JPWO2014208714A1 - Polyarylene sulfonic acids and precursors thereof, production method thereof, composite electrolyte membrane and production method thereof - Google Patents

Abstract

Polyarylene sulfonic acid having a large amount of sulfonic acid groups in the molecule and introducing a structure (benzoyl structure) that becomes a reaction point with other reactive compounds can be converted to reactive compounds or proton molecules with proton conductive groups. In addition to a reactive compound composition comprising a reactive compound having two or more reactive groups, the pores of the porous substrate are filled with the reactive compound, and the reactive compound is polyarylenesulfonic acid or reactive by external stimulation. It has been found that by reacting with a compound, an excellent polymer electrolyte membrane that does not contain a large amount of fluorine atoms and has both proton conductivity and durability can be obtained.

Description

The present invention relates to polyarylene sulfonic acids and precursors thereof that can be used as a polymer electrolyte, a method for producing the same, and a composite polymer electrolyte membrane using the polyarylene sulfonic acids and a method for producing the same.

Polymer electrolytes are used in solid polymer fuel cells (hereinafter referred to as fuel cells). A fuel cell is a device that generates electricity through a chemical reaction between hydrogen and oxygen, and is expected to be a major source of energy for the next generation, especially in the automobile industry.

  The fuel cell supplies hydrogen to the fuel electrode and is oxidized at the fuel electrode to generate protons and electrons. The generated protons move to the air electrode side through the polymer electrolyte membrane, and the generated electrons move to the air electrode side through the connected circuit. At the air electrode, oxygen reacts with protons and electrons to produce water. Thus, a fuel cell is a device that generates electricity by a series of reactions.

  The polymer electrolyte membrane used here is required to have high proton conductivity. Other properties include high film strength, low hydrogen and oxygen permeability, and poor chemical oxidation. In addition, cost reduction is also eagerly desired. Examples of the polymer electrolyte membrane that satisfies these required characteristics include hydrocarbon polymer electrolyte membranes. In particular, polyarylene sulfonic acids having a main chain skeleton directly linked with aromatic rings and having a sulfonic acid group as a proton conductive group are promising as materials for polymer electrolyte membranes. It is disclosed that polyarylene sulfonic acid can be obtained by copolymerizing a monomer having a protected sulfonic acid group and deprotecting the obtained polyarylene sulfonic acid precursor (see Patent Documents 1 and 2). reference). The polyarylene sulfonic acid disclosed in the above patent document can be used as a polymer electrolyte membrane by molding into a membrane, but in order to prevent dissolution in water, it is necessary to introduce a water-insoluble site by copolymerization. The amount of sulfonic acid groups in the polymer could not be increased.

Up to now, polymer electrolyte membranes have high proton conductivity as cation exchange membranes, are sufficiently stable chemically, thermally, electrochemically and mechanically and can be used over a long period of time. Membranes have been used. However, it is known that perfluorocarbon sulfonic acid membranes generally undergo significant degradation due to hydrogen peroxide generated by the reaction between permeated hydrogen and oxygen and the resulting hydroxy radicals when gas leakage is large and held in an open circuit state. It has been. In addition, in order to recover the platinum catalyst from the used fuel cell, the resin component is combusted, but the perfluorocarbon sulfonic acid membrane contains a large amount of fluorine, which prevents corrosion of incineration facilities and discharges harmful gases. It is necessary to take sufficient measures to prevent it. Furthermore, problems have been pointed out with fluorine-based electrolytes, such as fluorine ions generated by electrolyte degradation when used over a long period of time, corroding the inside of the system.

On the other hand, as electrolyte membranes that replace perfluorocarbon sulfonic acid membranes, so-called hydrocarbon polymer solid electrolytes in which ionic groups such as sulfonic acid groups are introduced into polymers such as polyetheretherketone, polyethersulfone, and polysulfone have recently become popular. It is being considered. However, hydrocarbon-based polymer solid electrolytes tend to hydrate and swell compared to perfluorocarbon sulfonic acid, and have large dimensional changes, so there are problems with mechanical properties such as breakage due to repeated drying and wetting. .

As a method for increasing the strength and durability of the polymer solid electrolyte membrane, there is a method of crosslinking the electrolyte membrane. A cross-linked polymer electrolyte membrane obtained by reacting a radical polymerizable monomer in the presence of an initiator in the presence of a polyarylene-based electrolyte (see, for example, Patent Document 3) or a polyfunctional triazine compound or a polyfunctional triazine compound in the electrolyte membrane A cross-linked polymer electrolyte membrane having a casing and a reaction thereof (for example, see Patent Document 4) has been reported. In both cases, the durability is improved by crosslinking, but if the proton conductivity is increased by increasing the amount of sulfonic acid groups in the electrolyte, the crosslinking will not suppress the expansion of the polymer electrolyte when it contains water, resulting in damage to the membrane. There is a fear. Increasing the crosslink density in order to suppress the expansion reduces the sulfonic acid group in the electrolyte, and it is difficult to overcome the trade-off relationship between the improvement in proton conductivity and the durability.

  It has been disclosed that a carbonyl group and a methyl group in a molecule are reacted in order to cause the polymer electrolytes to react with each other and improve durability (see, for example, Patent Document 5). However, since the reactivity of both is low and it is a polymer reaction, it is difficult to proceed with the reaction. When the reactive group is increased, the concentration of the ionic group decreases and the proton conductivity decreases. It was.

  Furthermore, as a method for improving the mechanical strength of the polymer solid electrolyte membrane and suppressing the dimensional change, a composite polymer solid electrolyte membrane in which various reinforcing materials are combined with the polymer solid electrolyte membrane has been proposed. A composite polymer solid electrolyte membrane (see, for example, Patent Document 6) in which the void portion of the stretched porous polytetrafluoroethylene membrane is impregnated with a perfluorocarbon sulfonic acid polymer, which is an ion exchange resin, is a perfluorocarbon sulfonic acid polymer. Composite polymer solid electrolyte membranes (see, for example, Patent Document 7) in which fibrillated polytetrafluoroethylene is dispersed as a reinforcing material are described. However, it does not change that it contains fluorine as an element, and the problem of environmental pollution at the time of disposal and the problem of the fluorine film generated at the time of power generation are still not solved.

  On the other hand, a polymer solid electrolyte membrane (see, for example, Patent Document 8) in which a polybenzoxazole porous membrane and a polymer solid electrolyte are combined as a hydrocarbon polymer solid electrolyte reinforced with a hydrocarbon reinforcing material. Have been described. In addition, an electrolyte membrane obtained by polymerizing a polymer having ion conductivity from a monomer permeated into the porous substrate (see, for example, Patent Document 9) or a polymer having an ion exchange group is filled in the porous substrate. An electrolyte membrane (for example, see Patent Document 10) has been reported.

  However, in any case, since the proportion of the filled hydrocarbon polymer solid electrolyte is smaller than that of the hydrocarbon polymer solid electrolyte single membrane, the ion exchange capacity of the obtained composite electrolyte membrane is lowered. For this reason, the electrolyte membrane is not so high in proton conductivity and is considered to be insufficient in terms of power generation performance when applied to a fuel cell using hydrogen as a fuel.

JP 2007-284653 A JP 2010-70750 A JP 2003-82012 A JP 2007-335264 A JP 2004-26889 A JP-A-8-162132 JP 2001-35508 A International Publication No. WO00 / 22684 International Publication No. WO05 / 76396 JP 2010-40530 A

An object of the present invention is to solve the above-mentioned problems of the prior art, and (1) to provide a useful precursor for producing polyarylene sulfonic acids that dissolve in water, and to provide a production method thereof. (2) providing polyarylene sulfonic acids having a high ion exchange group capacity and a solubility in 100 g of water at 25 ° C. of 0.1 g or more, and a method for producing the same, (3) hydrocarbons To solve the shortage of mechanical strength, which was a problem of polymer electrolyte membranes, improve proton conductivity as a composite membrane, and improve durability and performance when used in fuel cells. It is intended to provide a composite polymer electrolyte membrane that can be produced, a polymer electrolyte / electrode assembly using the composite polymer electrolyte membrane, and a fuel cell.
In addition, for further commercialization and popularization of fuel cells, the problems of existing polymer electrolytes such as compatibility of proton conductivity and durability, and suppression of the impact on the external environment during disposal and continuous use will be solved. This is a problem.

In order to solve the above problems, the present inventors have continued intensive studies. As a result, polyarylene sulfonic acid having a large amount of sulfonic acid groups in the molecule and introducing a structure that becomes a reaction point with other reactive compounds can be incorporated into reactive compounds or molecules having proton conductive groups. A reactive compound composition composed of a reactive compound having two or more reactive groups, etc., is filled into the pores of the porous substrate, and the reactive compound is polyarylenesulfonic acid or a reactive compound by external stimulation. It has been found that an excellent polymer electrolyte membrane that does not contain a large amount of fluorine atoms and has both proton conductivity and durability can be obtained by reacting with. Further, in the process, polyarylene sulfonic acid having a large amount of sulfonic acid groups and introducing a structure that becomes a reactive site with other reactive compounds, the benzoyl group is effective as a reactive site, and It was clarified that the introduction amount of acid groups, that is, the ion exchange capacity is more than a specific value and that the solubility in water is more than a certain value greatly contributes to the improvement of the characteristics of the novel polymer electrolyte membrane. And found a suitable polyarylene sulfonic acid. Furthermore, as a result of studying the production method for the polyarylene sulfonic acid, an appropriate method was found, the proper structure of the polyarylene sulfonic acid precursor and the production method thereof, and the production of polyarylene sulfonic acid from the polyarylene sulfonic acid As for the methods to be performed, the inventors have found an appropriate method and completed the present invention.

  Patent Document 2 describes a polyarylene sulfonic acid having a benzoyl structure, but the polyarylene sulfonic acid is water-insoluble and is clearly different from the polyarylene sulfonic acid of the present invention. . In Patent Documents 3 and 4, there is no description or suggestion that a reactive site is introduced into the polymer electrolyte, which is different from the present invention in terms of technical idea. Further, Patent Document 5 discloses a reaction between electrolytes by a photoreaction of a benzoyl group and a saturated hydrocarbon group. Although it is common with the present invention in that the benzoyl group is focused on as a reaction point, a reactive compound is used instead of a low-efficiency saturated hydrocarbon group and a more reactive compound, and not a reaction between polymer electrolytes. The present invention, which allows the reaction to proceed efficiently by bonding between the polymer electrolytes through the invention, has a special effect on the invention disclosed in Patent Document 5 and cannot be easily conceived. Is obvious. Further, in the inventions related to the reinforced electrolyte membranes of Patent Documents 6 to 10, there is no description or suggestion about using a polyarylene sulfonic acid having a reactive site in the polymer electrolyte and being water-soluble, and the present invention is novel and advanced. It is clear that it has sex.

That is, the present invention is achieved by (1) to (40).
(1)
A polyarylene sulfonic acid precursor having a structure represented by formulas (1) and (2).

(In the formula, Ar ¹ is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar ² is a benzoyl group containing no sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. A divalent aromatic group having
(2)
The polyarylene sulfonic acid precursor according to (1), which is represented by the formula (3).

