JP4733352B2 - Polyarylene polymer composition and use thereof - Google Patents

Description

  The present invention relates to a polyarylene polymer composition and uses thereof, and more specifically, a polymer electrolyte membrane used in fuel cells, water electrolysis, hydrohalic acid electrolysis, salt electrolysis, oxygen concentrators, humidity sensors, gas sensors, and the like. In particular, the present invention relates to a polyarylene polymer composition which is a polymer electrolyte excellent in oxidation resistance and capable of being formed into a thin film, and uses thereof.

  A polyelectrolyte is a polymer material having an electrolyte group such as a sulfonic acid group in a polymer chain, and has a property of binding firmly to a specific ion or selectively permeating a cation or an anion. Since it has, it shape | molds in particle | grains, a fiber, or film | membrane form, and is utilized for various uses.

  Examples of the use of the polymer electrolyte include a solid polymer fuel cell known as a power generation system that has little adverse effect on the global environment in recent years. A polymer electrolyte fuel cell has a pair of electrodes on both surfaces of an electrolyte membrane, supplies a fuel gas containing hydrogen such as reformed gas to one electrode (fuel electrode), and an oxidant gas containing oxygen such as air Is supplied to the other electrode (air electrode), and the chemical energy generated when the fuel is oxidized is directly taken out as electric energy. The polymer electrolyte is also used for water electrolysis. Water electrolysis is the production of hydrogen and oxygen by electrolyzing water, and can be considered as the reverse reaction of a fuel cell.

By the way, when using a polymer electrolyte for such a fuel cell or water electrolysis, durability becomes a problem. In an actual fuel cell or water electrolysis reaction, a side reaction occurs in addition to the main reaction, and the polymer electrolyte deteriorates due to the side reaction. A typical side reaction is the generation of hydrogen peroxide (H ₂ O ₂ ). It is considered that this hydrogen peroxide is generated as a result of oxygen contained in the fuel gas mixed as an impurity or intentionally mixed, or oxygen dissolved in the polymer electrolyte at the oxygen electrode reacting on the hydrogen electrode. Hydrogen peroxide is a substance having a strong oxidizing power, and many organic compounds constituting the polymer electrolyte are oxidized by the hydrogen peroxide to deteriorate the polymer electrolyte. Although the mechanism of such deterioration has not been clarified in detail, in many cases, it is considered that hydrogen peroxide is radicalized and the generated hydrogen peroxide radical is a direct reactant of the oxidation reaction.

  As a method for improving the durability of a polymer electrolyte, a highly durable polymer electrolyte excellent in oxidation resistance against peroxide generated by a battery reaction has been disclosed (see Patent Document 1). In the method disclosed herein, a transition metal oxide having a catalytic ability to catalytically decompose peroxides is dispersed and blended in the polymer electrolyte, or a metal peroxide or the like that suppresses decomposition of the peroxides. At least one means of dispersing and blending an oxide stabilizer or introducing a phenolic hydroxyl group into the polymer electrolyte by a chemical bond is taken.

However, when a metal peroxide, which is not an organic compound, is blended in the polymer electrolyte, it does not mix evenly and generates microcracks, which causes the film strength to be extremely reduced. In general, it is known that the output of a fuel cell can be improved by thinning the polymer electrolyte membrane, and the durability is improved by adding a transition metal oxide or metal peroxide. However, it is a serious problem that the film strength is lowered.

In addition, in order to develop high radical resistance by the method of introducing a phenolic hydroxyl group into a polymer electrolyte by chemical bonding, it is necessary to introduce a very large amount of phenolic hydroxyl group, and the proton conductivity of the polymer electrolyte is lowered. Problems occur.
JP 2001-118591 A

  An object of the present invention is to provide a polymer electrolyte composition that has high oxidation resistance, high proton conductivity, high strength, and high elasticity and can be easily formed into a thin film, and uses thereof.

According to the present invention, the following polyarylene polymer composition, a polymer electrolyte comprising the same, and a proton conducting membrane are provided to achieve the object of the present invention.
(1)
A polyarylene having a sulfonic acid group obtained by hydrolyzing a polyarylene having a sulfonic acid ester group obtained by polymerizing a monomer containing a sulfonic acid ester compound represented by the following general formula (A);
A polyarylene polymer composition comprising at least one additive selected from the group consisting of a hindered phenol compound, a hindered amine compound, an organic phosphorus compound, and an organic sulfur compound;

(Wherein X represents a halogen atom excluding fluorine, an atom or group selected from —OSO ₃ CH ₃ and —OSO ₃ CF ₃ , A represents a divalent electron-withdrawing group, and B represents a divalent electron. donating group or a direct bond are shown, m represents an integer of 0, n represents an integer of 0, k is an integer of 1 to 4, R ^a is a hydrocarbon having 4-20 carbon atoms A group, Ar is —SO ₃ R ^b (wherein
R ^b represents a hydrocarbon group having 4 to 20 carbon atoms. ) Represents an aromatic group having a substituent represented by:
(2)
The polyarylene polymer composition as described in (1) above, wherein the additive contains 0.01 to 10 parts by weight of the total weight with respect to 100 parts by weight of the polyarylene having a sulfonic acid group.
(3)
A polymer electrolyte comprising the polyarylene polymer composition according to any one of (1) to (2) above.
(4)
A proton conducting membrane comprising the polyarylene polymer composition according to any one of (1) to (2) above.

  The polymer constituting the polyarylene polymer composition according to the present invention is a polyarylene having a sulfonic acid group and generally has a polyphenylene structure known as a polymer skeleton having high strength and high elasticity. A polymer electrolyte having strength and high elasticity and capable of being easily formed into a thin film can be produced.

  The polyarylene polymer composition according to the present invention has an effect of providing a polymer electrolyte membrane excellent in oxidation resistance since an additive for capturing generated radicals is introduced.

  Since the additive used in the polyarylene polymer composition according to the present invention is an organic compound, it has the effect of being uniformly mixed with the polyarylene having a sulfonic acid group and maintaining high breaking strength and elastic modulus. .

  Even if the additive used in the polyarylene polymer composition according to the present invention is added to a polyarylene having a sulfonic acid group, the polyarylene having a sulfonic acid group has an effect of maintaining high proton conductivity.

  Since the additive used in the polyarylene polymer composition according to the present invention can provide high radical durability while maintaining high strength, high elastic modulus, and high proton conductivity even in a thin film electrolyte, it has high output. It is possible to develop a fuel cell.

  The polymer constituting the polyarylene polymer composition according to the present invention does not reduce the proton conductivity because a large number of phenolic hydroxyl groups are not introduced into the electrolyte by chemical bonds.

  As described above, the polyarylene polymer composition according to the present invention, which is a polymer electrolyte, has high proton conductivity, high strength, and high elastic modulus, is excellent in durability, and can be easily thinned. Therefore, when this is applied to, for example, a fuel cell, it contributes to an increase in output and the like, and is an invention having an extremely large effect in the industry.

  Hereinafter, the polyarylene polymer composition according to the present invention, the polymer electrolyte comprising the same, and the proton conductive membrane will be described in detail.

