Anion exchange polymer electrolyte membrane, water electrolysis device, carbon dioxide electrolysis device, fuel cell, and method for producing anion exchange polymer electrolyte membrane

Abstract

An anion exchange-type polymer electrolyte membrane contains an ionic group-containing polymer having an ionic group part represented by formula (I) and a polymer part. In formula (I), Z- is at least one counter ion selected from the group consisting of OH-, HCO3 -, 1 / 2CO3 2-, Cl-, Br-, and I-, each of a, b, c, and d is a positive integer of at most 3, a plurality of Rs are each independently a C1-C10 hydrocarbon group, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. R1 is a hydrogen atom or a C1-C10 hydrocarbon group, and * represents a bonding position.

Description

[Technical Field]

[0001] The present disclosure relates to an anion-exchange polymer electrolyte membrane, a water electrolysis device, a carbon dioxide electrolysis device, a fuel cell, and a method for producing an anion-exchange polymer electrolyte membrane. [Background technology]

[0002] BACKGROUND ART Solid polymer electrolyte membranes are used in various fuel cells such as solid polymer fuel cells and solid alkaline fuel cells, and in various electrolysis techniques such as water electrolysis. As a solid polymer electrolyte membrane, the use of an anion-exchange polymer electrolyte membrane is being considered, since the reaction field becomes alkaline and metals other than noble metals can be used as electrode catalyst materials.

[0003] Patent Document 1 discloses an anion-conducting polymer membrane (hereinafter also referred to as an "anion-exchange polymer electrolyte membrane"). The membrane disclosed in Patent Document 1 is an anion-conducting polymer membrane containing a terpolymer of styrene, vinylbenzyl-Rs, and vinylbenzyl-Rx. Rs is a positively charged cyclic amine group. Rx is at least one element selected from the group consisting of Cl, OH, and OH, or a reaction product of Cl with an inorganic or organic species other than amines. The total mass of the vinylbenzyl-Rs groups is 15% to 90% by mass of the total mass of the terpolymer. The total mass of the vinylbenzyl-Rx groups is 1% to 25% by mass of the total mass of the terpolymer.

[0004] Patent Document 1: Patent No. 6585859 Summary of the Invention [Problem to be solved by the invention]

[0005] However, as a result of investigations by the inventors, it became clear that there is room for improvement in the flexibility of the anion-exchange polymer electrolyte membrane disclosed in Patent Document 1. If the anion-exchange polymer electrolyte membrane is not flexible, the membrane is prone to cracking and tearing, which may significantly impair the performance of the electrolyte membrane.

[0006] In view of the above circumstances, an object of the present disclosure is to provide an anion-exchange polymer electrolyte membrane, a water electrolysis device, a carbon dioxide electrolysis device, a fuel cell, and a method for producing an anion-exchange polymer electrolyte membrane, which are highly flexible. [Means for solving the problem]

[0007] The means for solving the above problems include the following embodiments.

[0008] <1> An anion-exchange polymer electrolyte membrane comprising an ionic group-containing polymer having an ionic group moiety represented by formula (I) and a polymer moiety.

[0009] [ka]

[0010] (In formula (I), Z - OH - , HCO3 - , 1 / 2CO3 2- , Cl - , Br - and I - where a, b, c, and d are each a positive integer of 3 or less, and the multiple Rs are each independently a hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. 1 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and * indicates the bonding position. <2> The ionic group-containing polymer contains a structural unit represented by formula (II). <1> The anion exchange polymer electrolyte membrane according to claim 1.

[0011] [ka]

[0012] (In formula (II), R 2a , R 2b , R 2c , R 2d and R 2e at least one group selected from the following is independently a group represented by formula (ii), and the remaining groups which are not a group represented by formula (ii) are independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 5 to 50,000; In formula (ii), Z - OH - , HCO3 - , 1 / 2CO3 2- , Cl - , Br - and I - and each of a, b, c, and d is 3 or less positive integers. The Rs are each independently a hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. 1 , R 3a and R 3b are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and ** indicates the bonding position.) <3> The ionic group-containing polymer further contains a structural unit represented by formula (III). <1> or <2> The anion exchange polymer electrolyte membrane according to claim 1.

[0013] [ka]

[0014] (In formula (III), R 4a , R 4b , R 4c , R 4d and R 4e at least one group selected from the following is independently a group represented by formula (iii), and the remaining groups which are not a group represented by formula (iii) are independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 5 to 50,000; In formula (iii), R 5a and R 5b are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a hydroxyl group, a chlorine atom, a bromine atom or an iodine atom, and *** indicates the bonding position. <4> The structural units represented by the formula (III) are partly crosslinked. <3> The anion exchange polymer electrolyte membrane according to claim 1. <5> The conductivity retention rate of the anion exchange polymer electrolyte membrane after the immersion test is 85% or more, The immersion test is a test in which the anion exchange polymer electrolyte membrane is immersed in a 1N potassium hydroxide aqueous solution at 80°C for 1000 hours. <1> ~ <4> 10. The anion exchange polymer electrolyte membrane according to claim 9, wherein the anion exchange polymer electrolyte membrane is an anion exchange polymer electrolyte membrane. <6> wherein R of the ionic group moiety represented by formula (I) is a methyl group or an ethyl group. <1> ~ <5> 10. The anion exchange polymer electrolyte membrane according to claim 9, wherein the anion exchange polymer electrolyte membrane is an anion exchange polymer electrolyte membrane. <7> R of the ionic group moiety represented by formula (I) 1 is a methyl group, an ethyl group, a propyl group, or an isopropyl group; <1> ~ <6> 10. The anion exchange polymer electrolyte membrane according to claim 9, wherein the anion exchange polymer electrolyte membrane is an anion exchange polymer electrolyte membrane. <8> The aforementioned is used to produce hydrogen by water electrolysis. <1> ~ <7> 10. The anion exchange polymer electrolyte membrane according to claim 9, wherein the anion exchange polymer electrolyte membrane is an anion exchange polymer electrolyte membrane. <9> The method for producing carbon monoxide by electrochemically reducing carbon dioxide, <1> ~ <7> 10. The anion exchange polymer electrolyte membrane according to claim 9, wherein the anion exchange polymer electrolyte membrane is an anion exchange polymer electrolyte membrane. <10> The above-mentioned fuel cell <1> ~ <7> 10. The anion exchange polymer electrolyte membrane according to claim 9, wherein the anion exchange polymer electrolyte membrane is an anion exchange polymer electrolyte membrane. <11> The aforementioned <1> ~ <7> 1. A water electrolysis device comprising the anion exchange polymer electrolyte membrane according to any one of claims 1 to 9. <12> The aforementioned <1> ~ <7> 10. A carbon dioxide electrolysis device comprising the anion exchange polymer electrolyte membrane according to any one of claims 1 to 9. <13> The aforementioned <1> ~ <7> 10. A fuel cell comprising the anion exchange polymer electrolyte membrane according to any one of claims 1 to 9. <14> The aforementioned <4> A method for producing the anion exchange polymer electrolyte membrane according to claim 1, applying a varnish containing the ionic group-containing polymer to a substrate and drying the varnish to form a polymer film on the substrate; treating the polymer membrane with an alkali hydroxide to form an anion exchange polymer electrolyte membrane; A method for producing an anion exchange polymer electrolyte membrane, comprising: [Effects of the Invention]

[0015] According to the present disclosure, there are provided an anion exchange polymer electrolyte membrane having excellent flexibility, a water electrolysis device, a carbon dioxide electrolysis device, a fuel cell, and a method for producing an anion exchange polymer electrolyte membrane. [Brief explanation of the drawings]

[0016] [Figure 1] FIG. 1 is a diagram showing a 1H-NMR measurement chart of the styrene / 4-vinylbenzyl chloride copolymer obtained in Example 1. [Figure 2] FIG. 2 is a chart showing the measurement result of 31P-NMR analysis of the third white solid obtained in Example 1. [Figure 3] FIG. 3 is a chart showing the measurement result of 31P-NMR analysis of the fourth white solid obtained in Example 1. [Figure 4] FIG. 4 is a cross-sectional view of a measurement cell for measuring the conductivity of the anion-exchange polymer electrolyte membrane of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0017] The present disclosure will now be described in detail with reference to examples of preferred embodiments, and these descriptions and examples are intended to illustrate the embodiments and are not intended to limit the scope of the embodiments. In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. In the following embodiments, the components (including element steps, etc.) are not essential unless otherwise specified, or unless they are clearly considered essential in principle, etc. The same applies to numerical values ​​and their ranges, and they do not limit the present invention. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In the numerical ranges described in this disclosure, the upper or lower limit value described in a certain numerical range may be replaced with the value shown in the examples. In this specification, the amount of each component in a composition means the total amount of the multiple substances present in the composition, unless otherwise specified, when multiple substances corresponding to each component are present in the composition. In the present disclosure, "mass %" and "weight %" are synonymous. In this specification, the term "process" includes not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved. In the description of a group (atomic group) in this specification, a description that does not specify whether it is substituted or unsubstituted includes both a group having no substituent and a group having a substituent. In the present disclosure, the term "layer" includes cases where the layer is formed over the entire area when the area in which the layer exists is observed, as well as cases where the layer is formed over only a portion of the area.

[0018] Hereinafter, embodiments of an anion-exchange polymer electrolyte membrane, a water electrolysis device, a carbon dioxide electrolysis device, and a fuel cell according to the present disclosure will be described with reference to the drawings.

[0019] The anion exchange polymer electrolyte membrane of the present disclosure can be used as an anion transport material for forming a membrane electrode assembly (MEA) used in anion exchange membrane fuel cells, water electrolysis devices, carbon dioxide electrolysis devices, etc. Here, the membrane electrode assembly includes a positive electrode catalyst layer, a negative electrode catalyst layer, and a polymer electrolyte membrane, and the positive electrode catalyst layer and the negative electrode catalyst layer act as a cathode and an anode, respectively, when used as a fuel cell, and act as an anode and a cathode, respectively, when used as a water electrolysis device or a carbon dioxide electrolysis device.

