JP2003201403A - Polyelectrolyte composition and proton conductive membrane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyelectrolyte composition having excellent constancy while maintaining essentially possessed high proton conductivity and useful as a proton conductive membrane such as an electrolyte for primary batteries, an electrolyte for secondary batteries, a solid polyelectrolyte for fuel cells, a display element, various sensors, a signal transmission medium, a solid capacitor and an ion exchange membrane. <P>SOLUTION: 1. The polyelectrolyte composition comprises (1) the polyelectrolyte and (2) an antioxidant containing (a) at least one kind of compound selected from the group consisting of a phenolic hydroxy group-containing compound and an amine compound and (b) at least one kind of compound selected from the group consisting of an organophosphorus compound and an organosulfur compound [with the proviso that the compound of (a) is not included in the organophosphorus compound and organosulfur compound of (a)]. 2. The proton conductive membrane comprises the polyelectrolyte composition. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a highly durable solid polymer electrolyte, more specifically, an oxidation resistance suitable for use in a polymer electrolyte membrane such as a polymer electrolyte fuel cell and a water electrolysis cell. The present invention relates to a highly durable solid polymer electrolyte having excellent properties.

[0002]

2. Description of the Related Art A solid polymer electrolyte is a solid polymer material having an electrolyte group such as a sulfonic acid group or a carboxylic acid group in the polymer chain, and is firmly bound to a specific ion, or a cation or anion. Since it has the property of selectively permeating ions, it is used as a polymer electrolyte membrane in polymer electrolyte fuel cells and water electrolysis cells. A polymer electrolyte fuel cell is provided with a pair of electrodes on both sides of a proton-conductive solid polymer electrolyte membrane, and supplies pure hydrogen or reformed hydrogen gas as fuel gas to one electrode (fuel electrode) to generate oxygen gas. Alternatively, air is supplied as an oxidant to different electrodes (air electrodes) to obtain an electromotive force. In water electrolysis, the electrolysis of water using a solid polymer electrolyte membrane causes a reverse reaction of a fuel cell reaction to produce hydrogen and oxygen.

However, in actual fuel cells and water electrolysis, side reactions occur in addition to these main reactions. A typical example is the production of hydrogen peroxide (H ₂ O ₂ ). To generate this hydrogen peroxide (H ₂ O ₂ ), at the hydrogen electrode, oxygen mixed in the gas as an impurity or by intentional mixing, or the oxygen electrode melts into the electrolyte and diffuses to the hydrogen electrode. Oxygen is considered to be involved in the reaction, while in water electrolysis, a side reaction that produces hydrogen peroxide (H ₂ O ₂ ) may occur in almost the same manner. The hydrogen peroxide generated on these electrodes is separated from the electrodes by diffusion or the like and moves into the electrolyte. Since this hydrogen peroxide has a strong oxidizing power, it oxidizes many organic substances that make up the electrolyte. Although the detailed mechanism has not been clarified, it is considered that hydrogen peroxide is radicalized in many cases, and the generated hydrogen peroxide radical is a direct reactant of the oxidation reaction.

Japanese Patent Laid-Open No. 2001-118591 discloses a highly durable polymer electrolyte excellent in oxidation resistance to peroxide generated by a battery reaction in order to improve the durability of the polymer electrolyte. . In this publication, specifically, a transition metal oxide having a catalytic ability for catalytically decomposing a peroxide is dispersed and blended in a polymer electrolyte, or a peroxide such as a metal peroxide which suppresses decomposition of the peroxide. The substance stabilizer is dispersed and blended, or the phenolic hydroxyl group is introduced into the electrolyte polymer by a chemical bond. However, if a metal peroxide is blended in the polymer electrolyte, the membrane strength will drop extremely, so the polymer electrolyte membrane will not be formed during the mounting work when actually using the polymer electrolyte membrane to make a fuel cell. It causes serious problems such as breaking. Also, in order to express high radical resistance by the method of introducing a phenolic hydroxyl group into the electrolyte polymer by a chemical bond, it is necessary to introduce a large number of phenolic hydroxyl groups,
Since there is a fatal problem that the proton conductivity of the polymer electrolyte decreases, the method of maintaining high radical resistance and tough film strength while maintaining high proton conductivity is limited and still insufficient. .

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a polymer electrolyte composition capable of maintaining high radical conductivity and high film strength while maintaining high intrinsic proton conductivity. It is what

[0006]

[Means for Solving the Problems] In order to solve the above-mentioned problems, firstly, the polymer electrolyte contains at least one compound selected from the group consisting of (a) phenolic hydroxyl group-containing compounds and amine compounds. Compounds and at least one compound selected from the group consisting of (a) organic phosphorus compounds and organic sulfur compounds (provided that the organic phosphorus compounds and organic sulfur compounds of the above (a) do not include the compounds according to the above (a)) The present invention provides a polymer electrolyte composition containing an antioxidant containing Further, the present invention secondly provides a proton conductive membrane comprising the polymer electrolyte composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 1. [Proton-Conducting Polymer Constituting Polymer Electrolyte] The proton-conducting polymer has an electrolyte group and a hydrocarbon moiety, and the electrolyte group is an ion-forming functional group such as a sulfonic acid group or a carboxylic acid group. Groups. Further, in the hydrocarbon part of the proton conductive polymer, the electrolyte group is introduced at a predetermined introduction rate with respect to the part into which the electrolyte group can be introduced.

Specific examples of the polymer compound having a hydrocarbon moiety into which the above-mentioned electrolyte group is introduced include polyarylene polymers, polyarylene sulfone resins, polyether sulfone resins, polyether ether ketone resins, and straight chain phenols. Formaldehyde resin, crosslinked phenol formaldehyde resin, linear polystyrene resin, crosslinked polystyrene resin, linear poly (trifluorostyrene)
Resin, cross-linked (trifluorostyrene) resin, poly (2,3-
Diphenyl-1,4-phenylene oxide) resin, poly (allyl ether ketone) resin, poly (arylene ether sulfone) resin, poly (phenylquinosan phosphorus) resin, poly (benzylsilane) resin, polystyrene-graft-ethylene tetrafluoroethylene Resin, polystyrene-graft-polyvinylidene fluoride resin, polystyrene-graft-tetrafluoroethylene resin and the like can be mentioned.

In the present invention, it is preferable to use sulfonated polyarylene as the proton conductive polymer from the viewpoints of durability, heat resistance, proton conductivity, processability and the like. As the polyarylene before the sulfonation reaction,
(A) Aromatic compound unit having an electron-withdrawing group in the main chain
A polyarylene-based polymer containing (hereinafter, referred to as a unit (A)) is preferable because the toughness is high because the unit (A) has a flexible structure in the main chain. Further, the unit may be a polyarylene-based copolymer containing the unit (A) and (b) an aromatic compound unit having no electron-withdrawing group in the main chain (hereinafter referred to as unit (B)). The upper limit of the amount of sulfonic acid groups introduced can be controlled by (B), and the toughness and hot water resistance do not easily decrease even when sulfonated, and the toughness, mechanical strength, elastic modulus, and anti-swelling property are excellent. ..

(1) Monomer constituting unit (A) As the monomer constituting the unit (A) (hereinafter referred to as "monomer (A)"), the following general formula (1) is preferable.
a-1m), (1a-2m) and (2am) (hereinafter referred to as “monomer (A1)”, “monomer (A2)” and “monomer (A3)” in order). <Monomer (A1)>

[0011]

[Chemical 8] … (1a-1m) (In formula (1a-1m), X is independently a chlorine atom or a bromine source.
Child, iodine atom or -OSO₂Y (where Y is Archi
Group, halogenated alkyl group or aryl group)
Where A is an electron-withdrawing group and R is¹~ R⁸Are the same
Different from hydrogen atom, fluorine atom, allyl group,
And a fluoroalkyl group. ) In the general formula (1a-1m), the electron-withdrawing group (A)
, -CO-, -CONH-,-(CF₂) p− (here
And p is an integer of 1 to 10), -C (CF₃) ₂-,-
COO-, -SO-, -SO₂-And the like. same
Similarly, the alkyl group may be a methyl group or an ethyl group.
What is a fluoroalkyl group?
Group, pentafluoroethyl group and the like. A girl
Jiku, -OSO₂Z in Y is an alkyl group
Methyl group, ethyl group, etc.
Trifluoromethyl group, pentafluoroethyl group, etc.
However, aryl groups such as phenyl group and p-tolyl group are
Can be mentioned.

