Anion exchange resin, electrolyte membrane, binder for forming electrode catalyst layer, and battery electrode catalyst layer

Abstract

Provided are: an anion exchange resin with which it is possible to produce an electrolyte membrane, a binder for forming an electrode catalyst layer, and a battery electrode catalyst layer, each of which has excellent electrical characteristics (anionic conductivity) and chemical characteristics (air permeability and water-containing properties); and an electrolyte membrane and a binder for forming an electrode catalyst layer, each of which is formed from the anion exchange resin. And a battery electrode catalyst layer formed from the binder for forming an electrode catalyst layer. For example, an anion exchange resin is used that contains: a hydrophobic unit in which a divalent hydrophobic group containing a bisphenol residue having an alicyclic structure is repeated via a carbon-carbon bond; a hydrophobic unit in which a divalent hydrophobic group comprising a plurality of aromatic rings bonded to each other via a divalent fluorine-containing hydrocarbon group is repeated via a carbon-carbon bond; and a hydrophilic unit having a fluorene ring bonded to a group containing an anion exchange group, the three units being bonded via a carbon-carbon bond.

Description

Technical Field

[0001] The present invention relates to an anion exchange resin, an electrolyte membrane, a binder for forming an electrode catalyst layer, and a battery electrode catalyst layer. Background Art

[0002] An anion exchange resin is known (Patent Document 1), characterized by comprising: a divalent hydrophobic group consisting of a single aromatic ring, or consisting of a plurality of aromatic rings bonded to each other via 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 carbon-carbon bond, A divalent hydrophilic group, which is composed of a single polycyclic compound, or a plurality of polycyclic compounds bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the polycyclic compound is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms; The anion exchange resin has: A hydrophobic unit, which is composed of the hydrophobic group monomer, or is composed of the hydrophobic group repeated via an ether bond, a thioether bond or a carbon-carbon bond, and A hydrophilic unit, which is composed of the hydrophilic group monomer, or is composed of the hydrophilic group repeated via an ether bond, a thioether bond or a carbon-carbon bond; The hydrophobic unit and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. Prior art literature Patent Literature

[0003] Patent Document 1: Japanese Patent Application Publication No. 2019-23258 Summary of the invention Problems to be solved by the invention

[0004] Although the anion exchange resin described in Patent Document 1 has successfully improved chemical properties (durability) and mechanical properties (flexibility of the film), it is desired to further improve electrical properties (anion conductivity) and chemical properties (air permeability and water content). In particular, the binder for forming the electrode catalyst layer requires regulation and control of gas diffusivity, so when considering using the anion exchange resin described in Patent Document 1 as a binder for forming the electrode catalyst layer, it is desired to further improve the air permeability.

[0005] Therefore, the object of the present invention is to provide an anion exchange resin capable of producing an electrolyte membrane having excellent electrical properties (anion conductivity) and chemical properties (air permeability and water content), an adhesive for forming an electrode catalyst layer and a battery electrode catalyst layer, an electrolyte membrane and an adhesive for forming an electrode catalyst layer formed by the anion exchange resin, and a battery electrode catalyst layer formed by the adhesive for forming an electrode catalyst layer. Means of solving problems

[0006] In order to solve the above-mentioned problems, the anion exchange resin of the present invention is characterized by comprising: A divalent hydrophobic group (a) comprising a bisphenol residue represented by the following formula (1): a divalent hydrophobic group (b) consisting of a single aromatic ring, or consisting of a plurality of aromatic rings bonded to each other via 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 carbon-carbon bond, and A divalent hydrophilic group, which is composed of a single aromatic ring, or a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the aromatic ring is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms; The anion exchange resin has: The hydrophobic unit (a) is composed of the hydrophobic group (a) monomer (single), or the hydrophobic group (a) is repeated via an ether bond, a thioether bond or a carbon-carbon bond, A hydrophobic unit (b) which is composed of the hydrophobic group (b) monomer (single), or the hydrophobic group (b) is repeated via an ether bond, a thioether bond or a carbon-carbon bond, and A hydrophilic unit, which is composed of the hydrophilic group monomer (single), or the hydrophilic group is repeated via an ether bond, a thioether bond or a carbon-carbon bond; The hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond.

[0007] [Chemistry 1] (In the formula, Alk is the same as or different from each other and represents an alkyl group or an aryl group, R represents a divalent hydrocarbon group forming an alicyclic structure, and a, b, c and d are the same as or different from each other and represent an integer of 0 to 4.)

[0008] In the anion exchange resin of the present invention, the hydrophobic group (a) preferably contains a bisphenol residue represented by the following formula (1').

[0009] [Chemistry 2] (In the formula, l represents an integer greater than 2.)

[0010] In the anion exchange resin of the present invention, the hydrophobic group (b) preferably contains a bisphenol residue represented by the following formula (2).

[0011] [Chemistry 3] (In the formula, Alk' represents an alkyl group or an aryl group which is the same or different from each other, a', b', c' and d' represent an integer of 0 to 4 which is the same or different from each other, and l' represents an integer greater than 1.)

[0012] In the anion exchange resin of the present invention, the hydrophobic group (b) preferably contains a bisphenol residue represented by the following formula (2').

[0013] [Chemistry 4] (In the formula, l' represents an integer greater than 1.)

[0014] In the anion exchange resin of the present invention, the hydrophobic group (b) preferably contains a bisphenol residue represented by the following formula (3).

[0015] [Chemistry 5] (In the formula, Alk" represents an alkyl group or an aryl group which is the same or different from each other, a", b", c" and d" represent an integer of 0 to 4 which is the same or different from each other, and l" represents an integer greater than 1.)

[0016] In the anion exchange resin of the present invention, the hydrophobic group (b) preferably contains a bisphenol residue represented by the following formula (3').

[0017] [Chemistry 6] (In the formula, "1" represents an integer greater than 1.)

[0018] In the anion exchange resin of the present invention, it is preferred that the hydrophilic group is composed of a single polycyclic compound, or is composed of a plurality of polycyclic compounds bonded to each other via a connecting group and / or a carbon-carbon bond, the connecting group is a divalent hydrocarbon group, 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, and at least one of the connecting group or the polycyclic compound is bonded to the anion exchange group via a divalent saturated hydrocarbon group having a carbon number of 2 or more.

[0019] In the anion exchange resin of the present invention, the hydrophilic group is preferably a fluorene residue represented by the following formula (4).

[0020] [Chemistry 7] (In the formula, A is the same as or different from each other and represents a group containing an anion exchange group or a cyclic structure containing an anion exchange group.)

[0021] In order to solve the above-mentioned problems, the electrolyte membrane of the present invention contains the above-mentioned anion exchange resin.

[0022] In order to solve the above-mentioned problems, the binder for forming an electrode catalyst layer of the present invention contains the above-mentioned anion exchange resin.

[0023] In order to solve the above-mentioned problems, the battery electrode catalyst layer of the present invention contains the above-mentioned binder for forming an electrode catalyst layer. Effects of the Invention

[0024] According to the present invention, there can be provided an anion exchange resin capable of producing an electrolyte membrane having excellent electrical properties (anion conductivity) and chemical properties (air permeability and water content), an adhesive for forming an electrode catalyst layer, and a battery electrode catalyst layer, an electrolyte membrane formed from the anion exchange resin and an adhesive for forming an electrode catalyst layer, and a battery electrode catalyst layer formed from the adhesive for forming an electrode catalyst layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a graph showing the results of hydrogen gas permeability of samples obtained in Examples and Comparative Examples. Figure 2 This is a graph showing the results of oxygen permeability of samples obtained in Examples and Comparative Examples. Figure 3 It is a graph showing the results of anion conductivity of samples obtained in Examples and Comparative Examples. Figure 4 It is a graph showing the results of the water contents of samples obtained in Examples and Comparative Examples. DETAILED DESCRIPTION

[0026] The anion exchange resin of the present invention contains a divalent hydrophobic group (a), a divalent hydrophobic group (b), and a divalent hydrophilic group.

[0027] In the anion exchange resin of the present invention, examples of the divalent hydrophobic group (a) include a group containing a bisphenol residue represented by the following formula (1).

