Ketoazine-based polymer, anion exchange membrane and preparation method and application thereof

Abstract

The invention discloses a ketoazine-based polymer, an anion exchange membrane and a preparation method and application of the ketoazine-based polymer and the anion exchange membrane. A first linking group and a second linking group are mixed and then mixed with an aryl monomer A in an aprotic solvent of halogen atoms; slowly adding a super acid mixture; performing polymerization reaction in an environment of-5 to 3 DEG C to obtain a reaction solution; pouring the reaction liquid into a first mixed solvent to obtain PAAz; carrying out primary quaternization reaction on PAAz through carbonate, bicarbonate or hydroxide salt of alkali metal, and adding an organic base catalyst to assist the primary quaternization reaction; in the first quaternization reaction, a quaternization reagent is added; and pouring into a second mixed solvent, and precipitating to obtain purified PAAz. Under the condition of super acid catalysis, two or more alicyclic amine derivatives containing ketone groups react with one or more aromatic fused rings to generate a polymer containing secondary or tertiary amine. And carrying out quaternization treatment to finally form the cationic polymer.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polymer material preparation, and in particular to a ketoxazine-based polymer, an anion exchange membrane and a preparation method and application thereof. BACKGROUND

[0002] Global energy demand and consumption continue to rise due to population growth, improved living standards, and industrial expansion in developing countries. Today, more than 95% of energy demand still relies on fossil fuels, but the use of fossil fuels releases high concentrations of greenhouse gases, exacerbating global warming and environmental pollution. To address these challenges, it is urgent to use renewable green energy to produce environmentally friendly energy carriers-hydrogen. Hydrogen is mainly prepared by water electrolysis, and water electrolysis hydrogen production systems can be divided into four categories: alkaline electrolysis, proton exchange membrane water electrolysis, anion exchange membrane water electrolysis (AEMWEs), and solid oxide membrane water electrolysis. Among them, anion exchange membrane water electrolysis technology has become one of the most promising solutions in the field of hydrogen production due to its low cost and wide applicability.

[0003] However, AEMWEs technology is still in its early stages and faces multiple challenges, mainly related to the properties of the membrane material, including insufficient alkaline stability, low ionic conductivity, weak mechanical strength, limited pore-forming ability, and long-term performance degradation. The core difficulty lies in the stability of the anion exchange membrane in a strong alkaline environment. Currently, its service life is only about 1000-1500 hours, mainly due to molecular chain rupture caused by Hoffmann degradation. Therefore, it is crucial to develop an anion exchange membrane with high mechanical performance, excellent ionic conductivity (such as ≥50 mS / cm at room temperature), and strong alkaline stability. SUMMARY

[0004] Based on the technical problems existing in the background technology, the present application proposes a ketoxazine-based polymer, an anion exchange membrane and a preparation method and application thereof.

[0005] The present application proposes a ketoxazine-based polymer, which includes a polyarylazine; the polyarylazine includes one or more linking groups connecting the same or different types of aromatic fused rings;

[0006] The chemical formula of the polyarylazine is:

[0007]

[0008] wherein R1 is -H or -CH3; R2 is -CH3; X is I - , CO3 2- , Br - , Cl - , OH - or CF3SO3- ;

[0009] A is a heteroatom-free aromatic fused ring and / or a heteroatom-containing aromatic fused ring;

[0010] B is an azine-based linker, or a combination with a combination linker; wherein the combination linker includes a trifluorocarbonyl derivative, a ketone derivative of an alicyclic amine, and a ketone derivative of an aromatic amine.

[0011] Further, when A is a heteroatom-free aromatic fused ring, at least includes:

[0012]

[0013] wherein R is a -H, -CF3, -CH3, or -OH group; n is an alkyl chain or methylene group including 1-9 carbon atoms.

[0014] Further, when A is a heteroatom-containing aromatic fused ring, at least includes:

[0015]

[0016] wherein R' is -H or -OH; R1 is -H, -OH, or -CH3; R2 is -CH3, -H, or a long alkyl chain side chain with 1-9 carbon atoms, wherein the number of the long alkyl chain side chain is 1 or 2; the end group of the long alkyl chain side chain includes at least sulfonyl, hydroxyl, -CF3, and -CH3; X is -CF3, -CH3, or -OH; n is an alkyl chain or methylene group including 1-9 carbon atoms; R3 is a -CH3 or -CF3 functional group.

[0017] Further, when the combination linker is a trifluorocarbonyl derivative, at least includes:

[0018]

[0019] wherein R' and R" are a methyl group, a benzene ring, or an alkyl chain including 1-9 carbon atoms, and the end of the alkyl chain includes a halogen group.

[0020] Further, when the combination linker is a ketone derivative of an alicyclic amine or a ketone derivative of an aromatic amine, at least includes the following structure:

[0021]

[0022] wherein R4 is -H, -CH3, or a long alkyl chain side chain with 1 or 2, including 1-9 carbon atoms, and the end group of the long alkyl chain side chain includes sulfonyl, hydroxyl, -CF3, or -CH3.

[0023] Further, when the combination connecting group is the alicyclic ketone derivative, at least includes the following structure:

[0024]

[0025] The present application provides a preparation method of a ketazine-based polymer, comprising the following steps:

[0026] S1, mixing the first connecting group and the second connecting group;

[0027] S2, mixing with 0.1-1.5 moles of aryl monomer A in an aprotic solvent containing at least one or more halogen atoms;

[0028] S3, slowly adding the superacid mixture;

[0029] S4, placing in an environment of-5℃-3℃ for 5-48h of polymerization reaction to obtain a reaction liquid;

[0030] S5, pouring the reaction liquid into a first mixed solvent to obtain PAAz; wherein the first mixed solvent comprises water and ethanol, and the volume ratio of water and ethanol is 2:1 or 1:1;

[0031] S6, under alkaline conditions, the PAAz is subjected to a first quaternary ammonium reaction by a carbonate, bicarbonate or hydroxide salt of an alkali metal, and an organic base catalyst is added to assist the first quaternary ammonium reaction;

[0032] S7, in the first quaternary ammonium reaction, a quaternary ammonium reagent is added; wherein the quaternary ammonium reagent includes alkyl halides, dihalides and derivatives thereof with different chain lengths;

[0033] S8, setting the reaction temperature to 20-40℃ and reacting for 8-48h;

[0034] S9, pouring into a second mixed solvent to precipitate to obtain a purified PAAz; wherein the second mixed solvent is isopropyl alcohol and ethyl acetate, and the volume ratio is 1:2.

