Copolymer, anion exchange membrane containing copolymer, anion exchange membrane water electrolysis cell or fuel cell, method for producing hydrogen using anion exchange membrane water electrolysis cell, method for producing polymer, and monomer contained in polymer

Abstract

To solve the problem in which: copolymers derived from conventional technologies have exhibited difficulty in achieving higher ion conductivity and ion exchange capacity while preserving their functionality as anion exchange membranes.SOLUTION: The present invention provides a copolymer containing a repeating unit formula (I) and a repeating unit formula (IIA) and / or (IIB), an anion exchange membrane containing the copolymer, an anion exchange membrane water electrolysis cell or fuel cell, a method for producing hydrogen using the anion exchange membrane water electrolysis cell, a method for producing a polymer, and a monomer contained in the polymer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a copolymer, an anion exchange membrane containing the copolymer, an anion exchange membrane water electrolysis cell or fuel cell, a method for producing hydrogen using an anion exchange membrane water electrolysis cell, a method for producing a polymer, and a monomer contained in the polymer. [Background technology]

[0002] In order to break away from a society dependent on fossil fuels that generate greenhouse gases, there is a need to produce and use clean energy that will reduce carbon dioxide emissions to virtually zero. Hydrogen produced by water electrolysis does not emit carbon dioxide when burned, and fuel cells produced from the resulting hydrogen also do not emit carbon dioxide. These materials are being actively researched because they are useful as clean energy sources.

[0003] Ion exchange membranes (electrolyte membranes) are used in water electrolysis and fuel cells, and are required to have excellent ion conductivity as well as durability as a membrane. In particular, anion exchange membrane electrolysis technology, which uses anion exchange membranes to electrolyze water and produce hydrogen, has attracted attention, and research has been conducted on improving the ion conductivity and ion exchange capacity of anion exchange membranes, as well as on increasing their durability under alkaline conditions.

[0004] Patent documents 1 and 2 disclose hydroxide exchange membranes or hydroxide exchange ionomers formed from poly(arylpiperidinium) polymers having piperidinium, an alkaline stable cation, incorporated into a rigid aromatic polymer backbone that does not contain ether linkages.

[0005] However, the anion exchange membranes produced from the polymers disclosed in Patent Documents 1 and 2 have insufficient ion conductivity and ion exchange capacity because the number of cations contained in the molecule is small.

[0006] Patent Document 3 discloses a specific polymer having excellent ion conductivity and membrane-formability and a method for easily producing the polymer, a precursor suitable for producing the polymer, an electrolyte membrane using the polymer and having excellent chemical durability and membrane strength, and a fuel cell using the electrolyte membrane.

[0007] However, the anion exchange membrane produced from the polymer disclosed in Patent Document 3 also has insufficient ion conductivity and ion exchange capacity. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Special Publication No. 2019-518809 [Patent Document 2] Special Publication No. 2020-536165 [Patent Document 3] Patent Publication No. 2021-42351 Summary of the Invention [Problem to be solved by the invention]

[0009] It has been difficult to increase the ion conductivity and ion exchange capacity of polymers obtained by conventional techniques while maintaining their function as an anion exchange membrane.

[0010] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a copolymer for producing an anion exchange membrane having high ion conductivity and ion exchange capacity, an anion exchange membrane containing the copolymer, an anion exchange membrane water electrolysis cell or fuel cell, a hydrogen production method using an anion exchange membrane water electrolysis cell, a polymer production method, and a monomer contained in the polymer. [Means for solving the problem]

[0011] The present inventors have conducted extensive research into the above-mentioned problems and have arrived at the present invention. That is, the object of the present invention is achieved by a copolymer comprising the repeating unit formula (I) and the repeating unit formula (IIA) and / or (IIB): [ka] [In the formula (I), X is C 1 ~C 12 X may form a 5- or 6-membered ring together with a carbon atom of an adjacent aromatic ring, and hydrogen atoms bonded to the aromatic ring are each independently selected from halogen, C 1 ~C 12 Alkyl groups of C 1 ~C 12 or an alkoxy group of C 6 ~C 12 At least one carbon atom of X may be substituted with an aryl group represented by the formula: A -R A is bonded, and L A is a divalent linking group, R A is N + and formula (I) includes a counter anion. [ka] [In formula (IIA), L B is a divalent linking group, R B is N + In formula (IIB), R c is N + which, together with the carbon to which it is attached, forms a 5- or 6-membered ring, and formula (IIA) and / or (IIB) contain a counter anion.