  The polyarylene polymer composition according to the present invention includes at least one additive selected from the group consisting of a polyarylene having a sulfonic acid group, a hindered phenol compound, a hindered amine compound, an organic phosphorus compound, and an organic sulfur compound. Contains.

(Polyarylene having a sulfonic acid group)
The polyarylene having a sulfonic acid group constituting the main part of the polyarylene polymer composition according to the present invention is obtained by polymerizing a monomer containing a sulfonic acid ester compound represented by the following general formula (A). It is a polymer or copolymer obtained by hydrolyzing the polyarylene having a sulfonic acid ester group.

In the formula (A), X represents a halogen atom other than fluorine (chlorine, bromine, iodine), —OSO ₂ Z (
Here, Z represents an alkyl group, a fluorine-substituted alkyl group or an aryl group. An atom or group selected from

A represents a divalent electron-withdrawing group, specifically, —CO—, —SO ₂ —, —SO—, —CO.
NH—, —COO—, — (CF ₂ ) ₁ — (wherein 1 is an integer of 1 to 10), —C (CF ₃ ) ₂ — and the like can be mentioned.

B represents a divalent electron-donating group or a direct bond. Specific examples of the electron-donating group include — (CH ₂ ) —, —C (CH ₃ ) ₂ —, —O—, —S—, —CH═. CH-, -C≡C- and

Etc.
The electron-withdrawing group means a group having a Hammett substituent constant of 0.06 or more when the phenyl group is in the m-position and 0.01 or more when the p-position is p-position.

R ^a represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, iso-propyl group, tert-butyl group, iso- Butyl, n-butyl, sec-butyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, cyclopentylmethyl, cyclohexylmethyl, adamantyl, adamantanemethyl, 2-ethylhexyl, bicyclo [2.2 .1] heptyl group, bicyclo [2.2.1] heptylmethyl group, tetrahydrofurfuryl group, 2-methylbutyl group, 3,3-dimethyl-2,4-dioxolanemethyl group, cyclohexylmethyl group, adamantylmethyl group , Straight chain hydrocarbon groups such as bicyclo [2.2.1] heptylmethyl group, branched hydrocarbon groups, alicyclic carbon groups Examples thereof include a hydrogen group and a hydrocarbon group having a 5-membered heterocyclic ring. Of these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is more preferable. .

Ar represents an aromatic group having a sulfonate group represented by —SO ₃ R ^b , and specific examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthyl group. Of these groups, a phenyl group and a naphthyl group are preferable.
The sulfonate group —SO ₃ R ^b is substituted with one or more aromatic groups, and when two or more substituents —SO ₃ R ^b are substituted, these sulfonate esters are substituted. The groups may be the same or different from each other.

Here, R ^b represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 4 to 20 carbon atoms, and specific examples thereof include the hydrocarbon groups having 1 to 20 carbon atoms. Of these, n-butyl group, neopentyl group, tetrahydrofurfuryl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, adamantylmethyl group, and bicyclo [2.2.1] heptylmethyl group are preferable, and neopentyl group is more preferable. .

  m represents an integer of 0 to 10, preferably 0 to 2, n represents an integer of 0 to 10, preferably 0 to 2, and k represents an integer of 1 to 4.

  Specific examples of the sulfonic acid ester compound represented by the formula (A) include the following compounds.

In addition, as the sulfonic acid ester compound represented by the general formula (A), a compound in which a chlorine atom is replaced with a bromine atom in the compound, -CO- is -SO ₂ in the compound.
- compounds replaced by a chlorine atom in the compound is replaced with a bromine atom, and -CO- is -SO ₂ - can also be mentioned such compounds replaced.

The R ^a and R ^b groups in the general formula (A) are derived from primary alcohol, and the β carbon is tertiary or quaternary carbon, which is excellent in stability during the polymerization process, and sulfonic acid by deesterification It is preferable in that it does not cause polymerization inhibition or cross-linking due to the formation of C, and it is preferable that these ester groups are derived from a primary alcohol and the β-position is a quaternary carbon.

  More preferably, the polyarylene having a sulfonic acid group used in the present invention is obtained by copolymerizing a sulfonic acid ester compound represented by the above general formula (A) and a compound represented by the following general formula (B). It is a copolymer obtained by hydrolyzing the resulting polyarylene having a sulfonic acid ester group, specifically a copolymer represented by the following general formula (C).

In the formula (B), R ′ and R ″ may be the same as or different from each other, and a halogen atom or —OSO ₂ Z excluding a fluorine atom (wherein Z represents an alkyl group, a fluorine-substituted alkyl group or an aryl group) The group represented by this is shown. Examples of the alkyl group represented by Z include a methyl group and an ethyl group, examples of the fluorine-substituted alkyl group include a trifluoromethyl group, and examples of the aryl group include a phenyl group and a p-tolyl group.

R ^{1 to} R ⁸ may be the same or different from each other, and are at least one atom selected from the group consisting of a hydrogen atom, a fluorine atom, an alkyl group, a fluorine-substituted alkyl group, an allyl group, an aryl group, and a cyano group, or Indicates a group.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, and a hexyl group, and a methyl group and an ethyl group are preferable.
Examples of the fluorine-substituted alkyl group include trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, trifluoromethyl group, pentafluoroethyl group, and the like. Etc. are preferable.
Examples of allyl groups include propenyl groups,
Examples of the aryl group include a phenyl group and a pentafluorophenyl group.

  W represents a single bond or a divalent electron-withdrawing group. Examples of the divalent electron withdrawing group include the same ones as described above.

  T represents a single bond or a divalent organic group. Specific examples of the divalent organic group include an electron-withdrawing group and an electron-donating group, and examples of the electron-withdrawing group and the electron-donating group include those described above.

  In the formula (B), p is 0 or a positive integer, and the upper limit is usually 100, preferably 10-80.

Specifically, as the compound represented by the general formula (B), when p = 0, for example, 4,4′-dichlorobenzophenone, 4,4′-dichlorobenzanilide, bis (chlorophenyl) difluoromethane, 2, 2-bis (4-chlorophenyl) hexafluoropropane, 4-chlorobenzoic acid-4-chlorophenyl, bis (4-chlorophenyl) sulfoxide, bis (4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 9,9- Bis (4-hydroxyphenyl) fluorene is mentioned. In these compounds, compounds in which a chlorine atom is replaced with a bromine atom or an iodine atom, and compounds in which at least one of halogen atoms substituted in the 4-position in these compounds are substituted in the 3-position are exemplified.

When p = 1, examples of the specific compound represented by the general formula (B) include 4,
4′-bis (4-chlorobenzoyl) diphenyl ether, 4,4′-bis (4-chlorobenzoylamino) diphenyl ether, 4,4′-bis (4-chlorophenylsulfonyl) diphenyl ether, 4,4′-bis (4- Chlorophenyl) diphenyl ether dicarboxylate, 4,4′-bis [(4-chlorophenyl) -1,1,1,3,3,3-hexafluoropropyl] diphenyl ether, 4,4′-bis [(4-chlorophenyl) Tetrafluoroethyl] diphenyl ether, compounds in which the chlorine atom is replaced with a bromine atom or iodine atom in these compounds, compounds in which the halogen atom substituted in the 4-position in these compounds is substituted in the 3-position, and further in these compounds, the diphenyl ether At least one of the groups substituted in the 4-position is in the 3-position And the like.

