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

Abstract

To provide an anion exchange resin capable of producing an electrolyte membrane, a binder for forming electrode catalyst layers, and a battery electrode catalyst layer, featuring superior chemical characteristic; an electrolyte membrane and a binder for forming electrode catalyst layers that are formed from the anion exchange resin; and a battery electrode catalyst layer that is formed from the binder for forming electrode catalyst layers.SOLUTION: The present invention employs an anion exchange resin 4-QPPAF-TMA, for example, represented by the following formula, the anion exchange resin having a hydrophobic group composed of a polycyclic part and a linkage part, and a hydrophilic group composed of a polycyclic part and a linkage part.SELECTED DRAWING: Figure 1

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 technology]

[0002] a divalent hydrophobic group consisting of 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 plurality of aromatic rings bonded to each other via carbon-carbon bonds, and a single polycyclic compound, or a linking group which 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 / or a plurality of polycyclic compounds bonded to each other via carbon-carbon bonds, wherein at least one of the linking group or the polycyclic compound is An anion exchange resin is known which is composed of a divalent hydrophilic group bonded to an anion exchange group via a divalent saturated hydrocarbon group having two or more carbon atoms, and which is composed of the hydrophobic group alone, or which has hydrophobic units repeated via ether bonds, thioether bonds, or carbon-carbon bonds, and the hydrophilic group alone, or which has hydrophilic units repeated via ether bonds, thioether bonds, or carbon-carbon bonds, and which is bonded to the hydrophilic units via ether bonds, thioether bonds, or carbon-carbon bonds. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2019-23258 A Summary of the Invention [Problem to be solved by the invention]

[0004] Although the anion exchange resin described in Patent Document 1 has excellent chemical properties (durability) and mechanical properties (flexibility of thin film), further improvement in chemical properties (durability, especially alkali resistance) is desired.

[0005] An object of the present invention is to provide an anion exchange resin capable of producing an electrolyte membrane having excellent chemical properties (durability, particularly alkali resistance), a binder for forming an electrode catalyst layer, and a battery electrode catalyst layer, an electrolyte membrane and a binder for forming an electrode catalyst layer formed from the anion exchange resin, and a battery electrode catalyst layer formed from the binder for forming an electrode catalyst layer. [Means for solving the problem]

[0006] In order to solve the above problems, the anion exchange resin of the present invention is A divalent hydrophobic group represented by the following formula (1), A divalent hydrophilic group represented by the following formula (2): It consists of: a hydrophobic unit consisting of the hydrophobic group alone or in which the hydrophobic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond; The hydrophilic group may be a hydrophilic unit consisting of a single hydrophilic group or a hydrophilic unit in which the hydrophilic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond. having The hydrophobic unit and the hydrophilic unit are bonded to each other via an ether bond, a thioether bond, or a carbon-carbon bond.

[0007] -R1-A1- (1) (In the formula, R1 is a single polycyclic compound, 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, or a divalent sulfur-containing group, or a plurality of polycyclic compounds bonded to each other via carbon-carbon bonds, and A1 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, which may be substituted with a halogen atom or a pseudohalide.)

[0008] -R2-A2- (2) (In the formula, R2 consists of a single polycyclic compound, or consists of a linking group which 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 / or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond, and at least one of the linking group or the polycyclic compounds is bonded to an anion exchange group-containing group, and A2 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 which may be substituted with a halogen atom or a pseudohalide.)

[0009] In the anion exchange resin of the present invention, it is preferable that R1 is represented by the following formula (R1') or the following formula (R1'').

[0010] [ka] (In the formula, l represents an integer of 1 or more.)

[0011] [ka] (In the formula, l represents an integer of 1 or more.)

[0012] The anion exchange resin of the present invention is preferably represented by the following formula (A1').

[0013] [ka] (In the formula, M1 and M1' are the same or different and are monovalent hydrocarbon groups which may be substituted with a halogen atom or a pseudohalide.)

[0014] In the anion exchange resin of the present invention, it is preferable that R2 is a fluorene residue represented by the following formula (R2').

[0015] [ka] (In the formula, A's may be the same or different and each represent an anion exchange group-containing group or a cyclic structure containing an anion exchange group.)

[0016] In the anion exchange resin of the present invention, it is preferable that A2 is represented by the following formula (A2'):

[0017] [ka] (In the formula, M2 and M2' are the same or different and each is a monovalent hydrocarbon group optionally substituted with a halogen atom or a pseudohalide.)

[0018] In order to solve the above problems, the electrolyte membrane of the present invention is characterized by containing the above anion exchange resin.

[0019] In order to solve the above problems, the binder for forming an electrode catalyst layer of the present invention is characterized by containing the above anion exchange resin.

[0020] In order to solve the above problems, the battery electrode catalyst layer of the present invention is characterized by including the above-mentioned binder for forming an electrode catalyst layer. Effect of the Invention

[0021] According to the present invention, it is possible to provide an anion exchange resin with which an electrolyte membrane having excellent chemical properties, a binder for forming an electrode catalyst layer, and a battery electrode catalyst layer can be produced, an electrolyte membrane and a binder for forming an electrode catalyst layer formed from the anion exchange resin, and a battery electrode catalyst layer formed from the binder for forming an electrode catalyst layer. [Brief description of the drawings]

[0022] [Figure 1] 1 is a graph showing the results of a durability test of the anion exchange resin membranes obtained in the Examples and Comparative Examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The anion exchange resin of the present invention comprises a divalent hydrophobic group and a divalent hydrophilic group.

[0024] In the anion exchange resin of the present invention, the divalent hydrophobic group has a structure represented by the following formula (1).

[0025] -R1-A1- (1) (In the formula, R1 is a single polycyclic compound, 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, or a divalent sulfur-containing group, or a plurality of polycyclic compounds bonded to each other via carbon-carbon bonds, and A1 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, which may be substituted with a halogen atom or a pseudohalide.)

