JP2018135450A - Anion exchange resin, electrolyte layer, binder for forming electrode catalyst layer, battery electrode catalyst layer and fuel battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an anion exchange resin capable of producing an electrolyte layer, a binder for forming an electrode catalyst layer and a battery electrode catalyst layer having excellent chemical stability, flexibility and heat resistance; an electrolyte layer, a binder for forming an electrode catalyst layer and a battery electrode catalyst layer formed from the anion exchange resin; and a fuel battery comprising the electrolyte layer or the battery electrode catalyst layer.SOLUTION: There is provided an anion exchange resin which, for example, has a bivalent hydrophobic unit composed of repetition of a bivalent saturated hydrocarbon group and a bivalent hydrophilic unit composed of repetition of an o-, m- or p-phenylene group substituted with a substituent having an anion exchange group and/or a diphenyl residue substituted with a substituent having an anion exchange group, wherein the hydrophobic unit and the hydrophilic unit bond to each other via a direct bond.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an anion exchange resin, an electrolyte membrane, a binder for forming an electrode catalyst layer, a battery electrode catalyst layer, and a fuel cell.

  A divalent hydrophobic group consisting of a plurality of aromatic rings bonded to each other via a divalent saturated hydrocarbon group and a plurality of aromatic rings consisting of a single aromatic ring or bonded to each other via a carbon-carbon bond The aromatic ring having an anion exchange group on the saturated hydrocarbon group has a carbon-carbon bond. A hydrophobic unit in which a hydrophobic group and a binding group are repeated via an ether bond, and a hydrophilic group and an x-bonding group are repeated via an ether bond. An anion exchange resin having a hydrophilic unit and a hydrophobic unit and a hydrophilic unit bonded through an ether bond is known (Patent Document 1).

  A single aromatic ring or a divalent hydrocarbon group, a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, a divalent sulfur-containing group Or a divalent hydrophobic group composed of a plurality of aromatic rings bonded to each other via a carbon-carbon bond and a single aromatic ring, or a divalent hydrocarbon group, a divalent silicon-containing group, 2 A valent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, a divalent sulfur-containing group, or a plurality of aromatic rings bonded to each other via a carbon-carbon bond, at least of the aromatic rings A hydrophobic unit, one of which consists of a divalent hydrophilic group having an anion exchange group and a divalent fluorine-containing group, wherein the hydrophobic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond; , Hydrophilic groups repeat through carbon-carbon bonds The hydrophobic unit and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond, and the divalent fluorine-containing group is a main chain of the hydrophobic unit. Anion exchange bonded through an ether bond, thioether bond, carbon-silicon bond, or carbon-carbon bond, or bonded through a carbon-carbon bond in the main chain of the hydrophilic unit. Resins are also known (Patent Document 2).

JP 2013-47309 A Japanese Patent No. 5960763

  However, the anion exchange resin described in Patent Document 1 has a problem that the chemical stability (durability, particularly alkali resistance) is not sufficient. The chemical stability is improved by changing the ether bond around the anion exchange group contained in the anion exchange resin described in Patent Document 1 to a carbon-carbon bond, but the machine is an advantage of the ether bond. Characteristic (especially flexibility) is reduced. If the aromatic ring (particularly the aromatic ring constituting the hydrophobic unit) contained in the anion exchange resin described in Patent Document 1 is changed to the perfluoroalkyl group shown in Patent Document 2, the chemical stability remains. Although flexibility is improved, there is a concern about a decrease in heat resistance, which is an advantage of the aromatic ring.

  Therefore, the present invention provides an electrolyte membrane excellent in chemical stability, flexibility and heat resistance, an electrode catalyst layer-forming binder, an anion exchange resin capable of producing a battery electrode catalyst layer, and an electrolyte formed from the anion exchange resin An object of the present invention is to provide a membrane and electrode catalyst layer-forming binder, a battery electrode catalyst layer formed from the electrode catalyst layer-forming binder, and a fuel cell comprising the electrolyte membrane or battery electrode catalyst layer.

In order to solve the above problems, the anion exchange resin of the present invention is
A divalent hydrophobic unit consisting of a hydrophobic group represented by the following formula (1) or a repeating hydrophobic group represented by the following formula (1);
An o-, m- or p-phenylene group substituted with a substituent having an anion exchange group represented by the following formula (2a) and / or an anion exchange group represented by the following formula (2b): Having a hydrophilic group consisting of a diphenyl residue substituted with a substituent having, or a divalent hydrophilic unit consisting of repetition of the hydrophilic group,
The hydrophobic unit and the hydrophilic unit are bonded via a direct bond.

（式中、Ｚ_１〜Ｚ_９は、互いに同一または相異なって、炭素原子またはケイ素原子を示し、Ｒ_１〜Ｒ_８は、互いに同一または相異なって、ケイ素含有基、窒素含有基、リン含有基、酸素含有基、硫黄含有基、または直接結合を示し、ａは、１以上の整数を示し、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、互いに同一または相異なって、０以上の整数を示す。）

(In the formula, Z _{1 to} Z ₉ are the same or different from each other, and represent a carbon atom or a silicon atom, and R _{1 to} R ₈ are the same or different from each other, and contain a silicon-containing group, a nitrogen-containing group, or a phosphorus-containing group. A group, an oxygen-containing group, a sulfur-containing group, or a direct bond, a represents an integer of 1 or more, b, c, d, e, f, g, h, and i are the same or different from each other; Indicates an integer of 0 or more.)

（式中、Ａｌｋは、アルキル基を示し、Ｉｏｎは、陰イオン交換基を有する置換基を示し、ａ’は、０〜４の整数を示し、ｓは、１〜４の整数を示す。）

(In the formula, Alk represents an alkyl group, Ion represents a substituent having an anion exchange group, a ′ represents an integer of 0 to 4, and s represents an integer of 1 to 4.)

（式中、Ｒは、前記陰イオン交換基を有する置換基で置換されていてもよい、炭化水素基、ケイ素含有基、窒素含有基、リン含有基、酸素含有基、硫黄含有基、芳香族基、または直接結合を示し、Ａｌｋは、互いに同一または相異なって、アルキル基を示し、Ｉｏｎは、互いに同一または相異なって、陰イオン交換基を有する置換基を示し、ａ’およびｂ’は、互いに同一または相異なって、０〜４の整数を示し、ｓ、ｔおよびｕは、互いに同一または相異なって、０〜４の整数を示すとともに、ｓ、ｔおよびｕの少なくとも一つが、１以上を示す。）

(In the formula, R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, which may be substituted with a substituent having the anion exchange group. A group, or a direct bond, Alk is the same or different from each other and represents an alkyl group, Ion is the same or different from each other, and represents a substituent having an anion exchange group, and a ′ and b ′ are Are the same or different from each other and represent an integer of 0 to 4, s, t and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t and u is 1 The above is shown.)

In the anion exchange resin of the present invention, in the formula (1), R _{1 to} R ₈ preferably represent a direct bond or an oxygen atom, and in particular, the hydrophobic group is a divalent saturated hydrocarbon group. It is preferable that

  In the anion exchange resin of the present invention, the divalent hydrophilic unit is represented by the following formula (2a ′), a p-phenylene group substituted with a substituent having an anion exchange group, and the following formula (2b) It is preferable to consist of repeating diphenylfluorene residues substituted with a substituent having an anion exchange group represented by ').

（式中、Ｉｏｎは、陰イオン交換基を有する置換基を示す。）

(In the formula, Ion represents a substituent having an anion exchange group.)

（式中、Ｉｏｎは、互いに同一または相異なって、陰イオン交換基を含む置換基または水素原子を示し、少なくとも１つは陰イオン交換基を含む置換基を示す。）

(In the formula, Ion is the same or different from each other and represents a substituent or a hydrogen atom containing an anion exchange group, and at least one represents a substituent containing an anion exchange group.)

  In order to solve the above problems, the electrolyte membrane of the present invention includes the anion exchange resin described above.

  In order to solve the above-mentioned problems, the binder for forming an electrode catalyst layer of the present invention is characterized by containing the above anion exchange resin.

  In order to solve the above-mentioned problems, the battery electrode catalyst layer of the present invention is characterized by including the above-mentioned binder for forming an electrode catalyst layer.

In order to solve the above problems, the fuel cell of the present invention comprises:
An electrolyte membrane comprising the above anion exchange resin;
A fuel-side electrode that is disposed opposite to the electrolyte membrane and is supplied with hydrogen-containing fuel; and an oxygen-side electrode that is supplied with oxygen or air;
It is provided with.