[0028] [Chemistry 8] (In the formula, Alk represents an alkyl group or an aryl group which is the same or different from each other, R represents a divalent hydrocarbon group which forms an alicyclic structure, and a, b, c and d represent an integer of 0 to 4 which is the same or different from each other.)

[0029] In the above formula (1), Alk is the same as or different from each other and represents an alkyl group or an aryl group. Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl; and cycloalkyl groups having 1 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the aryl group include phenyl, biphenyl, naphthyl, and fluorenyl.

[0030] In the above formula (1), R represents a divalent hydrocarbon group that forms an alicyclic structure. Examples of the alicyclic structure include: monocyclic cycloalkane structures such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, and cycloeicosane; monocyclic cycloolefin structures such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene; and monocyclic cycloalkene structures such as decalin, cyclonaphthalene, and cyclohexene. Polycyclic cycloalkane structures such as styraconane, cubane, adamantane, and dodecahedron, polycyclic cycloolefin structures such as norbornene, spirocyclic structures such as spiro[3.4]octane, spiro[4.5]decane, and spiro[5.5]undecane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, phosphane, phospharin, tetrahydrothiophene, cyclopentane, etc., containing one heteroatom, cyclic structures; imidazoline, pyrazoline, Oxazoline, Iso oxazoline, thiazoline, isothiazolin, dioxolane, dithiolane, piperazine, morpholine, thiomorpholine, dioxolane, alkane, dithiane, etc. contain 2 heteroatoms in the ring structure; hexahydro-1,3,5-triazine, tri A ring structure containing three heteroatoms such as alkanes and trithianes; a ring structure formed by combining these.

[0031] The above-mentioned alicyclic structure may also be substituted by an alkyl group, an aryl group or a halogen atom. As the alkyl group, the above-mentioned alkyl group may be mentioned. As the aryl group, the above-mentioned aryl group may be mentioned. As the halogen atom, fluorine atom, chlorine atom, bromine atom and iodine atom may be mentioned. It should be noted that when the alicyclic structure is substituted by an alkyl group or an aryl group, the number of substitutions and the substitution position of the alkyl group or the aryl group may be appropriately set according to the purpose and use.

[0032] In the above formula (1), a and b are the same as or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably both a and b represent 0.

[0033] In the above formula (1), c and d are the same as or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably both c and d represent 0.

[0034] Examples of such a hydrophobic group (a) include the following structures.

[0035] [Chemistry 9]

[0036] Preferred examples of such a hydrophobic group (a) include a bisphenol residue represented by the following formula (1').

[0037] [Chemistry 10] (In the formula, l represents an integer greater than 2.)

[0038] In the above formula (1′), l represents an integer of 2 or more, preferably an integer of 3 to 20, and more preferably an integer of 5 to 8.

[0039] In the anion exchange resin of the present invention, the divalent hydrophobic group (b) includes a hydrophobic group consisting of a single aromatic ring, or a hydrophobic group consisting of a plurality of (two or more, preferably two) aromatic rings bonded to each other via 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 carbon-carbon bond.

[0040] Examples of the aromatic ring include a benzene ring, a naphthalene ring, an indene ring, Monocyclic or polycyclic compounds having 6 to 14 carbon atoms, such as fluorene ring, anthracene ring, phenanthrene ring, and pyrrole, furan, thiophene, Heterocyclic compounds such as azole, thiazole, pyridine, etc.

[0041] As the aromatic ring, preferably, a monocyclic aromatic hydrocarbon having 6 to 14 carbon atoms is used, and more preferably, a benzene ring is used.

[0042] In addition, the aromatic ring may be substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, a pseudohalide, etc. as required. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of pseudohalides include trifluoromethyl, -CN, -NC, -OCN, -NCO, -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, and N3. Examples of the alkyl group include the above-mentioned alkyl groups. Examples of the aryl group include the above-mentioned aryl groups.

[0043] When the aromatic ring is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, a pseudo-halide, etc., the number and position of the substituent such as a halogen atom, an alkyl group, an aryl group, a pseudo-halide, etc. are appropriately set according to the purpose and application.

[0044] More specifically, examples of the aromatic ring substituted with a halogen atom include a benzene ring substituted with 1 to 4 halogen atoms (for example, a benzene ring substituted with 1 to 4 fluorine atoms, a benzene ring substituted with 1 to 4 chlorine atoms, a benzene ring substituted with 1 to 4 bromine atoms, a benzene ring substituted with 1 to 4 iodine atoms, and the 1 to 4 halogen atoms may all be the same or different).

[0045] Examples of the divalent hydrocarbon group include divalent saturated hydrocarbon groups having 1 to 20 carbon atoms, such as methylene (—CH2-), ethylene, propylene, isopropylene (—C(CH3)2-), butylene, isobutylene, sec-butylene, pentylene, isopentylene, sec-pentylene, hexylene, 3-methylpentylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, isodecylene, dodecylene, tetradecylene, hexadecylene and octadecylene.

[0046] As the divalent hydrocarbon group, preferably there can be mentioned a divalent saturated hydrocarbon group having 1 to 3 carbon atoms, specifically, there can be mentioned a methylene group (-CH2-), an ethylene group, a propylene group, and an isopropylene group (-C(CH3)2-); more preferably there can be mentioned a methylene group (-CH2-), an isopropylene group (-C(CH3)2-); and particularly preferably there can be mentioned an isopropylene group (-C(CH3)2-).

[0047] The divalent hydrocarbon group may be substituted by a monovalent residue in the above aromatic ring.

[0048] Preferred examples of such a hydrophobic group (b) include a bisphenol residue represented by the following formula (2) and a bisphenol residue represented by the following formula (3).

[0049] [Chemistry 11] (In the formula, Alk' represents an alkyl group or an aryl group which is the same or different from each other, a', b', c' and d' represent an integer of 0 to 4 which is the same or different from each other, and l' represents an integer greater than 1.)

[0050] [Chemistry 12] (In the formula, Alk" represents an alkyl group or an aryl group which is the same or different from each other, a", b", c" and d" represent an integer of 0 to 4 which is the same or different from each other, and l" represents an integer greater than 1.)

[0051] In the above formula (2), Alk' is the same as or different from each other and represents an alkyl group or an aryl group. Examples of the alkyl group include the above-mentioned alkyl group. Examples of the aryl group include the above-mentioned aryl group.

[0052] In the above formula (2), a' and b' are the same as or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably both a' and b' represent 0.

[0053] In the above formula (2), c' and d' are the same as or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably both c' and d' represent 0.

[0054] In the above formula (2), l' represents an integer of 1 or more, preferably an integer of 1-20, and more preferably an integer of 2-6.

[0055] In the above formula (3), "Alk" may be the same as or different from each other and represent an alkyl group or an aryl group. Examples of the alkyl group include the above-mentioned alkyl group. Examples of the aryl group include the above-mentioned aryl group.

[0056] In the above formula (3), a" and b" are the same as or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably both a" and b" represent 0.

[0057] In the above formula (2), c" and d" are the same as or different from each other and represent an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably both c" and d" represent 0.

[0058] In the above formula (2), "l" represents an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 2 to 6.

[0059] Particularly preferred examples of such a hydrophobic group (b) include a bisphenol residue represented by the following formula (2') and a bisphenol residue represented by the following formula (3').

[0060] [Chemistry 13] (In the formula, l' represents an integer greater than 1.)

[0061] [Chemistry 14] (In the formula, "1" represents an integer greater than 1.)

[0062] In the above formula (2'), l' has the same meaning as l' in the above formula (2), and represents an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 2 to 6.

[0063] In the above formula (3'), l" has the same meaning as l" in the above formula (3), and represents an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 2 to 6.

