JP2006338928A - Reinforced polyelectrolyte, electrode-polyelectrolyte membrane assembly, and fuel cell as well as method of manufacturing them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyelectrolyte membrane in which permeability of methanol can be suppressed while high proton conductivity is maintained, and in addition to this, swelling by water and methanol is small, and which has superior water resistance and methanol resistance, and provide an electrode-polyelectrolyte membrane assembly and a fuel cell using this membrane. <P>SOLUTION: This is a reinforced polyelectrolyte membrane, an electrode-polyelectrolyte membrane assembly using this, as well as a fuel cell in which a porous base material and a resin composition filled into the void and/or micro-pores of the porous base material are contained, and in which the resin composition contains the polyelectrolyte compound containing a copolymer having (a) a structural unit having a heterocyclic ring, (b) a structural unit having an aromatic ring into which a protonic acid group is introduced, and (c) a structural unit having an aromatic ring. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a reinforced polymer electrolyte membrane, an electrode-polymer electrolyte membrane assembly, a fuel cell using the same, and a method for producing them.

  A fuel cell is expected as a next-generation power generation device that has high power generation efficiency and a low environmental load, and that can contribute to solving environmental problems and energy problems that are currently a major issue. Among these fuel cells, solid polymer fuel cells are smaller and have higher output than any other system, and they are the next generation as small-scale on-site, mobile (on-vehicle) and portable fuel cells. It is said to be the main force.

  At present, solid polymer fuel cells are not yet in practical use, but as polymer electrolyte membranes for fuel cells used in trial production or testing, perfluoroalkylene groups are the main skeleton, and some "Nafion (registered trademark)", "Flemion (registered trademark)" and the like are known as fluorine-based polymer electrolyte membranes having ion-exchange groups such as sulfonic acid groups and carboxylic acid groups at the end of perfluorovinyl ether side chain. Yes.

However, in the currently used fuel cell polymer electrolyte membrane “Nafion (registered trademark)” and the like, when the operation is performed at a temperature exceeding 100 ° C., the moisture content of the polymer electrolyte membrane drops rapidly, Softening of the polymer electrolyte membrane is also remarkable. In particular, in direct methanol fuel cells, where the future is expected, when a fluorine-based proton conductive polymer material such as the conventional “Nafion (registered trademark)” is used as the electrolyte, the methanol passing through the anode is the electrolyte. It diffuses in and reaches the cathode, where it reacts directly with the oxidant (O ₂ ) on the cathode electrode, causing a short-circuit phenomenon (crossover), which significantly reduces battery performance and exhibits sufficient performance There is a problem that can not be.

  In order to solve such problems, various studies have been made on polymer electrolyte membranes in which a sulfonic acid group is introduced into a heat-resistant aromatic ring instead of a fluorine-based membrane. Considering the heat resistance and chemical stability of the polymer electrolyte membrane, aromatic polyarylene ether ketones such as polyether ether ketone are sulfonated as the compound skeleton of the polymer compound used in the polymer electrolyte membrane. (For example, Patent Document 1) and sulfonated polystyrene. Thus, proton conductivity can be imparted to the polymer electrolyte membrane by introducing an acid group such as a sulfonic acid group into the polymer compound.

  However, it is difficult to control the amount of sulfonic acid groups in a method in which the synthesized polymer is directly sulfonated with a strong acid such as sulfuric acid or fuming sulfuric acid. In addition, when the amount of sulfonic acid groups cannot be controlled and many sulfonic acid groups are introduced into the polymer, the water resistance of the polymer electrolyte membrane deteriorates due to the hydrophilicity of the sulfonic acid groups. The polymer electrolyte membrane may be damaged due to a decrease in strength of the molecular electrolyte membrane or the like. In direct methanol fuel cells, an aqueous methanol solution is used as the fuel, so methanol resistance may be one of the characteristics required for polymer electrolyte membranes. The membrane into which the acid group has been introduced has a problem that the swelling with respect to methanol is large and the methanol resistance is poor.

JP-A-6-93114

An object of the present invention is a reinforced polymer electrolyte membrane and electrode having a low swelling with respect to water and methanol, excellent water resistance, methanol resistance, and high ionic conductivity, particularly as a polymer electrolyte membrane for direct methanol fuel cells An object of the present invention is to provide a polymer electrolyte membrane assembly, a production method thereof, and a fuel cell using the same.
Another object of the present invention is to provide a co-polymer comprising (a) a structural unit having a heterocyclic ring, (b) a structural unit having an aromatic ring into which a protonic acid group is introduced, and (c) a structural unit having an aromatic ring. Reinforced polymer electrolyte filled with voids and / or pores of porous substrate with resin composition containing polymer electrolyte compound containing coal, electrode-polymer electrolyte membrane assembly and fuel cell using the same Is to provide.

The inventors have excellent water resistance and methanol resistance by combining a polymer electrolyte compound containing a copolymer having the structural units (a) to (c) above and a porous substrate, and A reinforced polymer electrolyte membrane having high ionic conductivity has been found.
That is, the present invention
1. A porous substrate and a resin composition filled in voids and / or pores of the porous substrate, the resin composition comprising (a) a structural unit having a heterocyclic ring, and (b) A reinforced polymer electrolyte membrane comprising a polymer electrolyte compound comprising a copolymer having a structural unit having an aromatic ring having a proton acid group introduced therein and (c) a structural unit having an aromatic ring .
2. (A) The structural unit having a heterocyclic ring is pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, quinoline, isoquinoline, quinoxaline, imidazole, benzimidazole, indole, purine, triazole, triazine, furan, thiophene, benzofuran, and these 2. The reinforced polymer electrolyte membrane according to 1 above, which is at least one heteroaromatic compound selected from the group consisting of derivatives.

[式(１)中、Ａは、直接結合、−O−、−S−、−S(O)−、−S(O)₂−、−C(O)−、−Ｐ(O)(C₆H₅)−、−C(CH₃)₂−、−C(CF₃)₂−、−C₆H₄CC₆H₄−または炭素数１〜６のアルキリデン基を示し；Rは、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から5の置換基数を表し；mは、０〜(5−n)の置換基数を表わす。]








式(２)：

[式(２)中、Yは、直接結合、−NH−、−N(CH₃)−、−NHC₆H₄O−、−N(CH₃)C₆H₄O−または炭素数１〜６のアルキリデン基を示し；Zは、直接結合、−NH−、−N(CH₃)−、−O−、−S−、−S(O)−、−S(O)₂−、−C(O)−または炭素数１〜６のアルキリデン基を示し；Rは、水素、炭素１〜６個を含む脂肪族基、メトキシ基、フェニル基、フェノキシ基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素示し；Xは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から5の置換基数を表わし；mは、０〜(5−n)の置換基数を表わす。]
式(３)：

[式(３)中、各Qは、同一でも異なっていてもよく、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロフェニル基、アルコキシフェニル基、フルオロフェニル基、クロロフェニル基、ブロモフェニル基、ヨードフェニル基、シアノフェニル基、アセトフェニル基、‐OH基、塩素、臭素、ヨウ素を示し；Rは、水素、炭素１〜６個を含む脂肪族基、メトキシ基、フェニル基、フェノキシ基、ニトロ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から5の置換基数を表し；mは、０〜(5−n)の置換基数を表わす。] 3. (A) The reinforced polymer electrolyte membrane according to the above 1 or 2, wherein the structural unit having a heterocyclic ring comprises the following formula (1) and / or formula (2) and / or formula (3).
Formula (1):

[In the formula (1), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; R is hydrogen Represents an aliphatic group containing 1 to 6 carbon atoms, phenyl group, nitro group, cyano group, alkoxy group, chlorine, bromine, iodine; X is selected from the group consisting of SO ₃ H, COOH, PO ₃ H ₂ N represents the number of substituents from 1 to 5; and m represents the number of substituents from 0 to (5-n). ]








Formula (2):

[In the formula (2), Y represents a direct bond, —NH—, —N (CH ₃ ) —, —NHC ₆ H ₄ O—, —N (CH ₃ ) C ₆ H ₄ O— 6 represents an alkylidene group; Z represents a direct bond, —NH—, —N (CH ₃ ) —, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O)-or an alkylidene group having 1 to 6 carbon atoms; R represents hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a methoxy group, a phenyl group, a phenoxy group, a nitro group, a cyano group, an alkoxy group, X represents chlorine, bromine or iodine; X represents a protonic acid group selected from the group consisting of SO ₃ H, COOH and PO ₃ H ₂ ; n represents the number of substituents from 1 to 5; This represents the number of substituents of (5-n). ]
Formula (3):

[In the formula (3), each Q may be the same or different and is hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitrophenyl group, an alkoxyphenyl group, a fluorophenyl group, a chlorophenyl group, A bromophenyl group, an iodophenyl group, a cyanophenyl group, an acetophenyl group, an —OH group, chlorine, bromine, iodine; R is hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a methoxy group, a phenyl group, X represents a protonic acid group selected from the group consisting of SO ₃ H, COOH, and PO ₃ H ₂ ; n represents the number of substituents of 1 to 5; phenoxy group, nitro group, chlorine, bromine, iodine; And m represents the number of substituents from 0 to (5-n). ]

［式(４)中、Ａは、直接結合、−O−、−S−、−S(O)−、−S(O)₂−、−C(O)−、−Ｐ(O)(C₆H₅)−、−C(CH₃)₂−、−C(CF₃)₂−、−C₆H₄CC₆H₄−または炭素数１〜６のアルキリデン基を示し；Ｒは、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から4の置換基数を表わし、mは、０〜(4−n)の置換基数を表わす。］


式(５)：

［式(５)中、Ｒは、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から4の置換基数を表わし；mは、０〜(4−n)の置換基数を表わす。］ 4). (B) The reinforced polymer according to any one of 1 to 3 above, wherein the structural unit having an aromatic ring into which a protonic acid group is introduced includes the following formula (4) and / or the following formula (5): The present invention relates to an electrolyte membrane.
Formula (4):

[In the formula (4), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; R is hydrogen Represents an aliphatic group containing 1 to 6 carbon atoms, phenyl group, nitro group, cyano group, alkoxy group, chlorine, bromine, iodine; X is selected from the group consisting of SO ₃ H, COOH, PO ₃ H ₂ N represents the number of substituents from 1 to 4, and m represents the number of substituents from 0 to (4-n). ]


Formula (5):

[In the formula (5), R represents hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; X represents SO ₃ H; Represents a protonic acid group selected from the group consisting of COOH and PO ₃ H ₂ ; n represents the number of substituents of 1 to 4; and m represents the number of substituents of 0 to (4-n). ]

［式(６)中、Aは、直接結合、−O−、−S−、−S(O)−、−S(O)₂−、−C(Ｏ)−、−Ｐ(O)(C₆H₅)−、−C(CH₃)₂−、−C(CF₃)₂−、−C₆H₄CC₆H₄−または炭素数１〜６のアルキリデン基を示し；Ｂ，Ｃ，Ｄ及びＥは、それぞれ独立に、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素又はヨウ素を示し；但し、Ｂ，Ｃ，Ｄ，Ｅのうち少なくとも２種は水素よりなる。］
式(７)：

［式(７)中、Ｆ及びＧは、それぞれ独立に、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素又はヨウ素を示し；但し、Ｆ及びＧのうち少なくとも１種は水素よりなる。］ 5. (C) It is related with the reinforced polymer electrolyte membrane as described in any one of said 1-4 whose structural unit which has an aromatic ring contains following formula (6) and / or following formula (7).
Formula (6):

[In the formula (6), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; D and E each independently represent hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; provided that B, C, D, At least two of E consist of hydrogen. ]
Formula (7):

[In formula (7), F and G each independently represent hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; , F and G consist of hydrogen. ]

6). (B) The reinforced polymer electrolyte according to any one of 1 to 5 above, wherein in the structural unit having an aromatic ring into which a proton acid group is introduced, the proton acid group is a sulfonic acid group or / and a phosphoric acid group. Relates to the membrane.
7). The present invention relates to a reinforced polymer electrolyte membrane comprising one or more reinforced polymer electrolyte membranes according to any one of 1 to 6 above.
8. An electrode-polymer electrolyte membrane assembly comprising two electrodes and the reinforced polymer electrolyte membrane according to any one of 1 to 7 disposed between the two electrodes.
9. A method for producing the electrode-polymer electrolyte membrane assembly according to 8 above, comprising disposing the reinforced polymer electrolyte membrane according to any one of 1 to 7 between two electrodes.
10. The present invention relates to a fuel cell comprising the electrode-polymer electrolyte membrane assembly according to 9 above.