  In the fuel cell of the present invention, it is preferable that the hydrogen-containing fuel is hydrogen, alcohol, or hydrazine.

In order to solve the above problems, the fuel cell of the present invention comprises:
An electrolyte membrane;
A fuel-side electrode that is disposed opposite to the electrolyte membrane and is supplied with hydrogen-containing fuel, and an oxygen-side electrode that is supplied with oxygen or air,
The fuel side electrode and / or the oxygen side electrode includes the battery electrode catalyst layer described above.

  In the fuel cell of the present invention, it is preferable that the hydrogen-containing fuel is hydrogen, alcohol, or hydrazine.

  According to the present invention, an electrolyte membrane excellent in chemical stability, flexibility and heat resistance, an electrode catalyst layer forming binder, an anion exchange resin capable of producing a battery electrode catalyst layer, and an electrolyte formed from the anion exchange resin A fuel cell comprising a membrane and electrode catalyst layer forming binder, a battery electrode catalyst layer formed from the electrode catalyst layer forming binder, and an electrolyte membrane or battery electrode catalyst layer thereof can be provided.

It is a schematic block diagram which shows one Embodiment of a fuel cell. It is a figure which shows the tension test result of an anion exchange membrane. It is a figure which shows the dynamic viscoelasticity test result of an anion exchange membrane.

  The anion exchange resin of the present invention comprises a divalent hydrophobic unit and a divalent hydrophilic unit.

  In the anion exchange resin of the present invention, the divalent hydrophobic unit consists of a hydrophobic group represented by the following formula (1) or a repeating hydrophobic group represented by the following formula (1).

（式中、Ｚ_１〜Ｚ_９は、互いに同一または相異なって、炭素原子またはケイ素原子を示し、Ｒ_１〜Ｒ_８は、互いに同一または相異なって、ケイ素含有基、窒素含有基、リン含有基、酸素含有基、硫黄含有基、または直接結合を示し、ａは、１以上の整数を示し、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、互いに同一または相異なって、０以上の整数を示す。）

(In the formula, Z _{1 to} Z ₉ are the same or different from each other, and represent a carbon atom or a silicon atom, and R _{1 to} R ₈ are the same or different from each other, and contain a silicon-containing group, a nitrogen-containing group, or a phosphorus-containing group. A group, an oxygen-containing group, a sulfur-containing group, or a direct bond, a represents an integer of 1 or more, b, c, d, e, f, g, h, and i are the same or different from each other; Indicates an integer of 0 or more.)

In the above formula (1), Z _{1 to} Z ₉ are the same or different from each other, and represent a carbon atom or a silicon atom, preferably a carbon atom.

  In the above formula (1), R's are the same or different from each other and each represents a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or a direct bond, preferably a direct bond or an oxygen atom More preferably direct bonding.

  In said formula (1), a shows an integer greater than or equal to 1, Preferably an integer of 2-20 is shown, More preferably, an integer of 2-12 is shown.

  In the above formula (1), b, c, d, e, f, g, h and i are the same or different from each other and represent an integer of 0 or more, preferably an integer of 0 to 10, more preferably Represents an integer of 0 to 3, more preferably 0 or 1.

  The hydrophobic group represented by the above formula (1) may form a divalent hydrophobic unit by bonding a plurality of types to each other in a random or alternating regular or block form. That is, in the anion exchange resin of the present invention, the hydrophobic group represented by the formula (1) may be repeatedly bonded to each other via a carbon-carbon bond to form a divalent hydrophobic unit. .

  Such a divalent hydrophobic unit is represented by the following formula (3).

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、ｌは、繰り返し単位である各疎水性基のモル分率を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h, and i have the same meanings, and l represents the mole fraction of each hydrophobic group that is a repeating unit.

  As such a hydrophobic group, Preferably, what has the following structures is mentioned.

  In the above formula, a and a ′ are the same as or different from each other, and represent an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 6.

  In said formula, k shows an integer greater than or equal to 0, Preferably it shows the integer of 0-20, More preferably, it shows the integer of 0-3, More preferably, it shows 0.

  As such a hydrophobic group, a divalent saturated hydrocarbon group is more preferable, and a hydrocarbon group represented by the following formula (1 ′ ″) or the following (1 ″ ″) is particularly preferable. Is mentioned.

  In the above formula, a and a ′ are the same as or different from each other, and represent an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 6.

  By having such a hydrophobic unit, it is possible to improve the mechanical properties (flexibility and heat resistance) of the membrane in a temperature range (60 ° C. or higher) above the actual operation when used as an electrolyte membrane.

  In the anion exchange resin of the present invention, the divalent hydrophilic unit is an o-, m- or p-phenylene group substituted by a substituent having an anion exchange group represented by the following formula (2a), and / Or consists of a hydrophilic group consisting of a diphenyl residue substituted with a substituent having an anion exchange group represented by the following formula (2b), or a repetition of the hydrophilic group.

（式中、Ａｌｋは、アルキル基を示し、Ｉｏｎは、陰イオン交換基を有する置換基を示し、ａ’は、０〜４の整数を示し、ｓは、１〜４の整数を示す。）

(In the formula, Alk represents an alkyl group, Ion represents a substituent having an anion exchange group, a ′ represents an integer of 0 to 4, and s represents an integer of 1 to 4.)

（式中、Ｒは、前記陰イオン交換基を有する置換基で置換されていてもよい、炭化水素基、ケイ素含有基、窒素含有基、リン含有基、酸素含有基、硫黄含有基、芳香族基、または直接結合を示し、Ａｌｋは、互いに同一または相異なって、アルキル基を示し、Ｉｏｎは、互いに同一または相異なって、陰イオン交換基を有する置換基を示し、ａ’およびｂ’は、互いに同一または相異なって、０〜４の整数を示し、ｓ、ｔおよびｕは、互いに同一または相異なって、０〜４の整数を示すとともに、ｓ、ｔおよびｕの少なくとも一つが、１以上を示す。）

(In the formula, R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, which may be substituted with a substituent having the anion exchange group. A group, or a direct bond, Alk is the same or different from each other and represents an alkyl group, Ion is the same or different from each other, and represents a substituent having an anion exchange group, and a ′ and b ′ are Are the same or different from each other and represent an integer of 0 to 4, s, t and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t and u is 1 The above is shown.)

  In the above formula (2a), Alk represents an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, a butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. C1-C20 alkyl groups; C1-C20 cycloalkyl groups, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, are mentioned.

  In the formula (2a), Ion represents a substituent having an anion exchange group. The anion exchange group is introduced into the main chain or the side chain in the hydrophilic group, and is not particularly limited, and includes a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a phosphine, Any known anion exchange group such as phosphazene, tertiary sulfonium group, quaternary boronium group, quaternary phosphonium group, and guanidinium group can be employed. From the viewpoint of anion conductivity, a quaternary ammonium group is preferable.

Preferred examples of the anion exchange group include —CH ₂ N ⁺ (CH ₃ ) ₃ OH ^— , and other examples include those having the following structures. In the following structural formulas, * represents a moiety bonded to an aromatic ring containing a substituent (an alkyl group moiety of a tertiary aminoalkyl group), and an anion is omitted.

（図中、Ａｌｋ、Ａｌｋ’、Ａｌｋ’’は、上記したアルキル基を示し、ｉＰｒはイソプロピル基を示す。）

(In the figure, Alk, Alk ′, and Alk ″ represent the above-described alkyl group, and iPr represents an isopropyl group.)

  In the formula (2a), a ′ represents an integer of 0 to 4. In the above formula (2a), the substitution position of the alkyl group when a ′ is in the range of 1 to 4 is appropriately set according to the purpose and application. The alkyl group when a 'is in the range of 2 to 4 is selected from the same or different from each other depending on the purpose and application.

  In said formula (2a), s shows the integer of 1-4. In the above formula (2a), the substitution position of the substituent having an anion exchange group is appropriately set according to the purpose and application. The substituents having an anion exchange group when s is in the range of 2 to 4 are selected from the same or different from each other depending on the purpose and application.

  Such a hydrophilic group represented by the formula (2a) is particularly preferably a p-phenylene group substituted by a substituent having an anion exchange group represented by the following formula (2a ′).

（式中、Ｉｏｎは、陰イオン交換基を含む置換基（好ましくは、−ＣＨ_２Ｎ^＋（ＣＨ_３）_３ＯＨ⁻）を示す。）

(In the formula, Ion represents a substituent containing an anion exchange group (preferably —CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ ).)