[0064] By introducing a divalent fluorine-containing group into the main chain of the hydrophobic group constituting the hydrophobic unit in this manner, the following effects can be obtained. · Improved solubility and flexibility due to the main chain with low intermolecular interactions · It imparts hydrophobicity, develops phase separation with the hydrophilic part (around the ion exchange group), and can form an ion conduction path Due to water repellency, hydrophilic hydroxide ions and oxidants are less likely to approach the main chain (alkaline resistance and chemical stability are improved) · Ability to adjust and control the rigidity of the main chain (improvement of the flexibility of the electrolyte membrane) Low glass transition temperature, allowing adhesion to the catalyst layer (reduced contact resistance) Ability to regulate and control gas diffusivity (increased diffusivity of oxygen and hydrogen when used as an adhesive)

[0065] In the anion exchange resin of the present invention, the divalent hydrophilic group includes a hydrophilic group composed of a single aromatic ring or a hydrophilic group composed of a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the aromatic ring is bonded to the anion exchange group via a divalent saturated hydrocarbon group having a carbon number of 2 or more. It should be noted that an anion exchange group bonded to a divalent saturated hydrocarbon group having a carbon number of 2 or more may be referred to as a group containing an anion exchange group.

[0066] The aromatic ring may be a monocyclic compound (benzene ring) or a polycyclic compound. Examples of the polycyclic compound include naphthalene ring, indene ring, The rings include a fluorene ring, an anthracene ring, a phenanthrene ring, a carbazole ring and an indole ring, and preferably a fluorene ring is used.

[0067] Examples of the divalent hydrocarbon group include the above-mentioned divalent hydrocarbon groups.

[0068] The anion exchange group is introduced into the side chain of the hydrophilic group. Specifically, there is no particular limitation, and quaternary ammonium groups, tertiary amino groups, secondary amino groups, primary amino groups, phosphine groups, phosphazenium groups, tertiary sulfonium groups, quaternary boron groups, etc. can be used. Base, quaternary phosphorus A known anion exchange group may be a quaternary ammonium group or a guanidine group. From the viewpoint of ease of synthesis and anion conductivity, a quaternary ammonium group is preferably used.

[0069] Preferred anion exchange groups include: -N+ (CH3)3, and other groups having the following structures can be mentioned. In the following structural formulae, * represents a portion bonded to an aromatic ring having a substituent.

[0070] [Chemistry 15] (In the formula, Alk, Alk', and Alk" represent the above-mentioned alkyl groups, and iPr represents an isopropyl group.)

[0071] Such anion exchange group is bonded to a linking group or an aromatic ring of a divalent hydrophilic residue via a divalent saturated hydrocarbon group, wherein the divalent hydrophilic residue is composed of a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, and the linking group is a divalent hydrocarbon group, 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.

[0072] The anion exchange group may be bonded to at least one of the linking groups or aromatic rings, may be bonded to multiple linking groups or aromatic rings, or may be bonded to all of the linking groups or aromatic rings. In addition, multiple anion exchange groups may be bonded to one linking group or aromatic ring.

[0073] The carbon number of the divalent saturated hydrocarbon group that bonds between the divalent hydrophilic residue composed of a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond or the aromatic ring and the anion exchange group is 2 or more, and the linking group is a divalent hydrocarbon group, 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 carbon number of the divalent saturated hydrocarbon group is preferably an integer of 2 to 20, more preferably an integer of 3 to 10, and even more preferably an integer of 4 to 8.

[0074] As the divalent saturated hydrocarbon group, preferred examples include straight-chain saturated hydrocarbon groups such as methylene (-(CH2)-), ethylene (-(CH2)2-), trimethylene (-(CH2)3-), tetramethylene (-(CH2)4-), pentamethylene (-(CH2)5-), hexamethylene (-(CH2)6-), heptamethylene (-(CH2)7-), and octamethylene (-(CH2)8-).

[0075] Preferred examples of the divalent hydrophilic group having such a structure include hydrophilic groups having a structure represented by the following formula.

[0076] [Chemistry 16]

[0077] [Chemistry 17]

[0078] [Chemistry 18] (In the formula, Ion is the same as or different from each other and represents a group containing an anion exchange group, a represents an integer greater than 0 and the number of groups containing anion exchange groups that can be bonded (preferably 0 or 1), and n represents an integer greater than 0.)

[0079] Preferred examples of the divalent hydrophilic group having such a structure include a fluorene residue represented by the following formula (4).

[0080] [Chemistry 19] (In the formula, A is the same as or different from each other and represents a group containing an anion exchange group or a cyclic structure containing an anion exchange group.)

[0081] Particularly preferably, as the divalent hydrophilic group having such a structure, there are hydrophilic groups represented by the following formula (4a), the following formula (4b), the following formula (4c) and the following formula (4d).

[0082] [Chemistry 20]

[0083] The anion exchange resin of the present invention comprises a hydrophobic unit (a), a hydrophobic unit (b) and a hydrophilic unit, wherein the hydrophobic unit (a) is composed of a monomer (single) of the hydrophobic group (a), or is composed of the hydrophobic group (a) repeated via an ether bond, a thioether bond or a carbon-carbon bond; the hydrophobic unit (b) is composed of a monomer (single) of the hydrophobic group (b), or is composed of the hydrophobic group (b) repeated via an ether bond, a thioether bond or a carbon-carbon bond; and the hydrophilic unit is composed of a monomer (single) of the hydrophilic group, or is composed of the hydrophilic group repeated via an ether bond, a thioether bond or a carbon-carbon bond. The hydrophobic unit (a) is preferably composed of a hydrophobic group (a) monomer (single) or composed of a hydrophobic group (a) repeated via a carbon-carbon bond; the hydrophobic unit (b) is preferably composed of a hydrophobic group (b) monomer (single) or composed of a hydrophobic group (b) repeated via a carbon-carbon bond; the hydrophilic unit is preferably composed of a hydrophilic group monomer (single) or composed of a hydrophilic group repeated via a carbon-carbon bond.

[0084] In addition, a unit corresponds to a block of a generally used block copolymer.

[0085] The hydrophobic unit (a) preferably includes a unit formed by bisphenol residues represented by the above formula (1) being bonded to each other via a carbon-carbon bond. The bisphenol residues represented by the above formula (1) may be a unit formed by plural types of bisphenol residues being bonded to each other in a random, alternating or other regular or block-like manner.

[0086] Such a hydrophobic unit (a) is represented by, for example, the following formula (11).

[0087] [Chemistry 21] (In the formula, R, Alk, a, b, c and d have the same meanings as those in the above formula (1), and q represents 1 to 200.)

[0088] In the above formula (11), q represents, for example, 1-200, preferably 1-50.

[0089] As such a hydrophobic unit (a), a unit in which bisphenol residues represented by the above formula (1') are bonded to each other via a carbon-carbon bond is more preferably mentioned.

[0090] Such a hydrophobic unit (a) is represented by, for example, the following formula (11').

[0091] [Chemistry 22] (In the formula, l has the same meaning as l in the above formula (1'), and q represents 1 to 200.)

[0092] In the above formula (11'), q represents, for example, 1-200, preferably 1-50.

[0093] As the hydrophobic unit (b), preferably, there can be mentioned a unit formed by a divalent hydrophobic group (b) bonded to each other via a carbon-carbon bond, wherein the divalent hydrophobic group (b) is composed of a single aromatic ring or a plurality of aromatic rings bonded to each other via 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 carbon-carbon bond. The hydrophobic group (b) may be a unit formed by a plurality of groups bonded to each other in a random, alternating or other regular or block-like manner.

[0094] More preferred examples of such hydrophobic units (b) include units formed by bisphenol residues represented by the above formula (2) being bonded to each other via a carbon-carbon bond, and units formed by bisphenol residues represented by the above formula (3) being bonded to each other via a carbon-carbon bond.

[0095] Such a hydrophobic unit (b) is represented by, for example, the following formula (12) or the following formula (13).

[0096] [Chemistry 23] (In the formula, Alk', a', b', c', d' and l' have the same meanings as Alk', a', b', c', d' and l' in the above formula (2), and r represents 1 to 200.)

[0097] [Chemistry 24] (In the formula, Alk", a", b", c", d" and l" have the same meanings as Alk", a", b", c", d" and l" in the above formula (3), and r represents 1 to 200.)

[0098] In the above formula (12) and the above formula (13), r represents, for example, 1 to 200, preferably 1 to 50.

[0099] Particularly preferred examples of such a hydrophobic unit (b) include a unit in which bisphenol residues represented by the above formula (2') are bonded to each other via a carbon-carbon bond, and a unit in which bisphenol residues represented by the above formula (3') are bonded to each other via a carbon-carbon bond.