[0012] The copolymer of the present invention is 6 ~C 20 It is preferable that the compound further contains a repeating unit of an arylene group of the formula:

[0013] The copolymer of the present invention, L A and L B are each independently 1 ~C 20Alkylene group, C 3 ~C 20 Cycloalkylene group, C 2 ~C 20 Alkenylene group, C 1 ~C 20 Polyoxyalkylene group, C 6 ~C 20 Arylene groups of the formula: -O-, -S-, -CO-, -COO-, -NH-, and -N(C 1 ~C 20 may be interrupted by alkyl)- 1 ~C 20 It is preferred that the alkylene group is selected from the group consisting of:

[0014] The copolymer of the present invention, R A and R B are each independently selected from the group consisting of an ammonium ion, an imidazolium ion, a pyrrolidinium ion, a pyridinium ion, a pyridazinium ion, a pyrimidinium ion, a pyrazinium ion, a pyrazolium ion, and a piperidinium ion. + R is an organic group containing c is selected from the group consisting of an imidazolium ion, a pyrrolidinium ion, a pyridinium ion, a pyridazinium ion, a pyrimidinium ion, a pyrazinium ion, a pyrazolium ion, and a piperidinium ion, together with the carbon to which it is bonded. + It is preferable to form an organic group comprising:

[0015] The counter anion of the copolymer of the present invention is OH - , COO - , F - , Cl - , Br - , I - , CO 3 2- , NO 3 - , S.O. 4 2- and P.O. 4 3- It is preferable that the number of the ions is one or more selected from the group consisting of:

[0016] In the copolymer of the present invention, the formula (I) is preferably one or more selected from the group consisting of the following formulas (III) and (IV): [ka] [ka] [In formula (III) and formula (IV), R 1 and R 2 are each independently hydrogen and C 1 ~C 12 and Y is selected from the group consisting of alkyl groups - each independently represents a counter anion, and a and b each independently represent an integer of 1 to 10.

[0017] In the copolymer of the present invention, the formula (IIA) is preferably the following formula (V): [ka] [In formula (V), R 3 are each independently hydrogen and C 1 ~C 12 and Y is selected from the group consisting of alkyl groups - is a counter anion and L is a divalent linking group.

[0018] In the copolymer of the present invention, the formula (IIB) is preferably the following formula (VI): [ka] [In formula (VI), R 4 are each independently hydrogen and C 1 ~C 12 and Y is selected from the group consisting of alkyl groups - is the counter anion].

[0019] The object of the present invention is also achieved by an anion exchange membrane comprising the above copolymer.

[0020] Furthermore, the object of the present invention is achieved by an anion exchange membrane water electrolysis cell provided with an anion exchange membrane.

[0021] Additionally, the object of the present invention is achieved by a method for producing hydrogen, which comprises a step of electrolyzing water using an anion exchange membrane water electrolysis cell.

[0022] The object of the present invention is also achieved by a fuel cell comprising an anion exchange membrane.

[0023] Further, the object of the present invention is to provide a compound of formula (VII): [ka] Or, formula (VIII): [ka] [In formula (VII) and formula (VIII), c and d each independently represent an integer of 1 to 10; Z 1 and Z 2 and each of the above-mentioned groups independently represents a halogen other than F.

[0024] In addition, the present invention provides a compound of formula (VII): [ka] [In formula (VII), c's each independently represent an integer of 1 to 10; Z 1 and each of the formula (I) is independently a halogen other than F. Effect of the Invention

[0025] The copolymer of the present invention comprising the repeating unit formula (I) and the repeating unit formula (IIA) and / or (IIB) can provide an anion exchange membrane having high ion conductivity and high ion exchange capacity, an anion exchange membrane water electrolysis cell or fuel cell, and a method for producing hydrogen using an anion exchange membrane water electrolysis cell.

[0026] The present invention can also provide a method for producing a polymer, which comprises polymerizing a monomer represented by formula (VII) or formula (VIII), and a compound represented by formula (VII). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] [Copolymer] The copolymer of the present invention is characterized in that it contains a repeating unit formula (I) and a repeating unit formula (IIA) and / or (IIB): [ka] [In the formula (I), X is C 1 ~C 12 X may form a 5- or 6-membered ring together with a carbon atom of an adjacent aromatic ring, and hydrogen atoms bonded to the aromatic ring are each independently selected from halogen, C 1 ~C 12 Alkyl groups of C 1 ~C 12 or an alkoxy group of C 6 ~C 12 At least one carbon atom of X may be substituted with an aryl group represented by the formula: A -R A is bonded, and L A is a divalent linking group, R A is N + and formula (I) includes a counter anion. [ka] [In formula (IIA), L B is a divalent linking group, R B is N + In formula (IIB), R c is N + which, together with the carbon to which it is attached, forms a 5- or 6-membered ring, and formula (IIA) and / or (IIB) contain a counter anion.