  In the above formula (2b), R represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, or a direct bond.

Examples of the hydrocarbon group include methylene (—CH ₂ —), ethylene, propylene, isopropylene (—C (CH ₃ ) ₂ —), butylene, isobutylene, sec-butylene, pentylene (pentene), isopentylene, sec- Divalent saturated carbon atoms having 1 to 20 carbon atoms such as pentylene, hexylene (hexamethylene), 3-methylpentene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, isodecylene, dodecylene, tetradecylene, hexadecylene, octadecylene, etc. A hydrogen group is mentioned. The hydrocarbon group is preferably a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically, methylene (—CH ₂ —), ethylene, propylene, isopropylene (—C (CH ₃ ) ₂ —. More preferably methylene (—CH ₂ —), isopropylene (—C (CH ₃ ) ₂ —), and particularly preferably isopropylene (—C (CH ₃ ) ₂ —). Can be mentioned. The divalent hydrocarbon group may be substituted with a monovalent residue.

Examples of the aromatic group include divalent residues having an aromatic ring. Examples of the aromatic ring include monocyclic or polycyclic aromatic hydrocarbons having 6 to 14 carbon atoms such as benzene ring, naphthalene ring, indene ring, azulene ring, fluorene ring, anthracene ring, phenanthrene ring, and azole, Examples include heterocyclic compounds such as oxole, thiophene, oxazole, thiazole, pyridine and the like. As an aromatic ring, Preferably, C6-C14 monocyclic aromatic hydrocarbon is mentioned, More preferably, a benzene ring is mentioned. In addition, the aromatic ring may be substituted with a substituent such as a halogen atom, an alkyl group, or a pseudohalide, if necessary. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The pseudohalide, trifluoromethyl, -CN, -NC, -OCN, -NCO , -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, is -N ₃ like . Preferred examples of the aromatic ring include a p-phenylene group and a fluorenyl group.

  Examples of the divalent silicon-containing group include dimethylsilane, diphenylsilane, methoxymethylsilane, dimethoxysilane and the like. Examples of the divalent nitrogen-containing group include amine, methylamine, and phenylamine. Examples of the divalent phosphorus-containing group include phosphine oxide, dimethylphosphine, diphenylphosphine, and phenylphosphine oxide. Examples of the divalent oxygen-containing group include ethers and ketones. Examples of the divalent sulfur-containing group include sulfide, disulfide, sulfoxide, sulfone and the like. When hydrogen is present in a divalent silicon-containing group, a divalent nitrogen-containing group, a divalent phosphorus-containing group, a divalent oxygen-containing group, or a divalent sulfur-containing group, the hydrogen is a halogen atom or a pseudo group. It may be substituted with a halide.

  In the above formula (2b), Alk is the same as or different from each other and represents the above-described alkyl group.

  In the above formula (2b), Ion is the same or different from each other, and represents a substituent containing the above-described anion exchange group, preferably the above-described quaternary ammonium group.

  In said formula (2b), a 'and b' show the integer of 0-4. In the above formula (2b), the substitution position of the alkyl group when a ′ and b ′ are in the range of 1 to 4 is appropriately set according to the purpose and application. The alkyl groups in the case where a 'and b' are in the range of 2 to 4 are selected from the same or different from each other depending on the purpose and application.

  In the formula (2b), s, t, and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t, and u represents 1 or more. In the above formula (2b), the substitution position of the substituent having an anion exchange group is appropriately set according to the purpose and application. Substituents having an anion exchange group when s, t, or u is in the range of 2 to 4 are selected from the same or different from each other depending on the purpose and application.

  Such a hydrophilic group represented by the formula (2b) is preferably a diphenyl residue having the following structure.

（式中、Ｉｏｎは、互いに同一または相異なって、陰イオン交換基を含む置換基（好ましくは、−ＣＨ_２Ｎ^＋（ＣＨ_３）_３ＯＨ⁻）または水素原子を示し、少なくとも１つは陰イオン交換基を含む置換基である。）

(In the formula, Ion is the same or different from each other, and represents a substituent containing an anion exchange group (preferably —CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ ) or a hydrogen atom, and at least one is an anion. It is a substituent containing an ion exchange group.)

  The hydrophilic group represented by the formula (2b) is particularly preferably a diphenylfluorene residue substituted with a substituent having an anion exchange group represented by the following formula (2b ′).

（式中、Ｉｏｎは、互いに同一または相異なって、陰イオン交換基を含む置換基（好ましくは、−ＣＨ_２Ｎ^＋（ＣＨ_３）_３ＯＨ⁻）または水素原子を示し、少なくとも１つは陰イオン交換基を含む置換基である。）

(In the formula, Ion is the same or different from each other, and represents a substituent containing an anion exchange group (preferably —CH ₂ N ⁺ (CH ₃ ) ₃ OH ⁻ ) or a hydrogen atom, and at least one is an anion. It is a substituent containing an ion exchange group.)

  In the anion exchange resin of the present invention, the divalent hydrophilic unit is composed of the hydrophilic group represented by the formula (2a) and / or the hydrophilic group represented by the formula (2b), or a repetition of the hydrophilic group. . That is, in the anion exchange resin of the present invention, the hydrophilic group represented by the formula (2a) and / or the hydrophilic group represented by the formula (2b) are both bonded to each other via a carbon-carbon bond. Thus, a divalent hydrophilic unit is formed.

  The hydrophilic group represented by the formula (2a) and / or the hydrophilic group represented by the hydrophilic group represented by the formula (2b) are bonded to each other in a random or alternating regular form or in a block form, A divalent hydrophilic unit may be formed. Further, when the hydrophilic group represented by the formula (2a) and / or the hydrophilic group represented by the formula (2b) are bonded to each other in a block shape, the hydrophilic group represented by the formula (2a) and / or the formula (2b) ) May be bonded to each other in a random shape, a regular shape such as alternating, or a block shape.

  Such a divalent hydrophilic unit is represented by the following formula (4).

（式中、Ｒ、Ａｌｋ、Ｉｏｎ、ａ’、ｂ’、ｓ、ｔおよびｕは、対応する式（２ａ）又は式（２ｂ）のＲ、Ａｌｋ、Ｉｏｎ、ａ’、ｂ’、ｓ、ｔおよびｕと同意義を示し、ｍおよびｎは、繰り返し単位である各親水性基のモル分率を示す。）

(Wherein R, Alk, Ion, a ′, b ′, s, t and u are R, Alk, Ion, a ′, b ′, s, t in the corresponding formula (2a) or (2b). And m and n represent the molar fraction of each hydrophilic group which is a repeating unit.)

  In the above formula (4), m and n are the same as or different from each other and represent arbitrary values.

  In the anion exchange resin of the present invention, the hydrophobic unit and the hydrophilic unit are bonded via a direct bond.

  Such an anion exchange resin is represented by the following formula (5).

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、Ｒ、Ａｌｋ、Ｉｏｎ、ａ’、ｂ’、ｓ、ｔおよびｕは、対応する式（２ａ）又は式（２ｂ）のＲ、Ａｌｋ、Ｉｏｎ、ａ’、ｂ’、ｓ、ｔおよびｕと同意義を示し、ｌ、ｍおよびｎは、各繰り返し単位のモル分率であり、任意の値を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h, and i have the same meaning, and R, Alk, Ion, a ′, b ′, s, t, and u are represented by the corresponding formula (2a Or R, Alk, Ion, a ′, b ′, s, t and u in the formula (2b), and l, m and n are mole fractions of each repeating unit, and any value Is shown.)

  The number average molecular weight of such an anion exchange resin is, for example, 10 to 1000 kDa, preferably 30 to 500 kDa.

  It does not restrict | limit especially as a method of manufacturing an anion exchange resin, A well-known method is employable. Preferably, a method using a polycondensation reaction is employed.

  In the case of producing an anion exchange resin by this method, for example, first, a monovalent hydrophilic unit is formed on a monomer for forming a divalent hydrophobic unit (herein referred to as “first monomer”). The monomer for this purpose (referred to herein as “second monomer”) is terminated by substitution or addition to obtain a hydrophobic / hydrophilic unit precursor comonomer (referred to herein as “first comonomer”). The obtained divalent first comonomer is polymerized by a polycondensation reaction either alone or with a divalent hydrophilic unit (herein referred to as “third monomer”), and then obtained an anion exchange resin precursor. A substituent having an anion exchange group is introduced into the polymer. Alternatively, the first monomer, not the first comonomer, can be directly polycondensed with the third monomer. Here, the hydrophobic unit and the hydrophilic unit have the same meaning as the above-described hydrophobic unit and the hydrophilic unit, and a plurality of types of the first monomer, the second monomer, and the third monomer may be used. The repeating units of the three monomers can be the same or different from each other.

