Polymerizable composition, ion exchange resin, ion exchange membrane, membrane electrode assembly, and hydrogen production device

Abstract

Provided are: a polymerizable composition containing a quaternary ammonium salt represented by formula (I), a polymerizable monomer, a linear or branched C1-4 alkylene glycol, and at least one hydroxyl group-containing compound selected from the group consisting of a C4-15 primary alcohol, a C4-15 secondary alcohol, and a C5-15 diol which has a hydroxy group bonded to a secondary carbon atom; an ion exchange resin; an ion exchange membrane; a membrane electrode assembly; and a hydrogen production device.

Description

[Technical Field]

[0001] The present invention relates to a polymerizable composition, an ion exchange resin, an ion exchange membrane, a membrane electrode assembly, and a hydrogen production device. [Background technology]

[0002] Water electrolysis, in which water is electrolyzed to produce hydrogen gas and oxygen gas, is being researched as a method for producing hydrogen. Hydrogen produced using energy obtained through a method that suppresses the generation of carbon dioxide as electricity is called CO2-free hydrogen, or green hydrogen, and is expected to be a next-generation clean energy source that will replace fossil fuels.

[0003] Among water electrolysis methods, AEM water electrolysis using an anion exchange membrane (AEM) is attracting attention because it does not require the use of expensive precious metals as a catalyst. An AEM water electrolysis device includes, for example, an AEM, and an anode chamber and a cathode chamber separated by the AEM and equipped with an anode and a cathode, respectively. The AEM is obtained, for example, by filling a porous substrate with an ion exchange resin. It is known to use a resin having a quaternary ammonium group as the ion exchange resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2022-502522 [Patent Document 2] International Publication No. 2016 / 027595 [Patent Document 3] International Publication No. 2011 / 125717 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a polymerizable composition from which a cured product can be efficiently produced, an ion exchange resin containing a cured product of the polymerizable composition, an ion exchange membrane, a membrane electrode assembly, and a hydrogen production device. [Means for solving the problem]

[0006] According to a first embodiment of the present invention, there is provided a polymerizable composition. The polymerizable composition includes a quaternary ammonium salt represented by the following formula (I), a polymerizable monomer, a linear or branched alkylene glycol having from 1 to 4 carbon atoms, and a hydroxyl group-containing compound. The hydroxyl group-containing compound includes at least one selected from the group consisting of a primary alcohol having from 4 to 15 carbon atoms, a secondary alcohol having from 4 to 15 carbon atoms, and a diol having from 5 to 15 carbon atoms and having a hydroxyl group bonded to a secondary carbon atom. [ka] In the above formula (I), R 1 is an alkenyl group having 2 to 5 carbon atoms. 2 is an alkylene group having 1 to 10 carbon atoms. 3 , R 4 , and R 5 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. - is an anion.

[0007] According to a second embodiment of the present invention, there is provided an ion exchange resin, which includes at least one of a cured product of the polymerizable composition according to the first embodiment and an ion exchanger of an anion of the cured product.

[0008] According to a third embodiment of the present invention, there is provided an ion exchange membrane, which includes the ion exchange resin according to the second embodiment and a substrate.

[0009] According to a fourth embodiment of the present invention, there is provided a membrane electrode assembly, which includes the ion exchange membrane according to the third embodiment and an electrode.

[0010] According to a fifth embodiment of the present invention, there is provided a hydrogen production device, which includes the ion exchange membrane according to the third embodiment. [Effects of the Invention]

[0011] According to the present invention, there are provided a polymerizable composition from which a cured product can be efficiently produced, an ion exchange resin containing a cured product of the polymerizable composition, an ion exchange membrane, a membrane electrode assembly, and a hydrogen production device. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a cross-sectional view schematically illustrating an example of a hydrogen production device according to an embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0013] Although the embodiments of the present invention will be described in detail below, the present invention is not limited to these details as long as they do not deviate from the gist of the present invention. Furthermore, the present invention can be implemented by making any modifications within the scope of the present invention. Furthermore, when a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, the expression "A or B" in this specification may be read as "at least one selected from the group consisting of A and B." Furthermore, the expression "amount of B relative to amount of A" in this specification means "amount of B / amount of A." Furthermore, although a number of embodiments are described in this specification, various conditions in each embodiment may be applied to each other to the extent that they are applicable.

[0014] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits, and "A to B" means A or more and B or less.

[0015] The polymerizable composition according to the first embodiment (hereinafter also simply referred to as "polymerizable composition") contains a quaternary ammonium salt represented by the above formula (I), a polymerizable monomer, a linear or branched alkylene glycol having from 1 to 4 carbon atoms, and a hydroxyl group-containing compound. The hydroxyl group-containing compound contains at least one selected from the group consisting of primary alcohols having from 4 to 15 carbon atoms, secondary alcohols having from 4 to 15 carbon atoms, and diols having from 5 to 15 carbon atoms and having a hydroxyl group bonded to a secondary carbon atom.

[0016] Such a polymerizable composition allows for efficient production of cured products. Generally, the compatibility of quaternary ammonium salts having a polymerizable group represented by formula (I) with polymerizable monomers tends to be lower than that of conventional primary ammonium salts having a polymerizable group. However, as a result of extensive research, the present inventors have discovered that by using a linear or branched alkylene glycol having 1 to 4 carbon atoms and a hydroxyl group-containing compound as a cosolvent, a polymerizable composition can be obtained in which the quaternary ammonium salt having a polymerizable group represented by formula (I) and the polymerizable monomer are less likely to separate. While the reason for this is unclear, it is thought that the hydroxyl group-containing compound has excellent compatibility with both the quaternary ammonium salt and the polymerizable monomer, or that the hydroxyl group-containing compound exerts a surfactant effect. By using such a polymerizable composition with excellent compatibility and less prone to phase separation, cured products can be continuously produced without stirring the polymerizable composition. Furthermore, the polymerizable composition according to the first embodiment can achieve excellent compatibility even when a photopolymerization initiator having low compatibility with a quaternary ammonium salt or a polymerizable monomer is added, and therefore, this polymerizable composition is suitable for use as a photocurable polymerizable composition.

[0017] [Polymerizable composition] The polymerizable composition is typically liquid at room temperature and pressure. Here, room temperature refers to a temperature of 20°C or higher and 40°C or lower, and normal pressure refers to 1 atmosphere. The viscosity of the polymerizable composition at 25°C, as measured by a tuning fork vibration viscometer, is, in one example, 300 mPa·s or lower, and in another example, 100 mPa·s or lower. Also, in one example, it is 75 mPa·s or higher, and in another example, it is 50 mPa·s or higher. The use of a liquid polymerizable composition allows for the realization of an ion exchange resin with high ion exchange performance.

[0018] The polymerizable composition contains a quaternary ammonium salt represented by the following formula (I), a polymerizable monomer, a linear or branched alkylene glycol having 1 to 4 carbon atoms, and a hydroxyl group-containing compound. [ka]

[0019] In the above formula (I), R 1 is an alkenyl group having 2 to 5 carbon atoms. 1 R may be linear or branched, but is preferably linear. 1 is preferably a vinyl group or an allyl group, more preferably a vinyl group.

[0020] R 2 is an alkylene group having 1 to 10 carbon atoms. 2 R may be linear or branched, but is preferably linear. 2 is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably a methylene group.

[0021] R 3 , R 4 , and R 5 are each independently a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. 3 , R 4, and R 5 are each independently preferably a linear alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. 3 ~R 5 may be the same or different, but are preferably all the same.

