JP2010090309A - Novel polymeric organic compound, ion exchanger using it, electrolyte membrane, catalyst, membrane electrode assembly, and fuel cell - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel polymeric organic compound having a nitrogen-containing heterocycle having a sulfonic acid group or a sulfonic acid salt group with a high anti-radical property, being excellent in a proton-transmitting property, having high ion exchange capacity and with high activity as an acid catalyst, an ion exchanger using it, an electrolyte membrane, a catalyst, a membrane electrode assembly, and a fuel cell. <P>SOLUTION: The polymeric organic compound includes at least a molecular structure represented by general formula (1) having both (A) a constitution unit comprising a silicon derivative having a nitrogen-containing heterocycle and (B) a constitution unit containing the sulfonic acid group or the sulfonic acid salt group in the molecule. The ion exchanger using it is provided. The electrolyte membrane, the catalyst, the membrane electrode assembly and the fuel cell are provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a new polymer organic compound and an ion exchanger, an electrolyte membrane, a catalyst, a membrane electrode assembly, and a fuel cell using the same.

Many organic compounds having nitrogen-containing heterocycles, particularly pyridine rings, exist as natural products, and there are many pharmaceutically important compounds. For example, β-picolinic acid having a nitrogen-containing heterocycle is an anti-dermatologic vitamin.
Vitamin B6 is also an organic compound having a nitrogen-containing heterocyclic ring.

  Nitrogen-containing heterocycles such as pyridine are electron-deficient aromatic rings, which are known to be inert to various electrophilic substitution reactions, and thus have very high chemical stability. For example, pyridine is used as a solvent in various chemical reactions. Tatsumi et al. Of Tokyo Institute of Technology perform a ring-opening reaction of catechol having two hydroxyl groups on the benzene ring in a pyridine solvent using a copper catalyst. This means that pyridine does not react with radicals generated in the reaction process and has a radical resistance much higher than that of the benzene ring (Non-patent Document 1).

Further, compounds having nitrogen-containing heterocycles such as pyridine form compounds coordinated with various organic metals, and these compounds are widely used as high-performance catalysts. In reactions using these organometallic reagents, radical species with high reactivity are often generated as reaction intermediates, and the catalyst is required to have high stability.
For example, Barton et al. Say that in the oxidation reaction of cyclohexane or hydrogen sulfide, the target product can be obtained in high yield by a catalyst in which picolinic acid or picolinic acid-N-oxide is coordinated with iron (Non-patent Document 2).
Bianchi et al. Also obtained a target phenol in a high yield using a catalyst in which pyridine-2-carboxylic acid or pyrazinecarboxylic acid is coordinated with iron in an oxidation reaction of toluene with hydrogen peroxide (non-patented). Reference 3).
As can be seen from these, compounds having a nitrogen-containing heterocycle, particularly a pyridine ring, can produce stable catalyst compounds because of their stability, and are also useful as catalysts.

  In addition, a polymer whose main chain is composed of a nitrogen-containing heterocyclic ring, particularly a polymer composed solely of a pyridine ring, that is, polypyridine, exhibits extremely high chemical stability and heat resistance as compared with other aromatic polymers. high. Therefore, it is a substance expected to be used for various purposes.

In order to put pyridine derivatives and polypyridine into practical use as functional materials, it is necessary to introduce functional groups for expressing the functions according to their use, that is, to chemically modify them.
However, as mentioned above, pyridine and polypyridine are extremely inactive for most electrophilic substitution reactions, so chemical modification is not easy.

  Examples of electrophilic substitution reactions include nitration, sulfonation, halogenation and Friedel-Crafts reactions, but in the case of pyridine these reactions are only under very severe conditions (the Friedel-Crafts reaction proceeds. Not) is known to be performed (Non-Patent Document 4).

The same applies to polymers consisting of nitrogen-containing heterocycles such as polypyridine, and the nitrogen-containing heterocycles such as pyridine, which is a constituent element, are chemically stable, and many electrophilic substitution reactions including sulfonation It is very difficult to directly chemically modify these macromolecules, as well as being inert to them.
In addition, unlike small molecules, many of these polymers are insoluble in general-purpose organic solvents, and the fact that the reaction is difficult to proceed is one factor that makes chemical modification difficult. Therefore, when taking sulfonation of polypyridine as an example, until we developed the method, there was no report example as long as we investigated (Patent Document 1).

In order to synthesize a polypyridine having a functional group such as a sulfonic acid group, there is a method of synthesizing a pyridine derivative having a target functional group and polymerizing it as a monomer, in addition to directly reacting polypyridine.
However, monomer synthesis is also not easy due to the high chemical stability of pyridine. Therefore, when the compound was investigated using CAS, for example, there were no reported examples of pyridine polymer organic compounds having silicon in the main chain and also having a sulfonic acid group as far as we investigated.

By the way, in recent years, environmental problems have been highlighted, and development of highly efficient catalysts and development of fuel cells have attracted attention. The former is expected to reduce the environmental load by suppressing the energy used during the reaction, and the latter is expected as a battery that produces high energy efficiency.
Here, the fuel cell is one that converts chemical energy of fuel into electric energy and extracts it by electrochemically oxidizing a fuel such as hydrogen or methanol using oxygen or air.

Such fuel cells are classified into a solid polymer type, a phosphoric acid type, a molten carbonate type, a solid oxide type, an alkaline type, and the like depending on the type of electrolyte used.
Among these, a polymer electrolyte fuel cell using a cation exchange membrane as an electrolyte can be operated at a high current because the internal resistance in the fuel cell can be reduced by thinning the electrolyte membrane to be used, and can be miniaturized. Because of these advantages, research on solid polymer fuel cells is actively conducted.

Here, the deterioration of the solid polymer electrolyte membrane due to radicals will be described.
As shown in FIG. 1 and FIG. 2, a single cell 11 of a conventional polymer electrolyte fuel cell (PEFC) has a solid polymer electrolyte membrane 1 (perfluorocarbon sulfonic acid membrane) as a carbon black particle and a catalytic substance [ An air electrode side catalyst layer 2 of a cell sandwiched between an air electrode side catalyst layer 2 supporting mainly platinum (Pt) or a platinum group metal (Ru, Rh, Pd, Os, Ir)] and a fuel electrode side catalyst layer 3; There is provided a membrane electrode assembly 12 in which the fuel electrode side catalyst layer 3 is sandwiched between the air electrode side gas diffusion layer 4 and the fuel electrode side gas diffusion layer 5 to form the air electrode 6 and the fuel electrode 7.
Then, a gas flow path 8 for reaction gas flow is provided facing the air electrode side gas diffusion layer 4 and the fuel electrode side gas diffusion layer 5, and a cooling water flow path 9 for cooling water flow is provided on the opposing main surface. A single cell 11 is formed by being sandwiched by a pair of separators 10 made of a gas-impermeable material.
An oxidant such as air is supplied to the air electrode 6, and a fuel gas containing hydrogen or an organic fuel is supplied to the fuel electrode 7 to generate electricity.

