Methods for manufacturing anion exchange resins and electrolyte membranes

Abstract

This invention provides a method for manufacturing anion exchange resin capable of producing electrolyte membranes with excellent mechanical properties (strength). In the presence of bis(1,5-cyclooctadiene)nickel (0) as a catalyst, 2,2'-bipyridine as a co-ligand, a bromide or iodide as a co-catalyst, and a reducing agent, when reacting a monomer for forming hydrophobic groups with a monomer for forming hydrophilic groups to produce anion exchange resin in which hydrophobic and hydrophilic groups are bonded via direct bonding, the molar number of bis(1,5-cyclooctadiene)nickel (0) is set to 0.3 to 1.8 times the total molar number of the monomers for forming hydrophobic and hydrophilic groups.

Description

Technical Field

[0001] This invention relates to methods for manufacturing anion exchange resins and electrolyte membranes. Background Technology

[0002] Known anion exchange resins, wherein the resin comprises a divalent hydrophobic group consisting of a single aromatic ring or multiple aromatic rings bonded together via divalent hydrocarbon groups, divalent silicon-containing groups, divalent nitrogen-containing groups, divalent phosphorus-containing groups, divalent oxygen-containing groups, divalent sulfur-containing groups, or carbon-carbon bonds; and a divalent polycyclic compound consisting of a single polycyclic compound or multiple polycyclic compounds bonded together via divalent hydrocarbon groups, divalent silicon-containing groups, divalent nitrogen-containing groups, divalent phosphorus-containing groups, divalent oxygen-containing groups, or divalent sulfur-containing groups (linking groups), and / or carbon-carbon bonds. The hydrophilic group, wherein at least one of the linking group or the polycyclic compound is bonded to the anion exchange group via a divalent saturated hydrocarbon group having two or more carbon atoms; the anion exchange resin has hydrophobic units consisting of individual hydrophobic groups or hydrophobic groups repeated via ether bonds, thioether bonds, or carbon-carbon bonds, and hydrophilic units consisting of individual hydrophilic groups or hydrophilic groups repeated via ether bonds, thioether bonds, or carbon-carbon bonds, wherein the hydrophobic units and the hydrophilic units are bonded via ether bonds, thioether bonds, or carbon-carbon bonds.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2019-23258 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] However, Patent Document 1 presents the following issue: in the polymerization reaction (cross-coupling) of monomers for manufacturing anion exchange resins in which hydrophobic and hydrophilic units are bonded via carbon-carbon bonds, a large amount of very expensive bis(1,5-cyclooctadiene)nickel(0) is used as a catalyst, making it difficult to reduce manufacturing costs. If the amount of catalyst used is reduced, there is a problem that the molecular weight (especially the weight-average molecular weight) of the obtained polymer decreases, and the mechanical properties (strength) of the anion exchange resin decreases.

[0008] Therefore, the object of the present invention is to provide a method for manufacturing an anion exchange resin capable of producing an electrolyte membrane with excellent mechanical properties (strength), and a method for manufacturing an electrolyte membrane formed from the anion exchange resin.

[0009] Methods for solving problems

[0010] To address the aforementioned issues, the method for manufacturing the anion exchange resin of the present invention includes the following steps:

[0011] (A) A process for preparing a monomer for forming a hydrophobic group, the monomer being 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 directly bonded, wherein two chlorine atoms are bonded to the aromatic ring.

[0012] (B) A step of preparing a monomer for forming a hydrophilic group, the monomer being composed of a single aromatic ring, or composed of multiple 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, or a divalent sulfur-containing group, i.e., a linking group, and / or direct bonding, wherein two chlorine atoms are bonded to the aromatic ring, and at least one of the linking groups or aromatic rings is bonded to an anion exchange group precursor functional group via a divalent saturated hydrocarbon group or direct bonding;

[0013] (C) A step of synthesizing a polymer by reacting the monomer for forming the hydrophobic group with the monomer for forming the hydrophilic group in the presence of bis(1,5-cyclooctadiene)nickel (0) as a catalyst, 2,2'-bipyridine as a co-ligand, a bromide or iodide as a co-catalyst, and a reducing agent; and

[0014] (D) The step of ionizing the functional group of the anion exchange group precursor to form an anion exchange group.

[0015] The characteristic feature is that the molar number of bis(1,5-cyclooctadiene)nickel(0) used in step (C) is 0.3 to 1.8 times the total molar number of the monomer for forming the hydrophobic group and the monomer for forming the hydrophilic group.

[0016] In the anion exchange resin,

[0017] The hydrophobic group is formed by the monomer residues forming a divalent hydrophobic group.

[0018] The hydrophilic group having the anion exchange group is formed by the monomer residues to form a divalent hydrophilic group.

[0019] The hydrophobic group and the hydrophilic group are bonded by direct bonding.

[0020] In the method for manufacturing the anion exchange resin of the present invention, the co-catalyst is preferably a quaternary ammonium bromide or a quaternary ammonium iodide.

[0021] In the method for manufacturing the anion exchange resin of the present invention, it is preferable that the molar number of the co-catalyst used in step (C) is 1.0 to 3.0 times the molar number of bis(1,5-cyclooctadiene)nickel(0).

[0022] In the manufacturing method of the anion exchange resin of the present invention, the reducing agent is preferably zinc or magnesium.

[0023] In the method for manufacturing the anion exchange resin of the present invention, it is preferable that the number of moles of 2,2′-bipyridine used in step (C) is 1.5 to 2.5 times the number of moles of bis(1,5-cyclooctadiene)nickel(0).

[0024] In the method for manufacturing the anion exchange resin of the present invention, it is preferable that the hydrophobic group comprises a bisphenol residue represented by the following formula (2), which can be substituted by a halogen atom or a halide-like compound or an alkyl or aryl group.

[0025] [Chemistry 1]

[0026]

[0027] (In the formula, R represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, or a direct bond; Alk may be the same or different and represent alkyl or aryl groups; X may be the same or different and represent halogen atoms or halide-like compounds; a, b, c, and d may be the same or different and represent integers from 0 to 4.)

[0028] In the method for manufacturing the anion exchange resin of the present invention, the hydrophobic group preferably comprises a bisphenol residue represented by the following formula (1), which can be substituted by a halogen atom or a halide-like compound or an alkyl or aryl group (in particular, in the following formula (1), Z is a carbon atom, R is a direct bond, X is a fluorine atom, and h, h', h”, i, i', i”, j and k are 0).

[0029] [Chemistry 2]

[0030]

[0031] (In the formula, Alk, X, a, b, c and d have the same meaning as Alk, X, a, b, c and d in the above formula (2), Z are the same or different and represent carbon atoms or silicon atoms, R are the same or different and represent silicon-containing groups, nitrogen-containing groups, phosphorus-containing groups, oxygen-containing groups, sulfur-containing groups or direct bonding, l represents an integer greater than 1, and h, h', h”, i, i', i”, j and k are the same or different and represent integers greater than 0.)

[0032] In the method for manufacturing the anion exchange resin of the present invention, the hydrophilic group is preferably a divalent hydrophilic group (particularly containing a fluorene residue represented by the following formula (3)): composed of a single polycyclic compound, or composed of multiple 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, i.e., a linking group and / or direct bonding, wherein at least one of the linking groups or the polycyclic compounds is bonded to the anion exchange group via a divalent saturated hydrocarbon group having two or more carbon atoms.