[0022] X - X may be a monovalent anion or a divalent anion. - is, for example, a halide ion, tetrafluoroborate, bicarbonate ion, hydroxide ion, triflate, or bistrifluoromethanesulfonimide. A halide ion is, for example, a fluoride ion, a chloride ion, or a bromide ion. X - is preferably a chloride ion, a triflate, or a bistrifluoromethanesulfonimide, and more preferably a chloride ion. - When X is a chloride ion, an ion exchange resin with a large amount of ion exchange groups per unit mass can be obtained. - However, when the quaternary ammonium salt is a triflate or bistrifluoromethanesulfonimide, the solubility of the composition increases, and the concentration of the quaternary ammonium salt in the polymerizable composition tends to be easily increased.

[0023] Specific examples of quaternary ammonium salts include (vinylbenzyl)trialkylammonium salts, 4-ethenyl-N,N-dimethylbenzeneethanaminium salts, and 4-ethenyl-N,N-dimethylbenzenepropanaminium salts. Specific examples of (vinylbenzyl)trialkylammonium salts include (vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium triflate, (vinylbenzyl)trimethylammonium bistrifluoromethanesulfonimide, (vinylbenzyl)dimethylethylammonium chloride, (vinylbenzyl)dimethylethylammonium triflate, (vinylbenzyl)dimethylethylammonium bistrifluoromethanesulfonimide, (vinylbenzyl)trimethylammonium tetrafluoroborate, (vinylbenzyl)trimethylammonium bicarbonate, and (vinylbenzyl)trimethylammonium hydroxide.

[0024] Other specific examples of quaternary ammonium salts include 4-ethenyl-N,N-dimethylbenzeneethanaminium chloride, 4-ethenyl-N,N-dimethylbenzeneethanaminium triflate, 4-ethenyl-N,N-dimethylbenzeneethanaminium bistrifluoromethansulfonium, 4-ethenyl-N,N-dimethylbenzeneethanaminium hydroxide, 4-ethenyl-N,N-dimethylbenzenepropanaminium chloride, 4-ethenyl-N,N-dimethylbenzenepropanaminium triflate, 4-ethenyl-N,N-dimethylbenzenepropanaminium bistrifluoromethansulfonium, 4-ethenyl-N,N-dimethylbenzenepropanaminium hydroxide, and the like.

[0025] As the quaternary ammonium salt, it is preferable to use a (vinylbenzyl)trialkylammonium salt, and it is more preferable to use at least one salt selected from the group consisting of (vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium triflate, and (vinylbenzyl)trimethylammonium bistrifluoromethanesulfonylimide.

[0026] In the polymerizable composition, the proportion (content) of the quaternary ammonium salt is, for example, 5% by mass or more and 95% by mass or less. This proportion is preferably 40% by mass or more, more preferably 50% by mass or more, and more preferably 60% by mass or more. When this proportion is high, an ion exchange resin with a large amount of ion exchange groups per unit mass tends to be obtained. This proportion may be 92% by mass or less, 85% by mass or less, or 80% by mass or less. The proportion of the quaternary ammonium salt in the polymerizable composition can be measured, for example, by subtracting the weight of the quaternary ammonium salt remaining unreacted after the polymerization reaction from the total mass of the quaternary ammonium salts used as raw materials.

[0027] The proportion of the quaternary ammonium salt in the polymerizable composition may vary depending on the type. The content of vinylbenzyltrimethylammonium chloride is, for example, 60% by mass or more and 70% by mass or less. The content of vinylbenzyltrimethylammonium triflate is, for example, 75% by mass or more and 85% by mass or less. The concentration of vinylbenzyltrimethylammonium bistrifluoromethanesulfonimide is, for example, 85% by mass or more and 95% by mass or less.

[0028] The polymerizable monomer may be a comonomer that polymerizes with the quaternary ammonium salt, and the polymerizable monomer may crosslink the quaternary ammonium salts together, thereby increasing the durability of the cured product. The polymerizable monomer may have one radical polymerizable group per molecule, or may have two or more radical polymerizable groups per molecule. Examples of the radical polymerizable group include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group, and it is preferable to use a vinyl group.

[0029] The polymerizable monomer is, for example, at least one selected from the group consisting of a vinyl compound having one vinyl group, a divinyl compound having two vinyl groups, an allyl compound having one allyl group, a diallyl compound having two allyl groups, and a diene. The polymerizable monomer preferably has two polymerizable groups, and is more preferably a divinyl compound.

[0030] Specific examples of the polymerizable monomer include divinylbenzene, divinylbenzene derivatives, divinyl sulfone, butadiene, chloroprene, divinylphenyl, trivinylbenzenes, divinylnaphthalene, allylamine, diallylamine, divinylpyridine, styrene, acrylonitrile, methylstyrene, acrolein, methyl vinyl ketone, vinyl biphenyl, diallyl isocyanurate, 1,2-bis(4-vinylphenyl)ethane, trivinylbenzene, 1,6-bis(4-vinylbenzyloxy)hexane, and N,N-dimethyl-N-(4-vinylbenzyl)-4-(4-vinylphenyl)butane-1-ammonium chloride.

[0031] As the radical polymerizable monomer, a styrene derivative is preferred, and among them, it is preferred to use at least one compound selected from the group consisting of divinylbenzene, 1,2-bis(4-vinylphenyl)ethane, trivinylbenzene, 1,6-bis(4-vinylbenzyloxy)hexane, and N,N-dimethyl-N-(4-vinylbenzyl)-4-(4-vinylphenyl)butane-1-ammonium chloride.

[0032] The proportion (content) of the polymerizable monomer in the polymerizable composition is, for example, 0.1% by mass or more and 50% by mass or less, preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 20% by mass or less, and particularly preferably 2% by mass or more and 10% by mass or less. A high proportion tends to increase the durability of the cured product. An excessively high proportion can reduce the performance of the ion exchange resin. This proportion can be measured, for example, by subtracting the weight of the polymerizable composition remaining unreacted after the polymerization reaction from the total mass of the polymerizable composition used as a raw material.

[0033] The ratio (M3 / M4) of the mass M3 of the quaternary ammonium salt to the mass M4 of the polymerizable monomer is, for example, 1 or more and 100 or less, preferably 3 or more and 50 or less, and more preferably 5 or more and 25 or less. When this ratio is high, the performance of the ion exchange resin tends to be improved. When this ratio is low, the durability of the cured body tends to be improved.

[0034] A linear or branched alkylene glycol having 1 to 4 carbon atoms can also function as an organic solvent. The alkylene glycol preferably has 1 to 3 carbon atoms, more preferably 2 carbon atoms. The boiling point of the alkylene glycol is preferably 110° C. or higher, and more preferably 120° C. or higher. There is no particular upper limit to this boiling point, but according to one example, it is 300° C. or lower. The flash point of the alkylene glycol is preferably 90° C. or higher, and more preferably 110° C. or higher. There is no particular lower limit to this flash point, but one example is 200° C. or higher.

[0035] Specific examples of alkylene glycol include methylene glycol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, tetramethylene glycol, etc. As the alkylene glycol, it is preferable to use ethylene glycol.

[0036] The proportion (content) of alkylene glycol in the polymerizable composition is, for example, 1% by mass or more and 50% by mass or less, preferably 5% by mass or more and 40% by mass or less, and more preferably 10% by mass or more and 35% by mass or less. When this proportion is high, the compatibility of the polymerizable composition tends to be enhanced. When this proportion is excessively high, the performance of the ion exchange resin may be reduced. This proportion can be measured, for example, by subtracting the weight of the polymerizable composition remaining unreacted after the polymerization reaction from the total mass of the polymerizable composition used as a raw material.

[0037] The ratio (M3 / M2) of the mass M3 of the quaternary ammonium salt to the mass M2 of the alkylene glycol is, for example, 0.01 or more and 95 or less, preferably 1 or more and 50 or less, and more preferably 1.8 or more and 10 or less. When this ratio is high, the performance of the ion exchange resin tends to be improved. When this ratio is low, the compatibility of the polymerizable composition tends to be improved.

