An anion exchange resin and ion exchange membrane containing a perfluorinated backbone and cross-linked structure, and a method for preparing the same.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WUHAN UNIV OF TECH
- Filing Date
- 2023-03-24
- Publication Date
- 2026-05-26
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Abstract
Description
Technical Field
[0001] This invention relates to the field of anion exchange membrane fuel cells, specifically to anion exchange resin and anion exchange membrane containing a perfluorinated backbone and cross-linked structure, and a method for preparing the same. Background Technology
[0002] Anion exchange membrane fuel cells (AEMFCs) have attracted widespread attention due to the potential applications of non-platinum electrocatalysts or carbon-free supports in their electrode structures. Anion exchange membranes (AEMs) play a crucial role in the ion exchange of hydroxide ions from the cathode to the anode. However, the practical application of AEMs remains limited by low OH... - The poor conductivity and alkali stability of AEMs are limitations, therefore, improving the ionic conductivity and alkali stability of AEMs remains a significant challenge. Recently, hydrocarbon-based aromatic polymers, such as polysulfone, polyoxyazole, polyimide, polyketone, and polyphenylene, have attracted considerable attention due to their inexpensive and readily available synthetic routes, and have been reported by numerous research groups.
[0003] For example, CN104877136A discloses a method for preparing long-branched polysulfone anion exchange membranes, which involves polysulfone acylation, carbonyl reduction, and quaternization to prepare a polysulfone anion exchange membrane. This method increases the ionic conductivity of the membrane by increasing the length of the polymer side chains to promote the formation of phase separation structures, thereby improving the connectivity of ion channels within the membrane. However, the anion exchange membrane prepared by this method still suffers from drawbacks such as low ionic conductivity, poor mechanical strength, and poor alkali stability.
[0004] CN108923056A discloses a novel method for preparing a polyphenylene ether (PPE) anion exchange membrane. The method involves modifying PPE by bromination and hydroxylation, reacting it with epichlorohydrin, followed by quaternization to obtain conductive sites, and then using heat treatment to generate a cross-linked structure, thus preparing a high-conductivity PPE anion exchange membrane. Although the anion exchange membrane prepared by this method has multiple conductive sites, it lacks a distinct hydrophobic-hydrophilic structure, resulting in low ionic conductivity. Furthermore, due to the poor stability of the ether bonds, the anion exchange membrane prepared by this method exhibits poor chemical and thermal stability.
[0005] Among the various aromatic polymer backbones reported to date, polystyrene has become the most advanced AEMs due to its excellent chemical stability. CN111276723A discloses a method for preparing a comb-shaped basic anion exchange membrane, which is prepared by casting a comb-shaped hydrogenated styrene-butadiene block copolymer. The main chain of the comb-shaped hydrogenated styrene-butadiene block copolymer is hydrogenated styrene-butadiene block copolymer, and the phenyl portion of the main chain is para-bonded with a cationic functional group containing a long alkyl chain through a methylene bond. However, since the main chain of this anion exchange membrane is carbon-hydrogen bonded, although it has high chemical stability, its high-temperature stability is low, so its high-temperature stability remains a problem. Summary of the Invention
[0006] The technical problem to be solved by this invention is to provide an anion exchange resin and an ion exchange membrane containing a perfluorinated backbone and cross-linked structure, as well as a method for preparing the same, addressing the shortcomings of the prior art. This invention solves the problems of poor chemical stability and low ionic conductivity in anion exchange membranes using carbon-hydrogen bonds as the polymer backbone, and provides an anion exchange membrane with good chemical stability, high ionic conductivity, and mechanical strength using carbon-fluorine bonds as the polymer backbone.
[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0008] An anion exchange resin containing a perfluorinated backbone and a cross-linked structure is characterized by mainly containing repeating units as shown in formula (1):
[0009]
[0010]
[0011] Where m is an integer from 2 to 5, n is an integer from 1 to 6, and the ion exchange equivalent (EW) is 880–1350 g / mol. EW refers to the mass of dry resin contained per mole of ion groups, expressed in g / mol, reflecting the concentration of ion exchange groups within the ion exchange membrane.