[0100] Such a hydrophobic unit (b) is represented by, for example, the following formula (12') or the following formula (13').

[0101] [Chemistry 25] (In the formula, l' has the same meaning as l' in the above formula (2'), and r represents 1 to 200.)

[0102] [Chemistry 26] (In the formula, l" has the same meaning as l" in the above formula (3'), and r represents 1 to 200.)

[0103] In the above formula (12') and the above formula (13'), r represents, for example, 1-200, preferably 1-50.

[0104] As the hydrophilic unit, preferably there can be mentioned: a unit formed by divalent hydrophilic groups bonded to each other via a carbon-carbon bond, wherein the divalent hydrophilic group is composed of a single aromatic ring, or is composed of a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the aromatic ring is bonded to a group containing an anion exchange group. As the hydrophilic unit, more preferably, there can be mentioned: a unit formed by bivalent hydrophilic groups mutually bonded via carbon-carbon bonds, the bivalent hydrophilic group is composed of a single polycyclic compound, or is composed of a plurality of polycyclic compounds mutually bonded via a linking group and / or a carbon-carbon bond, the linking group is a bivalent hydrocarbon group, a bivalent silicon-containing group, a bivalent nitrogen-containing group, a bivalent phosphorus-containing group, a bivalent oxygen-containing group or a bivalent sulfur-containing group, and at least one of the linking group or the polycyclic compound is bonded to the anion exchange group via a bivalent saturated hydrocarbon group having a carbon number of 2 or more. The bivalent hydrophilic group may be a unit formed by a plurality of groups mutually bonded in a regular form such as a random form, an alternating form or a block form.

[0105] As the hydrophilic unit, a unit in which fluorene residues represented by the above formula (4) are bonded to each other via a carbon-carbon bond is particularly preferred.

[0106] Such a hydrophilic unit is represented by, for example, the following formula (14).

[0107] [Chemistry 27] (In the formula, A has the same meaning as A in the above formula (4), and m represents 1 to 200.)

[0108] In the above formula (4), m represents, for example, 1-200, preferably 1-50.

[0109] Preferred examples of such hydrophilic units include: a unit formed by hydrophilic groups represented by the above formula (4a) being bonded to each other via a carbon-carbon bond; a unit formed by hydrophilic groups represented by the above formula (4b) being bonded to each other via a carbon-carbon bond; a unit formed by hydrophilic groups represented by the above formula (4c) being bonded to each other via a carbon-carbon bond; and a unit formed by hydrophilic groups represented by the above formula (4d) being bonded to each other via a carbon-carbon bond.

[0110] Such a hydrophilic unit is represented by, for example, the following formula (14a), the following formula (14b), the following formula (14c), or the following formula (14d).

[0111] [Chemistry 28] (In the formula, m represents 1 to 200.)

[0112] In the above formula (14a), the above formula (14b), the above formula (14c) and the above formula (14d), m represents, for example, 1 to 200, preferably 1 to 50.

[0113] In the anion exchange resin of the present invention, the hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. The hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are particularly preferably bonded via a carbon-carbon bond.

[0114] Preferred examples of such anion exchange resin include an anion exchange resin in which a hydrophobic unit (a) represented by the above formula (11), a hydrophobic unit (b) represented by the above formula (12) or the above formula (13), and a hydrophilic unit represented by the above formula (14) are bonded via a carbon-carbon bond.

[0115] Such an anion exchange resin is represented by, for example, the following formula (17) or the following formula (18).

[0116] [Chemistry 29] (In the formula, R, Alk, a, b, c and d have the same meanings as R, Alk, a, b, c and d in the above formula (11), Alk', a', b', c', d' and l' have the same meanings as Alk', a', b', c', d' and l' in the above formula (12), A has the same meaning as A in the above formula (14), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0117] [Chemistry 30] (In the formula, R, Alk, a, b, c and d have the same meanings as R, Alk, a, b, c and d in the above formula (11), Alk", a", b", c", d" and l" have the same meanings as Alk", a", b", c", d" and l" in the above formula (13), A has the same meaning as A in the above formula (14), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0118] As such an anion exchange resin, more preferably mentioned is an anion exchange resin in which a hydrophobic unit (a) represented by the above formula (11'), a hydrophobic unit (b) represented by the above formula (12') or the above formula (13'), and a hydrophilic unit represented by the above formula (14a), the above formula (14b), the above formula (14c) or the above formula (14d) are bonded via a carbon-carbon bond.

[0119] Such an anion exchange resin is represented by, for example, the following formula (17a), the following formula (17b), the following formula (17c), the following formula (17d), the following formula (18a), the following formula (18b), the following formula (18c) or the following formula (18d).

[0120] [Chemistry 31] (In the formula, l represents the same meaning as l in the above formula (11'), l' represents the same meaning as l' in the above formula (12'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0121] [Chemistry 32] (In the formula, l represents the same meaning as l in the above formula (11'), l' represents the same meaning as l' in the above formula (12'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0122] [Chemistry 33] (In the formula, l represents the same meaning as l in the above formula (11'), l' represents the same meaning as l' in the above formula (12'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0123] [Chemistry 34] (In the formula, l represents the same meaning as l in the above formula (11'), l' represents the same meaning as l' in the above formula (12'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0124] [Chemistry 35] (In the formula, l represents the same meaning as l in the above formula (11'), l" represents the same meaning as l" in the above formula (13'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0125] [Chemistry 36] (In the formula, l represents the same meaning as l in the above formula (11'), l" represents the same meaning as l" in the above formula (13'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0126] [Chemistry 37] (In the formula, l represents the same meaning as l in the above formula (11'), l" represents the same meaning as l" in the above formula (13'), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0127] [Chemistry 38]

[0128] In the anion exchange resin of the present invention, q, r and m represent the ratio or the number of repetitions, and o represents the number of repetitions, which are appropriately set according to the purpose and application. However, the percentage of the hydrophobic group (a) contained in the hydrophobic unit (hydrophobic unit (a) and hydrophobic unit (b)) contained in the anion exchange resin of the present invention (ratio of hydrophobic unit (a) = q / (q+r) × 100) is preferably 5 to 65, more preferably 10 to 60, and further preferably 15 to 55. Within this range, an anion exchange resin having excellent air permeability (especially oxygen permeability) is obtained.

[0129] As described above, the number average molecular weight of such an anion exchange resin is, for example, 10 to 1000 kDa, and preferably 30 to 500 kDa.

[0130] The method for producing the anion exchange resin is not particularly limited, and a known method can be used, but a method based on a polycondensation reaction is preferably used.

[0131] When an anion exchange resin is produced by this method, for example, a monomer for forming a hydrophobic group (a), a monomer for forming a hydrophobic group (b), and a monomer for forming a hydrophilic group having a group precursor functional group containing an anion exchange group are prepared, and the monomer for forming a hydrophobic group (a), the monomer for forming a hydrophobic group (b), and the monomer for forming a hydrophilic group having a group precursor functional group containing an anion exchange group are copolymerized to synthesize a polymer, and the group precursor functional group containing an anion exchange group in the polymer is ionized, thereby producing an anion exchange resin. Alternatively, a monomer for forming a hydrophobic group (a), a monomer for forming a hydrophobic group (b), and a monomer for forming a hydrophilic group are prepared, and the monomer for forming a hydrophobic group (a), the monomer for forming a hydrophobic group (b), and the monomer for forming a hydrophilic group are copolymerized to synthesize a polymer, and a substituent having a group containing an anion exchange group is introduced into the polymer, thereby producing an anion exchange resin.

[0132] For the polycondensation reaction, a conventionally known general method can be used, but a cross-coupling reaction to form a carbon-carbon bond is preferably used.

[0133] Preferred examples of the hydrophobic group-forming monomer (a) include compounds represented by the following formula (21) corresponding to the above formula (1).

[0134] [Chemistry 39] (In the formula, R, Alk, a, b, c and d have the same meanings as those in the above formula (1), and T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0135] As the hydrophobic group-forming monomer (a), particularly preferably, there can be mentioned a compound represented by the following formula (21') corresponding to the above formula (1').