[0026] In the above formula (1), R1 is a polycyclic moiety of a hydrophobic group, and is composed of a single polycyclic compound, or 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, or is a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond. R1 is preferably composed of a single polycyclic compound, or is a plurality of polycyclic compounds bonded to each other via a divalent hydrocarbon group.

[0027] The polycyclic compound may have a structure in which a plurality of aromatic rings are conjugated, and examples thereof include a biphenyl ring, a terphenyl ring, a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, a carbazole ring, and an indole ring, and preferably a biphenyl ring or a fluorene ring.

[0028] Furthermore, the polycyclic compound may be substituted with a substituent such as a halogen atom, an alkyl group, an aryl 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. Examples of the pseudohalide include a trifluoromethyl group, -CN, -NC, -OCN, -NCO, -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, and -N3. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, such as 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; and a cycloalkyl group having 1 to 20 carbon atoms, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and a fluorenyl group.

[0029] In addition, when a polycyclic compound is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide, the number and positions of the substituents such as a halogen atom, an alkyl group, an aryl group, or a pseudohalide are appropriately set depending on the purpose and application.

[0030] More specific examples of polycyclic compounds substituted with halogen atoms include biphenyl rings or fluorene rings substituted with 1 to 4 halogen atoms (e.g., a biphenyl ring or fluorene ring substituted with 1 to 4 fluorines, a biphenyl ring or fluorene ring substituted with 1 to 4 chlorines, a biphenyl ring or fluorene ring substituted with 1 to 4 bromines, a biphenyl ring or fluorene ring substituted with 1 to 4 iodines, etc., where the 1 to 4 halogen atoms may be the same or different).

[0031] Examples of the divalent hydrocarbon group include divalent saturated hydrocarbon groups having 1 to 20 carbon atoms, such as methylene (-CH2-), ethylene, propylene, i-propylene (-C(CH3)2-), butylene, i-butylene, sec-butylene, pentylene (pentene), i-pentylene, sec-pentylene, hexylene (hexamethylene), 3-methylpentene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, i-decylene, dodecylene, tetradecylene, hexadecylene, and octadecylene.

[0032] The divalent hydrocarbon group may be substituted with a monovalent residue in an aromatic ring. Examples of the aromatic ring include monocyclic or polycyclic compounds having 6 to 14 carbon atoms, such as a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring, and heterocyclic compounds such as an azole, an oxole, a thiophene, an oxazole, a thiazole, and a pyridine. Examples of the aromatic ring include monocyclic aromatic hydrocarbons having 6 to 14 carbon atoms, and more preferably a benzene ring.

[0033] The divalent hydrocarbon group may be substituted with a substituent such as the above halogen atom, the above alkyl group, the above aryl group, the above pseudohalide, etc. When the divalent hydrocarbon group is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, a pseudohalide, etc., the number and positions of the substituents such as the halogen atom, the alkyl group, the aryl group, the pseudohalide, etc. are appropriately set depending on the purpose and application.

[0034] R1 is more preferably represented by the following formula (R1') or (R1'').

[0035] [ka] (In the formula, l represents an integer of 1 or more.)

[0036] [ka] (In the formula, l represents an integer of 1 or more.)

[0037] In the above formula (R1′) and formula (R1″), l represents an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 2 to 6.

[0038] Other examples of R1 include those having the following structures:

[0039] [ka] (In the formula, Alk and Alk′ represent a monovalent hydrocarbon group.)

[0040] Examples of the monovalent hydrocarbon group include monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, pentyl, i-pentyl, sec-pentyl, hexyl, 3-methylpentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, i-decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl.

[0041] In the above formula (1), A1 is a connecting portion of a hydrophobic group, and 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, which may be substituted with a halogen atom or a pseudohalide. A1 is preferably a divalent hydrocarbon group which may be substituted with a halogen atom or a pseudohalide.

[0042] The divalent hydrocarbon group includes the divalent hydrocarbon groups described above.

[0043] A1 is more preferably represented by the following formula (A1').

[0044] [ka] (In the formula, M1 and M1' are the same or different and each is a monovalent hydrocarbon group which may be substituted with a halogen atom or a pseudohalide.)

[0045] Examples of the monovalent hydrocarbon group include monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms, such as methyl, ethyl, propyl, i-propyl, butyl, i-butyl, sec-butyl, pentyl, i-pentyl, sec-pentyl, hexyl, 3-methylpentyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, i-decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl.

[0046] The monovalent hydrocarbon group may be substituted with a monovalent residue in an aromatic ring. Examples of the aromatic ring include monocyclic or polycyclic compounds having 6 to 14 carbon atoms, such as a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring, and heterocyclic compounds such as an azole, an oxole, a thiophene, an oxazole, a thiazole, and a pyridine. Examples of the aromatic ring include monocyclic aromatic hydrocarbons having 6 to 14 carbon atoms, and more preferably a benzene ring.

[0047] The halogen atoms and pseudohalides include those described above.

[0048] The monovalent hydrocarbon group may be substituted with a substituent such as the above halogen atom, the above alkyl group, the above aryl group, the above pseudohalide, etc. When the monovalent hydrocarbon group is substituted with a substituent such as a halogen atom, an alkyl group, an aryl group, a pseudohalide, etc., the number and positions of the substituents such as the halogen atom, the alkyl group, the aryl group, the pseudohalide, etc. are appropriately set depending on the purpose and application.

[0049] The above formula (A1') is particularly preferably represented by the following formula (A 1a '), the following formula (A 1b '), or the following formula (A 1c ').

[0050] [ka]

[0051] In the anion exchange resin of the present invention, the divalent hydrophilic group has a structure represented by the following formula (2).

[0052] -R2-A2- (2) (In the formula, R2 consists of a single polycyclic compound, or consists of a linking group which 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 / or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond, and at least one of the linking group or the polycyclic compounds is bonded to an anion exchange group-containing group, and A2 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 which may be substituted with a halogen atom or a pseudohalide.)