By combining a polyelectrolyte compound containing a copolymer having the structural units (a) to (c) above and a porous substrate, it has excellent water resistance and methanol resistance, and also has high ionic conductivity. A reinforced polymer electrolyte membrane can be provided. In particular, by holding the electrolyte compound on the porous substrate, the swelling rate of the electrolyte membrane can be significantly suppressed, and an electrolyte membrane having excellent methanol resistance and stable quality can be provided.
Therefore, the reinforced polymer electrolyte of the present invention can suppress the permeability of methanol while maintaining a high proton conductivity, and has a small swelling with respect to water and methanol, so that the polymer has excellent water resistance and methanol resistance. It can be suitably used as a material for the electrolyte membrane.
Furthermore, since the reinforced polymer electrolyte membrane of the present invention uses a porous substrate excellent in dimensional stability, heat resistance, and chemical resistance, the swelling of the electrolyte can be suppressed even under high temperature conditions. Therefore, it is possible to provide an electrolyte membrane with stable quality. Further, since the porous substrate does not decompose into radical compounds such as hydrogen peroxide generated inside the electrolyte, a high battery output can be stably obtained for a long period of time.
Further, the reinforced polymer electrolyte membrane of the present invention has high strength and excellent workability, and it is easy to produce an electrode-polymer electrolyte membrane assembly, and a fuel cell using this has excellent electrochemical characteristics.

(1) Reinforced polymer electrolyte membrane The reinforced polymer electrolyte membrane of the present invention comprises a porous substrate and a resin composition filled in the voids and / or pores of the porous substrate. This will be described below.
(1-1) Porous base material Examples of the porous base material used in the present invention include non-woven fabrics and fiber sheets made of polyester fiber, glass fiber, aramid fiber and nylon fiber, and fibrillated polytetrafluoroethylene. The sheet | seat which consists of, or a porous organic material is mentioned. Among these, the nonwoven fabric and fiber sheet which consist of polyester fiber, glass fiber, aramid fiber, and nylon fiber can use the general purpose nonwoven fabric and fiber sheet which satisfy | fill conditions, such as the thickness mentioned later, a porosity, and an average hole diameter.
Examples of porous organic materials include polyethylene, polypropylene, polyether ketone, polysulfide, polyphosphazene, polyphenylene, polybenzimidazole, polyethersulfone, polyphenylene oxide, polyester, polycarbonate, polyurethane, polyamide, polyimide, polyquinoline, and polyquinoxaline. , Polyurea, polysulfone, polysulfonate, polybenzoxazole, polybenzothiazole, polythiazole, polyphenylquinoxaline, polyquinoline, polysiloxane, polytriazine, polydiene, polypyridine, polypyrimidine, polyoxathiazole, polytetrazapyrene, polyoxazole , Polyvinyl pyridine, polyvinyl imidazole, polypyrrolidone, polytetrafluoroethylene Emissions, polyvinylidene fluoride, polyacrylate derivatives, polymethacrylate derivatives, polystyrene derivatives, and the like. Among these, it is more preferable to contain any of polyester, polysulfone, polyethersulfone, polyarylate, polyamideimide, polyetherimide, and polyimide in terms of heat resistance and electrolytic solution resistance.
The thickness of these porous substrates is, for example, 5 to 200 μm, preferably 5 to 100 μm. Generally, if it is 5 μm or more, sufficient practical strength can be secured, and if it is 200 μm or less, there are no problems in handling and workability.
For example, the porosity of the porous substrate of the present invention is preferably 10 to 95%, and preferably 40 to 90%. If it is 10% or more, it is preferable because the resin composition of the present invention can be sufficiently filled in the voids and / or pores of the porous substrate, and sufficient ionic conductivity can be obtained. Moreover, if it is 95% or less, sufficient practical strength can be ensured.
The average pore diameter of the porous substrate of the present invention is, for example, 0.001 to 100 μm, preferably 0.01 to 10 μm. If it is 0.001 micrometer or more, the resin composition of this invention can fully be filled, and since it is easy to fix | immobilize the resin composition of this invention if it is 100 micrometers or less, it is preferable.

(1-2) Resin Composition The resin composition of the present invention comprises (a) a structural unit having a heterocyclic ring, (b) a structural unit having an aromatic ring having a proton acid group introduced therein, and (c) an aromatic ring. And a polyelectrolyte compound including a copolymer having a structural unit. Moreover, the resin composition of the present invention optionally contains other polymer compounds and other additives.
(1-2-1) Polyelectrolyte Compound The acid group-containing polymer compound of the present invention comprises (a) a structural unit having a heterocyclic ring, and (b) a structural unit having an aromatic ring into which a protonic acid group is introduced, (C) a copolymer having a structural unit having an aromatic ring and optionally (d) a structural unit other than the structural units (a) to (d) above.

[式(１)中、Ａは、直接結合、−O−、−S−、−S(O)−、−S(O)₂−、−C(O)−、−Ｐ(O)(C₆H₅)−、−C(CH₃)₂−、−C(CF₃)₂−、−C₆H₄CC₆H₄−または炭素数１〜６のアルキリデン基を示し；Rは、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から5の置換基数を表し；mは、０〜(5−n)の置換基数を表わす。]
















(1-2-1-1) Structure of polyelectrolyte compounds
(a) Structural unit having a heterocyclic ring
(a) The structural unit having a heterocyclic ring is not particularly limited, but pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, quinoline, isoquinoline, quinoxaline, imidazole, benzimidazole, indole, purine, triazole, triazine, furan, Examples include heteroaromatic compounds such as thiophene and benzofuran, and derivatives thereof. These can be used alone or in combination of two or more. Among these, a structural unit represented by the following formula (1) or / and (2) or / and (3) is preferable from the viewpoint of water resistance, methanol resistance and proton conductivity.
Formula (1):

[In the formula (1), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; R is hydrogen Represents an aliphatic group containing 1 to 6 carbon atoms, phenyl group, nitro group, cyano group, alkoxy group, chlorine, bromine, iodine; X is selected from the group consisting of SO ₃ H, COOH, PO ₃ H ₂ N represents the number of substituents from 1 to 5; and m represents the number of substituents from 0 to (5-n). ]

等が挙げられる。 As an example of Formula (1), for example,

Etc.

[式(２)中、Yは、直接結合、−NH−、−N(CH₃)−、−NHC₆H₄O−、−N(CH₃)C₆H₄O−または炭素数１〜６のアルキリデン基を示し；Zは、直接結合、−NH−、−N(CH₃)−、−O−、−S−、−S(O)−、−S(O)₂−、−C(O)−または炭素数１〜６のアルキリデン基を示し；Rは、水素、炭素１〜６個を含む脂肪族基、メトキシ基、フェニル基、フェノキシ基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素示し；Xは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から5の置換基数を表わし；mは、０〜(5−n)の置換基数を表わす。] Formula (2):

[In the formula (2), Y represents a direct bond, —NH—, —N (CH ₃ ) —, —NHC ₆ H ₄ O—, —N (CH ₃ ) C ₆ H ₄ O— 6 represents an alkylidene group; Z represents a direct bond, —NH—, —N (CH ₃ ) —, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O)-or an alkylidene group having 1 to 6 carbon atoms; R represents hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a methoxy group, a phenyl group, a phenoxy group, a nitro group, a cyano group, an alkoxy group, X represents chlorine, bromine or iodine; X represents a protonic acid group selected from the group consisting of SO ₃ H, COOH and PO ₃ H ₂ ; n represents the number of substituents from 1 to 5; This represents the number of substituents of (5-n). ]

等が挙げられる。 As an example of Formula (2), for example,

Etc.

[式(３)中、各Qは、同一でも異なっていてもよく、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロフェニル基、アルコキシフェニル基、フルオロフェニル基、クロロフェニル基、ブロモフェニル基、ヨードフェニル基、シアノフェニル基、アセトフェニル基、‐OH基、塩素、臭素、ヨウ素を示し；Rは、水素、炭素１〜６個を含む脂肪族基、メトキシ基、フェニル基、フェノキシ基、ニトロ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から5の置換基数を表し；mは、０〜(5−n)の置換基数を表わす。]
式（３）の例としては、例えば

等が挙げられる。 Formula (3):

[In the formula (3), each Q may be the same or different and is hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitrophenyl group, an alkoxyphenyl group, a fluorophenyl group, a chlorophenyl group, A bromophenyl group, an iodophenyl group, a cyanophenyl group, an acetophenyl group, an —OH group, chlorine, bromine, iodine; R is hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a methoxy group, a phenyl group, X represents a protonic acid group selected from the group consisting of SO ₃ H, COOH, and PO ₃ H ₂ ; n represents the number of substituents of 1 to 5; phenoxy group, nitro group, chlorine, bromine, iodine; And m represents the number of substituents from 0 to (5-n). ]
As an example of Formula (3), for example,

Etc.

  Here, the structural unit having a heterocyclic ring as the component (a) is not necessarily limited to one type, and two or more types of structural units may be included. In addition, the structural unit having a heterocyclic ring as component (a) may or may not have a protonic acid group introduced, and a structural unit having a protonic acid group introduced and a protonic acid group are introduced. Both of the structural units that are not made may be included.

［式(４)中、Ａは、直接結合、−O−、−S−、−S(O)−、−S(O)₂−、−C(O)−、−Ｐ(O)(C₆H₅)−、−C(CH₃)₂−、−C(CF₃)₂−、−C₆H₄CC₆H₄−または炭素数１〜６のアルキリデン基を示し；Ｒは、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から4の置換基数を表わし、mは、０−(4−n)の置換基数を表わす。］



































(b) Structural unit having an aromatic ring into which a protonic acid group is introduced
(b) The structural unit having an aromatic ring into which a protonic acid group is introduced is not particularly limited, but the structural unit represented by the following formula (4) or / and (5) is preferable from the viewpoint of heat resistance and proton conductivity. preferable.
Formula (4):

[In the formula (4), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; R is hydrogen Represents an aliphatic group containing 1 to 6 carbon atoms, phenyl group, nitro group, cyano group, alkoxy group, chlorine, bromine, iodine; X is selected from the group consisting of SO ₃ H, COOH, PO ₃ H ₂ N represents the number of substituents of 1 to 4, and m represents the number of substituents of 0- (4-n). ]

等が挙げられる。 As an example of Formula (4), for example,

Etc.

［式(５)中、Ｒは、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素、ヨウ素を示し；Ｘは、SO₃H、COOH、PO₃H₂からなる群から選択されるプロトン酸基を示し；ｎは、1から4の置換基数を表わし；mは、０−(4−n)の置換基数を表わす。］ Formula (5):

[In the formula (5), R represents hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; X represents SO ₃ H; A protonic acid group selected from the group consisting of COOH and PO ₃ H ₂ ; n represents the number of substituents 1 to 4; m represents the number of substituents 0- (4-n). ]

等が挙げられる。
ここで、（ｂ）成分のプロトン酸基を導入した芳香環を有する構造単位は、式（４）又は/及び（５）で表わされる構造単位であればどのような構造であってもよく、必ずしも一種類に限定されるものではなく、二種類以上の構造単位が含まれていてもよい。 As an example of Formula (5), for example,

Etc.
Here, the structural unit having an aromatic ring introduced with a protonic acid group as the component (b) may be any structure as long as it is a structural unit represented by the formula (4) or / and (5), It is not necessarily limited to one type, and two or more types of structural units may be included.