That is, when the reaction gas is supplied to each of the fuel electrode 7 and the air electrode 6, the following electrochemical reaction occurs and DC power is generated.
Fuel electrode ^{_{side: 2H 2 → 4H + + 4e}} -
Air electrode side: O ₂ + 4H ⁺ + 4e ⁻ → 2H ₂ O
The oxidation reaction of hydrogen molecules (H ₂ ) occurs on the fuel electrode side, and the reduction reaction of oxygen molecules (O ₂ ) occurs on the air electrode side, so that H ⁺ ions generated on the fuel electrode 7 side are solid polymer electrolytes. The film 1 moves toward the air electrode 6 side, and e ⁻ (electrons) move to the air electrode 6 side through an external load.
On the other hand, on the air electrode 6 side, oxygen contained in the oxidant gas reacts with H ⁺ ions and e ⁻ that have moved from the fuel electrode 7 side to generate water. Thus, the polymer electrolyte fuel cell generates a direct current from hydrogen and oxygen to generate water.

However, the reduction reaction on the air electrode side (4-electron reduction of oxygen molecules (O ₂ )) is difficult, and the following electrochemical reaction (2-electron reduction of oxygen molecules (O ₂ )) occurs as a side reaction on the air electrode side. A lot of H ₂ O ₂ is generated. When Fe (II) or the like is present as an impurity, H ₂ O ₂ is decomposed by the catalytic action, and OH · (OH radical) and OH ⁻ are generated.

Air electrode side: O ₂ + 2H ⁺ + 2e ⁻ → H ₂ O ₂
H ₂ O ₂ + Fe (II) → OH · + OH ⁻ + Fe (III)
The generated OH · (OH radical) has a large oxidizing power and oxidizes and decomposes and degrades the solid polymer electrolyte membrane 1.

Therefore, the electrolyte membrane used for the polymer electrolyte fuel cell is required to have high chemical stability, particularly high radical resistance. As proton conductive polymer electrolyte membrane materials having high radical resistance, sulfonic acid group-containing fluororesins such as the trade name Nafion (registered trademark, manufactured by DuPont) are known, but in recent years there are also problems with these resins. It has been pointed out.
First, since the synthesis route is complicated, the cost of raw materials and manufacturing processes is high. In addition, since the sulfonic acid group-containing fluororesin has a low glass transition temperature and low heat resistance, it has a problem that the operating temperature is as low as 80 ° C. or lower. Furthermore, since it is a halogen-based resin called fluorine, there is a drawback that the environmental load is large.

In order to overcome the above-mentioned problems, a proton conductive polymer electrolyte membrane having high temperature stability and a high-temperature stability using a hydrocarbon-based resin having a sulfonic acid group not containing fluorine as a raw material has been developed. It is inferior in radicality, and its chemical stability does not reach that of sulfonic acid group-containing fluororesins. Therefore, it has a proton conductive functional group such as sulfonic acid group, and has excellent radical resistance and heat resistance. There is an urgent need to develop hydrocarbon materials.
J. et al. Tsuji, J .; Am. Chem. Soc. 96, 7349 (1974) D. H. R. Barton et al. , Chem. Commun. 557 (1997) D. Bianchi et al. , J .; Mol. Catal. A: Chem. , 204-205, 419 (2003) Morrison ・ Boyd organic chemistry second volume Japanese Patent Application No. 2007-301841

The first object of the present invention is excellent in radical resistance and heat resistance, has high ion exchange capacity, high proton conductivity, and high activity as an acid catalyst. Therefore, an ion exchanger, an electrolyte membrane, It is to provide a new macromolecular organic compound containing a nitrogen-containing heterocycle having a sulfonic acid group or a sulfonate group, which can be effectively used as a catalyst, a membrane electrode assembly, and a fuel cell.
The second object of the present invention is to provide an ion exchanger, an electrolyte membrane, a catalyst, a membrane electrode assembly, and a fuel cell using a new polymer organic compound containing a nitrogen-containing heterocycle having a sulfonic acid group or a sulfonic acid group. Is to provide.

  As a result of intensive investigations to solve the above problems, the present inventors have (A) a constitutional unit comprising a silicon derivative having a nitrogen-containing heterocycle, and (B) a constitution containing a sulfonic acid group or a sulfonic acid group. High molecular organic compound having both units in the molecule has a strong acid group, high radical resistance, excellent proton conductivity, high ion exchange capacity, excellent heat resistance, acid catalyst Therefore, the present inventors have found that it can be used as a catalyst, an ion exchanger, an electrolyte membrane, a membrane electrode assembly, and a fuel cell, and completed the present invention.

  The invention according to claim 1 of the present invention includes both (A) a structural unit composed of a silicon derivative having a nitrogen-containing heterocyclic ring and (B) a structural unit containing a sulfonic acid group or a sulfonic acid group in the molecule. A new organic polymer compound having at least a molecular structure represented by the following general formula (1).

(HCy in formula (1) represents the same or different nitrogen-containing heterocycles, and compound represents a compound. The part enclosed in parentheses in formula (1) represents a unit constituting a new high molecular organic compound. , N is an integer that represents the number of structural units (A), m is an integer that represents the number of structural units (B), and the wavy line represents whether a sulfonic acid group or sulfonate is directly bonded to compound or interposed Represents that the compound may be indirectly bonded to the compound via a group, R ¹ and R ² each represent the same or different arbitrary substituents, and X ⁺ represents a cation.)

  The invention according to claim 2 of the present invention is the polymer organic compound according to claim 1, wherein the compound of the structural unit (B) is composed of a nitrogen-containing heterocyclic ring, and has a molecular structure represented by the following general formula (2): , At least.