(In the formula, m and n are positive integers satisfying m + n = 10 to 1000. Ar ¹ is an aromatic group containing a sulfonic acid group or a derivative of a sulfonic acid group that can be converted into a salt thereof. Ar ² does not include a sulfonic acid group or a derivative of a sulfonic acid group that can be converted into a salt thereof, and represents an aromatic group having a benzoyl group.)
(3)
The polyarylene sulfonic acid precursor according to (2), wherein the structural unit containing Ar ² in the formula (3) is represented by the formula (4).

(In the formula, n represents the same meaning as defined in Formula (3). R ¹ and R ² are hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , R ¹ and R ² may be the same or different, and R ³ is either an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. The substituent for R ³ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents may be the same or different. a represents an integer of 1 to 3, b represents an integer of 1 to 4. p and q are 0 or 1, and p + q = 1.
(4)
The polyarylene sulfonic acid precursor according to (3), wherein R ^{3 in the} formula (4) is an aryl group having 6 to 20 carbon atoms which may have a substituent.
(5)
The polyarylene sulfonic acid precursor according to any one of (3) and (4), wherein p = 0 and q = 1 in the formula (4).
(6)
The polyarylene sulfonic acid precursor according to any one of (3) and (4), wherein p = 1 and q = 0 in the formula (4).
(7)
The polyarylene sulfonic acid precursor according to any one of (2) to (6), wherein the structural unit containing Ar ¹ in the formula (3) has a structure represented by the formula (5).

(In the formula, m represents the same meaning as defined in formula (2). R ⁴ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. ^{May be the same} or different, r is 1 or 2, d is 4-r, A is OR ⁵ or N (R ⁶ ) (R ⁷ ), R ⁵ is hydrogen, Any one of an alkali metal and an alkyl group having 1 to 20 carbon atoms, R ⁶ and R ⁷ are either hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ may be the same; May be different.)
(8)
The polyarylene sulfonic acids according to (7), wherein 90% or more of R ⁵ in R in Formula (5) or R ⁶ and R ⁷ is an alkyl group having 1 to 20 carbon atoms. precursor.
(9)
The polyarylene according to any one of (1) to (8), wherein a composition containing at least the compounds represented by formulas (6) and (7) is subjected to coupling polymerization in the presence of a catalyst. A method for producing a sulfonic acid precursor.

(In the formula, X and Y are halogen atoms excluding fluorine, and X and Y may be the same or different. R ⁸ and R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. R ⁸ and R ⁹ may be the same or different, and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms that may have a substituent. Any one of ˜20, the substituent of R ^{10 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents are the same; A ′ is an integer of 1 to 3, b ′ is an integer of 1 to 4. p ′ and q ′ are 0 or 1, and p ′ + q ′ = 1.

(In the formula, X ′ and Y ′ are halogen atoms excluding fluorine, and X ′ and Y ′ may be the same or different. R ¹¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. Any of 20 aryl groups, the substituents may be the same or different, s is 1 or 2, e is 4-s, B is OR ¹² or N (R ¹³ ) (R ¹⁴ ), R ¹² represents any one of hydrogen, an alkali metal, or an alkyl group having 1 to 20 carbon atoms, and R ¹³ and R ¹⁴ are either hydrogen or an alkyl group having 1 to 20 carbon atoms. Yes, R ¹³ and R ¹⁴ may be the same or different.)
(10)
A composition comprising a nickel compound, a phosphorus ligand, zinc, and sodium iodide is used as the catalyst. The method for producing a polyarylene sulfonic acid precursor according to (9),
(11)
The polyarylenesulfonic acid precursor according to (10), wherein the nickel compound is bis (cyclooctadiene) nickel or nickel chloride bis (triphenylphosphine), and the phosphorus ligand is a triarylphosphine. Body manufacturing method.
(12)
Polyarylene sulfonic acids having a repeating structure of formula (8) and formula (9), having a solubility in 100 g of water at a temperature of 25 ° C. of 0.1 g or more and an ion exchange capacity of 3 meq / g or more.

(In the formula, Ar3 is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar3 is a divalent acid having a benzoyl group without containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. Of aromatic groups)
(13)
The polyarylene sulfonic acid according to (12), which has a structure represented by formula (10):

(Wherein, m1, n1 are, .Ar ³ is a sulfonic acid group showing a positive integer satisfying m1 + n1 = 10 to 1000, an aromatic group containing a sulfonate or sulfonic acid group derivative, Ar ⁴ is a sulfonic acid group, (Aromatic group having benzoyl group without sulfonate or sulfonic acid group derivative)
(14)
The structural unit containing Ar ⁴ in the formula (10) is represented by the formula (11), and the polyarylene sulfonic acids according to (13),

(In the formula, n1 represents the same meaning as defined in formula (10). R ¹⁵ and R ¹⁶ are any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , R ¹⁵ and R ¹⁶ may be the same or different, and R ¹⁷ represents either an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. The substituent of R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the substituents may be the same or different. ", B" represents an integer of 1 to 4. p ", q" is 0 or 1, indicating p "+ q" = 1)
(15)
R < ¹⁷ > of said Formula (11) is a C6-C20 aryl group which may have a substituent, The polyarylene sulfonic acids as described in (14) characterized by the above-mentioned.
(16)
The polyarylene sulfonic acids according to any one of (14) and (15), wherein p ″ = 0 and q ″ = 1 in the formula (11).
(17)
The polyarylene sulfonic acids according to any one of (14) and (15), wherein p ″ = 1 and q ″ = 0 in the formula (11).
(18)
The polyarylenesulfonic acid according to any one of (13) to (17), wherein the structural unit containing Ar ³ in the formula (10) has a structure represented by the formula (12).

(In the formula, m1 represents the same meaning as defined in formula (10). R ¹⁸ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. May be the same or different, r ′ is 1 or 2, d ′ represents 4-r ′, A ′ represents OR ¹⁹ , N (R ²⁰ ) ⁽ R ²¹ ), R ¹⁹ represents hydrogen, an alkali metal, an alkyl group having 1 to 20 carbon atoms, R ²⁰ and R ²¹ are either hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ²⁰ and R ²¹ are the same. May be different.)
(19)
In the formula (12), A ′ is OR ¹⁹ , and 80% or more of R ¹⁹ is hydrogen or an alkali metal, The polyarylene sulfonic acids according to (18),
(20)
The process according to any one of (12) to (19), which includes at least the following steps 1, 2, and 3, and is performed in the order of step 1, step 2, and step 3. A method for producing arylene sulfonic acids.
(Step 1) Step of coupling polymerization of a composition containing at least the compounds represented by Formula (13) and Formula (14) (Step 2) Deprotecting the sulfonic acid group derivative of the polymer produced in Step 1 Step of making a sulfonic acid group or a salt thereof (Step 3) Step of bringing the polymer produced in Step 2 into contact with an acid

(In the formula, X ¹ and Y ¹ are halogen atoms excluding fluorine, and X ¹ and Y ¹ may be the same or different. R ²² and R ²³ are hydrogen, an alkyl group having 1 to 20 carbon atoms, carbon R ²² or R ²³ may be the same or different, and R ²⁴ may have an alkyl group having 1 to 20 carbon atoms or a substituent. Any one of the preferable aryl groups having 6 to 20 carbon atoms, wherein the substituent of R ^{24 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; May be the same or different. A1 and b1 each represent an integer of 1 to 4. p1 and q1 are 0 or 1, and p1 + q1 = 1.

(In the formula, X ¹ ′ and Y ¹ ′ are halogen atoms excluding fluorine, and X ¹ ′ and Y ¹ ′ may be the same or different. R ²⁵ is hydrogen, an alkyl group having 1 to 20 carbon atoms, Any one of aryl groups having 6 to 20 carbon atoms, the substituents may be the same or different, s ′ is 1 or 2, e ′ is 4-s ′, B is OR ²⁶ or N (R ²⁷ ) (R ²⁸ ), R ²⁶ represents any one of hydrogen, an alkali metal, or an alkyl group having 1 to 20 carbon atoms, and R ²⁷ and R ²⁸ represent hydrogen or 1 to 20 carbon atoms. And R ²⁷ and R ²⁸ may be the same or different.)
(21)
The method for producing polyarylenesulfonic acids according to (20), wherein the deprotection in the step (b) uses an alkali metal halide or a quaternary ammonium halide.
(22)
The method for producing polyarylene sulfonic acids according to (20) or (21), wherein the acid in the step (c) is a solid acid.
(23)
The method for producing polyarylene sulfonic acids according to (22), wherein the solid acid is a cation exchange resin.
(24)
A composite polymer electrolyte membrane comprising a porous base material and a polymer electrolyte filled in its pores, wherein the polymer electrolyte is composed of two or more aromatic polymer electrolytes at sites other than ionic groups A composite polymer electrolyte membrane characterized by being connected by a compound having a structure different from that of the aromatic polymer electrolyte and having a repeating unit.
(25)
After filling the pores of the porous base material with a mixture containing an aromatic polymer electrolyte having a structure capable of generating radicals by external stimulation in the molecular chain and one or more radical polymerizable compounds, external stimulation is performed. The composite polymer electrolyte membrane according to (22) obtained by reacting the polymer electrolyte with the radical polymerizable compound.
(26)
The polymer electrolyte membrane according to (25), wherein at least one of the radical polymerizable compounds has a sulfonic acid group or a phosphonic acid group.
(27)
The composite polymer electrolyte membrane according to any one of (25) and (26), wherein at least one of the radical polymerizable compounds has two or more radical polymerizable groups.
(28)
The composite polymer electrolyte membrane according to any one of (25) to (27), wherein the external stimulus is ultraviolet ray irradiation or electron beam irradiation.
(29)
The composite polymer electrolyte membrane according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to claim 12.
(30)
The composite polymer electrolyte membrane according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to (13).
(31)
The composite polymer electrolyte membrane (32) according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to (14).
The composite polymer electrolyte membrane (33) according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to (15).
The composite polymer electrolyte membrane (34) according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acids described in (16).
The composite polymer electrolyte membrane (35) according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to (17).
The composite polymer electrolyte membrane (36) according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to (18).
The composite polymer electrolyte membrane (37) according to any one of (24) to (28), wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to (19).
The composite polymer electrolyte membrane according to any one of (24) to (36), wherein the porous substrate is mainly composed of a polymer material.
(38)
The composite polymer electrolyte membrane according to any one of (24) to (37), wherein the ion exchange capacity is 1.5 meq / g to 6.0 meq / g.
(39)
(24) -Polymer electrolyte membrane electrode assembly for fuel cells using the composite polymer electrolyte membrane according to any one of (38).
(40)
(39) A fuel cell using the polymer electrolyte membrane electrode assembly according to (39).

According to the present invention, polyarylene sulfonic acids having a high ion exchange capacity produced from polyarylene sulfonic acids having a specific structure can be suitably used as an electrolyte for a fuel cell. In addition, the composite electrolyte membrane in which the polyarylene sulfonic acids and the radically polymerizable monomer having an acidic group are filled in the pores of the porous membrane through crosslinking, realizes high proton conductivity due to high ion exchange capacity. In addition, since the crosslinked polymer electrolyte is filled in the pores of the porous substrate, hydration / swelling can be suppressed, dimensional change is reduced, and breakage occurs due to repeated drying / wetting. The problem of mechanical characteristics can be solved.