Further, the compound represented by the general formula (B) is 2,2-bis [4- {4- (4-
Chlorobenzoyl) phenoxy} phenyl] -1,1,1,3,3,3-hexafluoropropane, bis [4- {4- (4-chlorobenzoyl) phenoxy} phenyl] sulfone, and the following formula Compounds.

The compound represented by the general formula (B) can be synthesized, for example, by the method shown below.

  First, in order to convert the bisphenol linked with an electron-withdrawing group into the corresponding alkali metal salt of bisphenol, dielectrics such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, dimethylsulfoxide, etc. Add an alkali metal such as lithium, sodium or potassium, an alkali metal hydride, an alkali metal hydroxide, an alkali metal carbonate or the like in a polar solvent having a high rate.

Usually, the alkali metal is reacted in excess with respect to the hydroxyl group of phenol, and usually 1.1 to 2 times equivalent is used. Preferably, 1.2 to 1.5 times equivalent is used. In this case, fluorine, chlorine, etc. activated with an electron-withdrawing group in the presence of water and an azeotropic solvent such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole Aromatic halogen-substituted aromatic dihalide compounds such as 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-chlorofluorobenzophenone, bis (4-chlorophenyl) sulfone, bis (4 -Fluorophenyl) sulfone, 4-fluorophenyl-4'-chlorophenylsulfone, bis (3-nitro-4-chlorophenyl) sulfone, 2,6-dichlorobenzonitrile, 2,6-difluorobenzonitrile, hexafluorobenzene, deca Fluorobiphenyl, , 5-difluorobenzophenone, 1,3-bis (4-chlorobenzoyl) reacting benzene. In terms of reactivity, a fluorine compound is preferable, but in consideration of the following aromatic coupling reaction, it is necessary to assemble an aromatic nucleophilic substitution reaction so that the terminal is a chlorine atom. The active aromatic dihalide is used in an amount of 2 to 4 times mol, preferably 2.2 to 2.8 times mol, of bisphenol. Prior to the aromatic nucleophilic substitution reaction, an alkali metal salt of bisphenol may be used. The reaction temperature is 60 ° C to 300 ° C, preferably 80 ° C to 250 ° C. The reaction time ranges from 15 minutes to 100 hours, preferably from 1 hour to 24 hours. The most preferable method is to use a chlorofluoro compound having one halogen atom having a different reactivity as the active aromatic dihalide represented by the following formula, and a nucleophilic substitution reaction with phenoxide occurs preferentially by the fluorine atom. It is convenient to obtain the desired activated terminal chloro form.

(Wherein, W is as defined for general formula (B).)
Moreover, as a method of synthesizing the compound represented by the general formula (B), as described in JP-A-2-159, a nucleophilic substitution reaction and an electrophilic substitution reaction are combined, and the target electron-withdrawing group is obtained. There is a method for synthesizing a flexible compound comprising an electron-donating group.

Specifically, an aromatic bishalide activated with an electron-withdrawing group, for example, bis (4-chlorophenyl) sulfone is subjected to a nucleophilic substitution reaction with phenol to obtain a bisphenoxy substitution product. Subsequently, the compound of interest is obtained by Friedel-Craft reaction of this bisphenoxy-substituted product with, for example, 4-chlorobenzoic acid chloride. As the aromatic bishalide activated with the electron-withdrawing group used here, the compounds exemplified above can be applied. Although phenol may be substituted, an unsubstituted compound is preferable from the viewpoint of heat resistance and flexibility. In addition, it is preferable to use an alkali metal salt for the phenol substitution reaction, and the compounds exemplified above can be used as the alkali metal compound. The amount used is 1.2 to 2 moles per mole of phenol. In the reaction, the polar solvent described above or an azeotropic solvent with water can be used. In the Friedel-Crafts reaction, the bisphenoxy substituent is reacted with chlorobenzoic acid chloride as an acylating agent in the presence of an activator for the Lewis acid Friedel-Crafts reaction such as aluminum chloride, boron trifluoride, and zinc chloride. . Chlorobenzoic acid chloride is used in an amount of 2 to 4 times mol, preferably 2.2 to 3 times mol, of the bisphenoxy compound. The Friedel-Craft activator is used in an amount of 1.1 to 2 times equivalent to 1 mol of an active halide compound such as chlorobenzoic acid as an acylating agent. The reaction time ranges from 15 minutes to 10 hours, and the reaction temperature ranges from -20 ° C to 80 ° C. As the solvent used, chlorobenzene, nitrobenzene and the like which are inert to Friedel-Craft reaction can be used.

In the general formula (B), the compound in which p is 2 or more is, for example, a bisphenol serving as a source of etheric oxygen which is the electron donating group T in the general formula (B) and an electron withdrawing group W. A compound in combination with at least one group selected from> C═O, —SO ₂ — and> C (CF ₃ ) ₂ , specifically 2,2-bis (4-hydroxyphenyl) -1,1 1,3,3,3-hexafluoropropane, alkali metal salts of bisphenols such as 2,2-bis (4-hydroxyphenyl) ketone, 2,2-bis (4-hydroxyphenyl) sulfone and an excess of 4 Substitution reactions with active aromatic halogen compounds such as 1,4-dichlorobenzophenone and bis (4-chlorophenyl) sulfone can be performed using N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, etc. In the presence of an organic solvent, and sequentially polymerized by the above synthesis method.

  Examples of such compounds include compounds represented by the following formulas.

  In the above, p is 0 or a positive integer, and the upper limit is usually 100, preferably 10-80.

  The sulfonate compound represented by the general formula (A) (hereinafter also referred to as “monomer (A)”) and the compound represented by the general formula (B) (hereinafter also referred to as “oligomer (B)”). The copolymer preferably used in the present invention obtained by hydrolyzing a polyarylene having a sulfonic acid ester group obtained by copolymerization with a compound having a repeating unit represented by the following general formula (C) It is a copolymer.

In the formula (C), W, T, A, B, m, n, k, p and R ^{1 to} R ⁸ are respectively W, T, A, B in the general formulas (A) and (B). m, is synonymous n, k, and p and R ¹ to R ^8.

  x and y represent molar ratios when x + y = 100 mol%.

Ar ′ represents an aromatic group having a substituent represented by —SO ₃ H, and specific examples of the aromatic group include a phenyl group, a naphthyl group, an anthracenyl group, and a phenanthyl group. Of these groups, a phenyl group and a naphthyl group are preferable.

  The polyarylene having a sulfonic acid group used in the present invention contains 0.5 to 100 mol%, preferably 10 to 99.999 mol, of repeating units derived from the sulfonic acid ester compound represented by the general formula (A). % Having a sulfonate group containing 99.5 to 0 mol%, preferably 90 to 0.001 mol% of repeating units derived from the compound represented by formula (B) It can be synthesized by synthesizing arylene and then hydrolyzing the sulfonic acid ester group in the polyarylene to convert it into a sulfonic acid group.

  The polyarylene having a sulfonate group represented by the general formula (C) is synthesized by reacting the monomer (A) and the oligomer (B) in the presence of a catalyst. Is a catalyst system containing a transition metal compound. This catalyst system includes (1) a compound that becomes a transition metal salt and a ligand (hereinafter referred to as “ligand component”) or a ligand. In addition, a transition metal complex (including a copper salt) and (2) a reducing agent are essential components, and a “salt” may be added to increase the polymerization rate.