  About a polycondensation reaction, a conventionally well-known general method is employable. Preferably, the cross coupling which makes the dihalide react, and forms a carbon-carbon direct bond is employ | adopted.

  Examples of the first monomer for forming the divalent hydrophobic unit include a compound represented by the following formula (11) corresponding to the above formula (1).

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、ＸおよびＸ’は、互いに同一または相異なって、ハロゲン原子または擬ハロゲン化物を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h and i have the same meanings, and X and X ′ are the same or different from each other and represent a halogen atom or a pseudohalide.)

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The pseudohalide, trifluoromethyl, -CN, -NC, -OCN, -NCO , -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, is -N ₃ like .

  The monovalent second monomer for forming the divalent hydrophobic / hydrophilic unit precursor comonomer (first comonomer) is a compound represented by the following formula (12a) corresponding to the above formula (2a), and the above formula The compound shown by following formula (12b) corresponding to (2b) is mentioned.

（式中、Ａｌｋおよびａ’は、上記式（２ａ）のＡｌｋおよびａ’と同意義を示し、ＸおよびＸ’は、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物、または水素を示す。）

(In the formula, Alk and a ′ are the same as Alk and a ′ in the above formula (2a), and X and X ′ are the same as or different from each other, and represent a halogen atom, pseudohalide, or hydrogen. .)

（式中、Ｒ、Ａｌｋ、ａ’およびｂ’は、上記式（２ｂ）のＲ、Ａｌｋ、ａ’およびｂ’と同意義を示し、ＸおよびＸ’は、互いに同一または相異なって、ハロゲン原子、擬ハロゲン化物または水素を示す。）

Wherein R, Alk, a ′ and b ′ have the same meaning as R, Alk, a ′ and b ′ in the above formula (2b), and X and X ′ are the same or different from each other, Atom, pseudohalide or hydrogen.)

  The divalent first comonomer corresponds to the compound represented by the following formula (11a) corresponding to the above formula (1) and the above formula (2a), and the following corresponding to the above formula (1) and the above formula (2b). The compound shown by a formula (11b) is mentioned.

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、Ａｌｋ、およびａ’は、対応する式（２ａ）のＡｌｋ、およびａ’と同意義を示し、ＸおよびＸ’は、上記式（１２ａ）のＸおよびＸ’と同意義を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h and i have the same meaning, and Alk and a ′ have the same meaning as Alk and a ′ in the corresponding formula (2a). , X and X ′ have the same meaning as X and X ′ in the above formula (12a).

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、Ｒ、Ａｌｋ、ａ’ およびｂ’は、対応する式（２ｂ）のＲ、Ａｌｋ、ａ’ およびｂ’と同意義を示し、ＸおよびＸ’は、上記式（１２ｂ）のＸおよびＸ’と同意義を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h, and i have the same meaning, and R, Alk, a ′, and b ′ are R, Alk, a ′ in the corresponding formula (2b). And X ′ and X ′ are the same as X and X ′ in the above formula (12b).

  The third monomer for forming the divalent hydrophilic unit includes a compound represented by the following formula (12a ′) corresponding to the above formula (2a), and a formula (12b ′) corresponding to the above formula (2b). ).

（式中、Ａｌｋおよびａ’は、上記式（２ａ）のＡｌｋおよびａ’と同意義を示し、ＸおよびＸ’は、互いに同一または相異なって、ハロゲン原子または擬ハロゲン化物を示す。）

(In the formula, Alk and a ′ are the same as Alk and a ′ in the above formula (2a), and X and X ′ are the same as or different from each other and represent a halogen atom or a pseudohalide.)

（式中、Ｒ、Ａｌｋ、ａ’およびｂ’は、上記式（２ｂ）のＲ、Ａｌｋ、ａ’およびｂ’と同意義を示し、ＸおよびＸ’は、互いに同一または相異なって、ハロゲン原子または擬ハロゲン化物を示す。）

Wherein R, Alk, a ′ and b ′ have the same meaning as R, Alk, a ′ and b ′ in the above formula (2b), and X and X ′ are the same or different from each other, Indicates an atom or pseudohalide.)

  The method for synthesizing the first comonomer composed of the first monomer and the second monomer is not particularly limited, and a known method can be adopted. For example, a divalent hydrophobic / hydrophilic unit precursor comonomer in which a hydrophobic unit is introduced into a hydrophilic unit is synthesized by an aromatic alkylation reaction or an aromatic acylation reaction.

  When polymerizing the first comonomer alone or with the first comonomer and the third monomer by a cross-coupling reaction, the blending amounts of the first monomer, the second monomer, and the third monomer are respectively obtained by anion exchange. It adjusts so that it may become the compounding ratio of a desired hydrophobic unit and a hydrophilic unit in a resin precursor polymer. Here, in the polycondensation reaction by cross-coupling, by using the first comonomer, the difference in reactivity between the monomers is reduced, so that the polycondensation reaction is expected to proceed more uniformly.

  When the first monomer and the second monomer are polymerized by a cross-coupling reaction, the blending amounts of the first monomer and the second monomer are respectively the desired hydrophobic unit and hydrophilic unit in the obtained anion exchange resin precursor polymer. The blending ratio is adjusted.

  In these methods, the first comonomer and / or the first comonomer and the third monomer, or the first monomer and the second monomer are dissolved in a solvent such as N, N-dimethylacetamide, dimethyl sulfoxide, and the like. Known methods such as a polymerization method using bis (cycloocta-1,5-diene) nickel (0) as a catalyst can be employed.

  The reaction temperature in the cross coupling reaction is, for example, −100 to 300 ° C., preferably −50 to 200 ° C., and the reaction time is, for example, 1 to 48 hours, preferably 2 to 5 hours.

  Thereby, the anion exchange resin precursor polymer shown by following formula (15) and following formula (16) is obtained.

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、Ｒ、Ａｌｋ、ａ’およびｂ’は、対応する式（２ａ）又は式（２ｂ）のＲ、Ａｌｋ、ａ’およびｂ’と同意義を示し、ｌ、ｍおよびｎは、各繰り返し単位のモル分率であり、任意の値を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h, and i have the same meaning, and R, Alk, a ′, and b ′ are R in the corresponding formula (2a) or formula (2b). , Alk, a ′ and b ′ have the same meaning, and l, m and n are mole fractions of each repeating unit and represent arbitrary values.)

（式中、Ｚ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉは、上記式（１）のＺ_１〜Ｚ_９、Ｒ_１〜Ｒ_８、ａ、ｂ、ｃ、ｄ、ｅ、ｆ、ｇ、ｈおよびｉと同意義を示し、Ｒ、Ａｌｋ、ａ’およびｂ’は、対応する式（２ａ）又は式（２ｂ）のＲ、Ａｌｋ、ａ’およびｂ’と同意義を示し、ｌ、ｍおよびｎは、各繰り返し単位のモル分率であり、任意の値を示す。）

(In the formula, Z _{1 to} Z ₉ , R _{1 to} R ₈ , a, b, c, d, e, f, g, h, and i are Z _{1 to} Z ₉ , R ₁ to R in the above formula (1)). R ₈ , a, b, c, d, e, f, g, h, and i have the same meaning, and R, Alk, a ′, and b ′ are R in the corresponding formula (2a) or formula (2b). , Alk, a ′ and b ′ have the same meaning, and l, m and n are mole fractions of each repeating unit and represent arbitrary values.)

  Next, in this method, a substituent containing an anion exchange group is introduced into the anion exchange resin precursor polymer.

  The method for introducing a substituent containing an anion exchange group is not particularly limited, and a known method can be adopted.

  For example, after an anion exchange resin precursor polymer is chloroalkylated by a chloroalkylation reaction, the chloroalkylated anion exchange resin precursor polymer is quaternized (for example, an ammoniumation reaction). To introduce a substituent containing an anion exchange group.

  The chloroalkylation reaction is not particularly limited. For example, an anion exchange resin precursor polymer is dissolved in a solvent such as tetrachloroethane, and a Lewis acid such as iron chloride or zinc chloride is used as a catalyst to prepare chloromethylmethyl. Known methods such as a method of chloroalkylating by immersing in ether can be employed.

  The reaction temperature in the chloroalkylation reaction is, for example, 20 to 120 ° C., preferably 35 to 80 ° C., and the reaction time is, for example, 3 to 168 hours, preferably 6 to 12 hours.