[0038] The ratio (M4 / M2) of the mass M4 of the polymerizable monomer to the mass M2 of the alkylene glycol is, for example, 0.02 or more and 1 or less, preferably 0.05 or more and 0.5 or less, and more preferably 0.10 or more and 0.25 or less. When this ratio is high, the durability of the cured product tends to be enhanced. When this ratio is low, the compatibility of the polymerizable composition tends to be enhanced.

[0039] The hydroxyl group-containing compound can function as a stabilizer that suppresses separation of the polymerizable composition. The hydroxyl group-containing compound can also function as a surfactant. That is, a polymerizable composition containing a hydroxyl group-containing compound can have excellent wettability. Therefore, for example, the polymerizable composition can be quickly impregnated into a porous substrate, thereby improving the production efficiency of ion exchange membranes. The hydroxyl group-containing compound may be in a liquid state or a solid state at room temperature and normal pressure, but is preferably in a liquid state.

[0040] The boiling point of the hydroxyl group-containing compound is preferably 90° C. or higher, and more preferably 100° C. or higher. There is no particular upper limit to this boiling point, but according to one example, it is 300° C. or lower. The flash point of the hydroxyl group-containing compound is preferably 30° C. or higher, more preferably 50° C. or higher, and even more preferably 60° C. or higher. There is no particular upper limit to this flash point, but one example is 200° C. or lower.

[0041] The hydroxyl group-containing compound may be miscible with water or may be immiscible with water. The solubility of the hydroxyl group-containing compound in water at 20°C is, for example, 0.01 g / L or more and 100 g / L or less, preferably 0.1 g or more and 50 g / L or less, and more preferably 0.1 g or more and 30 g / L or less.

[0042] The molar mass of the hydroxyl group-containing compound is, for example, 70 g / mol or more and 300 g / mol or less, and preferably 80 g / mol or more and 200 g / mol or less.

[0043] The hydroxyl group-containing compound includes at least one selected from the group consisting of primary alcohols having 4 to 15 carbon atoms, secondary alcohols having 4 to 15 carbon atoms, and diols having 5 to 15 carbon atoms and having a hydroxy group bonded to a secondary carbon atom.

[0044] The number of carbon atoms in the primary alcohol is preferably 5 to 13, more preferably 6 to 11. The primary alcohol may be an aliphatic alcohol, an alicyclic alcohol, or an aromatic alcohol, and is preferably an aliphatic alcohol. The primary alcohol may be a linear or branched alcohol, and is preferably a linear alcohol.

[0045] The primary alcohol preferably includes at least one selected from the group consisting of 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, 1-undecanol, and 1-dodecanol. The primary alcohol preferably includes at least one selected from the group consisting of 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, and 1-undecanol. These compounds tend to have a high surfactant effect. A particularly preferred primary alcohol is at least one selected from the group consisting of 1-octanol, 1-nonanol, and 1-decanol.

[0046] The number of carbon atoms in the secondary alcohol is preferably 5 to 13, more preferably 7 to 12. The secondary alcohol may be an aliphatic alcohol, an alicyclic alcohol, or an aromatic alcohol, and is preferably an aliphatic alcohol. The secondary alcohol may be a linear or branched alcohol, and is preferably a linear alcohol.

[0047] The secondary alcohol preferably includes at least one selected from the group consisting of 2-butanol, 3-pentanol, 3-hexanol, 3-heptanol, 2-undecanol, 2-dodecanol, cyclopentanol, cyclohexanol, and cyclooctanol. The secondary alcohol preferably includes at least one selected from the group consisting of 3-heptanol, 2-undecanol, and 2-dodecanol. These compounds tend to have a high surfactant effect.

[0048] The diol preferably has 5 or more and 12 or less carbon atoms, more preferably 6 or more and 10 or less carbon atoms. The diol may be an aliphatic diol, an alicyclic diol, or an aromatic diol, and is preferably an aliphatic diol. The diol may be a linear diol or a branched diol, and is preferably a branched diol. The diol preferably includes at least one selected from the group consisting of 1,2-hexanediol, 1,2-octanediol, and 1,2-decanediol, and more preferably includes 1,2-decanediol.

[0049] The hydroxyl group-containing compound preferably contains at least one compound selected from the group consisting of primary aliphatic alcohols having 4 to 15 carbon atoms, secondary aliphatic alcohols having 4 to 15 carbon atoms, and aliphatic diols having 5 to 15 carbon atoms and having a hydroxy group bonded to a secondary carbon atom.

[0050] Furthermore, the hydroxyl group-containing compound more preferably includes at least one compound selected from the group consisting of 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, 1-undecanol, 1-dodecanol, 3-heptanol, 2-undecanol, 2-dodecanol, and 1,2-decanediol.

[0051] The proportion (content) of the hydroxyl group-containing compound in the polymerizable composition is, for example, 1% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less, and more preferably 1% by mass or more and 3% by mass or less. A higher proportion tends to increase the compatibility of the polymerizable composition. An excessively high proportion can reduce the performance of the ion exchange resin. This proportion can be measured, for example, by subtracting the weight of the polymerizable composition remaining unreacted after the polymerization reaction from the total mass of the polymerizable composition used as a raw material.

[0052] In the polymerizable composition, the amount of the hydroxyl group-containing compound relative to the quaternary ammonium salt may be, for example, 0.01 to 0.5 molar equivalents, preferably 0.03 to 0.25 molar equivalents, more preferably 0.03 to 0.15 molar equivalents.

[0053] The ratio (M3 / M1) of the mass M3 of the quaternary ammonium salt to the mass M1 of the hydroxyl group-containing compound is, for example, 5 to 95, preferably 15 to 70, and more preferably 25 to 50. When this ratio is high, the performance of the ion exchange resin tends to be improved. When this ratio is low, the compatibility of the polymerizable composition tends to be improved.

[0054] The ratio (M4 / M1) of the mass M4 of the polymerizable monomer to the mass M1 of the hydroxyl group-containing compound is, for example, 0.01 or more and 50 or less, preferably 0.25 or more and 25 or less, and more preferably 1 or more and 10 or less. When this ratio is high, the durability of the cured product tends to be enhanced. When this ratio is low, the compatibility of the polymerizable composition tends to be enhanced.

[0055] The ratio (M1 / M2) of the mass M1 of the hydroxyl group-containing compound to the mass M2 of the alkylene glycol is, for example, 0.02 or more and 10 or less, preferably 0.02 or more and 3 or less, and more preferably 0.03 or more and 0.3 or less. When this ratio is within this range, the compatibility of the polymerizable composition tends to be improved.

[0056] The polymerizable composition may contain, in addition to the components listed above, a polymerization initiator, an organic solvent, other additives, and the like. As the polymerization initiator, at least one of a thermal polymerization initiator and a photopolymerization initiator is used. Examples of the thermal polymerization initiator include benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl peroxide, and the like. Examples of the photopolymerization initiator include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-methylpropan-1-one. -Mo fluoropropan-1-one and the like. The polymerizable composition preferably contains at least one compound selected from the group consisting of the above-mentioned thermal polymerization initiators and photopolymerization initiators.

[0057] The proportion (content) of the polymerization initiator in the polymerizable composition is, for example, 0.1% by mass to 10% by mass, preferably 1% by mass to 5% by mass. This proportion can be measured, for example, by subtracting the weight of the polymerizable composition remaining unreacted after the polymerization reaction from the total mass of the polymerizable composition used as a raw material.

[0058] Examples of organic solvents other than the alkylene glycols and hydroxyl group-containing compounds include at least one selected from the group consisting of dialkylene glycols, dimethyl sulfoxide (DMSO), N,N'-dimethylpropylene urea (DMPU), 1-methyl-2-pyrrolidone, N-methyl-2-piperidone, 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-diethylformamide, N,N-diethylacetamide, and tetramethylurea. The amount of the organic solvent other than the alkylene glycol and the hydroxyl group-containing compound used is not particularly limited, but is, for example, 0 to 10 parts by mass per 100 parts by mass of the quaternary ammonium salt.