[0035] Further, after the step of pouring into a mixed solvent to precipitate to obtain a purified PAAz, comprising:

[0036] Under alkaline conditions, the same or different PAAz polymer chains are crosslinked by trihalide and / or dihalide derivatives to obtain:

[0037]

[0038] wherein Y is a halogen group; Z is -O-, -S-, -(N-CH3) or -(N-H)-; n is an alkyl chain or a methylene group containing 1-9 carbon atoms.

[0039] Further, the step of cross-linking the same or different PAAz polymer chains by trihalide and / or dihalide derivatives includes:

[0040] using a monoalkyl halide to perform a secondary quaternization reaction:

[0041] under alkaline conditions, using at least one alkali metal carbonate, bicarbonate, hydroxide salt, or organic base to perform the secondary quaternization reaction; wherein the secondary quaternization reaction has a reaction temperature of 20-80°C and a reaction time of 8-72h;

[0042] precipitating in a third mixed solvent; wherein the third mixed solvent includes isopropyl alcohol: ethyl acetate, and the volume ratio of isopropyl alcohol: ethyl acetate is 1:2.

[0043] Further, the molar ratio of the first linking group is 0.01-0.99, and the mass ratio is 0.1-99%;

[0044] the second linking group is 0.01-0.99 moles;

[0045] the first linking group includes 1-methylazepan-4-one and its copper amine derivatives;

[0046] the second linking group includes ketone amine derivatives, trifluoroacetyl derivatives, alicyclic ketone derivatives, aromatic ketone derivatives, or combinations with the first linking group.

[0047] Further, the molar ratio of the super acid mixture to the linking group 1 and the linking group 2 is 0.5-13; the super acid mixture includes trifluoroacetic acid and trifluoromethanesulfonic acid.

[0048] Further, dissolving the PAAz after the secondary quaternization reaction in a polar solvent with a concentration of 2%-40% to obtain a polymer solution;

[0049] filtering the polymer solution and casting it on a glass plate;

[0050] drying at 50°C-90°C for 8-24h to obtain an anion exchange membrane;

[0051] heating the anion exchange membrane to 90-100°C under vacuum for 12h;

[0052] immersing the anion exchange membrane in a 1M alkali solution to replace halide ions with hydroxide ions through ion exchange.

[0053] The present application provides a kind of anion exchange membrane based on ketazine-based polymer, by the preparation method of the anion exchange membrane based on ketazine-based polymer described.

[0054] The present application provides a kind of membrane electrode assembly for alkaline fuel cell, including anion exchange membrane based on ketazine-based polymer.

[0055] The present application provides a kind of alkaline fuel cell, including the anion exchange membrane based on ketazine-based polymer.

[0056] The present application provides a kind of water electrolytic device, including the anion exchange membrane based on ketazine-based polymer.

[0057] The present application has the following beneficial effects:

[0058] The present application focuses on the synthesis of homopolymer and block copolymer of 1-methyl azine-4-ketone and different alicyclic amines (containing ketone groups), which can produce thin film separators with excellent chemical stability, high ion conductivity and strong structure. Under the catalysis of super acid, two or more alicyclic amine derivatives containing ketone groups are reacted with one or more aromatic condensed rings in different molar ratios to form polymers containing secondary or tertiary amines. Subsequently, quaternary ammonium treatment is carried out by alkyl halide, and finally cationic polymers (CPs) are formed. The prepared CPs can be further used to develop cationic separators, and have high thermal stability, chemical stability, ion conductivity, water absorption and swelling capacity. Due to the introduction of larger alicyclic alkyl ring structure in the main chain, the film has excellent flexibility and pore-forming ability, which makes it significantly different from traditional cationic separators or membrane materials. Moreover, by constructing deformable pore structure, higher ion conductivity and alkali stability can be achieved.

[0059] The polymer prepared by the present application is an ionic polymer mainly composed of polyaryl azine (PAAz) monomer units, and is used to prepare anion exchange membrane (AEMs). The prepared ionic polymer uses quaternary nitrogen as a positive charge carrier in the main chain, and the counterion is hydroxide, chloride or other negatively charged ions. Such polymers can be applied to anion exchange membrane-based fuel cells, water electrolytic devices, water treatment, lithium extraction and flow batteries, etc.

[0060] The present application utilizes polyaromatic azacycloheptane homopolymer / copolymer and its derived ionic polymer to prepare an anion exchange membrane (AEM), which can be used as a catalyst binder, a gas separation medium, and a separator material in fuel cells and water electrolysis devices. Moreover, azacycloheptane (Az) is used as a core structural unit, and its seven-membered alkyl cyclic structure not only endows the membrane material with excellent flexibility and chemical corrosion resistance, but also enables the pore size to be adjustable and the ion conduction channel to be optimized through structural regulation, thereby significantly improving the degradation resistance of the membrane while maintaining low impedance characteristics. BRIEF DESCRIPTION OF DRAWINGS

[0061] Figure 1 A process flow chart of a preparation method of a ketazine-based polymer according to the present application is shown in the following figure.

[0062] Figure 2 A linear sweep voltammetry curve of different cross-linked PAAz anion exchange membranes in 1M KOH solution at 60°C is shown in the following figure.

[0063] Figure 3 A current (I) versus time (t) curve of different cross-linked PAAz anion exchange membranes in 1M KOH solution at 60°C is shown in the following figure.

[0064] Figure 4 A potential (E) versus time (t) curve of different cross-linked PAAz anion exchange membranes in 1M KOH solution at 60°C is shown in the following figure.

[0065] Figure 5 A process flow chart of a preparation method of a ketazine-based polymer anion exchange membrane according to the present application is shown in the following figure. DETAILED DESCRIPTION

[0066] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0067] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terminology used in the description of the present application herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0068] The application provides a ketazine-based polymer, including a polyarylazepine; the polyarylazepine includes one or more linking groups connected with the same or different types of aromatic fused rings;

[0069] The chemical formula of the polyarylazepine is:

[0070]

[0071] wherein R1 is -H or -CH3; R2 is -CH3; X is I - , CO3 2- , Br - , Cl - , OH - or CF3SO3 - ;

[0072] A is an aromatic fused ring without heteroatoms and / or an aromatic fused ring with heteroatoms;

[0073] B is an azepine group linking group, or a combination with a combination linking group, wherein the combination linking group includes a trifluorocarbonyl derivative, a ketone derivative of an alicyclic amine, a ketone derivative of an aromatic amine and an alicyclic ketone derivative.