[0028] In one embodiment, C 1 ~C 12 The alkylene group is a linear or branched divalent saturated hydrocarbon group and may be selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, and dodecylene. 1 ~C 12 The alkylene group is preferably methylene, ethylene, propylene, butylene, pentylene, or hexylene, and more preferably methylene.

[0029] In one embodiment, C 1 ~C 12 The alkyl group is a straight or branched chain monovalent saturated hydrocarbon group and may be selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl.

[0030] In one embodiment, C 1 ~C 12 The alkoxy groups may be selected from the group consisting of methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy.

[0031] In one embodiment, C 6 ~C 12 The aryl group is a substituted or unsubstituted monovalent aromatic group and may be selected from the group consisting of phenyl, tolyl, xylyl, benzyl, ethylbenzyl, naphthyl, and biphenyl. If the aromatic group is substituted, it may be selected from the group consisting of hydroxyl, halogen, C 1 ~C 12 or C 1 ~C 12 It may be substituted with an alkoxy group.

[0032] In one embodiment, the molar ratio of the repeating unit formula (I) to the repeating unit formula (IIA) and / or (IIB) [(I):((IIA)+(IIB))] may be in the range of 1:0.8 to 1:15, preferably 1:0.9 to 1:12, and more preferably 1:0.9 to 1:10.

[0033] In one embodiment, the repeating unit formula (I) and the repeating unit formula (IIA) or (IIB) may be linked alternately. By including the repeating unit formula (I) and the repeating unit formula (IIA) or (IIB) in the copolymer, an anion exchange membrane having high ion conductivity and ion exchange capacity can be obtained.

[0034] In one embodiment, the copolymer of the present invention is 6 ~C 20 The copolymer may further include a repeating unit of an arylene group of the formula: 6 ~C 20 By containing a repeating unit of an arylene group, the strength required for the anion exchange membrane is obtained.

[0035] In one embodiment, C 6 ~C 20 The arylene group is a substituted or unsubstituted divalent aromatic group, and the aromatic group may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, cumene, phenol, benzyl alcohol, anisole, acetophenone, cresol, catechol, resorcinol, hydroquinone, benzophenone, naphthalene, biphenyl, anthracene, phenanthrene, terphenyl, triphenylmethane, pyrene and tetracene, and is preferably phenyl, biphenyl or terphenyl, and more preferably biphenyl or terphenyl. When the aromatic group is substituted, it may be selected from the group consisting of hydroxyl, halogen, C 1 ~C 12 or C 1 ~C 12 It may be substituted with an alkoxy group.

[0036] In one embodiment, the repeating unit of formula (I) and the repeating unit of the arylene group may be linked via the repeating unit of formula (IIA) or (IIB).

[0037] In one embodiment, the molar ratio of the repeating unit formula (I) to the repeating unit of the arylene group [(I):arylene group] may be 1:0.8 to 1:12, preferably 1:0.9 to 1:10, and more preferably 1:0.9 to 1:9.

[0038] In one embodiment, the molar ratio of the repeating unit of the arylene group to the repeating unit formula (IIA) and / or (IIB) [(arylene group:((IIA)+(IIB))] may be 1:0.8 to 1:2.0, preferably 1:0.9 to 1:1.5, and more preferably 1:0.9 to 1:1.3.

[0039] In one embodiment, the molar ratio of the repeating units of the repeating unit formula (I) and the arylene group to the repeating units of the repeating units of the formula (IIA) and / or (IIB) [(I)+arylene group):((IIA)+(IIB))] may be in the range of 1:0.8 to 1:1.5, preferably 1:0.9 to 1:1.2, and more preferably 1:0.9 to 1:1.1.

[0040] In one embodiment, L A and L B are each independently 1 ~C 20 Alkylene group, C 3 ~C 20 Cycloalkylene group, C 2 ~C 20 Alkenylene group, C 1 ~C 20 Polyoxyalkylene group, C 6 ~C 20 Arylene groups of the formula: -O-, -S-, -CO-, -COO-, -NH-, and -N(C 1 ~C 20 may be interrupted by alkyl)- 1 ~C 20L may be selected from the group consisting of alkylene groups. A and L B is preferably C 1 ~C 20 or an alkylene group of C 6 ~C 20 More preferably, it is an arylene group of the formula: 1 ~C 12 More preferably, the alkylene group 1 ~C 6 is an alkylene group of the formula:

[0041] In one embodiment, C 1 ~C 20 The alkylene group is a straight or branched divalent saturated hydrocarbon group and may be selected from the group consisting of methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, and eicosylene.