[0012] The main steps of the preparation method of the above-mentioned anion exchange resin containing a perfluorinated backbone and cross-linked structure are as follows:
[0013] (1) The precursor perfluorosulfonic acid is reacted with liquid ammonia to form a salt by acid-base reaction, and then the perfluorosulfonamide resin is obtained by thermal induction dehydration.
[0014] (2) Grafting quaternary ammonium monomers containing epoxy alkyl groups onto perfluorosulfonamide resins to obtain perfluorosulfonamide resins containing hydroxyl groups; then replacing hydroxyl groups with bromine atoms through substitution reactions and eliminating bromine atoms through elimination reactions to obtain perfluorosulfonamide resins containing unsaturated double bonds.
[0015] (3) The perfluorosulfonamide resin containing unsaturated double bonds obtained in step (2) is used to prepare a perfluorosulfonamide resin containing a cross-linked structure through a thermally induced cross-linking reaction, namely an anion exchange resin containing a perfluorinated main chain and a cross-linked structure.
[0016] In the above scheme, the specific process of step (1) is as follows: perfluorosulfonic acid reacts with excess liquid ammonia at -40 to -80°C for 2 to 6 hours. After the reaction is completed, the excess liquid ammonia is released, and the mixture is thermally dehydrated at 200 to 250°C under inert gas protection to obtain perfluorosulfonamide resin. The inert gas is one or more of helium, neon, argon, etc.
[0017] In the above scheme, the molecular formula of the perfluorosulfonic acid is one of formulas (3), (4), (5), and (6):
[0018]
[0019]
[0020]
[0021]
[0022] Perfluorosulfonic acids having the structures shown in formulas (3), (4), (5) and (6) can be specifically selected from perfluorosulfonic acid resin D79 (labeled as: C2-PFSO3H, EW=790g / mol, Solvay), short side chain perfluorosulfonic acid resin (labeled as: C3-PFSO3H, EW=900g / mol, Asahi Kasei), perfluorosulfonic acid resin 3M-800 (labeled as: C4-PFSO3H, EW=800g / mol, 3M), and perfluorosulfonic acid resin D2020 (labeled as: C5-PFSO3H, EW=1100g / mol, DuPont).
[0023] In the above scheme, the specific process of step (2) is as follows: Dissolve the perfluorosulfonamide resin in an organic solvent with a solid content of 5% to 10%, and add a quaternary ammonium monomer containing an epoxy alkyl group. Control the reaction temperature to 60℃ to 120℃ and react for 24 to 72 hours under inert gas protection. Then wash with deionized water until neutral to obtain a perfluorosulfonamide resin containing hydroxyl groups. Dissolve the perfluorosulfonamide resin containing hydroxyl groups and N-bromosuccinimide in dichloromethane to form a solution with a solid content of 5% to 10%. Use dimethylthiourea as a catalyst and react at room temperature for 3 to 12 hours. Wash with methanol to remove impurities to obtain a crude perfluorosulfonamide resin containing bromine atoms. Add the crude product to an alkaline ethanol solution and react for 2 to 4 hours at a reaction temperature of 60 to 80℃. Wash with deionized water until neutral and dry to obtain a perfluorosulfonamide resin containing unsaturated double bonds.
[0024] In the above scheme, the quaternary ammonium monomer containing epoxy alkyl groups can be selected from one or more of the following chemical formulas.
[0025]
[0026] In the above scheme, in step (2), the molar ratio of the amino group in the perfluorosulfonamide resin to the quaternary ammonium monomer containing the epoxy alkyl group is 1:(1.5-3); the molar ratio of the perfluorosulfonamide resin containing hydroxyl group, N-bromosuccinimide and dimethylthiourea is 1:(1-2):(0.4-0.5).