[0020] (1) Anion-exchange polymer electrolyte membrane The anion exchange polymer electrolyte membrane of the present disclosure contains an ionic group-containing polymer having an ionic group moiety represented by formula (I) and a polymer moiety.

[0021] [ka]

[0022] In formula (I), Z - OH - , HCO3 - , 1 / 2CO3 2- , Cl - , Br - and I - where a, b, c, and d are each a positive integer of 3 or less, and the multiple Rs are each independently a hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. 1 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and * indicates the bonding position.

[0023] In the present disclosure, the term "ionic group-containing polymer" refers to a polymer having an ionic group moiety and a polymer moiety. The polymer may or may not have a crosslinked structure. In the present disclosure, "plurality of R" refers to (4×a+4×b+4×c+4×d+6) Rs in formula (I).

[0024] The anion-exchange polymer electrolyte membrane of the present disclosure has excellent flexibility because it contains an ionic group-containing polymer.

[0025] In formula (I), “Z - " is the counter ion of the quaternary salt type anion exchange group, and OH - , HCO3 - , 1 / 2CO3 2- , Cl - , Br - and I - "Z" is one or more counter ions selected from the group consisting of - " may be one type of counter ion, or two or more types of counter ions may be present in combination. Among them, Z - OH - It is preferable that:

[0026] In formula (I), "each of a, b, c, and d" is a positive integer of 3 or less. Each of a, b, c, and d is preferably a positive integer of 2 or less. Preferred combinations of a, b, c, and d include (2,2,2,2), (2,2,2,1), (2,2,1,1), (2,1,1,1), or (1,1,1,1), regardless of the order of a, b, c, and d, and a particularly preferred combination is (1,1,1,1).

[0027] In formula (I), the "plural R's" are each independently a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group represented by R is not particularly limited and may be a substituted or unsubstituted hydrocarbon group, or a substituted or unsubstituted aromatic hydrocarbon group. A "substituted hydrocarbon group" refers to an unsubstituted hydrocarbon group in which at least one hydrogen atom has been substituted with a substituent. A "substituted aromatic hydrocarbon group" refers to an unsubstituted aromatic hydrocarbon group in which at least one hydrogen atom has been substituted with a substituent. Specific examples of the substituent in the substituted hydrocarbon group and substituted aromatic hydrocarbon group include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, etc. The hydrocarbon group or aromatic hydrocarbon group may be substituted with one or more of these substituents, and may be substituted with a single or different types of substituents.

[0028] Examples of the substituted or unsubstituted hydrocarbon group include: linear alkyl groups having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or an n-octyl group; Isopropyl, isobutyl, sec-butyl, isopentyl, sec-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 1-n-propylbutyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1-methylheptyl monoalkyl-substituted alkyl groups having 2 to 10 carbon atoms, such as a 2-methylheptyl group, a 3-methylheptyl group, a 4-methylheptyl group, a 5-methylheptyl group, a 6-methylheptyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 4-ethylhexyl group, a 1-n-propylpentyl group, a 2-n-propylpentyl group, a 1-iso-propylpentyl group, a 2-iso-propylpentyl group, a 1-n-butylbutyl group, a 1-iso-butylbutyl group, a 1-sec-butylbutyl group, a 1-tert-butylbutyl group, and a 2-tert-butylbutyl group; tert-Butyl group, tert-pentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 1,4-dimethylpentyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3,4-dimethylpentyl group butyl group, 1-ethyl-1-methylbutyl group, 1-ethyl-2-methylbutyl group, 1-ethyl-3-methylbutyl group, 2-ethyl-1-methylbutyl group, 2-ethyl-3-methylbutyl group, 1,1-dimethylhexyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 1,4-dimethylhexyl group, 1,5-dimethylhexyl group, 2,2-dimethylhexyl group, 2,3-dimethylhexyl group, 2,4-dimethylhexyl group, 2,5-dimethylhexyl group, 3 ,3-dimethylhexyl group, 3,4-dimethylhexyl group, 3,5-dimethylhexyl group, 4,4-dimethylhexyl group, 4,5-dimethylhexyl group, 1-ethyl-2-methylpentyl group, 1-ethyl-3-methylpentyl group, 1-ethyl-4-methylpentyl group, 2-ethyl-1-methylpentyl group, 2-ethyl-2-methylpentyl group, 2-ethyl-3-methylpentyl group, 2-ethyl-4-methylpentyl group, 3-ethyl-1-methylpentyl group, 3-ethyl-2 dialkyl-substituted alkyl groups having 3 to 10 carbon atoms, such as a 1-methylpentyl group, a 3-ethyl-3-methylpentyl group, a 3-ethyl-4-methylpentyl group, a 1-n-propyl-1-methylbutyl group, a 1-n-propyl-2-methylbutyl group, a 1-n-propyl-3-methylbutyl group, a 1-iso-propyl-1-methylbutyl group, a 1-iso-propyl-2-methylbutyl group, a 1-iso-propyl-3-methylbutyl group, a 1,1-diethylbutyl group, and a 1,2-diethylbutyl group; 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1,1,2-trimethylbutyl group, 1,1,3-trimethylbutyl group, 1,2,3-trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 1,1,2-trimethylpentyl group, 1,1,3-trimethylpentyl group, 1,1,4-trimethylpentyl group, 1,2,2-trimethylpentyl group, 1,2,3-trimethylpentyl group, 1,2,4-trimethylpentyl group, 1,3,4-trimethylpentyl group, 2,2,3-trimethylpentyl group, 2,2,4-trimethylpentyl group trialkyl-substituted alkyl groups having 4 to 10 carbon atoms, such as a methyl group, a 2,3,4-trimethylpentyl group, a 1,3,3-trimethylpentyl group, a 2,3,3-trimethylpentyl group, a 3,3,4-trimethylpentyl group, a 1,4,4-trimethylpentyl group, a 2,4,4-trimethylpentyl group, a 3,4,4-trimethylpentyl group, a 1-ethyl-1,2-dimethylbutyl group, a 1-ethyl-1,3-dimethylbutyl group, a 1-ethyl-2,3-dimethylbutyl group, a 2-ethyl-1,1-dimethylbutyl group, a 2-ethyl-1,2-dimethylbutyl group, a 2-ethyl-1,3-dimethylbutyl group, and a 2-ethyl-2,3-dimethylbutyl group; cyclic alkyl groups having 3 to 20 carbon atoms, such as a cyclopentyl group and a cyclohexyl group; alkyl-substituted cyclic alkyl groups having 4 to 10 carbon atoms, such as a methylcyclopentyl group, a methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 1,4-dimethylcyclohexyl group, and an ethylcyclohexyl group; aryl-substituted alkyl groups having 7 to 10 carbon atoms, such as a benzyl group, a 4-methylbenzyl group, or a 4-ethylbenzyl group; halogenated alkyl groups having 1 to 10 carbon atoms and partially or fully substituted with halogen atoms, such as a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoroethyl group, a chloroethyl group, a bromoethyl group, a trifluoroethyl group, a pentafluoroethyl group, a tetrachloroethyl group, or a hexafluoroisopropyl group; Vinyl group, 1-propenyl group, allyl group (2-propenyl group), isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, 2-methyl-2-propenyl group, 1-methyl-2-propenyl group, 2-methyl-1-propenyl group, hexenyl group, ethynyl group, 1-propynyl group, 2-propynyl group (synonymous with propargyl group), 1-butynyl group, 2-butynyl group, 3-butynyl group linear or branched unsaturated aliphatic groups (i.e., alkenyl or alkynyl groups), such as 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 5-hexynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 2-methyl-3-pentynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1,1-dimethyl-2-butynyl, and 1-hexynyl; cycloaliphatic groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-cyclopentenyl group, and a 1-cyclohexenyl group; etc.

[0029] Examples of the substituted or unsubstituted aromatic hydrocarbon group include: an aryl group having 6 to 10 carbon atoms, such as a phenyl group or a naphthyl group; monoalkyl-substituted aryl groups having 7 to 10 carbon atoms, such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a propylphenyl group, and a butylphenyl group; dialkyl-substituted aryl groups having 8 to 10 carbon atoms, such as a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, and a 3,6-dimethylphenyl group; trialkyl-substituted aryl groups having 9 or 10 carbon atoms, such as a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,4,6-trimethylphenyl group, or a 3,4,5-trimethylphenyl group; a monoalkoxyaryl group having 7 to 10 carbon atoms substituted with a substituted or unsubstituted alkoxy group having 4 or less carbon atoms, such as a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 2-ethoxyphenyl group, a propoxyphenyl group, or a butoxyphenyl group; dialkoxyaryl groups having 8 to 10 carbon atoms substituted with a substituted or unsubstituted alkoxy group having 4 or less carbon atoms, such as a 2,3-dimethoxyphenyl group, a 2,4-dimethoxyphenyl group, a 2,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 3,5-dimethoxyphenyl group, or a 3,6-dimethoxyphenyl group; trialkoxyaryl groups having 9 or 10 carbon atoms substituted with a substituted or unsubstituted alkoxy group having 4 or less carbon atoms, such as a 2,3,4-trimethoxyphenyl group, a 2,3,5-trimethoxyphenyl group, a 2,3,6-trimethoxyphenyl group, a 2,4,5-trimethoxyphenyl group, a 2,4,6-trimethoxyphenyl group, or a 3,4,5-trimethoxyphenyl group; an aryl group having 6 to 10 carbon atoms substituted with a halogen atom, such as a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a bromophenyl group, a dibromophenyl group, an iodophenyl group, a fluorophenyl group, a chloronaphthyl group, a bromonaphthyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, or a pentafluorophenyl group; halogenated alkylaryl groups having 7 to 10 carbon atoms substituted with alkyl groups having 4 or less carbon atoms and which are partially or fully substituted with halogen, such as trifluoromethylphenyl groups and trichloromethylphenyl groups; N,N-disubstituted amino-substituted aryl groups having 10 or less carbon atoms, such as an N,N-dimethylaminophenyl group, an N,N-diethylaminophenyl group, an N-phenyl-N-methylaminophenyl group, an N-tolyl-N-ethylaminophenyl group, an N-chlorophenyl-N-cyclohexylaminophenyl group, or an N,N-ditolylaminophenyl group; alkylthioaryl groups or arylthioaryl groups such as a methylthiophenyl group, an ethylthiophenyl group, a methylthionaphthyl group, or a phenylthiophenyl group; etc.