[0042] In one embodiment, C 6 ~C 20 The arylene group is as defined above.

[0043] In one embodiment, R A and R B are each independently selected from the group consisting of an ammonium ion, an imidazolium ion, a pyrrolidinium ion, a pyridinium ion, a pyridazinium ion, a pyrimidinium ion, a pyrazinium ion, a pyrazolium ion, and a piperidinium ion. + R may be an organic group containing c is selected from the group consisting of an imidazolium ion, a pyrrolidinium ion, a pyridinium ion, a pyridazinium ion, a pyrimidinium ion, a pyrazinium ion, a pyrazolium ion, and a piperidinium ion, together with the carbon to which it is bonded. + An organic group containing the following may be formed.

[0044] In a preferred embodiment, R A and R B are each independently selected from the group consisting of an ammonium ion, a pyrrolidinium ion, and a piperidinium ion, and are more preferably an ammonium ion.

[0045] In a preferred embodiment, R c forms a pyrrolidinium ion or a piperidinium ion, and more preferably forms a piperidinium ion.

[0046] In the copolymer, R A And R B and / or R C By containing R, it is possible to obtain an anion exchange membrane having high ion conductivity and ion exchange capacity. A And, R B and / or R C Formed by N + It is preferable that the organic group containing different N + By including an organic group containing + When the organic group containing N deteriorates, the other N + Since the organic group containing the compound does not deteriorate at the same time, the compound has excellent durability.

[0047] In one embodiment, the counter anion is OH - , COO - , F - , Cl - , Br - , I - , CO 3 2- , NO 3 - , S.O. 4 2- and P.O. 4 3- The counter anion may be one or more selected from the group consisting of OH - , COO - , Cl - , or I - and more preferably OH -It is.

[0048] In one embodiment, X preferably forms a 5- or 6-membered ring together with the carbon of the adjacent aromatic ring. Preferred structures of formula (I) are one or more selected from the group consisting of formula (IX) or formula (X). More preferably, formula (I) has the structure of formula (IX): [ka] [ka] [In formula (IX) and formula (X), L A' and L A" are each independently the above L A As shown, R A' and R A" are each independently the above R A where formula (IX) and formula (X) contain a counter anion.

[0049] In one embodiment, formula (I) may be one or more selected from the group consisting of formula (III) and formula (IV): [ka] [ka] [In formula (III) and formula (IV), R 1 and R 2 are each independently hydrogen and C 1 ~C 12 and Y is selected from the group consisting of alkyl groups - each independently represents a counter anion, and a and b each independently represent an integer of 1 to 10.

[0050] In one embodiment, C 1 ~C 12 The alkyl group is as described above.

[0051] In a preferred embodiment, R 1and R 2 are each independently hydrogen, methyl or ethyl, more preferably methyl.

[0052] In one embodiment, the counter anion is as described above.

[0053] In a preferred embodiment, a and b are each independently an integer of 2 to 8, and more preferably an integer of 4 to 6.

[0054] In one embodiment, formula (IIA) may be formula (V): [ka] [In formula (V), R 3 are each independently hydrogen and C 1 ~C 12 and Y is selected from the group consisting of alkyl groups - is a counter anion and L is a divalent linking group.

[0055] In one embodiment, C 1 ~C 12 The alkyl group is as described above.

[0056] In a preferred embodiment, R 3 are each independently hydrogen, methyl or ethyl, more preferably methyl.

[0057] In one embodiment, the counter anion is as described above.

[0058] In one embodiment, each L is independently C 1 ~C 20 Alkylene group, C 3 ~C 20 Cycloalkylene group, C 2 ~C 20 Alkenylene group, C 1 ~C 20 Polyoxyalkylene group, C 6 ~C 20Arylene groups of the formula: -O-, -S-, -CO-, -COO-, -NH-, and -N(C 1 ~C 20 may be interrupted by alkyl)- 1 ~C 20 L may be selected from the group consisting of alkylene groups of the formula: 1 ~C 20 or an alkylene group of C 6 ~C 20 More preferably, it is an arylene group of the formula: 1 ~C 12 More preferably, the alkylene group 1 ~C 6 is an alkylene group of the formula:

[0059] In one embodiment, formula (IIB) may be formula (VI): [ka] [In formula (VI), R 4 are each independently hydrogen and C 1 ~C 12 and Y is selected from the group consisting of alkyl groups - is the counter anion].

[0060] In one embodiment, C 1 ~C 12 The alkyl group is as described above.

[0061] In a preferred embodiment, R 4 are each independently hydrogen, methyl or ethyl, more preferably methyl.

