Anion exchange resin as well as preparation method and application thereof

Abstract

The invention relates to the field of anion exchange resin preparation, and discloses anion exchange resin as well as a preparation method and application thereof. The anion exchange resin has a structural formula as shown in formula (1), in the formula (1), R1 is biaryl; r < 2 > is at least one of-CH3,-CH2CH3,-CF3 and-CH2CF3; r3 is alkyl with 1 to 6 carbon atoms; x is halogen. The membrane material prepared by adopting the anion exchange resin disclosed by the invention has relatively high heat-resistant and alkali-resistant stability.

Description

Technical Field

[0001] The present invention relates to the field of anion exchange resin preparation, and in particular to an anion exchange resin and a preparation method and application thereof. Background Art

[0002] In the fields of fuel cells, water electrolysis, carbon dioxide catalytic reduction, etc., diaphragms play two roles: one is to separate the H2 and O2 gases as raw materials or products on both sides of the membrane to avoid the danger of mixing the two; the other is to conduct hydroxide ions as a solid electrolyte. To ensure the safety of practical applications, the diaphragm needs to maintain long-term chemical stability. Therefore, the stability of the membrane material is required to be high, especially the stability under hot alkaline conditions. In order to achieve the dual effects of mass transfer and gas isolation, diaphragm materials are mostly prepared using anion exchange resins. Anion exchange resins consist of two parts: a polymer backbone and a cationic group. The polymer backbone determines its film-forming properties, mechanical strength, thermal stability, etc., while the cationic functional group provides OH - Transfer site, used to transfer OH - . There are many kinds of polymer main chains, and the commonly used ones are polyether ether sulfone, polyarylether ketone, polyphenylene ether, polyolefin, etc. Common ionic groups include amines, guanidines, phosphorus, sulfur, etc. Different types of main chain structures and cationic group combinations have different effects, which will have different effects on the mass transfer and stability of anion exchange resins. If the polymer main chain structure contains heteroatoms (O, S, etc.), the ether bond and quaternary carbon will produce a positive dipole moment, making these sites susceptible to OH - Nucleophilic attack and hydrolysis chain scission. Therefore, the main chain of the polymer composed of carbon-hydrogen bonds or aromatic main chains exhibits better alkali stability. Conventional quaternary ammonium cationic functional groups can be degraded by Hofmann elimination and nucleophilic substitution pathways in high pH environments. Piperidinium salts and spirocyclic salts These new quaternary ammonium salts can effectively improve chemical stability in strong alkaline conditions. Existing anion exchange resins often use piperidones such as N-methyl-4-piperidone, N-ethyl-4-piperidone, and N-ethylpropyl-4-piperidone. However, the resulting membrane materials are unable to withstand prolonged use in high-concentration hot alkali environments. Summary of the Invention

[0003] The purpose of the present invention is to overcome the problems existing in the prior art and provide an anion exchange resin and its preparation method and application. The membrane material prepared by using the anion exchange resin of the present invention has high heat and alkali stability.

[0004] In order to achieve the above object, the present invention provides an anion exchange resin having a structural formula shown in formula (1):

[0005] Wherein, R1 is a biaryl group; R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3; R3 is a C1-C6 alkyl group; and X is a halogen.

[0006] A second aspect of the present invention provides a method for preparing an anion exchange resin, the preparation method comprising the following steps:

[0007] (1) in the presence of a first solvent, polymerizing a piperidone, a biaryl compound, and a catalyst to obtain a polymer, and then subjecting the polymer to a first drying step;

[0008] (2) subjecting the polymer obtained by the first drying in step (1) to a quaternization reaction with an alkylating agent in the presence of a second solvent to obtain a quaternized polymer, and then subjecting the quaternized polymer to a second drying;

[0009] Wherein, the structural formula of the piperidone is Wherein, R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3.