[0059] The polymerizable composition preferably has a low content of alcohols having 1 to 3 carbon atoms. Specifically, the content of at least one selected from the group consisting of methanol, ethanol, 1-propanol, isopropanol, dialkylene glycol, and trihydric alcohol is preferably low. The inclusion of these compounds may reduce the compatibility of the polymerizable composition. The content of these compounds is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, and it is particularly preferable that the polymerizable composition does not contain these compounds. The lower limit of the content of these compounds is, for example, 0% by mass, and in another example, 100 ppm or more. This proportion can be measured, for example, by NMR (Nuclear Magnetic Resonance) or liquid chromatography.

[0060] The polymerizable composition preferably does not contain water. If the polymerizable composition contains water, components constituting the composition, such as polymerizable monomers and polymerization initiators, may precipitate. The concentration (content) of water in the polymerizable composition is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. The lower limit of the water concentration is, for example, 0% by mass, and, for another example, 100 ppm. This concentration can be measured, for example, by Karl Fischer water content measurement or gas chromatography.

[0061] Other additives that can be used include known additives such as antioxidants, polymerization inhibitors, plasticizers, and surfactants. Examples of the polymerization inhibitor include at least one selected from the group consisting of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (4-OH-TEMPO), 4-tert-butylcatechol (TBC), cupferron, and benzoquinone. The proportion (content) of the polymerization inhibitor in the polymerizable composition is, for example, 0.0001% by mass or more and 2% by mass or less, preferably 0.001% by mass or more and 1.0% by mass or less, and more preferably 0.005% by mass or more and 0.1% by mass or less. This proportion can be measured, for example, by gas chromatography.

[0062] [Method of producing polymerizable composition] The polymerizable composition according to the first embodiment can be obtained, for example, by mixing the above-described raw materials in a desired ratio at room temperature and normal pressure. The raw material compounds may be commercially available or may be synthesized by a known method. The order in which the raw materials are mixed is not particularly limited, and the raw materials may be mixed one by one in any order, or multiple raw materials that have been mixed in advance with an organic solvent or the like may be mixed together.

[0063] [Ion exchange resin] The ion exchange resin according to the second embodiment (hereinafter also simply referred to as "ion exchange resin") includes a cured product of the polymerizable composition according to the first embodiment (hereinafter also simply referred to as "cured product"). The cured product is obtained by photopolymerizing and / or thermally polymerizing the polymerizable composition according to the first embodiment by the method described below. The ion exchange resin may be a copolymer of a quaternary ammonium salt and a polymerizable monomer. The ion exchange resin may be an ion exchanger of the anion of this cured product. The ion exchanger of the anion of the cured product means a resin in which the anion of the quaternary ammonium group of the cured product is substituted with another type of anion. As long as it is obtained by curing the polymerizable composition according to the first embodiment, the product obtained by removing unreacted components, solvents, and the like after curing also corresponds to the cured product according to this embodiment.

[0064] Ion exchange resins can be suitably used as anion exchange resins. The ion exchange resin contains a quaternary ammonium group as an ion exchange group. The anion of the quaternary ammonium group is, for example, a halide ion, triflate, bistrifluoromethanesulfonimide, hydroxide ion, carbonate ion, or bicarbonate ion. The counter ion is preferably a hydroxide ion, carbonate ion, bicarbonate ion, or halide ion. Ion exchange resins containing these ions are suitable as anion exchange resins.

[0065] The weight average molecular weight of the ion exchange resin is, for example, from 1,000 to 1,000,000, and preferably from 5,000 to 500,000. The weight average molecular weight of the ion exchange resin can be measured, for example, by gel permeation chromatography or intrinsic viscosity method. Ion exchange resins have a structure in which, for example, a hydrocarbon main chain is bonded to a plurality of side chains containing quaternary ammonium groups. The plurality of main chains may be bonded via a crosslinking agent, which is a radical polymerizable monomer.

[0066] The ion exchange resin according to the embodiment has, for example, a structure represented by the following formula (IV): The ion exchange resin having the structure represented by formula (IV) can be obtained by curing a polymerizable composition containing divinylbenzene as a radical polymerizable monomer.

[0067] [ka]

[0068] In formula (IV), R 1a is an alkylene group having 1 to 4 carbon atoms. 2 , R 3 , R 4 , and R 5 Each of X1 independently has the same meaning as in formula (I). - X1 is a halide ion, triflate, bistrifluoromethanesulfonimide, hydroxide ion, carbonate ion, bicarbonate ion, or tetrafluoroborate. -is preferably a hydroxide ion, a carbonate ion, or a bicarbonate ion. m is an integer of 1 to 10, preferably an integer of 1 to 4.

[0069] [Method of manufacturing ion exchange resin] The ion exchange resin can be obtained, for example, by thermally polymerizing or photopolymerizing the polymerizable composition according to the embodiment. The method of photopolymerization (light irradiation) is not particularly limited, but the wavelength of ultraviolet light irradiation is, for example, 300 to 400 nm, preferably 330 to 380 nm. The intensity of ultraviolet light irradiation is, for example, 10 to 5000 mW / cm. 2 and preferably 50 to 3000 mw / cm 2 The irradiation time is, for example, from 0.5 seconds to 3 hours, and preferably from 2 seconds to 1 hour.

[0070] Examples of irradiation sources that can be used include ultraviolet light-emitting diodes (LEDs), halogen lamps, xenon lamps, tungsten lamps, and mercury lamps. LEDs are preferred because they are easy to control the irradiation wavelength and do not generate much heat.

[0071] The method of thermal polymerization (heat treatment) is not particularly limited, but the heating temperature is, for example, 50 to 150° C., and preferably 80 to 130° C. The heating time is, for example, 1 minute to 3 hours, and preferably 3 minutes to 1 hour. For the heating method, a hot plate, oven, infrared heater, heating furnace, etc. can be used. It is also possible to partially polymerize the polymerizable composition by ultraviolet irradiation and then completely polymerize the polymerizable composition by thermal polymerization. Alternatively, ultraviolet irradiation may be omitted and only heat treatment may be performed. Alternatively, ultraviolet irradiation may be performed after heat treatment.

[0072] The ion exchange resin obtained after light irradiation, heating, or both light irradiation and heating may be washed with water, an organic solvent (ethanol, acetone, chloroform, dichloromethane, etc.), or a mixed solvent thereof to wash away ethylene glycol and the like contained in the polymerizable composition. When water is used, an anion substitution treatment described below may also be carried out.

[0073] The ion exchange resin obtained by the above method may be subjected to a drying treatment. In the drying treatment, the drying temperature may be, for example, from 40° C. to 90° C., and the drying time may be, for example, from 3 hours to 24 hours.

[0074] The ion exchange resin obtained by the above method may be subjected to an anion substitution treatment. This allows the anion of the quaternary ammonium group of the ion exchange resin to be substituted with another type of anion. When the anion of the quaternary ammonium group is triflate or bistrifluoromethanesulfonimide, the anion can be substituted with a halide ion by immersing the ion exchange resin for a certain period of time in an aqueous solution containing a halogen compound, such as a hydrogen chloride solution or a hydrogen bromide solution. When the anion of the quaternary ammonium group is a halide ion, the anion can be substituted with a hydroxide ion by immersing the ion exchange resin for a certain period of time in an alkali metal hydroxide solution, such as a sodium hydroxide solution. When the anion of the quaternary ammonium group is a hydroxide ion, the anion can be substituted with a carbonate ion or a bicarbonate ion by immersing the ion exchange resin for a certain period of time in a carbonate solution, such as a potassium carbonate solution or a sodium bicarbonate solution. Alternatively, when the anion of the quaternary ammonium group is a hydroxide ion, the anion can be substituted with a carbonate ion or a bicarbonate ion by exposing the ion exchange resin to the atmosphere for a certain period of time.