[0030] R is preferably an unsubstituted hydrocarbon group, more preferably a methyl group or an ethyl group. From the viewpoint of producing an ionic group, it is particularly preferred that all of the multiple Rs are methyl groups.

[0031] In formula (I), "two R's on the same nitrogen atom" may be bonded to each other to form a ring structure. Examples of groups formed by bonding two R's on the same nitrogen atom to each other include alkylene groups having 2 to 10 carbon atoms, cycloalkylene groups having 3 to 10 carbon atoms, alkenylene groups having 2 to 10 carbon atoms, cycloalkenylene groups having 3 to 10 carbon atoms, arylene groups having 6 to 20 carbon atoms, and aralkylene groups having 8 to 20 carbon atoms. Examples of alkylene groups having 2 to 10 carbon atoms include dimethylene, trimethylene, tetramethylene, and pentamethylene. Examples of cycloalkylene groups having 3 to 10 carbon atoms include cyclohexylene. Examples of alkenylene groups having 2 to 10 carbon atoms include vinylene. Examples of cycloalkenylene groups having 3 to 10 carbon atoms include cyclohexenylene. Examples of the arylene group having 6 to 20 carbon atoms include phenylene, naphthylene, etc. Examples of the aralkylene group having 8 to 20 carbon atoms include phenylethylene, etc. Among these, the group formed by two Rs on the same nitrogen atom bonding to each other is preferably dimethylene or trimethylene. Such a ring structure may be formed for all or some of the nitrogen atoms to which the two Rs are bonded.

[0032] In formula (I), “R 1 " is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. 1 The hydrocarbon group represented by is not particularly limited, and may be a hydrocarbon group or an aromatic hydrocarbon group. Specific examples of the hydrocarbon group and aromatic hydrocarbon group are the same as those of R. 1 is preferably a hydrocarbon group, more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group, and particularly preferably a methyl group. In formula (I), the * indicating the bonding position is preferably the position where the ionic group portion is bonded to the polymer portion.

[0033] In the ionic group-containing polymer contained in the anion-exchange polymer electrolyte membrane of the present disclosure, the polymer site to which the ionic group represented by general formula (I) is bonded is not particularly limited, and any polymer having a group capable of bonding to the ionic group represented by formula (I) can be used. Various polymer moieties to which ionic groups are bonded are shown, for example, in "Catalyst Lectures, Vol. 10 (Industrial Catalytic Reactions, Part 4), Specific Topics in Catalysts," edited by the Catalysis Society of Japan, First Edition, Kodansha, 1986, pp. 133-163. Specific examples of polymer moieties to which ionic groups are bonded include organic polymers whose main chains are carbon-carbon bonds, such as polystyrene, polyvinylpyridine, polybutadiene, and polyvinyl chloride; organic polymers whose main chains contain oxygen, such as poly(meth)acrylic acid and poly(meth)acrylic acid esters; organic polymers whose main chains contain nitrogen, such as polyamide, polyurethane, and polyimide; organic polymers whose main chains contain silicon, such as polysiloxane and polysilane; organic polymers whose main chains contain sulfur, such as polysulfide and polysulfone; and crosslinked organic polymers, such as polymers in which the above-mentioned various organic polymers have an appropriate crosslinked structure. From the viewpoint of improving the mechanical strength of the anion-exchange polymer electrolyte membrane, the polymer moiety to which the ionic group is bonded is preferably an organic polymer having a main chain of carbon-carbon bonds, or a crosslinked organic polymer having a main chain of carbon-carbon bonds, and more preferably a polystyrene to which the ionic group represented by formula (I) can be bonded and which does not contain a crosslinked structure, or a polystyrene to which the ionic group represented by formula (I) can be bonded and which contains a crosslinked structure.

[0034] In the ionic group-containing polymer contained in the anion-exchange polymer electrolyte membrane of the present disclosure, other components may be copolymerized in the polymer moiety as necessary to adjust the reactivity and physical properties of the anion-exchange polymer electrolyte membrane, within limits that do not contradict the objectives of the present disclosure. Examples of such other components include aromatic vinyl compounds such as styrene, divinylbenzene, α-methylstyrene, vinylnaphthalene, acenaphthylene, vinylpyridine, vinylimidazole, and vinyloxazoline, as well as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, butadiene, and norbornene. The content of structural units derived from other components is not particularly limited and is preferably 0 to 95% by mass, and more preferably 0 to 90% by mass.

[0035] In the anion-exchange polymer electrolyte membrane of the present disclosure, the ionic group-containing polymer preferably contains a constituent unit represented by formula (II).

[0036] [ka]

[0037] In formula (II), R 2a , R 2b , R 2c , R 2d and R 2e at least one group selected from the following is independently a group represented by formula (ii), and the remaining groups which are not a group represented by formula (ii) are independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 5 to 50,000; In formula (ii), Z - OH - , HCO3 - , 1 / 2CO3 2- , Cl - , Br - and I -where a, b, c, and d are each a positive integer of 3 or less, and the multiple Rs are each independently a hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. 1 , R 3a and R 3b are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and ** indicates the bonding position.

[0038] The anion-exchange polymer electrolyte membrane of the present disclosure has excellent conductivity and reduced surface resistance due to the inclusion of an ionic group-containing polymer having a structural unit represented by formula (II). Furthermore, the anion-exchange polymer electrolyte membrane of the present disclosure can achieve long-term stability of conductivity and improved flexibility.

[0039] In formula (II), "R 2a , R 2b , R 2c , R 2d and R 2e "at least one group selected from" are each independently a group represented by formula (ii), and "the remaining groups other than the group represented by formula (ii)" (hereinafter also referred to as "first residues") are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R 2a , R 2b , R 2c , R 2d and R 2e may all be groups represented by formula (ii), or R 2a , R 2b , R 2c , R 2d and R 2e four of the groups may be groups represented by formula (ii), or R 2a , R 2b , R 2c , R 2d and R 2e three of the groups may be groups represented by formula (ii), or R 2a , R 2b , R 2c , R 2d and R 2etwo of the groups may be groups represented by formula (ii), or R 2a , R 2b , R 2c , R 2d and R 2e One of the groups may be a group represented by formula (ii). R 2a , R 2b , R 2c , R 2d and R 2e Among these, preferably R 2b , R 2c , and R 2d At least one group selected from each of the following is independently a group represented by formula (ii): 2b , R 2c , and R 2d Of these, it is preferred that the remaining groups other than the group represented by formula (ii) are hydrogen atoms. R 2a , R 2b , R 2c , R 2d and R 2e When one of the groups is a group represented by formula (ii), the group represented by formula (ii) may be at any of the ortho, meta, and para positions, and is preferably at the meta or para position. Each first residue is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group of the first residue is not particularly limited, and examples include the same hydrocarbon groups as those exemplified as the hydrocarbon group represented by R in formula (I). The first residue is preferably a hydrogen atom or an unsubstituted hydrocarbon group, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom.

[0040] In formula (II), "n" is an integer of 5 to 50,000. n is preferably 5 to 10,000, more preferably 6 to 8,000, even more preferably 7 to 5,000, and particularly preferably 7 to 3,000. From the viewpoint of reducing the surface resistance, n is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. From the viewpoint of increasing the film strength by crosslinking (described later), making the film thinner, and making it less susceptible to deterioration over time, n is preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more.

[0041] In formula (ii), "Z - " in formula (I) means "Z - " is the same as the example given above. In formula (ii), "each of a, b, c and d" is the same as "each of a, b, c and d" exemplified in formula (I). In formula (ii), "R" is the same as the examples of "R" in formula (I). In formula (ii), "two R's on the same nitrogen atom are bonded to each other to form a ring structure" means a ring structure represented by formula (I) This is the same as the example given in the above as "two R on the same nitrogen atom bond to each other to form a ring structure." In formula (ii), "R 1 " in formula (I) means "R 1 " is the same as the example is. In formula (ii), "R 3a and R 3b " are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R 3a and R 3b The hydrocarbon group represented by is not particularly limited, and examples thereof include the same hydrocarbon groups as those exemplified as the hydrocarbon group represented by R in formula (I). R 3a and R 3b is preferably a hydrogen atom or an unsubstituted hydrocarbon group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.

[0042] The proportion of the structural unit represented by formula (II) is not particularly limited. The proportion of the structural unit represented by formula (II) relative to all structural units in the polymer portion is preferably 99 mol% or less, more preferably 98 mol% or less, and even more preferably 95 mol% or less, from the viewpoint of easily improving film strength by crosslinking as described below. The proportion of the structural unit represented by formula (II) relative to all structural units in the polymer moiety is preferably 1 mol % or more, more preferably 2 mol % or more, and even more preferably 3 mol % or more, from the viewpoint of reducing surface resistance.

[0043] In the anion exchange polymer electrolyte membrane of the present disclosure, the ionic group-containing polymer preferably contains a constituent unit represented by formula (III).

[0044] [ka]

[0045] In formula (III), R 4a , R 4b , R 4c , R 4d and R 4e at least one group selected from the following is independently a group represented by formula (iii), and the remaining groups which are not a group represented by formula (iii) are independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 5 to 50,000; In formula (iii), R 5a and R 5b are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a hydroxyl group, a chlorine atom, a bromine atom or an iodine atom, and *** indicates the bonding position.

[0046] In the anion-exchange polymer electrolyte membrane of the present disclosure, the ionic group-containing polymer contains a constituent unit represented by formula (III), which allows a crosslinking reaction to proceed between the groups represented by formula (iii) contained in the constituent unit represented by formula (III), thereby improving the membrane strength, long-term stability of conductivity, and flexibility.