  Here, as the transition metal salt, nickel compounds such as nickel chloride, nickel bromide, nickel iodide, nickel acetylacetonate; palladium compounds such as palladium chloride, palladium bromide, palladium iodide; iron chloride, iron bromide And iron compounds such as iron iodide; cobalt compounds such as cobalt chloride, cobalt bromide, and cobalt iodide. Of these, nickel chloride, nickel bromide and the like are particularly preferable.

As the ligand component, triphenylphosphine, 2,2′-bipyridine, 1,5-
Examples include cyclooctadiene and 1,3-bis (diphenylphosphino) propane. Of these, triphenylphosphine and 2,2′-bipyridine are preferred. The compound which is the said ligand component can be used individually by 1 type or in combination of 2 or more types.

Furthermore, as the transition metal complex in which the ligand is coordinated, for example, nickel chloride bis (triphenylphosphine), nickel bromide bis (triphenylphosphine), nickel iodide bis (triphenylphosphine), 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 and the like. Of these, nickel chloride bis (triphenylphosphine) and nickel chloride (2,2′-bipyridine) are preferred.

  Examples of the reducing agent that can be used in the catalyst system include iron, zinc, manganese, aluminum, magnesium, sodium, calcium, and the like. Of these, zinc, magnesium and manganese are preferred. These reducing agents can be used after being more activated by bringing them into contact with an acid such as an organic acid.

  Examples of the “salt” that can be used in the above catalyst system include sodium compounds such as sodium fluoride, sodium chloride, sodium bromide, sodium iodide, sodium sulfate, potassium fluoride, potassium chloride, potassium bromide, Examples include potassium compounds such as potassium iodide and potassium sulfate; ammonium compounds such as tetraethylammonium fluoride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, and tetraethylammonium sulfate. Of these, sodium bromide, sodium iodide, potassium bromide, tetraethylammonium bromide, and tetraethylammonium iodide are preferred.

  The proportion of each component used is usually 0.0001 to 10 with respect to 1 mol of the total amount of the above-mentioned monomers (the total amount of monomers (A) + oligomer (B), hereinafter the same)) of the transition metal salt or transition metal complex. Mol, preferably 0.01 to 0.5 mol. When the amount is less than 0.0001 mol, the polymerization reaction may not proceed sufficiently. On the other hand, when the amount exceeds 10 mol, the molecular weight may decrease.

  In the above catalyst system, when a transition metal salt and a ligand component are used, the ratio of the ligand component used is usually 0.1 to 100 mol, preferably 1 to 10 mol, per 1 mol of the transition metal salt. It is. When the amount is less than 0.1 mol, the catalytic activity may be insufficient. On the other hand, when the amount exceeds 100 mol, the molecular weight may decrease.

  Moreover, the usage-amount of a reducing agent is 0.1-100 mol normally with respect to 1 mol of total of the said monomer, Preferably it is 1-10 mol. If the amount is less than 0.1 mol, polymerization may not proceed sufficiently. If the amount exceeds 100 mol, purification of the resulting polymer may be difficult.

  Furthermore, when using "salt", the usage-ratio is 0.001-100 mol normally with respect to the total of 1 mol of the said monomer, Preferably it is 0.01-1 mol. If it is less than 0.001 mol, the effect of increasing the polymerization rate may be insufficient, and if it exceeds 100 mol, purification of the resulting polymer may be difficult.

Examples of the polymerization solvent that can be used when the monomer (A) and the oligomer (B) are reacted include tetrahydrofuran, cyclohexanone, dimethyl sulfoxide, N,
N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N′-dimethylimidazolidinone and the like can be mentioned. Of these, tetrahydrofuran, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and N, N′-dimethylimidazolidinone are preferable. These polymerization solvents are preferably used after sufficiently dried.

The total concentration of the monomers in the polymerization solvent is usually 1 to 90% by weight, preferably 5 to 40% by weight.
Moreover, the superposition | polymerization temperature at the time of superposing | polymerizing is 0-200 degreeC normally, Preferably it is 50-120 degreeC. The polymerization time is usually 0.5 to 100 hours, preferably 1 to 40 hours.
The polyarylene having a sulfonic acid ester group obtained using the monomer (A) can be converted into a polyarylene having a sulfonic acid group by hydrolyzing the sulfonic acid ester group and converting it to a sulfonic acid group. .

Hydrolysis is
(1) A method in which polyarylene having the sulfonic acid ester group is added to an excess amount of water or alcohol containing a small amount of hydrochloric acid and stirred for 5 minutes or longer. (2) The sulfonic acid ester group is contained in trifluoroacetic acid. Method of reacting polyarylene for about 5 to 10 hours at a temperature of about 80 to 120 ° C. (3) 1 to 3 mol per mol of sulfonic acid ester group (—SO ₃ R) in polyarylene having a sulfonic acid ester group Examples include a method of reacting the polyarylene in a solution containing double moles of lithium bromide, such as N-methylpyrrolidone, at a temperature of about 80 to 150 ° C. for about 3 to 10 hours, and then adding hydrochloric acid. Can do.

In the polyarylene (C) having a sulfonic acid group produced by the method as described above, the amount of the sulfonic acid group is usually 0.3 to 5 meq / g, preferably 0.5 to 3 meq / g, more preferably 0.8 to 2.8 meq / g. If it is less than 0.3 meq / g, the proton conductivity is low and not practical. On the other hand, if it exceeds 5 meq / g, the water resistance may be significantly lowered, which is not preferable.
The amount of the sulfonic acid group can be adjusted, for example, by changing the type, use ratio, and combination of the monomer (A) and the oligomer (B).

  The molecular weight of the polyarylene having a sulfonic acid group thus obtained is 10,000 to 1,000,000, preferably 20,000 to 800,000 in terms of polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC).

(Additive)
The polyarylene polymer composition according to the present invention contains at least one additive selected from the group consisting of hindered phenol compounds, hindered amine compounds, organic phosphorus compounds, and organic sulfur compounds.

Hindered phenolic compounds;
Although the hindered phenol type compound used by this invention is not specifically limited, The hindered phenol type compound mentioned below is preferable.