[0033] [Chemistry 3]

[0034]

[0035] (In the formula, Ion and Ion' are the same or different from each other, representing anion exchange groups; y and z are the same or different from each other, representing integers from 2 to 20.)

[0036] To solve the above-mentioned problems, the method for manufacturing the electrolyte membrane of the present invention is characterized by comprising: a step of obtaining an anion exchange resin by the above-described method;

[0037] The process of obtaining an electrolyte membrane containing the above-mentioned anion exchange resin.

[0038] The effects of the invention

[0039] According to the present invention, an anion exchange resin capable of manufacturing an electrolyte membrane with excellent mechanical properties (strength) and an electrolyte membrane for fuel cells formed from the anion exchange resin can be provided. Attached Figure Description

[0040] Figure 1 This is a diagram illustrating the scheme of cross-coupling reaction without the use of a co-catalyst.

[0041] Figure 2 This is a diagram illustrating a scheme for cross-coupling reactions using a co-catalyst. Detailed Implementation

[0042] The anion exchange resin of the present invention is composed of divalent hydrophobic groups and divalent hydrophilic groups.

[0043] In the anion exchange resin of the present invention, the divalent hydrophobic group is composed of a single aromatic ring, or of multiple (two or more, preferably two) aromatic rings bonded together 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 by direct bonding (carbon-carbon bond). Such a divalent hydrophobic group is formed by residues of a monomer forming a hydrophobic group with two halogen atoms, a halide-like group, or a borate group bonded to the aromatic ring, either composed of a single aromatic ring or of multiple aromatic rings bonded together 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 by direct bonding.

[0044] Examples of aromatic rings include monocyclic or polycyclic compounds with 6 to 14 carbon atoms, such as benzene rings, naphthalene rings, indene rings, azulene rings, fluorene rings, anthracene rings, and phenanthrene rings, as well as heterocyclic compounds such as pyrrole, furan, thiophene, oxazole, thiazole, and pyridine.

[0045] As aromatic rings, monocyclic aromatic hydrocarbons with 6 to 14 carbon atoms are preferred, and benzene rings are more preferred.

[0046] Furthermore, the aromatic ring can be substituted with halogen atoms, alkyl groups, aryl groups, halide-like groups, etc., as needed. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. Examples of halide-like groups include trifluoromethyl, -CN, -NC, -OCN, -NCO, -ONC, -SCN, -NCS, -SeCN, -NCSe, -TeCN, -NCTe, and -N3. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, and octyl groups with 1 to 20 carbon atoms; and cycloalkyl groups with 1 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of aryl groups include phenyl, biphenyl, naphthyl, and fluorene.

[0047] It should be noted that when the aromatic ring is replaced by substituents such as halogen atoms, alkyl groups, aryl groups, or halide-like groups, the number of substitutions and the substitution positions of the substituents such as halogen atoms, alkyl groups, aryl groups, or halide-like groups are appropriately set according to the purpose and use.

[0048] However, the monomer for forming hydrophobic groups has at least two halogen atoms, halide-like groups, or borate groups bonded to its aromatic ring. Regarding the bonding positions of these two halogen atoms, halide-like groups, or borate groups, in the case of a monomer for forming hydrophobic groups consisting of a single aromatic ring, it is the aromatic ring itself; in the case of a monomer for forming hydrophobic groups having two aromatic rings, it is each aromatic ring; and in the case of a monomer for forming hydrophobic groups having three or more aromatic rings, it is the two terminal aromatic rings.

[0049] It should be noted that a divalent hydrophobic group is formed by removing two halogen atoms, halide-like groups, or borate groups bonded to an aromatic ring from the monomer used to form the hydrophobic group.

[0050] As an aromatic ring substituted with halogen atoms, more specifically, examples include benzene rings substituted with 1 to 4 halogen atoms (e.g., benzene rings substituted with 1 to 4 fluorine atoms, benzene rings substituted with 1 to 4 chlorine atoms, benzene rings substituted with 1 to 4 bromine atoms, benzene rings substituted with 1 to 4 iodine atoms, etc., where the 1 to 4 halogen atoms can be all the same or different).

[0051] Examples of divalent hydrocarbon groups include methylene (-CH2-), ethylene, propylene, isopropylene (-C(CH3)2-), butylene, isobutylene, secondary butylene, pentylene (pentylene), isopentylene, secondary pentylene, hexylene (hexamethylene), 3-methylpentylene, heptylene, octylene, 2-ethylhexylene, nonylene, decylene, isodelene, dodecylene, tetradecylene, hexadecylene, octadecylene, and other divalent saturated hydrocarbon groups with 1 to 20 carbon atoms.

[0052] As a divalent hydrocarbon group, divalent saturated hydrocarbon groups with 1 to 3 carbon atoms are preferably listed, specifically, methylene (-CH2-), ethylene, propylene, and isopropylene (-C(CH3)2-) are listed, more preferably methylene (-CH2-) and isopropylene (-C(CH3)2-) are listed, and isopropylene (-C(CH3)2-) is particularly preferred.

[0053] The divalent hydrocarbon group can be replaced by the monovalent residue in the aromatic ring mentioned above.

[0054] Examples of aromatic groups include divalent residues in the aromatic rings described above. Preferably, m-phenylene and fluorene groups are also mentioned.

[0055] As such a hydrophobic group, preferably bisphenol residues (divalent hydrophobic groups consisting of two benzene rings bonded together via R) that can be replaced by alkyl, aryl, halogen atoms or halide-like compounds as shown in formula (2) can be cited.

[0056] [Chemistry 4]

[0057]

[0058] (In the formula, R represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, an aromatic group, or a direct bond; Alk may be the same or different and represent alkyl or aryl groups; X may be the same or different and represent halogen atoms or halide-like compounds; a, b, c, and d may be the same or different and represent integers from 0 to 4.)

[0059] In the above formula (2), R represents a hydrocarbon group, a silicon-containing group, a nitrogen-containing group, a phosphorus-containing group, an oxygen-containing group, a sulfur-containing group, or a direct bond, preferably representing isopropylidene (-C(CH3)2-).

[0060] In formula (2) above, Alk may be the same or different from each other, representing alkyl or aryl groups. Examples of alkyl groups include the alkyl groups described above, and examples of aryl groups include the aryl groups described above.

[0061] In the above formula (2), X is the same or different from each other, representing the above-mentioned halogen atoms or halide-like compounds.

[0062] In the above formula (2), a and b are the same or different from each other, representing integers from 0 to 4, preferably representing integers from 0 to 2, and even more preferably both a and b represent 0.

[0063] In the above formula (2), c and d are the same or different from each other, representing integers from 0 to 4, preferably representing integers from 0 to 2, and even more preferably both c and d represent 0.

[0064] As such a hydrophobic group, bisphenol residues represented by the following formula (1) that can be substituted with halogen atoms or halides or alkyl or aryl groups are particularly preferred.

