JP4836539B2 - Fuel cell electrolyte - Google Patents
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- JP4836539B2 JP4836539B2 JP2005304521A JP2005304521A JP4836539B2 JP 4836539 B2 JP4836539 B2 JP 4836539B2 JP 2005304521 A JP2005304521 A JP 2005304521A JP 2005304521 A JP2005304521 A JP 2005304521A JP 4836539 B2 JP4836539 B2 JP 4836539B2
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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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Description
本発明は、固体高分子形燃料電池の電解質膜およびバインダーとして有用な、新規高分子電解質に関する。 The present invention relates to a novel polymer electrolyte useful as an electrolyte membrane and a binder for a polymer electrolyte fuel cell.
これまで、固体高分子形燃料電池用の電解質材料としては、（１）ナフィオン（デュポン社製）等のパーフルオロアルキルスルホン酸高分子（例えば、特許文献１参照）や、（２）ポリエーテルエーテルケトン等の耐熱性高分子の主鎖をスルホン化した高分子（例えば、特許文献２参照）、（３）スルホン酸化された側鎖を有する高分子（例えば、特許文献３、特許文献４、特許文献５参照）が知られている。しかしながら、これらの高分子は固体高分子形燃料電池用の電解質材料として、いずれも問題を有していた。すなわち、燃料電池の出力向上の点から１００℃以上の運転温度が望まれているが、上記（１）のパーフルオロアルキルスルホン酸ポリマーはガラス転移点が約１２０℃と低いため、使用温度が１００℃未満という制約がある。また、上記（２）および（３）の高分子は、耐酸化性が充分ではない。耐酸化性を向上させる方法としては、高分子電解質に酸化防止剤を添加する方法（例えば、特許文献６および特許文献７参照）が提案されている。しかしながら、添加量が不十分なためと推定されるが、効果はあまり高くない。また、特許文献８では側鎖の芳香族環を電子吸引性基で連結し、芳香族環の反応性を低下させて耐酸化性を発現させている。しかしながらまだ十分とは言えず、さらに耐酸化性の高い電解質材料が望まれていた。 Up to now, electrolyte materials for polymer electrolyte fuel cells include (1) perfluoroalkylsulfonic acid polymers such as Nafion (manufactured by DuPont) (see, for example, Patent Document 1), and (2) polyether ether. Polymers obtained by sulfonating the main chain of a heat-resistant polymer such as ketone (for example, see Patent Document 2), (3) polymers having a sulfonated side chain (for example, Patent Document 3, Patent Document 4, Patent) Document 5) is known. However, these polymers all have problems as electrolyte materials for polymer electrolyte fuel cells. That is, an operating temperature of 100 ° C. or higher is desired from the viewpoint of improving the output of the fuel cell. However, since the perfluoroalkylsulfonic acid polymer (1) has a low glass transition point of about 120 ° C., the operating temperature is 100. There is a restriction of less than ℃. Further, the polymers (2) and (3) have insufficient oxidation resistance. As a method for improving the oxidation resistance, a method of adding an antioxidant to the polymer electrolyte (for example, see Patent Document 6 and Patent Document 7) has been proposed. However, although it is estimated that the amount added is insufficient, the effect is not so high. Moreover, in patent document 8, the aromatic ring of a side chain is connected with an electron withdrawing group, the reactivity of an aromatic ring is reduced and oxidation resistance is expressed. However, it is still not sufficient, and an electrolyte material with higher oxidation resistance has been desired.
本発明は、固体高分子形燃料電池の電解質膜およびバインダーとして、耐酸化性が高く、プロトン伝導性の高い、新規な高分子電解質を提供することを目的とするものである。 An object of the present invention is to provide a novel polymer electrolyte having high oxidation resistance and high proton conductivity as an electrolyte membrane and a binder for a polymer electrolyte fuel cell.
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、スルホン酸が置換した芳香環がリン原子で連なる特定構造の側鎖を有する高分子スルホン酸からなる高分子電解質がその目的に適合しうることを見いだし、この知見に基づいて本発明をなすに至った。
すなわち、本発明は、以下の通りである。
１．少なくとも下記一般式（１）で表される繰り返し単位を有する事を特徴とする燃料電池用高分子電解質。
As a result of intensive studies to solve the above problems, the present inventors have found that a polymer electrolyte comprising a polymer sulfonic acid having a side chain having a specific structure in which an aromatic ring substituted with a sulfonic acid is linked by a phosphorus atom is obtained. It has been found that it can be adapted to the purpose, and the present invention has been made based on this finding.
That is, the present invention is as follows.
1. A polymer electrolyte for a fuel cell having at least a repeating unit represented by the following general formula (1).
（Ｙは芳香族残基を表し、Ｗは −ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ２−、−ＣＯＮＨ−、−Ｃ（ＣＦ３）２−、単結合から選ばれる連結基であり、ｋは１〜４の整数であって、式中の側鎖部分Ｚは、下記一般式（２）で表される。
Ｚ＝−Ｌ−（Ａｒ１Ｔ１（Ｂ１））−（Ａｒ２Ｔ２（Ｂ２））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ ・・・（２）
(Y represents an aromatic residue, and W is selected from —CO—, —O—, —S—, —SO—, —SO 2 —, —CONH—, —C (CF 3 ) 2 —, and a single bond. K is an integer of 1 to 4, and the side chain portion Z in the formula is represented by the following general formula (2).
Z = -L- (Ar 1 T 1 (B 1)) - (Ar 2 T 2 (B 2)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ... (2)
上記一般式（２）中のＢ１〜Ｂｎ−１は、側鎖部分Ｚにおける分岐鎖を意味し、以下の式で表される。
Ｂ１＝−〔（Ａｒ２Ｔ２（Ｂ２））−（Ａｒ３Ｔ３（Ｂ３））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ〕ｆ
Ｂ２＝−〔（Ａｒ３Ｔ３（Ｂ３））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ〕ｆ
・
・
・
Ｂｎ−１＝−〔Ａｒｎ〕ｆ
B 1 ~B n-1 in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B 1 = - [(Ar 2 T 2 (B 2 )) - (Ar 3 T 3 (B 3)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ] F
B 2 = - [(Ar 3 T 3 (B 3 )) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ] f
・
・
・
B n−1 = − [Ar n ] f
上記一般式（２）中
ｎは各々独立に２〜５の整数、
ｆは各々独立に０または１、
Ａｒ１〜Ａｒｎは各々独立に芳香族残基、
Ｔ１〜Ｔｎ−１は連結基ＰＯｘ（ｘは０〜４の整数）であり、
Ｌは−ＣＯ−、−ＣＯＮＨ−、−（ＣＦ２）ｐ−（ｐは１〜１０の整数）、−Ｃ（ＣＦ３）２−、−ＣＯＯ−、−ＳＯ−、−ＳＯ２−から選ばれる連結基である。
そして、−ＳＯ３Ｈ基が二個以上導入されたＺを有する。）
In said general formula (2), n is an integer of 2-5 each independently,
f is independently 0 or 1,
Ar 1 to Ar n are each independently an aromatic residue,
T 1 to T n-1 are linking groups POx (x is an integer of 0 to 4),
L is -CO -, - CONH -, - (CF 2) p - (p is an integer of from 1 to 10), - C (CF 3) 2 -, - COO -, - SO -, - SO 2 - selected from A linking group.
And it has Z in which two or more —SO 3 H groups are introduced. )
２．Ｗが −ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ２−、−Ｃ（ＣＦ３）２−から選ばれる連結基であることを特徴とする請求項１記載の燃料電池用高分子電解質
３．ｋが１〜２の整数であることを特徴とする請求項１または２記載の燃料電池用高分子電解質。
４．ｎが２、ｆが１である請求項１記載の燃料電池用高分子電解質
５．請求項１〜４のいずれかに記載の高分子電解質を用いることを特徴とする燃料電池用高分子電解質膜。
６．請求項１〜４のいずれかに記載の高分子電解質を用いることを特徴とする燃料電池。
2. 2. The polymer electrolyte for fuel cells according to claim 1, wherein W is a linking group selected from —CO—, —O—, —S—, —SO 2 —, and —C (CF 3 ) 2 —. 3. 3. The polymer electrolyte for a fuel cell according to claim 1, wherein k is an integer of 1 to 2.
4). 4. The polymer electrolyte for fuel cells according to claim 1, wherein n is 2 and f is 1. A polymer electrolyte membrane for a fuel cell, comprising the polymer electrolyte according to claim 1.
6). A fuel cell using the polymer electrolyte according to claim 1.
本発明の高分子電解質は、耐酸化性が高く、プロトン伝導性が高く、かつ、力学的性質にも優れた、新規な高分子電解質である。したがって、固体高分子形燃料電池の電解質膜およびバインダーとして好適に使用することができる。 The polymer electrolyte of the present invention is a novel polymer electrolyte having high oxidation resistance, high proton conductivity, and excellent mechanical properties. Therefore, it can be suitably used as an electrolyte membrane and a binder for a polymer electrolyte fuel cell.
以下、本発明について具体的に説明する。
本発明の高分子電解質は下記一般式（１）で表される繰り返し単位を有する。
Hereinafter, the present invention will be specifically described.