1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (
Product name: IRGANOX 1330), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (product name: IRGANOX 1010), 2,6-di-t-butyl -4-methylphenol (trade name: Sumilizer BHT), 2,5-di-t-butyl-hydroquinone (trade name: Nocrac NS-7), 2,6-di-t-butyl-4-ethylphenol (product) Name: Nocrac M-17), 2,5-di-t-amylhydroquinone (trade name: Nocrac DAH), 2,2'-methylenebis (4-methyl-6-t-butylphenol) (trade name: Nocrac NS- 6), 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester (trade name: IRGANOX 1222), 4,4'-thiobis (3-methyl-6-t-butylphenol) ( Product name: Nocrac 300), 2,2'-methylenebis (4-ethyl-6-t-butylphenol) (product name: Nocrac NS-5), 4,4'-butylidenebis (3-methyl-6-t-butylphenol) ) (ADK STAB AO-40), 2-t -Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM), 2- [1- (2-hydroxy-3,5-di- -T-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate (
Product name: Sumilizer GS), 2,2'-methylenebis [4-methyl-6- (α-methyl-cyclohexyl)
Phenol], 4,4'-methylenebis (2,6-di-t-butylphenol) (trade name: Cynox 226M), 4,6-bis (octylthiomethyl) -o-cresol (trade name: IRGANOX 1520L) 2,2'-ethylenebis (4,6-di-t-butylphenol), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX 1076), 1 , 1,3-Tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane (trade name: ADK STAB AO-30), triethylene glycol bis [3- (3-t-butyl-5- Methyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 245), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine (trade name: IRGANOX 565), N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (trade name: IRGANOX 1098), 1, 6-hexanediol-bis [3- (3,5-di -t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 259), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] ( Product name: IRGANOX 1035), 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] 1,1-dimethylethyl] 2,4,8, 10-tetraoxaspiro [5.5] undecane (trade name: Sumilizer GA-80), tris- (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate (trade name: IRGANOX 3114), bis (3 , 5-Di-t-butyl-4-hydroxybenzylphosphonate ethyl) calcium / polyethylene wax mixture (50:50) (trade name: IRGANOX 1425WL), isooctyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate (trade name: IRGANOX 1135), 4,4'-thiobis (6-t-butyl-3-methylphenol) (trade name: Sumilizer WX-R), 6- [3- (3- t-butyl -4-Hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d, f] [1,3,2] dioxaphosphepine (trade name: Sumilizer GP) Such.

  Of these hindered phenol compounds, it is more preferable to use a compound having a molecular weight of 500 or more. When a hindered phenol compound having a molecular weight of 500 or more is used, the polyarylene polymer composition is difficult to bleed out and is excellent in the effect of improving the durability of the electrolyte membrane.

Particularly preferably, IRGANOX 245, IRGANOX 259, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGAONOX 1098, IRGANOX 1330, IRGANOX 3114, Sumilizer GA-80 (
(Product name).

Hindered amine compounds;
The hindered amine compound used in the present invention is not particularly limited, but the hindered amine compounds listed below are preferable.

p, p'-dioctyldiphenylamine (trade name: IRGANOX 5057), phenyl-α-naphthylamine (Nocrac PA), poly (2,2,4-trimethyl-1,2-dihydroquinoline) (trade name: Nocrac224,224- S), 6-ethoxy-2,2,4-trimethyl-1,2-cyhydroquinoline (trade name: Nocrac AW), N, N'-diphenyl-p-phenylenediamine (trade name: Nocrac DP), N , N'-Di-β-naphthyl-p-phenylenediamine (trade name: Nocrac White), N-phenyl-N'-isopropyl-p-phenylenediamine (trade name: Nocrac 810NA), N, N'-diallyl- p-Phenylenediamine (trade name: Nonflex TP), 4,4 '(α, α-dimethylbenzyl) diphenylamine (trade name: Nocrac
CD), p, p-toluenesulfonylaminodiphenylamine (trade name: Nocrac TD), N-
Phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine (trade name: Nocrac G1), N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine (product) Name: Ozonon 35), N, N'-di-sec-butyl-p-phenylenediamine (trade name: Sumilizer BPA)
N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine (trade name: Antigene 6C), alkylated diphenylamine (trade name: Sumilizer 9A), dimethyl-1- (2-hydroxyethyl) succinate -4-Hydroxy-2,2,6,6-tetramethylpiperidine polycondensate (trade name: Tinuvin
622LD), 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]] (trade name: CHIMASSORB 944), 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 (trade name: CHIMASSORB 119FL), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (trade name: TINUVIN 123), bis (2,2,6,6-tetramethyl-4-piperidyl) Sebacate (trade name: TINUVIN 770), 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4 -Piperidyl) (trade name: TINUVIN 144), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: TINUVIN 765), tetrakis ( 1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate (trade name: LA-57), tetrakis (2,2,6,6-tetramethyl- 4-piperidyl) 1,2,3,4-butanetetracarboxylate (trade name: LA-52), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl- Mixed esterified product of 4-piperidinol and 1-tridecanol (trade name: LA-62), 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and 1 -Esterified products with tridecanol (trade name: LA-67), 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] undecane mixed ester (trade name: LA-63P), 1,2,3,4- Butanetetracarboxylic acid and 2,2,6,6-tetramethyl-4-piperidinol and And 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane (trade name: LA-68LD), (2 , 2,6,6, -Tetramethylene-4-piperidyl) -2-propylene carboxylate (trade name: ADK STAB LA-82), (1,2,2,6,6-pentamethyl-4-piperidyl) -2 -Propylene carboxylate (trade name: ADK STAB LA-87).

  Of these hindered amine compounds, it is more preferable to use a compound having a molecular weight of 500 or more. When a hindered amine compound having a molecular weight of 500 or more is used, the polyarylene polymer composition is difficult to bleed out and is excellent in the effect of improving the durability of the electrolyte membrane.

Particularly preferably, Tinuvin 622LD, CHIMASSORB 944, CHIMASSORB 119FL, TINUVIN 123, TINUVIN 144, TINUVIN 765, LA-57, LA-52, LA-62, LA-67, LA-63P, LA-68LD, ADK STAB LA-82 , ADK STAB LA-87 (trade name) and the like.

Organophosphorus compounds;
The organophosphorus compound used in the present invention is not particularly limited, but the organophosphorus compounds listed below are preferable.

Bis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Product name: SANKO-HCA), Triethyl phosphite (Product name: JP302), Tri-n-Butyl phosphite (Product name: JP304), Triphenyl phosphite (Product name: ADK STAB TPP), Diphenyl monooctyl phosphite (Product name: Adekastab C), Tri (p-cresyl) phosphite (Product name: Chelex-PC), Diphenyl monodecyl phosphite (Product name: Adekastab 135A), Diphenyl mono (tridecyl) phosphite (Product name: JPM313 ), Tris (2-ethylhexyl) phosphite (trade name: JP308), phenyl didecyl phosphite (ADK STAB 517)
, Tridecyl phosphite (trade name: ADK STAB 3010), tetraphenyldipropylene glycol diphosphite (trade name: JPP100), bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-24G), Tris (tridecyl) phosphite (trade name: JP333E), bis (nonylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-4C), bis (2,6-di-t-butyl) -4-methylphenyl) pentaerythritol diphosphite (trade name: ADK STAB PEP-36), bis [2,4-di (1-phenylisopropyl) phenyl] pentaerythritol diphosphite (trade name: ADK STAB PEP-45) , Trilauryl trithiophosphite (trade name: JPS312), tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS 168), tris (nonylph) Nyl) phosphite (trade name: ADK STAB 1178), distearyl pentaerythritol diphosphite (trade name: ADK STAB PEP-8), tris (mono, dinonylphenyl) phosphite (trade name: ADK STAB 329K), trioleylphos Phyto (trade name: Chelex-OL), tristearyl phosphite (trade name: JP318E), 4,4'-butylidenebis (3-methyl-6-t-butylphenylditridecyl) phosphite (trade name: JPH1200), Tetra (C12-C15 mixed alkyl) -4,4'-isopropylidene diphenyl diphosphite (trade name: Adekastab 1500), tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenol) Diphosphite (trade name: ADK STAB 260), hexa (tridecyl) -1,1,3-tris (2-methyl-5-t-butyl-4-hydroxyphenyl) butane-triphosphite (trade) Name: ADK STAB 522A
), Hydrogenated bisphenol A phosphite polymer (HBP), tetrakis (2,4-di-t-butylphenyloxy) 4,4'-biphenylene-di-phosphine (trade name: P-EPQ), tetrakis (2, 4-di-t-butyl-5-methylphenyloxy) 4,4'-biphenylene-di-phosphine (trade name: GSY-101P), 2-[[2,4,8,10-tetrakis (1,1 -Dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphepin6-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 (trade name: IRGAFOS 12), 2,2'-methylenebis ( 4,6-di-t-butylphenyl) octyl phosphite (trade name: Adeka Sab HP-10).