Specific examples of the above-mentioned monomer (A1) are shown below. (A1-1) 4,4'-dichlorobenzophenone, 2,4'-dichlorobenzophenone, 3,3'-dichlorobenzophenone, 4,4'-
Dibromobenzophenone, 2,4'-dibromobenzophenone, 3,3'-dibromobenzophenone, 4,4'-diiodobenzophenone, 2,4'-diiodobenzophenone, 3,3'-diiodobenzophenone, bis (4- Trifluoromethylsulfonyloxyphenyl) ketone, bis (3-trifluoromethylsulfonyloxyphenyl) ketone (A1-2) 4,4'-dichlorobenzanilide, 3,3'-dichlorobenzanilide, 3,4 ' -Dichlorobenzanilide, 4,4'-
Dibromobenzanilide, 3,3'-dibromobenzanilide, 3,4'-dibromobenzanilide, 4,4'-diiodobenzanilide, 3,3'-diiodobenzanilide, 3,4'-diiodobenz Anilid

(A1-3) bis (chlorophenyl) difluoromethane, bis (chlorophenyl) tetrafluoroethane,
Bis (chlorophenyl) hexafluoropropane, bis
(Chlorophenyl) octafluorobutane, bis (chlorophenyl) decafluoropentane, bis (chlorophenyl) dodecafluorohexane, bis (chlorophenyl) tetradecafluoroheptane, bis (chlorophenyl) hexadecafluorooctane, bis (chlorophenyl) octadecafluorononane, Bis (chlorophenyl) eicosafluorodecane; bis (bromophenyl) difluoromethane, bis (bromophenyl) tetrafluoroethane, bis' (bromophenyl) hexafluoropropane, bis (bromophenyl) octafluorobutane, bis (bromophenyl) Decafluoropentane, bis (bromophenyl) dodecafluorohexane, bis (bromophenyl) tetradecafluoroheptane, bis (bromophenyl) hexadecafluorooctane, bis (bromophenyl ) Octadecanols fluoro nonane, bis (bromophenyl) eicosa fluoro decane, bis (iodophenyl) difluoromethane, bis
(Iodophenyl) tetrafluoroethane, bis (iodophenyl) hexafluoropropane, bis (iodophenyl) octafluorobutane, bis (iodophenyl) decafluoropentane, bis (iodophenyl) dodecafluorohexane, bis (iodophenyl) tetra Decafluoroheptane, bis (iodophenyl) hexadecafluorooctane, bis (iodophenyl) octadecafluorononane, bis (iodophenyl) eicosafluorodecane

(A1-4) 2,2-bis (4-chlorophenyl) hexafluoropropane, 2,2-bis (3-chlorophenyl) hexafluoropropane, 2,2-bis (4-bromophenyl) hexafluoropropane 2,2-bis (3-bromophenyl) hexafluoropropane, 2,2-bis (4-iodophenyl) hexafluoropropane, 2,2-bis (3-iodophenyl) hexafluoropropane, bis (4- Trifluoromethylsulfonyloxyphenyl) hexafluoropropane, bis
(3-Trifluoromethylsulfonyloxyphenyl) hexafluoropropane (A1-5) 4-chlorophenyl 4-chlorobenzoate, 3-chlorophenyl 4-chlorobenzoate, 3-chlorophenyl 3-chlorobenzoate, 3 -Chlorobenzoic acid-4-chlorophenyl, 4-
Bromobenzoic acid-4-bromophenyl, 4-bromobenzoic acid-
3-Bromophenyl, 3-Bromobenzoic acid-3-Bromophenyl, 3-Bromobenzoic acid-4-Bromophenyl

(A1-6) bis (4-chlorophenyl) sulfoxide, bis (3-chlorophenyl) sulfoxide, bis (4-
Bromophenyl) sulfoxide, bis (3-bromophenyl) sulfoxide, bis (4-iodophenyl) sulfoxide, bis (3-iodophenyl) sulfoxide, bis (4-trifluoromethylsulfonyloxyphenyl) sulfoxide, bis (3- Trifluoromethylsulfonyloxyphenyl) sulfoxide (A1-7) bis (4-chlorophenyl) sulfone, bis (3-chlorophenyl) sulfone, bis (4-bromophenyl) sulfone, bis (3-bromophenyl) sulfone, bis ( 4-iodophenyl) sulfone, bis (3-iodophenyl) sulfone, bis (4-trifluoromethylsulfonyloxyphenyl) sulfone, bis (3-trifluoromethylsulfonyloxyphenyl) sulfone <monomer (A2)>

[0016]

[Chemical 9] ... (1a-2m) (In Formula (1a-2m), X and R < ¹ > -R < ⁸ > are Formula (1a-1).
m) and A is independently defined by formula (1a-1)
m) is an electron-withdrawing group as defined in R ^{1 ′ to} R
^8'is the same or different and is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group. The alkyl group and fluoroalkyl group in the general formula (1a-2m) are the same as those in the general formula (1a-1m).

Specific examples of the monomer (A2) are shown below. (A2-1) 4,4'-bis (4-chlorobenzoyl) diphenyl ether, 4,4'-bis (3-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-bromobenzoyl) diphenyl ether, 4,4 '-Bis (3-bromobenzoyl) diphenyl ether, 4,4'-bis (4-iodobenzoyl) diphenyl ether, 4,4'-bis (3-iodobenzoyl) diphenyl ether, 4,4'-bis (4-trifluoro Methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-Methylsulfonyloxyphenyl) diphenyl ether

(A2-2) 4,4'-bis (4-chlorobenzoylamino) diphenyl ether, 3,4'-bis (4-chlorobenzoylami) diphenyl ether, 4,4'-bis (3-chlorobenzoylamino) ) Diphenyl ether, 3,4'-bis (3-chlorobenzoyl) diphenyl ether, 4,4'-bis (4-bromobenzoylamino) diphenyl ether, 3,4'-bis
(4-Bromobenzoylamino) diphenyl ether, 4,4 '
-Bis (3-bromobenzoylamino) diphenyl ether, 3,4'-bis (3-bromobenzoylamino) diphenyl ether, 4,4'-bis (4-iodobenzoylamino) diphenyl ether, 3,4'-bis (4- Iodobenzoylamino) diphenyl ether, 4,4'-bis (3-iodobenzoylamino) diphenyl ether, 3,4'-bis (3-iodobenzoylamino) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyl) Roxyphenyl) diphenyl ether, 3,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-
Trifluoromethylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (4
-Methylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether, 4,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether, 3,4'-bis ( 3-Methylsulfonyloxyphenyl) diphenyl ether

(A2-3) 4,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 3,4'-bis (4-chlorophenylsulfonyl) diphenyl ether, 4,4'-bis (3-chlorophenylsulfonyl) diphenyl ether, 3,4'-bis (3-chlorophenylsulfonyl) diphenyl ether,
4,4'-bis (4-bromophenylsulfonyl) diphenyl ether, 3,4'-bis (4-bromophenylsulfonyl) diphenyl ether, 4,4'-bis (3-bromophenylsulfonyl) diphenyl ether, 3,4'- Bis (3-bromophenylsulfonyl) diphenyl ether, 4,4-bis (4-iodophenylsulfonyl) diphenyl ether, 3,4'-bis (4-
Iodophenylsulfonyl) diphenyl ether, 4,4'-
Bis (3-iodophenylsulfonyl) diphenyl ether, 3,4'-bis (3-iodophenylsulfonyl) diphenyl ether, 4,4'-bis (4-trifluoromethylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4'-
Bis (4-trifluoromethylsulfonyloxyphenylsulfonyl) diphenyl ether, 4,4'-bis (3-trifluoromethylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4'-bis (3-trifluoromethylsulfonyloxy) Phenylsulfonyl) diphenyl ether, 4,4'-bis (4-methylsulfonyloxyphenisulfonyl) diphenyl ether, 3,4'-bis (4-methylsulfonyloxyphenylsulfonyl) diphenyl ether,
4,4'-bis (3-methylsulfonyloxyphenylsulfonyl) diphenyl ether, 3,4'-bis (3-methylsulfonyloxyphenylsulfonyl) diphenyl ether

(A2-4) 4,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-chlorophenyl) diphenyl ether dicarboxylate,
4,4'-bis (3-chlorophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-chlorophenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-bromophenyl) diphenyl ether dicarboxylate, 3 ,
4'-bis (4-bromophenyl) diphenyl ether dicarboxylate, 4,4'-bis (3-bromophenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-bromophenyl) diphenyl ether dicarboxylate, 4 ,Four'-
Bis (4-iodophenyl) diphenyl ether dicarboxylate, 3,4′-bis (4-iodophenyl) diphenyl ether dicarboxylate, 4,4′-bis (3-iodophenyl) diphenyl ether dicarboxylate, 3,4 ′ -Screw
(3-iodophenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate,
3,4'-bis (4-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 4,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-trifluoromethylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 4,4'-bis (4-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (4-methylsulfonyloxyphenyl) ) Diphenyl ether dicarboxylate, 4,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate, 3,4'-bis (3-methylsulfonyloxyphenyl) diphenyl ether dicarboxylate

(A2-5) 4,4'-bis [(4-chlorophenyl)-
1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4 , 4'-bis [(3-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-chlorophenyl) -1,1,1,3 , 3,3-Hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) -1,1,
1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-bromophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4 ' -Bis [(3-bromophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-bromophenyl) -1,1,1,3, 3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) -1,1,1,
3,3,3-hexafluoropropyl] diphenyl ether,
3,4'-bis [(4-iodophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-
Iodophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-iodophenyl) -1,1,1,3,3,3-hexafluoro Propyl] diphenyl ether, 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4 -Trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl)-
1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) -1,1,1,3,3,3-hexa Fluoropropyl]
Diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 3,4'-bis [(4-methylsulfonyl Roxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-methylsulfonyloxyphenyl) -1,1,1,3,3,3 -Hexafluoropropyl] diphenyl ether, 3,4'-bis [(3-methylsulfonyloxyphenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether

(A2-6) 4,4'-bis [(4-chlorophenyl) tetrafluoroethyl] diphenyl ether, 4,4'bis [(3-chlorophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [ (4-chlorophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-
Chlorophenyl) hexafluoropropyl] diphenyl ether, 4,4'bis [(4-chlorophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-chlorophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [ (4-chlorophenyl) decafluoropentyl] diphenyl ether, 4,4′-bis [(3-chlorophenyl) decafluoropentyl] diphenyl ether, 4,
4'-bis [(4-bromophenyl) tetrafluoroethyl]
Diphenyl ether, 4,4'-bis [(3-bromophenyl)
Tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-Bromophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-bromophenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(4-bromophenyl) decafluoropentyl] diphenyl ether , 4,4'-bis [(3-bromophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) tetrafluoroethyl] diphenyl ether,
4,4'-bis [(3-iodophenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) hexafluoropropyl] diphenyl ether, 4,
4'-bis [(3-iodophenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-iodophenyl) octafluorobutyl] diphenyl ether, 4,4'-
Bis [(3-iodophenyl) octafluorobutyl] diphenyl ether, 4,4'bis [(4-iodophenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-
Iodophenyl) decafluoropentyl] diphenyl ether,

4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether , 4,4'-bis [(4-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4 , 4'-bis [(4-trifluoromethylsulfonoxyphenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4 ''-Bis [(4-trifluoromethylsulfonyloxyphenyl) decafluoropentyl Diphenyl ether, 4,4'-bis [(3-trifluoromethylsulfonyloxy) decafluoropentyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4 '-
Bis [(3-methylsulfonyloxyphenyl) tetrafluoroethyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(3-methyl Sulfonyloxyphenyl) hexafluoropropyl] diphenyl ether, 4,4'-bis [(4-methylsulfonyloxyphenyl) octafluorobutyl] diphenyl ether, 4,4'-bis [(3-methylsulfonyloxyphenyl)
Octafluorobutyl] diphenyl ether, 4,4'-bis [(4-methylsulfonoxyphenyl) decafluoropentyl] diphenyl ether, 4,4'-bis [(3-methylsulfonyloxy) decafluoropentyl] diphenyl ether <monomer (A3)>

[0024]

[Chemical 10] (2am) (In formula (2am), A is independently an electron-withdrawing group as defined in formula (1a-1m), B is independently an electron-donating atom or a divalent group, X is independently a chlorine atom,
A bromine atom or an iodine atom, R ^{1 to} R ⁸ are the same or different and each is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group, and n is 2 or more, preferably 2 to 100, particularly preferably Is an integer of 2 to 80. ) Examples of the electron-donating atom or the divalent group (B) in the general formula (2am) include —O—, —S—, and —CH═CH.
-, -C≡C-,

[0025]

[Chemical 11]

[0026]

[Chemical 12] And so on.

Specific examples of the above-mentioned monomer (A3) include:
For example, 2,2-bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexafluoropropane,
Bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl]
Examples thereof include sulfone, and those represented by the following chemical formulas.

[0028]

[Chemical 13] [In the above formula, X is as defined in the general formula (2am). ]

[0029]

[Chemical 14]

The above monomer (A3) that can be used in the present invention
In addition to the monomer represented by n = 2, "oligomer" or "polymer" in which n is larger than 2 can be used. As an example, the specific structural formula of an oligomer or polymer having a structure having an aromatic chloride at the molecular end is as follows.

[0031]

[Chemical 15]

[0032]

[Chemical 16]

The monomer (A3) includes, for example, when the electron donating group is --O--, bisphenol linked with the electron withdrawing group (A) and fluorine activated with the electron withdrawing group.
Aromatic dihalide compound substituted with a halogen atom such as chlorine, for example, 4,4'-difluorobenzophenone, 4,4'-
Dichlorobenzophenone, 4,4'-chlorofluorobenzophenone, bis (4-chlorophenyl) sulfone, bis (4-
Fluorophenyl) sulfone, 4-fluorophenyl-4'-
Chlorophenyl sulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 2,6-
Difluorobenzonitrile, hexafluorobenzene,
It can be synthesized by reacting decafluorobiphenyl, 2,5-difluorobenzophenone, 1,3-bis (4-chlorobenzoyl) benzene and the like. It is preferable to use a chlorofluoro compound having one halogen atom with different reactivity as the active aromatic dihalide, and since the fluorine atom preferentially causes the nucleophilic substitution reaction with the phenoxide as in the following reaction, the purpose is It is convenient to obtain the activated terminal chloro form of.

[0034]

[Chemical 17]

(2) Monomer constituting unit (B) As the monomer constituting the unit (B) (hereinafter referred to as “monomer (B)”), the following general formula (1) is preferable.
bm) to (4bm) (hereinafter, respectively,
"Monomer (B1)", "Monomer (B2)",
"Monomer (B3)" and "monomer (B4)"
Is mentioned. <Monomer (B1)>

[0036]

[Chemical 18] (1bm) (In formula (1bm), A is an electron-withdrawing group as defined in formula (1a-1m), and B is independently an electron-donating atom as defined in formula (2am) or And R ⁹
To R ¹⁵ are the same or different and each is a hydrogen atom, a fluorine atom,
It is an allyl group, an alkyl group or a fluoroalkyl group, Z is an aryl group, and m is an integer of 0, 1 or 2. ) Examples of the aryl group related to Z include, for example, a phenyl group, a naphthyl group, and the following formula:

[0037]

[Chemical 19] (In the formula, R ^{25 to} R ³³ have the same definitions as R ^{9 to} R ¹⁵ in the formula (1bm).). Monomer (B
Examples of 1) include compounds represented by the following formulas.

[0038]

[Chemical 20] [In the formula, X and Z are as defined in the general formula (1bm). ] More specifically, examples of the monomer (B1) include 2,
4-dichloro-4'-phenoxybenzophenone, 4'-phenoxyphenyl 2,5-dichlorobenzoate, 4'-phenoxyphenyl 2,4-dichlorobenzoate, and those represented by the following formula can be given.

[0039]

[Chemical 21]

[0040]

[Chemical formula 22]

[0041]

[Chemical formula 23]

[0042]

[Chemical formula 24]

[0043]

[Chemical 25]

The monomer (B1) is, for example, 2,5-dichloro-4 '-[(4-phenoxy) phenoxy] benzophenone, which is 2,5-dichloro-4'-fluorobenzophenone and p-phenoxy. Phenol is used as a starting reaction material, and potassium carbonate is added to this to convert it into a highly reactive phenoxide, and as a reaction solvent, an aprotic dipolar polar solvent such as dimethylacetamide, toluene, N-methylpyrrolidone, and dimethylsulfoxide. Can be used for the synthesis for 1 to 30 hours at a reaction temperature of 80 to 200 ° C. <Monomer (B2)>

[0045]

[Chemical formula 26] (2bm) <Monomer (B3)>

[0046]

[Chemical 27] (3bm) <Monomer (B4)>

[0047]

[Chemical 28] (4bm) (in the above formulas (2bm), (3bm) and (4bm),
R and R ′ are independently a chlorine atom, a bromine atom, an iodine atom or —OSO ₂ Y (wherein Y represents an alkyl group, a halogenated alkyl group or an aryl group), and R ¹⁷
To R ²⁴ are the same or different and each is a hydrogen atom, a fluorine atom,
It is an allyl group, an alkyl group or a fluoroalkyl group. In the general formulas (2bm) to (4bm), when R ^{17 to} R ²⁴ are alkyl groups, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and the like can be mentioned, and in the case of a fluoroalkyl group, Examples thereof include trifluoromethyl group and pentafluoroethyl group.

Specific examples of the monomer (B2) include:
These include: p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-dibromotoluene, 2,
5-diiodotoluene, 2,5-dimethylsulfonyloxybenzene, 2,5-dichloro-p-xylene, 2,5-dibromo-p-
Xylene, 2,5-diiodo-p-xylene, 2,5-dichlorobenzotrifluoride, 2,5-dibromobenzotrifluoride, 2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3, 5,6-tetrafluorobenzene, 1,4-dibromo-2,3,5,6-tetrafluorobenzene, 1,4-diiodo-2,
3,5,6-Tetrafluorobenzene Among the above, preferred are p-dichlorobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, and 2,5-dichlorobenzotrifluoride.