The polymer electrolyte of the present invention has a repeating unit represented by the following general formula (1).
上記一般式（１）中、ｋは通常１〜４の整数であって、好ましくは１または２である。
上記一般式（１）中、Ｙは（ｋ＋２）価の芳香族残基であり、例えば、下記一般式（７）に示す３価の芳香族残基、下記一般式（８）に示す４価の芳香族残基、下記一般式（９）に示す５価の芳香族残基などが挙げられる。これら芳香族残基の水素原子がアルキル基、ハロゲン原子、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、−ＣＮ、−ＮＯ2 、−ＣＯＲ、−ＣＯＯＲ（Ｒは水素原子、アルキル基、ハロゲン化アルキル基、アリール基から選ばれる。）、−ＣＯＮＲＲ’（Ｒ’はＲと同様である。）、−ＳＯ3 Ｒ、−ＳＯＲ、−ＳＯ2 Ｒで置換されていてもよい。
In the general formula (1), k is usually an integer of 1 to 4, and preferably 1 or 2.
In the general formula (1), Y is a (k + 2) -valent aromatic residue, for example, a trivalent aromatic residue represented by the following general formula (7), a tetravalent represented by the following general formula (8) And a pentavalent aromatic residue represented by the following general formula (9). The hydrogen atom of these aromatic residues is an alkyl group, a halogen atom, a halogenated alkyl group, an aryl group, a halogenated aryl group, —CN, —NO 2 , —COR, —COOR (where R is a hydrogen atom, an alkyl group, a halogen atom, alkyl group, selected from aryl group), -. CONRR '(R ' is the same as R), -. SO 3 R , -SOR, may be substituted with -SO 2 R.
上記一般式（７）〜（９）における２価の基Ｑは−ＣＯ−、−ＣＯＯ−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ2 −、−ＣＣＲ1 2−（Ｒ1 は水素原子、ハロゲン原子、アルキル基
、ハロゲン化アルキル基、アリール基から選ばれる）、単結合から選ばれ、好ましくは−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ2 −から選ばれる。
上記一般式（１）中、Ｗは −ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ２−、−ＣＯＮＨ−、−Ｃ（ＣＦ３）２−、単結合から選ばれる連結基であり、好ましくは、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ２−、−Ｃ（ＣＦ３）２−から選ばれる連結基であり、さらに好ましくは−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ２−から選ばれる連結基である。
In the general formulas (7) to (9), the divalent group Q is —CO—, —COO—, —O—, —S—, —SO—, —SO 2 —, —CCR 1 2 — (R 1 Is selected from a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group and an aryl group) and a single bond, and preferably selected from —CO—, —O—, —S— and —SO 2 —.
In the general formula (1), W is a linkage selected from —CO—, —O—, —S—, —SO—, —SO 2 —, —CONH—, —C (CF 3 ) 2 —, and a single bond. A linking group selected from —CO—, —O—, —S—, —SO 2 —, —C (CF 3 ) 2 —, and more preferably —CO—, —O—. , —S—, —SO 2 —.
上記一般式（１）中の側鎖部分Ｚは、一般式（２）で表される。
Ｚ＝−Ｌ−（Ａｒ１Ｔ１（Ｂ１））−（Ａｒ２Ｔ２（Ｂ２））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ （２）
上記一般式（２）中のＢ１〜Ｂｎ−１は、側鎖部分Ｚにおける分岐鎖を意味し、以下の式で表される。
Ｂ１＝−〔（Ａｒ２Ｔ２（Ｂ２））−（Ａｒ３Ｔ３（Ｂ３））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ〕ｆ
Ｂ２＝−〔（Ａｒ３Ｔ３（Ｂ３））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ〕ｆ
・
・
・
Ｂｎ−１＝−〔Ａｒｎ〕ｆ
The side chain portion Z in the general formula (1) is represented by the general formula (2).
Z = -L- (Ar 1 T 1 (B 1)) - (Ar 2 T 2 (B 2)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n (2)
B 1 ~B n-1 in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B 1 = - [(Ar 2 T 2 (B 2 )) - (Ar 3 T 3 (B 3)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ] F
B 2 = - [(Ar 3 T 3 (B 3 )) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ] f
・
・
・
B n−1 = − [Ar n ] f
上記一般式（２）中ｎはそれぞれ独立に２〜５から選ばれる整数を表し、好ましくは２〜４から選ばれ、さらに好ましくは２〜３から選ばれる。ｆはそれぞれ独立に０または１である。
上記一般式（２）において、ｆが１である場合、上記一般式（２）で表される側鎖は芳香族残基Ａｒ１ 〜Ａｒｎ−１ において分岐構造をとるが、その際、各分岐鎖は各々異なった鎖長および分岐構造をとることもできる。
上記一般式（２）におけるＴ１〜Ｔｎ-1は（ｆ＋２）価のＰＯｘ（ｘは０〜４の整数）を表し、ｘ＝０はホスフィン、ｘ＝１はホスフィンオキシド、ｘ＝３はホスファイト、ｘ＝４はホスフェイトである。Ｔ１〜Ｔｎ-1 は互いに同じであっても異なっていてもよい。
上記一般式（２）におけるＡｒ１〜Ａｒｎ-1は２価の芳香族残基を表し、例えば下記一般式（１１）に示す２価の芳香族残基が挙げられる。これら芳香族残基の水素原子がアルキル基、ハロゲン原子、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、−ＣＮ、−ＮＯ2 、−ＣＯＲ、−ＣＯＯＲ（Ｒは水素原子、アルキル基、ハロゲン化アルキル基、アリール基から選ばれる。）、−ＣＯＮＲＲ’（Ｒ’はＲと同様である。）、−ＳＯ3 Ｒ、−ＳＯＲ、−ＳＯ2 Ｒで置換されていてもよい。
In the general formula (2), each n independently represents an integer selected from 2 to 5, preferably selected from 2 to 4, and more preferably selected from 2 to 3. Each f is independently 0 or 1.
In the general formula (2), when f is 1, the side chain represented by the general formula (2) has a branched structure in the aromatic residues Ar 1 to Ar n-1 . Each branched chain may have a different chain length and branched structure.
In the general formula (2), T 1 to T n-1 represent (f + 2) -valent POx (x is an integer of 0 to 4), x = 0 is phosphine, x = 1 is phosphine oxide, and x = 3 is Phosphite, x = 4 is phosphate. T 1 to T n-1 may be the same as or different from each other.
Ar 1 to Ar n-1 in the general formula (2) represent a divalent aromatic residue, and examples thereof include a divalent aromatic residue represented by the following general formula (11). The hydrogen atom of these aromatic residues is an alkyl group, a halogen atom, a halogenated alkyl group, an aryl group, a halogenated aryl group, —CN, —NO 2 , —COR, —COOR (where R is a hydrogen atom, an alkyl group, a halogen atom, alkyl group, selected from aryl group), -. CONRR '(R ' is the same as R), -. SO 3 R , -SOR, may be substituted with -SO 2 R.
また上記一般式（２）におけるＬ は２価の連結基を表し、例えば、−ＣＯ−、−ＣＯＮＨ−、−（ＣＦ2 ）p −（ここで、ｐは１〜１０の整数である）、−Ｃ（ＣＦ3 ）2 −、−ＣＯＯ−、−ＳＯ−、−ＳＯ2 −などが挙げられ、好ましくは−ＣＯ−、−Ｃ（ＣＦ3 ）2 −、−ＳＯ−、−ＳＯ2 −さらに好ましくは−ＣＯ−、−ＳＯ−、−ＳＯ2 −などが用いられる。
さらに上記一般式（１）におけるＡｒｎは側鎖末端のアリール基を表し、例えば、下記一般式（１２）に示すアリール基が挙げられ、当該アリール基の水素原子がアルキル基、ハロゲン原子、ハロゲン化アルキル基、アリール基、ハロゲン化アリール基、−ＣＮ、−ＮＯ2 、−ＣＯＲ、−ＣＯＯＲ（Ｒは水素原子、アルキル基、ハロゲン化アルキル基、アリール基から選ばれる。）、−ＣＯＮＲＲ’（Ｒ’はＲと同様である。）、−ＳＯ3 Ｒ、−ＳＯＲ、−ＳＯ2 Ｒで置換されていてもよく、Ａｒｎは互いに同じであっても異なっていてもよい。
In addition, L in the general formula (2) Represents a divalent linking group, for example, —CO—, —CONH—, — (CF 2 ) p — (wherein p is an integer of 1 to 10), —C (CF 3 ) 2 —, —COO—, —SO—, —SO 2 — and the like are preferable, preferably —CO—, —C (CF 3 ) 2 —, —SO—, —SO 2 —, more preferably —CO—, —SO—. , —SO 2 — and the like are used.
In addition, Ar n in the general formula (1) represents an aryl group at the end of the side chain, and examples thereof include an aryl group represented by the following general formula (12), and the hydrogen atom of the aryl group is an alkyl group, a halogen atom, a halogen atom. Alkyl group, aryl group, halogenated aryl group, —CN, —NO 2 , —COR, —COOR (R is selected from a hydrogen atom, an alkyl group, a halogenated alkyl group, and an aryl group), —CONRR ′ ( R ′ is the same as R.), —SO 3 R, —SOR, —SO 2 R may be substituted, and Ar n may be the same or different from each other.