[0010] The third aspect of the present invention provides a use of the anion exchange resin described in the first aspect or the anion exchange resin prepared by the method described in the second aspect in a fuel cell, water electrolysis or carbon dioxide catalytic reduction.

[0011] Through the above technical solution, the beneficial effects of the present invention include:

[0012] The membrane material produced using the anion exchange resin of the present invention has high heat and alkali stability and a longer lifespan. When applied to fuel cells, water electrolysis, carbon dioxide catalytic reduction, and other fields, it is more conducive to the long-term stable operation of the system. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is the nuclear magnetic resonance spectrum of the anion exchange resin prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0014] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0015] Unless otherwise specified, the unit of weight average molecular weight mentioned in the present invention is Dalton.

[0016] The first aspect of the present invention provides an anion exchange resin having a structural formula shown in formula (1):

[0017] Wherein, R1 is a biaryl group; R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3; R3 is a C1-C6 alkyl group; and X is a halogen.

[0018] In the present invention, R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3, preferably -CH3 and / or -CF3. Controlling R2 to have a smaller molecular weight is more conducive to improving the thermal and alkaline stability of the membrane material subsequently prepared using the anion exchange resin of the present invention.

[0019] According to the present invention, preferably, the weight average molecular weight of the anion exchange resin is 20,000-80,000, preferably 30,000-70,000. By adopting this preferred embodiment, controlling the molecular weight of the anion exchange resin within the above range is beneficial to improving the thermal and alkaline stability of the membrane material prepared using the anion exchange resin of the present invention.

[0020] According to the present invention, preferably, the molecular weight distribution index D of the anion exchange resin is 1.5-3.5, preferably 1.5-2.5. With this preferred embodiment, the molecular weight distribution of the anion exchange resin is narrower, which is more conducive to improving the thermal and alkaline stability of the membrane material prepared using the anion exchange resin of the present invention.

[0021] The present invention has a wide range of choices for the type of R1, which can be various biaryl groups commonly used in the art. Preferably, R1 is selected from at least one of biphenyl, p-terphenyl, m-terphenyl, and p-quaterphenyl, more preferably biphenyl.

[0022] The present invention has a wide range of selections for the type of R3, which can be conventionally selected in the art. Preferably, R3 is selected from at least one of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0023] According to the present invention, preferably, X is I and / or Br.

[0024] The present invention has no particular limitation on the preparation method of the anion exchange resin, as long as the anion exchange resin of the above composition can be prepared. In order to further improve the performance of the anion exchange resin, the present invention also provides a preparation method of the anion exchange resin.

[0025] A second aspect of the present invention provides a method for preparing an anion exchange resin, the preparation method comprising the following steps:

[0026] (1) in the presence of a first solvent, polymerizing a piperidone, a biaryl compound, and a catalyst to obtain a polymer, and then subjecting the polymer to a first drying step;

[0027] (2) subjecting the polymer obtained by the first drying in step (1) to a quaternization reaction with an alkylating agent in the presence of a second solvent to obtain a quaternized polymer, and then subjecting the quaternized polymer to a second drying;

[0028] Wherein, the structural formula of the piperidone is Wherein, R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3.

[0029] In the present invention, R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3, preferably -CH3 and / or -CF3.

[0030] The present invention has a wide range of selections for the biaryl compound, which can be any biaryl compound commonly found in the art. Preferably, the biaryl compound is selected from at least one of biphenyl, p-terphenyl, m-terphenyl, and p-quaterphenyl.

[0031] According to the present invention, preferably, the conditions of the polymerization reaction in step (1) include: a temperature of -10 to 10°C, preferably -6 to 0°C, more preferably excluding 0, specifically, for example, -10°C, -9°C, -8°C, -7°C, -6°C, -5°C, -4°C, -3°C, -2°C, -1°C, 0, 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C, 10°C, and any value in the range formed by any two of these point values; a time of 8-35h, preferably 8-24h, specifically, for example, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 35h, and any value in the range formed by any two of these point values. Adopting this preferred embodiment is conducive to preparing a sample with a higher molecular weight.