[0053] In the above formula (2), R2 is a polycyclic portion of a hydrophilic group, and is composed of a single polycyclic compound, or a linking group that 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 / or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond, and at least one of the linking group or the polycyclic compounds is bonded to an anion exchange group-containing group. R2 is preferably composed of a single polycyclic compound bonded to an anion exchange group-containing group.

[0054] The polycyclic compound may be the polycyclic compound described above, and is preferably a fluorene ring.

[0055] The divalent hydrocarbon group includes the divalent hydrocarbon groups described above.

[0056] The anion-exchange group-containing group may be an anion-exchange group alone, or may be an anion-exchange group bonded via a divalent saturated hydrocarbon group.

[0057] The anion exchange group-containing group may be bonded to at least one of the linking groups or polycyclic compounds of the divalent hydrophilic residue, may be bonded to multiple linking groups or polycyclic compounds, or may be bonded to all of the linking groups or polycyclic compounds. In addition, multiple anion exchange groups may be bonded to one linking group or polycyclic compound.

[0058] The anion exchange group is introduced into the side chain of the hydrophilic group, and specifically, there is no particular limitation, and any of the known anion exchange groups can be used, such as a quaternary ammonium group, a tertiary amino group, a secondary amino group, a primary amino group, a phosphine, a phosphazene, a tertiary sulfonium group, a quaternary boronium group, a quaternary phosphonium group, a guanidium group, etc. From the viewpoint of anion conductivity, a quaternary ammonium group is preferable.

[0059] The anion exchange group is preferably -N +(CH3)3, but also those having the following structure: In the following structural formulas, * indicates the part bonded to the aromatic ring containing the substituent.

[0060] [ka] (In the diagram, Alk, Alk', and Alk'' represent the monovalent hydrocarbon groups described above, and iPr represents an i-propyl group.)

[0061] Preferred examples of the divalent saturated hydrocarbon group include linear 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-).

[0062] R2 is more preferably a fluorene residue represented by the following formula (R2').

[0063] [ka] (In the formula, A's may be the same or different and each represent an anion exchange group-containing group or a cyclic structure containing an anion exchange group.)

[0064] Particularly preferably, R2 is represented by the following formula (R 2a ), the following formula (R 2b ), the following formula (R 2c ), or the following formula (R 2d ) are included.

[0065] [ka]

[0066] In the above formula (2), A2 is a connecting portion of a hydrophilic group, and 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, which may be substituted with a halogen atom or a pseudohalide. A2 is preferably a divalent hydrocarbon group which may be substituted with a halogen atom or a pseudohalide.

[0067] The divalent hydrocarbon group includes the divalent hydrocarbon groups described above.

[0068] A2 is more preferably represented by the following formula (A2').

[0069] [ka] (In the formula, M2 and M2' are the same or different and each is a monovalent hydrocarbon group optionally substituted with a halogen atom or a pseudohalide.)

[0070] The monovalent hydrocarbon group includes the monovalent hydrocarbon group described above. The halogen atom and pseudohalide include the halogen atom and pseudohalide described above.

[0071] The above formula (A2') is particularly preferably represented by the following formula (A 2a '), the following formula (A 2b '), or the following formula (A 2c ').

[0072] [ka]

[0073] The anion exchange resin of the present invention has a hydrophobic unit consisting of the above-mentioned hydrophobic group or the above-mentioned hydrophobic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond, and a hydrophilic unit consisting of the above-mentioned hydrophilic group alone or the above-mentioned hydrophilic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond. The hydrophobic unit is preferably consisting of the hydrophobic group alone or the hydrophobic group is repeated via a carbon-carbon bond, and the hydrophilic unit is preferably consisting of the hydrophilic group alone or the hydrophilic group is repeated via a carbon-carbon bond.

[0074] The unit corresponds to a block of a commonly used block copolymer.

[0075] The hydrophobic unit is preferably a unit formed by bivalent hydrophobic groups represented by the above formula (1) bonding to each other via a carbon-carbon bond. A unit formed by a plurality of types of bivalent hydrophobic groups represented by the above formula (1) bonding to each other in a random or alternating order or in a block form may also be used.

[0076] Such a hydrophobic unit is represented, for example, by the following formula (3).

[0077] [ka] (In the formula, R1 and A1 are defined as R1 and A1 in the above formula (1), and q represents the number of repetitions and is 1 to 200.)

[0078] In the above formula (3), q represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0079] More preferably, such a hydrophobic unit is a unit formed by bonding together via a carbon-carbon bond, in which, in the above formula (1), R1 is represented by the above formula (R1') or (R1''), and A1 is a divalent hydrophobic group represented by the above formula (A1').

[0080] Such a hydrophobic unit may be a unit represented by the following formula (3') or (3'').

[0081] [ka] (In the formula, l has the same meaning as l in the above formula (R1'), M1 and M1' have the same meaning as M1 and M1' in the above formula (A1'), and q represents the number of repetitions and is 1 to 200.)

[0082] [ka] (In the formula, l has the same meaning as l in the above formula (R1″), M1 and M1′ have the same meaning as M1 and M1′ in the above formula (A1′), and q represents the number of repetitions and is 1 to 200.)

[0083] In the above formula (3′) and formula (3″), q represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0084] The hydrophilic unit is preferably a unit formed by bivalent hydrophilic groups represented by the above formula (2) bonded to each other via a carbon-carbon bond. A unit formed by a plurality of types of bivalent hydrophilic groups represented by the above formula (2) bonded to each other in a random or alternating order or in a block form may also be used.

[0085] Such a hydrophilic unit is represented, for example, by the following formula (4).

[0086] [ka] (In the formula, R2 and A2 are defined as the same as R2 and A2 in the above formula (2), and m represents the number of repetitions and is 1 to 200.)