[0027] In the above scheme, the specific process of step (3) is as follows: the perfluorosulfonamide resin containing unsaturated double bonds is thermally induced to react at 200-250°C for 1-2 hours under inert gas protection to obtain the perfluorosulfonamide resin containing cross-linked structure, that is, the anion exchange resin containing perfluorinated main chain and cross-linked structure.
[0028] In the above scheme, the organic solvent in step (2) or (3) is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, etc.; the inert gas is one or more of helium, neon, argon, etc.
[0029] This invention also provides a method for preparing an anion exchange membrane containing a perfluorinated backbone and a cross-linked structure. The method involves casting the aforementioned anion exchange resin containing a perfluorinated backbone and a cross-linked structure into a film. The specific process is as follows: The anion exchange resin containing a perfluorinated backbone and a cross-linked structure is uniformly dispersed in an organic solvent at 110–160°C to form a resin solution with a solid content of 5%–10%. The solution is then dried at 50–80°C using a casting method to form a film. The film is then immersed in an alkaline solution for 24–72 hours and washed with deionized water until neutral to obtain an anion exchange membrane containing a perfluorinated backbone and a cross-linked structure.
[0030] Compared with the prior art, the present invention has the following advantages and beneficial effects:
[0031] This invention uses soluble perfluorosulfonic acid resin as a raw material, reacting it with liquid ammonia to generate perfluorosulfonamide resin. Further, monomers containing epoxy groups and quaternary ammonium groups are grafted onto the sulfonamide-containing resin, followed by high-temperature treatment to obtain a perfluoro anion exchange resin with a cross-linked structure. This invention provides a novel method for preparing perfluorosulfonamide structures using acid-base and thermally induced reactions. Based on the highly soluble perfluorosulfonic acid resin as a raw material, it avoids the problem of incomplete reactions and high EW values in polymers due to the poor solubility of precursors such as perfluorosulfonyl fluoride. Furthermore, the perfluoro backbone exhibits good thermal stability, and the thermally induced cross-linked structure greatly enhances its physical stability. Additionally, the extreme hydrophobicity of the perfluoro backbone leads to the formation of a well-developed microphase separation structure, constructing a rapid and reliable ion transport channel, significantly improving the ionic conductivity of the membrane. Moreover, the anion exchange resin containing a fluorocarbon backbone and cross-linked structure described in this invention has good solubility and can be cast into a film in organic solvents. Therefore, the anion exchange membrane containing a perfluorinated backbone and cross-linked structure described in this invention has good physical and chemical stability and high ionic conductivity, solving the problems of insufficient physical stability, poor chemical stability and low ionic conductivity of anion exchange membranes with carbon-hydrogen bonds as polymer backbone in the prior art. Attached Figure Description
[0032] Figure 1 This is a circuit diagram illustrating the preparation of anion exchange resin containing a perfluorinated backbone and cross-linked structure, as designed in this invention. The accompanying drawings only show certain embodiments of the invention and should not be considered as limiting the scope. Those skilled in the art can obtain other related drawings based on these drawings without departing from the spirit and scope of the invention. Detailed Implementation
[0033] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the present invention is not limited to the following embodiments.
[0034] In the following examples, all reagents used are commercially available products.
[0035] Example 1
[0036] A method for preparing anion exchange resin and ion exchange membrane containing a perfluorinated backbone and cross-linked structure includes the following steps:
[0037] (1) Take 10g of C2-PFSO3H (EW=790g / mol) and react with 30ml of liquid ammonia at -80℃ for 3h. After the reaction is completed, slowly release the excess liquid ammonia and then dehydrate it under argon protection at 220℃ to obtain 10.13g of perfluorosulfonamide resin.