[0065] [Chemistry 5]

[0066]

[0067] (In the formula, Alk, X, a, b, c and d have the same meaning as Alk, X, a, b, c and d in the above formula (2), Z are the same or different and represent carbon atoms or silicon atoms, R are the same or different and represent silicon-containing groups, nitrogen-containing groups, phosphorus-containing groups, oxygen-containing groups, sulfur-containing groups or direct bonding, l represents an integer greater than 1, and h, h', h”, i, i', i”, j and k are the same or different and represent integers greater than 0.)

[0068] In the above formula (1), Z can be the same or different from each other, representing carbon atoms or silicon atoms, preferably carbon atoms.

[0069] In the above formula (1), R can be the same or different from each other, representing silicon-containing groups, nitrogen-containing groups, phosphorus-containing groups, oxygen-containing groups, sulfur-containing groups, or direct bonding, preferably representing direct bonding.

[0070] In the above formula (1), X may be the same or different from each other, representing the above-mentioned halogen atom or halide-like compound, or hydrogen atom, preferably representing halogen atom or hydrogen atom, more preferably representing fluorine atom.

[0071] In the above formula (1), l represents an integer greater than or equal to 1, preferably an integer from 1 to 20, and more preferably an integer from 2 to 6.

[0072] In the above formula (1), h, h', h”, i, i', i”, j and k are the same or different from each other, representing integers greater than or equal to 0, preferably representing integers from 0 to 20, more preferably representing integers from 0 to 3, and even more preferably representing 0 or 1.

[0073] As such a hydrophobic group, fluorinated bisphenol residues represented by the following formula (1') are particularly preferred.

[0074] [Chemistry 6]

[0075]

[0076] (In the formula, l has the same meaning as l in the above formula (1).)

[0077] Thus, by introducing divalent fluorinated groups into the main chain of hydrophobic groups, the following effects are achieved.

[0078] • Improved solubility and flexibility through a backbone with low intermolecular interactions.

[0079] • It imparts hydrophobicity and enhances phase separation from the hydrophilic part (near the ion exchange group), enabling the formation of ion-conducting pathways.

[0080] Due to its hydrophobic properties, hydrophilic hydroxide ions and oxidants have difficulty approaching the main chain (resulting in improved alkali resistance and chemical stability).

[0081] • It can control the rigidity of the main chain (improving the flexibility of the electrolyte membrane).

[0082] • Low glass transition temperature, enabling it to adhere to the catalyst layer (reduced contact resistance)

[0083] • It can control gas diffusion (increased oxygen diffusion when used as an adhesive).

[0084] Furthermore, as such a hydrophobic group, a divalent hydrophobic group consisting of two or more aromatic rings bonded together by direct bonding can be preferably cited. As a specific example, a linear oligophenylene represented by the following formula (2a) can be cited.

[0085] [Chemistry 7]

[0086]

[0087] (In the formula, x represents an integer from 2 to 8.)

[0088] By including a divalent hydrophobic group (preferably a linear oligophenylene group represented by formula (2a) above) consisting of two or more aromatic rings bonded together by direct bonding as the hydrophobic group, the electrical properties (conductivity) become excellent. In particular, even if the IEC (ion exchange capacity) increases, the water content of each ionic group is difficult to increase, making it easy to achieve high conductivity.

[0089] In the above formula (2a), x represents an integer from 2 to 8, preferably an integer from 2 to 6, and even more preferably 2 (i.e., biphenylene).

[0090] In addition to hydrophobic groups, groups having the following structures can also be listed.

[0091] [Chemistry 8]

[0092]

[0093] In the anion exchange resin of the present invention, the divalent hydrophilic group is composed of a single aromatic ring, or is composed of multiple 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, or a divalent sulfur-containing group, i.e., a linking group and / or direct bonding, wherein at least one of the above-mentioned linking groups or aromatic rings is bonded to the anion exchange group via a divalent saturated hydrocarbon group or direct bonding. Such a divalent hydrophilic group is formed by the residues of a product of anion exchange group formed by ionizing the anion exchange group precursor functional group of a hydrophilic group forming monomer. The hydrophilic group forming monomer consists of a single aromatic ring, or multiple 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, or a divalent sulfur-containing group, i.e., a linking group and / or direct bonding. Two halogen atoms, halide-like groups, or borate groups are bonded to the aromatic ring. At least one of the aforementioned linking groups or aromatic rings is bonded to the anion exchange group precursor functional group via a divalent saturated hydrocarbon group or direct bonding.

[0094] Examples of aromatic rings include the aromatic rings described above, with benzene rings being a preferred example.

[0095] Furthermore, preferably, polycyclic compounds can be cited as aromatic rings. Examples of polycyclic compounds include naphthalene rings, indene rings, azulene rings, fluorene rings, anthracene rings, phenanthrene rings, carbazole rings, and indole rings; preferably, fluorene rings are listed.

[0096] Examples of divalent hydrocarbon groups include the aforementioned divalent hydrocarbon groups.

[0097] An anion exchange group is introduced into the side chain of the hydrophilic group. Specifically, there are no particular limitations, and known anion exchange groups such as quaternary ammonium, tertiary amino, secondary amino, primary amino, phosphine, phosphazene, tertiary sulfonium, quaternary boronium, quaternary phosphonium, and guanidinium can all be used. From the viewpoint of anion conductivity, quaternary ammonium groups are preferred.

[0098] As anion exchange groups, -N is a preferred example. + (CH3)3, in addition to the above, anion exchange groups with the following structures can also be cited. It should be noted that in the following structural formulas, * indicates the portion bonded to the aromatic ring containing the substituent.

[0099] [Chemistry 9]

[0100]

[0101] (In the diagram, Alk, Alk', and Alk” represent the aforementioned alkyl groups, and iPr represents isopropyl.)

[0102] Such anion exchange groups are bonded to a linking group or aromatic ring of a divalent hydrophilic residue via a divalent saturated hydrocarbon group or direct bonding. The divalent hydrophilic residue is composed of multiple 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, or a divalent sulfur-containing group, i.e., a linking group and / or direct bonding.

[0103] An anion exchange group only needs to be bonded to at least one linking group or aromatic ring, and can be bonded to multiple linking groups or aromatic rings, or even to all of them. Alternatively, multiple anion exchange groups can be bonded to a single linking group or aromatic ring.

[0104] The number of carbon atoms in the divalent saturated hydrocarbon group, which is a linking group of divalent hydrophilic residues formed by 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 (i.e., a linking group), and / or directly bonded to each other, or where the aromatic rings are bonded to anion exchange groups, is preferably 2 or more. The number of carbon atoms in the divalent saturated hydrocarbon group is more preferably an integer from 2 to 20, further preferably an integer from 3 to 10, and particularly preferably an integer from 4 to 8.

[0105] As divalent saturated hydrocarbon groups, preferably linear saturated hydrocarbon groups such as ethylene (-(CH2)2-), trimethylene (-(CH2)3-), tetramethylene (-(CH2)4-), pentamethylene (-(CH2)5-), hexamethylene (-(CH2)6-), heptamethylene (-(CH2)7-), and octamethylene (-(CH2)8-) can be listed.

[0106] As such a hydrophilic group, preferably fluorene residues represented by the following formula (3) can be listed.

[0107] [Chemistry 10]

[0108]

[0109] (In the formula, Ion and Ion' are the same or different from each other, representing anion exchange groups; y and z are the same or different from each other, representing integers from 2 to 20.)