[0032] Preferably, the polymerization reaction is carried out under an inert atmosphere. By adopting this preferred embodiment, the influence of moisture in the air on the polymerization reaction can be isolated.

[0033] The present invention has no particular limitation on the inert atmosphere, and can be selected from conventional gas in the art, for example, at least one of nitrogen, helium, neon, and argon. Nitrogen is preferably used in the present invention due to its low cost and availability.

[0034] According to the present invention, preferably, the molar ratio of piperidone to biaryl compound is 1:0.8-1.2. This preferred embodiment is more conducive to improving the thermal alkaline stability of the anion exchange membrane obtained by using the anion resin prepared by the present invention.

[0035] The present invention has a wide range of first solvents, which can be conventionally selected in the art, for example, dichloromethane, chloroform, tetrachloroethane, toluene, etc. In order to avoid the introduction of water into the polymerization system, the present invention preferably uses ultra-dry dichloromethane as the first solvent. All of the above substances can be obtained commercially.

[0036] The present invention has no particular limitation on the amount of the first solvent, as long as the polymerization reaction proceeds smoothly. Preferably, the mass content of piperidone and biaryl compound is 10-40% based on the total mass of the first solvent, piperidone and biaryl compound.

[0037] According to the present invention, preferably, the volume ratio of the catalyst to the first solvent is 5-18:5-10.

[0038] The present invention has a wide range of catalyst types, which can be conventionally selected in the art, for example, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid and heptafluorobutyric acid, etc. Preferably, the catalyst is trifluoroacetic acid and trifluoromethanesulfonic acid.

[0039] More preferably, the volume ratio of trifluoroacetic acid, trifluoromethanesulfonic acid and the first solvent is 1-3:6-12:5-10.

[0040] According to a preferred embodiment of the present invention, trifluoroacetic acid and trifluoromethanesulfonic acid are introduced into the polymerization system in a dropwise manner.

[0041] According to a specific embodiment of the present invention, trifluoroacetic acid and trifluoromethanesulfonic acid are sequentially introduced into the polymerization system in a dropwise manner.

[0042] The present invention has no particular limitation on the order of adding the first solvent, piperidone, biaryl compound and catalyst in step (1). They can be added together or separately. In the embodiment of the present invention, the piperidone and biaryl compound are preferably dissolved in the first solvent first, and then the catalyst is added.

[0043] According to a specific embodiment of the present invention, piperidone and biaryl compound are first dissolved in a first solvent, cooled to the polymerization temperature, and then the catalyst is added.

[0044] According to the present invention, preferably, the method further comprises: washing the polymerization product with alcohol and washing with alkali in sequence to obtain a polymer.

[0045] The specific methods of the alcohol washing and alkali washing of the present invention are not particularly limited and can be carried out according to conventional methods in the art.

[0046] The alcohol wash of the present invention is used to remove residual small molecule impurities. The present invention has a wide range of alcohol types to choose from, and can be selected from conventional alcohols in the art. In the present embodiment, anhydrous ethanol is preferably used.

[0047] According to a specific embodiment of the present invention, the alcohol washing process includes: washing the obtained polymerization product with alcohol to obtain a filter cake; and washing the filter cake with water until the pH value of the washing filtrate reaches 7.

[0048] The alkali washing method of the present invention is used to remove the acidic catalyst. The alkali used in the alkali washing method of the present invention can be selected from a wide range of alkalis, which can be selected from conventional alkalis in the art. In the embodiment of the present invention, potassium carbonate is preferably used.

[0049] Preferably, the alkali used in the alkali washing is provided in the form of an alkali solution, and the concentration of the alkali solution is 0.5-5 mol / L.

