane electrode assemblies XVI, XVI ′, and XVI ″ of the present invention, respectively. Numeral 73 in FIG. 18 indicates a durability test result of a fuel cell single cell using a perfluorosulfonic acid (Nafion 117) solid polymer electrolyte membrane electrode assembly.

図１８中、７２は実施例１８のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜とアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、７３は実施例１８のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、７４は実施例１８のアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホン固体高分子電解質膜と、パーフルオロスルホン酸固体高分子電解質（ナフィオン１１７）の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化、７５はパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた燃料電池単セルの出力電圧の経時変化、７６は比較例１８のスルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質膜と、スルホン酸基が直接結合したポリエーテルエーテルスルホン固体高分子電解質の電極触媒被覆用溶液を用いた燃料電池単セルの出力電圧の経時変化である。   In FIG. 18, reference numeral 72 denotes a polyetherethersulfone solid polymer electrolyte membrane of Example 18 in which a sulfonic acid group is bonded via an alkylene group, and a polyetherethersulfone solid polymer electrolyte in which a sulfonic acid group is bonded via an alkylene group. 73 shows the change over time in the output voltage of a single cell of a fuel cell using the electrode catalyst coating solution, and 73 a polyetherethersulfone solid polymer electrolyte membrane in which a sulfonic acid group is bonded via an alkylene group in Example 18. Change with time of the output voltage of a fuel cell single cell using a solution for coating an electrode catalyst of a polyetherethersulfone solid polymer electrolyte to which groups were directly bonded, 74 indicates that a sulfonic acid group was bonded via an alkylene group in Example 18. Polyetherethersulfone solid polymer electrolyte membrane and perfluorosulfonic acid solid polymer electrolyte (naf On-time change of the output voltage of the fuel cell single cell using the solution for electrode catalyst coating of step 117), and 75 is the time-dependent change of the output voltage of the fuel cell single cell using the perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117). Reference numeral 76 denotes the polyetherethersulfone solid polymer electrolyte membrane to which the sulfonic acid groups were directly bonded, and the electrode catalyst coating solution of the polyetherethersulfone solid polymer electrolyte to which the sulfonic acid groups were directly bonded. It is a change with time of the output voltage of a single fuel cell.

図１８の７２および７４から分かるように固体高分子電解質膜電極接合体ＸＶＩおよびＸＶＩ''を用いた単電池セルの電圧は初期０．７９Ｖで、稼動時間５０００時間後でも初期と変わらず、図１８の７５のパーフルオロスルホン酸固体高分子電解質膜（ナフィオン１１７）を用いた結果と同等に初期と変化しなかった。   As can be seen from 72 and 74 in FIG. 18, the voltage of the single cell using the solid polymer electrolyte membrane electrode assemblies XVI and XVI ″ was initially 0.79 V, which was the same as the initial value even after the operation time of 5000 hours. There was no change from the initial stage, equivalent to the result obtained by using the 18-75 perfluorosulfonic acid solid polymer electrolyte membrane (Nafion 117).

一方、図１８中の７６（比較例３のスルホン化芳香族炭化水素固体高分子電解質ＸＶを使用した燃料電池単セル）の出力電圧は初期０．７３Ｖで、稼動時間６００時間後で出力が無くなった。   On the other hand, the output voltage of 76 (single fuel cell using the sulfonated aromatic hydrocarbon solid polymer electrolyte XV of Comparative Example 3) in FIG. 18 was initially 0.73 V, and the output disappeared after 600 hours of operation. Was.

このことから、芳香族炭化水素の芳香族環にアルキレン基を介してスルホン酸基を結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルが、スルホン基と直接結合した芳香族炭化水素系固体高分子電解質を用いた燃料電池単セルより耐久性に優れていることが明白である。   Thus, a fuel cell unit cell using an aromatic hydrocarbon-based solid polymer electrolyte in which a sulfonic acid group is bonded to an aromatic ring of an aromatic hydrocarbon via an alkylene group is not suitable for an aromatic hydrocarbon directly bonded to a sulfone group. It is clear that the durability is superior to the fuel cell unit cell using the hydrocarbon-based solid polymer electrolyte.