[0038] (2) The perfluorosulfonamide resin obtained by thermal induction dehydration is dissolved in N,N-dimethylformamide with a solid content of 10%, and quaternary ammonium monomer is added. 2.65 g (the molar ratio of amine groups to quaternary ammonium monomers in the perfluorosulfonamide resin is 1:1.5) was reacted at 60 °C for 24 h under an argon atmosphere and washed with deionized water until neutral to obtain a perfluorosulfonamide resin containing hydroxyl groups.
[0039] (3) Using a substitution reaction, 12.3 g of hydroxyl-containing perfluorosulfonamide resin, 0.52 g of dimethylthiourea and 2.3 g of N-bromosuccinimide were dissolved in 122 g of dichloromethane (the molar ratio of hydroxyl group, dimethylthiourea and N-bromosuccinimide in the hydroxyl-containing perfluorosulfonamide resin was 1:0.4:1), and reacted at room temperature for 3 h. The mixture was then washed with methanol to remove impurities, and a crude product of perfluorosulfonamide resin containing bromine atoms was obtained.
[0040] (4) Add 12.1g of the crude product after the substitution reaction in step (3) to 190g of KOH in ethanol solution to form a medium solid content. React for 2h at a reaction temperature of 60℃. Wash with deionized water until neutral and dry at 60℃ for 12h to obtain perfluorosulfonamide resin containing unsaturated double bonds.
[0041] (5) 11.7 g of perfluorosulfonamide resin containing unsaturated double bonds was thermally induced to react at 200 °C for 1 h under argon protection to obtain 10.9 g of perfluorosulfonamide resin containing a cross-linked structure, i.e., anion exchange resin containing a perfluorinated backbone and a cross-linked structure, as shown below:
[0042]
[0043] Where m = 2, n = 2, and EW = 900 g / mol was determined by back titration.
[0044] (6) 10.9 g of perfluorosulfonamide resin containing cross-linked structure was uniformly dispersed in isopropanol at 110 °C to form a solution with a solid content of 6 wt%; 17 g of the solution was taken and the solvent was removed by casting at 50 °C to form a film. The film was then placed in 1 M KOH solution for 24 h and washed with a large amount of deionized water until neutral to obtain an anion exchange membrane containing a perfluorinated main chain and cross-linked structure.
[0045] Example 2
[0046] A method for preparing anion exchange resin and ion exchange membrane containing a perfluorinated backbone and cross-linked structure includes the following steps:
[0047] (1) Take 10g of C4-PFSO3H (EW=800g / mol) and react with 30ml of liquid ammonia at -60℃ for 2h. After the reaction is completed, slowly release the excess liquid ammonia and then dehydrate it under argon protection at 200℃ to obtain 10.16g of perfluorosulfonamide resin.
[0048] (2) The perfluorosulfonamide resin obtained by thermal induction dehydration is dissolved in N,N-dimethylacetamide, with a solid content of 7%, and then added... 3.68 g (the molar ratio of amine groups to quaternary ammonium monomers in the perfluorosulfonamide resin is 1:2) was reacted at 80 °C for 36 h under a helium atmosphere and washed with deionized water until neutral to obtain a perfluorosulfonamide resin containing hydroxyl groups.
[0049] (3) Using a substitution reaction, 13.1 g of hydroxyl-containing perfluorosulfonamide resin, 0.59 g of dimethylthiourea and 3.34 g of N-bromosuccinimide were dissolved in 118 g of dichloromethane (the molar ratio of hydroxyl group, dimethylthiourea and N-bromosuccinimide in the hydroxyl-containing perfluorosulfonamide resin was 1:0.45:1.48). The mixture was reacted at room temperature for 5 h, and the residue was washed with methanol to remove impurities, thus obtaining a crude product of perfluorosulfonamide resin containing bromine atoms.
[0050] (4) 12.9 g of the product after the substitution reaction was reacted in 202 g of NaOH in an ethanol solution for 3 h at a reaction temperature of 70 °C. The product was washed with deionized water until neutral and dried at 60 °C for 12 h to obtain a perfluorosulfonamide resin containing unsaturated double bonds.