(HCy in the formula (2) represents the same or different nitrogen-containing heterocycles. The part enclosed in parentheses in the formula (2) represents a unit constituting a new high molecular organic compound, and n is a structural unit ( A is an integer representing the number of A, m is an integer representing the number of the structural unit (B), and the wavy line is obtained even when the sulfonic acid group or sulfonate is directly bonded to the nitrogen-containing heterocyclic ring or through an intervening group. And may be indirectly bonded to the nitrogen-containing heterocycle, R ¹ and R ² each represent the same or different arbitrary substituents, and X ⁺ represents a cation.)

  The invention according to claim 3 of the present invention is characterized in that, in the macromolecular organic compound according to claim 2, the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring or a heterocycle containing a pyridine ring. .

  According to a fourth aspect of the present invention, in the macromolecular organic compound according to the second aspect, the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring, and the compound of the structural unit (B) is a pyridine ring. And having at least a molecular structure represented by the following general formula (3).

(The part enclosed in parentheses in the formula (3) represents a unit constituting the new polymer organic compound, n is an integer representing the number of structural units (A), and m is the number of structural units (B). The wavy line represents that the sulfonic acid group or sulfonate may be directly bonded to the pyridine ring or indirectly bonded to the pyridine ring through an intervening group, and R ¹ and R ² are Each represents the same or different optional substituents, and X ⁺ represents a cation.)

According to a fifth aspect of the present invention, in the macromolecular organic compound according to the fourth aspect, the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring, and R ¹ and R ² are the same or different. It is an alkyl group.

  The invention according to claim 6 of the present invention is characterized in that, in the macromolecular organic compound according to claim 4 or 5, the structural unit (B) is represented by the following general formula (4).

(R in the formula (4) represents an alkylene group, and X ⁺ represents a cation.)

  The invention according to claim 7 of the present invention is characterized in that, in the macromolecular organic compound according to claim 4 or 5, the structural unit (B) is represented by the following general formula (5).

(R in the formula (5) represents an alkylene group, and X ⁺ represents a cation.)

  The invention according to claim 8 of the present invention is characterized in that, in the macromolecular organic compound according to claim 4 or 5, the structural unit (B) is represented by the following general formula (6).

(X ⁺ in formula (6) represents a cation.)

  The invention according to claim 9 of the present invention is the polymer organic compound according to any one of claims 1 to 8, wherein the sulfonic acid or sulfonate salt density is 0.1 to 5 meq / g. It is characterized by being.

  According to a tenth aspect of the present invention, in the macromolecular organic compound according to the sixth or seventh aspect, the alkylene group is an alkylene group having 3 or 4 carbon atoms or at least a part of the hydrogen thereof is a halogen element. It is a substituted alkylene group.

  The invention according to claim 11 of the present invention is an ion exchanger comprising the polymer organic compound according to any one of claims 1 to 10.

  The invention according to claim 12 of the present invention is an electrolyte membrane comprising the polymer organic compound according to any one of claims 1 to 10.

  A thirteenth aspect of the present invention is a catalyst comprising the polymer organic compound according to any one of the first to tenth aspects.

  A fourteenth aspect of the present invention is a membrane electrode assembly comprising the polymer organic compound according to any one of the first to tenth aspects.

  A fifteenth aspect of the present invention is a fuel cell comprising the polymer organic compound according to any one of the first to tenth aspects.

The invention according to claim 1 of the present invention includes (A) a structural unit composed of a silicon derivative having a nitrogen-containing heterocyclic ring and (B) a structural unit containing a sulfonic acid group or a sulfonic acid group. A new macromolecular organic compound having at least a molecular structure represented by the general formula (1)
Easy synthesis, high radical resistance, excellent proton conductivity, high ion exchange capacity, high activity as an acid catalyst, catalyst, ion exchanger, electrolyte membrane, membrane electrode junction Body and fuel cell can be effectively used.

The invention according to claim 2 of the present invention is the polymer organic compound according to claim 1, wherein the compound of the structural unit (B) is composed of a nitrogen-containing heterocyclic ring and has a molecular structure represented by the general formula (2). , At least characterized by having
It has structural units rich in radical resistance in the molecule and also has a sulfonic acid group, which is a strong acid group, so it has excellent proton conductivity, high ion exchange capacity, and it is a polymer, so it has good film-forming properties. In addition, since the activity as an acid catalyst is high, there is a further remarkable effect that it can be effectively used as a catalyst, an ion exchanger, an electrolyte membrane, a membrane electrode assembly, and a fuel cell.

The invention according to claim 3 of the present invention is characterized in that, in the macromolecular organic compound according to claim 2, the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring or a heterocycle containing a pyridine ring. Is,
Excellent radical resistance and heat resistance. In addition, it boasts high ion exchange capacity and proton conductivity. It is a polymer and has good film formation. In addition, its activity as an acid catalyst is high. It is possible to effectively use as a body, an electrolyte membrane, a membrane electrode assembly, and a fuel cell.

According to a fourth aspect of the present invention, in the macromolecular organic compound according to the second aspect, the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring, and the compound of the structural unit (B) is a pyridine ring. And having at least a molecular structure represented by the general formula (3),
Since the main chain of the obtained high molecular organic compound is composed of a pyridine ring having high chemical stability, it is possible to obtain a further remarkable effect that a product having excellent radical resistance and heat resistance can be obtained.

According to a fifth aspect of the present invention, in the macromolecular organic compound according to the fourth aspect, the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring, and R ¹ and R ² are the same or different. It is characterized by being an alkyl group,
The monomer in which R ¹ and R ² of the precursor are alkyl groups can be synthesized easily, so that the resulting high molecular organic compound has low cost, excellent proton conductivity, high ion exchange capacity, Since the activity as a catalyst is high, there is a further remarkable effect that it can be effectively used as a catalyst, an ion exchanger, an electrolyte membrane, a membrane electrode assembly, and a fuel cell.

The invention according to claim 6 of the present invention is characterized in that, in the macromolecular organic compound according to claim 4 or 5, the structural unit (B) is represented by the general formula (4),
The precursor monomer can be easily synthesized and has high radical resistance, so that the resulting high molecular organic compound has high radical resistance, excellent proton conductivity, and high ion exchange capacity. And has a high activity as an acid catalyst, so that it has a further remarkable effect that it can be effectively used as a catalyst, an ion exchanger, an electrolyte membrane, a membrane electrode assembly, and a fuel cell.