[0136] [Chemistry 40] (In the formula, l has the same meaning as l in the above formula (1'), and T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0137] Preferred examples of the hydrophobic group-forming monomer (b) include compounds represented by the following formula (22) corresponding to the above formula (2) and compounds represented by the following formula (23) corresponding to the above formula (3).

[0138] [Chemistry 41] (In the formula, Alk', a', b', c', d' and l' have the same meanings as Alk', a', b', c', d' and l' in the above formula (2), and T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0139] [Chemistry 42] (In the formula, Alk", a", b", c", d" and l" have the same meanings as Alk", a", b", c", d" and l" in the above formula (3), and T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0140] Particularly preferred examples of the hydrophobic group-forming monomer (b) include a compound represented by the following formula (22') corresponding to the above formula (2') and a compound represented by the following formula (23') corresponding to the above formula (3').

[0141] [Chemistry 43] (In the formula, l' has the same meaning as l' in the above formula (2'), and T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0142] [Chemistry 44] (In the formula, l" has the same meaning as l" in the above formula (3'), T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0143] Preferred examples of the hydrophilic group-forming monomer having a group precursor functional group containing an anion exchange group include compounds represented by the following formula (24) corresponding to the above formula (4).

[0144] [Chemistry 45] (In the formula, Pre is the same as or different from each other and represents a group precursor functional group containing an anion exchange group, and T and T' are the same as or different from each other and represent a halogen atom, a pseudohalide, a boronic acid group, a boronic acid derivative or a hydrogen atom.)

[0145] When a hydrophobic group-forming monomer (a), a hydrophobic group-forming monomer (b), and a hydrophilic group-forming monomer having a group precursor functional group containing an anion exchange group are copolymerized by cross coupling, the amount of each monomer is adjusted so as to achieve a desired ratio of hydrophobic unit (a), desired hydrophobic unit (b), and hydrophilic unit in the obtained anion exchange resin precursor polymer.

[0146] Among these methods, a known method can be used, such as a method in which a hydrophobic group-forming monomer (a), a hydrophobic group-forming monomer (b), and a hydrophilic group-forming monomer having a group precursor functional group containing an anion exchange group are dissolved in a solvent such as N,N-dimethylacetamide and dimethyl sulfoxide, and copolymerized using bis(cycloocta-1,5-diene)nickel(0) as a catalyst.

[0147] 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.

[0148] By coupling the compound represented by the above formula (21), the compound represented by the above formula (22) and the compound represented by the above formula (24), an anion exchange resin precursor polymer represented by the following formula (27) is obtained.

[0149] [Chemistry 46] (In the formula, R, Alk, a, b, c and d have the same meanings as R, Alk, a, b, c and d in the above formula (21), Alk', a', b', c', d' and l' have the same meanings as Alk', a', b', c', d' and l' in the above formula (22), Pre has the same meaning as Pre in the above formula (24), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0150] Furthermore, by coupling the compound represented by the above formula (21), the compound represented by the above formula (23) and the compound represented by the above formula (24), an anion exchange resin precursor polymer represented by the following formula (28) is obtained.

[0151] [Chemistry 47] (In the formula, R, Alk, a, b, c and d have the same meanings as R, Alk, a, b, c and d in the above formula (21), Alk", a", b", c", d" and l" have the same meanings as Alk", a", b", c", d" and l" in the above formula (23), Pre has the same meaning as Pre in the above formula (24), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0152] It is particularly preferred that the anion exchange resin precursor polymer represented by the following formula (27') is obtained by coupling the compound represented by the above formula (21'), the compound represented by the above formula (22') and the compound represented by the above formula (24).

[0153] [Chemistry 48] (In the formula, l represents the same meaning as l in the above formula (21'), l' represents the same meaning as l' in the above formula (22'), Pre represents the same meaning as Pre in the above formula (24), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0154] In addition, it is particularly preferred that the compound represented by the above formula (21'), the compound represented by the above formula (23') and the compound represented by the above formula (24) are coupled to obtain an anion exchange resin precursor polymer represented by the following formula (28').

[0155] [Chemistry 49] (In the formula, l represents the same meaning as l in the above formula (21'), l" represents the same meaning as l" in the above formula (23'), Pre represents the same meaning as Pre in the above formula (24), q, r and m represent the ratio or the number of repetitions, which are 1 to 200, and o represents the number of repetitions, which are 1 to 100.)

[0156] Then, in this method, the group precursor functional group containing an anion exchange group is ionized. There is no particular limitation on the ionization method, and a known method can be used.

[0157] A known method can be used, such as a method of dissolving an anion exchange resin precursor polymer in a solvent such as N,N-dimethylacetamide or dimethyl sulfoxide and ionizing it using methyl iodide or the like as an alkylating agent.

[0158] The reaction temperature in the ionization 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.

[0159] By ionizing the anion exchange resin precursor polymer represented by the above formula (27), the anion exchange resin represented by the above formula (17) can be obtained. Also, by ionizing the anion exchange resin precursor polymer represented by the above formula (28), the anion exchange resin represented by the above formula (18) can be obtained.

[0160] The ion exchange group capacity of the anion exchange resin is, for example, 0.1 to 4.0 meq. / g, and preferably 0.6 to 3.0 meq. / g.

[0161] The ion exchange group capacity can be obtained by the following formula (30). [Ion exchange group capacity (meq. / g)] = amount of anion exchange groups introduced per hydrophilic unit × number of repeating units 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) (30) The amount of ion exchange groups introduced 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 of the hydrophilic group.

[0162] Such anion exchange resins include: A divalent hydrophobic group (a) comprising a bisphenol residue represented by the above formula (1), a divalent hydrophobic group (b) consisting of a single aromatic ring, or consisting of a plurality of aromatic rings bonded to each other via 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 carbon-carbon bond, and A divalent hydrophilic group, which is composed of a single aromatic ring, or is composed of a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the aromatic ring is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms, The above anion exchange resin has: The hydrophobic unit (a) is composed of the above hydrophobic group (a) monomer (single), or the above hydrophobic group (a) is repeated via an ether bond, a thioether bond or a carbon-carbon bond, A hydrophobic unit (b) which is composed of the above hydrophobic group (b) monomer (single), or the above hydrophobic group (b) is repeated via an ether bond, a thioether bond or a carbon-carbon bond, and A hydrophilic unit, which is composed of the above hydrophilic group monomer (single), or the above hydrophilic group is repeated via an ether bond, a thioether bond or a carbon-carbon bond; The hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. That is, since the divalent hydrophobic group (a) and the divalent hydrophilic group are introduced into the anion exchange resin, the anion exchange resin has excellent electrical properties (anion conductivity) and chemical properties (air permeability and water content).

[0163] In addition, in the case of a hydrophilic unit having a hydrophilic group repeated via a carbon-carbon bond, since no ether bond is contained, durability such as alkali resistance is excellent. More specifically, if an ether bond is contained in the hydrophilic unit, the following may occur: - ) due to decomposition, and sometimes the alkali resistance is insufficient.

[0164] [Chemistry 50]

[0165] In contrast, an anion exchange resin having a hydrophilic unit in which a hydrophilic group is repeated via a carbon-carbon bond does not contain an ether bond and thus does not undergo decomposition by the above mechanism, resulting in excellent durability such as alkali resistance.

[0166] The present invention includes an electrolyte layer (electrolyte membrane) obtained using such an anion exchange resin. The electrolyte membrane of the present invention can be applied to various electrochemical applications such as fuel cells, water electrolysis hydrogen production devices, electrochemical hydrogen pumps, and is particularly preferably used in water electrolysis hydrogen production devices. In fuel cells, electrochemical hydrogen pumps, and water electrolysis hydrogen production devices, the electrolyte membrane is used in a structural state in which a catalyst layer, an electrode substrate, and a diaphragm are sequentially stacked on both sides. Among them, a structure in which a catalyst layer and a gas diffusion substrate are sequentially stacked on both sides of the electrolyte membrane (a layer structure of a gas diffusion substrate / catalyst layer / electrolyte membrane / catalyst layer / gas diffusion substrate) is called a membrane electrode assembly (MEA), and the electrolyte membrane of the present invention is suitable for use as an electrolyte membrane constituting such an MEA.