Of these, ADK STAB PEP-36, P-EPQ, ADK STAB PEP-45, which have excellent hydrolysis resistance
IRGAFOS 168 and the like are particularly preferably used.

Organic sulfur compounds;
The organic sulfur compound used in the present invention is not particularly limited, but the organic sulfur compounds listed below are preferable.

Dilauryl-3,3'-thiodipropionate (trade name: Sumilizer TPL-R), dimyristyl-3,3'-thiodipropionate (trade name: Sumilizer TPM), distearyl-3,3'-thiodipro Pionate (trade name: Sumilizer TPS), pentaerythritol tetrakis (3-lauryl thiopropionate) (trade name: Sumilizer TP-D), ditridecyl-3,3'-thiodipropionate (trade name: Sumilizer TL) 2-mercaptobenzimidazole (trade name: Sumilizer MB), ditridecyl-3,3'-thiodipropionate (trade name: Adekastab AO-503A), 1,3,5-tris-β-stearylthiopropionyloxyethyl Isocyanurate, 3,3′-thiobispropionic acid didodecyl ester (trade name: IRGANOX PS 800FL), 3,3′-thiobispropionic acid diocdecyl ester (trade name: IRGANOX PS 802FL), etc.

  In the present invention, the amount of the additive to be added is not particularly limited, but an optimal amount can be used according to the oxidation resistance, proton conductivity, strength, elastic modulus and the like required for the polymer electrolyte. That's fine. Preferably, the total weight of the additive is 0.001 to 30 parts by weight based on 100 parts by weight of the polyarylene having a sulfonic acid group. Furthermore, it is more preferable to mix 0.01-10 weight part. Moreover, an additive may be used independently and may use 2 or more types together.

(Polymer electrolyte membrane)
The polymer electrolyte membrane of the present invention is produced by a casting method or the like in which the polyarylene having the sulfonic acid group and an additive are mixed in an organic solvent, and cast on a substrate to form a film. Can do. Here, the substrate is not particularly limited as long as it is a substrate used in a normal solution casting method. For example, a substrate made of plastic, metal, or the like is used, and preferably a heat treatment such as polyethylene terephthalate (PET) film. A substrate made of a plastic resin is used.

The solvent for mixing the polyarylene having the sulfonic acid group and the additive may be any solvent that dissolves or swells them. For example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, aprotic polar solvents such as γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, dimethylurea, dimethylimidazolidinone, acetonitrile, dichloromethane, chloroform, 1,2-dichloroethane,
Chlorinated solvents such as chlorobenzene and dichlorobenzene, alcohols such as methanol, ethanol, propanol, iso-propyl alcohol, sec-butyl alcohol, tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl Examples include solvents such as alkylene glycol monoalkyl ethers such as ether, ketones such as acetone, methyl ethyl ketone, cyclohexanone, and γ-butyl lactone, and ethers such as tetrahydrofuran and 1,3-dioxane. These solvents can be used alone or in combination of two or more. In particular, N-methyl-2-pyrrolidone (hereinafter also referred to as “NMP”) is preferable in terms of solubility and solution viscosity.

  When a mixture of an aprotic polar solvent and another solvent is used as the solvent, the composition of the mixture is 95 to 25% by weight of the aprotic polar solvent, preferably 90 to 25% by weight, The solvent is 5 to 75% by weight, preferably 10 to 75% by weight (however, the total is 100% by weight). When the amount of the other solvent is within the above range, the effect of lowering the solution viscosity is excellent. In this case, the combination of the aprotic polar solvent and the other solvent is preferably NMP as the aprotic polar solvent and methanol having an effect of lowering the solution viscosity in a wide composition range as the other solvent.

  The polymer concentration of the solution in which the polymer and the additive are dissolved depends on the molecular weight of the polyarylene having a sulfonic acid group, but is usually 5 to 40% by weight, preferably 7 to 25% by weight. If it is less than 5% by weight, it is difficult to form a thick film, and pinholes are easily generated. On the other hand, if it exceeds 40% by weight, the solution viscosity is so high that it is difficult to form a film, and surface smoothness may be lacking.

The solution viscosity depends on the molecular weight of the polyarylene having the sulfonic acid group, the polymer concentration, and the concentration of the additive, but is usually 2,000 to 100,000 mPa · s, preferably 3,000 to 50. 1,000 mPa · s. If it is less than 2,000 mPa · s, the retention of the solution during film formation is poor, and it may flow from the substrate. On the other hand, 100,000 mPa ·
If it exceeds s, the viscosity is too high to be extruded from the die, and it may be difficult to form a film by the casting method.

  After film formation as described above, when the obtained undried film is immersed in water, the organic solvent in the undried film can be replaced with water, and the amount of residual solvent in the resulting polymer electrolyte membrane is reduced. can do.

  In addition, after film formation, before immersing an undried film in water, you may predry an undried film. The preliminary drying is performed by holding the undried film at a temperature of usually 50 to 150 ° C. for 0.1 to 10 hours.

  When immersing an undried film (including a pre-dried film; the same shall apply hereinafter) in water, a batch method in which a single wafer is immersed in water may be used, and the film is formed on a substrate film (for example, PET). A continuous system may be used in which the laminated film is left as it is, or the film separated from the substrate is immersed in water and wound up. Moreover, in the case of a batch system, in order to suppress the formation of wrinkles on the treated film surface, it is preferable to immerse the film in water by a method such as placing an undried film on a frame.

  The amount of water used in immersing the undried film in water is 10 parts by weight or more, preferably 30 parts by weight or more, more preferably 50 parts by weight or more with respect to 1 part by weight of the undried film. If the amount of water used is in the above range, the amount of residual solvent in the resulting proton conducting membrane can be reduced. In addition, the amount of residual solvent in the resulting polymer electrolyte membrane can be reduced by changing the water used for immersion or overflowing it so that the organic solvent concentration in the water is always kept below a certain level. It is effective for. Furthermore, in order to suppress the in-plane distribution of the amount of the organic solvent remaining in the polymer electrolyte membrane, it is effective to homogenize the concentration of the organic solvent in water by stirring or the like.