The invention according to claim 7 of the present invention is characterized in that, in the macromolecular organic compound according to claim 4 or 5, the structural unit (B) is represented by the general formula (5),
The precursor monomer is easy to synthesize and has high radical resistance. As a result, the resulting high molecular organic compound has high radical resistance, excellent proton conductivity, high ion exchange capacity, and high activity as an acid catalyst. Therefore, the catalyst, ion exchanger, There is a further remarkable effect that it can be effectively used as an electrolyte membrane, a membrane electrode assembly, and a fuel cell.

The invention according to claim 8 of the present invention is characterized in that, in the macromolecular organic compound according to claim 4 or 5, the structural unit (B) is represented by the general formula (6),
The precursor monomer is easy to synthesize and has high radical resistance. As a result, the resulting high molecular organic compound has high radical resistance, excellent proton conductivity, high ion exchange capacity, and high activity as an acid catalyst. Therefore, the catalyst, ion exchanger, There is a further remarkable effect that it can be effectively used as an electrolyte membrane, a membrane electrode assembly, and a fuel cell.

The invention according to claim 9 of the present invention is the polymer organic compound according to any one of claims 1 to 8, wherein the sulfonic acid or sulfonate salt density is 0.1 to 5 meq / g. It is characterized by being,
It is suitable for a fuel cell, and when the sulfonic acid or sulfonate density (acid value) is within this range, it has a further remarkable effect of reliably having excellent high proton conductivity.

  According to a tenth aspect of the present invention, in the macromolecular organic compound according to the sixth or seventh aspect, the alkylene group is an alkylene group having 3 or 4 carbon atoms or at least a part of the hydrogen thereof is a halogen element. It is characterized by being a substituted alkylene group, and the synthesis of the target compound can be easily synthesized with commercially available reagents, and the radical resistance of the obtained organic compound is also high. There is a further remarkable effect.

  Invention of Claim 11 of this invention is an ion exchanger characterized by including the high molecular organic compound as described in any one of Claims 1-10, and has high proton conductivity. In addition to having a large ion exchange capacity, the chemical stability is high.

  Invention of Claim 12 of this invention is an electrolyte membrane characterized by using the high molecular organic compound as described in any one of Claims 1-10, and has high radical resistance and heat resistance. At the same time, it has a remarkable effect of having excellent proton conductivity.

  Invention of Claim 13 of this invention is a catalyst characterized by using the high molecular organic compound as described in any one of Claims 1-10, and has a sulfonic acid group which is a strong acid group Therefore, the activity as an acid catalyst is high, and in addition, there is a remarkable effect that it is chemically and thermally stable.

  A fourteenth aspect of the present invention is a membrane electrode assembly using the polymer organic compound according to any one of the first to tenth aspects. Sulfonic acid group-containing fluororesins and membrane electrode assemblies using the same have a high environmental impact, and the environmental impact of fuel cells used as next-generation clean energy is a problem. The membrane / electrode assembly of the present invention, which can achieve a reduction in environmental burden under such circumstances, has a great effect, and also has high proton conductivity suitable for fuel cells as an electrolyte membrane, and is excellent in radical resistance and heat resistance. There is a remarkable effect.

  A fifteenth aspect of the present invention is a fuel cell characterized by using the polymer organic compound according to any one of the first to tenth aspects. Sulfonic acid group-containing fluororesins and membrane electrode assemblies using the same have a high environmental impact, and the environmental impact of fuel cells used as next-generation clean energy is a problem. Since the fuel cell of the present invention that can achieve a reduction in environmental load in a situation where it is not necessary, the electrolyte membrane of the present invention that has high proton conductivity and excellent radical resistance and heat resistance is used. The power generation efficiency is high and the reliability is high.

Hereinafter, the present invention will be described in detail.
The new polymer organic compound of the present invention comprises (A) a structural unit comprising a silicon derivative having a nitrogen-containing heterocycle (hereinafter sometimes referred to as a structural unit (A)), and (B) a sulfonic acid group or a sulfonate. Characterized by having at least a molecular structure represented by the general formula (1) having both a structural unit (hereinafter sometimes referred to as a structural unit (B)) in the molecule. To do.

  In the above general formulas (1) and (2), HCy and compound showed two bonds, but the number of bonds of HCy and compound is not limited to two. There may be three or more. The number of bonds of HCy and compound is determined in consideration of the characteristics, ease of synthesis, cost, etc. of the new macromolecular organic compound of the present invention.

The nitrogen-containing heterocyclic ring refers to a cyclic compound in which one or more elements constituting the ring are nitrogen atoms and has aromaticity.
Examples of such a ring include a pyridine ring, a pyrrole ring, a thiazole ring, an oxazole ring, an imidazole ring, a pyrazole ring, a triazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, and a polycyclic heterocyclic ring partially containing these. (For example, indole ring, purine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinazoline ring, quinoxaline ring, phthalazine ring, pteridine ring, acridine ring, phenazine ring, phenanthroline ring, etc.) can be exemplified.

  Examples of the heterocyclic ring containing a pyridine ring in the present invention include a phenanthroline ring, a quinoline ring, a naphthyridine ring, a phenanthridine ring, and an acridine ring. Examples thereof include those obtained by chemically modifying these with a nitro group, a hydroxyl group, a carboxyl group, a halogen group or the like. In the present invention, among these nitrogen-containing heterocycles, a pyridine ring is particularly preferable because of its high chemical stability, and a nitrogen-containing heterocycle containing a pyridine ring is more preferable because of its high chemical stability.

  The structural unit (A) refers to a structural element surrounded by left parentheses in the general formula (1). HCy in the general formula (1) represents a nitrogen-containing heterocyclic ring.

In order to have the structural unit (A) in the polymer organic compound, it is a particularly good method to use, as a monomer, a silicon derivative having two nitrogen-containing heterocycles to which one or more halogens are bonded. As will be described later, this is because a desired high molecular organic compound can be suitably obtained by a dehalogenation polycondensation method using an organometallic reagent.
One method for synthesizing such a monomer is by lithiation of a dihalogenated nitrogen-containing composite ring and reaction with a dihalogenated silane.
Among the nitrogen-containing heterocycles, the pyridine ring is easy to synthesize, has good durability, and is particularly good.