[0050] According to a specific embodiment of the present invention, the alkali washing process comprises: washing the filter cake after alcohol washing with an alkali solution to obtain a filter cake; and washing the filter cake with water until the pH value of the washing filtrate reaches 7.

[0051] The present invention has no particular limitation on the first drying, and it can be carried out according to conventional methods in the art. In the embodiment of the present invention, vacuum drying is preferably used.

[0052] The present invention has no particular limitation on the conditions of the quaternization reaction, and the reaction can be carried out according to conventional methods in the art. Preferably, the conditions of the quaternization reaction in step (2) include: a temperature of 20-40° C. and a time of 12-24 hours.

[0053] According to the present invention, preferably, the quaternization reaction in step (2) is carried out under light-proof conditions. This preferred embodiment can avoid the decomposition loss of the quaternization agent.

[0054] According to the present invention, preferably, in step (1), the mass ratio of the first dried polymer to the alkylating agent is 1:1-3.

[0055] The present invention allows for a wide range of types of alkylating agents, and can be any of the various alkylating agents commonly used in quaternization reactions in the art. Preferably, the alkylating agent is at least one selected from methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, cyclopropane bromide, cyclobutane bromide, cyclopentane bromide, and cyclohexane bromide.

[0056] The present invention has a wide range of types for the second solvent, which can be conventionally selected in the art, such as dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide. In the embodiment of the present invention, dimethyl sulfoxide is used as an example.

[0057] The present invention has no particular limitation on the amount of the second solvent, as long as the quaternization reaction proceeds smoothly. Preferably, in step (1), the amount of the first dried polymer is 5-10 wt% of the amount of the second solvent.

[0058] The present invention does not particularly limit the order of adding the second solvent in step (2), the first dried polymer in step (1), and the alkylating agent; they may be added together or separately. In the embodiment of the present invention, the first dried polymer in step (1) is preferably dissolved in the second solvent first, and then the alkylating agent is added. Stirring or ultrasonication may be used during the addition of the above materials to accelerate mixing.

[0059] According to the present invention, preferably, the method further comprises: washing the quaternized reaction product with an organic solvent to obtain a quaternized polymer.

[0060] Preferably, the organic solvent is ethyl acetate and / or diethyl ether. The above substances are conventionally selected in the art and can be obtained commercially.

[0061] The specific method of washing with an organic solvent according to the present invention is not particularly limited and can be carried out according to conventional methods in the art.

[0062] According to a specific embodiment of the present invention, the organic solvent washing process comprises: adding the quaternization reaction product dropwise to an organic solvent, filtering to obtain a filter cake, and then washing the filter cake with the organic solvent until the filtrate is colorless.

[0063] The present invention has no particular limitation on the second drying process, and the drying process can be carried out according to conventional methods in the art. In the embodiment of the present invention, vacuum drying is preferably used.

[0064] The third aspect of the present invention provides a use of the anion exchange resin described in the first aspect or the anion exchange resin prepared by the method described in the second aspect in a fuel cell, water electrolysis or carbon dioxide catalytic reduction.

[0065] The membrane material produced using the anion exchange resin of the present invention has high heat and alkali stability and a longer lifespan. When applied to fuel cells, water electrolysis, carbon dioxide catalytic reduction, and other fields, it is more conducive to the long-term stable operation of the system.

[0066] The present invention will be described in detail below through examples.

[0067] The raw materials in the following examples are all commercially available products.

[0068] Example 1

[0069] (1) Polymerization reaction

[0070] Piperidineacetophenone and biphenyl were dissolved in ultra-dry dichloromethane at a molar ratio of 1:1, with the combined concentration of piperidineacetophenone and biphenyl reaching 20 wt%. The mixture was cooled to -5°C under nitrogen atmosphere, and trifluoroacetic acid and trifluoromethanesulfonic acid (in a volume ratio of 1:12:10 to ultra-dry dichloromethane) were added dropwise. The mixture was then allowed to react at -5°C for 24 h.