[0047] In formula (III), "R 4a , R 4b , R 4c , R 4d and R 4e "at least one group selected from" are each independently a group represented by formula (iii), and "the remaining groups other than the group represented by formula (iii)" (hereinafter referred to as "second residues") are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R 4a , R 4b , R 4c , R 4d and R 4e may all be groups represented by formula (iii), or R 4a , R 4b , R 4c , R 4d and R 4e four of the groups may be groups represented by formula (iii), or R 4a , R 4b , R 4c , R 4d and R 4e three of the groups may be groups represented by formula (iii), or R 4a , R 4b , R 4c , R 4d and R 4e two of the groups may be groups represented by formula (iii), or R 4a , R 4b , R 4c , R 4d and R 4e One of the groups may be a group represented by formula (iii). R 4a , R 4b , R 4c , R 4d and R 4e Among these, preferably R 4b , R 4c , and R 4d At least one group selected from each of the following is independently a group represented by formula (iii): 4b , R 4c , and R 4dOf these, it is preferred that the remaining groups other than the group represented by formula (iii) are hydrogen atoms. R 4a , R 4b , R 4c , R 4d and R 4e When one of the groups is a group represented by formula (iii), the group represented by formula (iii) may be at any of the ortho, meta, and para positions, and is preferably at the meta or para position. The second residues are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group of the second residue is not particularly limited, and examples thereof include the same hydrocarbon groups as those exemplified as the hydrocarbon group represented by R in formula (I). The second residue is preferably a hydrogen atom or an unsubstituted hydrocarbon group, more preferably a hydrogen atom, a methyl group, or an ethyl group, and even more preferably a hydrogen atom.

[0048] In formula (III), "m" is an integer of 5 to 50,000. m is preferably 5 to 10,000, more preferably 6 to 8,000, even more preferably 7 to 5,000, and particularly preferably 7 to 3,000. From the viewpoint of improving the long-term stability of conductivity and flexibility, m is preferably 10,000 or less, more preferably 8,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. From the viewpoint of increasing the film strength by crosslinking (described later), making the film thinner, and making it less susceptible to deterioration over time, m is preferably 5 or more, more preferably 6 or more, and even more preferably 7 or more.

[0049] In formula (iii), "R 5a and R 5b " are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. R 5a and R 5b The hydrocarbon group represented by is not particularly limited, and examples thereof include the same hydrocarbon groups as those exemplified as the hydrocarbon group represented by R in formula (I). 5a and R 5bis preferably a hydrogen atom or an unsubstituted hydrocarbon group, more preferably a hydrogen atom, a methyl group or an ethyl group, and even more preferably a hydrogen atom.

[0050] In formula (iii), "X" is a hydroxyl group, a chlorine atom, a bromine atom, or an iodine atom. Of these, "X" is preferably a hydroxyl group or a chlorine atom.

[0051] The proportion of the structural unit represented by formula (III) is not particularly limited. The proportion of the structural unit represented by formula (III) relative to all structural units in the polymer moiety is preferably 99 mol % or less, more preferably 98 mol % or less, and even more preferably 95 mol % or less, from the viewpoint of reducing surface resistance. The proportion of the structural unit represented by formula (III) relative to all structural units in the polymer portion is preferably 0.1 mol % or more, more preferably 0.2 mol % or more, and even more preferably 0.3 mol % or more, from the viewpoint of increasing film strength by crosslinking as described below, thinning the film, and making it less susceptible to deterioration over time.

[0052] The ionic group moiety is, in formula (I), R is a methyl group or an ethyl group, and R 1 is a methyl group, and Z - OH - or Cl - Preferably, Z - OH - It is more preferable that: The ionic group-containing polymer preferably has at least one of a meta position and a para position. The meta position is represented by R 2b , and R 2d is a group represented by formula (ii), and R 2a , R 2b , R 2c , R 2d and R 2e In the formula (ii), the remaining groups that are not the groups represented by formula (ii) are hydrogen atoms, and in formula (ii), R is a methyl group, and R 1 is a methyl group, and R 3aand R 3b is a hydrogen atom, and Z - OH - The para position is represented by R 2c is a group represented by formula (ii), and R 2a , R 2b , R 2c , R 2d and R 2e In the formula (ii), the remaining groups that are not the groups represented by formula (ii) are hydrogen atoms, and in formula (ii), R is a methyl group, and R 1 is a methyl group, and R 3a and R 3b is a hydrogen atom, and Z - OH - is.

[0053] Specific examples of ionic group moieties are shown below. The present disclosure is not limited to the following specific examples of ionic group moieties. Specific examples of ionic group moieties include ionic group moieties represented by formulae (I-1) to (I-10).

[0054] [ka]

[0055] [ka]

[0056] Specific examples of the ionic group-containing polymer include the ionic group-containing polymers represented by (II-1), (II-2), and (III-1) to (III-8). In the formulas (II-1), (II-2), and (III-1) to (III-8), q, m, and n represent positive integers and can be appropriately selected within the molecular weight range of the polymer moiety of the ionic group-containing polymer described below. In the ionic group-containing polymers represented by (II-1), (II-2), and (III-1) to (III-8), the bonding position of the ionic group bonded to the polymer moiety is the ortho, meta, or para position. The bonding position of the ionic group bonded to the polymer moiety is preferably the meta or para position, and more preferably the para position. In the ionic group-containing polymers represented by (III-1) to (III-8), the bonding position of the chloromethyl group (-CH2Cl) or methylol group (-CH2OH) bonded to the phenylene group is preferably the ortho, meta, or para position. The bonding position of the chloromethyl group (-CH2Cl) or methylol group (-CH2OH) bonded to the phenylene group is preferably the meta or para position, and more preferably the para position.

[0057] [ka]

[0058] [ka]

[0059] Further specific examples of the ionic group-containing polymer include the ionic group-containing polymers represented by formulas (III-9) to (III-12). In formulas (III-9) to (III-12), q, m1, m2, n1, and n2 represent positive integers and can be appropriately selected within the molecular weight range of the polymer moiety of the ionic group-containing polymer described below.

[0060] [ka]

[0061] As a further specific example of the ionic group-containing polymer, the ionic group portion may be 1,1,1-tris{[tris(dimethylamino)phosphoranylidene]amino}-3,3-bis(dimethylamino)-3-methylamino-1λ5,3λ5-diphosphazene (hereinafter also referred to as "PZNB"), and the polymer portion may be a copolymer of styrene and 4-vinylbenzyl chloride. The proportion of the structural units derived from styrene is preferably 0 mol % to 99 mol %, more preferably 0 mol % to 95 mol %, and even more preferably 0 mol % to 90 mol %, relative to the total amount of structural units constituting the ionic group-containing polymer. The proportion of the structural units derived from PZNB relative to the total amount of structural units constituting the ionic group-containing polymer is preferably 1 mol % to 99 mol %, more preferably 3 mol % to 98 mol %, and even more preferably 5 mol % to 97 mol %. The proportion of the structural units derived from 4-vinylbenzyl chloride is preferably 1 mol % to 99 mol %, more preferably 1 mol % to 95 mol %, and even more preferably 1 mol % to 90 mol %, relative to the total amount of structural units constituting the ionic group-containing polymer.

[0062] When some of the constituent units represented by formula (III) contained in the ionic group-containing polymer are not crosslinked, the number average molecular weight (Mn) of the polymer moiety contained in the ionic group-containing polymer is preferably 5,000 to 5,000,000, and more preferably 6,000 to 200,000. When some of the constituent units represented by formula (III) contained in the ionic group-containing polymer are not crosslinked, the molecular weight distribution (Mw / Mn) of the polymer moiety contained in the ionic group-containing polymer is preferably 1.0 to 10.0, more preferably 1.0 to 9.0, even more preferably 1.0 to 8.0, and particularly preferably 1.0 to 7.5. The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) of the polymer moiety of the ionic group-containing polymer are measured by the same methods as those described in the examples.

[0063] In the anion-exchange polymer electrolyte membrane of the present disclosure, it is preferable that some of the constitutional units represented by formula (III) contained in the ionic group-containing polymer are crosslinked.

[0064] In the anion-exchange polymer electrolyte membrane of the present disclosure, a portion of the constitutional units represented by formula (III) of the ionic group-containing polymer is crosslinked, thereby improving the mechanical strength, long-term stability of conductivity, and flexibility of the anion-exchange polymer electrolyte membrane.

[0065] One embodiment for forming a crosslinked structure is shown below, but the method for forming a crosslinked structure is not limited to this and may be any other embodiment. For example, when an ionic group-containing polymer represented by formula (III-5) or (III-6) is contacted with an aqueous potassium hydroxide solution, chloride ions in the ionic group-containing polymer represented by formula (III-5) or (III-6) are ion-exchanged with hydroxide ions, and at the same time, the hydroxide ions in the potassium hydroxide react with some of the benzyl chloride moieties to form a potassium salt of benzyl alcohol. This potassium salt of benzyl alcohol reacts with the benzyl chloride moieties of another ionic group-containing polymer represented by formula (III-5) or (III-6), forming a bond having a dibenzyl ether partial structure. In this way, a bond-forming reaction occurs between different polymer chains, resulting in the formation of a crosslinked structure.

[0066] The thickness of the anion-exchange polymer electrolyte membrane of the present disclosure is not particularly limited. The thickness of the anion exchange polymer electrolyte membrane of the present disclosure is preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 300 μm or less, from the viewpoint of obtaining an anion exchange polymer electrolyte membrane with low resistance per unit area. The thickness of the anion exchange polymer electrolyte membrane of the present disclosure is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 3 μm or more, from the viewpoint of ensuring the strength of the anion exchange polymer electrolyte membrane. From these viewpoints, the thickness of the anion-exchange polymer electrolyte membrane is preferably 1 μm to 500 μm, more preferably 2 μm to 400 μm, and even more preferably 3 μm to 300 μm. The method for measuring the thickness of the anion-exchange polymer electrolyte membrane is the same as that described in the Examples.

[0067] The anion-exchange polymer electrolyte membrane of the present disclosure preferably has a conductivity retention rate of 85% or more after an immersion test (hereinafter also referred to as a "first immersion test") of the anion-exchange polymer electrolyte membrane. The first immersion test refers to a test in which the anion-exchange polymer electrolyte membrane is immersed in a potassium hydroxide solution.

[0068] In the present disclosure, the "conductivity maintenance rate after the immersion test of the anion-exchange polymer electrolyte membrane" refers to the ratio ([b1 / a1] × 100) (%) of the conductivity (b1) of the anion-exchange polymer electrolyte membrane after the first immersion test to the conductivity (a1) of the anion-exchange polymer electrolyte membrane before the first immersion test.