¹ is a ¹ H-NMR spectrum (solvent: chloroform-d6) of a polyarylene sulfonic acid precursor obtained in Example 2. ^{1 is} a ¹ H-NMR spectrum (solvent: heavy water) of polyarylenesulfonic acids obtained in Example 6.

  Hereinafter, the present invention will be described in detail.

The first invention of the present application relates to a polyarylene sulfonic acid precursor and a method for producing the same.
The polyarylene sulfonic acid precursor of the present invention is:
A polyarylene sulfonic acid precursor having a structure represented by formula (1) and formula (2).

(In the formula, Ar ¹ is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar ² is a benzoyl group containing no sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. A divalent aromatic group having

  A further preferred embodiment of the polyarylene sulfonic acid precursor of the present invention is a polyarylene sulfonic acid precursor having a structure represented by the following formula (3).

(In the formula, m and n are positive integers, and m + n = 10 to 1000. Ar ¹ is an aromatic group containing a sulfonic acid group, a sulfonic acid salt or a sulfonic acid group derivative, Ar ² is a sulfonic acid group, (Aromatic group having benzoyl group without sulfonate or sulfonic acid group derivative)

In the formula (3), if m + n is less than 10, it is difficult to maintain the shape as the electrolyte precursor, and if m + n exceeds 1000, polymerization is difficult, which is not preferable. The more preferable range of m + n is 15 to 500, and more preferably 20 to 100. In addition, it is preferable to use the average value of all molecules for m + n. m: n = 70: 30 to 99: 1 is preferable, and 80:20 to 90:10 is more preferable.

The structural units containing Ar ¹ and Ar ² in the formula (3) are represented by formula (4) and formula (5), respectively.

(In the formula, n represents the same meaning as defined in the above formula (2). R ¹ and R ² are either hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. R ¹ and R ² may be the same or different, and R ³ is either an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. The substituent for R ³ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents may be the same or different. a represents an integer of 1 to 3, b represents an integer of 1 to 4. p and q are 0 or 1, and p + q = 1.

(In the formula, m represents the same meaning as defined in the above formula (2). R ⁴ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The groups may be the same or different, r is 1 or 2, d is 4-r, A is OR ⁵ or N (R ⁶⁾ (R ⁷ ), and R ⁵ is hydrogen , An alkali metal, an alkyl group having 1 to 20 carbon atoms, R ⁶ and R ⁷ are either hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ are the same. May be different.)

R ^{1 to} R ⁴ may be the same group or different groups. Among them, R ¹ , R ² and R ⁴ are preferably hydrogen, and R ³ is an aryl group having 6 to 20 carbon atoms which may have a substituent from the viewpoint of chemical stability and reactivity. Are preferable, and a phenyl group is particularly preferable.

When R ^{1 to} R ⁴ are an alkyl group having 1 to 20 carbon atoms, examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- Butyl group, n-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n -Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, 1,3-butadiene-1,4-diyl And a straight-chain, branched or cyclic structure such as a group, butane-1,4-diyl group, pentane-1,5-diyl group. Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group, and 2-anthryl group.

In the formula (4), a is an integer of 1 to 3, b is an integer of 1 to 4, p and q are 0 or 1, and p + q = 1. That is, p = 1, q = 0 or p = 0, q = 1. Of these, p = 0 and q = 1 are preferable from the viewpoint of reactivity.

In the formula (4), r is 1 or 2, d is 4-r, r is 1, and d is preferably 3.

From the viewpoint of stability as a precursor, it is preferable that 90% or more of R ⁵ in A of the formula (5) or R ⁶ and R ⁷ is an alkyl group having 1 to 20 carbon atoms, and 95% More preferably, it is the above. R ⁵ in A in the formula (5) may be a hydrogen atom or an alkali metal atom other than the alkyl group having 1 to 20 carbon atoms.

Hereafter, the manufacturing method of the polyarylene sulfonic acid precursor of this invention is demonstrated.

Examples of the first component of the raw material compound for producing the polyarylene sulfonic acid precursor represented by the formula (1) include a dihalobenzene compound which may have a substituent represented by the formula (6).

(In the formula, X and Y are halogen atoms excluding fluorine, and X and Y may be the same or different. R ⁸ and R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. R ⁸ and R ⁹ may be the same or different, and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms that may have a substituent. Any one of ˜20, the substituent of R ^{10 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents are the same; A ′ is an integer of 1 to 3, b ′ is an integer of 1 to 4. p ′ and q ′ are 0 or 1, and p ′ + q ′ = 1.

Examples of the compound represented by the formula (6) include 2,4-dichlorobenzophenone, 2,5-dichlorobenzophenone, 3,4-dichlorobenzophenone, 2,4′-dichlorobenzophenone, which may have a substituent, 4,4′-dichlorobenzophenone, 2,4-dibromobenzophenone, 2,5-dibromobenzophenone, 3,4-dibromobenzophenone, 2,4′-dibromobenzophenone, 4,4′-dibromobenzophenone, and derivatives thereof Can be mentioned. Among these, 2,5-dichlorobenzophenone, 4,4′-dichlorobenzophenone and derivatives thereof which may have a substituent are preferable, 2,5-dichlorobenzophenone and 4,4′-dichlorobenzophenone are more preferable, and 2 More preferred is, 5-dichlorobenzophenone.

Dihalobenzenesulfonic acid ester or dihalobenzene which may have a substituent represented by formula (7) as the second component of the raw material compound for producing the polyarylenesulfonic acid precursor of formula (2) And sulfonic acid amides.

(In the formula, X ′ and Y ′ are halogen atoms excluding fluorine, and X ′ and Y ′ may be the same or different. R ⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. is either an aryl group having 20, Table substituents may optionally be the same or different .s is 1 or 2, e is .B showing a 4-s with oR ⁸ or NR ⁹ ₂ R ⁸ represents either hydrogen, an alkali metal or an alkyl group having 1 to 20 carbon atoms, and R ⁹ represents either hydrogen or an alkyl group having 1 to 20 carbon atoms.)

Examples of the compound represented by the formula (7) include isopropyl 2,5-dichlorobenzenesulfonate, isobutyl 2,5-dichlorobenzenesulfonate, 2,5-dichlorobenzenesulfonate (2,2-dimethylpropyl), Cyclohexyl 2,5-dichlorobenzenesulfonate, n-octyl 2,5-dichlorobenzenesulfonate, n-pentadecyl 2,5-dichlorobenzenesulfonate, n-icosyl 2,5-dichlorobenzenesulfonate, 3,5 -Isopropyl dichlorobenzenesulfonate, isobutyl 3,5-dichlorobenzenesulfonate, 3,5-dichlorobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 3,5-dichlorobenzenesulfonate, 3,5-dichlorobenzene N-octyl sulfonate, 3,5- N-pentadecyl chlorobenzenesulfonate, n-icosyl 3,5-dichlorobenzenesulfonate, isopropyl 2,5-dibromobenzenesulfonate, isobutyl 2,5-dibromobenzenesulfonate, 2,5-dibromobenzenesulfonate (2, 2-dimethylpropyl), cyclohexyl 2,5-dibromobenzenesulfonate, n-octyl 2,5-dibromobenzenesulfonate, n-pentadecyl 2,5-dibromobenzenesulfonate, n- 2,5-dibromobenzenesulfonate Icosyl, isopropyl 3,5-dibromobenzenesulfonate, isobutyl 3,5-dibromobenzenesulfonate, 3,5-dibromobenzenesulfonate (2,2-dimethylpropyl), cyclohexyl 3,5-dibromobenzenesulfonate, 3, , 5- N-octyl bromobenzenesulfonate, n-pentadecyl 3,5-dibromobenzenesulfonate, n-icosyl 3,5-dibromobenzenesulfonate, 2,4-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), 2 , 4-Dibromobenzenesulfonic acid (2,2-dimethylpropyl), 2,5-dichlorosulfonic acid amide, N-methyl-2,5-dichlorosulfonic acid amide, N, N-dimethyl-2,5-dichlorosulfone Acid amide, N-ethyl-2,5-dichlorosulfonic acid amide, N, N-diethyl-2,5-dichlorosulfonic acid amide, N-propyl-2,5-dichlorosulfonic acid amide, N, N-dipropyl- 2,5-dichlorosulfonic acid amide, N-butyl-2,5-dichlorosulfonic acid amide, N, N-dibutyl-2, 5-dichlorosulfonic acid amide, 2,4-dichlorosulfonic acid amide, N-methyl-2,4-dichlorosulfonic acid amide, N, N-dimethyl-2,4-dichlorosulfonic acid amide, N-ethyl-2, 4-dichlorosulfonic acid amide, N, N-diethyl-2,4-dichlorosulfonic acid amide, N-propyl-2,4-dichlorosulfonic acid amide, N, N-dipropyl-2,4-dichlorosulfonic acid amide, N-butyl-2,4-dichlorosulfonic acid amide, N, N-dibutyl-2,4-dichlorosulfonic acid amide, 3,5-dichlorosulfonic acid amide, N-methyl-3,5-dichlorosulfonic acid amide, N, N-dimethyl-3,5-dichlorosulfonic acid amide, N-ethyl-3,5-dichlorosulfonic acid amide, N, N-diethyl-3,5-di Lorosulfonic acid amide, N-propyl-3,5-dichlorosulfonic acid amide, N, N-dipropyl-3,5-dichlorosulfonic acid amide, N-butyl-3,5-dichlorosulfonic acid amide, N, N-dibutyl -3,5-dichlorosulfonic acid amide, 2,5-dibromosulfonic acid amide, N-methyl-2,5-dibromosulfonic acid amide, N, N-dimethyl-2,5-dibromosulfonic acid amide, N-ethyl -2,5-dibromosulfonic acid amide, N, N-diethyl-2,5-dibromosulfonic acid amide, N-propyl-2,5-dibromosulfonic acid amide, N, N-dipropyl-2,5-dibromosulfone Acid amide, N-butyl-2,5-dibromosulfonic acid amide, N, N-dibutyl-2,5-dibromosulfonic acid amide, 2,4-dibu Mosulfonic acid amide, N-methyl-2,4-dibromosulfonic acid amide, N, N-dimethyl-2,4-dibromosulfonic acid amide, N-ethyl-2,4-dibromosulfonic acid amide, N, N-diethyl -2,4-dibromosulfonic acid amide, N-propyl-2,4-dibromosulfonic acid amide, N, N-dipropyl-2,4-dibromosulfonic acid amide, N-butyl-2,4-dibromosulfonic acid amide N, N-dibutyl-2,4-dibromosulfonic acid amide, 3,5-dibromosulfonic acid amide, N-methyl-3,5-dibromosulfonic acid amide, N, N-dimethyl-3,5-dibromosulfone Acid amide, N-ethyl-3,5-dibromosulfonic acid amide, N, N-diethyl-3,5-dibromosulfonic acid amide, N-propyl-3,5 -Dibromosulfonic acid amide, N, N-dipropyl-3,5-dibromosulfonic acid amide, N-butyl-3,5-dibromosulfonic acid amide, N, N-dibutyl-3,5-dibromosulfonic acid amide It is done. Among them, 2,5-dichlorobenzenesulfonic acid (2,2-dimethylpropyl), isobutyl 2,5-dichlorobenzenesulfonic acid, and cyclohexyl 2,5-dichlorobenzenesulfonic acid are from the viewpoint of stability as a sulfonic acid group precursor. preferable. 2,5-dichlorobenzenesulfonic acid amide, N-methyl-2,5-dichlorobenzenesulfonic acid amide, N, N-dimethyl-2,5-dichlorobenzenesulfonic acid amide, N-ethyl-2,5- Dichlorobenzenesulfonic acid amide, N, N-diethyl-2,5-dichlorobenzenesulfonic acid amide, N-propyl-2,5-dichlorobenzenesulfonic acid amide, N-butyl-2,5-dichlorobenzenesulfonic acid amide It is preferable from the viewpoint of stability during polymerization.