[0074] In the embodiment, a cationic polymer PAAz (polyarylazepine) with a specific structure is synthesized by two same or different types of monomers A or linking groups B, or a combination of the two, so as to prepare an anion exchange membrane with excellent performance. Wherein R1 is -H (hydrogen atom) or -CH3 (methyl); R2 is -CH3 (methyl); X is I - (iodine ion), CO3 2- (carbonate ion), Br - (bromine ion), Cl - (chlorine ion), OH - (hydroxyl ion) or CF3SO3 - (triflate ion);

[0075] Specifically, the monomer A includes an aromatic fused ring without heteroatoms and an aromatic fused ring with heteroatoms, and the two can be used alone or in combination;

[0076] When the monomer A is an aromatic fused ring without heteroatoms, at least includes:

[0077]

[0078] wherein R is -H (hydrogen atom), -CF3 (trifluoromethyl), -CH3 (methyl) or -OH (hydroxyl) group; n is an alkyl chain or methylene (-CH2-) including 1-9 carbon atoms.

[0079] When monomer A is a heteroatom-containing aromatic fused ring, at least includes:

[0080]

[0081] wherein R' is -H or -OH; R1 is -H, -OH or -CH3; R2 is -CH3, -H or a long alkyl chain side chain with 1-9 carbon atoms; more specifically, the number of long alkyl chain side chain is 1 or 2. The end group of long alkyl chain side chain at least includes sulfonyl (-SO3H), hydroxyl (-OH), -CF3(trifluoromethyl) and -CH3(methyl); in an embodiment, any one of sulfonyl, hydroxyl, -CF3and -CH3may be used as the end group of long alkyl chain side chain. X is a terminal group, which can be -CF3, -CH3or -OH; n is an alkyl chain or methylene (-CH2-) with 1-9 carbon atoms; R3 is -CH3or -CF3functional group.

[0082] Specifically, B is a single azepan linker, or a combination of the azepan linker and a combination linker; wherein the combination linker includes a trifluoromethylcarbonyl derivative, a ketone derivative of an alicyclic amine and a ketone derivative of an aromatic amine.

[0083] Further, when the combination linker is a trifluoromethylcarbonyl derivative, at least includes:

[0084]

[0085] wherein R' and R" are methyl, benzene ring or alkyl chain with 1-9 carbon atoms, and the end of the alkyl chain can have a halogen group, such as sulfonyl, hydroxyl, -CF3, -CH3.

[0086] Further, when the combination linker is a ketone derivative of an alicyclic amine or a ketone derivative of an aromatic amine, at least includes the following structure:

[0087]

[0088] wherein R4 is -H, -CH3and 1 or 2 long alkyl chain side chains, the long alkyl chain side chain includes 1-9 carbon atoms, and the end group of the long alkyl chain side chain includes sulfonyl, hydroxyl, -CF3or -CH3, and any one of sulfonyl, hydroxyl, -CF3and -CH3may be used as the end group of the long alkyl chain side chain.

[0089] Further, when the combination linker is a ketone derivative of an alicyclic amine, at least includes the following structure:

[0090]

[0091] Referring to the drawings Figure 1A preparation method of a ketazine-based polymer according to an embodiment of the present application, comprising the following steps:

[0092] S1, mixing the first and second linking groups;

[0093] S2, mixing with 0.1-1.5 moles of aryl monomer A in an aprotic solvent containing one or more halogen atoms;

[0094] S3, slowly adding the superacid mixture;

[0095] S4, placing in an environment of -5-3°C for 5-48h of polymerization reaction to obtain a reaction solution;

[0096] S5, pouring the reaction solution into the first mixed solvent to obtain PAAz; wherein the first mixed solvent comprises water and ethanol, and the volume ratio of water to ethanol is 2:1 or 1:1;

[0097] S6, under alkaline conditions, the first quaternary ammonium reaction of PAAz is carried out by alkali metal carbonate, bicarbonate or hydroxide salt, and an organic base catalyst is added to assist the first quaternary ammonium reaction;

[0098] S7, adding a quaternary ammonium reagent in the first quaternary ammonium reaction; wherein the quaternary ammonium reagent includes alkyl halides, dihalides and their derivatives of different chain lengths;

[0099] S8, setting the reaction temperature to 20-40°C, and reacting for 8-48h;

[0100] S9, precipitating in the second mixed solvent to obtain purified PAAz(poly(aryl-azepan)); wherein the second mixed solvent is isopropyl alcohol and ethyl acetate, and the volume ratio is 1:2.

[0101] In the above steps, first, the first linking group and the second linking group are mixed; wherein the molar ratio of the first linking group is 0.01-0.99, and the mass ratio is 0.1-99%; the second linking group is 0.01-0.99 moles; the first linking group includes 1-methylazepan-4-one and its copper amine derivatives; the second linking group includes ketone amine derivatives, trifluoroacetyl derivatives, alicyclic ketone derivatives, aromatic ketone derivatives, or combinations with the first linking group. Then slowly pour into the superacid mixture, and the molar ratio of the superacid mixture to the linking group 1 and the linking group 2 is 0.5-13; wherein the superacid mixture includes trifluoroacetic acid and trifluoromethane sulfonic acid. Then place in an environment with a reaction temperature of -5°C-3°C to carry out the polymerization reaction, and the reaction time is 5-48h to obtain a reaction liquid. Then pour the reaction liquid into the first mixed solvent to obtain PAAz; wherein the first mixed solvent includes water and ethanol, and the volume ratio of water to ethanol is 2:1 or 1:1. Then, under alkaline conditions, the first quaternization reaction of PAAz is carried out by using alkali metal carbonate, bicarbonate or hydroxide salt, and an organic base catalyst is added to assist the first quaternization reaction; wherein the hydroxide salt includes sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide and potassium hydroxide. The organic base catalyst includes triethylamine and trimethylamine. In the first quaternization reaction, a quaternization reagent is added; the quaternization reagent includes alkyl halides, dihalides and their derivatives of different chain lengths. Preferably, methyl iodide, ethyl iodide, butyl iodide, propyl iodide, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, 2-bromoethanol, 1,4-dibromo butane, 1,3-dibromopropane and 1,5-dibromopentane are used. Finally, the reaction and purification are carried out again, the reaction temperature is set to 20-40°C, the reaction is carried out for 8-48h, then poured into the second mixed solvent to precipitate, and the purified PAAz (poly(aryl-azepan)) is obtained. Preferably, the second mixed solvent is isopropanol and ethyl acetate, and the volume ratio is 1:2.