［式(６)中、Aは、直接結合、−O−、−S−、−S(O)−、−S(O)₂−、−C(Ｏ)−、−Ｐ(O)(C₆H₅)−、−C(CH₃)₂−、−C(CF₃)₂−、−C₆H₄CC₆H₄−または炭素数１〜６のアルキリデン基を示し；Ｂ，Ｃ，Ｄ及びＥは、それぞれ独立に、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素又はヨウ素を示し；但し、Ｂ，Ｃ，Ｄ，Ｅのうち少なくとも２種は水素よりなる。］






































(C) The reinforced polymer electrolyte membrane according to claim 1, wherein the structural unit having an aromatic ring includes the following formula (6) and / or the following formula (7).






Formula (6):

[In the formula (6), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; D and E each independently represent hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; provided that B, C, D, At least two of E consist of hydrogen. ]

等が挙げられる。





As an example of Formula (6), for example,

Etc.

［式(７)中、Ｆ及びＧは、それぞれ独立に、水素、炭素１〜６個を含む脂肪族基、フェニル基、ニトロ基、シアノ基、アルコキシ基、塩素、臭素又はヨウ素を示し；但し、Ｆ及びＧのうち少なくとも１種は水素よりなる。］ Formula (7):

[In formula (7), F and G each independently represent hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; , F and G consist of hydrogen. ]

等が挙げられる。 As an example of Formula (7), for example

Etc.

  Here, the structural unit having an aromatic ring as the component (c) may be any structure as long as it is a structural unit represented by the formula (5) or / and (6), and is not necessarily limited to one type. It is not a thing and two or more types of structural units may be included.

(D) Structural units other than the structural units (a) to (d) In the present invention, structural units other than the structural units (a) to (c) may be included.
The structural units other than the structural units (a) to (c) in the present invention are not particularly limited. For example, alkylene ethers such as ethylene oxide, propylene oxide, and tetramethylene oxide, perfluoroalkylene ethers, aromatic imides, and amides. And aromatic ethers having such bonds.

  In the present invention, (a) a structural unit having a heterocyclic ring, (b) a structural unit having an aromatic ring into which a protonic acid group is introduced, (c) a structural unit having an aromatic ring, and optionally (d) the above (a ) To (d) other than the structural units are bonded, they may be bonded in the form of random copolymerization or may be bonded in the form of block copolymerization.

The content of the component (a) in the polymer electrolyte compound of the present invention is preferably 1 to 50 mol%, and preferably 5 to 45 mol% with respect to the total amount of the components (a) to (d). It is more preferable that the content be 10 to 40 mol%. If this content is 1 mol% or more, there is a tendency that the intermolecular crosslinking density does not decrease and swelling with respect to water and methanol can be sufficiently suppressed, and if it is 50 mol% or less, proton conductivity is low. Since it does not become low, it is suitable.
The content of the component (b) in the polymer electrolyte compound of the present invention is preferably 10 to 90 mol% with respect to the total amount of the components (a) to (d), and is preferably 20 to 80 mol%. It is more preferable that the content be 30 to 70 mol%. If the content is 10 mol% or more, the proton conductivity is not lowered, and if it is 90 mol% or less, the swelling with respect to water and methanol can be sufficiently suppressed.
The content of the component (c) in the polymer electrolyte compound of the present invention is preferably 9 to 89 mol% with respect to the total amount of the components (a) to (d), and 15 to 75 mol%. It is more preferable to set it as 20 to 60 mol%. If the content is 9 mol% or more, the synthesis of the polymer electrolyte compound is easy, and if it is 60 mol% or less, the proton conductivity is not lowered, which is preferable.
The content of the component (d) in the polymer electrolyte compound of the present invention is preferably 30 mol% or less, and preferably 20 mol% or less, based on the total amount of the components (a) to (d). More preferred is 5 mol% or less. If the content is 30 mol% or less, the proton conductivity is not lowered, which is preferable.

  Here, the number average molecular weight of the polyelectrolyte compound of the present invention is preferably, for example, 1,000 to 1,000,000, and from the viewpoint of the strength and workability of the molded body, 5,000 to 500,000. 000 is more preferable, and 10,000 to 200,000 is particularly preferable. A number average molecular weight of 1,000 or more is preferable because sufficient strength of the polymer electrolyte membrane obtained from the polymer electrolyte compound can be obtained. Moreover, since it will not become difficult if it is 1,000,000 or less, it is preferable.

(1-2-1-2) Introduction of Protic Acid Group The heterocyclic ring or aromatic ring having a structure represented by formulas (1) to (5) in the present invention has or can have a protonic acid group. . Examples of a method for introducing a protonic acid group into these heterocycles or aromatic rings include the following methods.
(i) A monomer compound having no proton acid group corresponding to each of the formulas (1) to (5) and a compound having a suitable proton acid group (protonating agent) are reacted in an organic solvent to produce the present invention. A method for obtaining a protonic acid group-containing monomer that can be used for the synthesis of a copolymer contained in the polyelectrolyte compound;
(ii) a method of synthesizing a protonic acid group-containing monomer using a protonating agent;
(iii) After synthesizing a copolymer having no proton acid group from a monomer compound having no proton acid group corresponding to each formula of (1) to (5), the obtained copolymer, a protonating agent, To introduce protonic acid groups into the copolymer.

(a) Protonic acid group Examples of the protonic acid group introduced into the monomer compound having no protonic acid group and the copolymer having no protonic acid group include functional groups that readily release protons. The protonic acid group used in the present invention is, for example, at least selected from the group consisting of a sulfonic acid group (—SO ₃ H), a carboxylic acid group (—COOH), and a phosphoric acid group (—PO ₃ H ₂ ). One or more types are included. A part of the sulfonic acid group, carboxylic acid group, and phosphoric acid group may be substituted with an alkyl group, sodium, potassium, calcium, or the like. The alkyl group and alkylene group contained in the acid group may contain 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.

(b) Protonating agent In order to introduce the protonic acid group such as a sulfonic acid group, a carboxylic acid group, and a phosphoric acid group into a monomer compound or copolymer having no protonic acid group, various known functional groups are used. A group introduction reaction can be used. For example, in order to introduce a sulfonic acid group into a heterocyclic ring or an aromatic ring having a structure represented by the formulas (1) to (5), a monomer compound and a copolymer having no proton acid group and an appropriate sulfone group are used. The agent may be reacted in an organic solvent. Such a sulfonating agent is not particularly limited, and examples thereof include concentrated sulfuric acid, fuming sulfuric acid, chlorosulfuric acid, and anhydrous sulfuric acid complex.

  Among them, as the sulfonating agent, the sulfonating agent described in Japanese Patent No. 2884189, namely 1,3,5-trimethylbenzene-2-sulfonic acid, 1,3,5-trimethylbenzene-2,4 -Disulfonic acid, 1,2,4-trimethylbenzene-5-sulfonic acid, 1,2,4-trimethylbenzene-3-sulfonic acid, 1,2,3-trimethylbenzene-4-sulfonic acid, 1,2, 3,4-tetramethylbenzene-5-sulfonic acid, 1,2,3,5-tetramethylbenzene-4-sulfonic acid, 1,2,4,5-tetramethylbenzene-3-sulfonic acid, 1,2 , 4,5-tetramethylbenzene-3,6-disulfonic acid, 1,2,3,4,5-pentamethylbenzene-6-sulfonic acid, 1,3,5-triethylbenzene-2-sulfone 1-ethyl-3,5-dimethylbenzene-2-sulfonic acid, 1-ethyl-3,5-dimethylbenzene-4-sulfonic acid, 1-ethyl-3,4-dimethylbenzene-6-sulfonic acid, 1 -Ethyl-2,5-dimethylbenzene-3-sulfonic acid, 1,2,3,4-tetraethylbenzene-5-sulfonic acid, 1,2,4,5-tetraethylbenzene-3-sulfonic acid, 1,2 , 3,4,5-pentaethylbenzene-6-sulfonic acid, 1,3,5-triisopropylbenzene-2-sulfonic acid, 1-propyl-3,5-dimethylbenzene-4-sulfonic acid, etc. Is possible.

  Among the sulfonating agents described above, compounds in which a lower alkyl is substituted at both ortho positions of the sulfonic acid group, for example, 1,3,5-trimethylbenzene-2-sulfonic acid, 1,2,4,5-tetra Methylbenzene-3-sulfonic acid, 1,2,3,5-tetramethylbenzene-4-sulfonic acid, 1,2,3,4,5-pentamethylbenzene-6-sulfonic acid, 1,3,5- Trimethylbenzene-2,4-disulfonic acid, 1,3,5-triethylbenzene-2-sulfonic acid, and the like are particularly preferable, and 1,3,5-trimethylbenzene-2-sulfonic acid is most preferable.

(c) Introduction of a protonic acid group As a method for introducing a protonic acid group into a monomer compound or copolymer having no protonic acid group, the above protonating agent is used and reaction conditions are selected according to the compound structure. Can be implemented.
For example, a monomer compound or copolymer having no proton acid group and a protonating agent are reacted in the presence of a catalyst in a reaction temperature range of −20 to 150 ° C. and a reaction time range of 0.5 to 50 hours. Thus, a sulfonic acid group can be introduced. If the reaction temperature is −20 ° C. or higher, the protonation reaction proceeds rapidly, and if the reaction temperature is 150 ° C. or lower, it is preferable because a protonic acid group can be introduced only into a specific aromatic ring.
Here, as the catalyst, alkali catalysts such as potassium carbonate, sodium carbonate, calcium carbonate, and cesium carbonate, and metal halides such as cesium fluoride can be used. The catalyst amount can be 0.1 to 100 times the total number of moles of monomers or copolymers to be reacted.

  The introduction of the protonic acid group may be performed in a solvent such as water and an organic solvent. The organic solvent is not particularly limited, and any conventionally known organic solvent can be used as long as it does not adversely affect the introduction of a protonic acid group. The organic solvent is not particularly limited, and any conventionally known organic solvent can be used as long as it does not adversely affect the sulfonation reaction. Specific examples include halogenated aliphatic hydrocarbons such as chloroform, dichloromethane, 1,2-dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and tetrachloroethylene, halogenated aromatic hydrocarbons such as dichlorobenzene and trichlorobenzene, N- Nitro compounds such as methylpyrrolidone, nitromethane and nitrobenzene, alkylbenzenes such as trimethylbenzene, tributylbenzene, tetramethylbenzene and pentamethylbenzene, heterocyclic compounds such as sulfolane, straight chain such as octane, decane and cyclohexane, Examples include branched or cyclic aliphatic saturated hydrocarbons, as well as acetone.

These solvents may be used alone or in combination of two or more, and the amount used is appropriately selected, but is usually in the range of 100 to 2000 parts by mass with respect to 100 parts by mass of the sulfonating agent. Preferably there is. When the amount of the solvent is 100 parts by mass or more, the protonation reaction can proceed uniformly. When the amount of the solvent is 2,000 parts by mass or less, separation of the solvent and the reagent after the reaction, It is preferable because recovery is easy.
When producing the protonic acid group-containing monomer of the present invention, these protonating agents are preferably added in the range of, for example, 30 to 5000 parts by mass, with respect to 100 parts by mass of the monomer, If it adds in the range, it is still more preferable. When the addition amount of the protonating agent is 30 parts by mass or more, the introduction of the protonic acid group is sufficiently performed, and when the addition amount of the protonating agent is 5000 parts by mass or less, the treatment with the protonating agent after the reaction is performed. Since it becomes easy, it is preferable.
Moreover, when producing the protonic acid group-containing copolymer of the present invention, it is preferable to add these protonating agents in the range of, for example, 1 to 20000 parts by mass with respect to 100 parts by mass of the copolymer. It is more preferable to add in the range of 5 to 10000 parts by mass. When the addition amount of the protonating agent is 1 part by mass or more, the introduction of the protonic acid group is sufficiently performed, and when the addition amount of the protonating agent is 20000 parts by mass or less, the treatment of the protonating agent after the reaction is performed. Since it becomes easy, it is preferable.