The polyarylene sulfonic acid precursor of the present invention can be polymerized by a coupling reaction of the first synthetic component and the second synthetic component, but in that case, it is preferable to use a catalyst. Is preferably a composition containing a nickel compound, a ligand, and a reducing agent, and more preferably an iodine compound or the like is used as a reaction accelerator.

As nickel compounds, nickel (0) bis (cyclooctadiene), nickel (0) (ethylene) bis (triphenylphosphine), nickel (0) tetrakis (triphenylphosphine) and other zerovalent nickel compounds, nickel fluoride, Nickel halides such as nickel chloride, nickel bromide and nickel iodide, nickel carboxylates such as nickel formate and nickel acetate, nickel sulfate, nickel carbonate, nickel nitrate, nickel acetylacetonate, bis (triphenylphosphine) nickel dichloride And divalent nickel compounds such as nickel (0) bis (cyclooctadiene), nickel halide, and bis (triphenylphosphine) nickel dichloride are preferable.

The used amount of the nickel compound is preferably 0.01 to 500 mol% with respect to the monomer, and if the used amount of the nickel compound is too large, the molecular weight tends to decrease. Further, it is practically 100 mol% or less due to difficulty in purification and cost. On the other hand, if the amount is too small, the catalytic ability may be lost due to the influence of water present in the system, and it is practically 1 mol% or more. That is, 1-100 mol %% is preferable.

Examples of the ligand include nitrogen-containing bidentate ligands and phosphorus ligands. Examples of the nitrogen-containing bidentate ligand include 2,2'-bipyridine, 1,10-phenanthroline, methylenebisoxazoline, N, N'-tetramethylethylenediamine, and the like. On the other hand, as the phosphorus ligand, triphenylphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, tris (p-tolyl) phosphine, 1,2-bis (diphenylphosphino) ethane, 1, 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, Triphenylphosphine, tris (o-tolyl) phosphine, tris (m-tolyl) phosphine, and tris (p-tolyl) phosphine are preferable. The amount of the ligand used is 0.5 to 8.0 equivalents, preferably 1.0 to 44.0 equivalents, with respect to the nickel compound.

Zinc is preferably used as the reducing agent. The amount used is usually 1 equivalent or more with respect to the monomer, and there is no upper limit. Practically, in consideration of purification after polymerization, it is 5 equivalents or less, preferably 2 equivalents or less. Moreover, it is preferable that zinc is a powder and it is preferable to wash | clean with an acid etc. before use.

  As an iodine compound used as a compound for promoting the reaction, sodium iodide, potassium iodide, or the like can be used, and sodium iodide can be used. It is presumed that the iodine compound acts on the monomer and substitutes the halogen group with the iodine group to further improve the reactivity.

The polymerization solvent may be any solvent that can dissolve the monomer, the catalyst composition, and the polyarylenesulfonic acid precursor to be produced. Specific examples of such solvents include aromatic hydrocarbon solvents such as toluene and xylene, ether solvents such as tetrahydrofuran and 1,4-dioxane, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide. And aprotic polar solvents such as N, N-dimethylacetamide, and halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, and chloroform. A solvent may be used independently and may be used in mixture of 2 or more types. Of these, ether solvents and aprotic polar solvents are preferable, and tetrahydrofuran, dimethyl sulfoxide, N-methyl-2-pyrrolidone and N, N-dimethylacetamide are more preferable. When the amount of the solvent used is too large, polyarylene having a small molecular weight is easily obtained, and when the amount is too small, it is not preferable from the viewpoint of the solubility of the monomer composition and the resulting polyarylene. It is 1-200 weight times normally with respect to the monomer in a monomer composition, Preferably it is 5-100 weight times.

The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas. The polymerization time is preferably 0.5 to 48 hours, and the reaction temperature is preferably from room temperature to the boiling point of the solvent.

The polyarylene sulfonic acid precursor is reprecipitated by introducing the solution after the reaction into an acidic aqueous solution, and then the polyarylene sulfonic acid precursor is obtained by removing impurities using an organic solvent. The solvent used for removing impurities is preferably a solvent that does not dissolve the polyarylene sulfonic acid precursor but can dissolve organic impurities such as monomers, oligomer components, and ligand components. The molecular weight and structure of the obtained polyarylene sulfonic acid precursor can be analyzed by ordinary analysis means such as gel permeation chromatography and NMR. Examples of the solvent used for removing impurities include alcohols such as methanol, ethanol and 2-propanol, acetone and acetonitrile, and 2-propanol and acetone are preferable.

The second invention of the present application relates to polyarylene sulfonic acids and a method for producing the same.
The polyarylene sulfonic acids of the present invention are
Polyarylene sulfonic acids having a repeating structure of formula (8) and formula (9), a solubility in 100 g of water at a temperature of 25 ° C. of 0.1 g or more and an ion exchange capacity of 3 meq / g or more.

(In the formula, Ar3 is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar3 is a divalent acid having a benzoyl group without containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. Of aromatic groups)

  A more preferred embodiment of the polyarylene sulfonic acid of the present invention is polyarylene sulfonic acids having a structure represented by the following formula (10).

(Wherein, m1, n1 are, .Ar ³ is a sulfonic acid group showing a positive integer satisfying m1 + n1 = 10 to 1000, an aromatic group containing a sulfonate or sulfonic acid group derivative, Ar ⁴ is a sulfonic acid group, (Aromatic group having benzoyl group without sulfonate or sulfonic acid group derivative)

In formula (10), if m1 + n1 is less than 10, it is difficult to maintain the shape as an electrolyte, and if m1 + n1 exceeds 1000, polymerization becomes difficult, which is not preferred. The more preferable range of m1 + n1 is 15 to 500, and more preferably 20 to 100. In addition, it is preferable to use the average value of all molecules for m1 + n1. It is preferable that it is the range of m1: n1 = 70: 30-99: 1, and it is more preferable that it is the range of 80: 20-90: 10.

The ion exchange capacity is the sulfonic acid group concentration per unit weight. When the molecular weight in the unit structure is defined as M and the number of sulfonic acid groups in the unit structure is defined as N, the ion exchange capacity K “milliequivalent / g” is Can be expressed as
K = 1000 × N / M

From the viewpoint of proton conductivity of the electrolyte, the ion exchange capacity is preferably in the range of 3 to 16 meq / g. More preferably, the ion exchange capacity is 3.0 to 8.4 meq / g, more preferably 3.5 to 8.0 meq / g, and more preferably 4.0 to 7.5 meq / g. Further preferred.

The structural units containing Ar ³ and Ar ⁴ in formula (10) are structures represented by formulas (11) and (12), respectively.

(In Formula (11), n1 represents the same meaning as defined in Formula (10). R ¹⁵ and R ¹⁶ are any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. R ¹⁵ and R ¹⁶ may be the same or different, and R ¹⁷ is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. The substituent for R ^{17 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents may be the same or different. A ″ and b ″ are integers of 1 to 4. p ″ and q ″ are 0 or 1, and p ″ + q ″ = 1. In Formula (12), m1 is defined by Formula (10). the ^{.R 18} represent the same meaning as hydrogen, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms Is either aryl group 20, the substituents may optionally be the same or different .r 'is 1 or 2, d' is '.A showing a' 4-r is OR ^19, N (R ²⁰ ) represents ⁽ R ²¹ ), R ¹⁹ represents hydrogen, an alkali metal, or an alkyl group having 1 to 20 carbon atoms, and R ²⁰ and R ²¹ are either hydrogen or an alkyl group having 1 to 20 carbon atoms. And R ²⁰ and R ²¹ may be the same or different.)

R ^{15 to} R ¹⁸ may be the same group or different groups. Among them, R ¹⁵ , R ¹⁶ and R ¹⁸ are preferably hydrogen, and R ¹⁷ is an aryl group having 6 to 20 carbon atoms which may have a substituent from the viewpoint of chemical stability and reactivity. Are preferable, and a phenyl group is particularly preferable.

When R ^{15 to} R ¹⁸ are an alkyl group having 1 to 20 carbon atoms, examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Butyl group, n-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n -Tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, 1,3-butadiene-1,4-diyl And a straight-chain, branched or cyclic structure such as a group, butane-1,4-diyl group, pentane-1,5-diyl group. Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 3-phenanthryl group, and 2-anthryl group.

In formula (11), a ″ and b ″ represent integers of 1 to 4, p ″ and q ″ are 0 or 1, and p ″ + q ″ = 1. That is, either p ″ = 1 and q ″ = 0 or p ″ = 0 and q ″ = 1. Of these, p ″ = 0 and q ″ = 1 are preferable from the viewpoint of reactivity.

In the formula (12), r ′ is 1 or 2, d ′ is 4-r ′, r ′ is 1, and d ′ is preferably 3.

In view of proton conductivity as an electrolyte, A ′ in the formula (12) is preferably OH, at least 80% of A ′ is more preferably OH, and more preferably 90% or more, More preferably 95% or more. A ′ other than OH may be OR ¹⁹ in which R ¹⁹ is other than H, or N (R ²⁰ ) ⁽ R ²¹ ), or OR ¹⁹ in which R ¹⁹ is an alkali metal atom.

Hereinafter, the manufacturing method of the polyarylene sulfonic acids of this invention is demonstrated.

The polyarylene sulfonic acids of the present invention include at least the following Step 1, Step 2, and Step 3, and can be produced by carrying out in the order of Step 1, Step 2, and Step 3.
(Step 1) Step of coupling polymerization of a composition containing at least the compounds represented by Formula (13) and Formula (14) (Step 2) Deprotecting the sulfonic acid group derivative of the polymer produced in Step 1 Step of making a sulfonic acid group or a salt thereof (Step 3) Step of bringing the polymer produced in Step 2 into contact with an acid

(In the formula, X ¹ and Y ¹ are halogen atoms excluding fluorine, and X ¹ and Y ¹ may be the same or different. R ²² and R ²³ are hydrogen, an alkyl group having 1 to 20 carbon atoms, carbon R ²² or R ²³ may be the same or different, and R ²⁴ may have an alkyl group having 1 to 20 carbon atoms or a substituent. Any one of the preferable aryl groups having 6 to 20 carbon atoms, wherein the substituent of R ^{24 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; May be the same or different. A1 and b1 each represent an integer of 1 to 4. p1 and q1 are 0 or 1, and p1 + q1 = 1.