[0110] In the above formula (3), Ion and Ion' are the same or different from each other, representing anion exchange groups, preferably the same or different from each other, representing the above-mentioned quaternary ammonium groups, and particularly preferably -N + (CH3)3.

[0111] In the above formula (3), y and z are the same or different from each other, representing integers from 2 to 20, preferably integers from 3 to 10, and even more preferably integers from 4 to 8.

[0112] As such a hydrophilic group, fluorene residues represented by the following formula (3') are particularly preferred.

[0113] [Chemistry 11]

[0114]

[0115] In the anion exchange resin of the present invention, the hydrophobic group and the hydrophilic group described above are bonded by direct bonding. In the anion exchange resin of the present invention, it is preferable that the hydrophobic group forms a repeating hydrophobic unit via ether bonds, thioether bonds, or direct bonding. In the anion exchange resin of the present invention, it is preferable that the hydrophilic group forms a repeating hydrophilic unit via ether bonds, thioether bonds, or direct bonding. Hereinafter, a hydrophobic unit refers to a unit composed of a hydrophobic group monomer or a unit formed by repeating hydrophobic groups via direct bonding, and a hydrophilic unit refers to a unit formed by repeating hydrophilic group monomers or a unit formed by repeating hydrophilic groups via direct bonding.

[0116] It should be noted that sometimes a unit corresponds to a block in a commonly used block copolymer.

[0117] As a hydrophobic unit, preferably, it is a unit formed by direct bonding of bisphenol residues, which can be replaced by alkyl, aryl, halogen atoms or halide-like compounds, as shown in formula (2) above. The bisphenol residues can be various units formed by bonding with each other in a random, alternating, or block manner.

[0118] Such a hydrophobic unit is represented, for example, by the following equation (7).

[0119] [Chemistry 12]

[0120]

[0121] (In the formula, R, Al, X, a, b, c and d have the same meaning as R, Al, X, a, b, c and d in the above formula (2), and q represents 1 to 200.)

[0122] In the above formula (7), q represents, for example, 1 to 200, preferably 1 to 50.

[0123] As such a hydrophobic unit, a more preferably example is a unit formed by direct bonding of bisphenol residues that can be substituted with halogen atoms or halides or alkyl or aryl groups, as represented by the above formula (1).

[0124] Such a hydrophobic unit is represented, for example, by the following equation (7a).

[0125] [Chemistry 13]

[0126]

[0127] (In the formula, Alk, X, a, b, c and d have the same meaning as Alk, X, a, b, c and d in the above formula (2), Z, R, X, l, h, h', h”, i, i', i”, j and k have the same meaning as Z, R, X, l, h, h', h”, i, i', i”, j and k in the above formula (1), and q represents 1 to 200.)

[0128] In the above formula (7), q represents, for example, 1 to 200, preferably 1 to 50.

[0129] Such a hydrophobic unit is particularly preferably represented by the following formula (7a').

[0130] [Chemistry 14]

[0131]

[0132] (In the formula, l has the same meaning as l in the above formula (1), and q represents 1 to 200 (preferably 1 to 50).)

[0133] As a hydrophilic unit, preferably, it is a unit formed by bonding the fluorene residues (hydrophilic groups) shown in formula (3) above together via ether bonds, thioether bonds, or direct bonding (preferably direct bonding). The fluorene residues can be various units formed by bonding each other in a random, alternating, or blocky manner.

[0134] Such a hydrophilic unit is represented, for example, by the following equation (9).

[0135] [Chemistry 15]

[0136]

[0137] (In the formula, Ion, Ion', y and z are the same or different from each other, indicating the same meaning as Ion, Ion', y and z in the above formula (3), and m represents 1 to 200 (preferably 1 to 50).)

[0138] As such a hydrophilic unit, particularly preferably, is a unit formed by direct bonding of fluorene residues as shown in the above formula (3').

[0139] Such a hydrophilic unit is represented, for example, by the following equation (9′).

[0140] [Chemistry 16]

[0141]

[0142] (In the formula, Ion and Ion' are the same or different from each other, indicating the same meaning as Ion and Ion' in the above formula (3), and m represents 1 to 200 (preferably 1 to 50).)

[0143] In the anion exchange resin of the present invention, it is preferable that the hydrophobic unit and the hydrophilic unit described above are bonded by direct bonding.

[0144] As such anion exchange resin, a preferred example is an anion exchange resin in which the hydrophobic unit shown in formula (7) and the hydrophilic unit shown in formula (9) are bonded together by direct bonding, as shown in formula (13) below.

[0145] [Chemistry 17]

[0146]

[0147] (In the formula, R, Al, X, a, b, c and d have the same meaning as R, Al, X, a, b, c and d in the above formula (7), Ion, Ion', y and z have the same meaning as Ion, Ion', y and z in the above formula (9), q and m represent the proportion or number of repetitions, ranging from 1 to 100, and o represents the number of repetitions, ranging from 1 to 100.)

[0148] More preferably, an anion exchange resin is one in which the hydrophobic unit shown in formula (7a) and the hydrophilic unit shown in formula (9) are bonded together by direct bonding, as shown in formula (13').

[0149] [Chemistry 18]

[0150]

[0151] As such anion exchange resin, particularly preferred examples are anion exchange resins in which the hydrophobic unit shown in formula (7a') and the hydrophilic unit shown in formula (9') are bonded together by direct bonding, as shown in formula (13").

[0152] [Chemistry 19]

[0153]

[0154] (In the formula, l has the same meaning as l in the above formula (7a'), Ion and Ion' have the same meaning as Ion and Ion' in the above formula (9'), q and m represent the proportion or number of repetitions, ranging from 1 to 100, and o represents the number of repetitions, ranging from 1 to 100.)

[0155] Such anion exchange resins have a number-average molecular weight of, for example, 10 to 1000 kDa, preferably 30 to 500 kDa, and a weight-average molecular weight of, for example, 20 to 3000 kDa, preferably 40 to 1000 kDa.

[0156] As a method for manufacturing anion exchange resins, a method based on polycondensation reaction is employed, particularly cross-coupling that forms direct bonds (carbon-carbon bonds).

[0157] In the case of manufacturing anion exchange resin using this method, a monomer for forming hydrophobic groups is prepared, and a monomer for forming hydrophilic groups having anion exchange group precursor functional groups is prepared. A polymer is synthesized by causing the monomer for forming hydrophobic groups to undergo a polymerization reaction with the monomer for forming hydrophilic groups, thereby ionizing the anion exchange group precursor functional groups in the polymer, and thus manufacturing anion exchange resin.

[0158] As monomers for forming hydrophobic groups, examples include monomers consisting of a single aromatic ring or multiple 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 directly bonded, wherein two chlorine atoms are bonded to the aromatic ring. Preferably, examples include compounds corresponding to the above formula (2) and shown in the following formula (22).

[0159] [Chemistry 20]

[0160]

[0161] (In the formula, Alk, R, X, a, b, c and d have the same meaning as Alk, R, X, a, b, c and d in the above formula (2), and Y and Y' are the same or different from each other, representing chlorine atoms.)

[0162] As a monomer for forming hydrophobic groups, particularly preferred examples are compounds corresponding to the above formula (1) and shown in the following formula (21).