本発明の膜電極接合体ＸＶＩを用いた燃料電池単セルの耐久性は、膜電極接合体ＸＶＩ'を用いた燃料電池単セルの耐久性より優れている。即ち、電極触媒被覆用溶液ＸＶＩは電極触媒被覆用溶液ＸＶより膜電極接合体の電極触媒被覆に適している。   The durability of the fuel cell unit cell using the membrane electrode assembly XVI of the present invention is superior to the durability of the fuel cell unit cell using the membrane electrode assembly XVI ′. That is, the electrode catalyst coating solution XVI is more suitable for the electrode catalyst coating of the membrane electrode assembly than the electrode catalyst coating solution XV.

また、実施例１８および比較例３の膜電極接合体の白金担持量が０．２５ｍｇ／ｃｍ２と同じであるにも拘わらず、実施例１８の燃料電池単セルの出力電圧が比較例３の燃料電池単セルの出力電圧より大きい理由は実施例１８の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率が比較例３の膜電極接合体の固体高分子電解質膜および電極触媒被覆用溶液のイオン導電率より高いからである。 In addition, the output voltage of the single cell of the fuel cell of Example 18 was lower than that of Comparative Example 3 even though the supported amount of platinum of the membrane electrode assemblies of Example 18 and Comparative Example 3 was the same as 0.25 mg / cm 2 . The reason why the output voltage is higher than that of the single cell of the fuel cell is that the solid polymer electrolyte membrane of the membrane electrode assembly of Example 18 and the ionic conductivity of the solution for coating the electrode catalyst are the solid polymer electrolyte membrane of the membrane electrode assembly of Comparative Example 3. And higher than the ionic conductivity of the electrode catalyst coating solution.

（５） 燃料電池の作製
前記（４）で作製した単電池セルを３６層積層し、固体高分子型燃料電池を作製したところ、３ｋＷの出力を示した。 (5) Production of Fuel Cell When the single cell produced in the above (4) was laminated in 36 layers to produce a polymer electrolyte fuel cell, an output of 3 kW was shown.

実施例３と４から分かるようにスルホン酸当量重量が５３０〜９７０ｇ／当量であるスルホアルキル化ポリエーテルエーテルスルホン固体電解質を用いた燃料電池単セルの初期の出力電圧はパーフルオロスルホン酸（ナフィオン１１７）膜を用いた燃料電池単セルの出力電圧と同等以上であり、５０００時間稼動させても劣化せず特に好ましい。   As can be seen from Examples 3 and 4, the initial output voltage of a fuel cell unit cell using a sulfoalkylated polyetherethersulfone solid electrolyte having a sulfonic acid equivalent weight of 530 to 970 g / equivalent was determined to be perfluorosulfonic acid (Nafion 117 ) The output voltage is equal to or higher than the output voltage of a single cell of a fuel cell using a membrane, and is particularly preferable because it does not deteriorate even after operating for 5000 hours.

実施例１１，９，１０，１２の（１）および（２）から分かるように化３で表されるアルキレン基のｎの数が１，３，４，６のスルホアルキル化ポリ１，４−ビフェニレンエーテルエーテルスルホン固体電解質のイオン交換基当量重量（ｇ／当量）はそれぞれ６６０，６８０，６７０，６７０と殆ど同じである。それに対応する固体高分子電解質膜のイオン伝導度Ｓ／ｃｍは、それぞれ７，１５，２５，３５である。   As can be seen from (1) and (2) of Examples 11, 9, 10, and 12, the sulfoalkylated poly 1,4- having an alkylene group represented by Chemical Formula 3 in which the number of n's is 1, 3, 4, 6 The ion exchange group equivalent weight (g / equivalent) of the biphenylene ether ether sulfone solid electrolyte is almost the same as 660, 680, 670, and 670, respectively. The corresponding ion conductivity S / cm of the solid polymer electrolyte membrane is 7, 15, 25, and 35, respectively.