[0167] As the electrolyte membrane, the above-mentioned anion exchange resin can be used (that is, the electrolyte membrane contains the above-mentioned anion exchange resin).

[0168] It is explained that, as an electrolyte membrane, for example, a well-known reinforcing material such as a porous substrate can be used for reinforcement, and then, for example, various treatments such as biaxial stretching treatment for controlling molecular orientation, and / or heat treatment for controlling crystallinity and residual stress can be performed. In addition, in order to improve the mechanical strength of the electrolyte membrane, a well-known filler can be added, and the electrolyte membrane can be composited with a reinforcing agent such as a glass nonwoven fabric by pressing.

[0169] In addition, the electrolyte membrane may contain various commonly used additives appropriately within the range that does not affect the processing and performance of the electrolyte membrane, such as a compatibilizer for improving compatibility, an antioxidant for preventing resin degradation, an antistatic agent or lubricant for improving operability in the molding process of the membrane, etc.

[0170] The thickness of the electrolyte membrane is not particularly limited and can be appropriately set depending on the purpose and application.

[0171] The thickness of the electrolyte membrane is, for example, 1.2 to 350 μm, or preferably 5 to 200 μm.

[0172] In addition, the present invention includes an electrode catalyst layer-forming binder containing the anion exchange resin, and a battery electrode catalyst layer containing the electrode catalyst layer-forming binder. Since the anion exchange resin has excellent anion conductivity and air permeability, it is easy to adjust and control gas diffusivity by using it as an electrode catalyst layer-forming binder.

[0173] As a method for making the binder for forming an electrode catalyst layer contain an anion exchange resin, specifically, for example, the binder for forming an electrode catalyst layer is prepared by chopping the anion exchange resin into small pieces and dissolving the fine pieces in an appropriate amount of an organic solvent such as alcohol.

[0174] The content ratio of the anion exchange resin in the binder for forming an electrode catalyst layer is, for example, 2 to 10 parts by mass, or preferably 2 to 5 parts by mass, relative to 100 parts by mass of the binder for forming an electrode catalyst layer.

[0175] Furthermore, by using the binder for forming an electrode catalyst layer (battery electrode catalyst layer) to form a catalyst layer of an electrode (battery electrode catalyst layer), an anion exchange resin can be contained in the catalyst layer (battery electrode catalyst layer).

[0176] As mentioned above, although embodiment of this invention was described, embodiment of this invention is not limited to this, and design can be changed suitably within the range which does not change the meaning of this invention. Example

[0177] Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[0178] [Example 1: Anion exchange resin QC6 17 Synthesis of PA (IEC = 1.7 meq. / g, q / (q+r)×100=17, m / (q+r+m)×100=38)] <Synthesis of Monomer 1> Cyclohexanone (12.0 g, 122 mmol), aniline (50.0 g, 536 mmol), 12 M hydrochloric acid (40.0 mL) were added to a 300 mL round-bottom three-necked flask with a nitrogen inlet and a condenser, and the temperature was gradually raised and stirred at 80 ° C for 24 hours. Then it was cooled, and ion exchange water (80.0 mL) and sodium hydroxide were added to neutralize the solution. The target product was extracted from the reaction solution with ethyl acetate, and the obtained organic layer was washed with water and then dehydrated with sodium sulfate. The solution was concentrated and aniline was removed from the solution by reduced pressure distillation. The crude product was purified using silica gel column chromatography (developing solvent: hexane: ethyl acetate = 4: 1 → 2: 1 → 1: 1) and vacuum dried for 12 hours to obtain the precursor compound with a yield of 40%.

[0179] The precursor compound (1.00 g, 3.75 mmol) and 6 M hydrochloric acid (10 mL) were added to a 100 mL eggplant-shaped flask, and ion exchange water (10 mL) dissolved with sodium nitrite (0.620 g, 8.99 mmol) was slowly added dropwise while the flask was cooled in an ice bath at 0°C. Then, the reaction was carried out at 0°C for 30 minutes. Then, concentrated hydrochloric acid (10 mL) dissolved with copper (I) chloride (1.50 g, 15.1 mmol) was added and the reaction was carried out for 8 hours. Cooled to room temperature, filtered through diatomaceous earth with hexane. Then extracted with hexane, washed with pure water, and then dehydrated with sodium sulfate. The dehydrating agent was removed by filtration and then concentrated with an evaporator. The resulting residue was purified by silica gel column chromatography (developing solvent: hexane). The resulting solution was concentrated and vacuum dried overnight to obtain monomer 1 represented by the following formula with a yield of 57%.

[0180] [Chemistry 51]

[0181] <Synthesis of Monomer 2> 1,6-diiodoperfluorohexane (5.54 g, 10.0 mmol), 3-chloroiodobenzene (11.9 g, 50 mmol), and dimethyl sulfoxide (60 mL) were added to a 100 mL round-bottom three-necked flask with a nitrogen inlet and a condenser. After the mixture was stirred into a uniform solution, copper powder (9.53 g, 150 mmol) was added and reacted at 120°C for 48 hours. The reaction solution was added dropwise to a 0.1 M aqueous nitric acid solution to stop the reaction. The precipitate recovered by filtration from the mixture was washed with methanol, and the filtrate was recovered. The same operation was repeated, and then the white solid precipitated by adding pure water to the combined filtrate was filtered and recovered, washed with a mixed solution of pure water and methanol (pure water / methanol = 1 / 1), and then vacuum dried (60°C) overnight to obtain a monomer 2 (white solid) represented by the following formula with a yield of 84%.

[0182] [Chemistry 52]

[0183] <Synthesis of Monomer 3> Fluorene (83.1 g, 0.50 mol), N-chlorosuccinimide (167 g, 1.25 mol), and acetonitrile (166 mL) were added to a 500 ml round-bottom three-necked flask. After the mixture was stirred into a uniform solution, 12 M hydrochloric acid (16.6 mL) was added and reacted at room temperature for 24 hours. The precipitate recovered from the reaction solution by filtration was washed with methanol and pure water, and then vacuum dried (60° C.) overnight to obtain a monomer 3 (white solid) represented by the following formula with a yield of 65%.

[0184] [Chemistry 53]

[0185] <Synthesis of Monomer 4> Monomer 3 (8.23 g, 35.0 mmol) and 1,6-dibromohexane (53 mL) were added to a 300 mL round-bottom three-necked flask. After the mixture was stirred into a uniform solution, a mixed solution of tetrabutylammonium (2.26 g, 7.00 mmol), potassium hydroxide (35.0 g), and pure water (35 mL) was added and reacted at 80°C for 1 hour. Pure water was added to the reaction solution to stop the reaction. The target product was extracted from the aqueous layer with dichloromethane, and the combined organic layer was washed with pure water and brine, and then the water, dichloromethane and 1,6-dibromohexane were distilled off. The crude product was purified by silica gel column chromatography (developing solvent: dichloromethane / hexane = 1 / 4), and then vacuum dried (60°C) overnight to obtain monomer 4 (light yellow solid) represented by the following formula with a yield of 75%.

[0186] [Chemistry 54]

[0187] <Synthesis of Monomer 5> Monomer 4 (13.2 g, 23.4 mol) and tetrahydrofuran (117 mL) were added to a 300 mL round-bottom three-necked flask. After the mixture was stirred into a uniform solution, a 40 wt% aqueous solution of dimethylamine (58.6 mL) was added and the mixture was reacted at room temperature for 24 hours. A saturated aqueous solution of sodium bicarbonate was added to the reaction solution to stop the reaction. After removing tetrahydrofuran, hexane was added to extract the target component. After washing the organic layer with brine, water and hexane were distilled off. The mixture was vacuum dried overnight at 40°C to obtain a monomer 5 (light yellow solid) represented by the following formula in a yield of 75%.