Specific examples of the above-mentioned monomer (B3) include:
These include: 4,4'-dimethylsulfonyloxybiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl,
4,4'-dibromobiphenyl, 4,4'-diiodobiphenyl,
4,4'-Dimethylsulfonyloxy-3,3'-dimethylbiphenyl, 4,4'-dimethylsulfonyloxy-3,3'-difluorobiphenyl, 4,4'-dimethylsulfonyloxy-3,3 ' ,
5,5'-tetrafluorobiphenyl, 4,4'-dibromooctafluorobiphenyl, 4,4'-methylsulfonoxyoctafluorobiphenyl Among the above, preferred ones are 4,4'-dimethylsulfonoxybiphenyl, 4,4'-dibromobiphenyl, 4,
These are 4'-diiodobiphenyl and 4,4'-dimethylsulfonyloxy-3,3'-dipropenylbiphenyl.

Specific examples of the above monomer (B4) include:
These include: m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, m-dimethylsulfonoxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene, 2,
4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene, 3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene, 2,6-diiodotoluene, 3,5-Dimethylsulfonyloxytoluene, 2,6-Dimethylsulfonyloxytoluene, 2,4-Dichlorobenzotrifluoride, 2,4-Dibromobenzotrifluoride, 2,4-Diiodobenzotrifluoride, 3, 5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride, 3,5-diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene Among the above, preferred ones are: These are m-dichlorobenzene, 2,4-dichlorotoluene, 3,5-dimethylsulfonyloxytoluene and 2,4-dichlorobenzotrifluoride.

As the monomer (B) for constituting the unit (b) of the polyarylene copolymer of the present invention,
Among the above monomers (B1) to (B4), solubility,
From the viewpoint of increasing the molecular weight, in particular, a dichlorobenzophenone derivative, for example, 2,5-dichloro-4′-phenoxybenzophenone, 2,4-dichloro-4′-phenoxybenzophenone, 2,
It is preferable to use 5-dichloro-4 ′-[(4-phenoxy) phenoxy] benzophenone, 2,5-dichloro-4′-phenoxyphenylbenzophenone, 2,4-dichloro-4′-phenoxyphenylbenzophenone.

(3) Synthesis of Polyarylene Copolymer (a) An aromatic compound unit having an electron-withdrawing group in the main chain, and (b) an aromatic compound unit having no electron-withdrawing group in the main chain Is a copolymer having the above general formula (1a-1)
m), at least one monomer (A) selected from the group consisting of compounds represented by (1a-1m) and (2am), and a compound represented by the above general formulas (1bm) to (4bm). It can be synthesized by a reaction with at least one monomer (B) selected from the group. The amount of the monomer (A) used is preferably 80 to 1 mol% of the total monomers, more preferably 60 to 2 mol%. The amount of the monomer (B) used is preferably 20 to 99 mol% of all the monomers, and more preferably 40 to 98 mol%.

The catalyst used in the production of the polyarylene copolymer is a catalyst system containing a transition metal compound, and the catalyst system includes (1) a compound which becomes a transition metal salt and a ligand ( Hereinafter, referred to as a ligand component), or a transition metal complex (including a copper salt) coordinated with a ligand, and
(2) A reducing agent is an essential component, and a “salt” may be added to further increase the polymerization rate. Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide and nickel acetylacetonate, palladium compounds such as palladium chloride, palladium bromide and palladium iodide, iron chloride, iron bromide Iron compounds such as iron iodide, cobalt compounds such as cobalt chloride, cobalt bromide, and cobalt iodide. Of these, nickel chloride and nickel bromide are particularly preferable.

Examples of the ligand component include triphenylphosphine, 2,2'-bipyridine, 1,5-cyclooctadiene and 1,3-bis (diphenylphosphino) propane. Phosphine and 2,2'-bipyridine are preferred. The compound that is the ligand component may be used alone or in combination of two or more. Furthermore, examples of the transition metal complex in which a ligand is coordinated in advance include nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis (triphenylphosphine), and nickel nitrate. Bis (triphenylphosphine), nickel chloride (2,
2'-bipyridine), nickel bromide (2,2'-bipyridine), nickel iodide (2,2'-bipyridine), nickel nitrate (2,2'-
Bipyridine), bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, tetrakis (triphenylphosphite) nickel, tetrakis (triphenylphosphine) palladium, etc. Phenylphosphine),
Nickel chloride (2,2'-bipyridine) is preferred.

Examples of the reducing agent that can be used in the catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium and calcium, with zinc, magnesium and manganese being preferred. These reducing agents can be further activated and used by bringing them into contact with an acid such as an organic acid. Further, as the "salt" which can be used in the catalyst system, sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide and sodium sulfate, potassium fluoride, potassium chloride, potassium bromide, iodide Potassium compounds such as potassium iodide and potassium sulfate, tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, ammonium compounds such as tetraethylammonium sulfate, and the like,
Sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide and tetraethylammonium iodide are preferred.

The proportion of each component used in the catalyst system is such that the transition metal salt or transition metal complex is usually 0.0001-10 mol, preferably 0.01-0.
It is 5 mol. If it is less than 0.0001 mol, the polymerization reaction will not proceed sufficiently, while if it is more than 10 mol, the molecular weight will decrease. When a transition metal salt and a ligand component are used in the catalyst system, the ratio of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol, based on 1 mol of the transition metal salt. If it is less than 0.1 mol, the catalytic activity will be insufficient, while if it exceeds 100 mol, the molecular weight will decrease. Further, the ratio of the reducing agent used in the catalyst system to the total amount of the above monomers is 1 mol,
Usually, it is 0.1 to 100 mol, preferably 1 to 10 mol. 0.
If it is less than 1 mol, the polymerization will not proceed sufficiently, while if it is more than 100 mol, purification of the obtained polymer will be difficult. Furthermore, when a "salt" is used in the catalyst system, the usage ratio thereof is usually 0.001 to 100 mol, preferably 0.01 to 1 mol, based on 1 mol of the total amount of the above monomers.
If it is less than 0.001 mol, the effect of increasing the polymerization rate is insufficient, while if it exceeds 100 mol, there is a problem that purification of the resulting polymer becomes difficult.

As the polymerization solvent which can be used for the synthesis of the polyarylene copolymer, for example, tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl- 2-pyrrolidone, γ-butyrolactone, γ-butyrolactam and the like can be mentioned, and tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone are preferable.
It is preferable to use these polymerization solvents after drying them sufficiently. The total concentration of the above-mentioned monomers in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight. The polymerization temperature at the time of polymerizing the polyarylene copolymer is usually 0 to 200 ° C, preferably 50 to 120 ° C. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.

Here, for example, by polymerizing the monomer (A3) and the monomer (B1) under the above conditions,
General formula:

[0059]

[Chemical 29] (Here, A, B, Z, R ^{1 to} R ¹⁵ , m and n are as described above, p and q each independently represent the number of repeating units, and the ratio of p / q (that is, the above The molar ratio of the two repeating units is from 99/1 to 20/80)). The structure of the polyarylene copolymer is
For example, depending on the infrared absorption spectrum, 1,230-1,250
C-O-C absorption at cm ^-1, C = O of 1,640～1,660Cm ^-1
It can be confirmed by absorption or the like, and its structure can be confirmed by a nuclear magnetic resonance spectrum ( ¹ H-NMR) from the peak of the aromatic proton at 6.8 to 8.0 ppm.

(4) Synthesis of Polyarylene Polymer Using the same method and conditions as in the case of the above polyarylene copolymer, the polyarylene of the following structural formula (A) is prepared by using only the monomer (A3) as a raw material. Based polymers can be synthesized.

[0061]

[Chemical 30] (A) (where A, B, Z, R ^{1 to} R ⁸ , and n are as described above, and s is the number of repeating units).

(5) Sulfonation of polyarylene type (co) polymer Next, the (co) polymer having a sulfonic acid group is treated with a sulfonating agent on the above (co) polymer having no sulfonic acid group. It can be obtained by using a conventional method and introducing a sulfonic acid group. As a method of introducing a sulfonic acid group,
For example, the copolymer having no sulfonic acid group, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfuric acid, using a known sulfonating agent such as sodium bisulfite, in the absence of a solvent, or in the presence of a solvent, It can be sulfonated under known conditions. Examples of the solvent include hydrocarbon solvents such as n-hexane, ether solvents such as tetrahydrofuran and dioxane, aprotic polar solvents such as dimethylacetamide, dimethylformamide and dimethylsulfoxide, and tetrachloroethane, dichloroethane, chloroform and chloride. Examples thereof include halogenated hydrocarbons such as methylene. The reaction temperature is not particularly limited, but is usually -50 to 200 ° C, preferably -10 to 100 ° C. The reaction time is usually 0.5 to 1,000 hours, preferably 1 to 200 hours.

The amount of the sulfonic acid group in the sulfonic acid group-containing (co) polymer of the present invention thus obtained is 0.5
-3 mg equivalent / g, preferably 0.8-2.8 mg equivalent / g.
If it is less than 0.5 mg equivalent / g, the proton conductivity does not increase, while if it exceeds 3 mg equivalent / g, the hydrophilicity is improved and it becomes a water-soluble polymer, or the durability decreases even if it does not reach water solubility. To do. The amount of the sulfonic acid group can be easily adjusted by changing the use ratio of the monomer (A) and the monomer (B), and the type and combination of the monomer (A) and the monomer (B).