  The temperature of water when the undried film is immersed in water is usually in the range of 5 to 80 ° C., preferably 10 to 60 ° C., from the viewpoint of the replacement speed and ease of handling. The higher the temperature, the faster the substitution rate of the organic solvent and water, but the greater the amount of water absorbed by the film, so the surface state of the polymer electrolyte membrane obtained after drying may deteriorate. Further, the immersion time of the film is usually in the range of 10 minutes to 240 hours, preferably 30 minutes to 100 hours, although it depends on the initial residual solvent amount, the amount of water used and the treatment temperature.

  When the undried film is immersed in water and dried as described above, a film with a reduced amount of residual solvent is obtained. The residual solvent amount of the film thus obtained is usually 5% by weight or less. Further, depending on the dipping conditions, the amount of residual solvent in the obtained film can be set to 1% by weight or less. As such conditions, for example, the amount of water used relative to 1 part by weight of the undried film is 50 parts by weight or more, the temperature of the water when immersed is 10 to 60 ° C., and the immersion time is 10 minutes to 10 hours. is there.

  After immersing the undried film in water as described above, the film is dried at 30-100 ° C, preferably 50-80 ° C, for 10-180 minutes, preferably 15-60 minutes, and then at 50-150 ° C. The film can be obtained by vacuum drying under reduced pressure of 500 mmHg to 0.1 mmHg for 0.5 to 24 hours.

  The polymer electrolyte membrane obtained by the method of the present invention has a dry film thickness of usually 10 to 100 μm, preferably 20 to 80 μm.

  In addition, after the polyarylene having the sulfonic acid ester group and the additive are formed into a film by the above-described method, the polymer electrolyte membrane according to the present invention is manufactured by appropriate post-treatment such as hydrolysis. You can also Specifically, a polymer composed of polyarylene having a sulfonic acid group is formed by forming a polyarylene having a sulfonic acid ester group and an additive into a film by the method described above and then hydrolyzing the film. An electrolyte membrane can be manufactured.

Further, when producing the polymer electrolyte membrane, in addition to the polyarylene having the sulfonic acid group and the additive, inorganic acids such as sulfuric acid and phosphoric acid, phosphate glass, tungstic acid, phosphate hydrate, β- Inorganic proton conductor particles such as alumina proton-substituted products and proton-introduced oxides, organic acids containing carboxylic acids, organic acids containing sulfonic acids, organic acids containing phosphonic acids, and appropriate amounts of water may be used in combination.

  The polymer electrolyte membrane of the present invention includes, for example, electrolytes for primary batteries, secondary batteries, fuel cells and the like, ion exchange membranes such as hydrohalic acid electrolysis and salt electrolysis, various sensors such as humidity sensors and gas sensors, water It can be used for electrolysis, signal transmission media, solid capacitors, display elements, oxygen concentrators, and the like.

[Example]
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example.

[Reference Example 1]
The structure of polyarylene having a sulfonic acid group used for the polymer electrolyte membrane is shown below.

(In the formula, x and y represent the molar ratio of repeating units, and p represents the number of repeating units.)
Synthesis of polyarylene having a sulfonic acid group represented by the above formula (I) was performed as follows.

(Oligomer synthesis)
2,2-bis (4-hydroxyphenyl) -1,1,1,3 was added to a 1 L three-necked flask equipped with a stirrer, thermometer, cooling tube, Dean-Stark tube, and three-way cock for introducing nitrogen. , 3,3-hexafluoropropane (bisphenol AF) 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 and toluene 150 mL were taken, heated in an oil bath under a nitrogen atmosphere, and reacted at 130 ° C. with stirring. When water produced by the reaction was azeotroped with toluene and reacted while being removed from the system with a Dean-Stark tube, almost no water was produced in about 3 hours. The reaction temperature was gradually increased from 130 ° C to 150 ° C. Most of the toluene was removed while the reaction temperature was gradually raised to 150 ° C., and the reaction was continued at 150 for 10 hours. Then, 10.0 g of 4,4′-DCBP (0
. 040 mol) was added and the reaction was continued for another 5 hours. The resulting reaction solution was allowed to cool, and then the by-product inorganic compound precipitate was removed by filtration, and the filtrate was put into 4 L of methanol. The precipitated product was separated by filtration, collected, dried, and dissolved in 300 mL of tetrahydrofuran. This was reprecipitated in 4 L of methanol to obtain 95 g (yield 85%) of the target compound.

The number average molecular weight in terms of polystyrene determined by GPC (THF solvent) of the obtained compound was 11,200. Further, the obtained compound was soluble in THF, NMP, DMAc, sulfolane and the like, Tg was 110 ° C., and thermal decomposition temperature was 498 ° C.

  The obtained compound was an oligomer represented by the formula (II) (hereinafter referred to as “BCPAF oligomer”).

(In the formula, p represents the number of repeating units.)
(Synthesis of polyarylene having a sulfonic acid group)
To a 1 L three-necked flask equipped with a stirrer, thermometer, cooling tube, Dean-Stark tube and nitrogen-introduced three-way cock, 4- (2,5-dichlorobenzoyl) benzenesulfonic acid neo-pentyl (A- SO ₃ neo-Pe) 33.2 g (82.7 mmol), BCPAF oligomer (Mn = 11,200) 20.4 g (1.8 mmol), Ni (PPh ₃ ) ₂ Cl ₂ 1.66 g
(2.5 mmol), PPh ₃ 8.87 g (33.8 mmol), NaI 0.38 g (
2.5 mmol), 13.3 g (202.8 mmol) of zinc dust, 123 mL of dry NMP were added under nitrogen. The reaction system was heated with stirring (finally heated to 75 ° C.) and allowed to react for 3 hours. The polymerization reaction liquid was diluted with 250 mL of THF, stirred for 30 minutes, Celite was used as a filter aid, the filter paper and the filtrate were poured into 1500 mL of a large excess of methanol, and solidified. The coagulum was collected by filtration, air-dried, redissolved in THF / NMP (200/300 mL each), and coagulated with 1500 mL of a large excess of methanol. After air drying, 47.0 g (yield 99%) of a copolymer (PolyAB-SO ₃ neo-Pe) composed of a sulfonic acid derivative protected with a target yellow fibrous neopentyl group was obtained by heat drying. The molecular weight by GPC is Mn = 47,600, Mw
= 159,000.

Thus obtained 5.1 g of PolyAB-SO ₃ neo-Pe was dissolved in 60 mL of NMP and heated to 90 ° C. To the reaction system, a mixture of 50 mL of methanol and 8 mL of concentrated hydrochloric acid was added at a time. While in suspension, the reaction was allowed to proceed for 10 hours under mild reflux conditions. A distillation apparatus was installed, and excess methanol was distilled off to obtain a light green transparent solution. This solution was poured into a large amount of water / methanol (1: 1 weight ratio) to solidify the polymer, and then the polymer was washed with ion-exchanged water until the pH of the washing water became 6 or more. From the IR spectrum of the polymer thus obtained and the quantitative analysis of the ion exchange capacity, it was found that the sulfonic acid ester group (—SO ₃ R ^a ) was quantitatively converted to the sulfonic acid group (—SO ₃ H). .

  The molecular weight of the obtained polyarylene having a sulfonic acid group represented by the formula (I) by GPC was Mn = 53,200, Mw = 185,000, and the sulfonic acid equivalent was 1.9 meq / g. It was.