[0075] [Ion exchange membrane] An ion exchange membrane according to a third embodiment (hereinafter also simply referred to as "ion exchange membrane") includes the ion exchange resin according to the second embodiment and a substrate. The ion exchange resin can be supported on the substrate. The ion exchange membrane according to the embodiment can be suitably used as an anion exchange membrane (AEM).

[0076] The ion exchange membrane can be used in hydrogen production devices, water electrolysis devices, fuel cells, electrodialysis devices, diffusion dialysis devices, pure water production devices, ion-exchanged water production devices, etc. The ion exchange membrane can be suitably used as an anion exchange membrane for an AEM-type hydrogen production device, an AEM-type water electrolysis device, or a fuel cell.

[0077] The thickness of the ion exchange membrane is, for example, 1 μm or more and 500 μm or less. When a thick ion exchange membrane is used, the membrane resistance tends to increase. When a thin ion exchange membrane is used, the membrane resistance tends to decrease. The thickness of the ion exchange membrane is preferably 10 μm or more and 200 μm or less, and more preferably 20 μm or more and 100 μm or less. The method for measuring the thickness of the ion exchange membrane will be described later in the Examples.

[0078] The ion exchange capacity (IEC) of the ion exchange membrane is, for example, 1.0 mmol / g or more, in another example, 2.0 mmol / g or more, and in yet another example, 2.5 mmol / g or more. The ion exchange membrane can achieve a high ion exchange capacity because a polymerizable composition with a high concentration of quaternary ammonium salt can be used. There is no particular upper limit to the ion exchange capacity, but in one example, it is 4.0 mmol / g or less, and in another example, it is 3.0 mmol / g or less. The method for measuring the ion exchange capacity will be described later in the Examples. The ratio of the IEC to the thickness of the ion exchange membrane (IEC / membrane thickness) is preferably 0.04 to 0.10, more preferably 0.06 to 0.10. When the ratio is within the above range, the performance as an ion exchange membrane is excellent.

[0079] The membrane resistance of the ion exchange membrane is, for example, 2.0 Ω cm 2 or less, and according to other examples, 1.0 Ω cm 2There is no particular lower limit for the membrane resistance, but one example is 0.1 Ω cm 2 or more, and according to other examples, 0.2 Ω cm 2 The method for measuring the membrane resistance will be described later in the Examples.

[0080] The water content of the ion exchange membrane is, for example, 20% or more, in another example, 30% or more, and in yet another example, 40% or more. When the water content of the ion exchange membrane is high, the ionic conductivity of water tends to increase, and it is thought that the conductivity improves. From the viewpoint of increasing the mechanical strength of the membrane, the water content of the ion exchange membrane is preferably 120% or less, and more preferably 100% or less. The method for measuring the water content will be described later in the examples.

[0081] The substrate functions as a support for the ion exchange resin. The substrate is preferably a porous membrane. Examples of the substrate that can be used include porous films, woven fabrics, nonwoven fabrics, sponges, and films. When a porous membrane is used as the substrate, it is preferable that the pores of the substrate are filled with the ion exchange resin.

[0082] The substrate may be, for example, a polyolefin resin, a fluorine-based resin, polyacrylonitrile, polyvinyl chloride, polyester, polyamide, polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylene sulfide, polyimide, polyethermide, polyamideimide, polycarbonate, polyacrylate, cellulose acetate, polyetheretherketone, or a copolymer thereof. Polyolefin resins include polyethylene, polypropylene, polybutadiene, polymethylpentene, polybutene, polypentene, polyhexene, polymethylheptene, and copolymers thereof. Fluorine-based resins include polytetrafluoroethylene, poly(tetrafluoroethylene-hexafluoropropylene), polyvinylidene fluoride, polyhexafluoropropylene, polychlorotrifluoroethylene, and copolymers thereof. The substrate preferably contains a polyolefin resin, and more preferably contains at least one of polyethylene and polypropylene.

[0083] The film thickness of the substrate is, for example, 1 μm or more and 500 μm or less, preferably 5 μm or more and 200 μm or less, more preferably 10 μm or more and 150 μm or less, and even more preferably 20 μm or more and 100 μm or less.

[0084] The porosity of the substrate is, for example, 25% or more and 60% or less, preferably 30% or more and 50% or less, and more preferably 35% or more and 45% or less.

[0085] [Method of manufacturing ion exchange membrane] Examples of methods for producing an ion exchange membrane include a method including a step of contacting a polymerizable composition with a substrate to obtain a first structure, and a step of irradiating the first structure with ultraviolet light to obtain a second structure (photopolymerization step). This manufacturing method uses a polymerizable composition containing a quaternary ammonium salt, which eliminates the need for a step of introducing ion-exchange groups into the polymerized resin, as compared with a method using a polymerizable composition consisting solely of a compound without ion-exchange groups. Furthermore, because a portion or all of the polymerizable composition is polymerized by ultraviolet irradiation, the ion-exchange membrane can be manufactured in a shorter time than with a thermal polymerization method. In addition to the photopolymerization step, the method may further include a thermal polymerization step.

[0086] The manufacturing method will be described in detail below. The method for contacting the polymerizable composition with the substrate is not particularly limited. The polymerizable composition may be applied to the substrate by coating, spraying, or dripping. Alternatively, the substrate may be immersed in the polymerizable composition. The amount of the polymerizable composition per 1 g of substrate may be, for example, 0.2 g or more and 2.0 g or less. The substrate may be subjected to a surface treatment such as corona treatment, glow discharge treatment, or alkali treatment to enhance adhesion to the polymerizable composition.

[0087] In the first structure, a polymerizable composition is supported on a substrate. Preferably, at least one main surface of the substrate of the first structure is coated with a resin film, and more preferably, both surfaces are coated with a resin film. By coating with a resin film, compositional changes in the polymerizable composition supported on the first structure can be suppressed. This is because, when the polymerizable composition contains an organic solvent, the composition of the polymerizable composition can change due to the evaporation of the organic solvent. By coating with a resin film, the evaporation of the organic solvent can be suppressed. Furthermore, by coating with a resin film, the surface smoothness of the ion exchange membrane is improved, and an ion exchange membrane with a uniform thickness can be obtained.

[0088] Examples of the resin for the resin film include polyethylene terephthalate, polyester, perfluoroethylene propene copolymer, tetrafluoroethylene-hexaethylene propylene copolymer, and the like.

[0089] This first structure can be irradiated with ultraviolet light to photopolymerize it, thereby obtaining a second structure in which the polymerizable composition is polymerized. The obtained second structure may be used as an ion exchange membrane containing a cured product of the polymerizable composition. The ultraviolet light irradiation conditions and irradiation source are the same as those described in the section [Method for producing an ion exchange resin].

[0090] As described above, when the polymerizable composition contains an organic solvent, the composition of the polymerizable composition may change due to evaporation of the organic solvent. Therefore, it is preferable to irradiate the first structure with ultraviolet light immediately after obtaining the first structure. Specifically, ultraviolet light is irradiated preferably within 0.5 hours, more preferably within 0.1 hours, after the production of the first structure. Note that the organic solvent volatilizes during ultraviolet light irradiation or the heat treatment described below, and therefore does not remain in the ion exchange membrane.

[0091] After irradiating the first structure with ultraviolet light to obtain a second structure, the second structure may be heat-treated to obtain an ion exchange membrane containing a cured product of the polymerizable composition. That is, after partially polymerizing the polymerizable composition by ultraviolet light irradiation, the polymerizable composition may be completely polymerized by thermal polymerization. The conditions and method of the heat treatment are the same as those described in the section [Method for producing an ion exchange resin].