(1-2-1-3) Method for Producing Polyelectrolyte Compound In the present invention, (a) a structural unit having a heterocyclic ring, (b) a structural unit having an aromatic ring into which a protonic acid group is introduced, and (c) There is no particular limitation on the method of producing a copolymer by chemically bonding a structural unit having an aromatic ring and optionally (d) each precursor monomer of a structural unit other than the structural units (a) to (d) above. Instead, a known method suitable for each combination of structural units can be used.

(a) Monomer The polymer electrolyte compound comprising the structural units (a) to (d) of the present invention is, for example,
(M) a precursor monomer having two or more functional groups capable of substitution reaction;
(N) The precursor monomer can be synthesized by a condensation reaction with a precursor monomer having two or more functional groups capable of reacting.

  Examples of the precursor monomer having two or more substitution-reactive functional groups as component (m) are dihalogen, trihalogen or tetrahalogenated compounds. Examples of halogen include fluorine, chlorine, bromine and iodine. It is done. Examples of the dihalogenated compounds include compounds having a structure in which the terminal oxa group (—O—) of the structures of formulas (1) to (7) is changed to a direct bond and halogens are bonded to both terminals. These halogenated monomers may be the same halogenated monomer or different types of halogenated monomers.

The monomer (n) having two or more functional groups capable of undergoing substitution reaction that can react with the monomer (m) includes dihydroxy, trihydroxy or tetrahydroxy compounds; dithiophenol, trithiophenol or tetrathio Examples thereof include phenol compounds; diamino, triamino or tetraamino compounds; dimonosubstituted amino, trimonosubstituted amino or tetramonosubstituted amino compounds. Preferably, p-aminophenol is used. As an example of a dihydroxy compound, the compound of the structure which changed the oxa group (-O-) of the terminal of the structure of Formula (1)-(7) into the direct bond, and couple | bonded the hydroxyl group with the both terminal is mentioned, for example. .
These monomers (m) and (n) may be the same as or different from each other.

(b) Preparation of polyelectrolyte compound For the polymerization of the polyelectrolyte compound or hydrocarbon polymer, known polymerization methods such as condensation polymerization, addition polymerization, radical polymerization and ring-opening polymerization can be used. Although superposition | polymerization temperature is based also on the superposition | polymerization method, it is 0-350 degreeC, for example, Preferably it is 40-260 degreeC. The polymerization time is, for example, 2 to 500 hours although it depends on the polymerization method.
The polymerization can be carried out in a solvent in the presence of a catalyst. As the catalyst, alkali catalysts such as potassium carbonate, calcium carbonate and cesium carbonate and metal halides such as cesium fluoride can be used. The catalyst amount can be 0.1 to 100 times the total number of moles of monomers to be reacted.
As a reaction solvent, aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-methyl-2-pyrrolidone, hexamethylphosphonamide, methanol, ethanol, etc. However, the present invention is not limited to these alcohols. A plurality of these solvents may be used as a mixture within a possible range. The amount of the solvent can be used in a range of 0.01 to 2 times the total mass of the monomer and catalyst to be reacted.

The number average molecular weight of the obtained polymer electrolyte compound is, for example, 1,000 to 1,000,000, preferably 5,000 to 500,000, and more preferably 10,000 to 100,000. It is.
A number average molecular weight of 1,000 or more is preferable because sufficient strength of a polymer electrolyte compound into which a protonic acid group is introduced and a polymer electrolyte membrane obtained from the polymer can be obtained. Moreover, since it will not become difficult if it is 1,000,000 or less, it is preferable.

(c) Purification of polyelectrolyte compound As the polyelectrolyte compound purification method of the present invention, conventionally known purification methods can be suitably used. For example, the obtained polyelectrolyte containing a protonic acid group If the compound is in a solid state, it is washed with a solvent after filtration and dried.If the compound is in an oily state, it is separated, and if dissolved in the reaction solution, the organic solvent is removed by evaporation. Can be purified. In addition, water is added to the reaction solution containing the polymer electrolyte compound of the present invention, and if necessary, an alkali component is added and dissolved, and after separation into a solvent phase and an aqueous phase, acid precipitation, salting out, etc. from the aqueous phase It is also possible to purify by precipitation by the above method, washing with a solvent after filtration and drying.
In the case where the reaction is carried out only with a sulfonating agent such as concentrated sulfuric acid, it is also effective to precipitate the compound by pouring the reaction solution into water for recovery and purification.

(1-2-2) Other polymer compound The resin composition of the present invention may be a resin composition comprising only one type of the polymer electrolyte compound of the present invention. Two or more types of resin compositions may be used.
In addition, the resin composition of the present invention may be a resin composition comprising only the polymer electrolyte compound of the present invention, but other polymers having one or more different structures within a range that does not significantly deteriorate the characteristics. A compound (resin) may be contained.

  Specific examples of such other polymer compounds include polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl methacrylate (PMMA), ABS resin, AS resin, and other general-purpose resins, polyacetate (POM), polycarbonate (PC), polyamide (PA: nylon), engineering plastics such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and polyphenylene sulfide (PPS), polyethersulfone (PES), polyketone (PK) ), Polyimide (PI), polycyclohexanedimethanol terephthalate (PCT), polyarylate (PAR), and various liquid crystal polymers (LCP), epoxy resins, phenol resins, Rack resin thermosetting resins such as including but not limited to.

(1-2-3) Other Additives The resin composition of the present invention is, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, if necessary. Various additives such as an antistatic agent, an antibacterial agent, an antifoaming agent, a dispersant, and a polymerization inhibitor may be contained.

(1-2-4) Composition of Resin Composition In the resin composition of the present invention, the polymer electrolyte compound of the present invention is preferably 50% by mass to 100% by mass, more preferably 70% by mass of the entire resin composition. It is desirable to contain more than 100% by mass. If the content of the polymer compound of the present invention is 50% by mass or more of the entire resin composition, the acid group concentration in the resin composition of the polymer electrolyte membrane containing this resin composition can be sufficiently maintained, and good Proton conductivity is obtained. Moreover, the mobility of the ion to conduct can fully be maintained, without the unit containing an acid group becoming a discontinuous phase.
Further, the resin composition of the present invention preferably contains other polymer compound in an amount of preferably 50% by mass or less, more preferably 30% by mass or less, based on the entire resin composition. In the resin composition of the present invention, the ratio of the polymer compound of the present invention to the other polymer compound is, for example, 7: 3 to 8: 2, preferably 8: 2 to 9: 1. It is. Furthermore, the resin composition of the present invention preferably contains other additives, preferably 10% by mass or less, more preferably 5% by mass or less, based on the entire resin composition.

(1-3) Filling the resin composition into the voids and / or pores of the porous substrate The resin composition of the present invention is filled into the voids and / or pores of the porous substrate. This is a reinforced polymer electrolyte membrane. The method of filling the porous substrate with the resin composition of the present invention is not particularly limited.For example, (a) a method of polymerizing monomers in the pores of the porous substrate, and (b) a porous group Examples thereof include a method of introducing a resin composition into the pores of a porous substrate by impregnating a material with a solvent solution of the resin composition.
(a) The method of polymerizing the monomer in the pores of the porous substrate comprises the following steps:
(1) a step of holding a monomer for forming a resin composition in the pores of the porous substrate; and
(2) a step of polymerizing the monomer in the pores;
It is appropriate to include.
This polymerization method is preferable in that a part of the pores of the porous substrate of the present invention and a part of the resin composition can be reacted to form a crosslink. The obtained reinforced polymer electrolyte membrane can sufficiently suppress swelling and has reduced methanol permeability. Further, the resin composition held in the pores of the porous substrate does not elute to the outside of the pores, so that a long-life reinforced polymer electrolyte membrane can be produced. In particular, a part of the pores and a part of the aromatic hydrocarbon resin of the resin composition (polymer electrolyte compound), preferably an end part of the aromatic hydrocarbon resin, are cross-linked, and the aromatic hydrocarbon resin It is preferable to fix the proton conductive polymer composition containing s in the pores.

A specific reaction method first holds a monomer for forming the resin composition or the polymer electrolyte compound of the present invention in the pores. That is, a solution in which the monomer for forming the resin composition or the polymer electrolyte compound of the present invention is used as it is or in a solvent is prepared.
Here, as the monomer, the monomers described in the above (1-2-1-3) (a) can be used.
Examples of the solvent include aprotic polar solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, N-methyl-2-pyrrolidone, hexamethylphosphonamide, methanol, ethanol An appropriate alcohol can be selected from alcohols such as, but not limited to. A plurality of these solvents may be used as a mixture within a possible range.
The monomer is then polymerized in the pores. As the polymerization conditions, normal conditions for polymerizing the above monomers can be adopted. For example, after heat treatment at 60 to 200 ° C, preferably 80 to 180 ° C for 1 to 24 hours, preferably 2 to 12 hours, the temperature is further increased to 150 to 250 ° C, preferably 160 to 200 ° C higher than the above temperature. Warm and hold for an additional 8-64 hours, preferably 12-48 hours.

During the polymerization, it is preferable to seal the pores of the porous substrate. Sealing the pores means that the solvent inside the pores is prevented from scattering. By sealing, the solvent is less likely to be scattered, and the solvent is slowly removed over the time required for the polymerization. It becomes like this. In this sense, the sealing here does not mean a complete sealing in which the solvent does not scatter at all, and the scatter of the solvent is, for example, at least 70%, preferably 80% to 99.9%, more preferably, refers to a state in which 90 to 99% is suppressed. Sealing is performed by covering the both surfaces of the porous substrate with a resin film such as non-porous polyimide or a glass substrate.
After completion of the polymerization reaction, it is washed with water and vacuum-dried at 40 to 120 ° C., preferably 80 to 100 ° C. for 0.5 to 10 hours, preferably 1 to 5 hours to remove water, and the reinforced polymer electrolyte of the present invention. Get a membrane.
In addition, you may perform introduction | transduction of a proton acid group after superposition | polymerization in the pore of the said monomer, or after filling with a resin composition.

(b) A method of introducing a resin composition into pores of a porous substrate by impregnating a porous substrate with a solvent solution of the resin composition A method of impregnating a porous substrate with a solvent solution of a resin composition The following steps,
(1) introducing the resin composition into the pores of the porous substrate by immersing the porous substrate in a solvent solution of the resin composition; and
(2) A step of holding the porous substrate holding the resin composition at a temperature of 60 ° C. or higher for at least 1 hour;
It is appropriate to include.
Specifically, the porous substrate is first immersed in a solvent solution of the resin composition. Thereby, the resin composition is introduced into the pores of the porous substrate.
The obtained solvent solution contains the resin composition (nonvolatile content) in an amount of, for example, 5 to 40% by mass, preferably 10 to 30% by mass. As the solvent, for example, the same solvent as that used in the above method (a) can be used. In particular, by using acetone, impurities in the porous substrate and the solvent solution can be removed. This is preferable because it can be removed.
Furthermore, it is preferable to immerse the porous substrate while degassing under reduced pressure. In addition, a crosslinking agent may be added to crosslink part of the pores and part of the proton conductive polymer composition. In order to make it bridge | crosslink, it is preferable to use the aromatic hydrocarbon resin containing a bismaleimide, an epoxy group, and an acrylate as a resin composition.