  Thereby, a chloroalkylated anion exchange resin precursor polymer can be obtained.

  In the quaternization reaction, a chloroalkylated anion exchange resin precursor polymer is formed into a film by a known method if necessary, and for example, amine, phosphine, phosphazene, sulfide, boron compound, etc. are added at an appropriate ratio. Then, a substituent containing an anion exchange group is introduced by substituting the chlorine atom of the chloroalkyl group with them.

  Examples of the amine include secondary amines such as dimethylamine, diethylamine, diallylamine, di-n-propylamine, di-n-butylamine, and di-n-pentylamine, such as trimethylamine, N, N-dimethylethanolamine, triethylamine, triethylamine, and the like. Examples include tertiary amines such as allylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, and tri-n-hexylamine, for example, cyclic amines such as pyridine, quinoline, and imidazole, for example, guanidine.

  These amines can be used alone or in combination of two or more.

  The reaction temperature in the quaternization reaction is, for example, 0 to 100 ° C., preferably 20 to 80 ° C., and the reaction time is, for example, 24 to 72 hours, preferably 48 to 72 hours.

  In this method, the quaternization reaction can be performed, for example, in a solution state without forming the anion exchange resin precursor polymer.

  In this method, if necessary, the amine, phosphine, phosphazene, sulfide, boron compound and the like are removed by a known method.

  Thereby, the substituent containing an anion exchange group is introduce | transduced into the said anion exchange resin precursor polymer, and the anion exchange resin shown by the said Formula (5) is obtained.

  Moreover, the ion exchange group capacity | capacitance (IEC) of an anion exchange resin is 0.1-4.0 meq. / G, preferably 0.6 to 3.0 meq. / G.

The ion exchange group capacity can be obtained by the following formula (24).
[Ion exchange group capacity (meq./g)]=anion exchange group introduction amount per hydrophilic unit × repeating unit of hydrophilic unit × 1000 / (molecular weight of hydrophobic unit × number of repeating units of hydrophobic unit + molecular weight of hydrophilic unit × Number of repeating units of hydrophilic unit + molecular weight of ion exchange group × number of repeating units of hydrophilic unit) (24)
The ion exchange group introduction amount is defined as the number of ion exchange groups per unit hydrophilic group. The amount of anion exchange groups introduced is the number of moles (mol) of the anion exchange groups introduced into the main chain or side chain in the hydrophilic group.

  Such an anion exchange resin includes a divalent hydrophobic unit composed of a hydrophobic group represented by the above formula (1) or a repeating hydrophobic group represented by the above formula (1); An o-, m- or p-phenylene group substituted with a substituent having an anion exchange group represented by the above formula (2a), and / or an anion exchange group represented by the above formula (2b). Having a hydrophilic group composed of a diphenyl residue substituted with a substituent having a divalent residue or a divalent hydrophilic unit composed of repetition of the hydrophilic group, and the hydrophobic unit and the hydrophilic unit are directly bonded to each other. Are connected through. An anion exchange resin having such a structure is excellent in chemical stability, flexibility and heat resistance.

  In particular, the hydrophobic unit has heat resistance because the hydrophobic group represented by the formula (1) is repeated via a carbon-carbon bond or a carbon-silicon bond, and the hydrophobic unit has an aromatic property. It does not contain a ring and is excellent in flexibility. Moreover, since a part formed by repeating a hydrophobic group (phenyl group) represented by the formula (2a) through a carbon-carbon bond exists in a part of the hydrophilic unit, the heat resistance is further improved. It will be a thing. Furthermore, since the hydrophilic group is formed by repeating the hydrophilic group represented by the formula (2a) and / or the formula (2b) via a carbon-carbon bond, the hydrophilic unit does not contain an ether bond. It is excellent in chemical durability such as alkali resistance.

In addition, when an ether bond is contained in the hydrophilic unit, decomposition due to hydroxide ions (OH ⁻ ) may occur as described below, and the alkali resistance may not be sufficient.

  On the other hand, since the hydrophilic unit of the anion exchange resin having a hydrophilic unit in which the hydrophilic group is repeated through a carbon-carbon bond does not contain an ether bond, the above mechanism does not cause decomposition, and as a result As such, it has excellent durability such as alkali resistance.

  The present invention includes an electrolyte layer (electrolyte membrane) obtained by using such an anion exchange resin, and further a fuel cell including the electrolyte membrane as an electrolyte layer.

  FIG. 1 is a schematic configuration diagram showing an embodiment of a fuel cell of the present invention. In FIG. 1, the fuel cell 1 includes a fuel cell S, and the fuel cell S includes a fuel side electrode 2, an oxygen side electrode 3, and an electrolyte membrane 4, and the fuel side electrode 2 and the oxygen side electrode 3. However, they are opposed to each other with the electrolyte membrane 4 sandwiched between them.

  As the electrolyte membrane 4, the above-described anion exchange resin can be used (that is, the electrolyte membrane 4 includes the above-described anion exchange resin).

  The electrolyte membrane 4 can be reinforced with, for example, a known reinforcing material such as a porous substrate, and further, for example, biaxial stretching treatment for controlling molecular orientation or the like, Various treatments such as heat treatment for controlling the residual stress can be performed. In addition, a known filler can be added to the electrolyte membrane 4 in order to increase its mechanical strength, and the electrolyte membrane 4 and a reinforcing agent such as a glass nonwoven fabric can be combined by pressing.

  In the electrolyte membrane 4, various commonly used additives, for example, a compatibilizer for improving compatibility, for example, an antioxidant for preventing resin degradation, for example, handling property in molding as a film. An antistatic agent, a lubricant, and the like for improving the viscosity can be appropriately contained within a range that does not affect the processing and performance of the electrolyte membrane 4.

  The thickness of the electrolyte membrane 4 is not particularly limited, and is appropriately set according to the purpose and application.

  The thickness of the electrolyte membrane 4 is, for example, 1.2 to 350 μm, preferably 5 to 200 μm.

  The fuel side electrode 2 is in opposed contact with one surface of the electrolyte membrane 4. The fuel side electrode 2 includes, for example, a catalyst layer (battery electrode catalyst layer) in which a catalyst is supported on a porous carrier.

  The porous carrier is not particularly limited and includes a water-repellent carrier such as carbon.

  The electrode catalyst is not particularly limited, and examples thereof include periodic table elements 8 to 10 (IUPAC Periodic) of platinum group elements (Ru, Rh, Pd, Os, Ir, Pt), iron group elements (Fe, Co, Ni), and the like. According to Table of the Elements (version date 19 February 2010), the same shall apply hereinafter) group elements, Group 11 elements of the periodic table such as Cu, Ag, Au, etc., and combinations thereof, and more preferably , Pt (platinum).

  For the fuel side electrode 2, for example, the porous simple substance and the catalyst are dispersed in a known electrolyte solution to prepare an electrode ink. Next, if necessary, the viscosity of the electrode ink is adjusted by blending an appropriate amount of an organic solvent such as alcohols, and then the electrode ink is prepared by an electrolyte membrane by a known method (for example, spray method, die coater method, etc.). 4 is applied to one surface of the electrode 4 and dried at a predetermined temperature, thereby being bonded to one surface of the electrolyte membrane 4 as a thin electrode film.

Loading amount of the electrode catalyst in the fuel-side electrode 2 is not particularly limited, for example, 0.1 to 10.0 mg / cm ^2, preferably from 0.5 to 5.0 / cm ^2.

In the fuel side electrode 2, as will be described later, the supplied fuel and the hydroxide ions (OH ⁻ ) that have passed through the electrolyte membrane 4 are reacted to generate electrons (e ⁻ ) and water (H ₂ O). Generate. For example, when the fuel is hydrogen (H ₂ ), only electrons (e ⁻ ) and water (H ₂ O) are generated, and when the fuel is alcohol, the electrons (e ⁻ ) and water are generated. When (H ₂ O), carbon dioxide (CO ₂ ), etc. are generated and the fuel is hydrazine (NH ₂ NH ₂ ), electrons (e ⁻ ), water (H ₂ O) and nitrogen (N ₂ ) ) Is generated.

  The oxygen side electrode 3 is opposed to the other surface of the electrolyte membrane 4. The oxygen side electrode 3 includes, for example, a catalyst layer (battery electrode catalyst layer) in which a catalyst is supported on a porous carrier.