[0188] [Chemistry 55]

[0189] (Copolymerization Reaction) Monomer 1 (0.120 g, 0.394 mmol), monomer 2 (1.03 g, 1.97 mmol), monomer 5 (0.695 g, 1.42 mmol), 2,2'-bipyridine (2.84 g, 18.2 mmol), and N,N-dimethylacetamide (15.8 mL) were added to a 100 mL round-bottom three-necked flask with a nitrogen inlet and a condenser. After the mixture was stirred into a uniform solution, bis(1,5-cyclooctadiene)nickel (0) (2.50 g, 9.09 mmol) was added and reacted at 85°C for 3 hours. The reaction mixture was added dropwise to a mixed solution of methanol and 12M hydrochloric acid (methanol / 12M hydrochloric acid = 1 / 8) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with hydrochloric acid, potassium carbonate aqueous solution and pure water, and then vacuum dried (60°C, 24 hours) to obtain an anion exchange resin precursor polymer C6 represented by the following formula with a yield of 98%. 17 PA (pale yellow solid).

[0190] [Chemistry 56]

[0191] (Quaternization reaction and film formation) Add anion exchange resin precursor polymer C6 to a 100 mL eggplant flask. 17 PA (1.52 g), N,N-dimethylacetamide (21.3 mL). The mixture was stirred at 50°C to form a uniform solution, and then dimethylsulfuric acid (6.87 mL, 72.4 mmol) was added and reacted at 50°C for 48 hours. The reaction solution was added dropwise to pure water to stop the reaction. The precipitate recovered from the mixture by filtration was washed with pure water and then vacuum dried (50°C, 24 hours) to obtain anion exchange resin QC6 17PA (light yellow solid). Add the obtained anion exchange resin QC6 to the eggplant-shaped flask 17 PA (about 180 mg) and N,N-dimethylacetamide (about 3.0 mL). The mixture was stirred to a uniform solution and then filtered. The filtrate was poured onto a glass plate bordered with silicone rubber and dried on a horizontally adjusted hot plate (45°C). Thus, an anion exchange resin QC6 represented by the following formula was obtained 17 PA membrane.

[0192] [Chemistry 57]

[0193] [Example 2: Anion exchange resin QC6 33 Synthesis of PA (IEC = 1.6 meq. / g, q / (q+r)×100=33, m / (q+r+m)×100=38)] Using the above monomer 1, monomer 2 and monomer 5, the same method as above is adopted, and the amount of the reagent added is changed as needed, thereby obtaining anion exchange resin QC6 33 PA membrane.

[0194] [Example 3: Anion exchange resin QC6 50 Synthesis of PA (IEC = 1.7 meq. / g, q / (q+r)×100=50, m / (q+r+m)×100=38)] Using the above monomer 1, monomer 2 and monomer 5, the same method as above is adopted, and the amount of reagent added is changed as needed, thereby obtaining anion exchange resin QC6 50 PA membrane.

[0195] [Example 4: Anion exchange resin QC6 17 Synthesis of PA (IEC = 2.2 meq. / g, q / (q+r)×100=17, m / (q+r+m)×100=38)] Using the above monomer 1, monomer 2 and monomer 5, the same method as above is adopted, and the amount of the reagent added is changed as needed, thereby obtaining anion exchange resin QC6 17 PA membrane.

[0196] [Example 5: Anion exchange resin QC6 50 Synthesis of PA (IEC = 2.2 meq. / g, q / (q+r)×100=50, m / (q+r+m)×100=38)] Using the above monomer 1, monomer 2 and monomer 5, the same method as above is adopted, and the amount of the reagent added is changed as needed, thereby obtaining anion exchange resin QC6 50 PA membrane.

[0197] [Comparative Example 1: Synthesis of anion exchange resin QPAF-4 (IEC = 1.5 meq. / g, q / (q+r)×100=0, m / (q+r+m)×100=38)] The above-mentioned monomer 2 and monomer 5 were used in the same manner as above, and the amount of reagent added was changed as necessary to obtain a membrane of an anion exchange resin QPAF-4 represented by the following formula.

[0198] [Chemistry 58]

[0199] [Comparative Example 2: Synthesis of anion exchange resin QPAF-4 (IEC = 2.0 meq. / g, q / (q+r)×100=0, m / (q+r+m)×100=38)] The above-mentioned monomer 2 and monomer 5 are used in the same manner as above, and the amount of reagent added is changed as necessary, thereby obtaining a membrane of the anion exchange resin QPAF-4 represented by the above-mentioned formula.

[0200] <Gas Permeability> The permeability of hydrogen and oxygen was measured for the membranes of the anion exchange resin obtained in the examples and comparative examples. Specifically, the membranes of the anion exchange resin obtained in the examples and comparative examples were cut into membranes with a width of 4.5 cm and a length of 4.5 cm as measurement samples. The measurement device used a gas permeability measurement device (manufactured by GTR TEC, trade name: GTR-20TXFYC). A test gas (hydrogen or oxygen) was passed through the upper part of the membrane, and a carrier gas (argon when the test gas was hydrogen, and helium when the test gas was oxygen) was passed through the lower part of the membrane. The test gas that permeated the membrane was measured together with the carrier gas using gas chromatography (manufactured by Yanaco Analytical Systems, trade name: G2700). The gas permeability P (cm 3 (STP) cm s -1 cm -2 cmHg -1 ) is calculated from the battery temperature T(K), the volume of the permeated gas q(cm 3 ), film thickness d (cm), time to pass through the measuring tube t (s), permeation area a (cm 2 ), the partial pressure p (cmHg) of the test gas is calculated by the following formula. P=(273 / T)×((q×d) / (t×a×p))

[0201] The results of hydrogen permeability are as follows Figure 1As shown. In Comparative Example 1, Example 1, Example 2, and Example 3 having low IEC, the hydrogen permeability showed values ​​of the same degree. On the other hand, the results of oxygen permeability were as follows Figure 2 As shown. In Comparative Example 1, Example 1, Example 2, and Example 3 having low IEC, the oxygen permeability tends to increase with the increase in the hydrophobic unit (a) ratio (q / (q+r)×100). Example 3 having the maximum hydrophobic unit (a) ratio (q / (q+r)×100=50) shows an oxygen permeability that is about 3.2 times higher than that of Comparative Example 1 that does not contain a hydrophobic unit (a). Examples 4 and 5 having high IEC show a hydrogen permeability that is about 8 to 25 times higher and an oxygen permeability that is 14 to 19 times higher than that of Examples 1, Example 2, and Example 3 having low IEC.

[0202] <Anion conductivity> The hydroxide ion conductivity of the anion exchange resin membrane obtained in the examples and comparative examples was measured. Specifically, the anion exchange resin membrane obtained in the examples and comparative examples was cut into a membrane with a width of 1 cm and a length of 4 cm as a measurement sample, and immersed in a 1M potassium hydroxide aqueous solution (80°C) for 48 hours to form a hydroxide ion type. The sample taken out from the 1M potassium hydroxide aqueous solution (80°C) was washed with degassed pure water, and then the hydroxide ion conductivity was measured in degassed pure water by a four-terminal method (300mV, 10-100000Hz) using alternating current. The measuring device used was Solartolon 1255B / 1287, and the probe used was a φ1mm gold wire. Hydroxide ion conductivity σ (S·cm -1 ) is determined by the distance between the probes L (1 cm), the impedance Z (Ω), the cross-sectional area A (cm 2 ), calculated by the following formula. σ=(L / Z)×1 / A

[0203] The results are as follows Figure 3 As shown. In Comparative Example 1, Example 1, Example 2, and Example 3 having low IEC, Example 2 and Example 3 having large hydrophobic unit (a) ratios (q / (q+r)×100) show high hydroxide ion conductivity compared to Comparative Example 1 not containing a hydrophobic unit (a). Example 4 and Example 5 having high IEC show high hydroxide ion conductivity compared to Example 1 and Example 3 having low IEC. Example 5 having the largest hydrophobic unit (a) ratio (q / (q+r)×100=50) shows about twice as high hydroxide ion conductivity as Comparative Example 2 not containing a hydrophobic unit (a).