(In the formula, X ¹ ′ and Y ¹ ′ are halogen atoms excluding fluorine, and X ¹ ′ and Y ¹ ′ may be the same or different. R ²⁵ is hydrogen, an alkyl group having 1 to 20 carbon atoms, Any one of aryl groups having 6 to 20 carbon atoms, the substituents may be the same or different, s ′ is 1 or 2, e ′ is 4-s ′, B is OR ²⁶ or N (R ²⁷ ) (R ²⁸ ), R ²⁶ represents any one of hydrogen, an alkali metal, or an alkyl group having 1 to 20 carbon atoms, and R ²⁷ and R ²⁸ represent hydrogen or 1 to 20 carbon atoms. And R ²⁷ and R ²⁸ may be the same or different.)

Step 1 is described in the method for producing the polyarylene sulfonic acid precursor of the present invention. In Step 2, a sulfonic acid group or a salt thereof can be obtained by deprotecting the sulfonic acid ester group or sulfonic acid amide group of the polyarylenesulfonic acid precursor. Further, in step 3, the salt of the sulfonic acid group is converted into a sulfonic acid group by contacting with an acid. Through the above steps, the polyarylene sulfonic acids of the present invention can be produced.

The deprotection in step 2 is preferably performed by hydrolysis, and is preferably decomposed in the presence of water and an acid or alkali. When an acidic or alkaline aqueous solution is used as the acid or alkali, the water-soluble polyarylene sulfonic acids of the present invention are difficult to purify. Therefore, it is preferable to perform deprotection in an organic solvent using an alkali metal halide or a quaternary ammonium halide.

Examples of the alkali metal halide include lithium bromide and sodium iodide. Examples of the amine hydrochloride include trimethylamine hydrochloride and triethylamine hydrochloride. Lithium bromide and trimethylamine hydrochloride are preferable, and trimethylamine is preferable. Hydrochloride is more preferred. The amount used is 1.1 to 10 equivalents, preferably 2 to 8 equivalents, relative to the sulfonic acid ester or sulfonic acid amide in the polymer.

The solvent used for the reaction is preferably a solvent in which the deprotecting agent is dissolved and the polyarylenesulfonic acid precursor is dissolved. For example, an aprotic polar solvent such as N-methylpyrrolidone can be used. The reaction temperature is usually 0 to 200 ° C, preferably 80 to 160 ° C.

In the solution after the reaction, polyarylene sulfonic acids converted into an ammonium sulfonate type or a metal salt type of sulfonic acid, a reaction residue of a deprotecting agent, and a reaction solvent are present, so purification is necessary. Solvents used for purification are those in which polyarylene sulfonic acids converted to ammonium sulfonate type or sulfonic acid metal salt type do not dissolve and the reaction residue of the deprotecting agent dissolves, or ammonium sulfonate type or sulfonic acid metal salt type There is a need for a solvent in which the polyarylene sulfonic acids converted into bis are dissolved and the reaction residue of the deprotecting agent is not dissolved. Examples of the solvent in which the produced polyarylene sulfonic acids are not dissolved and the reaction residue of the deprotecting agent is dissolved include a halogenated hydrocarbon solvent. Of these, chloroform is preferred. Extraction is preferred as a purification method.

When the polyarylene sulfonic acid is converted into an ammonium sulfonate type or a metal salt of sulfonic acid and brought into contact with the acid, it is preferable to use a solid acid for ease of separation. As the solid acid, an inorganic solid acid such as a heteropoly acid, sulfonated amorphous carbon, and a cation exchange resin can be used. From the viewpoint of improving production efficiency and purity, a cation-sensitive resin can be used. More preferred. The amount of the cation exchange resin used depends on the ion exchange capacity of the cation exchange resin, but since it is an equilibrium reaction, a considerable amount more than 10 times the ion exchange capacity of the target polymer is required. Although there is no particular upper limit, it is practically 20 times or less. The acid treatment may be carried out in two or more stages. The contact with the solid acid is preferably performed in water.

The polyarylene sulfonic acids of the present invention can be produced by filtering the solid acid from the polyarylene sulfonic acid aqueous solution in which the solid acid is dispersed, concentrating and drying.

The polyarylene sulfonic acids of the present invention can be used for an electrolyte membrane of a fuel cell. The film forming method is not particularly limited, but it is dissolved in a solvent containing water, applied onto a flat substrate, dried and formed into a film. The solvent is dried at room temperature to 200 ° C. to obtain a dried film. It may be combined with a porous film, non-woven fabric, or fine particles, and after film formation, heat treatment, light irradiation, electron beam irradiation, or the like can be performed. The solvent used in this case is not limited to the following, but examples include an aprotic solvent and an alcohol solvent, and an alcohol is preferable. The thickness of the film is 1 to 200 μm, preferably 5 to 100 μm. The film thickness depends on the concentration of the coating solution or the coating thickness on the flat substrate. A substrate containing a film or metal oxide is preferred as the planar substrate.

The third invention of the present application relates to a composite polymer electrolyte membrane and a method for producing the same.
The composite polymer electrolyte membrane of the present invention is a composite electrolyte membrane in which a polymer electrolyte having an aromatic ring in the main chain and a radically polymerizable compound are filled in the pores of a porous base material. The polyelectrolyte is characterized in that two or more molecules of an aromatic polymer electrolyte are connected by a compound having a structure different from that of the aromatic polymer electrolyte and having a repeating unit at a site other than the ionic group. And a composite polymer electrolyte membrane.

Further, the composite polymer electrolyte membrane of the present invention comprises a porous group comprising a mixture containing an aromatic polymer electrolyte having a structure capable of generating radicals by external stimulation in a molecular chain and one or more radical polymerizable compounds. A composite polymer electrolyte membrane obtained by applying an external stimulus after filling into the pores of the material and reacting the polymer electrolyte with the radical polymerizable compound is preferable.

More preferably, at least one of the radical polymerizable compounds has a sulfonic acid group or a phosphonic acid group, and at least one of the radical polymerizable compounds not having a sulfonic acid group or a phosphonic acid group is 2 More preferably, it has at least one radical polymerizable group. The external stimulus is preferably ultraviolet irradiation or electron beam irradiation, ultraviolet irradiation is preferable for ease of reaction, and electron beam irradiation is preferable for improving reactivity.

  The polymer electrolyte in the composite polymer electrolyte membrane of the present invention has a repeating structure of formula (8) and formula (9), has a solubility in 100 g of water at a temperature of 25 ° C. of 0.1 g or more, and an ion exchange capacity. It is preferable to use polyarylene sulfonic acids having an amount of 3 meq / g or more.

(In the formula, Ar3 is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar3 is a divalent acid having a benzoyl group without containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. Of aromatic groups)
The preferred embodiments of the polyarylene sulfonic acids of the present invention are as described above.

Next, the radical polymerizable compound in the composite polymer electrolyte membrane of the present invention will be described. The radical polymerizable compound to be used may be one or more, but preferably two or more.

It is preferable that at least one of the radical polymerizable compounds to be used has a sulfonic acid group or a phosphonic acid group. Specifically, vinylsulfonic acid, vinylphosphonic acid, styrenesulfonic acid, 2-acrylamido-2-methyl Propanesulfonic acid and their salts are raised. It is more preferable to have a sulfonic acid group from the viewpoint of proton conductivity.

Furthermore, at least one of the above radical polymerizable compounds preferably has two or more radical polymerizable groups per molecule, and more preferably three or more from the viewpoint of crosslinkability.

Below, the example of the compound which shows bifunctional or more radical polymerizability is shown.
Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydro (Diethyl) isocyanurate di (meth) acrylate, bis (hydroxymethyl) tricyclodecane di (meth) acrylate, di (meth) acrylate of diol which is an adduct of bisphenol A ethylene oxide or propylene oxide, hydrogenated bisphenol A Di (meth) acrylate of diol, which is an adduct of ethylene oxide or propylene oxide, epoxy (meth) acrylate obtained by adding hydroxyalkyl (meth) acrylate such as hydroxy (meth) acrylate to diglycidyl ether of bisphenol A, polyoxy Examples thereof include di (meth) acrylate of alkyleneated bisphenol A, p- or m-divinylbenzene, triethylene glycol divinyl ether, divinyl sulfone and the like.

Examples of commercially available monomers having two or more radically polymerizable groups in one molecule include KAYARAD-DPHA, KAYARAD R-604, DPCA-20, -30, -60, -120, HX-620, D -310, D-330 (Nippon Kayaku Co., Ltd.) Iupimer UV SA1002, SA2007 (Mitsubishi Chemical Corporation), Biscote # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 700 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, BP-4PA, PE-3A, PE- 4A, DPE-6A (above, manufactured by Kyoeisha Chemical Co., Ltd.), Aronix M-208, M-210, M-215, M-220, M-240, M-30 5, M-309, M-315, M-325 (above, manufactured by Toa Gosei Co., Ltd.) and the like.

The material of the porous substrate used in the present invention is not particularly limited as long as it does not block or interfere with proton conduction. However, in view of heat resistance and physical strength reinforcement effect, An aromatic polymer, an aromatic polymer, or a fluorine-containing polymer is preferably used. Examples of the aliphatic polymer include, but are not limited to, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, and ethylene-vinyl alcohol copolymer. In addition, polyethylene here is a general term for ethylene-based polymers having a polyethylene crystal structure. For example, in addition to linear high-density polyethylene (HDPE) and low-density polyethylene (LDPE), ethylene and other polymers are used. It also includes a copolymer with a monomer, and specifically includes a copolymer with ethylene and α-olefin, which is called linear low density polyethylene (LLDPE), and an ultrahigh molecular weight polyethylene. Polypropylene as used herein is a general term for polypropylene-based polymers having a polypropylene crystal structure, and generally used propylene-based block copolymers, random copolymers, etc. (these are copolymers with ethylene, 1-butene, etc.). Which is a polymer).

Examples of the aromatic polymer include polyphenylene sulfide, polyethersulfone, polysulfidesulfone, polyethylene terephthalate, polycarbonate, polyimide, polyetherimide, polyetherketone, polyetheretherketone, polyphenyleneoxide, aromatic polyamide, and polyamideimide. Is mentioned. Furthermore, cellulose and polylactic acid can also be used.

As the fluorine-containing polymer, a thermoplastic resin having at least one carbon-fluorine bond in the molecule is used, but all or most of the hydrogen atoms of the aliphatic polymer are substituted with fluorine atoms. Those having a different structure are preferably used. Specific examples thereof include polytrifluoroethylene, polytetrafluoroethylene, polychlorotrifluoroethylene, poly (tetrafluoroethylene-hexafluoropropylene), poly (tetrafluoroethylene-perfluoroalkyl ether), and polyvinylidene fluoride. Although it is mentioned, it is not limited to these. Of these, polytetrafluoroethylene and poly (tetrafluoroethylene-hexafluoropropylene) are preferable, and polytetrafluoroethylene is particularly preferable. These porous materials may be used alone or in combination with other materials.

When a porous film is selected as the porous material, an aliphatic polyolefin film typified by polyethylene or polypropylene is preferable from the viewpoint of electrochemical stability and cost.