[0051] (5) 12.1 g of perfluorosulfonamide resin containing unsaturated double bonds was thermally induced to react at 220 °C for 1.5 h under argon protection to obtain 11.4 g of perfluorosulfonamide resin containing a cross-linked structure, i.e., anion exchange resin containing a perfluorinated backbone and a cross-linked structure, the structure of which is shown below:
[0052]
[0053] Where m = 4, n = 1, EW = 900 g / mol.
[0054] (6) 11.4g of perfluorosulfonamide resin containing cross-linked structure was uniformly dispersed in isopropanol solution at 130℃ to form a solution with a solid content of 6wt%. 17g of the solution was taken and the solvent was removed by casting at 55℃ to form a film. The film was then placed in 1M KOH solution for 36h and washed with a large amount of deionized water until neutral to obtain an anion exchange membrane containing perfluorinated main chain and cross-linked structure.
[0055] Example 3
[0056] A method for preparing anion exchange resin and ion exchange membrane containing a perfluorinated backbone and cross-linked structure includes the following steps:
[0057] (1) Take 10g of C5-PFSO3H (EW=1100g / mol) and 27ml of liquid ammonia and react them at -40℃ for 6h. After the reaction is completed, the excess liquid ammonia is slowly released and then dehydrated under argon protection at 250℃ to obtain 9.8g of perfluorosulfonamide resin.
[0058] (2) The perfluorosulfonamide resin obtained by thermal induction dehydration is dissolved in N-methylpyrrolidone, with a solid content of 5%, and then added... 5.37 g (the molar ratio of amine groups to quaternary ammonium monomers in the perfluorosulfonamide resin is 1:3) was reacted at 120 °C for 72 h under a helium atmosphere and washed with deionized water until neutral to obtain a perfluorosulfonamide resin containing hydroxyl groups.
[0059] (3) Using a substitution reaction, 12.4 g of hydroxyl-containing perfluorosulfonamide resin, 0.47 g of dimethylthiourea and 3.24 g of N-bromosuccinimide were dissolved in 117 g of dichloromethane (the molar ratio of hydroxyl group, dimethylthiourea and N-bromosuccinimide in the hydroxyl-containing perfluorosulfonamide resin was 1:0.5:2). The mixture was reacted at room temperature for 12 h, and then washed with methanol to remove impurities, to obtain crude perfluorosulfonamide resin containing bromine atoms.
[0060] (4) 11.6 g of the product after the substitution reaction was reacted in 182 g of NaOH in an ethanol solution for 4 h at a reaction temperature of 80 °C. The product was washed with deionized water until neutral and dried at 60 °C for 12 h to obtain a perfluorosulfonamide resin containing unsaturated double bonds.
[0061] (5) 10.8 g of perfluorosulfonamide resin containing unsaturated double bonds was thermally induced to react at 250 °C for 2 h under argon protection to obtain 10.2 g of perfluorosulfonamide resin containing a cross-linked structure, i.e., anion exchange resin containing a perfluorinated backbone and a cross-linked structure, the structure of which is shown below:
[0062]
[0063] Where m = 5, n = 1, EW = 1250 g / mol.
[0064] (6) 10.2g of perfluorosulfonamide resin containing cross-linked structure was uniformly dispersed in dimethyl sulfoxide solution at 160℃ to form a solution with a solid content of 6wt%. 17g of the solution was taken and the solvent was removed by casting at 80℃ to form a film. The film was then placed in 1M KOH solution for 72h and washed with a large amount of deionized water until neutral to obtain an anion exchange membrane containing perfluorinated main chain and cross-linked structure.