(Production of polymer electrolyte membrane)
Put polyarylene having a sulfonic acid group represented by the formula (I) (100 g) and NMP (900 g) in a flask containing a stir bar so that the solid content is 10% by weight, and heat and dissolve at 80 ° C. It was. 1,3,5-trimethyl-2,4,6-tris (3,5-tris) as a hindered phenol compound with respect to 100 parts by weight of the solid content of the polyarylene having a sulfonic acid group represented by the formula (I) 1 part by weight of di-t-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330) was added, and the mixture was stirred and dissolved for 2 hours with a mix rotor to prepare a polymer solution.

Using a doctor blade (for 40 μm), this polymer varnish was applied onto a PET substrate and then preliminarily dried using an oven at 100 ° C. for 1 hour to peel the coating film from the PET substrate. The film was fixed on an aluminum plate with heat-resistant tape, and further dried at 150 ° C. for 1 hour using an oven. Next, in order to completely remove NMP remaining in the coating film,
It was immersed in 00 times the amount of ion exchange water at 25 ° C. for 2 days to remove NMP and dried at 50 ° C. for 1 hour to obtain the intended polymer electrolyte membrane (37 μm).

N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N as a hindered amine compound instead of a hindered phenol compound as an additive
- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate (trade name: CHIMASSORB 119FL) except for using the Reference Example 1 Similarly, a polymer electrolyte membrane was obtained.

1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (hindered amine compounds instead of hindered phenol compounds as additives 2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] similar to Reference Example 1 except that a mixed ester product (trade name: LA-63P) with undecane was used Thus, a polymer electrolyte membrane was obtained.

In addition to 1 part by weight of 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330), an organophosphorus compound bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite (
Product name: ADK STAB PEP-36) A polymer electrolyte membrane was obtained in the same manner as in Reference Example 1 except that 2 parts by weight were added.

Pentaerythrityl instead of hindered phenolic compound 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330) -Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010) 1 part by weight, and further organic sulfur compound distearyl-3,3'-thiodipro A polymer electrolyte membrane was obtained in the same manner as in Reference Example 1 except that 1 part by weight of pionate (trade name: Sumilizer TPS) was added.

(Comparative Example 1)
The hindered phenol compound 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene (trade name: IRGANOX 1330) was not added, but the formula (I A polymer electrolyte membrane was obtained in the same manner as in Reference Example 1 except that a membrane having only a polyarylene having a sulfonic acid group represented by formula (1) was produced.

(Evaluation of physical properties)
About the polymer electrolyte membrane containing the additive obtained in Reference Example 1 and Examples 1 to 4 and the polymer electrolyte membrane not containing the additive obtained in Comparative Examples 1 and 2, the sulfonic acid equivalent, Proton conductivity, breaking strength, elastic modulus, and Fenton resistance were evaluated. The results are shown in Table 1.
In addition, the measuring methods of sulfonic acid equivalent, proton conductivity, breaking strength, elastic modulus, and Fenton resistance are as follows.

<Measurement of sulfonic acid equivalent>
The obtained polymer electrolyte membrane is washed until the washing water becomes neutral, thoroughly washed with water except for free remaining acid, dried, weighed a predetermined amount, and mixed with a THF / water mixed solvent. Using dissolved phenolphthalein as an indicator, titration was performed using a standard solution of NaOH, and the sulfonic acid equivalent was determined from the neutralization point.

<Measurement of proton conductivity>
The AC resistance was obtained by pressing a platinum wire (f = 0.5 mm) on the surface of a strip-shaped sample film having a width of 5 mm, holding the sample in a constant temperature and humidity device, and measuring AC impedance between the platinum wires. . That is, the impedance at AC 10 kHz was measured in an environment of 85 ° C. and relative humidity 90%. A chemical impedance measurement system manufactured by NF Circuit Design Block Co., Ltd. was used as the resistance measurement device, and JW241 manufactured by Yamato Scientific Co., Ltd. was used as the constant temperature and humidity device. Five platinum wires were pressed at intervals of 5 mm, the distance between the wires was changed to 5 to 20 mm, and the AC resistance was measured. The specific resistance of the membrane was calculated from the line-to-line distance and the resistance gradient, and the proton conductivity was calculated from the reciprocal of the specific resistance.

Specific resistance R (Ω · cm) = 0.5 (cm) × film thickness (cm) × resistance-to-resistance gradient (Ω / cm)
<Measurement of breaking strength and elastic modulus>
The measurement of breaking strength and elastic modulus was performed according to JIS K7113 (Tensile speed:
50 mm / min). However, the elastic modulus was calculated with the distance between marked lines as the distance between chucks. According to JISK7113, the sample was conditioned for 48 hours under conditions of a temperature of 23 ± 2 ° C. and a relative humidity of 50 ± 5%. However, the No. 7 dumbbell described in JIS K6251 was used for punching the sample. As the tensile test measurement device, 5543 manufactured by INSTRON was used.

<Fenton test>
A Fenton reagent was prepared so that iron sulfate heptahydrate and iron ion concentration were 20 ppm in 3% by weight of hydrogen peroxide. 200 g of Fenton reagent was collected in a 250 ml polyethylene container, a polymer electrolyte membrane cut to 3 cm × 4 cm was added, sealed, and then immersed in a constant temperature water bath at 45 ° C. for 15 hours Fenton test. After the Fenton test, the film was taken out, washed with ion-exchanged water, prepared for conditions for 12 hours at 25 ° C. and 50%, and various physical properties were measured. The weight retention rate in the Fenton test was calculated by the following mathematical formula.
Weight retention (%) in Fenton test = film weight after Fenton test / film weight before Fenton test × 100

As shown in Examples 1 to 4 , the polymer electrolyte membrane mixed with the additive suppresses deterioration of the film after the Fenton test, and thus has a high oxidation resistance and produces a high output fuel cell. Because it is very advantageous.

Claims (4)

A polyarylene having a sulfonic acid group obtained by hydrolyzing a polyarylene having a sulfonic acid ester group obtained by polymerizing a monomer containing a sulfonic acid ester compound represented by the following general formula (A);
(I) or (ii) below
(I) Hindered amine compounds
(Ii) At least one selected from the group consisting of an organic phosphorus compound and an organic sulfur compound and a hindered phenol compound
A polyarylene polymer composition comprising an additive selected from :

(Wherein X represents a halogen atom excluding fluorine, an atom or group selected from —OSO ₃ CH ₃ and —OSO ₃ CF ₃ , A represents a divalent electron-withdrawing group, and B represents a divalent electron. donating group or a direct bond are shown, m represents an integer of 0, n represents an integer of 0, k is an integer of 1 to 4, R ^a is a hydrocarbon having 4-20 carbon atoms A group, Ar is —SO ₃ R ^b (wherein
R ^b represents a hydrocarbon group having 4 to 20 carbon atoms. ) Represents an aromatic group having a substituent represented by:   2. The polyarylene polymer composition according to claim 1, wherein the additive comprises 0.01 to 10 parts by weight of the total weight with respect to 100 parts by weight of the polyarylene having a sulfonic acid group.   A polymer electrolyte comprising the polyarylene polymer composition according to claim 1.   A proton conducting membrane comprising the polyarylene polymer composition according to claim 1.