[0092] The ion exchange membrane obtained after light irradiation, heating, or both light irradiation and heating may be subjected to washing, drying, and anion substitution treatment in the same manner as described above in the section [Method for producing ion exchange resin].

[0093] [Membrane electrode assembly] A membrane electrode assembly (hereinafter also simply referred to as "membrane electrode assembly") according to a fourth embodiment includes the ion exchange membrane according to the third embodiment and electrodes. In the membrane electrode assembly (MEA), the ion exchange membrane and the electrodes are integrated. The electrodes may include a first electrode that is a cathode and a second electrode that is an anode. The membrane electrode assembly may have an ion exchange membrane interposed between the first electrode and the second electrode.

[0094] The membrane electrode assembly can be used for hydrogen production devices, water electrolysis devices, fuel cells, and the like.

[0095] The electrode may contain a metal catalyst and, optionally, an ion conductive agent, a conductive agent, and a binder. The proportions (contents) of the metal catalyst, the ion conductive agent, the conductive agent, and the binder in the electrode may be, for example, 50% by mass or more and 99% by mass or less, 0.1% by mass or more and 30% by mass or less, 0.1% by mass or more and 30% by mass or less, and 0.1% by mass or more and 30% by mass or less, respectively.

[0096] The metal catalyst promotes the oxidation or reduction reaction. The metal catalyst is typically in particle form. Examples of the metal catalyst include platinum, gold, silver, palladium, iridium, rhodium, ruthenium, tin, iron, cobalt, nickel, manganese, molybdenum, tungsten, vanadium, chromium, tantalum, zirconium, aluminum, zinc, oxides or hydroxides thereof, or alloys thereof. The metal catalyst for the anode preferably contains nickel. The metal catalyst for the cathode preferably contains platinum, gold, silver, palladium, iridium, rhodium, ruthenium, tin, iron, cobalt, nickel, manganese, or alloys thereof.

[0097] The ion conductive agent enhances the ionic conductivity of the electrode. Examples of the ion conductive agent include perfluorocarbon polymers, aromatic polyether ether ketones, polysulfones, polyfluorenes, and polystyrenes having basic functional groups. An ion exchange resin may be used as the ion conductive agent. The ion exchange resin used as the ion conductive agent may be the ion exchange resin according to the second embodiment, or other ion exchange resins may be used. Examples of other ion exchange resins include ion exchange resins having imidazole groups.

[0098] The conductive agent enhances the electronic conductivity of the electrode. The conductive agent may be used as a support for the metal catalyst. Examples of the conductive agent include carbon black, activated carbon, graphite, fullerene, carbon nanotubes, and mixtures thereof.

[0099] The binder increases the rigidity of the electrode and may be polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluorine-based rubber, polyacrylic acid compound, imide compound, or a mixture thereof.

[0100] The membrane electrode assembly is produced, for example, by the following method. First, an ion exchange membrane is prepared by the method described above. The ion exchange membrane may be in a wet state, but is preferably in a dry state. Next, a metal catalyst is mixed with, optionally, an ion conductive agent, a conductive agent, a binder, and an organic solvent to prepare a composition for forming a first electrode. This composition for forming a first electrode is applied, for example, to a release paper to obtain a first coating film. This first coating film is dried. After drying, the first coating film is peeled off from the release paper and laminated on one main surface of the ion exchange membrane. An ion conductive agent may be applied to one main surface of the ion exchange membrane. Alternatively, the composition for forming a first electrode may be applied directly to one main surface of the ion exchange membrane to form the first coating film.

[0101] Next, a metal catalyst is mixed with, optionally, an ion conductive agent, a conductive agent, a binder, and an organic solvent to prepare a composition for forming a second electrode. This composition for forming a second electrode is applied, for example, to a release paper to obtain a second coating film. This second coating film is dried. After drying, the second coating film is peeled off from the release paper and laminated on the other main surface of the ion exchange membrane. An ion conductive agent may be applied to the other main surface of the ion exchange membrane. The first electrode composition may be applied directly to the other main surface of the ion exchange membrane to form a second coating film. Alternatively, the first coating film may be formed after the second coating film is formed.

[0102] The thickness of the first coating film and the second coating film may be, for example, 1 to 50 μm, and is preferably 5 to 30 μm.

[0103] The resulting laminate is then heated, pressurized, or both to integrate the first and second coating films with the ion exchange membrane. This results in a membrane / electrode assembly in which the first electrode, ion exchange membrane, and second electrode are stacked in this order. Note that the first electrode or second electrode may be omitted.

[0104] Heating conditions include, for example, 50 to 80°C and 10 to 120 minutes.

[0105] [Hydrogen production equipment] A hydrogen production device according to a fifth embodiment (hereinafter also simply referred to as a "hydrogen production device") includes the ion exchange membrane according to the third embodiment. The hydrogen production device may include the membrane electrode assembly according to the fourth embodiment. The hydrogen production device includes the ion exchange membrane according to the embodiment, and therefore can efficiently decompose water.

[0106] Hereinafter, a hydrogen production device including a membrane electrode assembly will be described in detail with reference to FIG. Fig. 1 is a cross-sectional view schematically illustrating an example of a hydrogen production device. The hydrogen production device 1 shown in Fig. 1 includes a membrane electrode assembly 4, and a first electrode chamber 2 and a second electrode chamber 3 separated by the membrane electrode assembly 4.

[0107] The membrane electrode assembly 4 includes an anion exchange membrane 5, a first electrode 6 supported on one main surface of the anion exchange membrane 5, and a second electrode 7 supported on the other main surface of the anion exchange membrane. The first electrode 6 and the second electrode 7 are connected to a power source via conductors (not shown). Gas diffusion layers may be provided on the surfaces of the first electrode 6 and the second electrode 7. Examples of gas diffusion layers that can be used include carbon paper, carbon cloth, nickel foam, titanium foam, and porous graphite.

[0108] The first electrode chamber 2 is provided with a first electrode 6 and is connected to a hydrogen discharge pipe 8. The hydrogen discharge pipe 8 is connected to a hydrogen tank (not shown). The first electrode chamber 2 may be provided with a first partition wall (not shown). The first partition wall is preferably provided with a plurality of grooves connecting to the first electrode chamber 2 and a hydrogen discharge channel connected to these grooves and the hydrogen discharge pipe 8. The first partition wall is preferably made of an electron-conductive material. For example, a metal plate can be used for the first partition wall. The first partition wall may be in contact with the gas diffusion layer described above.

[0109] The second electrode chamber 3 is equipped with a second electrode 7, and is connected to an oxygen exhaust pipe 9 and a water supply pipe 10. The oxygen exhaust pipe 9 is connected to an oxygen tank (not shown). The water supply pipe 10 is connected to a water supply device (not shown). The second electrode chamber 3 may be provided with a second partition wall (not shown). The second partition wall preferably has a plurality of grooves connecting to the second electrode chamber 3, and oxygen exhaust channels connected to these grooves, the oxygen exhaust pipe 9, and the water supply pipe 10. The second partition wall is preferably made of an electron-conductive material. For example, a metal plate can be used for the second partition wall. The second partition wall may be in contact with the gas diffusion layer described above.

[0110] Next, a hydrogen production method using the hydrogen production device will be described in detail with reference to FIG. First, the liquid to be treated is supplied to the second electrode chamber 3 via the water supply pipe 10. The liquid to be treated may be water or an alkaline aqueous solution. The alkaline aqueous solution is, for example, an aqueous solution of an alkali metal hydroxide, carbonate, or bicarbonate. The pH of the alkaline aqueous solution at 20°C is, for example, 10 to 14. The concentration of the alkaline aqueous solution is, for example, 0.1% by mass to 30% by mass.