本発明では、通常、非分岐型側鎖、分岐型側鎖から選ばれる側鎖が用いられ、好ましくは分岐型側鎖が用いられる。分岐型側鎖は、（ｉ）スルホン化が容易な末端芳香環の数が多く、高分子（主鎖）までの距離が同じスルホン酸基を同一側鎖に複数導入することが可能であり、プロトン伝導性に必要なイオンクラスター構造を形成し易く、それゆえプロトン伝導性が高いものと考えられる。また、（ｉｉ）側鎖の形状が嵩高くなるので異なる高分子鎖間の側鎖が互いに絡み合うものと推察され、その結果、電解質膜の強度が高く、寸法安定性も高いものと考えられる。 In the present invention, a side chain selected from an unbranched side chain and a branched side chain is usually used, and a branched side chain is preferably used. The branched side chain (i) has a large number of terminal aromatic rings that can be easily sulfonated, and multiple sulfonic acid groups having the same distance to the polymer (main chain) can be introduced into the same side chain. It is considered that an ion cluster structure necessary for proton conductivity is easily formed, and therefore proton conductivity is high. Further, (ii) since the shape of the side chain becomes bulky, it is presumed that the side chains between different polymer chains are entangled with each other. As a result, the strength of the electrolyte membrane is high and the dimensional stability is also considered high.
本発明の高分子電解質は、少なくとも上記一般式（１）で表される繰り返し単位を有する。本発明の高分子電解質としては、通常、上記一般式（１）で表される繰り返し単位を１〜１００モル％、好ましくは５〜９５モル％、さらに好ましくは１０〜８０モル％、特に好ましくは１５〜７５モル％含み、その重量平均分子量が１０００〜１００万、好ましくは１万〜１００万、さらに好ましくは２万〜８０万、特に好ましくは３万〜４０万の重合体である高分子電解質が挙げられる。 The polymer electrolyte of the present invention has at least a repeating unit represented by the general formula (1). As the polymer electrolyte of the present invention, the repeating unit represented by the general formula (1) is usually 1 to 100 mol%, preferably 5 to 95 mol%, more preferably 10 to 80 mol%, particularly preferably. A polymer electrolyte containing 15 to 75 mol% and having a weight average molecular weight of 1,000 to 1,000,000, preferably 10,000 to 1,000,000, more preferably 20,000 to 800,000, particularly preferably 30,000 to 400,000 Is mentioned.
本発明の高分子電解質が、従来の高分子電解質と比較して、（１）耐酸化性が高く、（２）プロトン伝導性が高いという、優れた性能を併せ持つ理由はおよそ次のように推定される。
（１）耐酸化性が高い理由：燃料電池運転時には過酸化水素や・ＯＯＨラジカルのような酸化性物質が生成することが知られている。そのため、高分子電解質としては化学的に安定な高分子パーフルオロスルホン酸が用いられてきた。従来の炭化水素系高分子スルホン酸では耐酸化性が不十分であるため、例えば特許文献６および７においては、耐酸化性を補うために酸化防止剤を併用することも行われている。しかし、酸化防止剤を添加剤として加える方法ではポリマーとの相溶性の問題があり、添加量には制限がある。加えて加工時や燃料電池運転時に脱落するおそれもある。対して本発明の電解質は主鎖に結合する側鎖自身がホスフィン、ホスファイト、ホスフェイトなどの酸化防止効果を有する構造を持つので、実用上十分な量の酸化防止剤の導入が可能となる。さらに加工時や電池運転時にも実質的に脱落しない。それゆえ、耐酸化性が高いものと考えられる。
The reason why the polymer electrolyte of the present invention has the excellent performance of (1) high oxidation resistance and (2) high proton conductivity compared with the conventional polymer electrolyte is estimated as follows. Is done.
(1) Reason for high oxidation resistance: It is known that oxidizing substances such as hydrogen peroxide and .OOH radicals are generated during fuel cell operation. Therefore, chemically stable polymer perfluorosulfonic acid has been used as the polymer electrolyte. Since conventional hydrocarbon polymer sulfonic acids have insufficient oxidation resistance, for example, in Patent Documents 6 and 7, an antioxidant is also used in combination to supplement the oxidation resistance. However, the method of adding an antioxidant as an additive has a problem of compatibility with the polymer, and the addition amount is limited. In addition, there is a risk of falling off during processing or fuel cell operation. On the other hand, since the electrolyte of the present invention has a structure in which the side chain itself bonded to the main chain has an antioxidant effect such as phosphine, phosphite, and phosphate, a practically sufficient amount of antioxidant can be introduced. Furthermore, it does not drop out substantially during processing or battery operation. Therefore, it is considered that the oxidation resistance is high.
（２）プロトン伝導度が高い理由：本発明では、通常、非分岐型側鎖、分岐型側鎖から選
ばれる側鎖が用いられ、好ましくは分岐型側鎖が用いられる。分岐型側鎖は、（ｉ）スルホン化が容易な末端芳香環の数が多く、高分子（主鎖）までの距離が同じスルホン酸基を同一側鎖に複数導入することが可能であり、プロトン伝導性に必要なイオンクラスター構造を形成し易く、それゆえプロトン伝導性が高いものと考えられる。また、（ｉｉ）側鎖の形状が嵩高くなるので異なる高分子鎖間の側鎖が互いに絡み合うものと推察され、その結果、電解質膜の強度が高く、寸法安定性も高いものと考えられる。
(2) Reason for high proton conductivity: In the present invention, a side chain selected from an unbranched side chain and a branched side chain is usually used, and a branched side chain is preferably used. The branched side chain (i) has a large number of terminal aromatic rings that can be easily sulfonated, and multiple sulfonic acid groups having the same distance to the polymer (main chain) can be introduced into the same side chain. It is considered that an ion cluster structure necessary for proton conductivity is easily formed, and therefore proton conductivity is high. Further, (ii) since the shape of the side chain becomes bulky, it is presumed that the side chains between different polymer chains are entangled with each other, and as a result, the strength of the electrolyte membrane is high and the dimensional stability is also considered high.
本発明の高分子電解質の製造方法は特に限定されるものではない。例えば、高分子に側鎖導入剤を反応させて側鎖を導入する方法を用いることができる。すなわち、一般式（１）においてＺが置換していない構造に相当する、−Ｙ−Ｗ−（Ｙは２価の芳香族残基、Ｗは前記のとおり）を繰り返し単位として有する高分子へ側鎖導入剤を反応させてＺを導入させても良いし、予め反応性の置換基を導入した−Ｙ（Ｍ）−Ｗ−（Ｙは３価の芳香族残基、Ｍは反応性基、Ｗは前記のとおり）に、Ｍと反応する側鎖導入剤を反応させることによりＺを導入しても良い。
前記方法で通常用いられる具体例を次に示す。すなわち、下記一般式（３）で表される繰り返し単位を有する高分子と下記一般式（４）で表される側鎖導入剤を反応させることにより、上記一般式（１）で示される高分子電解質を製造することができる。なお、この場合には、上記一般式（２）におけるＸは−ＣＯ−および−ＳＯ２−から選ばれる。
The method for producing the polymer electrolyte of the present invention is not particularly limited. For example, a method of introducing a side chain by reacting a polymer with a side chain introducing agent can be used. That is, to the polymer having -Y-W- (Y is a divalent aromatic residue, W is as described above) as a repeating unit corresponding to the structure in which Z is not substituted in the general formula (1). Z may be introduced by reacting a chain introducing agent, or -Y (M) -W- (Y is a trivalent aromatic residue, M is a reactive group, and a reactive substituent is introduced in advance. As described above, W may be introduced by reacting a side chain introducing agent that reacts with M.
Specific examples usually used in the above method are shown below. That is, by reacting a polymer having a repeating unit represented by the following general formula (3) with a side chain introducing agent represented by the following general formula (4), the polymer represented by the above general formula (1). An electrolyte can be manufactured. In this case, X in the general formula (2) is selected from —CO— and —SO 2 —.
上記一般式（３）において、ＹおよびＷは上記一般式（１）に記載のものと同様であり、Ｕは水素原子、−ＣＯＸ、−ＳＯ２Ｘから選ばれる反応性基であり、Ｘはハロゲン原子、ＯＲ（Ｒは水素原子、アルキル基、またはアリール基）、水酸基から選ばれる。
Ｚ’−Ｖ （４）
上記一般式（３）のＵが水素原子の場合、Ｖは−ＣＯＸ、−ＳＯ２Ｘから選ばれる反応性基であり、Ｕが−ＣＯＸ、−ＳＯ２Ｘから選ばれる反応性基である場合には、Ｖは水素原子であり、Ｚ’は下記一般式（５）で表される。
Ｚ’＝−（Ａｒ１Ｔ１（Ｂ１））−（Ａｒ２Ｔ２（Ｂ２））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ （５）
In the general formula (3), Y and W are the same as those described in the general formula (1), U is a reactive group selected from a hydrogen atom, —COX, and —SO 2 X, and X is It is selected from a halogen atom, OR (R is a hydrogen atom, an alkyl group or an aryl group), and a hydroxyl group.