  For the oxygen side electrode 3, for example, the porous simple substance and the catalyst are dispersed in a known electrolyte solution to prepare an electrode ink. Next, if necessary, the viscosity of the electrode ink is adjusted by blending an appropriate amount of an organic solvent such as alcohols, and then the electrode ink is prepared by an electrolyte membrane by a known method (for example, spray method, die coater method, etc.). 4 is applied to the other surface of the electrode 4 and dried at a predetermined temperature to be bonded to the other surface of the electrolyte membrane 4 as a thin electrode film.

  As a result, the electrolyte membrane 4, the fuel side electrode 2, and the oxygen side electrode 3 are joined to the thin film fuel side electrode 2 on one surface of the electrolyte membrane 4, and the thin film oxygen side electrode 3 on the other surface of the electrolyte membrane 4. A membrane / electrode assembly is formed by bonding.

Amount of catalyst supported in the oxygen-side electrode 3 is not particularly limited, for example, 0.1 to 10.0 mg / cm ^2, preferably from 0.5 to 5.0 / cm ^2.

In the oxygen side electrode 3, as will be described later, oxygen (O ₂ ) supplied, water (H ₂ O) that has passed through the electrolyte membrane 4, and electrons (e ⁻ ) that have passed through the external circuit 13 are reacted. Thus, hydroxide ions (OH ⁻ ) are generated.

  The fuel cell S further includes a fuel supply member 5 and an oxygen supply member 6. The fuel supply member 5 is made of a gas-impermeable conductive member, and one surface thereof is in opposed contact with the fuel-side electrode 2. The fuel supply member 5 is formed with a fuel-side flow path 7 for bringing fuel into contact with the entire fuel-side electrode 2 as a distorted groove recessed from one surface. The fuel-side flow path 7 is formed with a supply port 8 and a discharge port 9 passing through the fuel supply member 5 at the upstream end and the downstream end, respectively.

  Similarly to the fuel supply member 5, the oxygen supply member 6 is made of a gas-impermeable conductive member, and one surface thereof is opposed to the oxygen side electrode 3. The oxygen supply member 6 is also formed with an oxygen-side flow channel 10 for contacting oxygen (air) with the entire oxygen-side electrode 3 as a distorted groove recessed from one surface. The oxygen-side flow path 10 also has a supply port 11 and a discharge port 12 that pass through the oxygen supply member 6 continuously formed at the upstream end portion and the downstream end portion thereof.

  The fuel cell 1 is actually formed as a stack structure in which a plurality of the fuel cells S described above are stacked. Therefore, the fuel supply member 5 and the oxygen supply member 6 are actually configured as separators in which the fuel side flow path 7 and the oxygen side flow path 10 are formed on both surfaces.

  Although not shown, the fuel cell 1 is provided with a current collector plate formed of a conductive material, and an electromotive force generated in the fuel cell 1 is taken out from a terminal provided on the current collector plate. It is configured to be able to.

  In FIG. 1, the fuel supply member 5 and the oxygen supply member 6 of the fuel cell S are connected by an external circuit 13, and a voltage meter 14 is interposed in the external circuit 13 to measure the generated voltage. I am doing so.

  In the fuel cell 1, the fuel is supplied to the fuel side electrode 2 directly without going through reforming or the like or after going through reforming or the like.

  Examples of the fuel include hydrogen-containing fuel.

  The hydrogen-containing fuel is a fuel containing hydrogen atoms in the molecule, and examples thereof include hydrogen gas, alcohols, and hydrazines, and preferably hydrogen gas or hydrazines.

Specific examples of hydrazines include hydrazine (NH ₂ NH ₂ ), hydrated hydrazine (NH ₂ NH ₂ .H ₂ O), hydrazine carbonate ((NH ₂ NH ₂ ) ₂ CO ₂ ), hydrazine hydrochloride ( NH ₂ NH ₂ · HCl), hydrazine sulfate _{(NH 2 NH 2 · H 2} SO 4), monomethyl hydrazine _(CH 3 NHNH _2), dimethylhydrazine _{((CH 3) 2 NNH 2} , CH 3 NHNHCH 3), a carboxylic hydrazide ((NHNH ₂ ) ₂ CO) and the like. The fuels illustrated above can be used alone or in combination of two or more.

Among the above fuel compounds, compounds that do not contain carbon, that is, hydrazine, hydrated hydrazine, hydrazine sulfate, etc., do not generate CO and CO ₂ , and do not cause catalyst poisoning. Can be achieved, and substantially zero emission can be realized.

  Further, as the above exemplified fuel, the above fuel compound may be used as it is. However, the above exemplified fuel compound may be water and / or alcohol (for example, lower alcohol such as methanol, ethanol, propanol, isopropanol, etc.) ) And the like. In this case, the concentration of the fuel compound in the solution varies depending on the type of the fuel compound, but is, for example, 1 to 90% by mass, preferably 1 to 30% by mass. The above exemplified solvents may be used alone or in combination of two or more.

  Further, as the fuel, the above-described fuel compound can be used as a gas (for example, vapor).

Then, if the above-described fuel is supplied to the fuel-side channel 7 of the fuel supply member 5 while supplying oxygen (air) to the oxygen-side channel 10 of the oxygen supply member 6, As described, electrons (e ⁻ ) generated at the fuel side electrode 2 and moving via the external circuit 13 react with water (H ₂ O) and oxygen (O ₂ ) generated at the fuel side electrode 2. Thus, hydroxide ions (OH ⁻ ) are generated. The generated hydroxide ions (OH ⁻ ) move from the oxygen side electrode 3 to the fuel side electrode 2 through the electrolyte membrane 4 made of an anion exchange membrane. Then, in the fuel-side electrode 2, the hydroxide ions pass through the electrolyte membrane 4 (OH ^-) and, by the reaction with the fuel, electronic (e ^-) and the water (H 2 _O) to generate. The generated electrons (e ⁻ ) are moved from the fuel supply member 5 to the oxygen supply member 6 via the external circuit 13 and supplied to the oxygen side electrode 3. Further, the generated water (H ₂ O) moves the electrolyte membrane 4 from the fuel side electrode 2 to the oxygen side electrode 3. An electromotive force is generated by such an electrochemical reaction in the fuel side electrode 2 and the oxygen side electrode 3, and power generation is performed.

  The operating conditions of the fuel cell 1 are not particularly limited. For example, the pressure on the fuel side electrode 2 side is 200 kPa or less, preferably 100 kPa or less, and the pressure on the oxygen side electrode 3 side is 200 kPa or less. Preferably, it is 100 kPa or less, and the temperature of the fuel cell S is set to 0 to 120 ° C., preferably 20 to 80 ° C.

  In such a fuel cell 1, an electrolyte membrane containing the anion exchange resin having excellent durability is used for the electrolyte membrane 4.

  Therefore, the electrolyte membrane of the present invention obtained by using the anion exchange resin of the present invention, and the fuel cell including such an electrolyte membrane are excellent in durability.

  The present invention also includes an electrode catalyst layer forming binder containing the anion exchange resin described above, a battery electrode catalyst layer containing the electrode catalyst layer forming binder, and a fuel cell comprising the battery electrode catalyst layer. Yes.

  That is, in the fuel cell 1, an anion exchange resin can be contained in the electrode catalyst layer forming binder when the fuel side electrode 2 and / or the oxygen side electrode 3 are formed.

  As a method for incorporating the anion exchange resin into the binder for forming the electrode catalyst layer, specifically, for example, the anion exchange resin is shredded and dissolved in an appropriate amount of an organic solvent such as alcohol to thereby form the electrode catalyst layer. A forming binder is prepared.

  In the electrode catalyst layer forming binder, the content ratio of the anion exchange resin is, for example, 2 to 10 parts by mass, or preferably 2 to 5 parts by mass with respect to 100 parts by mass of the electrode catalyst layer forming binder.

  Further, by using the electrode catalyst layer forming binder in the formation of the catalyst layer (battery electrode catalyst layer) of the fuel side electrode 2 and / or the oxygen side electrode 3 described above, the anion exchange resin is used as the catalyst layer (battery layer). Thus, the fuel cell 1 having a catalyst layer (battery electrode catalyst layer) containing an anion exchange resin can be obtained.

  And in such a fuel cell 1, in formation of a battery electrode catalyst layer, the binder for electrode catalyst layer formation containing the anion exchange resin excellent in said durability is used.

  Therefore, the electrode catalyst layer-forming binder of the present invention obtained using the anion exchange resin of the present invention, and the battery electrode catalyst layer obtained using the electrode catalyst layer-forming binder are excellent in durability. Excellent anion conductivity can be ensured.