[0071] (2) Precipitation and washing

[0072] After the polymerization reaction is completed, the obtained polymerization product is poured into an anhydrous ethanol solution with a volume ratio of anhydrous ethanol to polymerization product of 5:1, filtered to obtain a filter cake, and washed with deionized water until the pH value of the washing filtrate is 7.

[0073] (3) Neutralization washing

[0074] The filter cake after washing in step (2) was dispersed in 1M potassium carbonate solution, placed at 60°C for 24 hours, and filtered to obtain a filter cake. The filter cake was washed with deionized water until the pH value of the washing filtrate was 7 to obtain a polymer.

[0075] (4) Vacuum drying

[0076] The obtained polymer was dried at 60 °C under vacuum for 24 h.

[0077] (5) Quaternization reaction

[0078] The dried polymer was dispersed in dimethyl sulfoxide solvent at room temperature, with the mass fraction of the dried polymer in the dimethyl sulfoxide solvent being 5 wt %. Iodomethane twice the mass of the polymer was added while stirring, and the mixture was reacted at room temperature in the dark for 24 h.

[0079] (6) Precipitation and washing

[0080] After the quaternization reaction is completed, the quaternization reaction product is added dropwise to ethyl acetate in a volume ratio of ethyl acetate to quaternization reaction product of 6:1, filtered to obtain a filter cake, and washed with ethyl acetate six times.

[0081] (7) Vacuum drying

[0082] The quaternized polymer was dried at 60°C under vacuum for 24 hours to obtain an anion exchange resin. Its structural formula is shown below:

[0083] The nuclear magnetic resonance spectrum of the anion exchange resin prepared in Example 1 is shown as follows: Figure 1 As shown. Figure 1 It can be seen that the nuclear magnetic resonance hydrogen spectrum is Figure 1 As shown, the peak at 7.18ppm-7.75ppm is the signal peak of hydrogen on the skeleton benzene ring; the signal peak at 3.83ppm is attributed to the connection N + The signal peak of hydrogen on the benzene ring; the peak at 3.38ppm is the signal peak of water; the signal peak at 3.15ppm is attributed to the connection of N + The peak at 2.54 ppm is the signal of the hydrogen on the piperidine ring; the peak at 2.50 ppm is the signal peak of the solvent DMSO. According to the attribution of the peaks, it can be seen that the target product was successfully prepared.

[0084] The composition of anion exchange resin is shown in Table 1.

[0085] Example 2

[0086] (1) Polymerization reaction

[0087] Piperidineacetophenone and biphenyl were dissolved in ultra-dry dichloromethane at a molar ratio of 1:0.8, with the combined mass concentration of piperidineacetophenone and biphenyl reaching 10 wt%. The mixture was cooled to -5°C under nitrogen atmosphere, and trifluoroacetic acid and trifluoromethanesulfonic acid (the volume ratio of trifluoroacetic acid, trifluoromethanesulfonic acid, and ultra-dry dichloromethane in the solution was 1:6:5) were added dropwise. The mixture was then reacted at -5°C for 8 h.

[0088] (2) Precipitation and washing

[0089] After the polymerization reaction is completed, the obtained polymerization product is poured into an anhydrous ethanol solution with a volume ratio of anhydrous ethanol to polymer solution of 1:1, filtered to obtain a filter cake, and washed with deionized water until the pH value of the washing filtrate is 7.

[0090] (3) Neutralization washing

[0091] The filter cake after washing in step (2) was dispersed in 1M potassium carbonate solution, placed at 60°C for 6 hours, and filtered to obtain a filter cake. The filter cake was washed with deionized water until the pH value of the washing filtrate was 7 to obtain a polymer.

[0092] (4) Vacuum drying

[0093] The obtained polymer was dried at 60 °C under vacuum for 6 h.