Z'-V (4)
When U in the general formula (3) is a hydrogen atom, V is a reactive group selected from —COX and —SO 2 X, and U is a reactive group selected from —COX and —SO 2 X In the formula, V is a hydrogen atom, and Z ′ is represented by the following general formula (5).
Z '= - (Ar 1 T 1 (B 1)) - (Ar 2 T 2 (B 2)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ( 5)
本発明で使用する、上記一般式（３）で表される繰り返し単位を有する高分子の例を以下に示す。
Ｕが水素原子のもの：上記一般式（１１）で示される残基から選ばれる２価芳香族残基と、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ２−、−ＣＯＮＨ−、−Ｃ（ＣＦ３）２−、単結合から選ばれる連結基Ｗの組み合わせからなる高分子が通常用いられ、好ましくは、フェニレン、ナフチレン、ビフェニレンから選ばれる２価芳香族残基と−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ２−から選ばれる連結基Ｗの組み合わせが用いられ、より好ましくはポリエーテルケトン、ポリエーテルスルホン、ポリチオエーテルケトン、ポリチオエーテルスルホン、ポリエーテルエーテルスルホン、ポリエーテルエーテルケトンが用いられ、さらに好ましくは、下式で表される高分子においてＺが水素原子のものが用いられる。
Examples of the polymer having a repeating unit represented by the general formula (3) used in the present invention are shown below.
U those hydrogen atoms: and a divalent aromatic residue selected from residues represented by the general formula (11), -CO -, - O -, - S -, - SO -, - SO 2 -, A polymer composed of a combination of —CONH—, —C (CF 3 ) 2 — and a linking group W selected from a single bond is usually used, and preferably a divalent aromatic residue selected from phenylene, naphthylene, and biphenylene A combination of linking groups W selected from —CO—, —O—, —S—, —SO 2 — is used, more preferably polyether ketone, polyether sulfone, polythioether ketone, polythioether sulfone, polyether ether. Sulfone and polyetheretherketone are used, and more preferably, a polymer represented by the following formula having Z as a hydrogen atom is used.
Ｕが−ＣＯＸまたは−ＳＯ２Ｘのもの：上記一般式（１１）で示される残基から選ばれる２価芳香族残基と、−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ２−、−ＣＯＮＨ−、−Ｃ（ＣＦ３）２−、単結合から選ばれる連結基Ｗの組み合わせからなる高分子に−ＣＯＸまたは−ＳＯ２Ｘを導入したものが通常用いられ、好ましくは、フェニレン、ナフチレン、ビフェニレンから選ばれる２価芳香族残基と−ＣＯ−、−Ｏ−、−Ｓ−、−ＳＯ２−から選ばれる連結基Ｗの組み合わせの高分子に−ＣＯＸまたは−ＳＯ２Ｘを導入したものが用いられ、より好ましくはポリエーテルケトン、ポリエーテルスルホン、ポリチオエーテルケトン、ポリチオエーテルスルホン、ポリエーテルエーテルスルホン、ポリエーテルエーテルケトンに−ＣＯＸまたは−ＳＯ２Ｘを導入したものが用いられる。上記一般式（３）ＵのＣＯＸ、ＳＯ２ＸにおけるＸは、通常、ハロゲン原子、ＯＲ（Ｒは水素原子、アルキル基、またはアリール基）、水酸基から選ばれ、好ましくは、ハロゲン原子、水酸基から選ばれる。上記一般式（４）で表される側鎖導入剤の例を次に示す。
側鎖導入剤がスルホン酸基またはその前駆体を有し、かつ、側鎖導入剤のＸが電子吸引性の連結基であり、さらに、Ｖが−ＣＯＸ、−ＳＯ２Ｘから選ばれる反応性基である場合の、好ましいＺ’−Ｖの例を下記式（１３）に示す。（式中、−ＳＯ３Ｒはスルホン酸基またはその前駆体を表し、Ｒは水酸基、アルキル基、アルカリ金属、アルカリ土類金属から選ばれる。）
When U is —COX or —SO 2 X: a divalent aromatic residue selected from the residues represented by the general formula (11), —CO—, —O—, —S—, —SO—, A polymer in which —COX or —SO 2 X is introduced into a polymer composed of a combination of a linking group W selected from —SO 2 —, —CONH—, —C (CF 3 ) 2 —, and a single bond is usually used. Is a polymer of a combination of a divalent aromatic residue selected from phenylene, naphthylene, and biphenylene and a linking group W selected from —CO—, —O—, —S—, and —SO 2 —. which was introduced 2 X is used, more preferably polyether ketone, polyether sulfone, polythioether ketone, polythioether sulfone, polyether ether sulfone, polyether ether ketone Which was introduced COX or -SO 2 X is used. X in the COX and SO 2 X of the general formula (3) U is usually selected from a halogen atom, OR (R is a hydrogen atom, an alkyl group, or an aryl group), and a hydroxyl group, preferably from a halogen atom and a hydroxyl group. To be elected. Examples of the side chain introducing agent represented by the general formula (4) are shown below.
Reactivity in which the side chain introducing agent has a sulfonic acid group or a precursor thereof, X in the side chain introducing agent is an electron-withdrawing linking group, and V is selected from —COX and —SO 2 X An example of preferable Z′-V in the case of a group is shown in the following formula (13). (In the formula, —SO 3 R represents a sulfonic acid group or a precursor thereof, and R is selected from a hydroxyl group, an alkyl group, an alkali metal, and an alkaline earth metal.)
側鎖導入剤がスルホン酸基またはその前駆体を有せず、かつ、Ｖが−ＣＯＸ、−ＳＯ２Ｘから選ばれる反応性基である場合の、好ましいＺ’−Ｖの例を下記式（１４）に示す。
Ｖが水素原子である場合の好ましいＺ’−Ｖの例を下記式（１５）に示す。
Preferred examples of Z′-V in the case where the side chain introducing agent does not have a sulfonic acid group or a precursor thereof and V is a reactive group selected from —COX and —SO 2 X are represented by the following formula ( 14).
An example of preferred Z′-V when V is a hydrogen atom is shown in the following formula (15).
上記一般式（４）のＶにおけるＸは通常、ハロゲン原子、ＯＲ（Ｒは水素原子、アルキル基、またはアリール基）、水酸基から選ばれ、好ましくは、ハロゲン原子、水酸基から選ばれる。
高分子に側鎖導入剤を反応させる際の反応の種類は、特に制限されない。上記一般式（
３）で表される高分子と上記一般式（４）で表される側鎖導入剤を反応させる際の好ましい方法としては次の方法が挙げられる。
X in V in the general formula (4) is usually selected from a halogen atom, OR (R is a hydrogen atom, an alkyl group, or an aryl group), and a hydroxyl group, and preferably selected from a halogen atom and a hydroxyl group.
The type of reaction when the side chain introduction agent is reacted with the polymer is not particularly limited. General formula (
As a preferable method for reacting the polymer represented by 3) with the side chain introducing agent represented by the general formula (4), the following method may be mentioned.
（ｉ）上記一般式（３）のＵが水素原子で、式（４）のＶが−ＣＯＸ（Ｘがハロゲン原子または水酸基）であるか、または、上記一般式（３）のＵが−ＣＯＸ（Ｘがハロゲン原子）で、上記一般式（４）のＶが水素原子である場合：フリーデル・クラフツ−アシル化反応を用いることができる。
（ｉｉ）上記一般式（３）のＵが水素原子で、上記一般式（４）のＶが−ＳＯ２Ｘ（Ｘがハロゲン原子または水酸基）であるか、または、上記一般式（３）のＵが−ＳＯ２Ｘ（Ｘがハロゲン原子）で、上記一般式（４）のＶが水素原子である場合：フリーデル・クラフツ型スルホニル化反応を用いることができる。
（ｉｉｉ）上記一般式（３）のＵが水素原子で、上記一般式（４）のＶが−ＣＯＯＨまたは−ＳＯ３Ｈであるか、または、上記一般式（３）のＵが−ＣＯＯＨまたは−ＳＯ３Ｈで、式（４）のＶが水素原子である場合：脱水縮合反応を用いることができる。
(I) U in the general formula (3) is a hydrogen atom, V in the formula (4) is -COX (X is a halogen atom or a hydroxyl group), or U in the general formula (3) is -COX. When X is a halogen atom and V in the general formula (4) is a hydrogen atom: Friedel-Crafts-acylation reaction can be used.
(Ii) U in the general formula (3) is a hydrogen atom, V in the general formula (4) is —SO 2 X (X is a halogen atom or a hydroxyl group), or in the general formula (3) When U is —SO 2 X (X is a halogen atom) and V in the general formula (4) is a hydrogen atom: Friedel-Crafts type sulfonylation reaction can be used.
(Iii) U in the general formula (3) is a hydrogen atom, V in the general formula (4) is —COOH or —SO 3 H, or U in the general formula (3) is —COOH or When —SO 3 H and V in Formula (4) are a hydrogen atom: a dehydration condensation reaction can be used.