[0062] In one embodiment, the counter anion is as described above.

[0063] In one embodiment, the copolymer preferably has a weight average molecular weight of 5000 to 500000. The weight average molecular weight may be measured by gel permeation chromatography (GPC) analysis. [Anion exchange membrane]

[0064] The anion exchange membrane of the present invention is characterized by containing the above-mentioned copolymer.

[0065] In one embodiment, the above copolymer may be dissolved in a solvent capable of dissolving the copolymer (e.g., dimethyl sulfoxide, alcohol, an aqueous alcohol solution, etc.) to prepare a polymer solution, which may then be coated using a coating means known in the art and dried to produce an anion exchange membrane.

[0066] In one embodiment, the thickness of the anion exchange membrane is not particularly limited, but may be, for example, 1 μm to 200 μm, specifically 5 μm to 200 μm, and more specifically 10 μm to 200 μm. When the thickness of the anion exchange membrane is within the above range, it is possible to reduce electric shorts and crossover of electrolytes, raw materials in fuel cells, products in electrolysis, and the like.

[0067] In one embodiment, the ion conductivity of the anion exchange membrane is 20 mS / cm to 500 mS / cm, preferably 50 mS / cm to 300 mS / cm, and more preferably 100 mS / cm to 250 mS / cm.

[0068] The ionic conductivity of the anion exchange membrane may be measured by AC impedance measurement. The specific measurement method is not particularly limited as long as it is a method known in the art, but for example, the anion exchange membrane is sandwiched between glass plates fixed so that the distance between two platinum electrodes is 1.0 cm, and the AC amplitude is scanned from 10 to 100 mV and the frequency range from 10 MHz to 0.1 Hz using an FRA (FRA51615, NF circuit block) under conditions of a temperature of 80° C. and a relative humidity of 95%.

[0069] In one embodiment, the ionic conductivity of the anion exchange membrane may be measured under a humidified condition. In this specification, the humidified condition means a relative humidity (RH) of 10% to 100%. More preferably, the ionic conductivity of the anion exchange membrane is measured under a relative humidity (RH) of 95%.

[0070] In one embodiment, the anion exchange membrane has an ion exchange capacity (IEC) value of 2.5 meq / g to 7.5 meq / g, preferably 3.0 meq / g to 6.0 meq / g, and more preferably 4.0 meq / g to 5.5 meq / g. When the ion exchange capacity of the anion exchange membrane is within the above range, an ion channel is formed in the anion exchange membrane, and the copolymer can be ionically conductive.

[0071] The ion exchange capacity of the anion exchange membrane may be measured by titration using silver nitrate according to the Mohr method. The specific measurement method is not particularly limited as long as it is a method known in the art. For example, the ion exchange capacity of the anion exchange membrane (OH - The weight of the sample (before exchange treatment) was measured, and 1.0 mol / L NaNO 3 The anion exchange membrane was then immersed in the aqueous solution for 24 hours, and the membrane was then removed. 2 CrO 4 Using an aqueous solution as an indicator, AgNO 3 The titration was performed with an aqueous solution, and the amount of AgNO 3 The ion exchange capacity is calculated from the amount. [Anion exchange membrane water electrolysis cell]

[0072] The anion exchange water electrolysis cell of the present invention is characterized by comprising the above-mentioned anion exchange membrane.

[0073] In one embodiment, the anion exchange type water electrolysis cell is not particularly limited, and may include, for example, a membrane electrode assembly including an anode and a cathode separated by an anion exchange membrane, a separator, a power source for applying a voltage, a system for supplying water to the cell, a system for discharging oxygen produced at the anode, and a system for discharging hydrogen at the cathode, etc. These may be assembled by methods well known in the art. [Hydrogen production methods]

[0074] The method for producing hydrogen of the present invention is characterized by comprising a step of electrolyzing water using the anion exchange membrane water electrolysis cell described above.

[0075] In one embodiment, the reactions at the anode and cathode of the water electrolysis cell may be, for example, as follows: (Anode) 4OH - →O 2 +2H 2 O+4e - (Cathode) 4H 2 O+4e - →2H 2 +4OH - OH is transported from the cathode to the anode through the anion exchange membrane of the present invention. - Ions are supplied.

[0076] In the above reaction, the cell system becomes alkaline, but the anion exchange membrane of the present invention is stable even under alkaline conditions and can therefore function as an anion exchange membrane.

[0077] The hydrogen produced at the cathode may be recovered by methods known in the art and used, for example, as a fuel cell. [Fuel cell]

[0078] The fuel cell of the present invention is characterized by comprising the above-mentioned anion exchange membrane.