[0087] In the above formula (4), m represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0088] More preferably, such a hydrophilic unit is a unit formed by bonding together via a carbon-carbon bond in the above formula (2), where R2 is represented by formula (R2') and A1 is a divalent hydrophilic group represented by the above formula (A2').

[0089] An example of such a hydrophilic unit is a unit represented by the following formula (4').

[0090] [ka] (In the formula, A has the same meaning as A in the above formula (R2'), M2 and M2' have the same meaning as M2 and M2' in the above formula (A2'), and m represents the number of repetitions and is 1 to 200.)

[0091] In the above formula (4′), m represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0092] Particularly preferred examples of such hydrophilic units include units represented by the following formula (4a'), (4b'), (4c'), or (4d').

[0093] [ka] (In the formula, M2 and M2' are defined as M2 and M2' in the above formula (4'), and m represents the number of repetitions and is 1 to 200.)

[0094] In the above formulae (4a'), (4b'), (4c'), and (4d'), m represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0095] In the anion exchange resin of the present invention, the hydrophobic unit and the hydrophilic unit are bonded to each other via an ether bond, a thioether bond, or a carbon-carbon bond. In particular, it is preferable that the hydrophobic unit and the hydrophilic unit are bonded to each other via a carbon-carbon bond.

[0096] As such an anion exchange resin, preferably, as shown in the following formula (5), a hydrophobic unit represented by the above formula (3) and a hydrophilic unit represented by the above formula (4) are bonded via a carbon-carbon bond are mentioned.

[0097] [ka] (In the formula, R1 and A1 are the same as R1 and A1 in the above formula (3), R2 and A2 are the same as R2 and A2 in the above formula (4), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0098] In the above formula (5), q and m represent a compounding ratio or a repeating number, and may be the same or different and represent, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0099] In the above formula (5), o represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0100] More preferred examples of such anion exchange resin include an anion exchange resin in which a hydrophobic unit represented by the above formula (3') and a hydrophilic unit represented by the above formula (4') are bonded via a carbon-carbon bond as shown in the following formula (5'), and an anion exchange resin in which a hydrophobic unit represented by the above formula (3'') and a hydrophilic unit represented by the above formula (4') are bonded via a carbon-carbon bond as shown in the following formula (5'').

[0101] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3'), A, M2, and M2' are the same as A, M2, and M2' in the above formula (4'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0102] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3''); A, M2, and M2' are the same as A, M2, and M2' in the above formula (4'); q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200; and o represents a repeating number, which represents 1 to 200.)

[0103] In the above formula (5') and formula (5''), q and m represent a compounding ratio or a repeating number, and are the same or different and represent, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0104] In the above formula (5′) and formula (5″), o represents the number of repetitions and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0105] More preferred examples of such an anion exchange resin include an anion exchange resin in which the hydrophobic unit represented by the above formula (3') and the hydrophilic unit represented by the above formula (4a') are bonded via a carbon-carbon bond as shown in the following formula (5a'); an anion exchange resin in which the hydrophobic unit represented by the above formula (3') and the hydrophilic unit represented by the above formula (4b') are bonded via a carbon-carbon bond as shown in the following formula (5b'); an anion exchange resin in which the hydrophobic unit represented by the above formula (3') and the hydrophilic unit represented by the above formula (4b') are bonded via a carbon-carbon bond as shown in the following formula (5c'); and an anion exchange resin in which the hydrophobic unit represented by the above formula (3') and the hydrophilic unit represented by the above formula (4c') are bonded via a carbon-carbon bond as shown in the following formula (5d'). Examples of the anion exchange resin include an anion exchange resin in which the hydrophobic unit represented by the above formula (3'') and the hydrophilic unit represented by the above formula (4a') are bonded via a carbon-carbon bond as shown in the following formula (5a''); an anion exchange resin in which the hydrophobic unit represented by the above formula (3'') and the hydrophilic unit represented by the above formula (4b') are bonded via a carbon-carbon bond as shown in the following formula (5b''); an anion exchange resin in which the hydrophobic unit represented by the above formula (3'') and the hydrophilic unit represented by the above formula (4c') are bonded via a carbon-carbon bond as shown in the following formula (5c''); and an anion exchange resin in which the hydrophobic unit represented by the above formula (3'') and the hydrophilic unit represented by the above formula (4d') are bonded via a carbon-carbon bond as shown in the following formula (5d'').

[0106] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3'), M2 and M2' are the same as M2 and M2' in the above formula (4a'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0107] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3'), M2 and M2' are the same as M2 and M2' in the above formula (4b'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0108] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3'), M2 and M2' are the same as M2 and M2' in the above formula (4c'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0109] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3'), M2 and M2' are the same as M2 and M2' in the above formula (4d'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0110] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3''), M2 and M2' are the same as M2 and M2' in the above formula (4a'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0111] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3''), M2 and M2' are the same as M2 and M2' in the above formula (4b'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0112] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3''), M2 and M2' are the same as M2 and M2' in the above formula (4c'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0113] [ka] (In the formula, l, M1, and M1' are the same as l, M1, and M1' in the above formula (3''), M2 and M2' are the same as M2 and M2' in the above formula (4d'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0114] In the above formula (5a'), (5b'), (5c'), (5s'), (5a'', (5b'', (5c'', and (5d'',), q and m represent a compounding ratio or a repeating number, and are the same or different and represent, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0115] In the above formula (5a'), formula (5b'), formula (5c'), formula (5s'), formula (5a'', formula (5b'', formula (5c'', and formula (5d'', o represents the number of repeats and is, for example, 1 to 200, preferably 1 to 100, and more preferably 1 to 50.

[0116] As described above, the number average molecular weight of such an anion exchange resin is, for example, 10 to 1000 kDa, or preferably 30 to 500 kDa.

[0117] The method for producing the anion exchange resin is not particularly limited, and any known method can be used. Preferably, a method using a polymerization reaction of an aromatic ring compound with a super acid such as trifluoromethanesulfonic acid is used.