[0069] When an anion-exchange polymer electrolyte membrane is immersed in a potassium hydroxide aqueous solution at high temperatures for a long period of time, the ion exchange capacity decreases due to Hoffmann decomposition, which is generally considered to be a problem for anion-exchange polymer electrolyte membranes. As a result, the conductivity of the anion-exchange polymer electrolyte membrane decreases. Therefore, a conductivity retention rate of 85% or more after the first immersion test indicates that the anion-exchange polymer electrolyte membrane of the present disclosure has excellent long-term stability of conductivity.

[0070] From the viewpoint of further improving the long-term stability of the conductivity of the anion-exchange polymer electrolyte membrane, the conductivity retention rate after the first immersion test is more preferably 86% or more, even more preferably 87% or more, particularly preferably 90% or more, even more preferably 94% or more, and even more preferably 95% or more. The conductivity retention rate after the first immersion test is preferably 100%, and may be 99% or less, or may be 98% or less.

[0071] The first immersion test is carried out in accordance with the immersion test described in Examples. The test conditions for the first immersion test are not particularly limited and are appropriately selected depending on the application of the anion-exchange polymer electrolyte membrane, etc.

[0072] The anion-exchange polymer electrolyte membrane of the present disclosure preferably has a conductivity retention rate of 85% or more after an immersion test (hereinafter also referred to as a "second immersion test") of the anion-exchange polymer electrolyte membrane. The second immersion test is a test in which the anion-exchange polymer electrolyte membrane is immersed in a 1N potassium hydroxide aqueous solution at 80°C for 1000 hours.

[0073] In the present disclosure, the "conductivity maintenance rate after the immersion test of the anion-exchange polymer electrolyte membrane" refers to the ratio ([b2 / a2] × 100) (%) of the conductivity (b2) of the anion-exchange polymer electrolyte membrane after the second immersion test to the conductivity (a2) of the anion-exchange polymer electrolyte membrane before the second immersion test.

[0074] A conductivity retention rate of 85% or more after the second immersion test indicates that the anion exchange polymer electrolyte membrane of the present disclosure has excellent long-term conductivity stability.

[0075] From the viewpoint of further improving the long-term stability of the conductivity of the anion-exchange polymer electrolyte membrane, the conductivity retention rate after the second immersion test is more preferably 86% or more, even more preferably 87% or more, particularly preferably 90% or more, even more preferably 94% or more, and even more preferably 95% or more. The conductivity retention rate after the second immersion test is preferably 100%, and may be 99% or less, or may be 98% or less. The method for measuring the conductivity after the second immersion test was the same as that described in the Examples.

[0076] The anion-exchange polymer electrolyte membrane of the present disclosure is preferably used to produce hydrogen by water electrolysis.

[0077] When the anion exchange polymer electrolyte membrane of the present disclosure is used to produce hydrogen by water electrolysis, an anode is placed on one side of the anion exchange polymer electrolyte membrane of the present disclosure, and a cathode is placed on the other side. When an external voltage is applied, water receives electrons at the cathode, generating hydroxide ions while generating hydrogen. These hydroxide ions migrate to the anode via the anion exchange polymer electrolyte membrane, where they generate water while generating oxygen and release electrons. The reaction formula at each electrode is as follows: Anode: 4OH - → O2 + 2H2O + 4e - Cathode: 4H2O + 4e - → 2H2+ 4OH -

[0078] The anion exchange polymer electrolyte membrane of the present disclosure is preferably used to produce carbon monoxide by electrochemically reducing carbon dioxide.

[0079] When the anion-exchange polymer electrolyte membrane of the present disclosure is used to produce carbon monoxide by electrochemically reducing carbon dioxide, hydroxide ions produced at the cathode are transferred to the anode through the anion-exchange polymer electrolyte membrane and reacted with carbon dioxide supplied to the cathode to produce carbon monoxide. The reaction formulas at each electrode are as follows: Anode: 4OH - → O2 + 2H2O + 4e - Cathode: 2CO2 + 2H2O + 4e - → 2CO + 4OH -

[0080] The anion exchange polymer electrolyte membrane of the present disclosure is preferably used in a fuel cell.

[0081] When the anion exchange polymer electrolyte membrane of the present disclosure is used in a fuel cell, for example, a membrane electrode assembly is formed by disposing a cathode on one side of the anion exchange polymer electrolyte membrane of the present disclosure and an anode on the other side, and oxygen is supplied to the cathode and fuel is supplied to the anode, and OH generated at the cathode is - The carbon monoxide migrates to the anode through the anion-exchange polymer electrolyte membrane, where it generates water, generating electricity. The fuel is not particularly limited and can be appropriately selected from conventionally known fuels, such as hydrogen, methanol, ethanol, ethylene glycol, formate, hydrazine, sodium borohydride, and ammonia. As representative examples, reactions at each electrode when hydrogen, methanol, and formate are used as fuels are shown.

[0082] <Fuel cell using hydrogen> Anode: 4OH - + 2H2 → 4H2O + 4e - Cathode: O2+ 2H2O + 4e - → 4OH -

[0083] <Methanol fuel cell> Anode: 12OH - + 2CH3OH → 2CO2+ 10H2O + 12e - Cathode: 3O2 + 6H2O + 12e - → 12OH -

[0084] <Fuel cell using formate> Anode: 2HCOO - + 6OH - → 4H2O + 2CO3 2- + 4e - Cathode: O2+ 2H2O + 4e - → 4OH -

[0085] (2) Water electrolysis equipment The water electrolysis device of the present disclosure includes the anion exchange polymer electrolyte membrane of the present disclosure. The water electrolysis device may have a conventionally known configuration, except for using the anion exchange polymer electrolyte membrane of the present disclosure.

[0086] (3) Carbon dioxide electrolysis device The carbon dioxide electrolysis device of the present disclosure includes the anion exchange polymer electrolyte membrane of the present disclosure. The carbon dioxide electrolysis device may have a conventionally known configuration, except for using the anion-exchange polymer electrolyte membrane of the present disclosure.

[0087] (4)Fuel cell The fuel cell of the present disclosure comprises the anion exchange polymer electrolyte membrane of the present disclosure. The fuel cell may have a conventionally known configuration, except for using the anion exchange polymer electrolyte membrane of the present disclosure.

[0088] (5) Method for producing anion-exchange polymer electrolyte membrane The method for producing an anion-exchange polymer electrolyte membrane of the present disclosure is a method for producing an anion-exchange polymer electrolyte membrane of the present disclosure in which a portion of the structural units represented by formula (III) of an ionic group-containing polymer is crosslinked. The method for producing an anion-exchange polymer electrolyte membrane of the present disclosure includes a step of applying a varnish containing the ionic group-containing polymer to a substrate and drying the varnish to form a polymer membrane on the substrate (hereinafter referred to as the "membrane formation step"), and a step of treating the polymer membrane with an alkali hydroxide to form an anion-exchange polymer electrolyte membrane (hereinafter referred to as the "alkali treatment step"). The membrane formation step and the alkali treatment step are performed in this order.

[0089] (5.1) Film formation process In the film forming step, a varnish containing an ionic group-containing polymer is applied to a substrate, and the varnish is dried to form a polymer film on the substrate.

[0090] (5.1.1) Varnish The varnish contains an ionic group-containing polymer. The varnish may contain an organic solvent that dissolves the ionic group-containing polymer. Examples of organic solvents include dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, propylene carbonate, diethyl carbonate, dimethyl carbonate, γ-butyrolactone, acetonitrile, tetrahydrofuran, nitrobenzene, acetone, methanol, ethanol, 1-propanol, 2-propalkol, 1-butanol, isobutyl alcohol, 2-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol, dimethylacetamide, and 1,3-dimethyl-2-imidazolidinone. The content of the ionic group-containing polymer is not particularly limited, and is preferably 1% by mass to 99% by mass, and more preferably 5% by mass to 95% by mass, relative to the total amount of the varnish. The method for preparing the varnish is not particularly limited, and any known method may be used.

[0091] (5.1.2) Base material The substrate is not particularly limited as long as it is a substrate from which the polymer film can be peeled off, and examples thereof include a resin substrate (e.g., a polyethylene terephthalate (PET) substrate), a release substrate (e.g., a release PET substrate), and release paper. The release substrate has a known substrate (e.g., a resin substrate) and a known release layer (e.g., a silicone-based release layer) laminated on at least one main surface of the substrate. Examples of the release substrate include the Therapeel (registered trademark) series manufactured by Toray Industries, Inc.

[0092] (5.1.3) Application method The method for applying the varnish is not particularly limited, and any known method may be used, such as a bar coater, applicator, wire bar coater, roll coater, curtain flow coater, or the like.

[0093] (5.1.4) Drying method The method for drying the varnish is not particularly limited, and examples thereof include a method of heating using a heating device (for example, an oven, a hot press, etc.). The heating temperature is not particularly limited, and is preferably 40° C. to 250° C., and more preferably 50° C. to 200° C. The heating time is not particularly limited, and is preferably 1 minute to 100 minutes, and more preferably 2 minutes to 50 minutes.

[0094] (5.1.5) Polymer Film The thickness of the polymer membrane is adjusted appropriately depending on the thickness of the anion-exchange polymer electrolyte membrane and other factors.

[0095] (5.1.6) Method for preparing polymers containing ionic groups The method for preparing the ionic group-containing polymer is not particularly limited, and examples thereof include the first and second production methods described below.

[0096] (5.1.6.1) First Method The first production method includes a step of reacting a styrene-based polymer having a halogenated alkyl group on an aromatic ring with a phosphazene compound represented by formula (IV), thereby obtaining an anion-exchange polymer electrolyte membrane containing an ionic group-containing polymer whose polymer moiety has structural units represented by formula (II) and / or formula (III).