The structural unit (B) refers to a constituent element surrounded by a right parenthesis in the general formula (1). Compound in the general formula (1) represents a compound, and | compound | _{m only} needs to form a polymer skeleton.
Examples of such compounds include aliphatic hydrocarbons such as ethylene, propylene, and butadiene, aromatic hydrocarbons such as benzene and naphthalene, heterocycles such as thiophene and pyridine, silicon compounds such as silicone, or fluorine compounds thereof. Examples thereof include chemical modifications such as those described above, or combinations thereof.
Examples thereof include those obtained by chemically modifying these with a nitro group, a hydroxyl group, a carboxyl group, a halogen group or the like.
Among these compounds, the nitrogen-containing heterocycle is preferable from the viewpoint of chemical stability. Among them, compound containing a pyridine ring is particularly good for the same reason.

  Examples of the structural unit (B) containing a sulfonate group or a sulfonate group comprising a compound containing a pyridine ring include an O-alkylene sulfonate group or an O-alkylene sulfonate group as shown in the following general formula (4) Pyridine having N-alkylenesulfonic acid group or N-alkylenesulfonic acid group as shown in the following general formula (5), sulfonated pyridyloxy group or sulfonated pyridyloxy as shown in the following general formula (6) A pyridine having a group is particularly good because it is easy to synthesize monomers and has high chemical stability.

(R in the formula (4) represents an alkylene group, and X ⁺ represents a cation.)

(R in the formula (5) represents an alkylene group, and X ⁺ represents a cation.)

(X ⁺ in formula (6) represents a cation.)

Here, the general formula (4) in O- alkylene sulfonic acid group or O- alkylene sulfonate pyridine with, the -O-R-SO ₃ pyridine ^- X ⁺ groups are introduced one or more Refers to things. ^{_{Further, -O-R-SO 3 -}} X + nitro group other than a hydroxyl group, a halogen group, may be provided with a suitable functional group such as a carbonyl group.

That said in the general formula (4), -O-R- SO 3 - an example is shown having one X ^{+ _{group, -O-R-SO 3 -}} X + group of two or more organic it may also be, also -O-R-SO ₃ ^- is that X ⁺ other nitro group, a hydroxyl group, a halogen group, which may have a functional group such as a carbonyl group.

The length of the carbon chain of the alkylene group in the general formula (4) is not particularly limited as long as the performance of the obtained organic compound is not impaired, but those having 3 and 4 carbon atoms are inexpensive propane. Sultone and 1,4-butane sultone can be used as raw materials, respectively, and the desired product can be obtained under relatively mild reaction conditions.
R is an alkylene group having 3 or 4 carbon atoms in which at least a part of hydrogen is substituted with a halogen element, for example, an alkylene group such as monofluoro, difluoro, trifluoro, perfluoro, monochloro, dichloro, trichloro, and perchloro Is preferable, and chemical durability is easily improved.

Those X ⁺ groups are introduced one or more ^- including pyridine having the general formula (5) in N- alkylene sulfonic acid group or N- alkylene sulfonate, and -N-R-SO ₃ in pyridine Point to. ^{_{Further, -N-R-SO 3 -}} X + nitro group other than a hydroxyl group, a halogen group, may be provided with a suitable functional group such as a carbonyl group.

-N-R-SO ₃ ^- in amine in X ⁺ group there are three types of secondary amines, tertiary amines, quaternary amines. For tertiary and quaternary ^{_{amines, -N-R-SO 3 -}} X + well be contained, in the case of secondary amine ^{_{-NH-R-SO 3 - X}} + only present To do.

In other words, the general formula (5) as ^{_{-N-R-SO 3 - X}} + of the group exemplified what has one, -N-R-SO ₃ ^- have X ⁺ group of two or more and it may also ring -N-R-SO ₃ ^- is that X ⁺ nitro group other than a hydroxyl group, as a halogen group, may have an appropriate functional group such as a carbonyl group.

  In the general formula (6), those having one pyridyloxy group to which a sulfonated pyridyloxy group or a sulfonate is bonded are exemplified, and these groups may be 1 or more, and pyridine includes There may be other functional groups such as alkyl groups, nitro groups, hydroxyl groups, halogen groups, carboxyl groups.

X ⁺ in the present invention will be described.
X ⁺ represents a cation. X ⁺ is, for example, hydrogen, a group 1 element, a group 2 element, aluminum, a transition metal, a chemical species such as a metal complex or metal oxide containing these, or various inorganic and organic chemical species. It is in an ionic state.
The Group 1 element is an alkali metal from Li to Fr, and the Group 2 element is an alkaline earth metal from Be, Mg, and Ca to Ra.
Examples of transition metals are Fe, Ni, Cu, and Zn.
Specific examples of chemical species such as metal complexes and metal oxides include alkali metal crown ether complexes, ferrocenium, tris (1,10-phenanthroline) iron (II), and UO ₂ .
As various inorganic and organic chemical species, specifically, ammonium (NH ₄ ) or quaternary nitrogen compound (R ³ R ⁴ R ⁵ R ⁶ N) (R ³ , R ⁴ , R ⁵ and R ⁶ are each an alkyl group. And an aromatic group, an alkyl group and an alkenyl group, an alkynyl group, and other various functional groups, all of which may be the same or part or all of which may be different.) Nitrogen-containing compounds, quaternary phosphonium compounds, quaternary arsonium compounds, triphenylmethane compounds, and the like.
Specific examples of quaternary nitrogen compounds include tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, tetraoctylammonium, phenyltrimethylammonium, dodecyltrimethylammonium, didodecyldimethyl. Examples include ammonium, choline, and acetylcholine.
Specific examples of other nitrogen-containing compounds include pyridinium, cetylpyridinium, and bis (triphenylphosphine) iminium.
Specific examples of the quaternary phosphonium compound include tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetraphenylphosphonium, butyltriphenylphosphonium, and benzyltriphenylphosphonium. Examples of the quaternary arsonium compound include tetra Phenylarsonium is mentioned.
Specific examples of the triphenylmethane compound include crystal violet, ethyl violet, and malachite green.
Among the examples given above, hydrogen, Group 1 elements and Group 2 elements are good in cost, and among them, hydrogen, Li, Na and K are particularly good in cost and easy to use.

  Since the high molecular organic compound of the present invention represented by the general formula (1) contains a sulfonic acid group which is a strong acid group, it has high proton conductivity, and also has excellent radical resistance and heat resistance. It can be suitably used for fuel cell applications.