[0163] [Chemistry 21]

[0164]

[0165] (In the formula, Alk, R, X, Z, a, b, c, d, l, h, h', h”, i, i', i”, j and k have the same meaning as Alk, R, X, Z, a, b, c, d, l, h, h', h”, i, i', i”, j and k in the above formula (1), and Y and Y' are the same or different from each other, representing chlorine atoms.)

[0166] As monomers for forming hydrophilic groups, examples include monomers consisting of a single aromatic ring or multiple aromatic rings bonded together by 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 (i.e., a linking group), and / or directly bonded, wherein two chlorine atoms are bonded to the aromatic ring, and at least one of the aforementioned linking groups or aromatic rings is bonded to an anion exchange group precursor functional group via a divalent saturated hydrocarbon group or directly bonded. Preferably, examples include compounds corresponding to the above formula (3) and shown in the following formula (23).

[0167] [Chemistry 22]

[0168]

[0169] (In the formula, y and z have the same meaning as y and z in the above formula (3), Pre and Pre' are the same or different and represent the anion exchange group precursor functional group, and Y and Y' are the same or different and represent the chlorine atom.)

[0170] When polymerizing monomers for forming hydrophobic groups and monomers for forming hydrophilic groups by cross-coupling, the amount of each monomer is adjusted in such a way that it becomes the desired ratio of hydrophobic and hydrophilic units in the resulting anion exchange resin precursor polymer.

[0171] In this invention, monomers for forming hydrophobic and hydrophilic groups are dissolved in solvents such as N,N-dimethylacetamide and dimethyl sulfoxide, and polymerization is carried out using bis(cyclooctyl-1,5-diene)nickel (0) (hereinafter sometimes referred to as "Ni(cod)2") as a catalyst. Furthermore, during the cross-coupling reaction in the presence of bis(cyclooctyl-1,5-diene)nickel (0) as a catalyst, 2,2'-bipyridine (hereinafter sometimes referred to as "bpy") is present as a co-ligand.

[0172] Here, as in Figure 1 As shown in the diagram above, the cross-coupling reaction proceeds while consuming Ni(cod)₂ as a catalyst. If a reducing agent (Red...) can be used... 0 If Ni is reduced from Ni(bpy)Cl2, which is a used catalyst, the overall reaction cycle is valid, thus reducing the amount of very expensive Ni(cod)2 used. However, Ni from Ni(bpy)Cl2, which is a used catalyst, is difficult to reduce and cannot be reduced with common reducing agents.

[0173] Therefore, in this invention, during the aforementioned cross-coupling reaction, the bromide or iodide acting as a co-catalyst and the reducing agent coexist. For example, in Figure 2 The diagram illustrates a scheme for a cross-coupling reaction where bromide or iodide, acting as a co-catalyst, and a reducing agent coexist. With the co-catalyst, once the chloride ions of the consumed catalyst residue (Ni(bpy)Cl2) are replaced by bromide or iodide ions, the replaced catalyst residue can be reduced with a common reducing agent, thus establishing an overall reaction cycle. Therefore, the amount of very expensive Ni(cod)2 used can be reduced, easily lowering manufacturing costs.

[0174] In this invention, the molar number of bis(1,5-cyclooctadiene)nickel (0) used as a catalyst can be set to 0.3 to 1.8 times the total molar number of the monomers for forming hydrophobic and hydrophilic groups, preferably 0.4 to 1.5 times, and more preferably 0.5 to 1.0 times. In this case, the molar number of 2,2'-bipyridine used as a co-ligand is preferably 1.5 to 2.5 times the molar number of bis(1,5-cyclooctadiene)nickel (0) used as a catalyst, more preferably 1.8 to 2.2 times. This increases the molecular weight of the obtained polymer and improves the mechanical properties (strength) of the anion exchange resin.

[0175] As a cocatalyst, bromides or iodides can be used, and more preferably, quaternary ammonium bromides or quaternary ammonium iodides can be used. Examples of quaternary ammonium bromides include tetramethylammonium bromide, tetraethylammonium bromide, and tetrabutylammonium bromide. Examples of quaternary ammonium iodides include tetramethylammonium iodide, tetraethylammonium iodide, and tetrabutylammonium iodide. The molar number of the cocatalyst used in the above-mentioned cross-coupling reaction is preferably 1.0 to 3.0 times the molar number of bis(1,5-cyclooctadiene)nickel(0), more preferably 1.5 to 2.5 times.

[0176] As a reducing agent, zinc or magnesium can be used, for example. The molar number of the reducing agent used in the above-described cross-coupling reaction is preferably 1.0 to 3.0 times the molar number of the co-catalyst, more preferably 1.5 to 2.5 times.

[0177] 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.

[0178] Thus, the anion exchange resin precursor polymers shown in formula (15) and formula (16) are obtained.

[0179] [Chemistry 23]

[0180]

[0181] (In the formula, Alk, R, X, a, b, c and d have the same meaning as Alk, R, X, a, b, c and d in the above formula (1), y and z have the same meaning as y and z in the above formula (3), Pre and Pre' are the same or different from each other, representing the anion exchange group precursor functional group, q and m represent the coordination ratio or repetition number, representing 1 to 100, o represents the repetition number, representing 1 to 100.)

[0182] [Chemistry 24]

[0183]

[0184] (In the formula, Alk, R, X, Z, a, b, c, d, l, h, h', h”, i, i', i”, j and k have the same meaning as Alk, R, X, Z, a, b, c, d, l, h, h', h”, i, i', i”, j and k in the above formula (1), y and z have the same meaning as y and z in the above formula (3), Pre and Pre' are the same or different from each other, representing the anion exchange group precursor functional group, q and m represent the coordination ratio or repetition number, representing 1 to 100, o represents the repetition number, representing 1 to 100.)

[0185] Next, in this method, the anion exchange group precursor functional group is ionized. There are no particular limitations on the ionization method; well-known methods can be used.

[0186] Known methods can be used, such as dissolving the anion exchange resin precursor polymer in solvents such as N,N-dimethylacetamide or dimethyl sulfoxide, using iodomethane as an alkylating agent, and then ionizing it.

[0187] 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.

[0188] Thus, the anion exchange resins shown in formulas (13) and (13') above are obtained.

[0189] The ion exchange group capacity of the anion exchange resin is, for example, 0.1 to 4.0 meq. / g, preferably 0.6 to 3.0 meq. / g.

[0190] It should be noted that the capacity of the ion exchange group can be determined according to the following formula (24).

[0191] [Ion exchange group capacity (meq. / g)] = Anion exchange group introduction amount 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) (24)

[0192] It should be noted that the amount of ion exchange groups introduced is defined as the number of ion exchange groups per unit of hydrophilic group. Conversely, the amount of anion exchange groups introduced is the number of moles (mol) of the aforementioned anion exchange groups introduced into the main chain or side chain of the hydrophilic group.

[0193] Furthermore, such anion exchange resins are composed of a single aromatic ring, or multiple aromatic rings bonded together via a divalent hydrophobic 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 directly bonded to each other, and at least one of the aforementioned linking groups or aromatic rings is directly bonded to the anion exchange group via a divalent saturated hydrocarbon group or a divalent hydrophilic group directly bonded to the anion exchange group. Such anion exchange resins exhibit excellent mechanical properties (strength).