本発明の高分子電解質の製造方法において、スルホン酸基を導入する方法として、スルホン基を含有しない高分子をスルホン酸化することにより導入する場合には、スルホン酸化剤による常法のスルホン酸化を用いることができる。スルホン酸基を導入する方法としては、例えば、上記スルホン酸基を有しない高分子を、無水硫酸、発煙硫酸、クロルスルホン酸、硫酸、亜硫酸水素ナトリウムなどの公知のスルホン酸化剤を用いて、公知の条件でスルホン酸化することができる（本発明において、スルホン酸化とは、−Ｈなる基の水素原子をＳＯ3 Ｈで置換する反応を示す。）。 In the method for producing a polymer electrolyte of the present invention, as a method for introducing a sulfonic acid group, when introducing a polymer not containing a sulfone group by sulfonating, a conventional sulfonation with a sulfonating agent is used. be able to. As a method for introducing a sulfonic acid group, for example, the above-described polymer having no sulfonic acid group is known by using a known sulfonating agent such as sulfuric anhydride, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, sodium hydrogen sulfite and the like. (In the present invention, sulfonation refers to a reaction in which a hydrogen atom of a group —H is substituted with SO 3 H).
このスルホン酸化の反応条件としては、上記スルホン酸基を有しない高分子を、無溶剤下、あるいは溶剤存在下で、上記スルホン酸化剤と反応させる。溶剤としては、例えばｎ−ヘキサンなどの炭化水素系溶剤、テトラヒドロフラン、ジオキサンなどのエーテル系溶剤、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルスルホキシドのような非プロトン系極性溶剤のほか、テトラクロロエタン、ジクロロエタン、クロロホルム、塩化メチレンなどのハロゲン化炭化水素などが挙げられる。反応温度は特に制限はないが、通常、−５０〜２００℃、好ましくは−１０〜１００℃である。また、反応時間は、通常、０．５〜１，０００時間、好ましくは１〜２００時間である。 As the reaction conditions for the sulfonation, the polymer having no sulfonic acid group is reacted with the sulfonated agent in the absence of a solvent or in the presence of a solvent. Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide, and dimethylsulfoxide, tetrachloroethane, dichloroethane, chloroform, And halogenated hydrocarbons such as methylene chloride. The reaction temperature is not particularly limited, but is usually −50 to 200 ° C., preferably −10 to 100 ° C. Moreover, reaction time is 0.5 to 1,000 hours normally, Preferably it is 1 to 200 hours.
このようにして得られる、本発明のスルホン酸基含有重合体中の、スルホン酸基量は、０．５〜５ミリグラム当量／ｇ、好ましくは０．７〜４ミリグラム当量／ｇ、さらに好ましくは０．８〜３ミリグラム当量／ｇである。低いスルホン酸基量では、プロトン伝導性が上がらず、一方、スルホン酸基量が高いと、親水性が向上し、構造によっては水溶性ポリマーとなってしまう。上記のスルホン酸基量は、反応条件（温度、時間）や仕込量（組成）により調整することができる。 The amount of sulfonic acid group in the sulfonic acid group-containing polymer of the present invention thus obtained is 0.5 to 5 milligram equivalent / g, preferably 0.7 to 4 milligram equivalent / g, more preferably 0.8-3 milligram equivalent / g. When the amount of sulfonic acid group is low, proton conductivity does not increase. On the other hand, when the amount of sulfonic acid group is high, hydrophilicity is improved, and depending on the structure, a water-soluble polymer is obtained. The amount of the sulfonic acid group can be adjusted by the reaction conditions (temperature, time) and the charged amount (composition).
また、このようにして得られる本発明の高分子電解質の、スルホン酸化前またはスルホン酸の前駆体のポリマーの分子量は、ポリスチレン換算重量平均分子量で、１０００〜１００万、好ましくは１万〜１００万、さらに好ましくは２万〜８０万、特に好ましくは３万〜４０万である。１０００未満では、成形フィルムが割れ易く、また強度的性質にも問題がある。一方、１００万を超えると、溶解性が不充分となり、また溶液粘度が高く、加工性が不良になるなどの問題がある。
次に、本発明の高分子電解質は、上記スルホン酸基含有重合体からなるが、上記スルホン酸基含有重合体以外に、硫酸、リン酸などの無機酸、カルボン酸を含む有機酸、適量の水などを併用しても良い。
The molecular weight of the polymer electrolyte of the present invention thus obtained before sulfonation or sulfonic acid precursor is 1,000 to 1,000,000, preferably 10,000 to 1,000,000 in terms of polystyrene-converted weight average molecular weight. More preferably, it is 20,000 to 800,000, particularly preferably 30,000 to 400,000. If it is less than 1000, the molded film is liable to break, and there is also a problem in strength properties. On the other hand, if it exceeds 1,000,000, there are problems such as insufficient solubility, high solution viscosity, and poor processability.
Next, the polymer electrolyte of the present invention comprises the sulfonic acid group-containing polymer. In addition to the sulfonic acid group-containing polymer, an inorganic acid such as sulfuric acid and phosphoric acid, an organic acid containing a carboxylic acid, an appropriate amount You may use water together.
本発明の高分子電解質をフィルム化するには、例えば本発明のスルホン酸基含有重合体
を溶剤に溶解したのち、塗布によりフィルム状に成形するキャスト法や、溶融成形法などが挙げられる。ここで、キャスト法における溶剤としては、ジメチルアセトアミド、ジメチルホルムアミド、Ｎ−メチルピロリドン、ジメチルスルホキシドなどの非プロトン系極性溶剤やメタノールなどのアルコール系溶剤などが挙げられる。
本発明の高分子電解質の構造は、例えば、赤外線吸収スペクトルや核磁気共鳴スペクトル（１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ）により確認することができる。また、組成比は元素分析によっても測定でき、スルホン酸の含量は中和滴定によって測定することができる。
In order to form the polymer electrolyte of the present invention into a film, for example, a casting method in which the sulfonic acid group-containing polymer of the present invention is dissolved in a solvent and then formed into a film by coating, a melt molding method, or the like can be mentioned. Here, examples of the solvent in the casting method include aprotic polar solvents such as dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and dimethylsulfoxide, and alcohol solvents such as methanol.
The structure of the polymer electrolyte of the present invention can be confirmed by, for example, an infrared absorption spectrum or a nuclear magnetic resonance spectrum ( 1 H-NMR, 13 C-NMR). The composition ratio can also be measured by elemental analysis, and the sulfonic acid content can be measured by neutralization titration.
以下、実施例を挙げ本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、実施例中の各種の測定項目は、下記のようにして求めた。
［イオン交換容量］得られたポリマーの水洗水が中性になるまで充分に水洗し、乾燥後、所定量を秤量し、ＴＨＦ／水の混合溶剤に溶解し、フェノールフタレインを指示薬とし、ＮａＯＨの標準液にて滴定し、中和点から、イオン交換容量（スルホン酸化当量）を求めた。
［プロトン伝導度の測定］１００％相対湿度下に置かれた厚み４０〜６０μｍのフィルム状試料を、白金電極に挟み、複素インピーダンス測定を行い、プロトン伝導度を算出した。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In addition, various measurement items in the examples were obtained as follows.
[Ion exchange capacity] The obtained polymer is sufficiently washed with water until it becomes neutral, dried, weighed in a predetermined amount, dissolved in a THF / water mixed solvent, phenolphthalein as an indicator, NaOH The ion exchange capacity (sulfonated equivalent) was determined from the neutralization point.
[Measurement of proton conductivity] A film sample having a thickness of 40 to 60 µm placed under 100% relative humidity was sandwiched between platinum electrodes, and complex impedance measurement was performed to calculate proton conductivity.
［フェントン試験］過酸化水素濃度が３重量％、且つ硫酸第２鉄・７水和物を鉄イオンの濃度が２０ｐｐｍになるようにフェントン試薬を調製した。２５０ｃｃのポリエチレン製容器に２００ｇのフェントン試薬を採取し、３ｃｍ×４ｃｍ、膜厚４０〜６０μｍに切削した高分子電解膜を投入後、密栓後、５０℃の恒温水槽に浸漬させ、６時間のフェントン試験を行った。フェントン試験後、フィルムを取り出し、イオン交換水にて水洗後、２５℃・５０％ＲＨ２４時間保持して調湿を行い、重量測定を行った。フェントン試験における重量保持率は、下記の数式により算出した。
フェントン試験における重量保持率（％）＝（フェントン試験後のフィルム重量／フェントン試験前のフィルム重量）×１００
[Fenton test] A Fenton reagent was prepared so that the hydrogen peroxide concentration was 3% by weight and the ferric sulfate heptahydrate concentration was 20 ppm. 200 g of Fenton reagent was collected in a 250 cc polyethylene container, a polymer electrolyte membrane cut to 3 cm × 4 cm and a film thickness of 40 to 60 μm was added, sealed, and then immersed in a constant temperature water bath at 50 ° C. for 6 hours. A test was conducted. After the Fenton test, the film was taken out, washed with ion-exchanged water, kept at 25 ° C. and 50% RH for 24 hours to adjust the humidity, and weighed. The weight retention rate in the Fenton test was calculated by the following mathematical formula.