  The molecular weight represented by the mass average molecular weight of the macromolecular organic compound referred to in the present invention is not particularly limited because the optimum value varies depending on the use, but 1000 to 10 million is usually preferred. If it is less than 1000, it may be unsuitable for fields requiring mechanical strength, while if it exceeds 10 million, workability may be deteriorated.

The polymer organic compound of the present invention may contain other structural units (C) in addition to the structural unit (A) and the structural unit (B).
The constitution (C) contained in the polymer organic compound is preferably composed of a compound that does not impair the heat resistance and radical resistance of the resulting polymer organic compound. As an example of such a configuration, one containing an aromatic ring is preferable because, for example, the heat resistance becomes higher and the cost is reduced.

The aromatic ring mentioned here is a nitrogen-containing heterocycle such as a benzene ring, a naphthalene ring condensed with a benzene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a pyrrole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring. Rings, sulfur-containing heterocycles such as thiophene rings, oxygen-containing heterocycles such as furan rings, indole rings, benzothiophene rings, benzofuran rings, phenanthroline rings, and purine rings that include these heterocycles in part or in whole A condensed ring can be illustrated.
Moreover, the aromatic ring which chemically modified these can also be illustrated. Further, a complex ring or copolymer composed of two or more types of rings may be used.

  Among these, many nitrogen-containing heterocycles are rich in chemical stability, and among them, the pyridine ring exhibits particularly high radical resistance. Therefore, a high molecular weight organic compound composed of only a pyridine ring is preferable because it shows particularly excellent chemical stability.

In this case, the pyridine ring may be unsubstituted or have a suitable functional group such as a nitro group, a hydroxyl group, a halogen group, or a carbonyl group, as long as the properties of the resulting macromolecular organic compound are not impaired. May be.
Further, the bonding position with the adjacent structural unit is not particularly limited, and a pyridine ring structural unit having a different bonding position may be copolymerized by mixing two or more types of pyridine ring structural units. Further, it may be a pyridine ring having three or more bonds.

The polymer organic compound of the present invention contains the structural unit (A) and the structural unit (B) represented by the general formula (1) in the polymer main chain. In some cases, in addition to that, (C) other structural units may be bonded.
The order of the structural unit represented by (A), the structural unit represented by (B), and (C) the other structural units is not particularly limited. For example, even in the case of an alternating copolymer, It may be a polymer, a random copolymer, or a graft copolymer.

  For example,-(A)-(B)-(A)-(B)-(A)-(B)-,-(A)-(B)-(C)-(A)-(B)-( C)-,-(A)-(A)-(A)-(B)-(B)-(B)-(C)-(C)-,-(A)-(C)-(B) Any of-(A)-(B)-(C)-or a graft structure represented by the general formula (7) may be used, and the order of the respective structural units is not limited. Further, the ratio of the number of structural units (A), (B), and (C) is not limited. There are no particular limitations on the position of coupling with the adjacent structural unit.

  Among the polymer organic compounds of the present invention, (A) a structural unit comprising a silicon derivative having a nitrogen-containing heterocycle, (B) a structural unit containing a sulfonic acid group or a sulfonic acid group, and (C) any other structure The ratio of the number of units is not particularly limited, but when the proportion of the structural unit represented by the general formula (B) increases, it may become soluble in water. Therefore, it is desirable to change the ratio according to the application.

Examples of the synthesis method for obtaining the polymer organic compound of the present invention include an oxidative polymerization method and an organometallic polycondensation method, and are not particularly limited as long as the performance of the resulting polymer organic compound is not impaired. Absent.
Among these, the target high molecular organic compound of the present invention can be suitably obtained by a dehalogenation polycondensation method using an organometallic reagent using an organic compound containing two halogens as a monomer.

  The polymer organic compound of the present invention is excellent in proton conductivity and has a high ion exchange capacity, and therefore can be used as an ion exchanger.

  Moreover, since it has a sulfonic acid group in a molecule | numerator, it can be used also as a catalyst.

  Furthermore, an electrolyte membrane is produced using the polymer organic compound of the present invention, and a membrane electrode assembly (MEA) having the configuration shown in FIG. 1 and a membrane electrode assembly (MEA) thereof are provided. It is also possible to produce a single cell of the fuel cell having the configuration shown in FIG.

  In order to produce an electrolyte membrane using the polymer organic compound of the present invention, the membrane is formed by heat melting, or dissolved in an appropriate solvent, applied to an appropriate substrate or support, and then dried. Examples include a so-called solution process method for forming a film, and the formation method is not particularly limited.

  The solvent used in forming the polymer organic compound of the present invention by the solution process as described above is not particularly limited as long as it can dissolve the sample, but is easily available industrially. More preferable are those which are easily distilled off during film formation and drying, and examples thereof include chloroform, methylene chloride, ether, dioxane, hexane, cyclohexane, tetrahydrofuran, acetone, methanol, ethanol, formic acid, and the like. A mixture of these solvents may also be used.

  When the polymer organic compound of the present invention is used to produce an ion exchanger or catalyst, it can be formed by heat melting as described above, and after being dissolved in an appropriate solvent, it is applied to a support. -It can form by coating or carrying, The formation method is not specifically limited.

  In addition, a binder may be used. As the binder, a suitable resin can be used alone or in combination of two or more. Further, modified products and copolymers of these resins may be used. For example, proton conductivity can be further improved by using modified products obtained by introducing sulfonic acid groups into these resins. Used.

Specific examples of the resin herein include epoxy resin, urea resin, silicone resin, propylene resin, phenol resin, xylene resin, melamine resin, polyester resin, alkyd resin, vinylidene resin, furan resin, urethane resin, phenylene ether. Examples include resins, polycarbonate resins, acrylic resins, amide resins, imide resins, vinyl resins, carboxylic acid resins, fluororesins, nylon resins, styrene resins, engineering plastics, and the like.
In addition to the organic resins as described above, organic-inorganic hybrid resins, silicate resins, water glass, various inorganic polymers, and the like can be used. As described above, modified products in which sulfonic acid groups or hydroxyl groups are introduced into these resins are also preferably used.