The molecular weight of the polymer of the precursor thus obtained before the sulfonation of the sulfonic acid group-containing polyarylene (co) polymer is 10 × 10 ³ to 1,000 × in terms of polystyrene equivalent weight average molecular weight. 10 ³ , preferably 20 × 10 ³
~ 800 x 10 ³ . When it is less than 10 × 10 ³ , the coating film properties are insufficient, such as cracks in the molded film, and the strength properties are also problematic. On the other hand, when it exceeds 1,000 × 10 ³ , there are problems that the solubility becomes insufficient, the solution viscosity is high, and the workability becomes poor. The structure of the sulfonic acid group-containing polyarylene-based (co) polymer is 1,030 to 1,045 cm ^-1 , 1,160
S = O absorption of 1,190cm ^-1, of 1,130~1,250cm ^-1 C-
It can be confirmed by O—C absorption, C═O absorption at 1,640 to 1,660 cm ⁻¹ , and their composition ratio can be known by neutralization titration of sulfonic acid or elemental analysis. In addition, by a nuclear magnetic resonance spectrum ( ¹ H-NMR), 6.8 to 8.0 ppm
The structure can be confirmed from the peak of the aromatic proton of. Further, an inorganic acid such as sulfuric acid and phosphoric acid, an organic acid such as carboxylic acid, and an appropriate amount of water may be used together with the sulfonic acid group-containing (co) polymer according to the present invention.

2. [Antioxidant] The antioxidant to be added / blended to the polymer electrolyte in the present invention is at least one compound selected from the group consisting of (a) phenolic hydroxyl group-containing compound and amine compound, and (a) organic compound. A multi-component system comprising at least one compound selected from the group consisting of phosphorus compounds and organic sulfur compounds (provided that the organic phosphorus compound and organic sulfur compound in (a) above do not include the compound according to (a) above) belongs to. Then, due to the synergistic action and effect of the combination of the (A) component and the (A) component, a polymer electrolyte having extremely excellent durability can be obtained as described later.

<Phenolic hydroxyl group-containing compound> As the phenolic hydroxyl group-containing compound of the component (a),
For example: 1,3,5-trimethyl-2,4,6
-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330, manufactured by Ciba Specialty Chemicals Co., Ltd.), pentaerythrityl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate]
(IRGANOX 1010, Ciba Specialty Chemicals
Co., Ltd.), 2,6-di-t-butyl-4-methylphenol (Sumi
lizer BHT, Sumitomo Chemical Co., Ltd.), 2,5-di-t-butyl-hydroquinone (Nocrac NS-7, Ouchi Shinko Co., Ltd.), 2,6-di-
t-Butyl-4-ethylphenol (Nocrac M-17, Emerging Ouchi
Co., Ltd.), 2,5-di-t-amylhydroquinone (Nocrac DA
H, Ouchi Shinko Co., Ltd.), 2,2'-methylenebis (4-methyl-6-
t-Butylphenol) (Nocrac NS-6, Ouchi Shinko Co., Ltd.)
3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester (IRGANOX 1222, Ciba.
Specialty Chemicals Co., Ltd.), 4,4'-thiobis (3-methyl-6-t-butylphenol) (Nocrac 300, Ouchi Shinko Co., Ltd.), 2,2'-methylenebis (4-ethyl) -6-t-butylphenol) (Nocrac NS-5, Ouchi Shinko Co., Ltd.),

4,4'-butylidene bis (3-methyl-6-t-butylphenol) (Adecastabu AO-40, manufactured by Asahi Denka Co., Ltd.), 2
-t-Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (Sumilizer GM,
Sumitomo Chemical Co., Ltd.), 2- [1- (2-hydroxy-3,5-di-t-
Pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (Sumilizer GS, Sumitomo Chemical Co., Ltd.),
2,2'-Methylenebis [4-methyl-6- (α-methyl-cyclohexyl) phenol], 4,4'-Methylenebis (2,6-di-t-butylphenol) (Cynox 226M, Shiroishi Industry Co., Ltd.) Made), 4,6-
Bis (octylthiomethyl) -o-cresol (IRGANOX 152
0L, Ciba Specialty Chemicals Co., Ltd., 2,
2'-ethylenebis (4,6-di-t-butylphenol), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076, Ciba Specialty Chemicals Co., Ltd. )), 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane (adecastabe AO-3
0, manufactured by Asahi Denka Co., Ltd., triethylene glycol bis
[3- (3-t-Butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX 245, Ciba Specialty
Chemicals Co., Ltd.), 2,4-bis- (n-octylthio) -6- (4
-Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX 565, manufactured by Ciba Specialty Chemicals Co., Ltd.), N, N'-hexamethylenebis (3,5- Di-t-butyl-4-hydroxy-hydrocinnamamide) (IRGANOX 109
8, Ciba Specialty Chemicals Co., Ltd., 1,6
-Hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX 259, Ciba
Specialty Chemicals Co., Ltd.),

2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (IRGANOX
1035FF, Ciba Specialty Chemicals Co., Ltd.
Manufactured), 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} 1,1-dimethylethyl] 2,4,8,10-tetraoxa Spiro [5.5] Undecane (Sum
ilizerGA-80, manufactured by Sumitomo Chemical Co., Ltd., tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (IRGANO
X 3114, Ciba Specialty Chemicals Co., Ltd.
), Bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium / polyethylene wax mixture (50:50) (IRGANOX 1425WL, Ciba Specialty Chemicals Co., Ltd.), isooctyl -3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate (IRGAN
OX 1135, Ciba Specialty Chemicals Co., Ltd.
Manufactured), 4,4'-thiobis (6-t-butyl-3-methylphenol)
(Sumilizer WX-R, manufactured by Sumitomo Chemical Co., Ltd.), 6- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,
8,10-Tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine (Sumilizer GP, Sumitomo Chemical Co., Ltd.) Of these compounds, bleed-out property from the electrolyte membrane From the viewpoint of the effect of improving the durability of the electrolyte membrane, it is particularly preferable to use a compound having a molecular weight of 500 or more.

<Amine-Based Compound> Examples of the amine-based compound as the component (a) include the following. p, p'-dioctyldiphenylamine (IRGANOX 5057, Ciba Specialty Chemicals Co., Ltd.), phenyl
-α-naphthylamine (Nocrac PA, Ouchi Shinko Co., Ltd.),
Poly (2,2,4-trimethyl-1,2-dihydroquinoline) (Nocra
c 224,224-S, Ouchi Shinko Co., Ltd., 6-ethoxy-2,2,4-trimethyl-1,2-sihydroquinoline (NocracAW, Ouchi Shinko)
Co., Ltd.), N, N'-diphenyl-p-phenylenediamine (No
crac DP, Ouchi Shinko Co., Ltd.), N, N'-di-β-naphthyl-p-
Phenylenediamine (Nocrac White, Ouchi Shinko Co., Ltd.)
, N-phenyl-N'-isopropyl-p-phenylenediamine (Nocrac 810NA, manufactured by Ouchi Shinko Co., Ltd.), N, N'-diallyl-p-phenylenediamine (NonflexTP, Seiko Chemical Co., Ltd.)
), 4,4 '(α, α-dimethylbenzyl) diphenylamine (Nocrac CD, Ouchi Shinko Co., Ltd.), p, p-toluenesulfonylaminodiphenylamine (Nocrac TD, Ouchi Shinko)
Co., Ltd.), N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine (Nocrac G
1, Ouchi Shinko Co., Ltd.), N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine (Ozonon 35, Seiko Chemical Co., Ltd.)
, N, N'-di-sec-butyl-p-phenylenediamine (Sum
ilizer BPA, Sumitomo Chemical Co., Ltd.), N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (Antigene 6C, Sumitomo Chemical Co., Ltd.), alkylated diphenylamine (Sumili
zer 9A, Sumitomo Chemical Co., Ltd.),

Dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate (Tinuvin 622LD, manufactured by Ciba Specialty Chemicals Co., Ltd.), Poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-
Tetramethyl-4-piperidyl) imino} hexamethylene
{(2,2,6,6-Tetramethyl-4-piperidyl) imino}] (CHIM
ASSORB 944, Ciba Specialty Chemicals Co., Ltd.
Manufactured), N, N'-bis (3-aminopropyl) ethylenediamine-
2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate (CH
IMASSORB 119FL, Ciba Specialty Chemicals
Co., Ltd.), bis (1-octyloxy-2,2,6,6-tetramethyl
-4-piperidyl) sebacate (TINUVIN123, manufactured by Ciba Specialty Chemicals Co., Ltd.), bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (TINUVIN 770, Ciba Specialty Chemicals (TINUVIN 770) Co., Ltd.), 2- (3,5-
Di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) (TINUV
IN 144, Ciba Specialty Chemicals Co., Ltd.
), Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (TINUVIN 765, manufactured by Ciba Specialty Chemicals Co., Ltd.),

Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate (LA-
57, manufactured by Asahi Denka Kogyo Co., Ltd., tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate (LA-52, Asahi Denka Kogyo Co., Ltd. )), A mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 1-tridecanol (LA-62, Asahi Denka Kogyo ( Co., Ltd.), a mixed esterified product of 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1-tridecanol (LA-6
7, Asahi Denka Kogyo Co., Ltd.), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy- 1,1-dimethylethyl) -2,4,8,
Mixed ester compound with 10-tetraoxaspiro [5.5] undecane (LA-63P, manufactured by Asahi Denka Co., Ltd.), 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Mixed esterification product with methyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (LA-68LD, Asahi Denka Kogyo Co., Ltd.) (2,2,
6,6, -Tetramethylene-4-piperidyl) 2-propylenecarboxylate (ADEKASTAB LA-82, manufactured by Asahi Denka Co., Ltd.),
(1,2,2,6,6-pentamethyl-4-piperidyl) 2-propylenecarboxylate (ADEKASTAB LA-87, Asahi Denka Co., Ltd.)
Among these compounds, it is preferable to use a compound in which a hydrogen atom is not substituted on the nitrogen atom, and further, from the viewpoint of the bleed-out property from the electrolyte membrane and the effect of improving the durability of the electrolyte membrane, a molecular weight of 500 or more. It is particularly preferable to use the compound of

<Organophosphorus Compound> Examples of the organophosphorus compound as the component (a) include the following. Bis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4 '
-Diylbisphosphite, 9,10-dihydro-9-oxa-10
-Phosphaphenanthrene-10-oxide (SANKO-HCA,
Sanko Co., Ltd.), triethyl phosphite (JP302, Johoku Chemical Co., Ltd.), tri-n-butyl phosphite (JP304, Johoku Chemical Co., Ltd.), triphenyl phosphite (adecastafu
TPP, manufactured by Asahi Denka Kogyo Co., Ltd., diphenylmonooctyl phosphite (Adecastabu C, manufactured by Asahi Denka Kogyo Co., Ltd.), tri (p
-Cresyl) phosphite (Chelex-PC, Sakai Chemical Co., Ltd.)
Made), diphenyl monodecyl phosphite (adecastabute 1
35A, manufactured by Asahi Denka Kogyo Co., Ltd., diphenylmono (tridecyl) phosphite (JPM313, manufactured by Johoku Chemical Co., Ltd.), Tris
(2-Ethylhexyl) phosphite (JP308, Johoku Chemical
Phenyl didecyl phosphite (Adecastabu 5)
17, Asahi Denka Kogyo Co., Ltd.), tridecyl phosphite (ADECASTAB 3010, Asahi Denka Kogyo KK), tetraphenyldipropylene glycol diphosphite (JPP100, Johoku Chemical Co., Ltd.), bis (2 , 4-Di-t-butylphenyl) pentaerythritol diphosphite (ADECASTAB PEP-24G, manufactured by Asahi Denka Co., Ltd.), tris (tridecyl) phosphite (JP
333E, manufactured by Johoku Chemical Co., Ltd., bis (nonylphenyl) pentaerythritol diphosphite (ADEKASTAB PEP-4C, manufactured by Asahi Denka Co., Ltd.), bis (2,6-di-t-butyl-4-methyl) (Phenyl) pentaerythritol diphosphite (Adecastabe PEP-36, manufactured by Asahi Denka Kogyo Co., Ltd.), bis [2,4-di (1-phenylisopropyl) phenyl] pentaerythritol diphosphite (Adekastab PEP-45, Asahi Denka) Industrial Co., Ltd.),

Trilauryl trithiophosphite (JPS3
12, manufactured by Johoku Chemical Co., Ltd., tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS 168, manufactured by Ciba Specialty Chemicals Co., Ltd.), tris (nonylphenyl) phosphite (adecastafu 1178, manufactured by Asahi Denka Kogyo Co., Ltd., distearyl pentaerythritol diphosphite (Adecastabe PEP-8, manufactured by Asahi Denka Kogyo Co., Ltd.), tris (mono, dinonylphenyl) phosphite (Adekastaf 329K, Asahi Denka Kogyo) Co., Ltd.), trioleyl phosphite (Chelex-OL,
Sakai Chemical Co., Ltd.)), tristearyl phosphite (JP31
8E, manufactured by Johoku Chemical Co., Ltd., 4,4'-butylidene bis (3-methyl
-6-t-Butylphenylditridecyl) phosphite (JPH1
200, manufactured by Johoku Chemical Co., Ltd.), tetra (C12-C15 mixed alkyl)
-4,4'-Isopropylidene diphenyldiphosphite (ADEKASTAB 1500, manufactured by Asahi Denka Co., Ltd.), tetra (tridecyl) -4,4'-butylidene bis (3-methyl-6-t-butylphenol) diphosphite (ADEKASTAB) 260, Asahi Denka Kogyo Co., Ltd.
Hexa (tridecyl) -1,1,3-tris (2-methyl-5-t)
-Butyl-4-hydroxyphenyl) butane-triphosphite (ADECASTAB 522A, manufactured by Asahi Denka Co., Ltd.), hydrogenated bisphenol A phosphite polymer (HBP, Johoku Chemical Co., Ltd.)
Manufactured), tetrakis (2,4-di-t-butylphenyloxy) 4,
4'-biphenylene-di-phosphine (P-EPQ, Clariant jan
Ltd.), tetrakis (2,4-di-t-butyl-5-methylphenyloxy) 4,4'-biphenylene-di-phosphine (GSY-10
1P, made by Yoshitomi Fine Chemical Co., Ltd., 2-[[2,4,8,10-Tetrakis
(1,1-Dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphepin 6-yl] oxy] -N, N-bis [2-[[2,4,8,10 -
Tetrakis (1,1dimethylethyl) dibenzo [d, f] [1,3,2,]
Dioxaphosphepin-6-yl] oxy] -ethyl] ethanamine (IRGAFOS 12, Ciba Specialty Chemicals), 2,2'-methylenebis (4,6-di-t-butylphenyl) Octyl phosphite (Adekas Abu HP-10, manufactured by Asahi Denka Kogyo Co., Ltd.) Among these compounds, in this application, the molecular weight is 500 or more from the viewpoint of bleed-out property from the electrolyte membrane and the effect of improving the durability of the electrolyte membrane. It is preferable to use the compound (1) and a compound excellent in hydrolysis resistance. As a compound with such conditions, bis (2,6-di-t-butyl
-4-Methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyloxy) 4,4'-
Biphenylene-di-phosphine, bis [2,4-di (1-phenylisopropyl) phenyl] pentaerythritol diphosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferably used.

<Organic Sulfur Compound> Examples of the organic sulfur compound as the component (a) include the following. Dilauryl-3,3'-thiodipropionate (Sumilize
r TPL-R, manufactured by Sumitomo Chemical Co., Ltd., dimyristyl-3,3'-thiodipropionate (Sumilizer TPM, Sumitomo Chemical Co., Ltd.)
Made), distearyl-3,3'-thiodipropionate (Sumi
lizer TPS, manufactured by Sumitomo Chemical Co., Ltd., pentaerythritol tetrakis (3-lauryl thiopropionate) (Sumilize
r TP-D, Sumitomo Chemical Co., Ltd.), ditridecyl-3,3'-thiodipropionate (Sumilizer TL, Sumitomo Chemical Co., Ltd.), 2-
Mercaptobenzimidazole (Sumilizer MB, manufactured by Sumitomo Chemical Co., Ltd.), ditridecyl-3,3'-thiodipropionate (Adecastatub AO-503A, manufactured by Asahi Denka Co., Ltd.), 1,3,5-Tris-β- Stearyl thiopropionyloxyethyl isocyanurate, 3,3'-thiobispropionic acid didodecyl ester (IRGANOX PS 800FL, Ciba Specialty
Chemicals Co., Ltd.), 3,3'-thiobispropionic acid diocdecyl ester (IRGANOX PS 802FL, Ciba Specialty Chemicals Co., Ltd.) Among these compounds, bleed-out property from the electrolyte membrane, From the viewpoint of the effect of improving the durability of the electrolyte membrane, it is particularly preferable to use a compound having a high molecular weight.

3. [Polymer Electrolyte Composition] (1) The ratio of the total amount of the components (2) (a) and (a) to 100 parts by weight of the polymer electrolyte is 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight. is there. Further, the ratio of the component (a) to 1 part by weight of the component (a) is
It is 0.01 to 50 parts by weight, preferably 0.03 to 5 parts by weight. If the ratio of the component (a) is less than 0.01 part by weight, the synergistic effect of the component (a) and the component (a) does not work. If it is too much, it will adversely affect the strength and proton conductivity of the electrolyte membrane. Examples of the method of mixing (1) the polymer electrolyte and (2) the antioxidant include a method of mixing the polymer electrolyte dissolved in an organic solvent and the antioxidant, a method of mixing both in a molten state, and the like.

[0076]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. The various measurement items in the examples were obtained as follows. Weight average molecular weight The number average molecular weight and the weight average molecular weight of the precursor polymer before sulfonation are determined by gel permeation chromatography (GP) using tetrahydrofuran (THF) as a solvent.
The molecular weight in terms of polystyrene was determined by C). Sulfonated number average molecular weight, weight average molecular weight was added LiBr, H ₃ PO ₄ as solvent N- methyl-2-pyrrolidone (N
The molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using MP) as the eluent.