  As a result, the fuel cell provided with such a battery electrode catalyst layer is excellent in durability and can ensure excellent anion conductivity.

  As mentioned above, although embodiment of this invention was described, embodiment of this invention is not limited to this, A design can be suitably changed in the range which does not change the summary of this invention.

  Applications of the fuel cell of the present invention include, for example, power sources for driving motors in automobiles, ships, airplanes, etc., and power sources in communication terminals such as mobile phones.

  Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example.

[Example 1: Synthesis of anion exchange resin QPA (C3)]
<Synthesis of alkyl monomer>
4-Chlorobenzaldehyde (7.03 g, 50.0 mmol) and ethanol (100 mL) were added to a 300 mL round bottom three-necked flask equipped with a nitrogen inlet and a condenser to dissolve, and 3M sodium hydroxide (50 mL, 150 mmol) was dissolved. And 4′-chloroacetophenone (6.5 mL, 50.0 mmol) were added and reacted at room temperature for 3 h.

  After the reaction, the deposited pale yellow composition organism was collected by filtration, washed with pure water, collected by filtration, and then vacuum dried at 60 ° C. overnight to collect a pale yellow solid. As a result, 4,4'-dichlorochalcone as an intermediate product was obtained in a yield of 90%.

  A 300 mL round bottom three-necked flask equipped with a nitrogen inlet and a condenser tube was charged with 4,4′-dichlorochalcone (12.5 g, 45.1 mmol), dichloromethane (52 mL), triethylsilane (26 mL, 163 mmol) and trifluoroacetic acid ( 26 mL, 340 mmol) was added and completely dissolved, and then the temperature was raised to 50 ° C. and the reaction was performed for 45 hours.

  After the reaction, the reaction solution was neutralized with sodium hydrogen carbonate, then transferred to a separatory funnel, dichloromethane was added, and the organic layer was recovered. The obtained organic layer was separated by silica gel column chromatography using hexane as a developing solvent after removing dichloromethane. Hexane was removed and the resulting white crystals were vacuum dried at 60 ° C. overnight. The obtained solid was dissolved in a 10% ethanol solution, a small amount of Pd / C (about 1 wt%) was added, and the mixture was stirred in a hydrogen atmosphere and then separated by silica gel column chromatography to remove ethanol. White solids were vacuum dried at 60 ° C. overnight.

  As a result, a white alkyl monomer (1 = 3) represented by the following formula was obtained in a yield of 80%.

<Synthesis of anion exchange resin precursor polymer>
To a 100 mL round bottom three-necked flask equipped with a nitrogen inlet, a mechanical stirrer and a condenser tube, the above alkyl oligomer (0.252 g, 0.65 mmol), 9,9-bis (4-(-chlorophenyl) fluorene (0.500 g, 1.62 mmol), 2,2′-bipyridine (0.534 g, 3.41 mmol), N, N-dimethylacetamide (15 mL) was added and the mixture was stirred to give the alkyl oligomer, 9,9-bis ( After 4-(-chlorophenyl) fluorene and 2,2′-bipyridine are dissolved, bis (cycloocta-1,5-diene) nickel (0) (0.940 g, 3.41 mmol) is added and heated to 80 ° C. And reacted for 3 hours.

  The reaction mixture was dropped into 200 mL of methanol to stop the reaction, and a crude product was precipitated. The crude product was collected by filtration, stirred in 100 mL of concentrated hydrochloric acid overnight, collected by filtration, washed several times with pure water and methanol, and then vacuum dried at 60 ° C. overnight.

  As a result, a pale yellow anion exchange resin precursor polymer PA (C3) (l = 3, m = 1, n = 0.17) represented by the following formula was obtained in a yield of 86%.

<Introducing anion exchange groups>
(Chloromethylation reaction)
An anion exchange resin precursor polymer (0.31 g) and 1,1,2,2-tetrachloroethane (21 mL) were added to a 100 mL glass reaction vessel. The mixture was stirred to dissolve the anion exchange resin precursor polymer and then in a glove box substituted with argon, chloromethyl methyl ether (4 mL), zinc chloride (0.029 g, 0.21 mmol), thionyl chloride. (0.3 mL) was added and reacted at 80 ° C. for 3 hours.

  The reaction mixture was dropped into methanol to stop the reaction, and the product was precipitated. The product was collected by filtration, washed several times with methanol, and then vacuum dried at 60 ° C. overnight.

  As a result, a chloromethylated anion exchange resin precursor polymer represented by the following formula was obtained in a yield of 92%.

（式中、ｌ＝３、ｍ＝１、ｎ＝０．１７、Ｒは、クロロメチル基または水素原子を示し、親水部芳香環あたりのクロロメチル基の導入量は、０．２個を示す。）

(Wherein, l = 3, m = 1, n = 0.17, R represents a chloromethyl group or a hydrogen atom, and the introduction amount of the chloromethyl group per hydrophilic part aromatic ring represents 0.2. .)

<Film formation>
A chloromethylated anion exchange resin precursor polymer was formed by a solution casting method.

  That is, a chloromethylated anion exchange resin precursor polymer (0.1 g) was dissolved in 1,1,2,2-tetrachloroethane (2 mL) and filtered with a syringe filled with cotton. The filtrate was poured onto a glass plate bordered to 5 × 5 cm with silicon rubber, allowed to stand on a horizontally adjusted hot plate at 50 ° C., and dried to obtain a transparent film having a thickness of about 25 μm.

(Quaternization reaction)
The membrane of the chloromethylated anion exchange resin precursor polymer was immersed in an aqueous solution of 45% by mass of trimethylamine at 40 ° C. for 2 days and reacted in a heterogeneous system.

  In addition, since the counter ion of the ion exchange group (ammonio group) is a chloride ion, this membrane is immersed in a 1 mol / L potassium hydroxide aqueous solution for 2 days and washed with deaerated pure water to obtain a hydroxide. Converted to ionic form.

  As described above, an anion exchange resin QPA (C3) (l = 3, m = 1, n = 0.17, IEC = 0.58 meq./g) represented by the following formula was obtained.

（式中、ｌ＝３、ｍ＝１、ｎ＝０．１７、Ｒは、−ＣＨ_２Ｎ^＋（ＣＨ_３）_３または水素原子を示す。）

(In the formula, l = 3, m = 1, n = 0.17, R represents —CH ₂ N ⁺ (CH ₃ ) ₃ or a hydrogen atom.)

[Example 2: Synthesis of anion exchange resin QPA (C6)]
<Synthesis of alkyl monomer>
Monochlorobenzene (50 mL) and aluminum (III) chloride (13.33 g, 100 mmol) were added to a 300 mL round bottom three-necked flask equipped with a nitrogen inlet and a condenser, and after sufficient stirring in an ice bath, adipoyl chloride was added. (7.32 g, 40.0 mmol) was gradually added dropwise. After stirring for 30 minutes, the temperature was raised to 60 ° C. and the reaction was performed for 24 hours.

  After the reaction, the reaction solution was dropped into 100 mL of 0.2 M hydrochloric acid aqueous solution to stop the reaction, 200 mL of 2-propanol was added, and the resulting white precipitate was collected by filtration. The obtained white solid was washed with 100 mL of 2-propanol, collected by filtration, and then vacuum-dried at 60 ° C. overnight to collect a white solid. Thereby, the alkylene precursor monomer 1,6-bis (chlorophenyl) hexanedione as an intermediate product was obtained in a yield of 65%.

  In a 100 mL eggplant flask equipped with a condenser, 1,6-bis (chlorophenyl) hexanedione (3.36 g, 10.0 mmol), triethylsilane (7.96 mL, 50.0 mmol) and trifluoroacetic acid (15 mL) were added. In addition, the temperature was raised to 40 ° C. and the reaction was carried out for 20 hours.

  After the reaction, the reaction solution was neutralized with sodium hydrogen carbonate, then transferred to a separatory funnel, dichloromethane was added, and the organic layer was recovered. The obtained organic layer was separated by silica gel column chromatography using a developing solvent hexane after removing excess dichloromethane with an evaporator. Hexane was removed and the resulting white crystals were vacuum dried at 60 ° C. overnight.

  As a result, a white alkyl monomer (1 = 6) represented by the following formula was obtained in a yield of 61%.

  By using the above-mentioned alkyl oligomer and changing the amount of the reagent as necessary in the same manner as described above, the anion exchange resin QPA (C6) (l = 6, m = 1, n = 0. 44, IEC = 0.87 meq./g).