[0097] [ka]

[0098] In formula (IV), a, b, c, and d are each a positive integer of 3 or less, and the multiple Rs are each independently a hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. 1 is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0099] In formula (IV), "each of a, b, c and d" is the same as "each of a, b, c and d" exemplified in formula (I). In formula (IV), "R" is the same as the examples of "R" in formula (I). In formula (IV), "two R's on the same nitrogen atom are bonded to each other to form a ring structure" is the same as the example of "two R's on the same nitrogen atom are bonded to each other to form a ring structure" in formula (I). In formula (IV), "R 1 " in formula (I) means "R 1 " is the same as the example given above.

[0100] (5.1.1.6.1) Styrenic polymers having halogenated alkyl groups on the aromatic ring The method for synthesizing a styrene-based polymer having a halogenated alkyl group on an aromatic ring is not particularly limited, and examples thereof include Method 1 and Method 2. The first method is a method in which a polymerizable composition containing an aromatic vinyl compound having a halogenated alkyl group on the aromatic ring is polymerized in advance. The second method is a method in which a halogenated alkyl group is introduced into the aromatic ring of a styrene-based polymer obtained by polymerizing a polymerizable composition containing an aromatic vinyl compound to which a halogenated alkyl group can be introduced after polymerization.

[0101] In the first method, a polymerizable composition containing an aromatic vinyl compound having a halogenated alkyl group on the aromatic ring is polymerized in advance by a known method. The aromatic vinyl compound having a halogenated alkyl group on the aromatic ring may be polymerized alone or copolymerized with other aliphatic vinyl compounds and / or aromatic vinyl compounds. In an aromatic vinyl compound having a halogenated alkyl group on an aromatic ring, the number of carbon atoms in the methylene chain connecting the aromatic ring and the halogen atom is not particularly limited, and is preferably 1 to 10, more preferably 1. An example of a preferred aromatic vinyl compound is chloromethylstyrene. Other aliphatic vinyl compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, butadiene, norbornene, etc. Examples of aromatic vinyl compounds include styrene, divinylbenzene, α-methylstyrene, vinylnaphthalene, acenaphthylene, vinylpyridine, vinylimidazole, vinyloxazoline, etc. In the polymerizable composition containing an aromatic vinyl compound having a halogenated alkyl group on an aromatic ring, the content of the aromatic vinyl compound having a halogenated alkyl group on an aromatic ring is preferably 1 part by mass to 100 parts by mass, more preferably 5 parts by mass to 100 parts by mass, per 100 parts by mass of the polymerizable composition. As a method for polymerizing a polymerizable composition containing an aromatic vinyl compound having a halogenated alkyl group on an aromatic ring in advance, a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, etc. The polymerization method is not particularly limited and may be appropriately selected depending on the monomer composition of the polymerizable composition, etc.

[0102] In the second method, a polymerizable composition containing an aromatic vinyl compound having a structure to which a halogenated alkyl group can be introduced is polymerized. After polymerization, a halogenated alkyl group is introduced into the structure to obtain a styrene-based polymer having a halogenated alkyl group on the aromatic ring. As the styrene-based polymer into which a halogenated alkyl group can be introduced, it is possible to use a polymer obtained by polymerizing styrene alone or a copolymerization of styrene with an aliphatic and / or aromatic vinyl compound other than styrene. Among the compounds other than styrene, examples of aliphatic compounds include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, butadiene, and norbornene, and examples of aromatic vinyl compounds include divinylbenzene, α-methylstyrene, vinylnaphthalene, acenaphthylene, vinylpyridine, vinylimidazole, and vinyloxazoline. The method for introducing a halogenated alkyl group into a styrene-based polymer after polymerization is not particularly limited, and any known method may be used. Specifically, when styrene is used as an aromatic vinyl compound into which a halogenated alkyl group can be introduced after polymerization, a method for introducing a chloromethyl group using zinc chloride and chloromethyl methyl ether is available. As a method for polymerizing a polymerizable composition containing an aromatic vinyl compound to which a halogenated alkyl group can be introduced after polymerization, a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, etc. The polymerization method is not particularly limited and may be appropriately selected depending on the monomer composition of the polymerizable composition, etc.

[0103] (5.1.6.2) Second manufacturing method The second production method includes a step of reacting an aromatic vinyl compound having a halogenated alkyl group on the aromatic ring with a phosphazene compound represented by formula (IV) to obtain a first monomer, and a step of polymerizing a polymerizable composition containing the first monomer, thereby obtaining an anion-exchange polymer electrolyte membrane containing an ionic group-containing polymer whose polymer moiety has the structural units represented by formula (II) and / or formula (III).

[0104] Examples of the aromatic vinyl compound having a halogenated alkyl group on the aromatic ring include the same compounds as those exemplified as the aromatic vinyl compound having a halogenated alkyl group on the aromatic ring in the first method. The method for reacting an aromatic vinyl compound having a halogenated alkyl group on the aromatic ring with a phosphazene compound represented by formula (IV) is not particularly limited, and any known method can be used.

[0105] In the polymerization step, a polymerizable composition containing a first monomer is polymerized by a known method. The first monomer may be polymerized alone or copolymerized with other aliphatic vinyl compounds and / or aromatic vinyl compounds. Examples of the other aliphatic vinyl compounds include the same compounds as those exemplified as other aliphatic vinyl compounds in the first method. Examples of the aromatic vinyl compound include the same compounds as those exemplified as the aromatic vinyl compound in the first method. In the polymerizable composition containing the first monomer, the content of the first monomer is preferably 1 to 100 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the polymerizable composition. As a method for polymerizing the polymerizable composition containing the first monomer, a known polymerization method such as solution polymerization, suspension polymerization, emulsion polymerization, etc. The polymerization method is not particularly limited and may be appropriately selected depending on the monomer composition of the polymerizable composition, etc.

[0106] (5.2) Alkali treatment step In the alkali treatment step, the polymer membrane is treated with an alkali hydroxide to form an anion exchange polymer electrolyte membrane.

[0107] (5.2.1) Alkali hydroxide Examples of alkali hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Among these, the alkali hydroxide preferably contains sodium hydroxide or potassium hydroxide, and is preferably sodium hydroxide or potassium hydroxide.

[0108] (5.2.2) Processing method The method for treating the polymer membrane with an alkali hydroxide is not particularly limited, and any known method may be used. [Example]

[0109] Hereinafter, embodiments of the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to the descriptions of these examples.

[0110] The water used in this example was purified using the "MQ Academic A10 System" manufactured by Millipore Corporation.

[0111] [1]Measurement method [1.1] Measurement method for number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured using a gel permeation chromatography (GPC) system manufactured by Shimadzu Corporation, with polystyrene as the standard. The columns used were a PLgel MIXED-C column and a PLgel MIXED-D column manufactured by Agilent Technologies, Inc. The developing solvent was tetrahydrofuran (product code: 206-08744) manufactured by Fujifilm Wako Pure Chemical Corporation.

[0112] [1.2] 1 H-NMR and 31 P-NMR measurement method 1 H-NMR was performed using the "ECA400S" model manufactured by JEOL Ltd. 31 P-NMR measurements were performed using an ECA500 model manufactured by JEOL Ltd.

[0113] [1.3] Film thickness measurement method Using a NIKON film thickness meter (Digimicro, model: MFC-101A), an anion exchange type polyelectrolyte polymer was applied to a PET substrate, and the film thickness was measured in the dry state. Then, the thickness of the PET substrate was reduced to measure the film thickness.

[0114] [1.4] Conductivity maintenance rate measurement test The AC impedance of the ion-exchange polymer electrolyte membrane before and after the potassium hydroxide aqueous solution immersion test (hereinafter also referred to as "immersion test") described below was measured under the following measurement conditions to determine the conductivity retention rate.

[0115] [1.4.1] AC impedance measuring device An impedance analyzer manufactured by Keysight Technologies (E4990A model) was used.

[0116] [1.4.2] AC impedance measurement conditions The sweep frequency was set to 0.1 kHz to 50 MHz, the amplitude was set to 10 mV, and the number of averaging was set to 16.

[0117] [1.4.3] AC impedance measurement cell A cross-sectional view of a measurement cell for measuring the conductivity of an anion-exchange polymer electrolyte membrane is shown in Figure 4. In Figure 4, reference numeral "100" denotes the measurement cell, reference numeral "10" denotes the anion-exchange polymer electrolyte membrane, reference numeral "11" denotes a current collector (anion ionomer coated), reference numeral "12" denotes a gasket (spacer), reference numeral "13" denotes a separator with flow channels, reference numeral "14" denotes a lead, reference numeral "15" denotes an end plate, reference numeral "16" denotes a liquid inlet, and reference numeral "17" denotes a liquid outlet. The measurement jig used was a JARI standard cell ("Ex-2C", manufactured by FC Development Co., Ltd., measurement area: 10 mm × 10 mm). The measurement current collector used was carbon paper ("SGL Carbon 29BC" manufactured by SIGRACET) coated with an anion ionomer ("Sustanion (registered trademark) XB-7" manufactured by Dioxide Materials).

[0118] [1.4.4] AC impedance measurement A measurement cell as shown in Figure 4 was assembled using an anion-exchange polymer electrolyte membrane. The measurement cell was heated to 80°C while a 1 mol / L aqueous potassium hydroxide solution was passed through both sides of the cell, and the cell was filled with the 1 mol / L aqueous potassium hydroxide solution. Measurements were carried out for 24 hours while the temperature of the measurement cell was maintained at 80°C.

[0119] [1.4.5] Calculation of the conductivity of anion-exchange polymer electrolyte membranes The conductivity of the anion-exchange polymer electrolyte membrane before the immersion test (hereinafter also referred to as "initial conductivity") and the conductivity of the anion-exchange polymer electrolyte membrane after the immersion test were calculated from the results of the AC impedance measurement according to the following formula (A):

[0120] Formula (A): Conductivity σ=d / (R mem -R cell )×S In formula (A), Rmem is the resistance value when the imaginary axis component is zero in the AC impedance measurement of the measurement cell containing the anion exchange polymer electrolyte membrane. R cell is the resistance value when the imaginary axis component is zero in the AC impedance measurement of a measurement cell containing a gold plate instead of an anion-exchange polymer electrolyte membrane. d represents the thickness of the anion-exchange polymer electrolyte membrane. S represents the measurement area of ​​the anion-exchange polymer electrolyte membrane. Note that R cell The gold plate used for the calculation was a 100 μm product manufactured by Nilaco Corporation.