[0065] To evaluate the specific technical effects of the anion exchange membrane containing a perfluorinated backbone and cross-linked structure described in this invention, specific performance tests were conducted on Examples 1-3 in terms of ionic conductivity, water absorption, alkali resistance, and mechanical strength. The conductivity was measured using a two-electrode AC impedance method on an electrochemical workstation (Solartron-1287); the water absorption was measured by immersing the membrane in deionized water at 80°C for 24 hours; the alkali resistance of the membrane was measured by immersing the membrane in 2 mol / L KOH at 80°C for 30 days and calculating the rate of change in conductivity. Mechanical strength included tensile strength and elongation at break. The mechanical strength was tested using a universal testing machine (CMT6202) at 25°C with a tensile rate of 5 mm / min. Each sample was tested three times, and an average value was obtained. Specific test data are shown in Table 1.
[0066] Table 1
[0067] Group number Example 1 Example 2 Example 3 Commercial membrane FAA-3-50 <![CDATA[Conductivity (mS cm -1 )]]> 107 91 74 53.8 Water absorption rate (%) 11.4 9.6 7.2 104.1 Alkali resistance (%) 4.3 5.1 5.7 89.4 Tensile strength (MPa) 43.7 38.4 35.5 14 Elongation at break (%) 79.1 95.8 72.2 59.4
[0068] As shown in Table 1, the conductivity of the anion exchange membrane containing a perfluorinated backbone and cross-linked structure prepared in this invention is not less than 70 mS / cm. -1 It can reach 110 mS cm -1Compared to the commercial FAA-3-50 membrane, the conductivity is at least 40%, and in some cases, up to 100%; the water absorption rate is no more than 12%, and can be as low as 7%, only about 1 / 10 of that of the commercial FAA-3-50 membrane; the alkali resistance is 4-6%, far higher than that of the commercial FAA-3-50 membrane; the tensile strength is above 30 MPa, reaching about 45 MPa, which is 2 to 3 times that of the commercial FAA-3-50 membrane; the elongation at break is above 70%, reaching about 96%, which is 20-60% higher than that of the commercial FAA-3-50 membrane. Therefore, the anion exchange resin containing a perfluorinated backbone and cross-linked structure described in this invention not only has a low EW value, but also has high ionic conductivity due to the well-developed microphase separation structure within the anion exchange membrane containing the perfluorinated backbone and cross-linked structure, which constructs a rapid ion transport channel. Furthermore, due to the good thermal stability of the perfluorinated backbone and the thermally induced cross-linking structure, the water absorption rate of the anion exchange membrane containing the perfluorinated backbone and cross-linking structure is significantly reduced, and its tensile strength is effectively improved. Its alkali resistance is also far superior to that of the commercial membrane FAA-3-50. Therefore, the anion exchange membrane containing the perfluorinated backbone and cross-linking structure described in this invention possesses high ionic conductivity and physical and chemical stability.
[0069] The above description is only a preferred embodiment of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the inventive concept of the present invention, and these all fall within the protection scope of the present invention.
Claims
1. An anion exchange resin containing a perfluorinated backbone and a cross-linked structure, characterized in that, The structure of the anion exchange resin has repeating units as shown in formula (1) or formula (2): Equation (1) Equation (2) Where m is an integer from 2 to 5, n is an integer from 1 to 6, and the ion exchange equivalent (EW) is 800 to 1400 g / mol.
2. The method for preparing the anion exchange resin containing a perfluorinated backbone and cross-linked structure as described in claim 1, characterized in that, The following steps are adopted: (1) The precursor perfluorosulfonic acid is reacted with liquid ammonia to form a salt by acid-base reaction, and then the perfluorosulfonamide resin is obtained by thermal induction dehydration. (2) Grafting quaternary ammonium monomers containing epoxy alkyl groups onto perfluorosulfonamide resins to obtain perfluorosulfonamide resins containing hydroxyl groups; then replacing hydroxyl groups with bromine atoms through substitution reactions and eliminating bromine atoms through elimination reactions to obtain perfluorosulfonamide resins containing unsaturated double bonds. (3) The perfluorosulfonamide resin containing unsaturated double bonds obtained in step (2) is used to prepare a perfluorosulfonamide resin containing a cross-linked structure through a thermally induced cross-linking reaction, that is, an anion exchange resin containing a perfluorinated main chain and a cross-linked structure. The precursor perfluorosulfonic acid has an end-effector weight (EW) in the range of 700–1200 g / mol and has a structural formula of one of formulas (3), (4), and (5): Equation (3) Equation (4) Equation (5) Equations (3), (4) and (5) are respectively denoted as C2-PFSO3H, C3-PFSO3H and C4-PFSO3H.