同様に実施例１５，１３，１４，１６から分かるようにｎの数が１，３，４，６のスルホアルキル化ポリ１，４−フェニレンエーテルエーテルスルホン固体電解質のイオン交換基当量重量（ｇ／当量）はそれぞれ６５０，６７０，６５０，６６０と殆ど同じである。それに対応する固体高分子電解質膜のイオン伝導度Ｓ／ｃｍはそれぞれ５，１５，２５，４０である。   Similarly, as can be seen from Examples 15, 13, 14, and 16, the ion exchange group equivalent weight (g / g) of the sulfoalkylated poly-1,4-phenylene ether ether sulfone solid electrolyte in which the number n is 1, 3, 4, 6 Is equivalent to 650, 670, 650, 660, respectively. The corresponding ion conductivity S / cm of the solid polymer electrolyte membrane is 5, 15, 25, and 40, respectively.

即ち、スルホアルキル化芳香族炭化水素固体電解質のｎの数が大きいほどイオン伝導度が大きく、プロトンの伝達性が大きくなり固体高分子型燃料電池として優れている。   That is, the larger the number n of the sulfoalkylated aromatic hydrocarbon solid electrolyte, the higher the ionic conductivity and the greater the proton transferability, which is excellent as a polymer electrolyte fuel cell.

一方、コストの観点からスルトンとの１段反応により合成できるスルホプロピル化芳香族炭化水素系固体高分子電解質とスルホブチル化芳香族炭化水素系高分子固体電解質が、２段階反応によって合成されるスルホヘキサメチル化芳香族炭化水素系高分子固体電解質やスルホメチル化芳香族炭化水素系高分子固体電解質より有利である。即ち、イオン伝導度とコストとの両立の観点からｎの数は３〜４が好ましい。   On the other hand, from the viewpoint of cost, a sulfopropylated aromatic hydrocarbon-based solid polymer electrolyte and a sulfobutylated aromatic hydrocarbon-based polymer solid electrolyte which can be synthesized by a one-step reaction with sultone are synthesized by sulfohexa synthesized by a two-step reaction. It is more advantageous than a methylated aromatic hydrocarbon-based polymer solid electrolyte or a sulfomethylated aromatic hydrocarbon-based polymer solid electrolyte. That is, the number n is preferably 3 to 4 from the viewpoint of achieving both ion conductivity and cost.

実施例１の本発明に係る固体高分子型燃料電池用電池単セルの構造を示す模式斜視図である。1 is a schematic perspective view showing the structure of a single cell for a polymer electrolyte fuel cell according to the present invention in Example 1. FIG. 実施例１の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。3 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 1. 実施例２の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。5 is a graph showing a durability test result of a single cell of a polymer electrolyte fuel cell of Example 2. 実施例３の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。9 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 3. 実施例４の固体高分子型燃料電池用電池単セルの出力性能を表す電流密度−電圧のグラフである。11 is a current density-voltage graph showing the output performance of the single cell of the polymer electrolyte fuel cell of Example 4. 実施例４の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。9 is a graph showing a durability test result of a single cell of a polymer electrolyte fuel cell of Example 4. 実施例１０の固体高分子型燃料電池用電池単セルの出力性能を表す電流密度−電圧のグラフである。14 is a current density-voltage graph showing the output performance of the single cell of the polymer electrolyte fuel cell of Example 10. 実施例１０の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。14 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 10. 実施例１１の固体高分子型燃料電池用電池単セルの出力性能を表す電流密度−電圧のグラフである。14 is a current density-voltage graph showing the output performance of the single cell of the polymer electrolyte fuel cell of Example 11. 実施例１１の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。14 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 11. 実施例１２の固体高分子型燃料電池用電池単セルの出力性能を表す電流密度−電圧のグラフである。14 is a current density-voltage graph showing the output performance of a single cell of a polymer electrolyte fuel cell of Example 12. 実施例１２の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。14 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 12. 実施例１３の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。19 is a graph showing a durability test result of the single cell for the polymer electrolyte fuel cell of Example 13. 実施例１４の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。18 is a graph showing a durability test result of the single cell for the polymer electrolyte fuel cell of Example 14. 実施例１５の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。18 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 15. 実施例１６の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。19 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 16. 実施例１７の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。19 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 17. 実施例１８の固体高分子型燃料電池用電池単セルの耐久性試験結果を示すグラフである。19 is a graph showing a durability test result of the single cell of the polymer electrolyte fuel cell of Example 18.