Sulfonation equivalent washes of the obtained polymer was washed until the water became neutral, the remaining residual acid was removed, the polymer was thoroughly washed with water, and after drying, a predetermined amount was weighed, and THF / water was added. Dissolved in a mixed solvent of
Phenolphthalein was used as an indicator and titrated with a standard solution of NaOH, and the sulfonation equivalent was determined from the neutralization point. Measurement of Proton Conductivity A film sample with a diameter of 13 mm placed under 100% relative humidity is sandwiched between platinum electrodes and enclosed in a closed cell, using an impedance analyzer (HYP4192A), frequency 5-13 MHz, applied voltage 12 mV. , Temperature 20 ℃, 50 ℃, 10
The absolute value of the cell impedance and the phase angle were measured at 0 ° C. The obtained data was subjected to complex impedance measurement at an oscillation level of 12 mV using a computer to calculate the proton conductivity. Tensile strength Tensile strength was measured by a tensile test of the obtained film at room temperature.

Fenton Test A Fenton reagent was prepared by adding iron sulfate heptahydrate to 3 wt% hydrogen peroxide so that the concentration of iron ions was 20 ppm. 200 g of Fenton's reagent was collected in 250 cc of polyethylene solution, polymer electrolyte membrane cut into 3 cm x 4 cm and film thickness = 55 μm was put into it, and after tightly sealing it, it was immersed in a constant temperature water bath at 40 ° C for 40 hours of Fenton's test. I went. After the Fenton test, the film was taken out, washed with ion-exchanged water, and then adjusted at 25 ° C. and 50% RH for 12 hours, and various physical properties were measured. The weight retention rate in the Fenton test was calculated by the following mathematical formula. Weight retention rate in Fenton test (%) = film weight after Fenton test / film weight before Fenton test x 100

[Reference Example 1 Synthesis of sulfonated polymer A] 2,5-dichloro-4'-phenoxybenzophenone 193.5
g (540 mmol), 4,4'-dichlorobenzophenone 15.1
g (60 mmol), sodium iodide 11.7 g (78 mmo
l), bistriphenylphosphine nickel dichloride 11.8 g (1.8 mmol), triphenylphosphine 63.
0 g (240 mmol) and 94.1 g (1.44 mol) zinc were placed in a three-necked flask equipped with a reflux tube and a three-way cock, and the temperature was 70 ° C.
Immerse in an oil bath and replace with nitrogen, then N-
1,000 mL of methyl-2-pyrrolidone was added to start the reaction. After reacting for 20 hours, diluted with 500 mL of N-methyl-2-pyrrolidone, poured the polymerization reaction solution into a 1:10 hydrochloric acid / methanol solution, precipitated the polymer, washed, filtered, and vacuum dried to obtain a white powder. . The yield was 153g. The weight average molecular weight was 159,000. The obtained polymer is N-
A film was formed using methyl-2-pyrrolidone and immersed in methanol, but no swelling was observed. To 150 g of the polymer obtained above, 1,500 mL of concentrated sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours to carry out a sulfonation reaction. After the reaction, it was poured into a large amount of pure water to precipitate the sulfonated polymer. pH 7
The polymer was continuously washed with water until, and after filtration, the sulfonated polymer was recovered and vacuum dried at 90 ° C. The yield of sulfonated polymer was 179 g. The polystyrene-reduced number average molecular weight of the sulfonated polymer determined by GPC (NMP) was 73,000, and the weight average molecular weight was 468,000.

[Reference Example 2 Synthesis of sulfonated polymer B] (Preparation of oligomer) Stirrer, thermometer, cooling tube, Dean-S
In a 1-L three-necked flask equipped with a tark tube and a three-way cock for introducing nitrogen, 2.2-bis (4-hydroxyphenyl) -1,
1,1,3,3,3-hexafluoropropane (bisphenol A
F) 67.3 g (0.20 mol), 4,4'-dichlorobenzophenone (4,4'-DCBP) 60.3 g (0.24 mol), potassium carbonate 71.9 g (0.52 mol), N, N-dimethylacetamide (DMAc) 300 mL 150 mL of toluene was taken, heated in an oil bath under a nitrogen atmosphere, and reacted at 130 ° C. with stirring. The water produced by the reaction is azeotroped with toluene and Dean
-When the reaction was carried out while removing it to the outside of the system with a Stark tube, almost no water was formed in about 3 hours. Reaction temperature
The temperature was gradually raised from 130 ° C to 150 ° C. After that, most of the toluene was removed while gradually raising the reaction temperature to 150 ° C, and the reaction was continued at 150 ° C for 10 hours, and then 4,4'-DCBP10.0
g (0.040 mol) was added and the reaction was continued for 5 hours. The obtained reaction solution was allowed to cool, the precipitate of by-produced inorganic compound was removed by filtration, and the filtrate was put into 4 L of methanol. The precipitated product is filtered off, collected and dried, then tetrahydrofuran
Dissolved in 300 mL. This was reprecipitated in 4 L of methanol to obtain 95 g of the desired compound (yield 85%). The polystyrene equivalent number average molecular weight of the obtained polymer determined by GPC (THF solvent) was 4,200, and the weight average molecular weight was 8,300. The obtained polymer is THF, NMP, DMA.
c, soluble in sulfolane, etc., Tg was 110 ° C, and thermal decomposition temperature was 498 ° C. The resulting polymer has the formula (I):

[0081]

[Chemical 31] It was presumed to have a structure represented by (I), and the average value of n was determined to be 7.8 from the structure and the above number average molecular weight.

(Synthesis of Polyarylene Copolymer) 28.4 g (2.87 mmo) of the oligomer of the formula (I) obtained above
l), 2,5-dichloro-4 ′-(4-phenoxy) phenoxybenzophenone (DCPPB) 29.2 g (67.1 mmol), bis (triphenylphosphine) nickel dichloride 1.37 g
(2.1 mmol), sodium iodide 1.36 g (9.07 mm
ol), 7.34 g of triphenylphosphine (28.0 mmo
1) and 11.0 g (168 mmol) of zinc dust were placed in a flask and purged with dry nitrogen. N-methyl-2-pyrrolidone 130mL
Was added, and the mixture was heated to 80 ° C. and stirred for 4 hours to carry out polymerization. The polymerization solution was diluted with THF, coagulated and recovered with hydrochloric acid / methanol, and washed with methanol repeatedly, and dissolved with THF.
Purification by reprecipitation in methanol and filtration of the polymer collected by filtration gave 50.7 g (96%) of the desired copolymer. GP
The polystyrene-equivalent number average molecular weight determined by C (THF) was 40,000, and the weight average molecular weight was 145,000.

(Preparation of Sulfonated Polymer B) 25 g of the copolymer obtained above was placed in a 500 mL separable flask, 250 mL of 96% sulfuric acid was added, and the mixture was stirred under a nitrogen stream for 24 hours. The obtained solution was poured into a large amount of ion-exchanged water to precipitate the polymer. The polymer was washed repeatedly until the pH of the wash water reached 5. After drying, 29 g (96
%) Of the sulfonated polymer was obtained. The polystyrene-converted number average molecular weight of the sulfonated polymer determined by GPC (NMP) was 67,000, and the weight average molecular weight was 277,000.

Example 1 100 g of sulfonated polymer A and 900 g of NMP were placed in a flask equipped with a stir bar so that the solid content of sulfonated polymer A was 10 wt%, and heated and dissolved at 80 ° C. To this polymer varnish, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) was added to 100 parts by weight of the solid content of the sulfonated polymer A. benzene
1 part by weight and 2 parts by weight of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite were added, and the mixture was stirred for 2 hours in a mix rotor to dissolve the desired polymer varnish. Obtained. This polymer varnish was applied onto a glass substrate using a doctor blade (for 70 μm) and then preliminarily dried in an oven at 75 ° C. for 1 hour to peel off the coating film from the glass substrate. After fixing the film on an aluminum plate with a heat-resistant tape, it was further dried in an oven at 150 ° C. for 1 hour. Then, in order to completely remove the NMP remaining in the coating film, the NMP was removed by immersing it in ion-exchanged water of 1,000 times the coating film weight at 25 ° C. for 2 days. After preparing the film at 25 ° C and 50% RH for 12 hours,
Various physical properties were measured. The results are shown in Table 1. The obtained composition maintains high proton conductivity and high tensile strength without deterioration of the film throughout the Fenton test.
The balance of physical properties was extremely excellent.

Example 2 Instead of bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite in Example 1, bis [2,4-di (1-phenylisopropyl) was used. The same evaluation was performed except that phenyl] pentaerythritol diphosphite was used. The resulting composition was used throughout the Fenton test.
The film had high proton conductivity and high tensile strength without deterioration of the film, and had an excellent balance of physical properties.