[0204] <Water content> The water content of the anion exchange resin membrane obtained in the examples and comparative examples was measured. Specifically, the anion exchange resin membrane obtained in the examples and comparative examples was cut into a membrane with a width of 1 cm and a length of 4 cm as a measurement sample, and immersed in a 1M potassium hydroxide aqueous solution (80°C) for 48 hours to form a hydroxide ion type. The water content (%) is calculated by the water-containing membrane mass: W wet (g) Dry film mass: W dry (g) is calculated by the following formula. Moisture content (%) = ((W wet -W dry ) / W dry )×100 W wet It is obtained by the following method: After washing the sample taken out from 1M potassium hydroxide aqueous solution (80°C) with degassed pure water, immerse the sample in pure water for more than 24 hours, wipe off the water droplets on the surface of the sample with a paper towel, quickly transfer it to a pre-weighed sample test tube bottle, weigh it with the lid closed, and calculate the difference. W dry The molecular weight is determined by vacuum drying a sample containing water (50° C.) overnight, quickly transferring it to a sample test tube bottle weighed in advance, weighing it with the lid closed, and calculating the difference.

[0205] The results are as follows Figure 4 As shown. In Comparative Example 1, Example 1, Example 2, and Example 3 having low IEC, the water content tends to decrease as the hydrophobic unit (a) ratio (q / (q+r)×100) increases. Example 3 having the maximum hydrophobic unit (a) ratio (q / (q+r)×100=50) shows a water content that is about 1 / 2 times lower than that of Comparative Example 1 that does not contain a hydrophobic unit (a). In Comparative Example 2, Example 4, and Example 5 having high IEC, the water content tends to decrease as the hydrophobic unit (a) ratio (q / (q+r)×100) increases. Example 5 having the maximum hydrophobic unit (a) ratio (q / (q+r)×100=50) shows a water content that is about 1 / 3 times lower than that of Comparative Example 2 that does not contain a hydrophobic unit (a).

[0206] As described above, it is understood that the anion exchange resin obtained in Examples has superior electrical properties (high anion conductivity) and chemical properties (high air permeability and low water content) as compared with the anion exchange resin obtained in Comparative Examples.

[0207] This specification discloses at least the following inventions. [1] An anion exchange resin, characterized in that it comprises: A divalent hydrophobic group (a) comprising a bisphenol residue represented by the following formula (1): a divalent hydrophobic group (b) consisting of a single aromatic ring, or consisting of a plurality of aromatic rings bonded to each other via 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 carbon-carbon bond, and A divalent hydrophilic group, which is composed of a single aromatic ring, or a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the aromatic ring is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms; The anion exchange resin has: The hydrophobic unit (a) is composed of the hydrophobic group (a) monomer, or is composed of the hydrophobic group (a) repeated via an ether bond, a thioether bond or a carbon-carbon bond, A hydrophobic unit (b), which is composed of the hydrophobic group (b) monomer, or the hydrophobic group (b) is repeated via an ether bond, a thioether bond or a carbon-carbon bond, and A hydrophilic unit, which is composed of the hydrophilic group monomer, or is composed of the hydrophilic group repeated via an ether bond, a thioether bond or a carbon-carbon bond; The hydrophobic unit (a), the hydrophobic unit (b), and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. [2] The anion exchange resin according to [1], wherein the hydrophobic group (a) contains a bisphenol residue represented by the formula (1'). [3] The anion exchange resin according to [1] or [2], wherein the hydrophobic group (b) contains a bisphenol residue represented by the formula (2). [4] The anion exchange resin according to [3], wherein the hydrophobic group (b) contains a bisphenol residue represented by the formula (2'). [5] The anion exchange resin according to [1] or [2], wherein the hydrophobic group (b) contains a bisphenol residue represented by the formula (3). [6] The anion exchange resin according to [5], wherein the hydrophobic group (b) contains a bisphenol residue represented by the formula (3'). [7] An anion exchange resin as described in any one of [1] to [6], characterized in that the hydrophilic group is composed of a single polycyclic compound, or is composed of a plurality of polycyclic compounds bonded to each other via a connecting group and / or a carbon-carbon bond, the connecting group is a divalent hydrocarbon group, 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, and at least one of the connecting group or the polycyclic compound is bonded to the anion exchange group via a divalent saturated hydrocarbon group having at least 2 carbon atoms. [8] The anion exchange resin according to [7], wherein the hydrophilic group is a fluorene residue represented by the formula (4). [9] An electrolyte membrane comprising the anion exchange resin according to any one of [1] to [8].

[10] A binder for forming an electrode catalyst layer, comprising the anion exchange resin according to any one of [1] to [8].

[11] A battery electrode catalyst layer, characterized by containing the binder for forming an electrode catalyst layer according to

[10] .

Claims

1. Anion exchange resin, characterized in that Include: A divalent hydrophobic group (a) comprising a bisphenol residue represented by the following formula (1): a divalent hydrophobic group (b) consisting of a single aromatic ring, or consisting of a plurality of aromatic rings bonded to each other via 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 carbon-carbon bond, and A divalent hydrophilic group, which is composed of a single aromatic ring, or a plurality of aromatic rings bonded to each other via a linking group and / or a carbon-carbon bond, wherein the linking group is a divalent hydrocarbon group, 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, and at least one of the linking group or the aromatic ring is bonded to an anion exchange group via a divalent saturated hydrocarbon group having 2 or more carbon atoms; The anion exchange resin has: The hydrophobic unit (a) is composed of the hydrophobic group (a) monomer, or is composed of the hydrophobic group (a) repeated via an ether bond, a thioether bond or a carbon-carbon bond, A hydrophobic unit (b), which is composed of the hydrophobic group (b) monomer, or the hydrophobic group (b) is repeated via an ether bond, a thioether bond or a carbon-carbon bond, and A hydrophilic unit, which is composed of the hydrophilic group monomer, or is composed of the hydrophilic group repeated via an ether bond, a thioether bond or a carbon-carbon bond; The hydrophobic unit (a), the hydrophobic unit (b) and the hydrophilic unit are bonded via an ether bond, a thioether bond or a carbon-carbon bond, In the formula, Alk represents an alkyl group or an aryl group which is the same as or different from each other, R represents a divalent hydrocarbon group which forms an alicyclic structure, and a, b, c and d represent an integer of 0 to 4 which is the same as or different from each other.

2. The anion exchange resin according to claim 1, characterized in that The hydrophobic group (a) contains a bisphenol residue represented by the following formula (1'): In the formula, l represents an integer greater than or equal to 2.

3. The anion exchange resin according to claim 1, characterized in that The hydrophobic group (b) contains a bisphenol residue represented by the following formula (2): In the formula, Alk' represents an alkyl group or an aryl group which is the same as or different from each other, a', b', c' and d' represent an integer of 0 to 4 which is the same as or different from each other, and l' represents an integer of 1 or more.

4. The anion exchange resin according to claim 3, characterized in that The hydrophobic group (b) contains a bisphenol residue represented by the following formula (2'): In the formula, l' represents an integer greater than 1.

5. The anion exchange resin according to claim 1, characterized in that The hydrophobic group (b) contains a bisphenol residue represented by the following formula (3): In the formula, Alk" represents an alkyl group or an aryl group which is the same as or different from each other, a", b", c" and d" represent integers of 0 to 4 which are the same as or different from each other, and l" represents an integer greater than 1.

6. The anion exchange resin according to claim 5, characterized in that The hydrophobic group (b) contains a bisphenol residue represented by the following formula (3'): In the formula, "1" represents an integer greater than 1.

7. The anion exchange resin according to claim 1, characterized in that The hydrophilic group is composed of a single polycyclic compound, or is composed of a plurality of polycyclic compounds bonded to each other via a connecting group and / or a carbon-carbon bond, wherein the connecting group is a divalent hydrocarbon group, 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, and at least one of the connecting group or the polycyclic compound is bonded to the anion exchange group via a divalent saturated hydrocarbon group having a carbon number of 2 or more.

8. The anion exchange resin according to claim 7, characterized in that The hydrophilic group is a fluorene residue represented by the following formula (4): In the formula, A is the same as or different from each other and represents a group containing an anion exchange group or a cyclic structure containing an anion exchange group.

9. An electrolyte membrane, characterized in that Contains the anion exchange resin according to any one of claims 1 to 8.

10. A binder for forming an electrode catalyst layer, characterized in that: Contains the anion exchange resin according to any one of claims 1 to 8.

11. A battery electrode catalyst layer, characterized in that: Contains the binder for forming an electrode catalyst layer according to claim 10.

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