[Example 3: Synthesis of anion exchange resin QPA (C10)]
<Synthesis of alkyl monomer>
Monochlorobenzene (50 mL) and aluminum (III) chloride (13.33 g, 100 mmol) were added to a 300 mL round bottom three-necked flask equipped with a nitrogen inlet and a condenser, and after sufficient stirring in an ice bath, sebacoyl chloride ( 7.32 g, 40.0 mmol) was gradually added dropwise. After stirring for 30 minutes, the temperature was raised to 60 ° C. and the reaction was performed for 24 hours.

  After the reaction, the reaction solution was dropped into 100 mL of 0.2 M hydrochloric acid aqueous solution to stop the reaction, 200 mL of 2-propanol was added, and the resulting white precipitate was collected by filtration. The obtained white solid was washed with 100 mL of 2-propanol, collected by filtration, and then vacuum-dried at 60 ° C. overnight to collect a white solid. Thereby, the alkylene precursor monomer 1,10-bis (chlorophenyl) decanedione which is an intermediate product was obtained in a yield of 78%.

  Add 1,10-bis (chlorophenyl) decanedione (3.36 g, 10.0 mmol), trifluoroacetic acid (15 mL) and triethylsilane (7.96 mL, 50.0 mmol) to a 100 mL eggplant flask equipped with a condenser. The temperature was raised to 40 ° C. and the reaction was carried out for 20 hours.

  After the reaction, the reaction solution was neutralized with sodium hydrogen carbonate, then transferred to a separatory funnel, dichloromethane was added, and the organic layer was recovered. The obtained organic layer was separated by silica gel column chromatography using a developing solvent hexane after removing excess dichloromethane with an evaporator. Hexane was removed and the resulting white crystals were vacuum dried at 60 ° C. overnight.

  As a result, a white alkyl monomer (1 = 10) represented by the following formula was obtained in a yield of 86%.

  By using the above alkyl oligomer and changing the amount of the reagent charged as necessary in the same manner as described above, the anion exchange resin QPA (C10) (l = 10, m = 1, n = 0. 51, IEC = 2.10 meq./g).

[Evaluation]
<Durability test>
Durability tests were performed on the anion exchange resin membranes obtained in Examples 1-3. Specifically, IR measurement of the anion exchange resin membrane before the test and IR measurement of the anion exchange resin membrane after 1000 hours of immersion in a 1M KOH aqueous solution (60 ° C.) were performed.

  In the anion exchange resin membranes obtained in Examples 1 to 3, no peak (peak based on C—H) suggesting cleavage of the polymer main chain was observed even after the durability test, and excellent chemical stability was obtained. Had.

<Tensile test>
A tensile test was performed on the anion exchange resin membranes obtained in Examples 1 to 3. The test was performed in a chamber controlled at constant temperature and humidity using a Shimazu universal testing instrument Autograph AGS-J500N equipped with a Toshin Kogyo temperature control unit Bethel-3. Measurement is performed by holding a dumbbell-shaped sample (DIN-53504-S3) of 12 mm × 2 mm (total area: 35 mm × 6 mm) under the conditions of 80 ° C. and 60% RH, and pulling at a speed of 10 mm / min. A stress-strain curve was obtained (FIG. 2). Under measurement conditions, the temperature and humidity stabilization waiting time was 3 hours. In addition, in FIG. 2, the result of having done the tension test with respect to the film | membrane of the anion exchange resin (IEC = 1.26) synthesize | combined based on the Example described in patent document 2 is also shown as a comparative example. It was.

  In general, when the IEC is high (IEC> 2 meq./g), the ionic groups tend to entrap water and the flexibility of the entire membrane tends to decrease. From FIG. 2, the ion exchange resins obtained in Examples 1 to 3 This film exhibited a high maximum stress over a wide range of IEC and had excellent flexibility. The elongation was sufficient for battery applications.

<Dynamic viscoelasticity test>
A dynamic viscoelasticity test was performed on the anion exchange resin films obtained in Examples 1 to 3. Using ITK DVA-225 dynamic viscoelasticity analyzer, storage elastic modulus (E ′ (Pa)), loss elastic modulus (E ″ (Pa)) and tan δ at 60% relative humidity and 40 ° C. to 90 ° C. The temperature dependence of was measured. The sample was cut out and installed at 5 mm × 30 mm and about 25 μm, and the conditions were a humidification rate of 1% / min and a heating rate of 1 ° C./min. In FIG. 3, as a comparative example, the results of a dynamic viscoelasticity test performed on a membrane of an anion exchange resin (IEC = 1.26) synthesized based on the example described in Patent Document 2 are also shown. Also shown.

  From FIG. 3, the anion exchange resin membranes obtained in Examples 1 to 3 had no temperature dependency of storage elastic modulus and loss elastic modulus, and had excellent heat resistance.

DESCRIPTION OF SYMBOLS 1 Fuel cell 2 Fuel side electrode 3 Oxygen side electrode 4 Electrolyte membrane S Fuel cell

Claims (11)

A divalent hydrophobic unit consisting of a hydrophobic group represented by the following formula (1) or a repeating hydrophobic group represented by the following formula (1);
An o-, m- or p-phenylene group substituted with a substituent having an anion exchange group represented by the following formula (2a) and / or an anion exchange group represented by the following formula (2b): Having a hydrophilic group consisting of a diphenyl residue substituted with a substituent having, or a divalent hydrophilic unit consisting of repetition of the hydrophilic group,
The anion exchange resin, wherein the hydrophobic unit and the hydrophilic unit are bonded via a direct bond.

(In the formula, Z _{1 to} Z ₉ are the same or different from each other, and represent a carbon atom or a silicon atom, and R _{1 to} R ₈ are the same or different from each other, and contain a silicon-containing group, a nitrogen-containing group, or a phosphorus-containing group. A group, an oxygen-containing group, a sulfur-containing group, or a direct bond, a represents an integer of 1 or more, b, c, d, e, f, g, h, and i are the same or different from each other; Indicates an integer of 0 or more.)

(In the formula, Alk represents an alkyl group, Ion represents a substituent having an anion exchange group, a ′ represents an integer of 0 to 4, and s represents an integer of 1 to 4.)

(In the formula, R is a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, which may be substituted with a substituent having the anion exchange group. A group, or a direct bond, Alk is the same or different from each other and represents an alkyl group, Ion is the same or different from each other, and represents a substituent having an anion exchange group, and a ′ and b ′ are Are the same or different from each other and represent an integer of 0 to 4, s, t and u are the same or different from each other and represent an integer of 0 to 4, and at least one of s, t and u is 1 The above is shown.) In the formula (1), R ₁ to R ₈ are characterized by exhibiting a direct bond or an oxygen atom, an anion exchange resin according to claim 1.   The anion exchange resin according to claim 2, wherein the hydrophobic group is a divalent saturated hydrocarbon group. The divalent hydrophilic unit includes a p-phenylene group substituted with a substituent having an anion exchange group represented by the following formula (2a ′), and an anion exchange represented by the following formula (2b ′). The anion exchange resin according to any one of claims 1 to 3, wherein the anion exchange resin comprises repeating diphenylfluorene residues substituted with a substituent having a group.

(In the formula, Ion represents a substituent having an anion exchange group.)

(In the formula, Ion is the same or different from each other and represents a substituent or a hydrogen atom containing an anion exchange group, and at least one represents a substituent containing an anion exchange group.)   An electrolyte membrane comprising the anion exchange resin according to any one of claims 1 to 4.   The binder for electrode catalyst layer formation characterized by including the anion exchange resin of any one of Claim 1 thru | or 4.   A battery electrode catalyst layer comprising the binder for forming an electrode catalyst layer according to claim 6. An electrolyte membrane comprising the anion exchange resin according to any one of claims 1 to 4,
A fuel-side electrode that is disposed opposite to the electrolyte membrane and is supplied with hydrogen-containing fuel; and an oxygen-side electrode that is supplied with oxygen or air;
A fuel cell comprising:   The fuel cell according to claim 7, wherein the hydrogen-containing fuel is hydrogen, alcohol, or hydrazine. An electrolyte membrane;
A fuel-side electrode that is disposed opposite to the electrolyte membrane and is supplied with hydrogen-containing fuel, and an oxygen-side electrode that is supplied with oxygen or air,
The fuel cell according to claim 7, wherein the fuel side electrode and / or the oxygen side electrode includes the battery electrode catalyst layer according to claim 7.   The fuel cell according to claim 10, wherein the hydrogen-containing fuel is hydrogen, alcohol, or hydrazine.

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