[0079] In one embodiment, the fuel cell may include, but is not limited to, a membrane electrode assembly including an anode and a cathode separated by an anion exchange membrane, a cathode catalyst layer and an anode gas diffusion layer included in the anode, and a cathode catalyst layer and a cathode gas diffusion layer included in the cathode, which may be assembled by a method known in the art.

[0080] In one embodiment, the fuel may be selected from those known in the art, such as, but not limited to, hydrogen, methanol, ethanol, propanol, butanol, ethylene glycol, or natural gas.

[0081] The reactions at the anode and cathode of a hydrogen fueled fuel cell may, for example, be as follows: (Anode) 2OH - +H 2 →2H 2 O+2e - (Cathode) O 2 +2H 2 O+4e - →4OH - OH is transported from the cathode to the anode through the anion exchange membrane of the present invention. - Ions are supplied. [Method of producing polymer]

[0082] The method for producing the polymer of the present invention comprises reacting a polymer represented by formula (VII): [ka] Or, formula (VIII): [ka] [In formula (VII) and formula (VIII), c and d each independently represent an integer of 1 to 10; Z 1 and Z 2 and each of the formula (I) and (II) is independently a halogen other than F.

[0083] In a preferred embodiment, c and d each independently represent an integer of 2 to 8, and more preferably an integer of 4 to 6.

[0084] In a preferred embodiment, Z 1 and Z 2 is Cl.

[0085] In one embodiment, the method for producing the polymer may be a method for copolymerizing a monomer represented by Formula (VII) or Formula (VIII) and another monomer that reacts with the monomer represented by Formula (VII) or Formula (VIII) by condensation polymerization.

[0086] In one embodiment, other monomers that react with the monomer of formula (VII) or (VIII) include, for example, monomers of formula (XI) and (XII): [ka] [In formula (XI), R 5 are each independently 1 ~C 20 is an alkylene group of the formula: [ka] [In formula (XII), R 6 is hydrogen or C 1 ~C 12 is an alkyl group.

[0087] In one embodiment, a method for preparing a polymer comprises the steps of: 6 ~C 20 The aromatic groups of the above may be copolymerized by condensation polymerization.

[0088] In one embodiment, C 6 ~C 20 may be selected from the group consisting of benzene, toluene, xylene, ethylbenzene, cumene, phenol, benzyl alcohol, anisole, acetophenone, cresol, catechol, resorcinol, hydroquinone, benzophenone, naphthalene, biphenyl, anthracene, phenanthrene, terphenyl, triphenylmethane, pyrene and tetracene, preferably phenyl, biphenyl or terphenyl, more preferably biphenyl or terphenyl.

[0089] In one embodiment, the method for producing a polymer comprises the steps of: 1 and / or Z 2 For example, the method may include a step of ionizing the halogen of the polymer and N(R 7 ) 3 By reacting 1 and / or Z 2 It is possible to ionize R 7 are each independently hydrogen and C 1 ~C 12 The alkyl group is selected from the group consisting of:

[0090] In one embodiment, the method for preparing the polymer may include a step of ionizing Cl in formula (XI). For example, the polymer may be reacted with N(R 8 ) 3 The Cl in formula (XI) can be ionized by reacting R 8 are each independently hydrogen and C 1 ~C 12 The alkyl group is selected from the group consisting of:

[0091] In one embodiment, the method for preparing the polymer may include a step of ionizing N in formula (XII). For example, the polymer and R 9 -Z 3 N in formula (XII) can be ionized by reacting R 9 is hydrogen and C 1 ~C 12 and Z is selected from the group consisting of alkyl groups 3 is Br or I.

[0092] In one embodiment, the method for preparing the polymer may include a step of exchanging the anion contained in the polymer. For example, the OH group can be exchanged by reacting the ionized polymer with NaOH or KOH. - As a result, a polymer having the following as a counter anion can be obtained. [Compound of formula (VII)]

[0093] The compounds of formula (VII) of the present invention have the following characteristics: [ka] [In formula (VII), c's each independently represent an integer of 1 to 10; Z 1 are each independently a halogen other than F.

[0094] In a preferred embodiment, each c is independently an integer of 2 to 8, and more preferably an integer of 4 to 6.

[0095] In a preferred embodiment, Z 1 is Cl.