[0194] Furthermore, in the case of hydrophilic units that repeat through direct bonding of hydrophilic groups, excellent durability, such as alkali resistance, is exhibited because no ether bonds are present. More specifically, if the hydrophilic unit contains ether bonds, then as described below, it is possible for hydroxide ions (OH-) to form... - Decomposition caused by alkali is sometimes due to insufficient alkali resistance.

[0195] [Chemistry 25]

[0196]

[0197] In contrast, in the hydrophilic units of anion exchange resins that have hydrophilic groups that repeat through direct bonding, since there are no ether bonds, decomposition based on the above mechanism does not occur, resulting in excellent durability such as alkali resistance.

[0198] This invention comprises an electrolyte layer (electrolyte membrane) obtained using such anion exchange resin. The electrolyte membrane of this invention can be applied to various electrochemical applications such as fuel cells, water electrolysis devices, and electrochemical hydrogen pumps, and is particularly preferred for use in water electrolysis devices. In fuel cells, electrochemical hydrogen pumps, and water electrolysis hydrogen generation devices, the electrolyte membrane is used in a structure in which a catalyst layer, an electrode substrate, and a separator are sequentially stacked on both sides. The product of sequentially stacking a catalyst layer and a gas diffusion substrate on both sides of the electrolyte membrane (a product of a layer structure 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 this invention is suitable for use as an electrolyte membrane constituting such a MEA.

[0199] As an electrolyte membrane, the above-mentioned anion exchange resin can be used (i.e., the electrolyte membrane contains the above-mentioned anion exchange resin).

[0200] It should be noted that, as an electrolyte membrane, it can be reinforced using known reinforcing materials such as porous substrates. Furthermore, it can undergo various treatments, such as biaxial stretching to control molecular orientation, and heat treatment to control crystallinity and residual stress. In addition, to improve the mechanical strength of the electrolyte membrane, known fillers can be added, or the electrolyte membrane can be composited with reinforcing agents such as glass nonwoven fabric by pressing.

[0201] In addition, without affecting the processing and performance of the electrolyte membrane, the electrolyte membrane may contain various commonly used additives, such as compatibilizers to improve compatibility, antioxidants to prevent resin deterioration, antistatic agents to improve the operability of the membrane during molding and processing, lubricants, etc.

[0202] There are no particular restrictions on the thickness of the electrolyte membrane; it can be set appropriately according to the purpose and application.

[0203] The thickness of the electrolyte membrane is, for example, 0.1 to 350 μm, preferably 1 to 200 μm.

[0204] The embodiments of the present invention have been described above, but the embodiments of the present invention are not limited thereto. Within the scope of the spirit of the present invention, the design can be appropriately modified.

[0205] Example

[0206] Next, the present invention will be described based on embodiments and comparative examples, but the present invention is not limited to the following embodiments.

[0207] <Synthesis of Monomer 1>

[0208] In a 100 mL round-bottom three-necked flask equipped with a nitrogen inlet and a condenser, 1,6-diiodoperfluorohexane (5.54 g, 10.0 mmol), 3-chloroiodobenzene (11.9 g, 50 mmol), and N,N-dimethyl sulfoxide (60 mL) were added. After stirring the mixture to form 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 was stopped by adding the reaction solution dropwise to a 0.1 M nitric acid aqueous solution. The precipitate recovered from the mixture was washed with methanol by filtration, and the filtrate was recovered. Repeating the same operation, the white solid precipitated by adding pure water to the combined filtrate was recovered by filtration, washed with a mixture of pure water and methanol (pure water / methanol = 1 / 1), and dried under vacuum (60 °C) overnight, thus yielding monomer 1 (white solid) as shown in the following formula in 84% yield.

[0209] [Chemistry 26]

[0210]

[0211] <Synthesis of Monomer 2>

[0212] In a 500 mL round-bottom three-necked flask, fluorene (83.1 g, 0.50 mol), N-chlorosuccinimide (167 g, 1.25 mol), and acetonitrile (166 mL) were added. The mixture was stirred to form a homogeneous solution, and then 12 M hydrochloric acid (16.6 mL) was added. The reaction was carried out at room temperature for 24 hours. The precipitate recovered from the reaction solution by filtration was washed with methanol and pure water, and then dried under vacuum (60 °C) overnight to give monomer 2 (white solid) as shown in the following formula in 65% yield.

[0213] [Chemistry 27]

[0214]

[0215] <Synthesis of Monomer 3>

[0216] In a 300 mL round-bottom three-necked flask, monomer 2 (8.23 g, 35.0 mmol) and 1,6-dibromohexane (53 mL) were added. After stirring the mixture to form a homogeneous solution, a mixture of tetrabutylammonium (2.26 g, 7.00 mmol), potassium hydroxide (35.0 g), and purified water (35 mL) was added, and the reaction was carried out at 80 °C for 1 hour. The reaction was stopped by adding purified water to the reaction solution. The target compound was extracted from the aqueous layer with dichloromethane. The combined organic layers were washed with purified water and brine, and water, dichloromethane, and 1,6-dibromohexane were removed by distillation. The crude product was purified by silica gel column chromatography (elution solvent: dichloromethane / hexane = 1 / 4), and then dried under vacuum (60 °C) overnight to give monomer 3 (pale yellow solid) in 75% yield.

[0217] [Chemistry 28]

[0218]

[0219] <Synthesis of Monomer 4>

[0220] Monomer 3 (13.2 g, 23.4 mol) and tetrahydrofuran (117 mL) were added to a 300 mL round-bottom three-necked flask. After stirring the mixture to form a homogeneous solution, 58.6 mL of 40 wt% dimethylamine aqueous solution was added, and the reaction was carried out at room temperature for 24 hours. The reaction was stopped by adding saturated sodium bicarbonate aqueous solution to the reaction solution. After removing the tetrahydrofuran, hexane was added for extraction of the target component. The organic layer was washed with brine, and water and hexane were removed by distillation. Monomer 4 (pale yellow solid) was obtained in 75% yield by vacuum drying at 40 °C overnight.

[0221] [Chemistry 29]

[0222]

[0223] [Example 1: Synthesis of Anion Exchange Resin 1]

[0224] (Polymerization reaction)

[0225] In a 100 mL three-necked flask equipped with a nitrogen inlet and a condenser, monomer 1 (1.05 g, 2.01 mmol), monomer 4 (0.295 g, 0.602 mmol), 2,2'-bipyridine (bpy, 0.496 g, 3.14 mmol, 1.2 eq.), and N,N-dimethylacetamide (6.3 mL) were added. The mixture was stirred to form a homogeneous solution and then heated to 80 °C. Bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2, 0.432 g, 1.57 mmol, 0.6 eq.) was added to this solution, and the reaction was carried out at 80 °C for 1 hour. Tetraethylammonium iodide (TEAI, 0.807 g, 3.14 mmol, 1.2 eq.) as a co-catalyst and zinc (Zn, 0.411 g, 6.28 mmol, 2.4 eq.) as a reducing agent were added to the obtained slurry, and the reaction was carried out at 80 °C for 2 hours. After the reaction mixture was naturally cooled to room temperature, it was added dropwise to a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2), 0.2 M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60 °C) overnight to obtain anion exchange resin precursor polymer 1 (yellow solid) in 96% yield.