Weight retention in Fenton test (%) = (film weight after Fenton test / film weight before Fenton test) × 100
［実施例１］
（１）ポリエーテルエーテルケトンのスルホン化
ポリエーテルエーテルケトン（ヴィクトレックス社製ポリエーテルエーテルケトン Ｖｉｃｔｒｅｘ ＰＥＥＫ４５０ＰＦ）２０．０ｇを０．５リットルの反応溶液に入れ、９６％硫酸０．２５リットルを加え、窒素下室温で２日間攪拌を続けた。得られた溶液を５リットルのイオン交換水の中に注ぎ入れることでポリマーを沈殿させた。洗浄液のｐＨが５になるまでポリマーの水洗を繰り返した。乾燥して、２３．７ｇ（９５％）のスルホン酸化ポリエーテルエーテルケトン［Ｓ−ＰＥＥＫ（下記式（１６））］を得た。
[Example 1]
(1) Sulfonation of polyetheretherketone 20.0 g of polyetheretherketone (Polyetheretherketone Victrex PEEK450PF manufactured by Victorex) was put into a 0.5 liter reaction solution, and 0.25 liter of 96% sulfuric acid was added, Stirring was continued for 2 days at room temperature under nitrogen. The resulting solution was poured into 5 liters of ion exchange water to precipitate the polymer. The polymer was repeatedly washed with water until the pH of the washing solution reached 5. By drying, 23.7 g (95%) of a sulfonated polyetheretherketone [S-PEEK (the following formula (16))] was obtained.
（２）トリフェニルホスフィンオキシドのＳ−ＰＥＥＫへの導入反応
Ｓ−ＰＥＥＫ４．５ｇを三口フラスコに入れ、窒素雰囲気下で攪拌しながら７０℃で塩化チオニル５０ｍｌを加えて３時間反応させた。過剰の塩化チオニルを減圧留去してスルホニルクロリド化したＰＥＥＫを得た。これにスルホラン２００ｍｌを加えて溶解した後、
トリフェニルホスフィンオキシド１３．９ｇ（５０ｍｍｏｌ）および塩化アルミニウム２．６７ｇ（２０ｍｍｏｌ）を加えて、90℃で30時間攪拌した。反応溶液を希塩酸（塩酸／水＝１０：１）１リットルに投入して、析出した固体を粉砕しながら撹拌した。この固体をろ過した後、水およびエタノールで洗浄し、さらにアセチルアセトン２％を含有する酢酸エチル３００ｍｌ、次いで80℃のトルエン３００ｍｌで２回洗浄した後、50℃で５時間真空乾燥してトルフェニルホスフィンオキシドを側鎖として導入したＰＥＥＫ５．２５ｇを得た。
(2) Reaction of introducing triphenylphosphine oxide into S-PEEK 4.5 g of S-PEEK was placed in a three-necked flask, and 50 ml of thionyl chloride was added at 70 ° C. with stirring under a nitrogen atmosphere for 3 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain sulfonyl chloride PEEK. After adding 200 ml of sulfolane and dissolving it,
13.9 g (50 mmol) of triphenylphosphine oxide and 2.67 g (20 mmol) of aluminum chloride were added and stirred at 90 ° C. for 30 hours. The reaction solution was poured into 1 liter of dilute hydrochloric acid (hydrochloric acid / water = 10: 1), and the precipitated solid was stirred while being pulverized. This solid was filtered, washed with water and ethanol, then washed twice with 300 ml of ethyl acetate containing 2% of acetylacetone and then with 300 ml of toluene at 80 ° C., and then vacuum-dried at 50 ° C. for 5 hours to obtain tolphenylphosphine. 5.25 g of PEEK into which an oxide was introduced as a side chain was obtained.
（３）トルフェニルホスフィンオキシドを側鎖として導入したＰＥＥＫのスルホン酸化
トルフェニルホスフィンオキシドを側鎖として導入したＰＥＥＫ５．００ｇを三口フラスコに入れ、１００ｍｌの９６％硫酸を加えて窒素雰囲気下室温で２０時間攪拌して得られた溶液を５リットルのイオン交換水の中に注ぎ入れることでポリマーを沈殿させた。洗浄液のｐＨが５になるまでポリマーの水洗を繰り返した。乾燥してトルフェニルホスフィンオキシドを側鎖として導入したＰＥＥＫのスルホン酸化物（下記式（１７））４．５０ｇを得た。
(3) Sulfonation of PEEK with Tolphenylphosphine Oxide as Side Chain 5.00 g of PEEK into which tolphenylphosphine oxide was introduced as a side chain was placed in a three-necked flask, and 100 ml of 96% sulfuric acid was added to it at room temperature under a nitrogen atmosphere. The polymer was precipitated by pouring the solution obtained by stirring for 5 hours into 5 liters of ion exchange water. The polymer was repeatedly washed with water until the pH of the washing solution reached 5. After drying, 4.50 g of PEEK sulfonated oxide (the following formula (17)) into which tolphenylphosphine oxide was introduced as a side chain was obtained.
（４）高分子電解質膜としての評価
上記の高分子電解質の固形分量が３０ｗｔ％となるように、高分子電解質１５ｇおよびＮＭＰをフラスコに入れて、攪拌しながら８０℃で加熱溶解させてポリマーワニスを得た。バーコーター（２００μｍ用）を用い、ガラス基板上に貼り付けたＰＥＴ薄膜上に塗布後、乾燥器にて８０℃、０．５時間予備乾燥させ、塗膜をＰＥＴ薄膜から剥がした。剥がした塗膜を真空乾燥器で１００℃、３時間乾燥した。さらに、塗膜重量の１，０００倍量のイオン交換水中に室温で２日間浸漬させることで、ＮＭＰを除去したフィルムを得た。次に、フィルムを２５℃・５０％ＲＨ環境に２４時間静置することで調湿後、各種物性測定を行った。結果を表１に示す。得られた高分子電解質フィルムはフェントン試験に高い耐性を示した。この結果は、本発明の高分子電解質が燃料電池用電解質材料として必要な高い耐酸化性と高プロトン伝導性を兼ね備えていることを示す。
(4) Evaluation as a polymer electrolyte membrane 15 g of the polymer electrolyte and NMP are placed in a flask so that the solid content of the polymer electrolyte is 30 wt%, and the polymer varnish is dissolved by heating at 80 ° C. with stirring. Got. Using a bar coater (for 200 μm), after coating on a PET thin film affixed on a glass substrate, it was preliminarily dried at 80 ° C. for 0.5 hours with a dryer, and the coating film was peeled off from the PET thin film. The peeled coating film was dried at 100 ° C. for 3 hours in a vacuum dryer. Furthermore, the film from which NMP was removed was obtained by immersing in ion-exchanged water of 1,000 times the coating weight at room temperature for 2 days. Next, various physical properties were measured after humidity control by allowing the film to stand in an environment of 25 ° C. and 50% RH for 24 hours. The results are shown in Table 1. The obtained polymer electrolyte film showed high resistance to the Fenton test. This result shows that the polymer electrolyte of the present invention has both high oxidation resistance and high proton conductivity required as an electrolyte material for fuel cells.
［実施例２］
（１）トリフェニルホスファイトのＳ−ＰＥＥＫへの導入反応
実施例１で得たＳ−ＰＥＥＫ４．５ｇを三口フラスコに入れ、窒素雰囲気下で攪拌しながら７０℃で塩化チオニル５０ｍｌを加えて３時間反応させた。過剰の塩化チオニルを減圧留去してスルホニルクロリド化したＰＥＥＫを得た。これにスルホラン２００ｍｌを加えて溶解した後、トリフェニルホスファイト１５．５ｇ（５０ｍｍｏｌ）および塩化アルミニウム２．６７ｇ（２０ｍｍｏｌ）を加えて、90℃で30時間攪拌した。反応溶液を希塩酸（塩酸／水＝１０：１）１リットルに投入して、析出した固体を粉砕しながら撹拌した
。この固体をろ過した後、水およびエタノールで洗浄し、さらにアセチルアセトン２％を含有する酢酸エチル３００ｍｌ、さらに80℃のトルエン３００ｍｌで２回洗浄した後、50℃で５時間真空乾燥してトルフェニルホスファイトを側鎖として導入したＰＥＥＫ５．７８ｇを得た。
（２）トルフェニルホスファイトを側鎖として導入したＰＥＥＫのスルホン酸化
トルフェニルホスファイトを側鎖として導入したＰＥＥＫ５．００ｇを三口フラスコに入れ、１００ｍｌの９６％硫酸を加えて窒素雰囲気下室温で２０時間攪拌して得られた溶液を５リットルのイオン交換水の中に注ぎ入れることでポリマーを沈殿させた。洗浄液のｐＨが５になるまでポリマーの水洗を繰り返した。乾燥してトルフェニルホスファイトを側鎖として導入したＰＥＥＫのスルホン酸化物（下記式（１８））４．５５ｇを得た。
[Example 2]
(1) Reaction of introducing triphenyl phosphite into S-PEEK 4.5 g of S-PEEK obtained in Example 1 was placed in a three-necked flask, and 50 ml of thionyl chloride was added at 70 ° C. with stirring in a nitrogen atmosphere for 3 hours. Reacted. Excess thionyl chloride was distilled off under reduced pressure to obtain sulfonyl chloride PEEK. After 200 ml of sulfolane was added and dissolved, 15.5 g (50 mmol) of triphenyl phosphite and 2.67 g (20 mmol) of aluminum chloride were added and stirred at 90 ° C. for 30 hours. The reaction solution was poured into 1 liter of dilute hydrochloric acid (hydrochloric acid / water = 10: 1), and the precipitated solid was stirred while being pulverized. This solid was filtered, washed with water and ethanol, further washed with 300 ml of ethyl acetate containing 2% of acetylacetone and further with 300 ml of toluene at 80 ° C., and then vacuum-dried at 50 ° C. for 5 hours, and then tolphenylphosphine. 5.78 g of PEEK introduced with phyto as a side chain was obtained.