[0111] The liquid to be treated that has come into contact with the membrane electrode assembly 4 is held by the anion exchange membrane 5. Then, the liquid to be treated is supplied to the first electrode chamber 2 via the anion exchange membrane 5. Next, power is supplied from a power source (not shown) to the first electrode 6 and the second electrode 7. As a result, at the first electrode 6, water (H2O) is decomposed to hydrogen (H2) and hydroxide ions (OH) as shown in the following formula (A): - The hydroxide ions thus produced are supplied to the second electrode 7 via the anion exchange membrane 5. At the second electrode 7, the supplied hydroxide ions are decomposed and synthesized into oxygen (O) and water (HO), as shown in the following formula (B): 2H2O+2e - → H2+2OH - (A) 2OH - → 1 / 2O2+H2O+2e- (B)

[0112] The hydrogen gas produced in the first electrode chamber 2 is supplied to a hydrogen tank via a hydrogen discharge pipe 8. The oxygen gas produced in the second electrode chamber 3 is supplied to an oxygen tank via an oxygen discharge pipe 9. [Example]

[0113] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0114] <Preparation of Polymerizable Composition> Example 1 A polymerizable composition was obtained by mixing 6 g of vinylbenzyltrimethylammonium chloride, 0.37 g of polymerizable monomer, 3.15 g of organic solvent, 0.1 equivalent of a hydroxyl group-containing compound, 0.09 g of photopolymerization initiator, 0.05 g of thermal polymerization initiator, and 0.0015 g of polymerization inhibitor at room temperature and atmospheric pressure. Divinylbenzene was used as the polymerizable monomer. Ethylene glycol was used as the organic solvent. 0.21 g of 1-butanol was used as the hydroxyl group-containing compound. 1-phenyl-2-hydroxy-2-methylpropan-1-one was used as the photopolymerization initiator. tert-Butyl peroxyoctoate was used as the thermal polymerization initiator. 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl was used as the polymerization inhibitor.

[0115] (Examples 2 to 23, Comparative Examples 1 to 16) Polymerizable compositions were prepared in the same manner as in Example 1, except that hydroxyl group-containing compounds or general-purpose solvents shown in Tables 1 and 2 were used instead of 1-butanol, which was used as the hydroxyl group-containing compound in Example 1.

[0116] <Evaluation test> (phase separation) The polymerizable compositions obtained in the examples and comparative examples were visually inspected for phase separation. Specifically, 10 g of the polymerizable composition in a screw tube was stirred for 300 seconds, and then allowed to stand for 10 minutes. If phase separation was visually observed, it was evaluated as "present," and if not, it was evaluated as "absent."

[0117] (impregnation) The impregnation of the polymerizable compositions obtained in the examples and comparative examples was confirmed. Specifically, when the porous substrate was immersed in the polymerizable composition, the presence or absence of impregnation into the porous substrate was visually confirmed. If the porous substrate was impregnated within 60 seconds, it was marked "yes," and if it was not impregnated, it was marked "no." As the porous substrate, a polyethylene porous substrate with a film thickness of 25 μm, a porosity of 40±5%, and an average pore size of 90 nm was used.

[0118] [Table 1]

[0119] [Table 2]

[0120] <Ion exchange membrane manufacturing> Example 24 First, a substrate was prepared. A polyethylene film with a thickness of 25 μm and a porosity of 42% was used as the substrate.

[0121] This substrate was immersed in the polymerizable composition of Example 1 and then pulled out of the polymerizable composition. In this way, a first structure in which the polymerizable composition was supported on the substrate was obtained. Both main surfaces of this first structure were covered with PET film. One main surface of the first structure was irradiated with ultraviolet light using an LED to obtain a second structure. The irradiation wavelength was 365 nm and the irradiation intensity was 100 mW / cm. 2 The irradiation time was 1 minute.

[0122] Next, the second structure was placed in a heat dryer and subjected to a heat treatment. The heating temperature was set to 120°C so that the surface temperature of the membrane would reach approximately 110°C, and the heating time was set to 15 minutes. After heating, the PET film was peeled off from the second structure to obtain an ion exchange membrane.

[0123] Examples 25 to 28 An ion exchange membrane was produced in the same manner as in Example 24, except that the polymerizable composition shown in Table 3 was used.

[0124] <Performance evaluation> (film thickness measurement) The thickness of the ion exchange membranes obtained in Examples 24 to 28 was measured. Specifically, the measurement was carried out using ID-H0530 manufactured by Mitutoyo Corporation.

[0125] (Measurement of ion exchange capacity and water content) The ion exchange capacity (IEC) and water content of the ion exchange membranes obtained in Examples 24 to 28 were measured. Specifically, the ion exchange membrane was first immersed in a 0.2 mol / L NaNO3 aqueous solution for 10 hours or more to replace the counter ions from chloride ions to nitrate ions. Note that for the ion exchange membranes of Examples 24 to 28, the counter ions were replaced with chloride ions prior to the conversion to nitrate ions. The replacement with chloride ions was carried out by immersing the ion exchange membrane in a 0.5 mol / L HCl aqueous solution for 10 hours or more.

[0126] The amount of chloride ions liberated during the substitution with nitrate ions was measured using a potentiometric titrator with a silver nitrate solution. The obtained value was designated as A (mol). The potentiometric titrator used was a COMTITE-900 manufactured by Hiranuma Sangyo Co., Ltd.

[0127] Next, the ion exchange membrane was immersed in a 1 mol / L HCl aqueous solution for 4 hours or more. After immersion, the ion exchange membrane was thoroughly rinsed with ion exchange water, the moisture on the surface was wiped off, and the weight of the ion exchange membrane was measured. The obtained value was designated W (g). The ion exchange membrane was dried under reduced pressure at 60°C for 5 hours, and the weight after drying was measured. The obtained value was designated D (g). Based on the amount of liberated chloride ions (A) and the weight of the ion exchange membrane after drying (D), the anion exchange capacity of the ion exchange membrane was calculated using the following formula. Anion exchange capacity [mmol / g-dry weight] = A × 1000 / D

[0128] Furthermore, the water content of the ion exchange membrane was calculated from the weight (W) of the wet ion exchange membrane and the weight (D) of the dried ion exchange membrane according to the following formula. Moisture content [%]=(WD) / D×100.

[0129] (membrane resistance measurement) The membrane resistance of the ion exchange membranes obtained in Examples 24 to 28 was measured, and the results are shown in Table 3. Specifically, the ion exchange membrane was first immersed in a 0.5 mol / L aqueous NaCl solution for 30 minutes or more. The immersed ion exchange membrane was placed in the center of a two-compartment cell equipped with platinum electrodes. Both sides of the ion exchange membrane were filled with a 0.5 mol / L aqueous NaCl solution, and the resistance between the electrodes at 25°C was measured using an AC bridge (frequency 1000 cycles / second). Next, the resistance between the electrodes without the ion exchange membrane was measured. The resistance between the electrodes without the ion exchange membrane was subtracted from the resistance between the electrodes with the ion exchange membrane installed. The obtained value was taken as the membrane resistance. [Table 3]

[0130] As is clear from the above examples, the polymerizable composition according to one embodiment of the present invention can be prepared without causing phase separation even when a photopolymerization initiator is used, and therefore the production efficiency of the cured product is excellent and the composition can be used as an ion exchange resin or an ion exchange membrane. In a preferred embodiment, the composition also has excellent impregnation properties. Furthermore, by using such a polymerizable composition, it is possible to efficiently produce a membrane electrode assembly or a hydrogen production device.