[0096] The present invention will be described below with reference to examples, but the present invention is not limited to these. EXAMPLES

[0097] Example 1: Preparation of copolymer 1. Preparation of the compound represented by formula (VII) [ka]

[0098] Add KOH (150 g) and n-Bu 4 NCl (556 mg) was added, dissolved in 300 mL of pure water under an Ar stream, and stirred at 90°C. Fluorene (2.5 g) was dissolved in 1,6-dichlorohexane (23.3 g) and added to a recovery flask all at once. After 3 hours, it was cooled to room temperature and extracted three times with dichloromethane (200 mL). After drying with sodium sulfate (50 g), it was filtered using filter paper and concentrated under vacuum. The compound was purified by silica gel column chromatography (developing solvent; hexane:dichloromethane = 9:1) to obtain a compound with a yield of 1.78 g and a yield of 54%.

[0099] 2. Preparation of copolymer [ka]

[0100] The compound obtained in 1 (161 mg), 1-methyl-4-piperidone (498 mg), biphenyl (555 mg), and dichloromethane (3.2 mL) were added to a 13.5 mL mighty vial. Trifluoroacetic acid (0.48 mL) was further added and stirred at 0°C. Trifluoromethanesulfonic acid (3.2 mL) was further added little by little and stirred at 0°C for 24 hours. The solution after the reaction was poured into a 1M KOH aqueous solution (100 mL). The copolymer was recovered by suction filtration and washed with pure water until the pH became neutral. The recovered copolymer was dried under vacuum at 80°C for 3 hours, and the copolymer was obtained in a yield of 1.6 g.

[0101] 3. Cationization reaction of copolymer 1 [ka]

[0102] The copolymer (1.6 g) obtained in 2 was added to a 300 mL beaker, DMSO (40 mL) was added, and the mixture was stirred at 80°C for 1 hour. After the solution was cooled to room temperature, potassium carbonate (2.5 g) and iodomethane (0.82 mL) were added. The solution was stirred for 24 hours in a darkened state. The reaction solution was evaporated (vacuum, 70°C, 1 hour) to remove unreacted iodomethane. The potassium carbonate remaining in the solution was removed by filtration to obtain a solution.

[0103] 4. Cationization reaction of copolymer 2 [ka]

[0104] The DMSO solution of the copolymer obtained in 3 was added to a 100 mL mighty vial, trimethylamine (3.2 M methanol solution, 1.25 mL) was added, and the mixture was stirred at 100 ° C for 24 hours. The reaction solution was added to ethyl acetate (400 mL), and the precipitated solid was collected by suction filtration and washed with 200 mL of pure water. The obtained copolymer was dried under vacuum at 80 ° C for 3 hours, and the copolymer of the present invention was obtained in a yield of 2.45 g.

[0105] Example 2: Preparation of copolymer The following copolymer of the present invention was obtained in a yield of 3.45 g by carrying out the same procedure as in Example 1, except that terphenyl (829 mg) was used instead of biphenyl in the preparation of the copolymer. [ka]

[0106] Example 3: Preparation of copolymer The following copolymer of the present invention was obtained in the same manner as in Example 1, 2. Preparation of the Copolymer, except that biphenyl was not used. [ka]

[0107] (Preparation of anion exchange membrane) The copolymers obtained in Examples 1 to 3 were dissolved in dimethyl sulfoxide (DMSO) at a concentration of 200 mg / 10 mL while heating to 80° C. to obtain a copolymer solution. The copolymer solution was then cast onto a 10 cm×10 cm glass plate and dried to obtain an anion exchange membrane with a thickness of 20 μm. The resulting anion exchange membrane (Cl - The anion exchange capacity of the resulting anion exchange membrane was measured by immersing it in a 1.0 M potassium hydroxide aqueous solution for 24 hours. - After the exchange treatment, the ionic conductivity of the resulting anion exchange membrane was measured, and the results are shown in Table 1.

[0108] (Ionic Conductivity) Ionic conductivity was measured by AC impedance measurement. The anion exchange membrane was sandwiched between two glass plates with the distance between the two platinum electrodes fixed at 1.0 cm, and measurements were performed under conditions of a temperature of 80°C and a relative humidity of 95%. Ionic conductivity was measured using an FRA (FRA51615, NF circuit block) with an AC amplitude of 10 to 100 mV and a frequency range of 10 MHz to 0.1 Hz. The results are shown in Table 1.

[0109] (Ion exchange capacity) The ion exchange capacity was measured by titration using silver nitrate by the Mohr method. - Before exchange process, Cl - The weight of the sample was measured and diluted with 1.0 mol / L NaNO 3 The anion exchange membrane is then soaked in the aqueous solution for 24 hours. 2 CrO 4 Using an aqueous solution as an indicator, AgNO 3 The titration was performed with an aqueous solution, and the amount of AgNO 3 The ion exchange capacity was calculated from the amount of the cellulose, and the results are shown in Table 1.