符号の説明Explanation of reference numerals

１…固体高分子電解質膜、２…空気極、３…酸素極、４…膜電極接合体、５…支持集電体、６…セパレータ、７…空気、８…空気＋水、９…水素＋水、１０…残留水素、１１…水。   DESCRIPTION OF SYMBOLS 1 ... Solid polymer electrolyte membrane, 2 ... Air electrode, 3 ... Oxygen electrode, 4 ... Membrane electrode assembly, 5 ... Supporting current collector, 6 ... Separator, 7 ... Air, 8 ... Air + water, 9 ... Hydrogen + Water, 10: residual hydrogen, 11: water.

Claims (16)

式〔１〕
Figure 2004152776
 （ｎは１〜６の整数）で示されるスルホアルキル基が結合したポリエーテルエーテルスルホンを電解質として用いたことを特徴とする固体高分子電解質。 Equation [1]
Figure 2004152776
 (N is an integer of 1 to 6) A solid polymer electrolyte using a polyetherethersulfone to which a sulfoalkyl group is bonded as an electrolyte. 式〔２〕
Figure 2004152776
 （ｎは１〜６の整数、ｍ，ａ，ｂは０〜４の整数で全てが０にはならない。ｘは１〜３の整数、ｙは１〜５の整数。Ａｒは芳香族残基を表す）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いたことを特徴とする固体高分子電解質。 Equation [2]
Figure 2004152776
 (N is an integer of 1 to 6, m, a, and b are integers of 0 to 4 and are not all 0. x is an integer of 1 to 3, y is an integer of 1 to 5. Ar is an aromatic residue. Wherein the polyether ether sulfone in which a sulfonic acid group is bonded via an alkylene group represented by the following formula: is used as the electrolyte. 式〔３〕
Figure 2004152776
 （ｎは１〜６の整数、ａ，ｂ，ｃ，ｄは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [3]
Figure 2004152776
 (N is an integer of 1 to 6, a, b, c and d are each an integer of 0 to 4 and not all 0) represented by the following formula: A solid polymer electrolyte characterized by being used as a solid polymer electrolyte. 式〔４〕
Figure 2004152776
 （ａ，ｂ，ｃ，ｄは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [4]
Figure 2004152776
 (A, b, c, d are each an integer of 0 to 4 and are not all 0), wherein a polyetherethersulfone having a sulfonic acid group bonded through an alkylene group is used as an electrolyte. Polymer electrolyte. 式〔５〕
Figure 2004152776
 （ａ，ｂ，ｃ，ｄは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [5]
Figure 2004152776
 (A, b, c, d are each an integer of 0 to 4 and are not all 0), wherein a polyetherethersulfone having a sulfonic acid group bonded through an alkylene group is used as an electrolyte. Polymer electrolyte. 式〔６〕
Figure 2004152776
 （ｎは１〜６の整数、ａ，ｂ，ｃは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [6]
Figure 2004152776
 (N is an integer of 1 to 6, a, b and c are each an integer of 0 to 4 and not all 0), and a polyetherethersulfone to which a sulfonic acid group is bonded via an alkylene group is used as an electrolyte. A solid polymer electrolyte, characterized in that: 式〔７〕
Figure 2004152776
 （ａ，ｂ，ｃは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [7]
Figure 2004152776
 (A, b, and c are integers from 0 to 4 and are not all 0), and a polyetherethersulfone having a sulfonic acid group bonded through an alkylene group is used as an electrolyte. Electrolytes. 式〔８〕
Figure 2004152776
 （ａ，ｂ，ｃは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [8]
Figure 2004152776
 (A, b, and c are integers from 0 to 4 and are not all 0), and a polyetherethersulfone having a sulfonic acid group bonded through an alkylene group is used as an electrolyte. Electrolytes. 式〔９〕
Figure 2004152776
 （ａ，ｂ，ｃ，ｄは０〜４の整数で全てが０にはならない）で示されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを電解質として用いることを特徴とする固体高分子電解質。 Equation [9]
Figure 2004152776