[0102] In an embodiment, after the step of pouring into the mixed solvent to precipitate to obtain the purified PAAz, the following steps are included:

[0103] Under alkaline conditions, the same or different PAAz polymer chains are crosslinked by trihalide and / or dihalide derivatives to obtain:

[0104]

[0105] wherein Y is a halogen group; Z is -O-, -S-, -(N-CH3) or -(N-H)-; n is an alkyl chain or a methylene group containing 1-9 carbon atoms.

[0106] Specifically, the same or different types of PAAz polymer chains are crosslinked by combining one or more of trihalide and dihalide derivatives. The crosslinking can increase the thermal stability, water absorption capacity and chemical stability of the prepared anion exchange membrane.

[0107] Further, after the step of crosslinking the same or different PAAz polymer chains by trihalide and / or dihalide derivatives, the following steps are included:

[0108] A second quaternization reaction is performed using a monoalkyl halide:

[0109] The second quaternization reaction is performed under alkaline conditions using at least one alkali metal carbonate, bicarbonate, hydroxide salt, or organic base; wherein the reaction temperature of the second quaternization reaction is 20-80℃, and the reaction time is 8-72h;

[0110] Precipitation in a third mixed solvent; wherein the second mixed solvent includes isopropanol: ethyl acetate, and the volume ratio of isopropanol: ethyl acetate is 1:2.

[0111] Specifically, after crosslinking the PAAz polymer chains, a second quaternization reaction is performed using a monoalkyl halide. The monoalkyl halide includes at least methyl iodide, ethyl iodide, butyl iodide, propyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, 2-bromoethanol, 1,4-dibromo-butane, 1,3-dibromo-propane, and 1,5-dibromo-pentane. The crosslinking and quaternization reaction of PAAz is performed under alkaline conditions, and the catalyst can use one or more alkali metal carbonates, bicarbonates, and hydroxides, such as sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; or an organic base such as triethylamine, trimethylamine. The second quaternization reaction is performed at a reaction temperature of 20-80℃ for 8-72h. Finally, precipitation in a second mixed solvent, wherein the second mixed solvent includes isopropanol: ethyl acetate, and the volume ratio of isopropanol: ethyl acetate is 1:2.

[0112] More specifically, after crosslinking, the final polymer needs to be further quaternized. Although the crosslinking reaction uses alkyl halide or aryl halide, quaternary ammonium products can also be generated, but the degree of quaternization of these products is low, and the performance is poor due to the low content of quaternary ammonium amine. Therefore, a second quaternization reaction is performed using a simple alkyl halide to convert the remaining tertiary amine into quaternary ammonium amine.

[0113] Please refer to the attached Figure 5 The present application provides a preparation method of a ketazine-based polymer anion exchange membrane, including a preparation method of a ketazine-based polymer, and further including the following steps:

[0114] Step one, dissolve PAAz after secondary quaternary ammonium reaction in polar solvent with concentration of 2%-40% to obtain polymer solution;

[0115] Step two, filter the polymer solution and cast on glass plate;

[0116] Step three, dry at 50-90℃ for 8-24h to obtain anion exchange membrane;

[0117] Step four, heat the anion exchange membrane to 90-100℃ under vacuum environment for 12h;

[0118] Step five, immerse the anion exchange membrane in 1M alkali solution to replace halogen ion with hydroxyl ion by ion exchange.

[0119] The application provides an anion exchange membrane based on ketazine polymer, which is prepared by a preparation method of an anion exchange membrane based on ketazine polymer.

[0120] The application provides a membrane electrode assembly for an alkaline fuel cell, which comprises an anion exchange membrane based on ketazine polymer.

[0121] The application provides an alkaline fuel cell, which comprises an anion exchange membrane based on ketazine polymer.

[0122] The application provides a water electrolysis device, which comprises an anion exchange membrane based on ketazine polymer.

[0123] Example 1

[0124] Synthesis of polytriphenylazepane (PTAz):

[0125]

[0126] In a 250mL three-necked flask, 20mL chloroform or 1,2-dichloroethane was added, followed by 0.1mol of triphenyl (TP), and the reaction was stirred for 10min until TP was completely dissolved, and then the reaction system was cooled to 0℃. As shown in the formula, reaction a is specifically: under cooling conditions, a coupling agent, i.e. 0.11mol of 1-methylazepan-4-one (mAz), was added, and the reaction temperature was maintained at 0℃. After the reagents were mixed thoroughly, 1 equivalent of a mixed acid of trifluoroacetic acid (TFA) and 10 equivalents of trifluoroethanesulfonic acid (TFSA) was slowly added. During the addition process, the reaction temperature was maintained at -2℃, and the reaction was continued at the same temperature for 36h. The viscous solution was poured into a volume ratio of 1:1 ethanol-water solution to obtain a solid PTAz polymer, which was filtered and washed with water for several times to obtain a pure PTAz polymer.

[0127] As shown in the scheme, reaction b is the quaternization of PTAz: PTAz polymer is dissolved in DMSO (dimethylsulfoxide) followed by the addition of more than 2-2.5 times the PTAz polymer of iodomethane. After stirring the mixture at room temperature for 36 hours, it is poured into a 1:3 volume ratio of ethyl acetate-isopropyl alcohol solution to obtain a brownish product. This is then washed several times with ethanol and then with water. The product is filtered and dried under vacuum at 55°C.

[0128] Membrane preparation: The polymer is dissolved in DMSO and stirred for at least 24 hours until a solution with a viscosity of 80-120 MPa-s is obtained. After filtration, the solution is cast on a 10 cm x 10 cm glass plate to obtain the initial membrane, which is further immersed in a 1 M KOH solution for anion exchange to convert it to the OH - form. It is then washed several times with distilled water and dried at room temperature to obtain the QPTAz, i.e. the anion-exchanged membrane of PTAz.