[0110] [Table 1]

[0111] The results in Table 1 show that the anion exchange membrane of the present invention has higher ion conductivity and ion exchange capacity than commercially available anion exchange membranes. [Industrial Applicability]

[0112] The anion exchange membrane containing the copolymer of the present invention has high ion conductivity and ion exchange capacity, and therefore can exhibit high performance, for example, in anion exchange membrane water electrolysis, which enables efficient extraction of hydrogen gas from water and contributes to solving energy problems.

Claims

1. A copolymer comprising the repeating unit formula (I) and the repeating unit formula (IIA) and / or (IIB): 【Chemistry 1】 [In the formula (I), X is C １ ~C １２ X may form a 5- or 6-membered ring together with a carbon atom of an adjacent aromatic ring, and hydrogen atoms bonded to the aromatic ring are each independently selected from halogen, C １ ~C １２ Alkyl groups of C １ ~C １２ or an alkoxy group of C ６ ~C １２ At least one carbon atom of X may be substituted with an aryl group represented by the formula: Ａ -R Ａ is bonded, and L Ａ is a divalent linking group, R Ａ is N ＋ and formula (I) includes a counter anion. 【Chemistry 2】 [In formula (IIA), L Ｂ is a divalent linking group, R Ｂ is N ＋ In formula (IIB), R ｃ is N ＋ which, together with the carbon to which it is attached, forms a 5- or 6-membered ring, and formula (IIA) and / or (IIB) includes a counter anion.

2. C ６ ~C ２０ The copolymer according to claim 1 , further comprising a repeating unit of an arylene group of the formula:

3. Said L Ａ and L B are each independently １ ~C 20 an alkylene group of C ３ ~C 20 a cycloalkylene group of C ２ ~C 20 an alkenylene group of C １ ~C 20 a polyoxyalkylene group of C ６ ~C 20 Arylene groups represented by the formula: -O-, -S-, -CO-, -COO-, -NH-, and -N(C １ ~C 20 C １ ~C 20 The copolymer of claim 1 , wherein the alkylene group is selected from the group consisting of:

4. The R Ａ and R Ｂ are each independently selected from the group consisting of an ammonium ion, an imidazolium ion, a pyrrolidinium ion, a pyridinium ion, a pyridazinium ion, a pyrimidinium ion, a pyrazinium ion, a pyrazolium ion, and a piperidinium ion. ＋ is an organic group containing ｃ is an N selected from the group consisting of an imidazolium ion, a pyrrolidinium ion, a pyridinium ion, a pyridazinium ion, a pyrimidinium ion, a pyrazinium ion, a pyrazolium ion, and a piperidinium ion, together with the carbon to which it is bonded. ＋ The copolymer according to claim 1 , which forms an organic group comprising:

5. The counter anion is OH － , COO － , F － , Cl － , B － , I － , CO ３ ２－ , NO ３ － , S.O. ４ ２－ and P.O. ４ ３－ The copolymer according to claim 1, wherein the copolymer is one or more selected from the group consisting of:

6. The copolymer according to claim 1 , wherein the formula (I) is at least one selected from the group consisting of the following formulas (III) and (IV): 【Chemistry 3】 【Chemistry 4】 [In formula (III) and formula (IV), R 1 and R ２ are each independently hydrogen and C １ ~C １２ and Y is selected from the group consisting of alkyl groups － are each independently a counter anion, and a and b are each independently an integer from 1 to 10.

7. The copolymer according to claim 1 , wherein the formula (IIA) is the following formula (V): 【Chemistry 5】 [In formula (V), R 3 are each independently hydrogen and C １ ~C １２ and Y is selected from the group consisting of alkyl groups － is a counter anion, and L is a divalent linking group.

8. The copolymer according to claim 1 , wherein the formula (IIB) is the following formula (VI): 【Chemistry 6】 [In formula (VI), R ４ are each independently hydrogen and C １ ~C １２ and Y is selected from the group consisting of alkyl groups － is the counter anion.

9. An anion exchange membrane comprising the copolymer according to any one of claims 1 to 8.

10. An anion exchange membrane water electrolysis cell comprising the anion exchange membrane according to claim 9.

11. A method for producing hydrogen, comprising a step of electrolyzing water using the anion exchange membrane water electrolysis cell according to claim 10.

12. A fuel cell comprising the anion exchange membrane according to claim 9.

13. Formula (VII): 【Chemistry 7】 Or, the formula (VIII): 【Chemistry 8】 [In formula (VII) and formula (VIII), c and d each independently represent an integer of 1 to 10; Z １ and Z ２ and each independently represent a halogen other than F.

14. Formula (VII): 【Chemistry 9】 [In formula (VII), c is independently an integer of 1 to 10; Z １ each independently represents a halogen other than F.

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