Example 3 In Example 1, 1,3,5-trimethyl-2,4,6-tris (3,
In place of 5-di-t-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was used. (2,6-Di-t-butyl-4-methylphenyl) pentaerythritol diphosphite In the same manner except that 1 part by weight of distearyl-3,3'-thiodipropionate was used instead of 2 parts by weight. evaluated. The obtained composition maintained high proton conductivity and high tensile strength without deterioration of the film throughout the Fenton test, and had an excellent balance of physical properties.

Example 4 In Example 1, 1,3,5-trimethyl-2,4,6-tris (3,
5-di-t-butyl-4-hydroxybenzyl) benzene instead of tris- (3,5-di-t-butyl-4-hydroxybenzyl)
With isocyanurate, bis (2,6-di-t-butyl
-4-Methylphenyl) pentaerythritol diphosphite Instead of 2 parts by weight, pentaerythrityl tetrakis
(3-lauryl thiopropionate) The same evaluation was performed except that 1 part by weight was used. The obtained composition maintained high proton conductivity and high tensile strength without deterioration of the film throughout the Fenton test, and had an excellent balance of physical properties.

Example 5 In Example 1, 1,3,5-trimethyl-2,4,6-tris (3,3
5-di-t-butyl-4-hydroxybenzyl) benzene instead of 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9 -Bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro
[5.5] The same evaluation was performed except that a mixed esterified product with undecane was used. The obtained composition has high proton conductivity throughout the Fenton test without film deterioration.
It maintained a high tensile strength and had an excellent balance of physical properties.

Example 6 The same evaluation as in Example 1 was carried out except that the sulfonated polymer B was used in place of the sulfonated polymer A. The obtained composition maintained high proton conductivity and high tensile strength without deterioration of the film throughout the Fenton test, and had an excellent balance of physical properties.

Example 7 In Example 1, sulfonated polymer B was used instead of sulfonated polymer A, and 1,3,5-trimethyl-
2,4,6-tris (3,5-di-butyl-4-hydroxybenzyl) benzene 1 part by weight was replaced by tris- (3,5-di-t-butyl-4)
-Hydroxybenzyl) isocyanurate was evaluated in the same manner except that 2 parts by weight was used. The obtained composition maintained high proton conductivity and high tensile strength without deterioration of the film throughout the Fenton test, and had an excellent balance of physical properties. The results of Examples 1 to 8 are shown in Table 1.

[0091]

[Table 1]

(Table Note) (A component) A 1: 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene A 2: pentaeryth Lityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] a3: tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate a4: 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4 1,8,10-Tetraoxaspiro [5.5] undecane mixed esterified product (component i) 1: bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite toy 2: bis [2,4-di (1-phenylisopropyl) phenyl]
Pentaerythritol diphosphite toy 3: Distearyl-3,3'-thiodipropionate I 4: Pentaerythrityl tetrakis (3-lauryl thiopropionate)

Comparative Example 1 In Example 1, 1,3,5-trimethyl-2,4,6-tris (3,
The same evaluation was performed except that 5-di-t-butyl-4-hydroxybenzyl) benzene and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite were not added. After the Fenton test the film was completely disassembled,
The durability was extremely poor.

Comparative Example 2 Evaluation was made in the same manner as in Example 1 except that bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite was not added. After the Fenton test, the film was completely disassembled and the durability was extremely poor.

Comparative Example 3 In Example 1, 1,3,5-trimethyl-2,4,6-tris (3,3
In place of 5-di-t-butyl-4-hydroxybenzyl) benzene, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was used, and bis (2 , 4-Di-t-butylphenyl) [1,1-biphenyl] -4,4'-
Example 1 except no diylbisphosphite was added
It evaluated similarly to. After the Fenton test, the film was completely disassembled and the durability was extremely poor.

Comparative Example 4 In Example 1, 1,3,5-trimethyl-2,4,6-tris (3,3
Evaluation was performed in the same manner as in Example 1 except that 5-di-t-butyl-4-hydroxybenzyl) benzene was not used. After the Fenton test, the film was completely disassembled and the durability was extremely poor.

Comparative Example 5 In Example 1, sulfonated polymer B was used in place of sulfonated polymer A, and 1,3,5-trimethyl-2,4,6-
Similar evaluation except that tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite were not added. did. After the Fenton test, the film was completely disassembled and the durability was extremely poor.

Comparative Example 6 In Example 1, sulfonated polymer B was used in place of sulfonated polymer A, and 1,3,5-trimethyl-2,4,6-
Bis (2,6-di-t-butyl-4-methylphenyl) without using tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene
The same evaluation was carried out except that distearyl-3,3′-thiodipropionate was used instead of pentaerythritol diphosphite. After the Fenton test, the film was completely disassembled and the durability was extremely poor. The results of Comparative Examples 1 to 6 are shown in Table 2.

[0099]

[Table 2]

[0100]

According to the present invention, it has become possible to provide a polymer electrolyte composition which maintains the originally required high proton conductivity and is extremely excellent in durability. Further, the proton conductive membrane composed of the polymer electrolyte composition of the present invention can be suitably used as a proton conductive membrane of a highly durable fuel cell.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/49 C08K 5/49 C08L 71/00 C08L 71/00 C25B 13/08 301 C25B 13/08 301 H01M 8/02 H01M 8/02 P 8/10 8/10 F term (reference) 4J002 BC031 BC111 BN001 CC031 CH091 CN031 EJ016 EJ026 EN016 EN036 EN056 EU196 EV006 EV066 EW006 EW066 FD076 GQ00 4J005 AA09 AA24 BD06 5H026 AA06 CX05 H05

Claims (8)

[Claims] 1. A polymer electrolyte (1) and (2) (a).
At least one compound selected from the group consisting of a phenolic hydroxyl group-containing compound and an amine compound, and (a) at least one compound selected from the group consisting of an organic phosphorus compound and an organic sulfur compound (provided that (a) The organic phosphorus compound and the organic sulfur compound contain an antioxidant containing the compound according to (a) above). 2. The antioxidant is (a) with respect to 1 part by weight of at least one compound selected from the group consisting of (a) phenolic hydroxyl group-containing compounds and amine compounds.
The polymer electrolyte composition according to claim 1, wherein 0.01 to 10 parts by weight of at least one compound selected from the group consisting of an organic phosphorus compound and an organic sulfur compound is mixed. 3. The polymer electrolyte composition according to claim 1 or 2, wherein the polymer electrolyte is a sulfonated polyarylene. 4. The sulfonated polyarylene is (a)
The polymer electrolyte composition according to claim 3, which is a sulfonated product of a polyarylene polymer containing an aromatic compound unit having an electron-withdrawing group in the main chain. 5. The polymer electrolyte composition according to claim 4, wherein the unit (a) is a unit represented by the following general formula (2a). [Chemical 1] (2a) (In the formula (2a), A is independently an electron-withdrawing group, and B is
Are independently electron-donating atoms or divalent groups, and R ¹ to
R ⁸ is the same or different and is a hydrogen atom, a fluorine atom, an allyl group, an alkyl group or a fluoroalkyl group,
n is an integer of 2 or more. ) 6. The polyarylene polymer contains (a) an aromatic compound unit having an electron-withdrawing group in the main chain and (b) an aromatic compound unit having no electron-withdrawing group in the main chain. The polymer electrolyte composition according to claim 4, which is a polyarylene-based copolymer. 7. The unit (a) is represented by the following general formula (1a):
And a unit selected from the group consisting of units represented by (2a)
At least one kind of unit, and the unit (b) is
Consists of units represented by the following general formulas (1b) to (4b)
Characterized by at least one unit selected from the group
The polymer electrolyte composition according to claim 6. [Chemical 2] … (1a) (In the formula (1a), A is independently an electron-withdrawing group, and R is¹
~ R⁸And R^{1 '}~ R^{8 '}Are the same or different and
Child, fluorine atom, allyl group, alkyl group or fluoro
It is an alkyl group, and r is an integer of 0 or 1. ) [Chemical 3] … (2a) (In formula (2a), A is independently an electron-withdrawing group, and B is
Are independently electron-donating atoms or divalent groups, R¹~
R⁸Are the same or different and are hydrogen atom, fluorine atom,
A ryl group, an alkyl group or a fluoroalkyl group,
n is an integer of 2 or more. ) [Chemical 4] … (1b) (In the formula (1b), A is an electron as in the general formula (1a).
Is a suction group, and B is independently the same as in the general formula (2a).
An electron-donating atom or divalent group, R ⁹~ R¹⁵
Are the same or different and are hydrogen atom, fluorine atom, allyl
A group, an alkyl group or a fluoroalkyl group, and Z is
Is an aryl group, m is an integer of 0, 1 or 2.
It ) [Chemical 5] … (2b) [Chemical 6] … (3b) [Chemical 7] … (4b) (In the above formulas (2b) to (4b), R¹⁷~ R^{twenty four}Are the same
Different from hydrogen atom, fluorine atom, allyl group,
And a fluoroalkyl group. ) 8. A proton conductive membrane comprising the polymer electrolyte composition according to any one of claims 1 to 7.