[0121] [1.4.6] Conductivity Maintenance Rate The conductivity retention rate was calculated according to the following formula (B).

[0122] Equation (B): Conductivity maintenance rate = (conductivity of anion-exchange polymer electrolyte membrane after immersion test ÷ initial conductivity of anion-exchange polymer electrolyte membrane) × 100

[0123] 1.4.7 Conductivity The conductivity of the anion-exchange polymer electrolyte membrane before and after the immersion test was calculated from the results of the AC impedance measurement according to the following formula (C).

[0124] Formula (C): Conductivity = Conductivity × Measurement Area (1 cm 2 ) ÷ film thickness

[0125] [1.4.8] Resistance per unit area The resistance per unit area of ​​the anion-exchange polymer electrolyte membrane before and after the immersion test was calculated from the results of the AC impedance measurement according to the following formula (D):

[0126] Formula (D): 1 ÷ conductivity × measurement area (1 cm 2 )

[0127] [1.5] Bending test Test pieces measuring 25 mm × 10 mm were cut out from each of the anion-exchange polymer electrolyte membranes before and after the immersion test, washed with pure water, and dried at room temperature for 2 hours. Then, 90° and 180° bending tests were performed.

[0128] [2] Example 1 [2.1] Anion-exchange polymer electrolyte membrane [2.1.1] Removal of polymerization inhibitors from styrene and 4-vinylbenzyl chloride A column was packed with a polymerization inhibitor / removal agent (Sigma-Aldrich, catalog number: 311340-250G) equivalent in mass to styrene. Next, styrene (Tokyo Chemical Industry Co., Ltd., product code: S0095) was passed through the column to remove the polymerization inhibitor contained in the styrene. Similarly, the polymerization inhibitor in 4-vinylbenzyl chloride (Tokyo Chemical Industry Co., Ltd., product code: C1792) was removed.

[0129] [2.1.2] Preparation of polymer parts <Copolymerization of styrene / 4-vinylbenzyl chloride> A 100 ml flask equipped with a stirring blade and thermometer was charged with 0.193 g (1.17 mmol) of 2,2'-azobis(isobutyronitrile) (Fujifilm Wako Pure Chemical Industries, Ltd., product code: 019-04932) and the atmosphere inside the flask was replaced with nitrogen. Next, under a nitrogen stream, 15.9 g of chlorobenzene (Fujifilm Wako Pure Chemical Industries, Ltd., product code: 032-07986), 10.9 g (105 mmol) of styrene from which the polymerization inhibitor had been removed, and 9.06 g (59.4 mmol) of 4-vinylphenyl chloride were sequentially charged into the flask. The internal temperature of the reaction system was adjusted to 65°C while stirring, and polymerization was carried out at that temperature for 3.5 hours. After cooling to room temperature, 40 ml of tetrahydrofuran (THF) was added. The resulting reaction solution was added dropwise to 1,000 ml of methanol, resulting in the precipitation of a white polymer. The polymer was recovered by filtration and dried under vacuum at 80° C. for 12 hours to obtain 5.20 g (yield 26%) of a styrene / 4-vinylbenzyl chloride copolymer. 35 mg of the obtained copolymer was dissolved in 665 mg of THF-d8, 1 H-NMR analysis was performed. The chemical shift [ppm] and integral value (ratio) of the obtained spectrum were as shown in Figure 1, and the composition ratio of styrene / 4-vinylbenzyl chloride (hereinafter also referred to as "sty / VBC") was 58 / 42. GPC measurement revealed that Mn was 4.5 x 10 4 , Mw / Mn was found to be 2.5.

[0130] [2.1.3] Preparation of ionic group moieties <Synthesis of 1,1,1-tris{[tris(dimethylamino)phosphoranylidene]amino}-3,3-bis(dimethylamino)-3-methylamino-1λ5,3λ5-diphosphazene (hereinafter abbreviated as "PZNB")> According to the description of Example 1 of Japanese Patent No. 4685011, 50.0 g of a pale yellow solid of PZNB was obtained. This pale yellow solid was dissolved in 100 ml of THF, and the contents were cooled in an ice bath. 70 ml of 1N hydrochloric acid was slowly added while stirring. After 30 minutes, THF and water were removed using a rotary evaporator. 300 ml of water was added to the residue to dissolve it, and then 8.33 g (75.9 mmol) of a 10% by mass aqueous solution of sodium tetrafluoroborate (Tokyo Chemical Industry Co., Ltd., product code: O0494) was added dropwise while stirring. The precipitated first white solid was collected by filtration and dried under vacuum at 100°C for 12 hours, yielding 39.2 g of a first white solid. 20.0 g of this first white solid was dissolved in 35.5 g of ultra-dehydrated methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., product code: 135-16771) in a glove box under a nitrogen atmosphere to obtain solution A. Similarly, in a glove box under a nitrogen atmosphere, 2.78 g of potassium tert-butoxide (Kanto Chemical Co., Ltd., product number: 32835-35) was dissolved in 15.0 g of ultra-dehydrated methanol, and the solution was slowly added dropwise to Solution A at room temperature, producing a second white solid. After stirring for 12 hours at room temperature in the glove box under a nitrogen atmosphere, the second white solid was filtered off, and the methanol in the filtrate was removed under vacuum at 50°C. The residue was then heated at 80°C and 2 x 10 -5After holding at 200 Pa for 6 hours, a slightly yellowish solid was obtained. In a glove box under a nitrogen atmosphere, 300 ml of ultra-dehydrated pentane (Fujifilm Wako Pure Chemical Industries, Ltd., product code: 166-24395) was added to this solid, and the insoluble matter was filtered. The pentane in the filtrate was removed under vacuum at room temperature, yielding 17.0 g of a third white solid. 70 mg of this third white solid was dissolved in 630 mg of N,N-dimethylformamide (DMF)-d7, and the resulting mixture was filtered. 31 P-NMR analysis revealed a doublet at 15.7 ppm, a doublet at 7.2 ppm, and a multiplet at -30.3 ppm (Fig. 2). The integral ratio of these peaks was approximately 1:3:1, and these peaks are presumably assigned to MeN=P(NMe2)2, (Me2N)3P, and the central phosphorus atom of PZNB, respectively.

[0131] [2.1.4] Preparation of polymers containing ionic groups <Reaction of styrene / 4-vinylbenzyl chloride copolymer with PZNB> In a glove box under a nitrogen atmosphere, 2.30 g of the above-mentioned styrene / 4-vinylbenzyl chloride copolymer was dissolved in 20.7 g of THF. Separately, 2.82 g (3.88 mmol) of the above-mentioned PZNB was dissolved in 13.7 g of THF, and the resulting solution was added to the styrene / 4-vinylbenzyl chloride copolymer THF solution at room temperature. After mixing at room temperature for 12 hours, the stirring was stopped and the mixture was allowed to stand, resulting in two layers: a slightly orange lower layer and a colorless upper layer. The upper and lower layers were separated, and the lower layer was washed twice with 3.0 g of THF. After washing, the lower layer weighed 14.4 g. The lower layer was added dropwise to 450 ml of hexane, producing a fourth white solid. This fourth white solid was filtered and dried in a vacuum oven at 60 °C for 12 hours, yielding 4.7 g of a fourth white solid. To 60.8 mg of this fourth white solid, 20.0 mg of tributyl phosphate (Tokyo Chemical Industry Co., Ltd., product code: P0266) was added as an internal standard substance, and the mixture was dissolved in 635 mg of DMF-d7. 31 P-NMR analysis was performed. As a result, a doublet at 8.4 ppm, a doublet at 7.3 ppm, and a quintet at -33.6 ppm were observed (Figure 3). The integral ratio of these peaks was approximately 1:3:1, and they are presumably assigned to the structure in which PZNB is attached to the benzyl chloride moiety in the styrene / 4-vinylbenzyl chloride copolymer. The phosphorus atom observed at 8.4 ppm is presumably assigned to the phosphorus atom close to the benzyl chloride moiety in the styrene / 4-vinylbenzyl chloride copolymer, resulting in the broadened peak. The singlet observed at 0.3 ppm is the internal standard tributyl phosphate. Based on the integral intensity ratio of the peaks assigned to tributyl phosphate and the structure in which PZNB is attached to the benzyl chloride moiety in the styrene / 4-vinylbenzyl chloride copolymer, the PZNB content in the fourth white solid was determined to be 0.68 meq. / g (17 mol%). The composition ratio of styrene / PZNB / 4-vinylbenzyl chloride (hereinafter also referred to as "sty / PZNB / VBC") was found to be 58 / 17 / 25.

[0132] [2.1.5] Film formation 4.0 g of the resulting fourth white solid, in which PZNB was adducted to a styrene / 4-vinylbenzyl chloride copolymer, was dissolved in 6.0 g of N,N-dimethylformamide (Fujifilm Wako Pure Chemical Industries, Ltd., product code: 045-32365) to prepare a 40% by mass varnish. The resulting varnish was applied to a 100 μm PET substrate and formed into a film using a bar coater. The formed varnish and the PET substrate were dried in an oven at 65°C for 5 minutes and then at 130°C for 5 minutes to remove the DMF solvent, resulting in a 60 μm-thick polymer membrane on the PET substrate (hereinafter referred to as the "dried membrane"). The polymer membrane, along with the PET substrate, was cut into a 50 mm x 50 mm size and immersed in a 1 N potassium hydroxide aqueous solution to obtain a free-standing membrane (hereinafter referred to as the "anion-exchange polymer electrolyte membrane") in which the polymer membrane was peeled from the PET substrate. The thickness of this anion-exchange polymer electrolyte membrane (hereinafter also referred to as "membrane thickness (wet)") was 64.6 μm.