[0129] Finally, the physical properties and electrochemical performance of the polytriphenylazepane (PTAz) anion exchange membrane are tested.

[0130] Example 2

[0131] Preparation of polyarylazepane copolymer containing two different aryl derivatives (PBTAz-80):

[0132]

[0133] As shown in the scheme, reaction a is: 10 mL of 1,2-dichloroethane is added to a 250 mL three-necked flask, followed by the addition of 0.08 moles of triphenyl (TP) and 0.02 moles of biphenyl (BP), stirring the reaction for 10 minutes until the TP is completely dissolved. The reaction system is then cooled to -5°C. 0.092 moles of 1-methylazepan-4-one (mAz) are added as a coupling agent under cooling conditions, maintaining the reaction temperature at -3°C. After vigorously mixing the reagents, 1.1 equivalents of trifluoroacetic acid (TFA) and 8.5 equivalents of trifluoromethanesulfonic acid (TFSA) are slowly added. The reaction temperature is maintained at no more than -2°C during the addition and the reaction is continued at the same temperature for 12 hours. The viscous solution is poured into an aqueous solution to obtain a solid PBTAz-80 polymer. The solid PBTAz-80 polymer is filtered, washed several times with a solution of potassium carbonate hydrate to remove the residual acid, washed with water and dried at 65°C for 24 hours.

[0134] Step b is the quaternization of PTAz-80: The quaternization of PTAz-80 is the same as in Example 1. Specifically, PTAz-80 polymer is dissolved in DMSO (dimethylsulfoxide) followed by the addition of greater than 2-2.5 times the PTAz-80 polymer of iodomethane. After stirring the mixture at room temperature for 36 hours, it is poured into a 1:3 volume ratio of ethyl acetate-isopropyl alcohol solution to obtain a tan-brown product. This is followed by multiple washings with ethanol and then water. The product is filtered and dried under vacuum at 55°C.

[0135] The preparation of PTAz-80 anion exchange membrane is the same as in Example 1. Specifically, the polymer is dissolved in DMSO and stirred for at least 24 hours until a solution with a viscosity of 80-120 MPa-s is obtained. After filtration, the solution is cast onto a 10 cm x 10 cm glass plate to obtain a primary membrane, which is further immersed in a 1 M KOH solution for anion exchange to convert it into OH - form. This is followed by multiple washings with distilled water and drying at room temperature to obtain QPTAz-80, the anion exchange membrane of PTAz-80.

[0136] Finally, the anion exchange membrane of a poly(benzazole) copolymer containing two different aryl derivatives (PBTAz-80) is tested for physical properties and electrochemical performance.

[0137] Example 3

[0138] Preparation of a poly(triphenylbenzazole) copolymer containing a trifluorophenyl derivative:

[0139]

[0140] Reaction a is shown in the formula: In a 250 mL three-necked flask, 10 mL of 1, -dichloromethane is added, followed by the addition of 0.1 mole of triphenyl (TP), and the reaction is stirred for 10 minutes until the TP is completely dissolved. The reaction system is cooled to 0°C, and 0.08 mole of coupling agent 1, specifically trifluoroacetophenone, is added. Under cooling conditions, 0.092 mole of coupling agent 2, specifically 1-methylazepan-4-one (mAz), is added, and the reaction temperature is maintained at 0°C. After the reagents are mixed vigorously, a mixture of acids, specifically 1.05 equivalents of trifluoroacetic acid (TFA) and 9 equivalents of trifluoromethanesulfonic acid (TFSA), is slowly added. The reaction temperature is maintained at no more than -2°C during the addition, and the reaction is continued at the same temperature for 36 hours. The viscous solution is poured into an aqueous solution to obtain a solid PTAz-8 polymer. After filtration, the polymer is washed multiple times with a potassium carbonate solution to remove residual acid, washed with water, and dried at 65°C for 24 hours.

[0141] Reaction b is the quaternization of PTAz-8. The quaternization of PTAz-8 is the same as in Example 1. Specifically, the quaternization of PTAz-8 is the same as in Example 1. Specifically, the PTAz-8 polymer is dissolved in DMSO (dimethylsulfoxide) and then more than 2-2.5 times the PTAz-8 polymer of methyl iodide is added. After stirring the mixture at room temperature for 36 hours, it is poured into a 1:3 volume ratio of ethyl acetate-isopropyl alcohol solution to obtain a brownish product. The product is then washed with ethanol several times and then with water. After the product is filtered, it is dried under vacuum at 55°C to obtain the purified PTAz-8.

[0142] The preparation of the anion exchange membrane of PTAz-8 is the same as in Example 1. Specifically, the polymer is dissolved in DMSO and stirred for at least 24 hours until a solution with a viscosity of 80-120 MPa-s is obtained. After filtration, the solution is cast on a 10 cm x 10 cm glass plate to obtain a primary membrane, which is further immersed in a 1 M KOH solution for anion exchange to convert it to the OH"form. It is then washed with distilled water several times and dried at room temperature to obtain QPTAz-8, the anion exchange membrane of PTAz-8.

[0143] Finally, the anion exchange membrane of the poly(triphenylazepine) copolymer containing a trifluorophenyl derivative is tested for physical properties and electrochemical performance.

[0144] Example 4

[0145] Preparation of the arylazepine copolymer containing 1-methyl-4-piperidinone (PTAzPip-20):

[0146]

[0147] As shown in the formula, reaction a is: 10 mL of 1,2-dichloromethane is added to a 250 mL three-necked flask, followed by 0.1 mol of triphenyl (TP), and the reaction is stirred for 10 minutes until the TP is completely dissolved. The reaction system is cooled to 0°C, and 0.080 mol of 1-methylazepin-4-one (mAz) is added as a coupling agent 1. Then, 0.02 mol of 1-methyl-4-piperidinone (mpip) is added as a coupling agent 2 under cooling, and the reaction temperature is maintained at 0°C. After the reagents are mixed vigorously, a mixed acid composed of 1 equivalent of trifluoroacetic acid (TFA) and 7.5 equivalents of trifluoromethanesulfonic acid (TFSA) is slowly added. The reaction temperature is maintained at no higher than -5°C during the addition, and the reaction is continued at 0°C for 24 hours. The viscous solution is poured into water to obtain a solid PTAzPip-20 polymer. After filtration, the polymer is washed with a potassium carbonate solution several times to remove residual acid, then washed with water and dried at 65°C for 24 hours.