Next, the porous substrate holding the resin composition is heat-treated. By this heat treatment, the resin composition is further introduced into the pores of the porous substrate, the solvent is removed, and the resin composition is filled (fixed / held) in the pores.
The heat treatment temperature is, for example, normal pressure and 60 ° C. to 200 ° C., preferably 80 ° C. to 180 ° C. The heat treatment time is suitably at least 1 hour, for example, 1 to 36 hours, preferably 1 to 30 hours, more preferably 2 hours to 24 hours. By setting the temperature to 60 ° C. or higher, the proton conductive polymer composition can be promptly introduced and fixed in the pores of the porous substrate. Further, if it is 1 hour or longer, the proton-conductive polymer composition will sufficiently penetrate into the pores, and if it is 36 hours or shorter, the porous substrate will not be thermally decomposed.
Then, for example, it is dried at 50 to 200 ° C., preferably 60 to 150 ° C. for 3 to 30 minutes, more preferably 5 to 10 minutes, and the solvent is removed to obtain the reinforced polymer electrolyte of the present invention.
During the heat treatment, the pores of the porous substrate are preferably sealed in the same manner as in the step (a).
In addition, you may introduce | transduce a proton acid group after filling with a resin composition.

In the present invention, in order to fill the porous substrate and the resin composition of the present invention with higher fillability, it is preferable to impregnate while degassing under reduced pressure. For example, the heat treatment may be performed at 0.1 to 70 Pa, preferably 0.1 to 30 Pa, 5 to 50 ° C., preferably 10 to 40 ° C., more preferably room temperature (25 ° C.).
Moreover, when filling the resin composition of this invention in a porous base material, you may insert a crosslinking agent as needed and may bridge | crosslink a part of said pore and a part of resin composition.
The film-like material obtained as described above is introduced as necessary by introducing a desired cation exchange group by a known treatment such as sulfonation, chlorosulfonation, phosphoniumation, hydrolysis, etc. A cation exchange resin membrane can be obtained.

(1-4) Properties of Reinforced Polymer Electrolyte Membrane Reinforced polymer electrolyte membrane of the present invention obtained by filling the voids and / or pores of the porous substrate with the resin composition of the present invention as described above. The film thickness can be set to an arbitrary film thickness depending on the purpose, but is preferably as thin as possible from the viewpoint of proton conductivity. Specifically, the dry film thickness is preferably 5 to 200 μm, more preferably 20 to 150 μm, and most preferably 40 to 100 μm. If the thickness of the polymer electrolyte membrane is 5 μm or less, handling of the reinforced polymer electrolyte membrane is easy, and there is a tendency that short circuit or the like does not easily occur when a fuel cell is manufactured. The electric power generation performance of the fuel cell can be sufficiently exhibited without the electric resistance value of the molecular electrolyte membrane becoming too high.
The proton conductivity of the reinforced polymer electrolyte membrane of the present invention is preferably 0.08 S / cm or more. When the proton conductivity is 0.08 S / cm or more, a good output tends to be obtained in a fuel cell using the reinforced polymer electrolyte membrane of the present invention.

(1-5) Configuration of Reinforced Polymer Electrolyte Membrane The reinforced polymer electrolyte membrane of the present invention obtained as described above may be a single layer or a laminate of two or more layers. Specifically, the same or different types of reinforced polymer electrolyte membranes of the present invention or other polymer electrolyte membranes may be laminated to form a multilayer reinforced polymer electrolyte membrane in which two or more types are laminated. Further, it may be a multilayer reinforced polymer electrolyte membrane including at least one reinforced polymer electrolyte membrane of the present invention. For example, the reinforced polymer electrolyte membrane according to the present invention may be formed by laminating a known fluorine-based polymer electrolyte membrane such as “Nafion (registered trademark)” or “Flemion (registered trademark)” on one side or both sides of the present invention. A polymer electrolyte membrane produced by laminating different types of polymer electrolyte membranes produced within the range of the above, and a polymer electrolyte membrane obtained by thinning the resin composition of the present invention without using a porous substrate and the present invention And a multi-layered laminate of the reinforced polymer electrolyte membrane. There are no particular restrictions on the multilayer structure in these multilayers, and it is sufficient that at least one type of the reinforced polymer electrolyte membrane of the present invention is included. In the laminated structure, it is preferable that they are in adhesive contact with each other so that there is no gap as an electrically nonconductive portion between adjacent layers. If there are independent gaps between the layers, the portion may cause an increase in the electric resistance of the battery. The thickness of the multilayer reinforced polymer electrolyte membrane is 5.0 to 200 μm, preferably 1.0 to 150 μm. If the thickness is 5 μm or more, handling of the multilayer reinforced polymer electrolyte membrane is easy, and there is a tendency that short circuit or the like does not easily occur when a fuel cell is manufactured. The electric resistance value of the reinforced polymer electrolyte membrane does not become too high, and the power generation performance of the fuel cell can be sufficiently exhibited.

When different types of reinforced polymer electrolyte membranes produced within the scope of the present invention are laminated to form a multilayer, the difference between the ion exchange capacity of at least one polymer electrolyte membrane and the ion exchange capacity of other polymer electrolyte membranes Is preferably 0.01 to 4.0 meq./g. Moreover, it is preferable that the ion exchange capacity of the polymer electrolyte membrane is 4.5 meq./g at the maximum.
The ion exchange capacity of the reinforced polymer electrolyte membrane of the present invention is preferably 0.03 to 4.5 meq./g. If it is 0.03 meq./g or more, the electric resistance of the battery does not increase excessively, and if it is 4.5 meq./g or less, it is preferable because sufficient mechanical strength of the polymer electrolyte membrane can be maintained.

(2) Electrode-Polymer Electrolyte Membrane Assembly The electrode-polymer electrolyte membrane assembly of the present invention is one or more of the above-mentioned reinforced polymer electrolyte membranes or the reinforced polymer electrolyte membrane of the present invention and other polymer electrolyte membranes. (Hereinafter, these membranes are simply referred to as polymer electrolyte membranes) and electrodes provided on at least one side of the polymer electrolyte membrane, usually both sides of the polymer electrolyte membrane.
(2-1) Electrode The electrode of the present invention has a gas diffusion layer and a catalyst layer provided on and / or in the gas diffusion layer.
(2-1-1) Gas Diffusion Layer As the gas diffusion layer, for example, a known substrate having air permeability such as carbon fiber woven fabric or carbon paper can be used. Preferably, those substrates and the like that have been subjected to water repellent treatment are used. The water-repellent treatment is performed, for example, by immersing these substrates in an aqueous solution of a water-repellent agent made of a fluororesin such as polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, drying, and firing. Done.

(2-1-2) Catalyst layer As the catalyst material used in the catalyst layer, for example, platinum group metals such as platinum, rhodium, ruthenium, iridium, palladium, osnium and alloys thereof are suitable. These catalytic materials and salts of the catalytic materials may be used alone or in combination. Among them, metal salts and complexes, particularly ammine complexes represented by [Pt (NH ₃ ) ₄ ] X ₂ or [Pt (NH ₃ ) ₆ ] X ₄ (X is a monovalent anion) are preferable. Moreover, when using a metal compound as a catalyst, the mixture of several compounds may be used and double salt may be sufficient. For example, by using a mixture of a platinum compound and a ruthenium compound, formation of a platinum-ruthenium alloy can be expected by a reduction process.
The particle size of the catalyst is not particularly limited, but it is preferable that the average particle size is 0.5 to 20 nm from the viewpoint of an appropriate size that increases the catalyst activity. In addition, in a study by K. Kinoshita et al. (J. Electrochem. Soc., 137, 845 (1990)), it is reported that the particle size of platinum having a high activity with respect to oxygen reduction is about 3 nm.
A cocatalyst can be further added to the catalyst used in the present invention. Examples of the cocatalyst include finely divided carbon. The finely divided carbon is preferably one in which the coexisting catalyst exhibits high activity.For example, when a platinum group metal compound is used as the catalyst, acetylene black such as Denka Black, Valcan XC-72, and Black Pearl 2000 is used. Is appropriate.
The amount of the catalyst varies depending on the deposition method and the like, but is deposited on the surface of the gas diffusion layer in the range of, for example, about 0.02 to about 20 mg / cm ² , preferably about 0.02 to about 20 mg / cm ^2. It is appropriate. Moreover, it is appropriate that it exists in the quantity of 0.01-10 mass% with respect to the total amount of an electrode, for example, Preferably, it is 0.3-5 mass%.

(2-1-3) Binder The electrode of the present invention preferably has a binder in and / or on the surface of the electrode. Such a binder promotes the bond between the gas diffusion layer and the catalyst layer and the bond between the electrode and the polymer electrolyte membrane. As the binder, for example, all polymers that can be used in the present invention, and fluorine-based solid polymer electrolytes such as Nafion (R) and Flemion (R) can be used.
(2-1-4) Properties of electrode The obtained electrode is porous. The average pore diameter of the electrode is, for example, 0.01 to 50 μm, preferably 0.1 to 40 μm. Furthermore, the porosity of the electrode is, for example, 10 to 99%, preferably 10 to 60%.

(2-2) Production of Electrode-Polymer Electrolyte Membrane Assembly The electrode-polymer electrolyte membrane assembly of the present invention is produced by providing the above electrode on a polymer electrolyte membrane. Preferably, the catalyst layer side of the electrode is joined to the polymer electrolyte membrane side. Examples of the method for producing the electrode-polymer electrolyte membrane assembly include the following three methods.
(1) A method of directly forming a catalyst layer on a polymer electrolyte membrane to form a catalyst layer and further forming a gas diffusion layer on the formed catalyst layer. For example, a perfluorocarbon polymer having an ion exchange group, a platinum group catalyst, a finely powdered carbon (carbon black) or other catalytic material containing an additive on the polymer electrolyte membrane by a method described in JP-T-2000-516014, There is a method in which a catalyst layer is formed by spraying, printing or the like, and a gas diffusion layer is heat-pressed on the catalyst layer by hot pressing or the like.
(2) A method of forming a catalyst layer by previously applying a catalyst material on a substrate, transferring the obtained catalyst layer onto a polymer electrolyte membrane, and forming a gas diffusion layer on the formed catalyst layer. For example, polytetrafluoroethylene in advance and platinum black synthesized by the Thomas method, etc., are uniformly mixed, applied onto a Teflon (registered trademark) sheet substrate, press-molded, and then transferred onto a polymer electrolyte membrane. Further, there is a method in which a gas diffusion layer is further disposed and the obtained laminate is pressure-bonded.
(3) A method in which an electrode is prepared in advance by immersing the gas diffusion layer in a solution of a catalyst substance and the obtained electrode is provided on the polymer electrolyte membrane. For example, the gas diffusion layer is immersed in a solution (paste) of a soluble platinum group salt to adsorb (ion exchange) the soluble platinum group salt on and in the gas diffusion layer. Next, there is a method in which a metal serving as a catalyst is deposited on a gas diffusion layer by dipping in a reducing agent solution such as hydrazine or Na ₂ BO ₄ .

A more preferable method for producing an electrode-polymer electrolyte membrane assembly of the present invention includes a method in which an electrode material containing a catalyst substance and a gas diffusion layer material is directly applied on the polymer electrolyte membrane. Specifically, catalyst-supporting carbon particles supporting a catalyst material such as platinum-ruthenium (Pt-Ru) platinum (Pt) are used as the catalyst material, and the catalyst material is used as a solvent such as water, a solid polymer electrolyte. And a water repellent such as polytetrafluoroethylene (PTFE) particles optionally used in the manufacture of the gas diffusion layer to make a paste. This paste is directly applied or sprayed onto the polymer electrolyte membrane of the present invention to form a film, and then heated and dried to form a catalyst layer (one of the gas diffusion layer when a water repellent is included) on the polymer electrolyte. Part of the water-repellent layer). On this catalyst layer, a gas diffusion layer such as carbon paper optionally treated with water repellency is hot-pressed to produce an electrode.
The thickness of the catalyst layer at this time is, for example, 0.1 to 1000 μm, preferably 1 to 500 μm.