[0094] (5) Quaternization reaction

[0095] The dried polymer was dispersed in dimethyl sulfoxide solvent at room temperature, with the mass fraction of the dried polymer in the dimethyl sulfoxide solvent being 5 wt %. Iodomethane (1.5 times the mass of the polymer) was added while stirring, and the mixture was reacted at room temperature in the dark for 12 h.

[0096] (6) Precipitation and washing

[0097] After the quaternization reaction is completed, the quaternization reaction product is added dropwise to ethyl acetate, with the volume ratio of ethyl acetate to polymer solution being 3:1, and filtered to obtain a filter cake, which is washed with ethyl acetate three times.

[0098] (7) Vacuum drying

[0099] The quaternized polymer was dried at 60° C. under vacuum for 6 h to obtain an anion exchange resin.

[0100] The composition of anion exchange resin is shown in Table 1.

[0101] Example 3

[0102] (1) Polymerization reaction

[0103] Piperidineacetophenone and biphenyl were dissolved in ultra-dry dichloromethane at a molar ratio of 1:1.2, with the combined mass concentration of piperidineacetophenone and biphenyl reaching 40 wt%. The mixture was cooled to -2°C under nitrogen atmosphere, and trifluoroacetic acid and trifluoromethanesulfonic acid (the volume ratio of trifluoroacetic acid, trifluoromethanesulfonic acid, and ultra-dry dichloromethane in the solution being 3:12:10) were added dropwise. The mixture was then allowed to react at this temperature for 24 hours.

[0104] (2) Precipitation and washing

[0105] After the polymerization reaction is completed, the obtained polymerization product is poured into an anhydrous ethanol solution with a volume ratio of anhydrous ethanol to polymer solution of 5:1, filtered to obtain a filter cake, and washed with deionized water until the pH value of the washing filtrate is 7.

[0106] (3) Neutralization washing

[0107] The filter cake after washing in step (2) was dispersed in 1M potassium carbonate solution, placed at 80°C for 24 hours, and filtered to obtain a filter cake. The filter cake was washed with deionized water until the pH value of the washing filtrate was 7 to obtain a polymer.

[0108] (4) Vacuum drying

[0109] The obtained polymer was dried at 60 °C under vacuum for 24 h.

[0110] (5) Quaternization reaction

[0111] The dried polymer was dispersed in dimethyl sulfoxide solvent at room temperature, with the mass fraction of the dried polymer in the dimethyl sulfoxide solvent being 10 wt %. Iodomethane 3 times the mass of the polymer was added while stirring, and the mixture was reacted for 24 h at room temperature in the dark.

[0112] (6) Precipitation and washing

[0113] After the quaternization reaction is completed, the quaternization reaction product is added dropwise to ethyl acetate, with the volume ratio of ethyl acetate to polymer solution being 6:1, and filtered to obtain a filter cake, which is washed with ethyl acetate six times.

[0114] (7) Vacuum drying

[0115] The quaternized polymer was dried at 60° C. under vacuum for 24 h to obtain an anion exchange resin.

[0116] The composition of anion exchange resin is shown in Table 1.

[0117] Example 4

[0118] The method of Example 1 was followed, except that the temperature of the polymerization reaction in step (1) was 7°C.

[0119] The composition of anion exchange resin is shown in Table 1.

[0120] Comparative Example 1

[0121] The method of Example 1 was followed, except that an equimolar amount of N-methyl-4-piperidone was used instead of piperidine acetophenone.

[0122] Comparative Example 2

[0123] The method of Example 1 was followed, except that an equal molar amount of 1-phenylethyl-4-piperidone was used instead of piperidine acetophenone.