[0148] Reaction b is the quaternization of PTAzPip-20. The quaternization of PTAzPip-20 is the same as in Example 1. Specifically, PTAzPip-20 polymer is dissolved in DMSO (dimethylsulfoxide) followed by the addition of greater than 2-2.5 times the amount of iodomethane than the PTAzPip-20 polymer. After stirring the mixture at room temperature for 36 hours, the brownish product is poured into a 1:3 volume ratio of ethyl acetate-isopropyl alcohol solution. The product is then washed several times with ethanol and then with water. The product is filtered and dried under vacuum at 55°C.

[0149] The preparation of the anion exchange membrane of PTAzPip-20 is also the same as in Example 1. Specifically, the polymer is dissolved in DMSO and stirred for at least 24 hours until a solution with a viscosity of 80-120 MPa-s is obtained. After filtration, the solution is cast onto a 10 cm x 10 cm glass plate to obtain a primary membrane, which is further immersed in a 1 M KOH solution for anion exchange to convert it to the OH - form. The QPTAzPip-20 is then washed several times with distilled water and dried at room temperature.

[0150] Finally, the physical properties and electrochemical performance of the anion exchange membrane of the aryl azacycloheptane copolymer containing 1-methyl-4-piperidone (PTAzPip-20) are tested.

[0151] Example 5

[0152] Preparation of aryl azacycloheptane copolymer containing quinuclidone (PTAzQui-10):

[0153]

[0154] As shown in the formula, reaction a is: 10 mL of 1,2-dichloromethane is added to a 250 mL three-necked flask, followed by the addition of 0.1 mol of terphenyl (TP), and the reaction is stirred for 10 minutes until the TP is completely dissolved. The reaction system is cooled to 0°C, and 0.090 mol of coupling agent 1, specifically 1-methylazacycloheptan-4-one (mAz), is added. The alkali-washed coupling agent 2, specifically 0.01 mol of quinuclidone (Qui), is added under cooling, and the reaction temperature is maintained at 0°C. After the reagents are mixed vigorously, a mixture of acids, i.e., 1 equivalent of trifluoroacetic acid (TFA) and 7.5 equivalents of trifluoromethanesulfonic acid (TFSA), is slowly added. The reaction temperature is maintained at no higher than -7°C during the addition, and the reaction is continued at 3°C for 72 hours. The viscous solution is poured into an aqueous solution to obtain a solid PTAzQui-10 polymer. After filtration, the polymer is washed several times with a potassium carbonate solution to remove residual acid, then washed with water, and dried at 65°C for 24 hours.

[0155] Reaction b is the quaternization of PTAzQui-10, and the quaternization procedure is the same as in Example 1. Specifically, the PTAz polymer is dissolved in DMSO (dimethyl sulfoxide), followed by the addition of iodomethane in a volume ratio of 2-2.5 times that of the PTAz polymer. After stirring and mixing at room temperature for 36 hours, the mixture is poured into an ethyl acetate-isopropanol solution with a volume ratio of 1:3 to obtain a brownish-red product. The product is then washed repeatedly with ethanol, followed by washing with water. After filtration, the product is dried under vacuum at 55°C.

[0156] The preparation steps for the PTAzQui-10 anion exchange membrane are the same as in Example 1. Specifically, the polymer is dissolved in DMSO and stirred for at least 24 hours until a solution with a viscosity between 80-120 MPa·s is obtained. After filtration, the solution is cast onto a 10cm × 10cm glass plate to obtain the initial membrane. The initial membrane is then further immersed in 1 M KOH solution for anion exchange, converting it to OH-. - The membrane was then washed several times with distilled water and dried at room temperature to obtain QPTAzQui-10, i.e., the anion exchange membrane of PTAzQui-10.

[0157] Finally, the physical properties and electrochemical performance of the aryl-azacycloheptanane copolymer (PTAzQui-10) anion exchange membrane containing quinuclidone were tested.

[0158] Specifically, after obtaining QPTAz, QPBTAz-80, QPTAz-8, QPTAzPip-20, and QPTAzQui-10, their ion exchange capacities (IEC) were tested. Specifically, the IEC values ​​were determined by Mohr titration. 100 mg of the chloride form (Cl...) was... - The AEM (anion exchange membrane) sample was thoroughly dried and weighed to obtain W. dry Ion exchange was performed in a 1 mol / L NaCl solution at 60°C for 24 hours. The sample was then repeatedly rinsed with deionized water. Next, the sample was immersed in a 0.5 mol / L Na₂SO₄ solution for another ion exchange at 60°C for 24 hours. Finally, the Na₂SO₄ solution was collected and titrated with a 0.1 mol / L AgNO₃ solution using K₂CrO₄ as an indicator. The solution was then corrected for Cl… - and OH - The mass difference was used to calculate OH. - IEC value in [form]. Record the volume of AgNO3 solution consumed during the test. And calculate IEC according to the following formula:

[0159]

[0160] wherein C AgNO3 represents the concentration of AgNO3.

[0161] Further, QPTAz, QPBTAz-80, QPTAz-8, QPTAzPip-20 and QPTAzQui-10 were further subjected to conductivity test, the ionic conductivity of the copolymer films of ketazine-based polymers was determined by electrochemical impedance spectroscopy (EIS). The conductivity test was conducted at four different temperatures between 30 °C and 80 °C, and data was recorded using a CORETEST electrochemical workstation (CS310M potentiostat / galvanostat / impedance analyzer) for each EIS test. In the EIS test, the frequency range was set to 100 kHz to 1 Hz, and the potential amplitude was set to 20 mV. The test sample was cut into a circular shape with a diameter of 10 centimeters and fixed in the test device; wherein the test device used platinum wire as the electrode and was configured with four electrodes. The humidity in the test chamber was controlled by passing nitrogen carrying water vapor, and the resistance value obtained from the Nyquist plot was used to calculate the ionic conductivity of the copolymer film, and the following formula defines the ionic conductivity of each film:

[0162]

[0163] wherein σ represents the ionic conductivity, L is the distance between the reference electrodes, A is the film area, and R is the sample resistance.