The following method can be shown as an example of a method for producing a membrane electrode assembly (MEA).
First, an electrolyte membrane is formed by the production method described above using the polymer organic compound of the present invention. Further, if necessary, a protective film is laminated thereon and stored. In use, the support and the protective film are peeled off, and then an electrode layer containing a catalyst layer and a gas diffusion layer is formed on both sides of the electrolyte membrane, whereby the membrane electrode assembly (MEA) shown in FIG. Is obtained. As shown in FIG. 2, this membrane electrode assembly (MEA) is assembled with a separator and auxiliary devices (not shown) (gas supply device, cooling device, etc.) and assembled, and a fuel cell is manufactured by single or stacking. can do.

  Moreover, the suitable thickness of the electrolyte membrane formed of the polymer organic compound in the present invention is usually about 0.1 to 500 μm, more preferably 10 μm to 150 μm. If the thickness exceeds 500 μm, the proton conductivity may be impaired, and if it is less than 0.1 μm, the physical properties of the electrolyte membrane may be impaired.

  Further, the polymer organic compound of the present invention is used as an electrolyte used for an electrode layer, and the membrane electrode assembly (MEA) having the configuration shown in FIG. 1 and the membrane electrode assembly (MEA) shown in FIG. 2 are shown. It is also possible to produce a single cell of a fuel cell having the above-described configuration. The catalyst layer is a layer containing at least a catalyst and an electrolyte, and the polymer organic compound of the present invention can be used as the electrolyte contained in the catalyst layer. In forming the catalyst layer, a coating solution containing at least an electrolyte and a catalyst is used, and the coating solution is applied directly to the electrolyte membrane, or the coating solution is applied to another substrate to form a coating film. The catalyst layer can be formed on both surfaces of the electrolyte membrane by a method of transferring to the electrolyte membrane.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example.

The compounds obtained in the following examples were identified by infrared absorption spectrum and elemental analysis. Each was measured using the following equipment.
[Infrared absorption spectrum]
A mixture of a small amount of sample and potassium bromide pressed into a pellet was used for the measurement. Measurement was performed using JASCO FT / IR-460 type.
[Elemental analysis]
Analysis of the amount of S by elemental analysis: The sample was measured with YS-10 manufactured by YANACO, and weight percent of S (sulfur) was obtained.

Example 1
[(A) A structural unit composed of a silicon derivative having a nitrogen-containing heterocyclic ring is pyridine, and (B) a structural unit containing a sulfonic acid group or a sulfonate group is represented by structural formula (8) composed of pyridine. Synthesis of molecular organic compounds)
N, N-dimethylformamide (DMF) was added to 0.92 g of nickel-1,5-cyclooctadiene complex [bis (1,5-cyclooctadiene) nickel (0), Ni (cod) ₂ ] and stirred. . To this, 0.41 ml of 1,5-cyclooctadiene and 0.52 g of 2,2′-bipyridyl were added and stirred.
N, N-dimethylformamide solution containing 0.062 g of the compound represented by formula (9), 0.199 g of the compound represented by formula (10) and 0.238 g of 2,5-dibromopyridine Was added and allowed to react.
The crude reaction product was collected, purified and dried to obtain 0.073 g of a sulfonic acid group-containing polypyridine represented by the structural formula (8).

(Parts enclosed in parentheses in the formula (8) indicate units constituting the macromolecular organic compound, and l, m, and n are integers representing the number of each structural unit.)
In the formulas (8) and (9), Me represents a methyl group.

(Example 2)
[(A) A structural unit composed of a silicon derivative having a nitrogen-containing heterocycle is pyridine, and (B) a structural unit containing a sulfonic acid group or a sulfonic acid group is represented by structural formula (11) composed of pyridine. Synthesis of molecular organic compounds)
N, N-dimethylformamide (DMF) was added to 0.41 g of nickel-1,5-cyclooctadiene complex [bis (1,5-cyclooctadiene) nickel (0), Ni (cod) ₂ ] and stirred. . To this, 0.18 ml of 1,5-cyclooctadiene and 0.23 g of 2,2′-bipyridyl were added and stirred.
To this, 0.166 g of a compound represented by formula (9) and 0.118 g of a N, N-dimethylformamide solution containing a compound represented by formula (10) were added and reacted.
The crude reaction product was collected, purified, and dried to obtain 2 mg of sodium sulfonate group-containing polypyridine represented by the structural formula (11).

(Parts enclosed in parentheses in the formula (11) represent units constituting the polymer organic compound, and l and m are integers representing the number of each structural unit.)
In the formula (11), Me represents a methyl group.

Infrared absorption spectra of the polymer organic compounds represented by structural formulas (8) and (11) obtained in Examples 1 and 2 were measured. The measurement result of the polymer organic compound represented by Structural Formula (8) is shown in FIG. 3, and the measurement result of the polymer organic compound represented by Structural Formula (11) is shown in FIG.
Any polymeric organic compound may, and around 1030~1050cm ^-1, 2 two characteristic strong absorption peak around 1170～1200Cm ^-1 were observed. These are due to the symmetric vibration and asymmetric vibration of the S═O group, respectively, and are absorption peaks peculiar to the sulfonic acid group or sodium sulfonate group. It was confirmed to have a group.

(Acid value)
For the polymer organic compound represented by Structural Formula (8) obtained in Example 1, the S content was measured by elemental analysis, and the acid value was calculated therefrom.

  As a result of elemental analysis, the acid value of the polymer organic compound represented by Structural Formula (8) was 1.9 meq / g.

(Film Formation of Polymer Organic Compound of the Present Invention)
The polymer organic compound represented by Structural Formula (8) obtained in Example 1 was dissolved in a solvent and applied, and the solvent was removed to obtain a film.

(Evaluation of radical resistance)
[Fenton test]
The film prepared by the above method using the polymer organic compound represented by the structural formula (8) obtained in Example 1 was put in Fenton reagent (15% H ₂ O ₂ , 20 ppm Fe ²⁺ ), and 60 It carried out on condition of 3 degreeC, and the change of the film was confirmed visually.
Under these test conditions, a normal hydrocarbon electrolyte membrane was decomposed by radicals, but no polymer organic compound membrane represented by the structural formula (8) was collected. From this result, it was found that the polymer organic compound of the present invention has excellent radical resistance.
On the other hand, in the sulfonated polyether ether ketone, which is a normal hydrocarbon electrolyte membrane, dripping was observed even at 60 ° C. for 3 hours, 3% H ₂ O ₂ , 4 ppm Fe ²⁺ , which is considerably weaker than this. .
Sagging was also observed in another hydrocarbon-based resin, polyphenylene resin.