  As for the said paste, it is desirable to adjust the viscosity to the range of 0.1-1000 Pa * S. This viscosity can either (i) select each particle size, (ii) adjust the composition of the catalyst particles and binder, (iii) adjust the water content, or (iv) The viscosity can be adjusted preferably by adding viscosity modifiers such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose and cellulose, and polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, sodium polyacrylate and polymethyl vinyl ether.

(3) Fuel cell The fuel cell of the present invention uses the electrode-polymer electrolyte membrane assembly. Examples of the fuel cell of the present invention include a solid polymer type (PEFC) and a direct methanol supply type fuel cell (DMFC).
The method for producing a fuel cell of the present invention includes a step of obtaining the electrode-polymer electrolyte membrane assembly by disposing the polymer electrolyte membrane between two electrodes.
Specifically, for example, a catalyst layer is attached on each surface of the polymer electrolyte membrane of the present invention, and further, an anode electrode and a cathode are further formed on each surface of the electrode-polymer electrolyte membrane assembly provided with a gas diffusion layer. Two electrode plates of electrodes are arranged or sandwiched, and a fuel chamber capable of holding normal pressure or pressurized hydrogen gas, pressurized methanol gas or aqueous methanol solution is arranged on one surface of the obtained laminate, A fuel cell is fabricated by disposing a gas chamber capable of holding atmospheric or pressurized oxygen or air on the other surface of the laminate. The fuel cell produced in this way takes out electrical energy generated by the reaction of hydrogen or methanol and oxygen.
Moreover, in order to take out required electric power, you may arrange | position many units in series or in parallel by setting this electrode-polymer electrolyte membrane assembly or laminated body as one unit.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

<Synthesis of (a) component precursor monomer having a heterocyclic ring>
Hereinafter, synthesis of a precursor monomer which is a structural unit having a heterocyclic ring as the component (a) will be described. In addition, the measuring method used for the detection of the obtained compound is as the following (1)-(5).
(1) Measurement of thermal mass reduction For measurement of thermal mass reduction, TG / DTA SII EXTAR-6300 manufactured by SEIKO was used. A sample of 10 to 20 mg was weighed and heated from room temperature to 500 ° C. at a rate of temperature increase of 10 ° C./min in air, and the temperature when 5% by mass decreased was determined.
(2) NMR spectrum measurement
AC400P manufactured by BRUKER was used for measurement of ¹ H-NMR spectrum and ¹³ C-NMR spectrum. The sample concentration was 5 to 10 mg / ml, and tetramethylsilane (TMS) was used.
(3) IR spectrum measurement
FT-IR JASCO7300 manufactured by JASCO Corporation was used for IR spectrum measurement. The sample was ground together with KBr, molded into a disk shape and measured.
(4) Elemental analysis For elemental analysis, a yanaco CHN CORDER MT-5 type manufactured by Yanagimoto Seisakusho was used.
(5) Melting point measurement MEL-TEMP II manufactured by Lavo DEVICES was used for melting point measurement.

[Synthesis Example 1] Synthesis of 6,6'-oxy-bis (2- (4-fluorophenyl) -4-phenylquinoline 5.9 g of 6-fluoronitrobenzene, 5.84 g of 4-nitrophenol, and potassium fluoride 5. 2 g was dissolved in 200 ml of dimethyl sulfoxide, the temperature was raised to 180 ° C., and the mixture was stirred for 30 minutes, and after cooling to room temperature, the reaction solution was added to 100 ml of distilled water, and the deposited precipitate was filtered and sufficiently washed with distilled water. After washing, the crystals were dried under reduced pressure for 12 hours to obtain 4,4′-dinitrodiphenyl ether as yellow crystals, followed by dissolving 15 g of sodium hydroxide in 80 g of methanol and stirring at 25 ° C. for 2 hours. To this solution, 9.6 g of 4,4′-dinitrodiphenyl ether obtained earlier was gradually added and stirred at 70 ° C. for 6 hours. After cooling the reaction solution to room temperature, 70 g of methanol was added, the deposited precipitate was filtered, and the solid obtained was recrystallized from toluene to give brown crystals of 5,5′-oxybis (3-phenyl- 2,1-benzoisoxazole) 3.5 g of 5,5′-oxybis (3-phenyl-2,1-benzisoxazole) obtained, 0.3 g of palladium-carbon, 1 g of triethylamine and 30 g of tetrahydrofuran Was put in an autoclave and heated to 70 ° C., and hydrogen gas was added up to 20 kg / m ^{2. The} reaction solution was cooled and filtered, the filtrate was evaporated under reduced pressure, and the remaining solid was recrystallized from toluene. As a result, 2 g of the yellow crystal obtained, 1.4 g of 4-fluoroacetophenone and 0.04 g of p-toluenesulfonic acid were mixed with xylene 50. The mixture was dissolved in 1 and stirred for 6 hours after raising the temperature to 140 ° C. After cooling to room temperature, the reaction solution was washed with 0.1N aqueous sodium hydroxide solution, and then the xylene phase was evaporated under reduced pressure. The remaining solid was recrystallized from toluene to obtain 6,6′-oxy-bis (2- (4-fluorophenyl) -4-phenylquinoline yellow crystals, which were the target product.

[Synthesis Example 2] Synthesis of 6-phenoxy-2,3,5-triazine-2,4-dichloride 3.9 g of 2,4,6-trichloro-1,3,5-triazine and 0.34 g of tetrabutylammonium bromide Was dissolved in 40 ml of acetone and cooled to 0-5 ° C. A solution prepared by dissolving 2 g of phenol in 10 ml of acetone was gradually added dropwise while maintaining the temperature at 0 to 5 ° C. and stirred for 1 hour. To this solution, a 10 ml aqueous solution of 1.25 g of sodium carbonate was gradually added while maintaining 0 to 10 ° C. so that the pH of the reaction solution was maintained at 7 to 8. After stirring for 2 hours, this solution was added to 200 ml of ice water, and the deposited precipitate was filtered, washed thoroughly with distilled water, and then dried under reduced pressure at room temperature for 12 hours to give 6-phenoxy-2,3,5-triazine. A white solid of -2,4-dichloride was obtained.
[Synthesis Example 3] Synthesis of 6-anilino-1,3,5-triazine-2,4-dichloride A stirrer, cyanuric chloride (55.31 g, 0.3 mol) and THF (150 mL) were placed in a three-flask (500 mL). Then, a thermometer, a dropping funnel with a side tube (100 mL) and a calcium chloride tube were attached and stirred to completely dissolve cyanuric chloride, and then cooled to 0 ° C. to 5 ° C. on an ice bath.
Aniline (27.94 g, 0.3 mol) was placed in a beaker, and THF (80 ml) was added to this and stirred to dissolve. This solution was transferred to a dropping funnel and slowly dropped with care so that the reaction temperature did not exceed 5 ° C. After dropping, the mixture was stirred at a reaction temperature of 0 to 5 ° C. for 2 hours.
Next, sodium carbonate (19.94 g, 0.15 mol) was placed in a beaker, and distilled water (90 ml) was added to the beaker and stirred until completely dissolved. This solution was transferred to a dropping funnel and slowly dropped while taking care that the reaction temperature did not exceed 5 ° C. to neutralize the by-product hydrochloride. After dropping, the mixture was stirred at 0 to 5 ° C. for 1 hour. If the reaction solution was acidic at this point, an aqueous sodium carbonate solution was added until neutrality, and the mixture was further stirred for 1 hour.
The reaction solution was transferred to a mold flask, THF was removed with an evaporator, and the solid was dissolved in chloroform and transferred to a separatory funnel. After the organic layer and the aqueous layer were separated, the organic layer was transferred to an Erlenmeyer flask containing a stirrer, and anhydrous sodium sulfate was added thereto and stirred overnight to dehydrate. After removing anhydrous sodium sulfate by filtration, chloroform was distilled off with an evaporator to obtain a yellow crude product.
This was recrystallized (hexane / toluene, twice), and then purified by sublimation (113 ° C./27 Pa (0.2 Torr)) with a sublimation apparatus to give 6-anilino-1,3,5-triazine-2,4-dichloride. Got.
Shape: Light yellow crystals Yield: 70% Yield: 50.63 g Melting point: 133 ° C
¹ H-NMR spectrum 400 MHz [CDCI ₃ , TMS]: δ = 7.22 (t, 1H), 7.41 (t, 2H), 7.73 (d, 2H), 9.86 (s, 1H); ¹³ C-NMR spectrum 101 MHz [ CDCI ₃ , TMS]: δ = 122.4, 126.0, 129.7, 137.9, 165.3, 170.5, 171.4; FT-IR spectrum KBr (cm ⁻¹ ): 3371 (N−H), 1604 (arom. C = C) , 1553 (triazine C = N), 1173 (triazine C-N); Elemental Anals [C ₉ H ₆ Cl ₂ N ₄ (241.08)]: Calcd. For C 44.84, H 2.51, N 23.24; Found C 44.96, H 2.62, N 23.46

Synthesis Example 4 Synthesis of 6- (N-methylanilino) -1,3,5-triazine-2,4-dichloride Except that N-methylaniline (32.15 g, 0.3 mol) was used instead of aniline, All in the same manner as in Synthesis Example 2, 6- (N-methylanilino) -1,3,5-triazine-2,4-dichloride was obtained.
Shape: Pale yellow needles Yield: 73% Yield: 56.9 g Melting point: 136 ° C
¹ H-NMR spectrum 400 MHz [CDCI ₃ , TMS]: δ = 3.54 (s, 3H), 7.25 (d, 2H), 7.35 <t, 1H>, 7.45 (t, 2H); ¹³ C-NMR spectrum 101 MHz [ CDCI ₃ , TMS]: δ = 39.2, 126.0, 127.8, 129.5, 142.0, 166.1, 169.9, 170.4; Elemental Analysis [C ₁₀ H ₈ Cl ₂ N ₄ (255.10)]: Calcd. For C 47.08, H 3.16, N 21.96; Found C 47.26, H 3.26, N 22.18
[Synthesis Example 5] Synthesis of 2,4-bis (4 monohydroxyanilino) -6-anilino-1,3,5-triazine In a three-flask (300 ml), a stirrer, 5.457 g (50 mmol) of p-aminophenol, N-methylpyrrolidone (80 ml) was added, a connecting tube and a ball-containing cooling tube were attached, and the mixture was stirred and dissolved completely under a nitrogen stream. Thereafter, 6.028 g (25 mmol) of 6-anilino-1,3,5-triazine-2,4-dichloride synthesized in Synthesis Example 2 was added and stirred at 100 ° C. for 24 hours.
After the reaction was completed, in order to neutralize by-produced HCl, an aqueous sodium hydroxide solution was added to make it alkaline, and then a slight insoluble matter was filtered off. The filtrate was poured into 2 L of distilled water, neutralized with dilute hydrochloric acid, and further made weakly acidic (pH = 5-6). The generated precipitate was filtered, washed with water, and then dried under reduced pressure (100 ° C., 12 hours, 1 torr) to obtain a crude product. This was recrystallized (methanol / water) and dried under reduced pressure (100 ° C., 12 hours, 1 torr) to give 2,4-bis (4-hydroxyanilino) -6-anilino-1,3,5-triazine. Got.
Shape: White needle crystal Yield: 4.31 g Yield: 45% Melting point: 217 ° C
¹ H-NMR spectrum 400 MHz [Acetpne-d6, TMS]: δ = 6.78 (d, 4H), 6.97 (t, 1H), 7.25 (t, 2H), 7.54 (d, 4H), 7.79 (t, 2H) , 8.05 (s, 2H), 8.27 (s, 2H), 8.42 (s, 1H); ¹³ C-NMR spectrum 101 MHz [Acetpne-d6, TMS]: δ = 115.7, 120.9, 122.7, 123.4, 129.1, 132.8, 141.1, 153.9, 165.5, 165.6; FT-IR spectrum KBr (cm ^-1 ): 3411, 3324 (OH), 3253, 3030 (NH), 1608 (arom. C = C), 1578 (triazine C = N ), 1168 (triazine C-N), 833 (arom. CH); Elemental Analyzes [C ₂₁ H ₁₈ NO ₂ (386.41)]: Calcd. For C 65.25, H 4.70, N 21.75; Found C 65.22, H 4.74, N 21.61