[0118] When producing an anion exchange resin by this method, for example, a monomer for forming a hydrophobic group polycyclic portion to form the above R1, a monomer for forming a hydrophobic group connecting portion to form the above A1, a monomer for forming a hydrophilic group polycyclic portion having an anion exchange group precursor functional group to form the above R2, and a monomer for forming a hydrophilic group connecting portion to form the above A2 are prepared, and these are polymerized to synthesize a polymer, and the anion exchange group precursor functional group in the polymer is ionized, thereby producing the anion exchange resin.

[0119] Alternatively, particularly when A1 and A2 are the same group, a polymer can be synthesized by polymerizing a monomer for forming a hydrophobic polycyclic portion to form R1, a monomer for forming a hydrophilic polycyclic portion having an anion exchange group precursor functional group to form R2, and a monomer for forming a connecting portion to form A1 and A2, and the anion exchange resin can be produced by ionizing the anion exchange group precursor functional group in the polymer.

[0120] Preferred examples of the hydrophobic group polycyclic moiety forming monomer for forming the above R1 include a compound represented by the following formula (11) which corresponds to the above formula (R1'), and a compound represented by the following formula (11') which corresponds to the above formula (R1'').

[0121] [ka] (In the formula, l has the same meaning as l in the above formula (R1').)

[0122] [ka] (In the formula, l has the same meaning as l in the above formula (R1″).)

[0123] As the hydrophobic group connector forming monomer for forming the above A1, a compound represented by the following formula (12) corresponding to the above formula (A1') can be preferably mentioned.

[0124] [ka] (In the formula, M1 and M1' have the same meanings as M1 and M1' in the above formula (A1').)

[0125] As a monomer for forming a hydrophilic group polycyclic portion having an anion exchange group precursor functional group for forming the above R1, a compound represented by the following formula (13) corresponding to the above formula (R2') can be preferably mentioned.

[0126] [ka] (In the formula, Pre may be the same or different and represents an anion-exchange-group-containing precursor functional group or a cyclic structure containing an anion-exchange-group precursor functional group.)

[0127] As the hydrophobic group connector forming monomer for forming the above A2, a compound represented by the following formula (14) corresponding to the above formula (A2') can be preferably mentioned.

[0128] [ka] (In the formula, M2 and M2' have the same meanings as M2 and M2' in the above formula (A2').)

[0129] By subjecting the compound represented by the above formula (11), the compound represented by the above formula (12), the compound represented by the above formula (13), and the compound represented by the above formula (14) to a polymerization reaction, an anion exchange resin precursor polymer represented by the following formula (15) is obtained.

[0130] [ka] (In the formula, l has the same meaning as l in the above formula (11), M1 and M1' have the same meaning as M1 and M1' in the above formula (12), Pre has the same meaning as Pre in the above formula (13'), M2 and M2' have the same meaning as M2 and M2' in the above formula (14), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0131] By subjecting the compound represented by the above formula (11'), the compound represented by the above formula (12), the compound represented by the above formula (13), and the compound represented by the above formula (14) to a polymerization reaction, an anion exchange resin precursor polymer represented by the following formula (15') is obtained.

[0132] [ka] (In the formula, l has the same meaning as l in the above formula (11'), M1 and M1' have the same meaning as M1 and M1' in the above formula (12), Pre has the same meaning as Pre in the above formula (13'), M2 and M2' have the same meaning as M2 and M2' in the above formula (14), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0133] By subjecting the compound represented by the above formula (11), the compound represented by the above formula (13), and the compound represented by the above formula (12) to a polymerization reaction, an anion exchange resin precursor polymer represented by the following formula (16) is obtained.

[0134] [ka] (In the formula, l has the same meaning as l in the above formula (11), M1 and M1' have the same meaning as M1 and M1' in the above formula (12), Pre has the same meaning as Pre in the above formula (13'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0135] By subjecting the compound represented by the above formula (11'), the compound represented by the above formula (13), and the compound represented by the above formula (12) to a polymerization reaction, an anion exchange resin precursor polymer represented by the following formula (16') is obtained.

[0136] [ka] (In the formula, l has the same meaning as l in the above formula (11'), M1 and M2' have the same meaning as M1 and M2' in the above formula (12), Pre has the same meaning as Pre in the above formula (13'), q and m represent a compounding ratio or a repeating number, which may be the same or different, and represent 1 to 200, and o represents a repeating number, which represents 1 to 200.)

[0137] Next, in this method, the anion exchange group precursor functional group is ionized. The method for ionization is not particularly limited, and any known method can be used.

[0138] A known method can be used, for example, by dissolving an anion exchange resin precursor polymer in a solvent such as N,N-dimethylacetamide or dimethylsulfoxide, and ionizing the polymer using methyl iodide, dimethyl sulfate, or the like as an alkylating agent.

[0139] The reaction temperature in the ionization reaction is, for example, 0 to 100° C., or preferably 20 to 80° C., and the reaction time is, for example, 24 to 72 hours, or preferably 48 to 72 hours.

[0140] The anion exchange resin represented by the formula (5') is obtained by ionizing the anion exchange resin precursor polymer represented by the formula (15') above. The anion exchange resin represented by the formula (5'') is obtained by ionizing the anion exchange resin precursor polymer represented by the formula (15'') above.

[0141] The ion exchange group capacity of the anion exchange resin is, for example, 0.1 to 4.0 meq. / g, or preferably 0.6 to 3.0 meq. / g.

[0142] The ion exchange group capacity can be calculated by the following formula (24). [Ion exchange group capacity (meq. / g)] = amount of anion exchange group introduced 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 amount of ion exchange groups introduced is defined as the number of ion exchange groups per unit hydrophilic group, and 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.