[0164] Further, QPTAz, QPBTAz-80, QPTAz-8, QPTAzPip-20 and QPTAzQui-10 were subjected to water uptake and swelling ratio test: each sample was cut into a size of 1 cm x 1 cm and immersed in water at a set temperature for 24 hours or 48 hours. The mass and length change of the measured sample were recorded, and then the sample was dried and its length and weight were measured again. The following formula was used to calculate the water uptake (WU) and swelling ratio (SR) of the film:

[0165]

[0166] wherein W and L represent the weight and length of the sample, respectively, and the subscripts w and d represent the wet sample and the dry sample, respectively.

[0167] Further, the mechanical properties of QPTAz, QPBTAz-80, QPTAz-8, QPTAzPip-20 and QPTAzQui-10 were tested by tensile strength, specifically, by HZ-1004B mechanical tester (Li Xian Instrument Co. Ltd) at a tensile rate of 5 mm / min. The wet film sample size was 5 x 0.5 cm.

[0168] Further, the electrochemical properties of QPTAz, QPBTAz-80, QPTAz-8, QPTAzPip-20 and QPTAzQui-10 were tested, and to expand the application of PAAz-based homopolymer / copolymer membranes, they were further used as anion exchange membranes in alkaline membrane electrolyzers to produce hydrogen. The cathode material was prepared by spraying Pt / C containing 75% Pt on carbon cloth, with a final Pt loading of 0.1-1.0 mg / cm 2 ; the anode material was prepared by coating nickel-iron layered double hydroxide (NiFe-LDH) on nickel foam, with a loading of 3-10 mg / cm 2 . Various electrochemical methods were used to verify the performance of PAAz membranes. Linear sweep voltammetry (LSV) was recorded at a voltage range of 1.0 V to 2.0 V, with a scan rate of 5 mV / s. Durability tests were performed at 60°C with a current density of 0.8 A / cm 2 for several hours.

[0169] Finally, the results of the physical properties and electrochemical performance tests of QPTAz, QPBTAz-80, QPTAz-8, QPTAzPip-20 and QPTAzQui-10 are shown in Table 1.

[0170] Table 1:

[0171]

[0172] Table 1 is a table of physical property data for different PAAz membranes.

[0173] As shown in Table 1, the physical properties of different PAAz membranes can be seen, and the anion exchange membranes (AEM) prepared by different combinations exhibit different characteristics. The tensile strength and tensile strain of the QPTAz membrane reach 44 MPa and 12%, respectively, while the anion exchange membranes containing copolymers of azepan-4-one and piperidinone have the same tensile strength of 40 MPa, such as QPTAzPiP-20 and QPTAzQUi-10, but the respective tensile strains are 20% and 15%. At the same time, as can be seen from Table 1, QPTAz and its anion exchange membranes with piperidinone (PiP) and quinacridone (Qui) exhibit similar swelling rate, water absorption rate and ionic conductivity. The anion exchange membrane of QPTAz-8 with a hydrophobic linker has lower water absorption rate, swelling rate, ionic conductivity and total exchange capacity (IEC), but the tensile stress increases.

[0174] The electrochemical performance of each ion exchange membrane was determined by experiment, and the results are shown in Figures 2-4 . Specifically, Figure 2 is the linear sweep voltammetry (LSV) curve of different PAAz anion exchange membranes; specifically, the tested potential range is 1.0 to 2.0 V; the scan rate is 10 mV / min; and the sample area is 1 cm 2 . Figure 3 is the current change graph under constant voltage; specifically, the applied potential tested is 2.0 V; and the sample area is 1 cm 2 . Figure 4 reflects the voltage change of each ion exchange membrane under constant current density. The test parameters are: current density 0.8 A / cm 2 ; and the sample area is 1 cm 2 . As can be seen from Figures 2-4 , the anion exchange membranes containing hydrophilic monomers, specifically QPTAz, QPBTAz-80, QPTAzPiP-20 and QPTAzQui-10, exhibit a current density of ≥1.0 A / cm 2 under a constant applied voltage of 2.0 V, and the voltage change is ≤1.87 V under a constant current density of 0.8 A / cm 2 .

[0175] In summary, the anion exchange membrane prepared based on the ketazine polymer has the characteristics of excellent chemical stability, high ion conductivity and strong structure. Under the catalysis of super acid, two or more kinds of alicyclic amine derivatives containing ketone groups are reacted with one or more kinds of aromatic condensed rings in different molar ratios to generate a polymer containing secondary or tertiary amine. Subsequently, quaternary ammonium treatment is carried out by alkyl halide, and finally a cationic polymer (CP) is formed. The prepared CPs can be further used to develop cationic separators, and have high thermal stability, chemical stability, ion conductivity, water absorption rate and swelling capacity. The introduction of a larger alicyclic alkyl ring structure in the main chain endows the film with excellent flexibility and pore-forming ability, which makes it significantly different from traditional cationic separators or membrane materials. Moreover, by constructing a deformable pore structure, higher ion conductivity and alkaline stability can be achieved.

[0176] The prepared ion polymer uses quaternary nitrogen as a positive charge carrier in the main chain, and the counterion is hydroxide, chloride or other negatively charged ions. Such polymers can be applied to anion exchange membrane-based fuel cells, water electrolysis devices, water treatment, lithium extraction and flow batteries, etc.

[0177] The present application uses polyaromatic azacycloheptane homopolymer / copolymer and its derived ion polymer to prepare an anion exchange membrane (AEM), which can be used as a catalyst binder, a gas separation medium, and a separator material in fuel cells and water electrolysis devices. Azacycloheptane (Az) is used as the core structural unit, and its seven-membered alkyl cyclic structure not only endows the membrane material with excellent flexibility and chemical corrosion resistance, but also enables the size of the pore size to be adjusted and the ion conduction channel to be optimized through structural regulation, significantly improving the degradation resistance of the membrane while maintaining low impedance characteristics.

[0178] The above is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can make equivalent replacement or change according to the technical solution and inventive concept of the present application within the technical range disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A ketazine-based polymer, characterized in that, comprising polyarylazines; the polyarylazines comprise the same or different kinds of aromatic fused rings connected by one or more linking groups; the chemical formula of the polyarylazines is: wherein R1 is -H or -CH3; R2 is -CH3; X is I - , CO3 2- , Br - , Cl - , OH - or CF3SO3 - ; A is an aromatic fused ring without heteroatoms and / or an aromatic fused ring with heteroatoms; B is an azine linking group, or a combination with a combination linking group; wherein the combination linking group comprises a trifluorocarbonyl derivative, a ketone derivative of a cycloaliphatic amine, a ketone derivative of an aromatic amine, and a cycloaliphatic ketone derivative.