[0133] [2.2] Potassium hydroxide aqueous solution immersion test An immersion test was conducted on the anion-exchange polymer electrolyte membrane described above. The details of the test method are described below. The anion-exchange polymer electrolyte membrane was placed in a Teflon cup containing 120 ml of 1N potassium hydroxide aqueous solution, and the Teflon cup was then placed in an autoclave equipped with a Teflon-coated thermometer. The autoclave was subjected to three cycles of nitrogen replacement by applying and releasing a nitrogen pressure of 0.5 MPa. An airtight test was then conducted for 10 minutes, with 0.5 MPa of nitrogen applied, to confirm that there was no pressure drop. The nitrogen in the autoclave was then vented to 0 MPa (gauge pressure). The autoclave was then placed in a personal organic synthesis apparatus (Tokyo Rikakiki Co., Ltd., "ChemiStation PPV-CTRL"), and the heater was set to raise the internal temperature to 80°C. This temperature was maintained for 1,000 hours. After cooling to room temperature, the autoclave was opened and the anion-exchange polymer electrolyte membrane was removed.

[0134] The conductivity retention rate was 94%. As a result, it was found that the anion-exchange polymer electrolyte membrane of Example 1 had excellent membrane flexibility before and after the [2.2] potassium hydroxide aqueous solution immersion test, and also had excellent long-term conductivity stability.

[0135] [2.3] Film evaluation The conductivity retention rate was measured and a bending test was carried out according to the description in paragraph 0114 and thereafter. The test results of the bending test are shown in Table 1.

[0136] [3] Comparative Example 1 The anion-exchange polymer electrolyte membrane used was a polystyrene-based polymer (Dioxide Materials' "Sustanion X37-50 RT") with imidazolidium salt as the ion-exchange group. The anion-exchange polymer electrolyte membrane had a thickness (wet) of 64.8 μm. The potassium hydroxide aqueous solution immersion test, conductivity retention measurement test, and bending test were carried out as described above. The calculated conductivity retention rate was 67%. The results of the bending test are shown in Table 1.

[0137] In the bending test, cracks immediately occurred in both the test specimens before and after the potassium hydroxide aqueous solution immersion test, and they could not be bent at 90° or 180°. As a result, it was found that the anion-exchange polymer electrolyte membrane of Comparative Example 1 had low flexibility and was not an anion-exchange polymer electrolyte membrane excellent in long-term stability of conductivity.

[0138] [4] Example 2 An anion-exchange polymer electrolyte membrane was obtained in the same manner as in Example 1, except that the thickness (dry) of the polymer membrane was changed to 8 μm in [2.1.5] above. The conductivity, conductivity, and resistance per unit area of ​​the obtained anion-exchange polymer electrolyte membrane were calculated using the methods described in paragraphs 0114 to 0127, and a bending test was carried out. The test results of the bending test are shown in Table 1. The thickness (wet) of the anion-exchange polymer electrolyte membrane was 8.0 μm. The conductivity was 22.0 mS / cm. The conductivity was 27.5 S. The resistance per unit area was 0.036 Ω·cm. 2 (80℃). The Advanced Research Projects Agency-Energy (ARPA-E), established under the U.S. Department of Energy, has set a development target value for the ionic area-specific resistance of hydroxide-type anion exchange membranes measured at 80°C of 0.04 Ω cm 2 The following is set. The resistance per unit area (ionic area-specific resistance) of the anion exchange polymer electrolyte membrane of Example 2 is the development target value set by the Advanced Research Projects Agency of Energy (ADRPA) of ≦0.04 [Ω·cm 2 ] was satisfied.

[0139] [5] Example 3 An anion-exchange polymer electrolyte membrane was obtained in the same manner as in Example 1, except that in [2.1.2] above, the sty / VBC ratio of the copolymer was changed to 19 / 81; in [2.1.4] above, the sty / PZNB / VBC ratio of the ionic group-containing polymer was changed to 19 / 32 / 50 (0.85 meq. / g (32 mol%)); and in [2.1.5] above, the thickness (dry) of the polymer membrane was changed to 20 μm. The conductivity, conductivity, and resistance per unit area of ​​the obtained anion-exchange polymer electrolyte membrane were calculated using the methods described in paragraphs 0114 to 0127, and a bending test was performed. The test results of the bending test are shown in Table 1. The thickness (wet) of the anion-exchange polymer electrolyte membrane was 26.0 μm. The conductivity was 64.4 mS / cm. The conductivity was 24.8 S. Resistivity per unit area is 0.040 Ω cm 2 (80℃), and the development target value set by ARPA-E is ≦0.04 [Ω·cm 2 ] was satisfied.

[0140] [6] Example 4 An anion-exchange polymer electrolyte membrane was obtained in the same manner as in Example 3, except that in [2.1.2] above, the sty / VBC ratio of the copolymer was changed to 30 / 70, and in [2.1.4] above, the sty / PZNB / VBC ratio of the ionic group-containing polymer was changed to 30 / 30 / 40 (0.84 meq. / g (30 mol%)). The conductivity, conductivity, and resistance per unit area of ​​the obtained anion-exchange polymer electrolyte membrane were calculated using the methods described in paragraphs 0114 to 0127, and a bending test was performed. The test results of the bending test are shown in Table 1. The membrane thickness (wet) of the anion-exchange polymer electrolyte membrane was 27.0 μm. The conductivity was 71.7 mS / cm. The conductivity was 26.6 S. The resistance per unit area was 0.038 Ω·cm. 2 (80℃), and the development target value set by ARPA-E is ≦0.04 [Ω·cm 2 ] was satisfied.

[0141] [7] Results [Table 1]

[0142] In Table 1, "A" in the 90° bending test indicates that the test specimen did not crack or break when bent 90°. "B" in the 90° bending test indicates that the test specimen cracked or broke when bent 90°. "A" in the 180° bending test indicates that the test specimen did not crack or break when bent 180°. "B" in the 180° bending test indicates that the test specimen cracked or broke when bent 180°.

[0143] The anion-exchange polymer electrolyte membranes of Examples 1 to 4 contain an ionic group-containing polymer having an ionic group moiety represented by the following formula (I-1) and a polymer moiety. In Examples 1 to 4, even when the test pieces before and after the immersion test were bent at 90° and 180°, no cracks or breaks occurred in the test pieces. These results demonstrate that the anion-exchange polymer electrolyte membranes of Examples 1 to 4 are anion-exchange polymer electrolyte membranes with excellent flexibility.

[0144] [ka]

[0145] The disclosures of Japanese Patent Application No. 2022-132031, filed on August 22, 2022, and Japanese Patent Application No. 2023-018743, filed on February 9, 2023, are incorporated herein by reference in their entireties. All publications, patent applications, and technical standards mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. An anion exchange polymer electrolyte membrane comprising an ionic group-containing polymer having an ionic group moiety represented by formula (I) and a polymer moiety. 【Chemistry 1】 (In formula (I), Z － Ha, OH － , HCO ３ － , 1 / 2CO ３ ２－ , Cl － ,Br － and I － where a, b, c, and d are each a positive integer of 3 or less, and the multiple Rs are each independently a hydrocarbon group having 1 to 10 carbon atoms, and two Rs on the same nitrogen atom may be bonded to each other to form a ring structure. １ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and * indicates the bonding position.

2. 2. The anion exchange polymer electrolyte membrane according to claim 1, wherein the ionic group-containing polymer comprises a structural unit represented by formula (II): 【Chemistry 2】 (In formula (II), R ２ａ , R ２ｂ , R ２ｃ , R ２ｄ and R ２ｅ is independently a group represented by formula (ii), and the remaining groups which are not groups represented by formula (ii) are independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 5 to 50,000; In formula (ii), Z － Ha, OH － , HCO ３ － , 1 / 2CO ３ ２－ , Cl － ,Br － and I － and each of a, b, c, and d is 3 or less positive integers. Each of the multiple R's is independently a hydrocarbon group having 1 to 10 carbon atoms, and two R's on the same nitrogen atom may be bonded to each other to form a ring structure. １ , R ３ａ and R ３ｂ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and ** indicates the bonding position.

3. 2. The anion exchange polymer electrolyte membrane according to claim 1, wherein the ionic group-containing polymer further comprises a structural unit represented by formula (III): 【Transformation 3】 (In formula (III), R ４ａ , R ４ｂ , R ４ｃ , R ４ｄ and R ４ｅ at least one group selected from the following is independently a group represented by formula (iii), and the remaining groups which are not a group represented by formula (iii) are independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m is an integer of 5 to 50,000; In formula (iii), R ５ａ and R ５ｂ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a hydroxyl group, a chlorine atom, a bromine atom or an iodine atom, and *** indicates the bonding position.

4. 4. The anion exchange polymer electrolyte membrane according to claim 3, wherein a portion of the constitutional units represented by formula (III) is crosslinked.

5. The conductivity retention rate of the anion exchange polymer electrolyte membrane after the immersion test is 85% or more, 2. The anion exchange polymer electrolyte membrane according to claim 1, wherein the immersion test is a test in which the anion exchange polymer electrolyte membrane is immersed in a 1N aqueous potassium hydroxide solution at 80°C for 1000 hours.

6. 2. The anion exchange polymer electrolyte membrane according to claim 1, wherein R of the ionic group moiety represented by formula (I) is a methyl group or an ethyl group.

7. R of the ionic group moiety represented by formula (I) １ The anion exchange polymer electrolyte membrane according to claim 1 , wherein is a methyl group, an ethyl group, a propyl group, or an isopropyl group.

8. The anion exchange polymer electrolyte membrane according to any one of claims 1 to 7, which is used for producing hydrogen by water electrolysis.

9. 8. The anion-exchange polymer electrolyte membrane according to claim 1, which is used for producing carbon monoxide by electrochemically reducing carbon dioxide.

10. The anion exchange polymer electrolyte membrane according to any one of claims 1 to 7, which is used in a fuel cell.

11. A water electrolysis device comprising the anion exchange polymer electrolyte membrane according to any one of claims 1 to 7.

12. A carbon dioxide electrolysis device comprising the anion exchange polymer electrolyte membrane according to any one of claims 1 to 7.

13. A fuel cell comprising the anion exchange polymer electrolyte membrane according to any one of claims 1 to 7.

14. A method for producing the anion exchange polymer electrolyte membrane according to claim 4, comprising: applying a varnish containing the ionic group-containing polymer to a substrate and drying the varnish to form a polymer film on the substrate; treating the polymer membrane with an alkali hydroxide to form an anion exchange polymer electrolyte membrane; A method for producing an anion exchange polymer electrolyte membrane, comprising:

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