(Evaluation of heat resistance)
[Thermogravimetric analysis]
In order to evaluate the heat resistance of the polymer organic compound represented by the structural formula (8) obtained in Example 1, a thermogravimetric analyzer TGA-50 manufactured by Shimadzu Corporation and a temperature analyzer TA-50WS manufactured by the same company were used. Thermogravimetric analysis was performed. In the measurement, about 5 mg of a sample was weighed and placed on a platinum vessel, and the temperature was raised from room temperature to 900 ° C. at a rate of 10 ° C. per minute in a nitrogen atmosphere, and the weight change during that time was plotted.

  As a result of the measurement, a weight loss of about 10% was observed up to 100 ° C. This is not the decomposition of the macromolecular organic compound represented by the structural formula (8) but the influence of the contained water. Thereafter, no weight loss was observed until the temperature exceeded 300 ° C. The 15% weight loss temperature was 340 ° C. It was found that it did not decompose even at a high temperature of 300 ° C. and had high thermal stability.

  From the above results, it was found that the polymer organic compound obtained by the present invention was excellent in film forming property and had both high radical resistance and heat resistance.

The new macromolecular organic compound of the present invention has high radical resistance not obtained with conventional hydrocarbon resins, excellent proton conductivity, high ion exchange amount, and activity as an acid catalyst. Because it is high, it has a remarkable effect that it can be used effectively as an ion exchanger, electrolyte membrane, catalyst, membrane electrode assembly, fuel cell,
And an ion exchanger excellent in radical resistance, heat resistance, proton conductivity and the like using the new polymer organic compound of the present invention, an electrolyte membrane, a membrane electrode assembly including the electrolyte membrane, and the membrane electrode assembly Therefore, it is possible to provide a fuel cell having a high acid catalyst activity and a high industrial utility value.

It is sectional explanatory drawing of one embodiment of the membrane electrode assembly which formed the electrode catalyst layer on both surfaces of the electrolyte membrane. FIG. 2 is an exploded cross-sectional view showing a configuration of a single cell of a fuel cell equipped with the membrane electrode assembly shown in FIG. 1. The infrared absorption spectrum of the high molecular organic compound represented by Structural formula (8) obtained in Example 1 is shown. The infrared absorption spectrum of the high molecular organic compound represented by Structural formula (11) obtained in Example 2 is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrolyte membrane 2 Air electrode side electrode catalyst layer 3 Fuel electrode side electrode catalyst layer 4 Air electrode side gas diffusion layer 5 Fuel electrode side gas diffusion layer 6 Air electrode 7 Fuel electrode 8 Gas flow path 9 Cooling water flow path 10 Separator 11 Single cell 12 Membrane electrode assembly

Claims (15)

It is represented by the following general formula (1) having in the molecule both (A) a structural unit composed of a silicon derivative having a nitrogen-containing heterocyclic ring and (B) a structural unit containing a sulfonic acid group or a sulfonic acid group. A high molecular weight organic compound having at least a molecular structure.

(HCy in formula (1) represents the same or different nitrogen-containing heterocycles, and compound represents a compound. The part enclosed in parentheses in formula (1) represents a unit constituting a macromolecular organic compound. , N is an integer that represents the number of structural units (A), m is an integer that represents the number of structural units (B), and the wavy line represents whether a sulfonic acid group or sulfonate is directly bonded to compound or interposed Represents that the compound may be indirectly bonded to the compound via a group, R ¹ and R ² each represent the same or different arbitrary substituents, and X ⁺ represents a cation.) The compound of the structural unit (B) is composed of a nitrogen-containing heterocyclic ring, and has at least a molecular structure represented by the following general formula (2).

(HCy in the formula (2) represents the same or different nitrogen-containing heterocycles. The part enclosed in parentheses in the formula (2) represents a unit constituting the macromolecular organic compound, and n represents a structural unit ( A is an integer representing the number of A, m is an integer representing the number of the structural unit (B), and the wavy line is obtained even when the sulfonic acid group or sulfonate is directly bonded to the nitrogen-containing heterocyclic ring or through an intervening group. And may be indirectly bonded to the nitrogen-containing heterocycle, R ¹ and R ² each represent the same or different arbitrary substituents, and X ⁺ represents a cation.)   3. The macromolecular organic compound according to claim 2, wherein the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring or a heterocycle containing a pyridine ring. The nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring, the compound in the structural unit (B) is a pyridine ring, and has at least a molecular structure represented by the following general formula (3) The macromolecular organic compound according to claim 2.

(The part enclosed in parentheses in the formula (3) represents a unit constituting the polymer organic compound, n is an integer representing the number of structural units (A), and m is the number of structural units (B). The wavy line represents that the sulfonic acid group or sulfonate may be directly bonded to the pyridine ring or indirectly bonded to the pyridine ring through an intervening group, and R ¹ and R ² are Each represents the same or different optional substituents, and X ⁺ represents a cation.) The high molecular organic compound according to claim 4, wherein the nitrogen-containing heterocycle in the structural unit (A) is a pyridine ring, and R ¹ and R ² are the same or different alkyl groups. A structural unit (B) is represented by the following general formula (4), The high molecular organic compound of Claim 4 or Claim 5 characterized by the above-mentioned.

(R in the formula (4) represents an alkylene group, and X ⁺ represents a cation.) 6. The high molecular weight organic compound according to claim 4, wherein the structural unit (B) is represented by the following general formula (5).

(R in the formula (5) represents an alkylene group, and X ⁺ represents a cation.) 6. The high molecular organic compound according to claim 4, wherein the structural unit (B) is represented by the following general formula (6).

(X ⁺ in formula (6) represents a cation.)   9. The macromolecular organic compound according to claim 1, wherein the sulfonic acid or sulfonate salt density is 0.1 to 5 meq / g.   The high molecular organic compound according to claim 6 or 7, wherein the alkylene group is an alkylene group having 3 or 4 carbon atoms or an alkylene group in which at least a part of hydrogen thereof is substituted with a halogen element.   An ion exchanger comprising the polymer organic compound according to any one of claims 1 to 10.   An electrolyte membrane comprising the polymer organic compound according to any one of claims 1 to 10.   The catalyst comprised using the high molecular organic compound as described in any one of Claims 1-10.   A membrane electrode assembly comprising the polymer organic compound according to any one of claims 1 to 10.   A fuel cell comprising the polymer organic compound according to any one of claims 1 to 10.

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