[0143] Such an anion exchange resin is composed of a divalent hydrophobic group represented by the above formula (1) and a divalent hydrophilic group represented by the above formula (2), and is composed of the hydrophobic group alone, or the hydrophobic group has a hydrophobic unit repeated via an ether bond, a thioether bond, or a carbon-carbon bond, and the hydrophilic group alone, or the hydrophilic group has a hydrophilic unit repeated via an ether bond, a thioether bond, or a carbon-carbon bond, and the hydrophobic unit and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. Such an anion exchange resin has excellent chemical properties (durability).

[0144] In particular, when the hydrophilic group has a hydrophilic unit repeated via a carbon-carbon bond, it does not contain an ether bond, and therefore has excellent durability such as alkali resistance. More specifically, when the hydrophilic unit contains an ether bond, hydroxide ions (OH - ) decomposition may occur, and alkali resistance may be insufficient.

[0145] [ka]

[0146] In contrast, the hydrophilic units of anion exchange resins having hydrophilic units in which hydrophilic groups are repeated via carbon-carbon bonds do not contain ether bonds, and therefore decomposition by the above mechanism does not occur, resulting in excellent durability such as alkali resistance.

[0147] The present invention includes an electrolyte layer (electrolyte membrane) obtained by using such an anion exchange resin. The electrolyte membrane of the present invention is applicable to various electrochemical applications such as fuel cells, water electrolysis hydrogen generation devices, and electrochemical hydrogen pumps, but is particularly suitable for use in water electrolysis hydrogen generation devices. In fuel cells, electrochemical hydrogen pumps, and water electrolysis hydrogen generation devices, the electrolyte membrane is used in a configuration in which a catalyst layer, an electrode substrate, and a separator are laminated in sequence on both sides. Among these, an electrolyte membrane in which a catalyst layer and a gas diffusion substrate are laminated in sequence on both sides (a layer configuration of 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.

[0148] The electrolyte membrane may be made of the above-mentioned anion exchange resin (that is, the electrolyte membrane contains the above-mentioned anion exchange resin).

[0149] The electrolyte membrane can be reinforced with a known reinforcing material such as a porous substrate, and can be subjected to various treatments such as biaxial stretching for controlling molecular orientation, and heat treatment for controlling crystallinity and residual stress. A known filler can be added to the electrolyte membrane to increase its mechanical strength, and the electrolyte membrane can be composited with a reinforcing material such as a glass nonwoven fabric by pressing.

[0150] Furthermore, various additives that are commonly used in electrolyte membranes, such as a compatibilizer for improving compatibility, an antioxidant for preventing resin deterioration, and an antistatic agent or a lubricant for improving handleability in molding and processing into a film, may be appropriately contained within a range that does not affect processing and performance as an electrolyte membrane.

[0151] The thickness of the electrolyte membrane is not particularly limited and may be appropriately set depending on the purpose and application.

[0152] The electrolyte membrane has a thickness of, for example, 1.2 to 350 μm, or preferably 5 to 200 μm.

[0153] The present invention also includes a binder for forming an electrode catalyst layer containing the above-mentioned anion exchange resin, and a battery electrode catalyst layer containing the binder for forming an electrode catalyst layer. The above-mentioned anion exchange resin has excellent chemical properties (durability, especially alkali resistance), so that the use of the above-mentioned anion exchange resin as a binder for forming an electrode catalyst layer makes it easy to impart alkali resistance.

[0154] 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 an alcohol, thereby preparing the binder for forming the electrode catalyst layer.

[0155] The content 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.

[0156] Furthermore, by using the binder for forming an electrode catalyst layer in the formation of a catalyst layer of an electrode (cell electrode catalyst layer), the anion exchange resin can be contained in the catalyst layer (cell electrode catalyst layer).

[0157] Although the embodiment of the present invention has been described above, the embodiment of the present invention is not limited to this, and the design can be appropriately modified within the scope that does not change the gist of the present invention. EXAMPLES

[0158] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples.

[0159] Example 1: Synthesis of anion exchange resin 4-QPPAF-TMA (IEC=2.0 meq. / g) <Synthesis of Monomer 1> In a 300 mL round-bottom three-neck flask, 1-iodobiphenyl (5.0 g, 18 mmol), 1,6-diiodoperfluorohexane (5.2 g, 9.4 mmol), copper powder (5.3 g, 82 mmol), and dimethyl sulfoxide (100 mL) were added. This mixture was stirred at 125°C for 48 hours. The reaction solution was dropped into a 0.1 M aqueous nitric acid solution to stop the reaction. The precipitate collected by filtration from the mixture was washed with pure water, then with ethyl acetate and methanol, and the filtrate was collected. The filtrate was distilled under reduced pressure to obtain a solid, which was recrystallized (from ethyl acetate and methanol) and then vacuum dried to obtain Monomer 1 (white solid) represented by the following formula in a yield of 70%.

[0160] [ka]

[0161] <Synthesis of Monomer 2a> Fluorene (10 g, 60 mmol), 1,6-dibromohexane (22 g, 89 mmol), and tetrabutylammonium bromide (3.9 g, 12 mmol) were added to a 300 mL round-bottom three-neck flask. Pure water (120 mL) was added to this mixture, and nitrogen bubbling was performed. After 10 minutes, potassium hydroxide (60 g) was added and the reaction was carried out at 80°C for 8 hours. Pure water was added to the reaction solution to stop the reaction. The target product was extracted from the aqueous layer with dichloromethane, and then water, dichloromethane, and 1,6-dibromohexane were distilled off under reduced pressure. The crude product was purified by silica gel column chromatography (developing solvent: hexane and dichloromethane) and then vacuum dried to obtain Monomer 2 (yellow liquid) represented by the following formula in a yield of 40%.