[0131] Preferred embodiments are described below. [1] A quaternary ammonium salt represented by the following formula (I), a polymerizable monomer; a linear or branched alkylene glycol having 1 to 4 carbon atoms; at least one hydroxyl group-containing compound selected from the group consisting of primary alcohols having from 4 to 15 carbon atoms, secondary alcohols having from 4 to 15 carbon atoms, and diols having from 5 to 15 carbon atoms and having a hydroxy group bonded to a secondary carbon atom; A polymerizable composition comprising: [ka] In the above formula (I), R 1 is an alkenyl group having 2 to 5 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, R 3 , R 4 , and R 5 are each independently a linear or branched alkyl group having from 1 to 4 carbon atoms, or a linear or branched alkoxy group having from 1 to 4 carbon atoms, X - is an anion. [2] The polymerizable composition according to [1], wherein the concentration of the quaternary ammonium salt represented by the formula (I) is 5% by mass or more and 95% by mass or less. [3] The polymerizable composition according to [1] or [2], wherein the concentration of the hydroxyl group-containing compound is 1% by mass or more and 10% by mass or less. [4] The polymerizable composition according to any one of [1] to [3], wherein the concentration of the alkylene glycol is 1% by mass or more and 50% by mass or less. [5] The polymerizable composition according to any one of [1] to [4], wherein the concentration of the polymerizable monomer is 1% by mass or more and 50% by mass or less. [6] The polymerizable composition according to any one of [1] to [5], wherein the quaternary ammonium salt includes at least one salt selected from the group consisting of (vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium triflate, and (vinylbenzyl)trimethylammonium bistrifluoromethanesulfonylimide. [7] The polymerizable composition according to any one of [1] to [6], wherein the hydroxyl group-containing compound includes at least one compound selected from the group consisting of primary aliphatic alcohols having from 4 to 15 carbon atoms, secondary aliphatic alcohols having from 4 to 15 carbon atoms, and aliphatic diols having from 5 to 15 carbon atoms and having a hydroxy group bonded to a secondary carbon atom. [8] The polymerizable composition according to any one of [1] to [6], wherein the hydroxyl group-containing compound contains at least one primary alcohol selected from the group consisting of 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, 1-undecanol, and 1-dodecanol. [9] The polymerizable composition according to any one of [1] to [6], wherein the hydroxyl group-containing compound contains at least one secondary alcohol selected from the group consisting of 2-butanol, 3-pentanol, 3-hexanol, 3-heptanol, 2-undecanol, 2-dodecanol, cyclopentanol, cyclohexanol, and cyclooctanol.

[10] The polymerizable composition according to any one of [1] to [6], wherein the hydroxyl group-containing compound contains at least one diol selected from the group consisting of 1,2-hexanediol, 1,2-octanediol, and 1,2-decanediol.

[11] The polymerizable composition according to any one of [1] to [6], wherein the hydroxyl group-containing compound includes at least one compound selected from the group consisting of 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, 1-undecanol, 1-dodecanol, 3-heptanol, 2-undecanol, 2-dodecanol, and 1,2-decanediol.

[12] The polymerizable composition according to any one of [1] to

[11] , wherein the hydroxyl group-containing compound has a flash point of 50° C. or higher.

[13] The polymerizable composition according to any one of [1] to

[12] , wherein the polymerizable monomer includes at least one compound selected from the group consisting of divinylbenzene, 1,2-bis(4-vinylphenyl)ethane, trivinylbenzene, 1,6-bis(4-vinylbenzyloxy)hexane, and N,N-dimethyl-N-(4-vinylbenzyl)-4-(4-vinylphenyl)butane-1-ammonium chloride.

[14] The polymerizable composition according to any one of [1] to

[13] , wherein the ratio M1 / M2 of the mass M1 of the hydroxyl group-containing compound to the mass M2 of the alkylene glycol is 0.02 or more and 10 or less.

[15] The polymerizable composition according to any one of [1] to

[14] , further comprising a polymerization initiator.

[16]

[15] The polymerizable composition according to

[15] , wherein the polymerization initiator includes at least one compound selected from the group consisting of benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl peroxyoctoate, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-2morpholinopropan-1-one.

[17] An ion exchange resin comprising a cured product of the polymerizable composition according to any one of [1] to

[16] .

[18]

[17] An ion exchange membrane comprising the ion exchange resin according to

[17] and a substrate.

[19]

[18] A membrane electrode assembly comprising the ion exchange membrane according to

[18] and an electrode.

[20] A hydrogen production device comprising the ion exchange membrane according to

[18] . [Explanation of symbols]

[0132] 1...hydrogen production device, 2...first electrode chamber, 3...second electrode chamber, 4...membrane electrode assembly, 5...anion exchange membrane 5, 6...first electrode, 7...second electrode, 8...hydrogen discharge pipe, 9...oxygen discharge pipe, 10...water supply pipe 10.

Claims

1. A quaternary ammonium salt represented by the following formula (I), a polymerizable monomer having two or more radical polymerizable groups selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group; a linear or branched alkylene glycol having 1 to 4 carbon atoms; at least one hydroxyl group-containing compound selected from the group consisting of 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, 1-undecanol, 1-dodecanol, 2-butanol, 3-pentanol, 3-hexanol, 3-heptanol, 2-undecanol, 2-dodecanol, cyclopentanol, cyclohexanol, cyclooctanol, 1,2-hexanediol, 1,2-octanediol, and 1,2-decanediol; A polymerizable composition comprising: 【Chemical 1】 In the above formula (I), R １ is an alkenyl group having from 2 to 5 carbon atoms, R ２ is an alkylene group having 1 to 10 carbon atoms, R ３ , R ４ , and R ５ are each independently a linear or branched alkyl group having from 1 to 4 carbon atoms, X － is an anion.

2. The polymerizable composition according to claim 1 , wherein the content of the quaternary ammonium salt is 5% by mass or more and 95% by mass or less.

3. The polymerizable composition according to claim 1 or 2, wherein the content of the hydroxyl group-containing compound is 1% by mass or more and 10% by mass or less.

4. The polymerizable composition according to claim 1 or 2, wherein the content of the alkylene glycol is 1% by mass or more and 50% by mass or less.

5. The polymerizable composition according to claim 1 or 2, wherein the content of the polymerizable monomer is 1% by mass or more and 50% by mass or less.

6. 3. The polymerizable composition according to claim 1, wherein the quaternary ammonium salt comprises at least one salt selected from the group consisting of (vinylbenzyl)trimethylammonium chloride, (vinylbenzyl)trimethylammonium triflate, and (vinylbenzyl)trimethylammonium bistrifluoromethanesulfonylimide.

7. 3. The polymerizable composition according to claim 1, wherein the hydroxyl group-containing compound comprises at least one compound selected from the group consisting of 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, isodecanol, tridecanol, 1-undecanol, 1-dodecanol, 3-heptanol, 2-undecanol, 2-dodecanol, and 1,2-decanediol.

8. The polymerizable composition according to claim 1 or 2, wherein the hydroxyl group-containing compound has a flash point of 50° C. or higher.

9. 3. The polymerizable composition according to claim 1, wherein the polymerizable monomer comprises at least one compound selected from the group consisting of divinylbenzene, 1,2-bis(4-vinylphenyl)ethane, trivinylbenzene, 1,6-bis(4-vinylbenzyloxy)hexane, and N,N-dimethyl-N-(4-vinylbenzyl)-4-(4-vinylphenyl)butane-1-ammonium chloride.

10. 3. The polymerizable composition according to claim 1, wherein a ratio (M1 / M2) of a mass M1 of the hydroxyl group-containing compound to a mass M2 of the alkylene glycol is 0.02 or more and 10 or less.

11. The polymerizable composition according to claim 1 or 2, further comprising a polymerization initiator.

12. 12. The polymerizable composition of claim 11, wherein the polymerization initiator comprises at least one compound selected from the group consisting of benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, lauroyl peroxide, acetyl peroxide, tert-butyl peroxyoctoate, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)butan-1-one, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one.

13. A method for producing an ion exchange resin, comprising curing the polymerizable composition according to claim 1 to obtain a cured product.

14. A method for producing an ion exchange membrane, comprising contacting the polymerizable composition according to claim 1 or 2 with a substrate, and then curing the polymerizable composition.

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