 (A, b, c, d are each an integer of 0 to 4 and are not all 0), wherein a polyetherethersulfone having a sulfonic acid group bonded through an alkylene group is used as an electrolyte. Polymer electrolyte. 前記スルホン酸基当量重量が５３０〜９７０ｇ／当量である請求項１〜９のいずれかに記載の固体高分子電解質。   The solid polymer electrolyte according to any one of claims 1 to 9, wherein the sulfonic acid group equivalent weight is 530 to 970 g / equivalent. 請求項１〜１０のいずれかに記載の固体高分子電解質を用いたことを特徴とする固体高分子電解質膜。   A solid polymer electrolyte membrane using the solid polymer electrolyte according to claim 1. 請求項１〜１０のいずれかに記載の固体高分子電解質を含むことを特徴とする電極触媒被覆用溶液。   A solution for coating an electrode catalyst, comprising the solid polymer electrolyte according to any one of claims 1 to 10. 固体高分子電解質膜とこの固体高分子電解質膜の両側に酸素極および水素極からなる一対の電極が配置された膜電極接合体において、前記固体高分子電解質膜が請求項１１の固体高分子電解質膜であることを特徴とする膜電極接合体。   12. A solid polymer electrolyte membrane comprising a solid polymer electrolyte membrane and a pair of electrodes comprising an oxygen electrode and a hydrogen electrode on both sides of the solid polymer electrolyte membrane, wherein the solid polymer electrolyte membrane is a solid polymer electrolyte according to claim 11. A membrane electrode assembly, which is a membrane. 固体高分子電解質膜とこの固体高分子電解質膜の両側に電極触媒被覆用溶液で被覆された酸素極および水素極からなる一対の電極が配置された膜電極接合体において、前記固体高分子電解質膜が前記式〔１〕〜式〔９〕のいずれかで表されるアルキレン基を介してスルホン酸基が結合したポリエーテルエーテルスルホンを用いた固体高分子電解質膜で、電極触媒被覆用溶液が請求項１２に記載の電極触媒被覆用溶液であることを特徴とする膜電極接合体。   A solid polymer electrolyte membrane and a membrane-electrode assembly comprising a pair of electrodes comprising an oxygen electrode and a hydrogen electrode coated on both sides of the solid polymer electrolyte membrane with an electrode catalyst coating solution, wherein the solid polymer electrolyte membrane is Is a solid polymer electrolyte membrane using a polyether ether sulfone in which a sulfonic acid group is bonded via an alkylene group represented by any of the above formulas [1] to [9], and a solution for coating an electrode catalyst is claimed. Item 13. The membrane electrode assembly, which is the solution for coating an electrode catalyst according to Item 12. 電極触媒被覆用溶液が、パーフルオロスルホン酸固体高分子電解質溶液である請求項１４に記載の膜電極接合体。   The membrane / electrode assembly according to claim 14, wherein the electrode catalyst coating solution is a perfluorosulfonic acid solid polymer electrolyte solution. 請求項１１に記載の固体高分子電解質膜と、該固体高分子電解質膜の両側に酸素極および水素極からなる一対の電極が配置された膜電極接合体と、該膜電極接合体の両面に配された一対の支持集電体と、該支持集電体の外周に配置されたセパレータを有することを特徴とする固体高分子型燃料電池。
A solid polymer electrolyte membrane according to claim 11, a membrane electrode assembly in which a pair of electrodes comprising an oxygen electrode and a hydrogen electrode are arranged on both sides of the solid polymer electrolyte membrane, and on both surfaces of the membrane electrode assembly. A polymer electrolyte fuel cell, comprising: a pair of support current collectors disposed therein; and a separator disposed on an outer periphery of the support current collector.
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WO2008038702A1 (en) * 2006-09-29 2008-04-03 Toyo Boseki Kabushiki Kaisha Sulfonic acid group-containing polymer, method for producing the same, polymer electrolyte membrane using sulfonic acid group-containing polymer, membrane electrode assembly, and fuel cell

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008038702A1 (en) * 2006-09-29 2008-04-03 Toyo Boseki Kabushiki Kaisha Sulfonic acid group-containing polymer, method for producing the same, polymer electrolyte membrane using sulfonic acid group-containing polymer, membrane electrode assembly, and fuel cell

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