[0226] [Chemistry 30]

[0227]

[0228] (Quercing reaction, membrane formation, ion exchange)

[0229] In a 50 mL round-bottom three-necked flask, 1.70 g of anion exchange resin precursor polymer 1 and 9.6 mL of N,N-dimethylacetamide were added. The mixture was stirred to form a homogeneous solution, and then 0.45 mL of methyl iodide (7.22 mmol) was added. The reaction was carried out at room temperature for 48 hours. The reaction solution containing 10 mL of N,N-dimethylacetamide was filtered. The filtrate was cast onto a glass plate edged with silicone rubber and dried on a leveled heating plate (50 °C). The membrane was washed in 2 L of pure water and then vacuum dried (60 °C) overnight to obtain a light brown, transparent membrane. This membrane was then immersed in a 1 M potassium hydroxide aqueous solution for 48 hours and washed with degassed pure water to convert the counter ion of the ion exchange group (quaternary ammonium group) from iodide ions to hydroxide ions. Thus, a membrane of anion exchange resin 1 (m / n = 1 / 0.30, hydroxide ion type) as shown in the following formula was obtained.

[0230] [Chemistry 31]

[0231]

[0232] [Example 2: Synthesis of Anion Exchange Resin 2]

[0233] Except for using anion exchange resin precursor polymer 2 obtained by the following polymerization reaction, the quaternization reaction, membrane preparation, and ion exchange were carried out in the same manner as in Example 1, thereby obtaining a membrane of anion exchange resin 2 (m / n = 1 / 0.30, hydroxide ion type).

[0234] (Polymerization reaction)

[0235] In a 100 mL three-necked flask equipped with a nitrogen inlet and a condenser, monomer 1 (1.05 g, 2.01 mmol), monomer 4 (0.295 g, 0.602 mmol), 2,2'-bipyridine (bpy, 0.496 g, 3.14 mmol, 1.2 eq.), and N,N-dimethylacetamide (6.3 mL) were added. The mixture was stirred to form a homogeneous solution and then heated to 80 °C. Bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2, 0.432 g, 1.57 mmol, 0.6 eq.) was added to this solution, and the reaction was carried out at 80 °C for 1 hour. Tetraethylammonium bromide (TEAB, 0.660 g, 3.14 mmol, 1.2 eq.) as a co-catalyst and zinc (Zn, 0.411 g, 6.28 mmol, 2.4 eq.) as a reducing agent were added to the obtained slurry, and the reaction was carried out at 80 °C for 2 hours. After the reaction mixture was naturally cooled to room temperature, it was added dropwise to a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2), 0.2 M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60 °C) overnight to obtain anion exchange resin precursor polymer 2 (yellow solid) in 97% yield.

[0236] [Example 3: Synthesis of Anion Exchange Resin 3]

[0237] Except for using anion exchange resin precursor polymer 3 obtained by the following polymerization reaction, the quaternization reaction, membrane formation, and ion exchange were carried out in the same manner as in Example 1 to obtain a membrane of anion exchange resin 3 (m / n = 1 / 0.30, hydroxide ion type).

[0238] (Polymerization reaction)

[0239] In a 100 mL three-necked flask equipped with a nitrogen inlet and a condenser, monomer 1 (1.05 g, 2.01 mmol), monomer 4 (0.295 g, 0.602 mmol), 2,2'-bipyridine (bpy, 0.331 g, 2.10 mmol, 0.8 eq.), and N,N-dimethylacetamide (6.3 mL) were added. The mixture was stirred to form a homogeneous solution and then heated to 80 °C. Bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2, 0.288 g, 1.05 mmol, 0.4 eq.) was added to this solution, and the reaction was carried out at 80 °C for 1 hour. Tetraethylammonium bromide (TEAB, 0.440 g, 2.10 mmol, 0.8 eq.) as a co-catalyst and zinc (Zn, 0.274 g, 4.19 mmol, 1.6 eq.) as a reducing agent were added to the obtained slurry, and the reaction was carried out at 80 °C for 2 hours. After the reaction mixture was naturally cooled to room temperature, it was added dropwise to a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2), 0.2 M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60 °C) overnight to obtain anion exchange resin precursor polymer 3 (yellow solid) in 100% yield.

[0240] [Example 4: Synthesis of Anion Exchange Resin 4]

[0241] Except for using anion exchange resin precursor polymer 4 obtained by the following polymerization reaction, the quaternization reaction, membrane formation, and ion exchange were carried out in the same manner as in Example 1 to obtain a membrane of anion exchange resin 4 (m / n = 1 / 0.30, hydroxide ion type).

[0242] (Polymerization reaction)

[0243] In a 100 mL three-necked flask equipped with a nitrogen inlet and a condenser, monomer 1 (1.05 g, 2.01 mmol), monomer 4 (0.295 g, 0.602 mmol), 2,2'-bipyridine (bpy, 0.248 g, 1.57 mmol, 0.6 eq.), and N,N-dimethylacetamide (6.3 mL) were added. The mixture was stirred to form a homogeneous solution and then heated to 80 °C. Bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2, 0.216 g, 0.785 mmol, 0.3 eq.) was added to this solution, and the reaction was carried out at 80 °C for 1 hour. Tetraethylammonium bromide (TEAB, 0.330 g, 1.57 mmol, 0.6 eq.) as a co-catalyst and zinc (Zn, 0.206 g, 3.14 mmol, 1.2 eq.) as a reducing agent were added to the obtained slurry, and the reaction was carried out at 80 °C for 2 hours. After the reaction mixture was naturally cooled to room temperature, it was added dropwise to a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2), 0.2 M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60 °C) overnight to obtain anion exchange resin precursor polymer 4 (yellow solid) in 100% yield.

[0244] [Comparative Example 1: Synthesis of Anion Exchange Resin C1]

[0245] Except for using the anion exchange resin precursor polymer C1 obtained by the following polymerization reaction, the quaternization reaction, membrane preparation, and ion exchange were carried out in the same manner as in Example 1, thereby obtaining a membrane of anion exchange resin C1 (m / n = 1 / 0.30, hydroxide ion type).

[0246] (Polymerization reaction)

[0247] In a 100 mL three-necked flask equipped with a nitrogen inlet and a condenser, monomer 1 (1.05 g, 2.01 mmol), monomer 4 (0.295 g, 0.602 mmol), 2,2'-bipyridine (bpy, 0.165 g, 1.05 mmol, 0.4 eq.), and N,N-dimethylacetamide (6.3 mL) were added. The mixture was stirred to form a homogeneous solution and then heated to 80 °C. Bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2, 0.144 g, 0.52 mmol, 0.2 eq.) was added to this solution, and the reaction was carried out at 80 °C for 1 hour. Tetraethylammonium bromide (TEAB, 0.220 g, 1.05 mmol, 0.4 eq.) as a co-catalyst and zinc (Zn, 0.137 g, 2.09 mmol, 0.8 eq.) as a reducing agent were added to the obtained slurry, and the reaction was carried out at 80 °C for 2 hours. After the reaction mixture was naturally cooled to room temperature, it was added dropwise to a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2) to stop the reaction. The precipitate recovered from the mixture by filtration was washed with a mixed solution of methanol / pure water / 12 M hydrochloric acid (1 / 1 / 2), 0.2 M potassium carbonate aqueous solution, and pure water, and then vacuum dried (60 °C) overnight to obtain anion exchange resin precursor polymer 3 (yellow solid) in 51% yield.