[0124] Test Example 1

[0125] Hot Alkali Stability: The anion exchange resins prepared in the Examples and Comparative Examples were dissolved in dimethyl sulfoxide (DMSO) to form a 3 wt% homogeneous anion exchange resin solution. This solution was then cast onto a glass plate and dried at 100°C for 8 hours to form a film (130 μm thick). The resulting film was removed and cut into 5 cm x 5 cm pieces. The film was immersed in 1 M KOH solution at 80°C for 24 hours, then placed in a fixture and its conductivity was measured. The hot alkaline stability of the film was evaluated by comparing the change in conductivity (conductivity retention) after 1000 hours, 2000 hours, and 4000 hours. The results are shown in Table 1.

[0126] Table 1

[0127]

[0128] The results in Table 1 show that the anion exchange membranes obtained using the anion exchange resins of the present invention have significantly higher thermal and alkaline stability and longer lifespan. Applications in fuel cells, water electrolysis, carbon dioxide catalytic reduction, and other fields facilitate long-term stable system operation.

[0129] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. An anion exchange resin, characterized in that The anion exchange resin has the structural formula shown in formula (1): Wherein, R1 is a biaryl group; R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3; R3 is a C1-C6 alkyl group; and X is a halogen.

2. The anion exchange resin according to claim 1, wherein The weight average molecular weight of the anion exchange resin is 20,000-80,000, preferably 30,000-70,000; Preferably, the molecular weight distribution index D of the anion exchange resin is 1.5-3.5, preferably 1.5-2.

5.

3. The anion exchange resin according to claim 1 or 2, wherein R1 is selected from at least one of biphenyl, p-terphenyl, m-terphenyl and p-quaterphenyl; Preferably, X is I and / or Br.

4. A method for preparing an anion exchange resin, characterized in that: The preparation method comprises the following steps: (1) in the presence of a first solvent, polymerizing a piperidone, a biaryl compound, and a catalyst to obtain a polymer, and then subjecting the polymer to a first drying step; (2) subjecting the polymer obtained by the first drying in step (1) to a quaternization reaction with an alkylating agent in the presence of a second solvent to obtain a quaternized polymer, and then subjecting the quaternized polymer to a second drying; Wherein, the structural formula of the piperidone is Wherein, R2 is at least one of -CH3, -CH2CH3, -CF3 and -CH2CF3.

5. The method according to claim 4, wherein The biaryl compound is at least one selected from biphenyl, p-terphenyl, m-terphenyl and p-quaterphenyl.

6. The method according to claim 4, wherein: The polymerization reaction conditions in step (1) include: temperature of -10 to 10°C, preferably -6 to 0°C; time of 8 to 35 hours, preferably 8 to 24 hours; Preferably, the polymerization reaction is carried out under an inert atmosphere.

7. The method according to any one of claims 4 to 6, wherein: The molar ratio of piperidone to biaryl compound is 1:0.8-1.2; Preferably, based on the total mass of the first solvent, piperidone and the biaryl compound, the mass content of piperidone and the biaryl compound is 10-40%; Preferably, the volume ratio of the catalyst to the first solvent is 5-18:5-10.

8. The method according to any one of claims 4 to 7, wherein: The conditions of the quaternization reaction in step (2) include: temperature of 20-40° C. and time of 12-24 h; Preferably, the quaternization reaction in step (2) is carried out under light-proof conditions; Preferably, in step (1), the mass ratio of the first dried polymer to the alkylating agent is 1:1-3; Preferably, the alkylating agent is selected from at least one of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, cyclopropane bromide, cyclobutane bromide, cyclopentane bromide and cyclohexane bromide.

9. The method according to any one of claims 4 to 8, wherein: The method further comprises: sequentially washing the polymerization reaction product with alcohol and alkali to obtain a polymer; Preferably, the method further comprises: washing the quaternized reaction product with an organic solvent to obtain a quaternized polymer; Preferably, the organic solvent is ethyl acetate and / or diethyl ether.

10. Use of the anion exchange resin according to any one of claims 1 to 3 or the anion exchange resin prepared by the method according to any one of claims 4 to 9 in a fuel cell, water electrolysis or carbon dioxide catalytic reduction.

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