Synthesis Example 6 Synthesis of 2,4-bis (N-methyl-4-hydroxyanilino) -6-anilino-1,3,5-triazine
Instead of p-aminophenol, 6.158 g (50 mmol) of N-methyl-p-aminophenol was used. In addition, 2,4-bis (N-methyl-4-hydroxyanilino) -6-anilino- was used in the same manner as in Synthesis Example 4 except that the reaction time was 12 hours and the recrystallization solvent was chloroform / hexane. 1,3,5-Triazine was obtained.
Shape: Pink solid Melting point: Yield: 4.6 g Yield: 45% Melting point: 207.5-208 ° C
¹ H-NMR spectrum 400 MHz [DMSO-d6, TMS]: δ = 3.40 (s, 3H), 3.34 (s, 3H), 6.78-6.83 (m, 5H), 7.02 (s (br.), 2H ), 7.06 (d, 4H), 7.53 (s (bT.), 2H), 8.87 (s, 1H), 9.39 (s, 2H); ¹³ C-NMR spectrum 101 MHz [DMSO-d6, TMS]: δ = 37.5, 115.1, 119.2, 120.9, 127.9, 136.0, 140.4, 155.1, 165.2; FT-IR spectrum KBr (cm ⁻¹ ): 3384 (N−H), 1531 (triazine C = N), 1391 (Ph− N), 1232 (CN)

Synthesis Example 7 Synthesis of 2,4-bis (4-hydroxyanilino) -6- (N-methylanilino) -1,3,5-triazine
Instead of 6-anilino-1,3,5-triazine-2,4-dichloride, 6.378 g of 6- (N-methylanilino) -1,3,5-triazine-2,4-dichloride synthesized in Synthesis Example 3 (25 mmol) was used. In addition, 2,4-bis (4-hydroxyanilino) -6- (N-methylanilino)-was used in the same manner as in Synthesis Example 4 except that the reaction time was 12 hours and the recrystallization solvent was tetrahydrofuran / hexane. 1,3,5-Triazine was obtained.
Shape: Melting point of pink solid Yield: 4.3 g Yield: 43% Melting point: 245.7-245.8 ° C
¹ H-NMR spectrum 400 MHz [DMSO-d6, TMS]: δ = 3.44 (s, 3H), 6.59 (s, 4H), 7.25 (t, 1H), 7.34-7.44 (m, 8H), 8.75 (s, 2H), 8.98 (s, 2H); ¹³ C-NMR spectrum 101 MHz [DMSO-d6, TMS]: δ = 37.4, 114.6, 121.6, 125.3, 127.0, 128.6, 131.7, 133.9, 144.9, 152.2, 163.7, 165.4; FT-IR spectrum KBr (cm ^-1 ): 3275 (NH), 1492 (C = C), 1551 (triazine C = N), 1166 (triazine C-N)

[Synthesis Example 8] Synthesis of 2,4-bis (N-methyl-4-hydroxyanilino) -6- (N-methylanilino) -1,3,5-triazine
6.158 g (50 mmol) of N-methyl-p-aminophenol instead of p-aminophenol, 6-synthesized in Synthesis Example 3 instead of 6-anilino-1,3,5-triazine-2,4-dichloride (N-methylanilino) -1,3,5-triazine-2,4-dichloride 6.378 g (25 mmol) was used. Further, 2,4-bis (N-methyl-4-hydroxyanilino) -6- (N was used in the same manner as in Synthesis Example 4 except that the reaction time was 12 hours and the recrystallization solvent was chloroform / hexane. -Methylanilino) -1,3,5-triazine was obtained.
Shape: Pink solid Melting point: Yield: 7.49 g Yield: 70% Melting point: 245.3-246.0 ° C
¹ H-NMR spectrum 400 MHz [DMSO-d6, TMS]: δ = 3.28 (d, 6H), 3.86 <8, 3H>, 6.69 (d, 4H), 7.08 (d, 5H), 7.22-7.30 (m , 4H), 9.27 (s, 2H); ¹³ C-NMR spectrum 101 MHz [DMSO-d6, TMS]: δ = 36.6, 37.1, 114.6, 125.7, 125.7, 127.2, 127.8, 135.8, 144.3, 154.5; Analsis [C ₂₄ H ₂₄ N ₆ O ₂ (428.49)]: Calcd. For C 67.27, H 5.65, N 19.61; Found C 67.24, H 5.88, N 19.64

Synthesis Example 9 Synthesis of 2,4-bis (4-hydroxyanilino) -6- (4- (4-hydroxysulfonyl) anilino-1,3,5-triazine 2,4,6-trichloro-1, 3.7 g of 3,5-triazine is dissolved in 10 ml of acetone, sufficiently stirred with a vibration mixer, and then poured into 20 ml of ice water, and the resulting slurry is added with a 20 ml aqueous solution of 3.5 g of sulfanilic acid and 1.1 g of sodium carbonate. Was added under ice cooling (about 0 ° C.) A 5 ml aqueous solution of 1.1 g of sodium carbonate was gradually added so as to keep the pH of the reaction solution at 7 to 8. This was filtered, washed thoroughly with distilled water, washed with 10 ml of acetone and dried under reduced pressure for 12 hours at room temperature.3 g of this compound and 1.91 g of p-aminophenol were dissolved in 10 ml of N-methylpyrrolidone, and the temperature was adjusted. 10 After stirring at 12 ° C. for 12 hours, N-methylpyrrolidone was distilled off under reduced pressure, and the remaining solid was recrystallized from hot water to give 2,4-bis (4-hydroxyanilino) -6- (A white powder of 4- (4-hydroxysulfonyl) anilino-1,3,5-triazine was obtained.

<Synthesis of Polymer Electrolyte Compounds (A) to (L)>
(A) The precursor monomers of Synthesis Examples 1 to 9 are used as the precursor monomer of the structural unit having a heterocyclic ring, and (b) the precursor monomer of the structural unit having an aromatic ring into which a protonic acid group is introduced is 4, 4'-dichlorodiphenylsulfone-3,3'-disulfonic acid sodium salt monohydrate is used, and (c) 4,4'-dichlorodiphenylsulfone as a precursor monomer of a structural unit having an aromatic ring, -Dihydroxydiphenylsulfone and dihydroxydiphenylsulfone were used.
20 ml of N-methylpyrrolidone as a solvent was added to a 50 ml four-necked round bottom flask equipped with a Dean-Stark trap, a condenser, a stirrer, and a nitrogen supply pipe, and the respective formulations (a) to (c) shown in Table 1 were added. In addition, potassium carbonate was added as a catalyst, heated to 100 ° C., 20 ml of toluene was added, heated to 160 ° C. and refluxed for 4 hours to distill off the toluene. The temperature was raised to 180 ° C. and stirred for 72 hours. After cooling, the solution was poured into 250 ml of 10% aqueous sulfuric acid solution and stirred for 1 hour, and then the solution was poured into distilled water to precipitate the compound, the precipitate was filtered, washed thoroughly with distilled water, and then at room temperature. The target polymer electrolyte compounds (A) to (L) were obtained by drying under reduced pressure for 12 hours.

[Production of polymer electrolyte membrane]
<Example 1>
3 g of the polymer electrolyte compound (C) was dissolved in 27 g of N-methylpyrrolidone as a solvent to prepare a solvent solution (nonvolatile content 10% by mass) of the polymer electrolyte compound (C). Moreover, the polyester nonwoven fabric base material (The Asahi Kasei Co., Ltd. make, EH-5035, thickness 45 micrometers) was prepared as a porous base material. This polyester nonwoven fabric substrate is immersed in a solvent solution of the above-mentioned polymer electrolyte compound (C) and allowed to stand at room temperature in a vacuum (0.5 Pa) for 30 minutes, and the polymer electrolyte compound (C) is placed in the voids of the polyester nonwoven fabric substrate. Filled. Thereafter, the excess polymer electrolyte compound (C) was removed by a suspension method, and the solvent was removed by drying for 1 hour in a dryer (750 ° C.) to obtain a reinforced polymer electrolyte membrane C having a thickness of about 80 μm. .

<Example 2>
A reinforced polymer electrolyte membrane E was produced in the same manner as in Example 1 except that the polymer electrolyte compound (E) was used instead of the polymer electrolyte compound (C).
<Example 3>
A reinforced polymer electrolyte membrane G was produced in the same manner as in Example 1 except that the polymer electrolyte compound (G) was used instead of the polymer electrolyte compound (C).
<Example 4>
A reinforced polymer electrolyte membrane I was produced in the same manner as in Example 1 except that the polymer electrolyte compound (I) was used instead of the polymer electrolyte compound (C).

<Example 5>
9 g of the polymer electrolyte compound (D) was dissolved in 21 g of N-methylpyrrolidone as a solvent to prepare a solvent solution (non-volatile content 30% by mass) of the polymer electrolyte compound (D). After casting this solvent solution on both surfaces of the reinforced polymer electrolyte membrane C obtained in Example 1, the solvent is distilled off by drying with a dryer (150 ° C.) for 1 hour to polymer electrolyte membrane D. A multilayer reinforced polymer electrolyte membrane M having a thickness of about 120 μm was obtained by laminating the reinforced polymer electrolyte membrane C as in D-C-D.
<Example 6>
9 g of the polymer electrolyte compound (H) was dissolved in 21 g of N-methylpyrrolidone as a solvent to prepare a solvent solution (non-volatile content 30% by mass) of the polymer electrolyte compound (H). After casting this solvent solution on one side of the reinforced polymer electrolyte membrane G obtained in Example 3, the solvent was distilled off by drying for 1 hour in a dryer (150 ° C.) to obtain a thickness of about 100 μm. A multilayer polymer electrolyte membrane N having a thickness of about 120 μm was obtained by laminating the polymer electrolyte membrane H and the reinforced polymer electrolyte membrane G like HG.

<Comparative Example 1>
A reference polymer electrolyte membrane 1 was produced in the same manner as in Example 1 except that the polymer electrolyte compound (L) was used instead of the polymer electrolyte compound (C).
<Comparative Example 2>
A reference polymer electrolyte membrane 2 having a thickness of about 50 μm was obtained using “Nafion (registered trademark) 112”.

<Measurement method and evaluation method>
(1) Evaluation of swelling ratio with respect to water and methanol The swelling ratio is 1 to 60 ° C. water or 25 ° C. methanol / polymer electrolyte membranes of 50 to 150 μm thickness cut into 2 cm × 2 cm. It was immersed for a period of time, and the area change before and after that was determined from the following formula. As for the area after immersion, the surface of the electrolyte membrane was lightly wiped with a paper towel, an image of what was sandwiched between two transparent glass plates was captured with a scanner, and the number of pixels in the membrane portion was counted by image analysis.
λ (area%) = {(p−p ₀ ) / p} × 100
λ: swelling rate (area%)
p ₀ : number of pixels of the polymer electrolyte membrane before swelling
p: Number of pixels of the polymer electrolyte membrane after swelling If the swelling rate is 5% or less, preferably 2% or less, it can be said that there is good swelling resistance.