Also, a process of adding an extractable to polyolefin, finely dispersing it, forming a sheet, extracting the extractable with a solvent or the like to form pores, and performing a stretching process before and / or after extraction as necessary. The porous material obtained by the wet method obtained by the extraction method which has can also be used. In addition, a porous material opened in a honeycomb shape by self-organization or a film made porous by stretching by adding a pore-forming agent such as calcium carbonate can be used.

The porosity of the porous substrate is appropriately determined experimentally depending on the ion exchange capacity of the polymer electrolyte to be used. From the viewpoint of proton conductivity of the composite polymer electrolyte membrane and ease of filling the polymer electrolyte solution, 30% or more and 90% or less are preferable, and 35% or more and 70% or less are more preferable. When the porosity is 35% or more, the polymer electrolyte solution can be easily filled up to the inside of the porous material, and the proton conduction path is easily formed continuously in the thickness aroma of the composite polymer electrolyte membrane. Moreover, if it is 90% or less, the workability | operativity in a film forming process will become favorable, and the reduction | decrease of the mechanical strength at the time of the wet / dry dimensional change of a composite polymer electrolyte membrane and water absorption can be suppressed.

The porosity of the porous substrate is obtained from the following equation by cutting the porous material into squares, measuring the length of one side L (cm), weight W (g), and thickness D (cm). Can do.
Porosity = 100-100 (W / ρ) / (L2 × D)
Ρ in the above formula indicates the film density. ρ uses a value obtained by the density gradient tube method of D method of JIS K7112 (1980). At this time, ethanol and water are used as the density gradient tube liquid.

The thickness of the porous substrate can be appropriately determined depending on the thickness of the target composite polymer electrolyte membrane, but is preferably 1 to 100 μm in practice. When the film thickness is less than 1 μm, the film may be stretched due to the tension in the film forming process and the secondary processing process, and vertical wrinkles may be generated or broken. On the other hand, if it exceeds 100 μm, the polymer electrolyte is insufficiently filled and the proton conductivity is lowered.

The composite polymer electrolyte membrane of the present invention can be obtained by impregnating the porous base material with a mixed solution of the aromatic polymer electrolyte and the radical polymerizable compound and then proceeding with crosslinking by external stimulation.

The ion exchange capacity of the composite polymer electrolyte membrane of the present invention may be 1.5 meq / g or more from the viewpoint of proton conductivity of the composite polymer electrolyte membrane. It is preferably 5 meq / g or more and 6.0 meq / g or less, and more preferably 2.0 meq / g or more and 4.0 meq / g. When the ion exchange capacity is lower than 1.5 milliequivalent / g, proton conductivity is insufficient, and when the ion exchange capacity is higher than 6.0 milliequivalent / g, there is a problem in the morphological stability of the membrane.

The method for producing the composite polymer electrolyte membrane of the present invention will be described below.
The method for impregnating the porous membrane with the mixed solution of the aromatic polymer electrolyte and the radical polymerizable compound is not particularly limited, and it is sufficient that the porous substrate and the mixed solution are in contact with each other. A step of removing the solvent after immersing the porous substrate in the pooled solution tank, a step of casting and impregnating the solution onto the porous substrate, and casting and applying the solution onto the substrate. And a step of impregnating and impregnating the porous substrate.

The mixing ratio of the aromatic polymer electrolyte and the radical polymerizable compound in the present invention is not particularly limited as long as it does not deviate from the range of the above ion exchange capacity, but the aromatic polymer electrolyte / radical polymerizable compound (mass%) Ratio) is preferably in the range of 90/10 to 40/60, and particularly preferably 75/25 to 50/50 in terms of proton conductivity, durability, and reactivity.

The concentration of the mixed solution of the aromatic polymer electrolyte and the radical polymerizable compound in the present invention is not particularly limited as long as it has fluidity, but is 1% by mass to 30% by mass, preferably , 5 mass% to 15 mass%.

  Examples of the solvent in the mixed solution include alcohols such as methanol, ethanol and isopropyl alcohol, aprotic organic solvents such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfoxide, and water. Each of these solvents may be mixed. From the viewpoint of drying speed and film-forming property, it is preferable to use a mixed solvent of an alcohol solvent and water, and more preferably a mixed solvent of methanol and water.

After impregnating the porous membrane with the mixed solution of the aromatic polymer electrolyte and the radical polymerizable compound, the resulting composite membrane is subjected to an external stimulus to cause a radical reaction and to proceed with crosslinking. A polymer electrolyte membrane can be obtained. Here, the external stimulus may be anything that can react a part of the aromatic polymer electrolyte and the radical polymerizable compound, and examples thereof include ultraviolet rays and electron beam irradiation. Of these, ultraviolet irradiation is preferred for the convenience of reaction, and electron beam irradiation is preferred for improving reactivity.

In addition, heat treatment can be performed in parallel with or after these treatments. It is sufficient that a part of the aromatic polymer electrolyte and the radical polymerizable compound can be reacted, and the specific heating conditions are not particularly limited, but the treatment is performed at a temperature of 50 ° C. to 150 ° C. in terms of reactivity. Is preferable, and it is more preferable to process at 80-150 degreeC.

The membrane / electrode assembly of the present invention can be obtained by bonding the composite polymer electrolyte membrane of the present invention to an electrode catalyst layer.
The electrode in the present invention comprises an electrode material and a layer (electrode catalyst layer) containing a catalyst formed on the surface thereof, and a known material can be used as the electrode material. For example, a conductive porous material such as carbon paper or carbon cloth can be used, but is not limited thereto. As the conductive porous material such as carbon paper or carbon cloth, a material subjected to surface treatment such as water repellent treatment or hydrophilic treatment can be used. A known material can be used for the catalyst. For example, platinum, an alloy of platinum and ruthenium, and the like can be given, but the invention is not limited to them.
An adhesive can be used for the catalyst and the electrode catalyst layer including the particles carrying the catalyst, and as the adhesive, a resin having proton conductivity can be used.

As a method for producing the membrane / electrode assembly, a conventionally known method can be used. For example, a method in which an adhesive is applied to the electrode surface to adhere the polymer electrolyte membrane and the electrode catalyst layer or There is a method of heating and pressurizing the polymer electrolyte membrane and the electrode catalyst layer. As the adhesive, a known one such as a Nafion (trade name) solution may be used, or an adhesive based on an ionic group-containing polymer constituting the composite polymer electrolyte membrane of the present invention may be used. You may use what has other hydrocarbon type proton conductive polymers as a main component. The method for producing the composite is preferably a method in which a composition containing an adhesive and a catalyst is applied and adhered to the electrode surface. In the composite polymer electrolyte membrane of the present invention, since the ionic group-containing polymer has an appropriate softening temperature, a method of joining the polymer electrolyte membrane and the electrode by pressure heating is particularly suitable.

The fuel cell of the present invention can be produced using the polymer electrolyte membrane or the polymer electrolyte membrane / electrode assembly of the present invention. The fuel cell of the present invention includes, for example, an oxygen electrode, a fuel electrode, a polymer electrolyte membrane sandwiched between the electrodes, an oxidant flow path provided on the oxygen electrode side, and a fuel electrode side. The fuel flow path is provided. A fuel cell stack can be obtained by connecting such unit cells with a conductive separator.

EXAMPLES Hereinafter, although this invention is demonstrated concretely using an Example, this invention is not limited to these Examples. Various measurements were performed as follows.
<Polymer electrolyte membrane evaluation method>
The evaluation method of a polymer electrolyte membrane is shown below. In the evaluation, unless otherwise specified, the purpose is to accurately measure the thickness and mass, and the room temperature is 20 ° C. and the relative humidity is 30 ± 5 RH.
Evaluation was carried out in a measurement room controlled at%. In the measurement, a sample that was allowed to stand in a measurement chamber for 24 hours or more was used.

<Thickness of polymer electrolyte membrane>
The thickness of the composite polymer electrolyte membrane was determined by measurement using a micrometer (Mitutoyo, standard micrometer). Measurement was performed at 10 locations, and the average value was taken as the thickness.

<Ion exchange capacity>
100 mg of the dried proton exchange membrane was immersed in 50 ml of 0.01 M NaOH aqueous solution and stirred at 25 ° C. for 2 hours. Thereafter, neutralization titration with 0.02 M aqueous HCl was performed. For neutralization titration, a potentiometric titrator COMMITE-980 manufactured by Hiranuma Sangyo Co., Ltd. was used. The ion exchange equivalent was calculated by the following formula.
Ion exchange capacity [milliequivalent / g] = (10-titer [ml]) / 2

<Proton conductivity>
A platinum wire (diameter: 0.2 mm) was pressed against the surface of the strip-shaped membrane sample on a self-made measuring probe (manufactured by Teflon (registered trademark)), and a constant temperature / humidity oven (Nagano Co., Ltd.) at 80 ° C. and 50% RH. The specimen was held in Science Machine Mfg. Co., Ltd., LH-20-01), and the impedance between the platinum wires was measured by SOLARTRON 1250 FREQUENCY RESPONSE ANALYSER. Proton conductivity (σ) with the contact resistance between the membrane and the platinum wire canceled by the following formula from the slope of the measured resistance value estimated from the distance between the poles and the C-C plot. Was calculated.
σ [S / cm] = 1 / film width [cm] × film thickness [cm] × resistance interelectrode gradient [Ω / cm]

<Repeated swelling / shrinkage (D / W) test method>
The swelling / contraction repeated test and durability of the polymer electrolyte membrane were measured by the following methods. The polymer electrolyte membrane was set in a self-made swelling / contraction repeated test cell (effective area about 15 cm ² ), and the cell temperature was heated to 85 ° C. Then, the test which repeats the cycle which flows non-humidified nitrogen in a cell for 270 seconds-full humid nitrogen for 30 seconds was implemented. Breaking of the membrane was confirmed by applying back pressure (50 kPa) to the cathode side every 6 cycles with the anode open (determined that membrane tearing occurred at back pressure ↓).
Measurement was made up to 500 cycles, and those that were torn were evaluated as x, and those that were not torn were evaluated as o.

<Bonding of polymer electrolyte membrane and electrode and power generation test>
It becomes uniform after adding commercially available 40% Pt catalyst-supported carbon (Tanaka Kikinzoku Kogyo TEC10V40E), a small amount of ultrapure water and isopropyl alcohol to a 20% Nafion (registered trademark) solution manufactured by DuPont. Until the catalyst paste was prepared. The catalyst paste was uniformly applied and dried on carbon paper (TGPH-060 manufactured by Toray Industries, Inc.) so that the amount of platinum deposited was 0.5 mg / cm ² to prepare a gas diffusion layer with an electrode catalyst layer. By sandwiching the polymer electrolyte membrane between the gas diffusion layers with the electrode catalyst layer so that the electrode catalyst layer is in contact with the membrane, and pressurizing and heating at 80 ° C. and 3 MPa for 4 minutes by a hot press method, A membrane-electrode assembly was obtained. This joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and power generation characteristics were evaluated by supplying hydrogen and oxygen at a cell temperature of 80 ° C. under conditions of an anode 26% RH and a cathode 16% RH. . Comparison was made between samples using the voltage at 1 A / cm ² after the performance was stabilized.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

<Synthesis of polyarylene sulfonic acid precursors>
Example 1
Poly [(p-phenylene sulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 90/10)
Weigh anhydrous nickel chloride (97 mg, 0.75 mmol), triphenylphosphine (780 mg, 3.0 mmol), sodium iodide (56 mg, 0.37 mmol), zinc powder (980 mg, 15 mmol) into a 30 ml reaction vessel <A>. 3 ml of tetrahydrofuran was added. The temperature was raised to 70 ° C. and stirred for 10 minutes. In a different 30 ml reaction vessel <B>, 2,2-dimethylpropyl 2,5-dimethylpropylsulfonate (2.0 g, 6.7 mmol), 2,5-dichlorobenzophenone (0.19 g, 0.75 mmol) and tetrahydrofuran (0.19 g, 0.75 mmol) were added. 7 ml) was added. The solution in the reaction vessel <B> was transferred to the reaction vessel <A> and stirred at 70 ° C. for 6 hours. The reaction solution was poured into 100 ml of 10% aqueous hydrochloric acid and filtered. Subsequently, it was dispersed in 100 ml of acetone, and the reaction mixture was dissolved and filtered to obtain the desired poly [(p-phenylenesulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 90 / It was possible to synthesize 1.3 g of 10). Mn calculated from the terminal method using 1H-NMR was 2500 g / mol. The chemical structure is shown in Formula (15).