2. The ketoxazine-based polymer according to claim 1, characterized in that, when A is an aromatic fused ring without heteroatoms, at least comprises: wherein R is a -H, -CF3, -CH3, or -OH group; n is an alkyl chain or methylene group comprising 1-9 carbon atoms; when A is an aromatic fused ring with heteroatoms, at least comprises: wherein R' is -H or -OH; R1 is -H, -OH, or -CH3; R2 is -CH3, -H, or a long alkyl chain side chain with 1-9 carbon atoms, wherein the number of the long alkyl chain side chain is 1 or 2; the end group of the long alkyl chain side chain at least comprises sulfonyl, hydroxyl, -CF3, and -CH3; X is -CF3, -CH3, or -OH; n is an alkyl chain or methylene group comprising 1-9 carbon atoms; R3 is a -CH3 or -CF3 functional group.

3. The ketoxazine-based polymer of claim 1, wherein, when the combination linking group is a trifluorocarbonyl derivative, at least comprises: wherein R' and R" are methyl, a benzene ring, or an alkyl chain comprising 1-9 carbon atoms, and the end of the alkyl chain comprises a halogen group; when the combination linking group is a ketone derivative of a cycloaliphatic amine or a ketone derivative of an aromatic amine, at least comprises the following structure: wherein R4 is -H, -CH3, and a long alkyl chain side chain with 1 or 2, the long alkyl chain side chain comprises 1-9 carbon atoms, and the end group of the long alkyl chain side chain comprises sulfonyl, hydroxyl, -CF3, or -CH3; when the combination linking group is the cycloaliphatic ketone derivative, at least comprises the following structure:

4. A process for the preparation of a ketazine-based polymer according to any one of claims 1 to 3, characterized in that, comprising the following steps: S1, mixing a first linking group and a second linking group; S2, mixing with 0.1-1.5 moles of aryl monomer A in an aprotic solvent containing at least one or more halogen atoms; S3, slowly adding a superacid mixture; S4, placing in an environment of -5°C-3°C for 5-48h of polymerization reaction to obtain a reaction solution; S5, pouring the reaction solution into a first mixed solvent to obtain PAAz; wherein the first mixed solvent comprises water and ethanol, and the volume ratio of water to ethanol is 2:1 or 1:1; S6, under alkaline conditions, the PAAz is subjected to a first quaternary ammonium reaction by alkali metal carbonate, bicarbonate, or hydroxide salt, and an organic base catalyst is added to assist the first quaternary ammonium reaction; S7, in the first quaternary ammonium reaction, a quaternary ammonium reagent is added; wherein the quaternary ammonium reagent comprises alkyl halides, dihalides, and derivatives thereof with different chain lengths; S8, setting the reaction temperature to 20-40°C, and reacting for 8-48h; S9, pouring into a second mixed solvent to precipitate to obtain a purified PAAz; wherein the second mixed solvent is isopropyl alcohol and ethyl acetate, and the volume ratio is 1:

2.

5. The process for the preparation of ketazine-based polymers according to claim 4, characterized in that, After the step of precipitating the PAAz in the mixed solvent, the method further comprises: cross-linking the same or different PAAz polymer chains by a trihalide and / or dihalide derivative under alkaline conditions, to obtain: wherein Y is a halogen group; Z is -O-, -S-, -(N-CH3) or -(N-H)-; n is an alkyl chain or methylene group containing 1-9 carbon atoms.

6. The method for preparing a ketazine-based polymer according to claim 4, characterized by, After the step of cross-linking the same or different PAAz polymer chains by a trihalide and / or dihalide derivative, the method further comprises: using a monoalkyl halide to perform a secondary quaternization reaction: using at least one alkali metal carbonate, bicarbonate, hydroxide salt or organic base to perform the secondary quaternization reaction under alkaline conditions; wherein the reaction temperature of the secondary quaternization reaction is 20-80℃, and the reaction time is 8-72h; precipitating in a third mixed solvent; wherein the third mixed solvent comprises isopropyl alcohol: ethyl acetate, and the volume ratio of the isopropyl alcohol: ethyl acetate is 1:

2.

7. The process for the preparation of ketazine-based polymers according to claim 4, characterized in that, The molar ratio of the first linking group is 0.01-0.99, and the mass ratio is 0.1-99%; The second linking group is 0.01-0.99 moles; The first linking group comprises 1-methylazepan-4-one and its copper amine derivative; The second linking group comprises a ketone amine derivative, a trifluoroacetyl derivative, an alicyclic ketone derivative, an aromatic ketone derivative, or a combination with the first linking group; The molar ratio of the super acid mixture to the linking group 1 and the linking group 2 is 0.5-13; The super acid mixture comprises trifluoroacetic acid and trifluoromethane sulfonic acid.

8. A method for producing a ketazine-based polymer anion exchange membrane, characterized by, The method for preparing the ketoxazine-based polymer according to any one of claims 4-7 further comprises the following steps: dissolving the PAAz after the secondary quaternization reaction in a polar solvent with a concentration of 2%-40% to obtain a polymer solution; filtering the polymer solution and casting it on a glass plate; drying at 50℃-90℃ for 8-24h to obtain an anion exchange membrane; heating the anion exchange membrane to 90-100℃ under vacuum for 12h; immersing the anion exchange membrane in a 1M alkali solution to replace halide ions with hydroxide ions through ion exchange.

9. A ketone-azine-based polymer-based anion exchange membrane, characterized by, The anion exchange membrane based on the ketoxazine-based polymer prepared by the method for preparing the anion exchange membrane based on the ketoxazine-based polymer according to claim 8.

10. A membrane electrode assembly for an alkaline fuel cell, characterized by, The anion exchange membrane based on the ketoxazine-based polymer according to claim 9.

11. An alkaline fuel cell characterised in that The anion exchange membrane based on the ketoxazine-based polymer according to claim 9.

12. A water electrolysis device, characterized by, The anion exchange membrane based on the ketoxazine-based polymer according to claim 9.

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