(2) Evaluation of methanol permeability Methanol permeability was evaluated using the cell (1) shown in FIG. The polymer electrolyte membranes of Examples and Comparative Examples were immersed in purified water for 2 hours, and then this polymer electrolyte membrane was placed in the cell (1). The polymer electrolyte membrane (2) separates the A chamber and the B chamber with an area of 8 cm ² . Furthermore, chamber A was charged with 200 ml of a 3.2% aqueous methanol solution, and chamber B was charged with 200 ml of purified water. Then, after leaving at 25 ° C. for 10, 30, 60, 120, 180 minutes, the methanol concentration in the B chamber containing purified water was measured by gas chromatography, and the slope value when this was plotted against time was determined. The value obtained in Comparative Example 2 using Nafion 112 was set to 100, and the methanol permeation coefficient was determined relative to the polymer electrolyte membranes of Examples and Comparative Examples.
If the methanol permeability coefficient is 100 or less, it can be said that it has good methanol permeability resistance.

(3) Measurement of proton conductivity On a probe for self-made measurement (manufactured by Teflon (registered trademark)), a platinum plate (width: 5 mm) was pressed against the surface of the strip-shaped membrane sample made of the polymer electrolyte membrane, The sample and the probe were immersed in a constant temperature layer at 60 ° C., and the impedance between the platinum plates was measured by 1260 FREQUENCY RESPONSE ANALYSER manufactured by SOLARTRON.
When measuring, change the distance between the poles, and cancel the contact resistance between the membrane and the platinum wire using the following formula from the gradient plotting the distance measured between the poles and the resistance measurement value estimated from the CC plot. And the proton conductivity of the polymer electrolyte membrane was calculated.
Formula for calculating conductivity: conductivity [S / cm] = 1 / film width [cm] × film thickness [cm] × resistance interelectrode gradient [Ω / cm]
If the proton conductivity is 0.08 S / cm or more, it can be said that the proton conductivity is good.
The results of the above (1) to (3) are shown in Table 3 below.

As shown in Table 3, it can be seen that the reinforced polymer electrolyte membranes of Examples 1 to 6 have a low swelling rate with respect to water and methanol, and can suppress the permeation of methanol while maintaining high proton conductivity.
On the other hand, Comparative Example 1 using the polymer electrolyte compound (L) outside of the present invention has a low swell ratio but large methanol permeability, and the polymer electrolyte membrane of Comparative Example 2 using Nafion 112 is Compared with the reinforced polymer electrolyte membranes of Examples 1 to 6, the swelling ratio with respect to methanol is large, and the permeability of methanol is also large.

[Production of electrode-polymer electrolyte membrane assembly]
<Example 7>
After 0.72 g of catalyst-supported carbon particles (Tanaka Kikinzoku Co., Ltd., TEC10V30E) having a platinum loading of 30% by mass were wetted with water, a Nafion (registered trademark) solution (DuPont, “Nafion (registered trademark) Catalyst paste C was prepared by mixing and dispersing 8.6 g of “5% solution” uniformly. Next, the catalyst paste C was applied to one side of the Teflon (registered trademark) film using an applicator and dried to form a catalyst layer C (thickness 150 μm) on the Teflon (registered trademark) film. Further, after 0.72 g of catalyst-supported carbon particles having a platinum loading of 33 wt% (Tanaka Kikinzoku Co., Ltd., TEC61V33E) were moistened with water, Nafion (registered trademark) solution (DuPont, “Nafion (registered trademark) Catalyst paste A was prepared by mixing and dispersing 8.6 g)) solution 5%) in a uniform manner. Next, the catalyst paste A (thickness 150 μm) was formed on the Teflon (registered trademark) film by applying and drying the catalyst paste A on one surface of the Teflon (registered trademark) film using an applicator. Subsequently, between the press plates of the flat plate press, the catalyst layers C and A are arranged so as to be in contact with the reinforced polymer electrolyte membrane C obtained in Example 1, and after being sandwiched for 3 minutes at 160 ° C. and 5 MPa, The catalyst layer was transferred to the reinforced polymer electrolyte membrane C by peeling the Teflon (registered trademark) film from the reinforced polymer electrolyte membrane C. Further, a carbon paper subjected to a water repellent treatment was sandwiched from both sides, and heat-pressed again at 160 ° C. and 5 MPa for 3 minutes to produce an electrode-polymer electrolyte membrane assembly C. At this time, the average pore diameter of the electrode was 2 μm, and the porosity was 40%.

<Example 8>
An electrode-polymer electrolyte membrane assembly M was produced in the same manner as in Example 7 except that the multilayer polymer electrolyte membrane M obtained in Example 5 was used instead of the reinforced polymer electrolyte membrane C.
<Comparative Example 3>
Reference electrode-polymer electrolyte membrane assembly P in the same manner as in Example 7 except that the polymer electrolyte membrane “Nafion (registered trademark) 112” used in Comparative Example 2 was used instead of the reinforced polymer electrolyte membrane C. Was made.

[Fabrication of fuel cell]
<Example 9>
A stainless steel electrode plate was provided on both sides of the electrode-polymer electrolyte membrane assembly C obtained in Example 7, and a fuel cell C comprising a methanol fuel chamber and an air chamber on the back of each electrode plate was produced.
<Example 10>
A fuel cell M was produced in the same manner as in Example 9 except that the electrode-polymer electrolyte membrane assembly M of Example 8 was used.
<Comparative Example 4>
A reference fuel cell P was produced in the same manner as in Example 9 except that the reference electrode-polymer electrolyte membrane assembly P of Comparative Example 3 was used.

[Evaluation of fuel cell]
The fuel cells C and M obtained in Example 9, Example 10, and Comparative Example 4 and the reference fuel cell P were evaluated by an electrochemical test. Electrochemical evaluation was performed under the conditions of a 30% by weight methanol aqueous solution in the methanol chamber (anode side) at 10 ml / min, oxygen in the air chamber (cathode side) at 100 ml / min, and a cell temperature of 50 ° C. The results are summarized in FIG.

  The results shown in FIG. 2 clearly show that the fuel cells C and M of Examples 9 and 10 have a higher output than the fuel cell P of Comparative Example 4.

It is the schematic of the cell used for evaluation of methanol permeability. It is a graph which shows the evaluation result of a fuel cell.

Explanation of symbols

1 Cell 2 Polymer Electrolyte Membrane 3 Methanol Aqueous Solution 4 Purified Water

Claims (10)

  A porous substrate and a resin composition filled in voids and / or pores of the porous substrate, the resin composition comprising (a) a structural unit having a heterocyclic ring, and (b) A reinforced polymer electrolyte membrane comprising a polymer electrolyte compound comprising a copolymer having a structural unit having an aromatic ring having a proton acid group introduced therein and (c) a structural unit having an aromatic ring.   (A) The structural unit having a heterocyclic ring is pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, quinoline, isoquinoline, quinoxaline, imidazole, benzimidazole, indole, purine, triazole, triazine, furan, thiophene, benzofuran, and these The reinforced polymer electrolyte membrane according to claim 1, which is at least one heteroaromatic compound selected from the group consisting of derivatives. (A) The reinforced polymer electrolyte membrane according to claim 1 or 2, wherein the structural unit having a heterocyclic ring comprises the following formula (1) and / or formula (2) and / or formula (3).
Formula (1):

[In the formula (1), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; R is hydrogen Represents an aliphatic group containing 1 to 6 carbon atoms, phenyl group, nitro group, cyano group, alkoxy group, chlorine, bromine, iodine; X is selected from the group consisting of SO ₃ H, COOH, PO ₃ H ₂ N represents the number of substituents from 1 to 5; and m represents the number of substituents from 0 to (5-n). ]
Formula (2):

[In the formula (2), Y represents a direct bond, —NH—, —N (CH ₃ ) —, —NHC ₆ H ₄ O—, —N (CH ₃ ) C ₆ H ₄ O— 6 represents an alkylidene group; Z represents a direct bond, —NH—, —N (CH ₃ ) —, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O)-or an alkylidene group having 1 to 6 carbon atoms; R represents hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a methoxy group, a phenyl group, a phenoxy group, a nitro group, a cyano group, an alkoxy group, X represents chlorine, bromine or iodine; X represents a protonic acid group selected from the group consisting of SO ₃ H, COOH and PO ₃ H ₂ ; n represents the number of substituents from 1 to 5; This represents the number of substituents of (5-n). ]
Formula (3):

[In the formula (3), each Q may be the same or different and is hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitrophenyl group, an alkoxyphenyl group, a fluorophenyl group, a chlorophenyl group, A bromophenyl group, an iodophenyl group, a cyanophenyl group, an acetophenyl group, an —OH group, chlorine, bromine, iodine; R is hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a methoxy group, a phenyl group, X represents a protonic acid group selected from the group consisting of SO ₃ H, COOH, and PO ₃ H ₂ ; n represents the number of substituents of 1 to 5; phenoxy group, nitro group, chlorine, bromine, iodine; And m represents the number of substituents from 0 to (5-n). ] (B) The reinforcing unit according to any one of claims 1 to 3, wherein the structural unit having an aromatic ring into which a protonic acid group is introduced includes the following formula (4) and / or the following formula (5). Molecular electrolyte membrane.
Formula (4):

[In the formula (4), A represents a direct bond, -O-, -S-, -S (O)-, -S (O) _2- , -C (O)-, -P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; R is hydrogen Represents an aliphatic group containing 1 to 6 carbon atoms, phenyl group, nitro group, cyano group, alkoxy group, chlorine, bromine, iodine; X is selected from the group consisting of SO ₃ H, COOH, PO ₃ H ₂ N represents the number of substituents from 1 to 4, and m represents the number of substituents from 0 to (4-n). ]
Formula (5):

[In the formula (5), R represents hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; X represents SO ₃ H; Represents a protonic acid group selected from the group consisting of COOH and PO ₃ H ₂ ; n represents the number of substituents of 1 to 4; and m represents the number of substituents of 0 to (4-n). ] (C) The reinforced polymer electrolyte membrane according to any one of claims 1 to 4, wherein the structural unit having an aromatic ring comprises the following formula (6) and / or the following formula (7).
Formula (6):

[In the formula (6), A represents a direct bond, —O—, —S—, —S (O) —, —S (O) ₂ —, —C (O) —, —P (O) (C ₆ H ₅ ) —, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —C ₆ H ₄ CC ₆ H ₄ — or an alkylidene group having 1 to 6 carbon atoms; D and E each independently represent hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; provided that B, C, D, At least two of E consist of hydrogen. ]
Formula (7):

[In formula (7), F and G each independently represent hydrogen, an aliphatic group containing 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, an alkoxy group, chlorine, bromine or iodine; , F and G consist of hydrogen. ]   (B) In the structural unit having an aromatic ring into which a proton acid group is introduced, the reinforced polymer according to any one of claims 1 to 5, wherein the proton acid group is a sulfonic acid group or / and a phosphoric acid group. Electrolyte membrane.   A reinforced polymer electrolyte membrane comprising at least one reinforced polymer electrolyte membrane according to any one of claims 1 to 6.   An electrode-polymer electrolyte membrane assembly comprising two electrodes and the reinforced polymer electrolyte membrane according to any one of claims 1 to 7 disposed between the two electrodes.   The manufacturing method of the electrode-polymer electrolyte membrane assembly of Claim 8 including arrange | positioning the reinforcement polymer electrolyte membrane of any one of Claims 1-7 between two electrodes.   A fuel cell comprising the electrode-polymer electrolyte membrane assembly according to claim 9.

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