3. The method for preparing anion exchange resin containing a perfluorinated backbone and cross-linked structure according to claim 2, characterized in that, Step (1) The specific process is as follows: the precursor perfluorosulfonic acid reacts with excess liquid ammonia at -80~-40℃ for 2h~6h. After the reaction is completed, the excess liquid ammonia is released and dehydrated under inert gas protection at 200~250℃ to obtain perfluorosulfonamide resin.
4. The method for preparing anion exchange resin containing a perfluorinated backbone and cross-linked structure according to claim 2, characterized in that, The specific process of step (2) is as follows: Dissolve the perfluorosulfonamide resin in an organic solvent with a solid content of 5%~10%, and add a quaternary ammonium monomer containing epoxy alkyl groups. Control the reaction temperature to 60℃~120℃ and react for 24~72h under inert gas protection. Then wash with deionized water until neutral to obtain a perfluorosulfonamide resin containing hydroxyl groups. Dissolve the perfluorosulfonamide resin containing hydroxyl groups and N-bromosuccinimide in dichloromethane. Use dimethylthiourea as a catalyst and react at room temperature for 3~12h. Wash with methanol to remove impurities to obtain a crude perfluorosulfonamide resin containing bromine atoms. React the crude product in an alkaline ethanol solution for 2~4h at a reaction temperature of 60~80℃. Wash with deionized water until neutral and dry to obtain a perfluorosulfonamide resin containing unsaturated double bonds.
5. The method for preparing anion exchange resin containing a perfluorinated backbone and cross-linked structure according to claim 2 or 4, characterized in that, The quaternary ammonium monomer containing epoxy alkyl groups is , , , , , , , , , , One or more of them.
6. The method for preparing anion exchange resin containing a perfluorinated backbone and cross-linked structure according to claim 2 or 4, characterized in that, In step (2), the molar ratio of the amino group in the perfluorosulfonamide resin to the quaternary ammonium monomer containing epoxy alkyl group is 1:(1.5~3); the molar ratio of the perfluorosulfonamide resin containing hydroxyl group, N-bromosuccinimide and dimethylthiourea is 1:(1~2):(0.4~0.5).
7. The method for preparing anion exchange resin containing a perfluorinated backbone and cross-linked structure according to claim 2, characterized in that, The specific process of step (3) is as follows: the perfluorosulfonamide resin containing unsaturated double bonds is thermally induced to react at 200~250℃ for 1~2h under inert gas protection to obtain the perfluorosulfonamide resin containing cross-linked structure, that is, the anion exchange resin containing perfluorinated main chain and cross-linked structure.
8. The method for preparing anion exchange resin containing a perfluorinated backbone and cross-linked structure according to claim 2, 4, or 7, characterized in that, The reaction solvent in step (2) or (3) is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, ethanol, and isopropanol.
9. A method for preparing an anion exchange membrane containing a perfluorinated backbone and a cross-linked structure, characterized in that, The anion exchange resin containing a perfluorinated main chain and cross-linked structure as described in claim 1 is uniformly dispersed in an organic solvent at 110~160℃, then dried at 50~80℃ by casting molding to form a film, and the film is immersed in an alkaline solution for 24~72h, and then washed with deionized water until neutral to obtain an anion exchange membrane containing a perfluorinated main chain and cross-linked structure.