(Example 2)
Poly [(p-phenylene sulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 80/20)
As in Example 1, with a weight ratio of 2,2-dimethylpropyl 2,5-dimethylpropyl sulfonate (2.0 g, 6.7 mmol) and 2,5-dichlorobenzophenone (0.42 g, 1.68 mmol) as raw materials Polymerized under various experimental conditions. 1.2 g of poly [(p-phenylene sulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 80/20) could be synthesized. Mn was 2900 g / mol

(Example 3)
Poly [(p-phenylenesulfonic acid) 2,2-dimethylpropyl / 4,4′-benzophenone] (molar ratio: 90/10)
Example 1 with a weight ratio of 2,2-dimethylpropyl 2,5-dichlorobenzenesulfonate (2.0 g, 6.7 mmol) and 4,4′-dichlorobenzophenone (0.19 g, 0.75 mmol) as raw materials Polymerization was conducted under similar experimental conditions. It was possible to synthesize 1.4 g of poly [(p-phenylene sulfonic acid) 2,2-dimethylpropyl / 4,4′-benzophenone] (molar ratio: 90/10). Mn was 2800 g / mol. The chemical structure is shown in Formula (16).

Example 4
Poly [(N, N-dimethyl-p-phenylenesulfonic acid amide / 4,4′-benzophenone] (molar ratio: 90/10)
Example 1 with a weight ratio of N, N-dimethyl-2,5-dichlorobenzenesulfonic acid amide (1.7 g, 6.7 mmol) and 2,5-dichlorobenzophenone (0.19 g, 0.75 mmol) as raw materials Polymerization was conducted under similar experimental conditions. Poly [(N, N-dimethyl-p-phenylenesulfonic acid amide / 4,4′-benzophenone] (molar ratio: 90/10)
Was able to be synthesized. Mn was 2400 g / mol.

(Comparative Example 1)
In a 30 ml reaction vessel <A>, anhydrous nickel chloride (140 mg, 1.1 mmol), triphenylphosphine (890 mg, 3.4 mmol), sodium iodide (120 mg, 0.84 mmol), zinc powder (2.2 g, 32 mmol) were added. Weigh and add 3 ml of N-methylpyrrolidone. The temperature was raised to 70 ° C. and stirred for 10 minutes. In a different 30 ml reaction vessel <B>, sodium 2,5-dichlorobenzenesulfonate (1.7 g, 6.7 mmol), 2,5-dichlorobenzophenone (0.42 g, 1.7 mmol) and N-methylpyrrolidone (7 ml) Was added. The solution in the reaction vessel <B> was transferred to the reaction vessel <A> and stirred at 70 ° C. for 6 hours. The reaction solution was poured into 100 ml of methanol to obtain a precipitate. The precipitate was washed several times with methanol. The obtained precipitate was not able to obtain a polymer only with unreacted raw materials. This is because the catalyst was deactivated by using a hygroscopic monomer.

<Synthesis of polyarylene sulfonic acids>
(Example 5)
Poly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 90/10)
A polyarylene sulfonic acid precursor synthesized in Example 1 (1 g, corresponding to 4.4 mmol of sulfonate unit), trimethylamine hydrochloride (2.1 g, 22 mmol), and 20 ml of NMP were weighed and stirred at 120 ° C. for 12 hours. did. The reaction mixture was washed with 100 ml of chloroform and washed with chloroform until the reaction residue of trimethylamine hydrochloride could be removed. A purified polymer, 10 g of a cation exchange resin (Dowex Monosphere 650C), and 10 g of pure water were weighed into a 100 ml Erlenmeyer flask and stirred at room temperature for 12 hours. The cation exchange resin was removed by filtration, and the polymer aqueous solution was concentrated and dried to synthesize 0.7 g of poly (p-phenylenesulfonic acid). The synthesized poly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 90/10) has an ion exchange capacity of 5.5 meq / g and a solubility in 100 g of pure water of 0.1 g or more. It was.

(Example 6)
Poly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 80/20)
Using the polyarylenesulfonic acid precursor obtained in Example 2, 0.6 g of poly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 80/20) was obtained in the same manner as in Example 5. I was able to synthesize. The ion exchange capacity was 4.8 meq / g, and the solubility in 100 g of pure water was 0.1 g or more.

(Example 7)
Poly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 90/10)
0.5 g of polypoly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 90/10) was used in the same manner as in Example 5 using the polyarylenesulfonic acid precursor obtained in Example 4. I was able to synthesize. The synthesized poly [(p-phenylenesulfonic acid) / 2,5-benzophenone] (molar ratio: 90/10) has an ion exchange capacity of 5.4 meq / g and a solubility in 100 g of pure water of 0.1 g or more. It was.

(Comparative Example 2)
Poly [(p-phenylenesulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 50/50)
In a 30 ml reaction vessel <A>, anhydrous nickel chloride (0.18 g, 1.35 mmol), triphenylphosphine (1.41 g, 5.4 mmol), sodium iodide (0.10 g, 0.67 mmol), zinc powder (0 .88 g, 13.5 mmol) was weighed and 3 ml of tetrahydrofuran was added. The temperature was raised to 70 ° C. and stirred for 10 minutes. In a different 30 ml reaction vessel <B>, 2,5-dimethylbenzenesulfonic acid 2,2-dimethylpropyl (2.0 g, 6.7 mmol), 2,5-dichlorobenzophenone (1.68 g, 6.73 mmol) and tetrahydrofuran ( 7 ml) was added. The solution in the reaction vessel <B> was transferred to the reaction vessel <A> and stirred at 70 ° C. for 6 hours. The reaction solution was poured into 100 ml of 10% aqueous hydrochloric acid and filtered. Subsequently, it was dispersed in 100 ml of acetone, the reaction mixture was dissolved and filtered to obtain the desired poly [(p-phenylenesulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 50 / 50 g of 50) could be synthesized. Mn was 2500 g / mol. Poly [(p-phenylene sulfonic acid) 2,2-dimethylpropyl / 2,5-benzophenone] (molar ratio: 50/50) was treated in the same manner as in Example 1, except that the polymer deprotected with trimethylamine hydrochloride was It did not dissolve in pure water.

(Example 8)
100 mg of the poly [(p-phenylenesulfonic acid) -2,5-benzophenone] (molar ratio: 90/10) obtained in Example 5, 40 mg of vinylsulfonic acid, and 20 mg of dipentaerythritol hexaacrylate were dissolved in methanol / water [90 / 10 (w / w)] was dissolved in a mixed solution of 4.4 g. Thereafter, a polyethylene porous membrane (size: 10 × 10 cm, film thickness: 15 μm, porosity: 49%) immersed in methanol was placed on a PTFE substrate, and the polymer solution was coated thereon, and a nitrogen atmosphere Dry at room temperature. The obtained composite film was irradiated with ultraviolet rays (20 J / cm ² ) under heating at 80 degrees. Further, heat treatment was performed at 120 ° C. for 1 hour. The obtained crosslinked composite membrane was immersed in pure water overnight and then dried to obtain a target composite polymer electrolyte membrane. The ion exchange capacity of the obtained membrane was 2.2 meq / g.

Example 9
100 mg of the poly [(p-phenylenesulfonic acid) -2,5-benzophenone] (molar ratio: 90/10) obtained in Example 5, 40 mg of vinylsulfonic acid, and 20 mg of dipentaerythritol hexaacrylate were dissolved in methanol / water [90 / 10 (w / w)] was dissolved in a mixed solution of 4.4 g. Thereafter, a polyethylene porous membrane (size: 10 × 10 cm, film thickness: 20 μm, porosity: 45%) immersed in methanol was placed on a PTFE substrate, and the polymer solution was coated thereon, and a nitrogen atmosphere Dry at room temperature. The obtained composite film was subjected to UV irradiation (20 J / cm ² ) under heating at 80 degrees. Further, heat treatment was performed at 120 ° C. for 1 hour. The obtained crosslinked composite membrane was immersed in pure water overnight and then dried to obtain a target composite polymer electrolyte membrane. The obtained membrane had an ion exchange capacity of 2.5 meq / g.

(Comparative Example 3)
Following formula (17);

A repeating unit represented by the following formula (18):

A polymer solution D was prepared by dissolving 12.00 g of a polymer D having a repeating unit represented by the formula (molecular weight: about 100,000) in 88.00 g of N-methyl-2-pyrrolidone.
This solution was cast on a 188 μm polyester film at room temperature and treated at 80 ° C. for 10 minutes, 100 ° C. for 10 minutes, and 130 ° C. for 10 minutes. Then, the obtained film-like film | membrane was immersed in the pure water of room temperature overnight, and the remaining solvent was removed. Thereafter, the obtained membrane is sandwiched between filter papers, and both sides are further sandwiched between glass plates. While applying a load, the membrane is left to dry for 2 days in a room at 20 ° C. and a relative humidity of 30% RH, and a polymer electrolyte membrane is obtained. Produced. The obtained polymer electrolyte membrane had a thickness of 17 μm and an ion exchange capacity of 2.1 meq / g.

(Comparative Example 4)
Comparison evaluation was carried out using Nafion NR211 (trade name), which is a commercially available perfluorosulfonic acid ion exchange membrane.

From Table 1, the composite polymer electrolyte membrane of the present invention showed no cracks, tears, pinholes or the like in the swelling / shrinkage repetition test of the polymer electrolyte membrane. Therefore, it can be seen that the durability of the composite polymer electrolyte membrane of the present invention is greatly improved as compared with the hydrocarbon electrolyte membrane of the comparative example. Further, it was confirmed that the power generation test showed higher performance than the comparative example. Proton conductivity also has excellent characteristics over Nafion in a low humidity environment, so it can be expected to be used as a fuel cell membrane.

  The composite polymer electrolyte membrane of the present invention showed high proton conductivity under low humidity and high durability against swelling / shrinkage tests. Therefore, by using the composite polymer electrolyte membrane of the present invention, It is possible to provide a fuel cell that is excellent in durability and can be operated under low humidity. The composite polymer electrolyte membrane of the present invention can be produced using the polyarylene sulfonic acids of the present invention. The polyarylene sulfonic acids of the present invention can be produced from the polyarylene sulfonic acid precursor of the present invention. The composite polymer electrolyte membrane of the present invention can be expected to greatly improve the practicality of a fuel cell using hydrogen as a fuel, which greatly contributes to the development of the industry.