[0162] [ka]

[0163] (Polymerization reaction) Monomer 1 (0.3 g, 0.5 mmol), monomer 2 (0.5 g, 1.0 mmol), and 1,1,1-trifluoroacetone (1.2 mL, 13 mmol) were added to a 50 mL round-bottom three-neck flask. Dichloromethane (5 mL) was added to this mixture under a nitrogen atmosphere and the mixture was stirred. The flask was immersed in an ice bath to cool the mixture, and trifluoromethanesulfonic acid (5 mL, 57 mmol) was slowly added to the mixture and reacted for 7 hours. The reaction mixture was diluted with dichloromethane, and the solid was crushed by ultrasonic treatment and dropped into methanol. The crude product was purified by reprecipitation (tetrahydrofuran and methanol) and then vacuum dried to obtain an anion exchange resin precursor polymer 4-PPAF-Br (white solid) represented by the following formula in a yield of 85%.

[0164] [ka]

[0165] (Quaternization reaction, membrane formation, ion exchange) 4-PPAF-Br (0.3 g) and tetrahydrofuran (20 mL) were added to a 50 mL round-bottom three-neck flask. A trimethylamine aqueous solution was added to this mixture, and when a precipitate formed, tetrahydrofuran was added. This operation was repeated three times. The reaction was carried out for 24 hours at room temperature under a nitrogen atmosphere. After distillation under reduced pressure, the anion exchange resin 4-QPPAF-TMA (IEC = 2.0 meq. / g, bromide ion type) was obtained by vacuum drying.

[0166] Anion exchange resin 4-QPPAF-TMA (bromide ion type) and N,N-dimethylacetamide were added to a 20 mL round-bottom three-neck flask. The mixture was stirred to make a homogeneous solution, and then filtered. The filtrate was poured onto a glass plate bordered with silicone rubber and dried on a hot plate adjusted to a horizontal position. The obtained anion exchange resin membrane was cut into a width of 1 cm and a length of 3 cm to be used as a measurement sample. The anion exchange resin membrane obtained above was immersed in a 1 M potassium hydroxide aqueous solution (80°C) for 48 hours, and then washed with degassed pure water to convert the counter ion of the ion exchange group (quaternary ammonium group) to a hydroxide ion. As a result, a membrane of anion exchange resin 4-QPPAF-TMA (IEC = 2.0 meq. / g, hydroxide ion type) represented by the following formula was obtained.

[0167] [ka]

[0168] Example 2: Synthesis of anion exchange resin 4-QPPAF-TMA (IEC=1.7 meq. / g) A membrane of anion exchange resin 4-QPPAF-TMA (IEC=1.7 meq. / g) was obtained in the same manner as in Example 1, by changing the amounts of reagents added as necessary.

[0169] Example 3: Synthesis of anion exchange resin 4-QPPAF-TMA (IEC=2.4 meq. / g) A membrane of anion exchange resin 4-QPPAF-TMA (IEC=2.4 meq. / g) was obtained in the same manner as in Example 1, by changing the amounts of reagents added as necessary.

[0170] Comparative Example 1: Synthesis of anion exchange resin QPAF-4 (IEC=1.5 meq. / g) <Synthesis of Monomer C1> 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-neck flask equipped with a nitrogen inlet and a cooling tube. After stirring the mixture to obtain a homogeneous solution, copper powder (9.53 g, 150 mmol) was added and the reaction was carried out at 120 ° C for 48 hours. The reaction solution was dropped into a 0.1 M aqueous nitric acid solution to stop the reaction. The precipitate collected by filtration from the mixture was washed with methanol, and the filtrate was collected. After repeating the same operation, pure water was added to the combined filtrate to collect the precipitated white solid by filtration, washed with a mixed solution of pure water and methanol (pure water / methanol = 1 / 1), and then vacuum dried overnight (60 ° C) to obtain Monomer C1 (white solid) represented by the following formula.

[0171] [ka]

[0172] <Synthesis of Monomer C2a> 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-neck flask. After stirring the mixture to obtain a homogeneous solution, 12 M hydrochloric acid (16.6 mL) was added and the reaction was carried out at room temperature for 24 hours. The precipitate collected by filtration from the reaction solution was washed with methanol and pure water, and then vacuum-dried overnight (60°C) to obtain Monomer C2a (white solid) represented by the following formula.

[0173] [ka]

[0174] <Synthesis of Monomer C2b> Monomer C2a (8.23 g, 35.0 mmol) and 1,6-dibromohexane (53 mL) were added to a 300 mL round-bottom three-neck flask. After stirring the mixture to obtain a homogeneous 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 the reaction was carried out at 80°C for 1 hour. Pure water was added to the reaction solution to stop the reaction. The target substance was extracted from the aqueous layer with dichloromethane, and the combined organic layer was washed with pure water and saline, after which 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 overnight (60°C) to obtain Monomer C2b (light yellow solid) represented by the following formula.

[0175] [ka]

[0176] <Synthesis of Monomer C2c> Monomer C2b (13.2 g, 23.4 mol) and tetrahydrofuran (117 mL) were added to a 300 mL round-bottom three-neck flask. After stirring the mixture to obtain a homogeneous solution, 40 wt% dimethylamine aqueous solution (58.6 mL) was added and the reaction was carried out 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. The organic layer was washed with saline, and then water and hexane were distilled off. The mixture was dried overnight in a vacuum (40°C) to obtain Monomer C2c (light yellow solid) represented by the following formula.

[0177] [ka]

[0178] (Polymerization reaction) Monomer C1 (9.94 g, 19.0 mmol), monomer C2c (4.93 g, 10.1 mmol), 2,2'-bipyridine (11.4 g, 72.7 mmol), and N,N-dimethylacetamide (72.7 mL) were added to a 500 mL round-bottom three-neck flask equipped with a nitrogen inlet and a cooling tube. After stirring the mixture to obtain a homogeneous solution, bis(1,5-cyclooctadiene)nickel(0) (20 g, 72.7 mmol) was added and reacted at 80°C for 3 hours. The reaction mixture was dropped into a mixed solution of methanol and hydrochloric acid (methanol / hydrochloric acid) to stop the reaction. The precipitate collected by filtration from the mixture was washed with methanol / hydrochloric acid, pure water, potassium carbonate aqueous solution, and pure water, and then vacuum dried overnight (60°C) to obtain an anion exchange resin precursor polymer PAF-4 (yellow solid) represented by the following formula.