(2) Sulfonation of PEEK introduced with tolphenyl phosphite as a side chain 5.00 g of PEEK introduced with tolphenyl phosphite as a side chain was placed in a three-necked flask, and 100 ml of 96% sulfuric acid was added at room temperature under a nitrogen atmosphere. The polymer was precipitated by pouring the solution obtained by stirring for 5 hours into 5 liters of ion exchange water. The polymer was repeatedly washed with water until the pH of the washing solution reached 5. After drying, 4.55 g of PEEK sulfonated oxide (following formula (18)) into which tolphenyl phosphite was introduced as a side chain was obtained.
（３）高分子電解質膜としての評価
実施例１と同様にして上記の高分子電解質のフィルムを得て、各種物性測定を行った。結果を表１に示す。得られた高分子電解質フィルムはフェントン試験に高い耐性を示した。この結果は、本発明の高分子電解質が燃料電池用電解質材料として必要な高い耐酸化性と高プロトン伝導性を兼ね備えていることを示す。
(3) Evaluation as a polymer electrolyte membrane In the same manner as in Example 1, the polymer electrolyte film was obtained, and various physical properties were measured. The results are shown in Table 1. The obtained polymer electrolyte film showed high resistance to the Fenton test. This result shows that the polymer electrolyte of the present invention has both high oxidation resistance and high proton conductivity required as an electrolyte material for fuel cells.
［実施例３］
（１）トリフェニルホスフェイトのＳ−ＰＥＥＫへの導入反応
実施例１で得たＳ−ＰＥＥＫ４．５ｇを三口フラスコに入れ、窒素雰囲気下で攪拌しながら７０℃で塩化チオニル５０ｍｌを加えて３時間反応させた。過剰の塩化チオニルを減圧留去してスルホニルクロリド化したＰＥＥＫを得た。これにスルホラン２００ｍｌを加えて溶解した後、トリフェニルホスフェイト１６．３ｇ（５０ｍｍｏｌ）および塩化アルミニウム２．６７ｇ（２０ｍｍｏｌ）を加えて、90℃で30時間攪拌した。反応溶液を希塩酸（塩酸／水＝１０：１）１リットルに投入して、析出した固体を粉砕しながら撹拌した。この固体をろ過した後、水およびエタノールで洗浄し、さらにアセチルアセトン２％を含有する酢酸エチル３００ｍｌ、さらに80℃のトルエン３００ｍｌで２回洗浄した後、50℃で５時間真空乾燥してトルフェニルホスフェイトを側鎖として導入したＰＥＥＫ６．１２ｇを得た。
（２）トルフェニルホスフェイトを側鎖として導入したＰＥＥＫのスルホン酸化
トルフェニルホスファイトを側鎖として導入したＰＥＥＫ５．００ｇを三口フラスコに入れ、１００ｍｌの９６％硫酸を加えて窒素雰囲気下室温で２０時間攪拌して得られた溶液を５リットルのイオン交換水の中に注ぎ入れることでポリマーを沈殿させた。洗浄液の
ｐＨが５になるまでポリマーの水洗を繰り返した。乾燥してトルフェニルホスフェイトを側鎖として導入したＰＥＥＫのスルホン酸化物（下記式（１９））４．６５ｇを得た。
[Example 3]
(1) Reaction of introducing triphenyl phosphate into S-PEEK 4.5 g of S-PEEK obtained in Example 1 was put into a three-necked flask, and 50 ml of thionyl chloride was added at 70 ° C. with stirring in a nitrogen atmosphere for 3 hours. Reacted. Excess thionyl chloride was distilled off under reduced pressure to obtain sulfonyl chloride PEEK. After 200 ml of sulfolane was added and dissolved, 16.3 g (50 mmol) of triphenyl phosphate and 2.67 g (20 mmol) of aluminum chloride were added and stirred at 90 ° C. for 30 hours. The reaction solution was poured into 1 liter of dilute hydrochloric acid (hydrochloric acid / water = 10: 1), and the precipitated solid was stirred while being pulverized. This solid was filtered, washed with water and ethanol, further washed with 300 ml of ethyl acetate containing 2% of acetylacetone and further with 300 ml of toluene at 80 ° C., and then vacuum-dried at 50 ° C. for 5 hours, and then tolphenylphosphine. 6.12 g of PEEK introduced with fate as a side chain was obtained.
(2) Sulfonation of PEEK with Tolphenyl Phosphate as Side Chain 5.00 g of PEEK into which tolphenyl phosphite was introduced as a side chain was placed in a three-necked flask, added with 100 ml of 96% sulfuric acid, and added at room temperature under a nitrogen atmosphere at room temperature. The polymer was precipitated by pouring the solution obtained by stirring for 5 hours into 5 liters of ion exchange water. The polymer was repeatedly washed with water until the pH of the washing solution reached 5. After drying, 4.65 g of PEEK sulfonated oxide (the following formula (19)) into which tolphenyl phosphate was introduced as a side chain was obtained.
（３）高分子電解質膜としての評価
実施例１と同様にして上記の高分子電解質のフィルムを得て、各種物性測定を行った。結果を表１に示す。得られた高分子電解質フィルムはフェントン試験に高い耐性を示した。この結果は、本発明の高分子電解質が燃料電池用電解質材料として必要な高い耐酸化性と高プロトン伝導性を兼ね備えていることを示す。
(3) Evaluation as a polymer electrolyte membrane In the same manner as in Example 1, the polymer electrolyte film was obtained, and various physical properties were measured. The results are shown in Table 1. The obtained polymer electrolyte film showed high resistance to the Fenton test. This result shows that the polymer electrolyte of the present invention has both high oxidation resistance and high proton conductivity required as an electrolyte material for fuel cells.
［実施例４］
（１）テトラフェニル−ｐ−フェニレン−ジフォスファイトのＳ−ＰＥＥＫへの導入反応
実施例１で得たＳ−ＰＥＥＫ４．５ｇを三口フラスコに入れ、窒素雰囲気下で攪拌しながら７０℃で塩化チオニル５０ｍｌを加えて３時間反応させた。過剰の塩化チオニルを減圧留去してスルホニルクロリド化したＰＥＥＫを得た。これにスルホラン２００ｍｌを加えて溶解した後、テトラフェニル−ｐ−フェニレン−ジフォスファイト２７．１ｇおよび塩化アルミニウム２．６７ｇ（２０ｍｍｏｌ）を加えて、90℃で30時間攪拌した。反応溶液を希塩酸（塩酸／水＝１０：１）１リットルに投入して、析出した固体を粉砕しながら撹拌した。この固体をろ過した後、水およびエタノールで洗浄し、さらにアセチルアセトン２％を含有する酢酸エチル３００ｍｌ、さらに80℃のトルエン３００ｍｌで２回洗浄した後、50℃で５時間真空乾燥してテトラフェニル−ｐ−フェニレン−ジフォスファイトを側鎖として導入したＰＥＥＫ８．３１ｇを得た。
（２）テトラフェニル−ｐ−フェニレン−ジフォスファイトを側鎖として導入したＰＥＥＫのスルホン酸化
テトラフェニル−ｐ−フェニレン−ジフォスファイトを側鎖として導入したＰＥＥＫ５．００ｇを三口フラスコに入れ、１００ｍｌの９６％硫酸を加えて窒素雰囲気下室温で２０時間攪拌して得られた溶液を５リットルのイオン交換水の中に注ぎ入れることでポリマーを沈殿させた。洗浄液のｐＨが５になるまでポリマーの水洗を繰り返した。乾燥してテトラフェニル−ｐ−フェニレン−ジフォスファイトを側鎖として導入したＰＥＥＫのスルホン酸化物（下記式（２０））４．６０ｇを得た。
[Example 4]
(1) Reaction of introducing tetraphenyl-p-phenylene-diphosphite into S-PEEK 4.5 g of S-PEEK obtained in Example 1 was placed in a three-necked flask and thionyl chloride at 70 ° C. with stirring in a nitrogen atmosphere. 50 ml was added and reacted for 3 hours. Excess thionyl chloride was distilled off under reduced pressure to obtain sulfonyl chloride PEEK. After 200 ml of sulfolane was added and dissolved therein, 27.1 g of tetraphenyl-p-phenylene-diphosphite and 2.67 g (20 mmol) of aluminum chloride were added and stirred at 90 ° C. for 30 hours. The reaction solution was poured into 1 liter of dilute hydrochloric acid (hydrochloric acid / water = 10: 1), and the precipitated solid was stirred while being pulverized. This solid was filtered, washed with water and ethanol, further washed with 300 ml of ethyl acetate containing 2% of acetylacetone and further with 300 ml of toluene at 80 ° C., and then vacuum-dried at 50 ° C. for 5 hours to give tetraphenyl- 8.31 g of PEEK into which p-phenylene-diphosphite was introduced as a side chain was obtained.