Claims (40)

A polyarylene sulfonic acid precursor having a structure represented by formulas (1) and (2).
(In the formula, Ar ¹ is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar ² is a benzoyl group containing no sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. A divalent aromatic group having It is shown by Formula (3), The polyarylene sulfonic acid precursor of Claim 1 characterized by the above-mentioned.
(In the formula, m and n are positive integers satisfying m + n = 10 to 1000. Ar ¹ is an aromatic group containing a sulfonic acid group or a derivative of a sulfonic acid group that can be converted into a salt thereof. Ar ² does not include a sulfonic acid group or a derivative of a sulfonic acid group that can be converted into a salt thereof, and represents an aromatic group having a benzoyl group.) The structural unit containing Ar ² of the formula (3) is represented by the formula (4), and the polyarylene sulfonic acid precursor according to claim 2.
(In the formula, n represents the same meaning as defined in Formula (3). R ¹ and R ² are hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. , R ¹ and R ² may be the same or different, and R ³ is either an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. The substituent for R ³ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents may be the same or different. a represents an integer of 1 to 3, b represents an integer of 1 to 4. p and q are 0 or 1, and p + q = 1. The polyarylene sulfonic acid precursor according to claim 3, wherein R ^{3 in the} formula (4) is an aryl group having 6 to 20 carbon atoms which may have a substituent. 5. The polyarylene sulfonic acid precursor according to claim 3, wherein in the formula (4), p = 0 and q = 1. 5. The polyarylene sulfonic acid precursor according to claim 3, wherein in the formula (4), p = 1 and q = 0. The polyarylene sulfonic acid precursor according to any one of claims 2 to 6, wherein the structural unit containing Ar ¹ in the formula (3) has a structure represented by the formula (5).
(In the formula, m represents the same meaning as defined in formula (2). R ⁴ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. ^{May be the same} or different, r is 1 or 2, d is 4-r, A is OR ⁵ or N (R ⁶ ) (R ⁷ ), R ⁵ is hydrogen, Any one of an alkali metal and an alkyl group having 1 to 20 carbon atoms, R ⁶ and R ⁷ are either hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ may be the same; May be different.) The polyarylene sulfonic acids according to claim 7, wherein 90% or more of R ⁵ in R of formula (5) or a total of R ⁶ and R ⁷ is an alkyl group having 1 to 20 carbon atoms. precursor. The polyarylene sulfonic acids according to any one of claims 1 to 8, wherein a composition containing at least the compounds represented by formulas (6) and (7) is subjected to coupling polymerization in the presence of a catalyst. A method for producing a precursor.
(In the formula, X and Y are halogen atoms excluding fluorine, and X and Y may be the same or different. R ⁸ and R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. R ⁸ and R ⁹ may be the same or different, and R ¹⁰ is an alkyl group having 1 to 20 carbon atoms, or 6 carbon atoms that may have a substituent. Any one of ˜20, the substituent of R ^{10 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, and the substituents are the same; A ′ is an integer of 1 to 3, b ′ is an integer of 1 to 4. p ′ and q ′ are 0 or 1, and p ′ + q ′ = 1.
(In the formula, X ′ and Y ′ are halogen atoms excluding fluorine, and X ′ and Y ′ may be the same or different. R ¹¹ is hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms. Any of 20 aryl groups, the substituents may be the same or different, s is 1 or 2, e is 4-s, B is OR ¹² or N (R ¹³ ) (R ¹⁴ ), R ¹² represents any one of hydrogen, an alkali metal, or an alkyl group having 1 to 20 carbon atoms, and R ¹³ and R ¹⁴ are either hydrogen or an alkyl group having 1 to 20 carbon atoms. Yes, R ¹³ and R ¹⁴ may be the same or different.) The method for producing a polyarylenesulfonic acid precursor according to claim 9, wherein a composition containing a nickel compound, a phosphorus ligand, zinc, and sodium iodide is used as the catalyst. 11. The polyarylene sulfonic acid precursor according to claim 10, wherein the nickel compound is bis (cyclooctadiene) nickel or nickel chloride bis (triphenylphosphine), and the phosphorus ligand is a triarylphosphine. Body manufacturing method. Polyarylene sulfonic acids having a repeating structure of formula (8) and formula (9), having a solubility in 100 g of water at a temperature of 25 ° C. of 0.1 g or more and an ion exchange capacity of 3 meq / g or more.
(In the formula, Ar3 is a divalent aromatic group containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative, and Ar3 is a divalent acid having a benzoyl group without containing a sulfonic acid group, sulfonic acid salt or sulfonic acid group derivative. Of aromatic groups) The polyarylene sulfonic acids according to claim 12, which have the structure of formula (10).
(Wherein, m1, n1 are, .Ar ³ is a sulfonic acid group showing a positive integer satisfying m1 + n1 = 10 to 1000, an aromatic group containing a sulfonate or sulfonic acid group derivative, Ar ⁴ is a sulfonic acid group, (Aromatic group having benzoyl group without sulfonate or sulfonic acid group derivative) The polyarylene sulfonic acids according to claim 13, wherein the structural unit containing Ar ⁴ in the formula (10) is represented by the formula (11).
(In the formula, n1 represents the same meaning as defined in formula (10). R ¹⁵ and R ¹⁶ are any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. , R ¹⁵ and R ¹⁶ may be the same or different, and R ¹⁷ represents either an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. The substituent of R ¹⁷ is hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and the substituents may be the same or different. ", B" represents an integer of 1 to 4. p ", q" is 0 or 1, indicating p "+ q" = 1) The polyarylene sulfonic acids according to claim 14, wherein R ^{17 in the} formula (11) is an aryl group having 6 to 20 carbon atoms which may have a substituent. 16. The polyarylene sulfonic acids according to claim 14, wherein p ″ = 0 and q ″ = 1 in the formula (11). 16. The polyarylene sulfonic acids according to claim 14, wherein p ″ = 1 and q ″ = 0 in the formula (11). The polyarylene sulfonic acids according to any one of claims 13 to 17, wherein the structural unit containing Ar ³ in the formula (10) has a structure represented by the formula (12).
(In the formula, m1 represents the same meaning as defined in formula (10). R ¹⁸ is any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. May be the same or different, r ′ is 1 or 2, d ′ represents 4-r ′, A ′ represents OR ¹⁹ , N (R ²⁰ ) ⁽ R ²¹ ), R ¹⁹ represents hydrogen, an alkali metal, an alkyl group having 1 to 20 carbon atoms, R ²⁰ and R ²¹ are either hydrogen or an alkyl group having 1 to 20 carbon atoms, and R ²⁰ and R ²¹ are the same. May be different.) The polyarylene sulfonic acids according to claim 18, wherein in the formula (12), A 'is OR ¹⁹ , and 80% or more of R ¹⁹ is hydrogen or an alkali metal. The polyarylene sulfone according to any one of claims 12 to 19, wherein the polyarylene sulfone according to any one of claims 12 to 19, which includes at least the following steps 1, 2, and 3 and is performed in the order of step 1, step 2, and step 3. A method for producing acids.
(Step 1) Step of coupling polymerization of a composition containing at least the compounds represented by Formula (13) and Formula (14) (Step 2) Deprotecting the sulfonic acid group derivative of the polymer produced in Step 1 Step of making a sulfonic acid group or a salt thereof (Step 3) Step of bringing the polymer produced in Step 2 into contact with an acid
(In the formula, X ¹ and Y ¹ are halogen atoms excluding fluorine, and X ¹ and Y ¹ may be the same or different. R ²² and R ²³ are hydrogen, an alkyl group having 1 to 20 carbon atoms, carbon R ²² or R ²³ may be the same or different, and R ²⁴ may have an alkyl group having 1 to 20 carbon atoms or a substituent. Any one of the preferable aryl groups having 6 to 20 carbon atoms, wherein the substituent of R ^{24 is} any one of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms; May be the same or different. A1 and b1 each represent an integer of 1 to 4. p1 and q1 are 0 or 1, and p1 + q1 = 1.
(In the formula, X ¹ ′ and Y ¹ ′ are halogen atoms excluding fluorine, and X ¹ ′ and Y ¹ ′ may be the same or different. R ²⁵ is hydrogen, an alkyl group having 1 to 20 carbon atoms, Any one of aryl groups having 6 to 20 carbon atoms, the substituents may be the same or different, s ′ is 1 or 2, e ′ is 4-s ′, B is OR ²⁶ or N (R ²⁷ ) (R ²⁸ ), R ²⁶ represents any one of hydrogen, an alkali metal, or an alkyl group having 1 to 20 carbon atoms, and R ²⁷ and R ²⁸ represent hydrogen or 1 to 20 carbon atoms. And R ²⁷ and R ²⁸ may be the same or different.) The method for producing polyarylenesulfonic acids according to claim 20, wherein the deprotection in the step (b) uses an alkali metal halide or a quaternary ammonium halide. The method for producing polyarylene sulfonic acids according to claim 20 or 21, wherein the acid in the step (c) is a solid acid. The method for producing polyarylene sulfonic acids according to claim 22, wherein the solid acid is a cation exchange resin. A composite polymer electrolyte membrane comprising a porous base material and a polymer electrolyte filled in its pores, wherein the polymer electrolyte is composed of two or more aromatic polymer electrolytes at sites other than ionic groups A composite polymer electrolyte membrane characterized by being connected by a compound having a structure different from that of the aromatic polymer electrolyte and having a repeating unit. After filling the pores of the porous base material with a mixture containing an aromatic polymer electrolyte having a structure capable of generating radicals by external stimulation in the molecular chain and one or more radical polymerizable compounds, external stimulation is performed. The composite polymer electrolyte membrane according to claim 22, which is obtained by reacting the polymer electrolyte with the radical polymerizable compound. 26. The polymer electrolyte membrane according to claim 25, wherein at least one of the radical polymerizable compounds has a sulfonic acid group or a phosphonic acid group. 27. The composite polymer electrolyte membrane according to claim 25 or 26, wherein at least one of the radical polymerizable compounds has two or more radical polymerizable groups. The composite polymer electrolyte membrane according to any one of claims 25 to 27, wherein the external stimulus is ultraviolet ray irradiation or electron beam irradiation. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acids according to claim 12. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acids according to claim 13. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to claim 14. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to claim 15. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to claim 16. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acid according to claim 17. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acids according to claim 18. The composite polymer electrolyte membrane according to any one of claims 24 to 28, wherein the aromatic polymer electrolyte is the polyarylene sulfonic acids according to claim 19. 37. The composite polymer electrolyte membrane according to claim 24, wherein the porous substrate is mainly made of a polymer material. 38. The composite polymer electrolyte membrane according to any one of claims 24 to 37, having an ion exchange capacity of 1.5 meq / g to 6.0 meq / g. A polymer electrolyte membrane electrode assembly for a fuel cell using the composite polymer electrolyte membrane according to any one of claims 24 to 38. 40. A fuel cell using the polymer electrolyte membrane electrode assembly according to claim 39.