[0248] [Comparative Example 2: Synthesis of Anion Exchange Resin C2]

[0249] Except for using the anion exchange resin precursor polymer C2 obtained by the following polymerization reaction, the quaternization reaction, membrane preparation, and ion exchange were carried out in the same manner as in Example 1, thereby obtaining a membrane of anion exchange resin C2 (m / n = 1 / 0.30, hydroxide ion type).

[0250] (Polymerization reaction)

[0251] In a 100 mL three-necked flask equipped with a nitrogen inlet and a condenser, monomer 1 (1.05 g, 2.01 mmol), monomer 4 (0.295 g, 0.602 mmol), 2,2'-bipyridine (bpy, 1.984 g, 12.56 mmol, 4.8 eq.), and N,N-dimethylacetamide (6.3 mL) were added. The mixture was stirred to form a homogeneous solution and then heated to 80 °C. Bis(1,5-cyclooctadiene)nickel(0) (Ni(cod)2, 1.728 g, 6.28 mmol, 2.4 eq.) was added to this solution, and the reaction was carried out at 80 °C for 3 hours. After the reaction mixture was allowed to cool naturally to room temperature, it was added dropwise to a 1 / 1 / 2 mixture of methanol / pure water / 12 M hydrochloric acid to stop the reaction. The precipitate recovered from the mixture by filtration was washed with a mixed solution of methanol / pure water / 12M hydrochloric acid (1 / 1 / 2), 0.2M potassium carbonate aqueous solution and pure water, and then vacuum dried (60°C) overnight to obtain the anion exchange resin precursor polymer C2 (yellow solid) in 100% yield.

[0252] <Molecular Weight Evaluation>

[0253] The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the anion exchange resin membranes obtained in the examples and comparative examples were determined. The determinations were performed using gel permeation chromatography. A Shodex K-805L column was used, and polystyrene was used as the standard. The results are shown in Table 1.

[0254] [Table 1]

[0255] Table 1

[0256] <![CDATA[Ni(cod)2 / monomer]]> co-catalyst Mn[kDa] Mw[kDa] Example 1 0.6 TEAI 9 81 Example 2 0.6 TEAB 20 208 Example 3 0.4 TEAB 18 150 Example 4 0.3 TEAB 16 116 Comparative Example 1 0.2 TEAB 4 7 Comparative Example 2 2.4 - 16 136

[0257] It can be seen that the molecular weight (especially the weight-average molecular weight) of the sample of the example is higher than that of the sample of the comparative example (especially the weight-average molecular weight), and the mechanical properties (strength) are excellent.

Claims

1. A method for manufacturing anion exchange resin, comprising the following steps: (A) A process for preparing a monomer for forming a hydrophobic group, the monomer being composed of a single aromatic ring or multiple 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 directly bonded, wherein two chlorine atoms are bonded to the aromatic ring. (B) A step of preparing a monomer for forming a hydrophilic group, the monomer being composed of a single aromatic ring, or composed of multiple 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, or a divalent sulfur-containing group, i.e., a linking group, and / or direct bonding, wherein two chlorine atoms are bonded to the aromatic ring, and at least one of the linking group or aromatic rings is bonded to an anion exchange group precursor functional group via a divalent saturated hydrocarbon group or direct bonding; (C) A step of synthesizing a polymer by reacting the monomer for forming the hydrophobic group with the monomer for forming the hydrophilic group in the presence of bis(1,5-cyclooctadiene)nickel(0) as a catalyst, 2,2'-bipyridine as a co-ligand, a bromide or iodide as a co-catalyst, and a reducing agent; and (D) The step of ionizing the functional group of the anion exchange group precursor to form an anion exchange group. Its features are, The molar number of bis(1,5-cyclooctadiene)nickel (0) used in step (C) is 0.3 to 1.8 times the total molar number of the monomer for forming the hydrophobic group and the monomer for forming the hydrophilic group. In the anion exchange resin, The hydrophobic group is formed by the residues of the monomer to form a divalent hydrophobic group, the hydrophobic group comprising a bisphenol residue represented by the following formula (2), which can be substituted with a halogen atom or a halide-like compound or an alkyl or aryl group. [Chemistry 1] In the formula, R represents a hydrocarbon group that can be substituted by a halogen atom or a halide-like compound, a silicon-containing group that can be substituted by a halogen atom or a halide-like compound, a nitrogen-containing group that can be substituted by a halogen atom or a halide-like compound, a phosphorus-containing group that can be substituted by a halogen atom or a halide-like compound, an oxygen-containing group that can be substituted by a halogen atom or a halide-like compound, or a directly bonded group; Alk may be the same or different and represent alkyl or aryl groups; X may be the same or different and represent halogen atoms or halide-like compounds; a, b, c, and d may be the same or different and represent integers from 0 to 4. The hydrophilic group having the anion exchange group is formed by the residues of the monomer forming a divalent hydrophilic group, the hydrophilic group comprising a fluorene residue represented by the following formula (3). [Chemistry 2] In the formula, Ion and Ion' are the same or different, representing anion exchange groups; y and z are the same or different, representing integers from 2 to 20. The hydrophobic group and the hydrophilic group are bonded by direct bonding.

2. The method for manufacturing the anion exchange resin according to claim 1, characterized in that, The co-catalyst is quaternary ammonium bromide or quaternary ammonium iodide.

3. The method for manufacturing the anion exchange resin according to claim 1 or 2, characterized in that, The number of moles of the co-catalyst used in step (C) is 1.0 to 3.0 times the number of moles of bis(1,5-cyclooctadiene)nickel(0).

4. The method for manufacturing the anion exchange resin according to claim 1, characterized in that, The reducing agent is metallic zinc or metallic magnesium.

5. The method for manufacturing the anion exchange resin according to claim 1, characterized in that, The number of moles of 2,2′-bipyridine used in step (C) is 1.5 to 2.5 times the number of moles of bis(1,5-cyclooctadiene)nickel (0).

6. The method for manufacturing the anion exchange resin according to claim 1, characterized in that, The hydrophobic group comprises a bisphenol residue represented by the following formula (1), which may be substituted with a halogen atom or a halide-like compound or an alkyl or aryl group. [Chemistry 3] In the formula, Alk, X, a, b, c and d have the same meaning as Alk, X, a, b, c and d in the formula (2), Z are the same or different and represent carbon atoms or silicon atoms, R are the same or different and represent silicon-containing groups, nitrogen-containing groups, phosphorus-containing groups, oxygen-containing groups, sulfur-containing groups or direct bonding, l represents an integer greater than 1, and h, h', h”, i, i', i”, j and k are the same or different and represent an integer greater than 0.

7. The method for manufacturing the anion exchange resin according to claim 6, characterized in that, In the above formula (1), Z is a carbon atom, R is a direct bond, X is a fluorine atom, and h, h', h”, i, i', i”, j and k are 0.

8. A method for manufacturing an electrolyte membrane, characterized in that, have: The process of obtaining anion exchange resin using the method according to any one of claims 1-7; and The process of obtaining an electrolyte membrane containing the anion exchange resin.

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