(2) Sulfonation of PEEK introduced with tetraphenyl-p-phenylene-diphosphite as a side chain PEEK 5.00 g introduced with tetraphenyl-p-phenylene-diphosphite as a side chain was placed in a three-necked flask, and 100 ml A solution obtained by adding 96% sulfuric acid and stirring at room temperature for 20 hours under a nitrogen atmosphere was poured into 5 liters of ion-exchanged water to precipitate a polymer. The polymer was repeatedly washed with water until the pH of the washing solution reached 5. After drying, 4.60 g of PEEK sulfonated oxide (following formula (20)) into which tetraphenyl-p-phenylene-diphosphite was introduced as a side chain was obtained.
（３）高分子電解質膜としての評価
実施例１と同様にして上記の高分子電解質のフィルムを得て、各種物性測定を行った。結果を表１に示す。得られた高分子電解質フィルムはフェントン試験に高い耐性を示した。この結果は、本発明の高分子電解質が燃料電池用電解質材料として必要な高い耐酸化性と高プロトン伝導性を兼ね備えていることを示す。
(3) Evaluation as a polymer electrolyte membrane In the same manner as in Example 1, the polymer electrolyte film was obtained, and various physical properties were measured. The results are shown in Table 1. The obtained polymer electrolyte film showed high resistance to the Fenton test. This result shows that the polymer electrolyte of the present invention has both high oxidation resistance and high proton conductivity required as an electrolyte material for fuel cells.
［比較例１］
特開２００３−２０１４０３号公報の参考例２に記載の方法で下記式（２１）に示すポリマーＢのスルホン酸化物を得て、このものの高分子電解質膜としての評価を行った。結果を表１に示す。
[Comparative Example 1]
A sulfone oxide of polymer B represented by the following formula (21) was obtained by the method described in Reference Example 2 of JP-A-2003-20143, and this was evaluated as a polymer electrolyte membrane. The results are shown in Table 1.
［比較例２］
ＷＯ２００５−７６３９７号の実施例に記載の方法で下記式（２２）に示す高分子電解
質を得て、このものの評価を行った。結果を表１に示す。
[Comparative Example 2]
A polymer electrolyte represented by the following formula (22) was obtained by the method described in the examples of WO2005-76397, and this was evaluated. The results are shown in Table 1.
［実施例５］
実施例２で得られた高分子電解質をＮＭＰ（Ｎ−メチルピロリドン）溶液とし、キャスト法でそれぞれ膜厚５０μｍのフイルムを作製した。このフイルムの両面を触媒付電極（エレクトロケム製ＥＣ−２０−１０−７）ではさみ、ホットプレスしてＭＥＡ（膜電極接合体）を作製した。このＭＥＡを純水に２時間浸漬し吸水させ、評価セル（エレクトロケム製ＦＣ−０５−０１−ＳＰ：２５ｃｍ２）に組み込んだ。
［発電特性評価］
８０℃に保った上記セルのアノード側へ水素（相対湿度３０％）を、カソード側へ空気（相対湿度５０％）を供給し、電流密度０．３Ａ／ｃｍ２で長時間稼動試験を行った。出力電圧が初期電圧の９０％になるまでの時間は８０００時間であった。
[Example 5]
The polymer electrolyte obtained in Example 2 was used as an NMP (N-methylpyrrolidone) solution, and films each having a thickness of 50 μm were prepared by a casting method. Both sides of this film were sandwiched between electrodes with a catalyst (EC-20-10-7 manufactured by Electrochem) and hot-pressed to prepare MEA (membrane electrode assembly). This MEA was immersed in pure water for 2 hours to absorb water, and incorporated in an evaluation cell (FC-05-01-SP manufactured by Electrochem: 25 cm 2 ).
[Evaluation of power generation characteristics]
Hydrogen (relative humidity 30%) was supplied to the anode side of the cell maintained at 80 ° C., and air (relative humidity 50%) was supplied to the cathode side, and a long-term operation test was performed at a current density of 0.3 A / cm 2 . . The time until the output voltage reached 90% of the initial voltage was 8000 hours.
［比較例３］
比較例１で得られた高分子電解質を用いたほかは、実施例５と同様に発電特性評価を行った。出力電圧が初期電圧の９０％になるまでの時間は、２８０時間であった。この結果は、実施例２で得た電解質膜の耐久性が非常に高いことを示す。
［比較例４］
比較例２で得られた高分子電解質を用いたほかは、実施例５と同様に発電特性評価を行った。出力電圧が初期電圧の９０％になるまでの時間は、７０００時間であった。この結果は、実施例２で得た電解質膜の耐久性が非常に高いことを示す。
［実施例６］
実施例４で得られた高分子電解質を用いたほかは、実施例５と同様にして発電特性評価を行った。出力電圧が初期電圧の９０％になるまでの時間は１００００時間以上であった。この結果は、実施例４で得た、より長い耐酸化性側鎖を導入した高分子電解質膜ではさらに高い耐久性を示すことがわかる。
[Comparative Example 3]
The power generation characteristics were evaluated in the same manner as in Example 5 except that the polymer electrolyte obtained in Comparative Example 1 was used. The time until the output voltage reached 90% of the initial voltage was 280 hours. This result shows that the durability of the electrolyte membrane obtained in Example 2 is very high.
[Comparative Example 4]
The power generation characteristics were evaluated in the same manner as in Example 5 except that the polymer electrolyte obtained in Comparative Example 2 was used. The time until the output voltage reached 90% of the initial voltage was 7000 hours. This result shows that the durability of the electrolyte membrane obtained in Example 2 is very high.
[Example 6]
The power generation characteristics were evaluated in the same manner as in Example 5 except that the polymer electrolyte obtained in Example 4 was used. The time until the output voltage became 90% of the initial voltage was 10,000 hours or more. This result shows that the polymer electrolyte membrane obtained by introducing the longer oxidation-resistant side chain obtained in Example 4 has higher durability.
本発明は、固体高分子形燃料電池の電解質およびバインダーとして有用である。 The present invention is useful as an electrolyte and a binder for a polymer electrolyte fuel cell.
Claims (6)
Ｚ＝−Ｌ−（Ａｒ１Ｔ１（Ｂ１））−（Ａｒ２Ｔ２（Ｂ２））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ ・・・（２）
上記一般式（２）中のＢ１〜Ｂｎ−１は、側鎖部分Ｚにおける分岐鎖を意味し、以下の式で表される。
Ｂ１＝−〔（Ａｒ２Ｔ２（Ｂ２））−（Ａｒ３Ｔ３（Ｂ３））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ〕ｆ
Ｂ２＝−〔（Ａｒ３Ｔ３（Ｂ３））−・・・−（Ａｒｎ−１Ｔｎ−１（Ｂｎ−１））−Ａｒｎ〕ｆ
・
・
・
Ｂｎ−１＝−〔Ａｒｎ〕ｆ
上記一般式（２）中
ｎは各々独立に２〜５の整数、
ｆは各々独立に０または１、
Ａｒ１〜Ａｒｎは各々独立に芳香族残基、
Ｔ１〜Ｔｎ−１は連結基ＰＯｘ（ｘは０〜４の整数）であり、
Ｌは−ＣＯ−、−ＣＯＮＨ−、−（ＣＦ２）ｐ−（ｐは１〜１０の整数）、−Ｃ（ＣＦ３）２−、−ＣＯＯ−、−ＳＯ−、−ＳＯ２−から選ばれる連結基である。
そして、−ＳＯ３Ｈ基が二個以上導入されたＺを有する。） A polymer electrolyte for a fuel cell having at least a repeating unit represented by the following general formula (1).
Z = -L- (Ar 1 T 1 (B 1)) - (Ar 2 T 2 (B 2)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ... (2)
B 1 ~B n-1 in the general formula (2) in means a branched chain in the side chain moiety Z, is expressed by the following equation.
B 1 = - [(Ar 2 T 2 (B 2 )) - (Ar 3 T 3 (B 3)) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ] F
B 2 = - [(Ar 3 T 3 (B 3 )) - ··· - (Ar n-1 T n-1 (B n-1)) - Ar n ] f
・
・
・
B n−1 = − [Ar n ] f
In said general formula (2), n is an integer of 2-5 each independently,
f is independently 0 or 1,
Ar 1 to Ar n are each independently an aromatic residue,
T 1 to T n-1 are linking groups POx (x is an integer of 0 to 4),
L is -CO -, - CONH -, - (CF 2) p - (p is an integer of from 1 to 10), - C (CF 3) 2 -, - COO -, - SO -, - SO 2 - selected from A linking group.
And it has Z in which two or more —SO 3 H groups are introduced. )
A fuel cell using the polymer electrolyte according to claim 1.
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