[0179] [ka]

[0180] (Quaternization reaction, membrane formation, ion exchange) An anion exchange resin precursor polymer (12 g) and N,N-dimethylacetamide (130 mL) were added to a 500 mL round-bottom three-neck flask. After stirring the mixture to obtain a homogeneous solution, dimethyl sulfate (9.2 mL, 94 mmol) was added and the reaction was carried out at 40°C for 48 hours. The reaction mixture was dropped into pure water to stop the reaction. The precipitate collected from the mixture by filtration was washed with pure water and then vacuum dried overnight (60°C) to obtain a membrane of anion exchange resin QPAF-4 (IEC = 1.5 meq. / g, methyl sulfate ion type).

[0181] Anion exchange resin QPAF-4 (methyl sulfate ion type) and N,N-dimethylacetamide were added to a 20 mL round-bottom three-neck flask. The mixture was stirred to make a homogeneous solution, and then filtered. The filtrate was poured onto a glass plate bordered with silicone rubber and dried on a hot plate adjusted to a horizontal position. The obtained anion exchange resin membrane was cut into a width of 1 cm and a length of 3 cm to be used as a measurement sample. The anion exchange resin membrane obtained above was immersed in a 1 M potassium hydroxide aqueous solution (80°C) for 48 hours, and then washed with degassed pure water to convert the counter ion of the ion exchange group (quaternary ammonium group) to a hydroxide ion. As a result, a membrane of anion exchange resin QPAF-4 (IEC = 1.5 meq. / g, hydroxide ion type) represented by the following formula was obtained.

[0182] [ka]

[0183] <Durability test> A durability test was carried out on the anion exchange resin membranes obtained in the examples and comparative examples. Specifically, the anion exchange resin membranes (hydroxide ion type) obtained above were immersed in an 8M potassium hydroxide aqueous solution (80°C) and the change in hydroxide ion conductivity over time was measured. The hydroxide ion conductivity was measured by washing the sample taken out of the 8M potassium hydroxide aqueous solution (80°C) with degassed pure water, and then measuring the conductivity in water at 40°C using an AC four-terminal method (300mV, 10-100000Hz). The measurement device used was Solartolon1255B / 1287, and the probe used a gold wire with a diameter of 1mm. The hydroxide ion conductivity σ (S / cm) was calculated from the following equation, taking into account the distance between the probes L (1cm), the impedance Z (Ω), and the membrane cross-sectional area A (cm 2 ) was calculated. σ = (L / Z) × 1 / A

[0184] The results are shown in Figure 1. The hydroxide ion conductivity of the anion exchange resin membrane obtained in Comparative Example 1 decreased over time, but the hydroxide ion conductivity of the anion exchange resin membranes obtained in Examples 1 to 3 maintained the initial hydroxide ion conductivity even after 1000 hours in all IEC samples.

[0185] As described above, it is evident that the anion exchange resins obtained in the Examples have superior chemical properties (durability, especially alkali resistance) compared to the anion exchange resins obtained in the Comparative Examples.

Claims

1. A divalent hydrophobic group represented by the following formula (1), A divalent hydrophilic group represented by the following formula (2): It consists of: a hydrophobic unit consisting of the hydrophobic group alone or in which the hydrophobic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond; The hydrophilic unit is composed of the hydrophilic group alone or the hydrophilic group is repeated via an ether bond, a thioether bond, or a carbon-carbon bond. having The hydrophobic unit and the hydrophilic unit are bonded via an ether bond, a thioether bond, or a carbon-carbon bond. An anion exchange resin comprising: -R １ -A １ - (1) (In the formula, R １ is a single polycyclic compound or a plurality of polycyclic compounds 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, or a divalent sulfur-containing group, or a carbon-carbon bond; １ 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, which may be substituted with a halogen atom or a pseudohalide. -R ２ -A ２ - (2) (In the formula, R ２ consists of a single polycyclic compound, or consists of a linking group which 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 / or a plurality of polycyclic compounds bonded to each other via a carbon-carbon bond, and at least one of the linking group or the polycyclic compounds is bonded to an anion exchange group-containing group; ２ 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, which may be substituted with a halogen atom or a pseudohalide.

2. The R １ is expressed by the following formula (R １ ') or the following formula (R １ '') The anion exchange resin according to claim 1 . 【Chemistry 1】 (In the formula, l represents an integer of 1 or more.) 【Chemistry 2】 (In the formula, l represents an integer of 1 or more.)

3. The above A １ is represented by the following formula (A １ ') The anion exchange resin according to claim 1 . 【Chemistry 3】 (In the formula, M １ and M. １ ' are the same or different and are monovalent hydrocarbon groups which may be substituted with halogen atoms or pseudohalides.

4. The R ２ is expressed by the following formula (R ２ ') is a fluorene residue. The anion exchange resin according to claim 1 . 【Chemistry 4】 (In the formula, A's may be the same or different and each represent an anion exchange group-containing group or a cyclic structure containing an anion exchange group.)

5. The above A ２ is represented by the following formula (A ２ ') The anion exchange resin according to claim 1 . 【Chemistry 5】 (In the formula, M ２ and M. ２ ' are the same or different and are monovalent hydrocarbon groups which may be substituted with halogen atoms or pseudohalides.

6. The anion exchange resin according to any one of claims 1 to 5 is included.

1. An electrolyte membrane comprising:

7. The anion exchange resin according to any one of claims 1 to 5 is included. A binder for forming an electrode catalyst layer, comprising:

8. The binder for forming an electrode catalyst layer according to claim 7 is included. A battery electrode catalyst layer.

Images