Method for preparing sulfonic acid group-type anion resin, sulfonic acid group-type anion resin, and anion exchange membrane

Abstract

The present application provides a method for preparing a sulfonic acid group-type anion resin: a sulfonate compound is used as a quaternization reagent to cause a nitrogen-containing compound to undergo a quaternization reaction, the reaction temperature being 25-120 °C, and the reaction time being 3-72 hours, thereby obtaining a sulfonic acid group-type anion resin; the nitrogen-containing compound comprises at least one of segment I, segment II, and segment III. Segment I is [Formula 1], segment II is [Formula 2], and segment III is [Formula 3].

Description

Method for preparing sulfonic acid group type anion resin, sulfonic acid group type anion resin and anion exchange membrane

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on January 29, 2024, with application number 2024101234039. The entire contents of the above application are incorporated by reference into this application. Technical Field

[0002] The present application belongs to the field of battery technology, and specifically relates to a method for preparing a sulfonic acid type anion resin, a sulfonic acid type anion resin, and an anion exchange membrane. Background Art

[0003] Anion exchange membranes are a crucial component of anion exchange membrane electrolyzers. Their function is to conduct OH- from the cathode to the anode while simultaneously preventing direct transfer of gases and electrons between the electrodes. Anion exchange membranes are typically composed of a polymer backbone and charged ion-conducting groups, connected by long or short side chains. In the prior art, anion exchange resins are typically prepared by quaternizing polymers containing tertiary amine nitrogen with halogenated hydrocarbons. Common halogenated hydrocarbons include methyl iodide, methyl bromide, propyl bromide, dibromopentane, methyl chloride, and benzyl chloride. While these reagents offer strong alkylation activity, they are all toxic. Furthermore, the presence of halide ions can poison the water electrolysis catalyst, thereby affecting electrolyzer performance. Technical issues

[0004] The present application aims to solve the following technical problems: reducing the use of highly toxic quaternary ammonium reagents in the preparation of anion exchange resins, improving the safety of the anion exchange resin preparation process, and reducing the adverse effects of residual quaternary ammonium reagents on electrolytic cell performance. Technical Solutions

[0005] In the first aspect, the present application provides a method for preparing a sulfonic acid anion resin: using a sulfonic acid ester compound as a quaternizing agent to cause a nitrogen-containing compound to undergo a quaternization reaction, the reaction temperature is 25 to 120° C., and the reaction time is 3 to 72 hours to prepare a sulfonic acid anion resin; the nitrogen-containing compound includes at least one of segment I, segment II, and segment III; segment I is Wherein, n1 represents the degree of polymerization of segment I, n1 is an integer selected from 10 to 1,000,000, Ar1 is an aromatic structural unit, a represents the number of methylene groups, a is a positive integer, R1 and R2 are independently selected from H, hydrocarbon groups or substituted hydrocarbon groups, or R1 and R2 are connected and form a polycyclic ring together with the nitrogen atoms to which they are connected; segment II is Wherein, n2 represents the degree of polymerization of segment II, Ar2 is an aromatic structural unit, R3 and R4 are independently selected from H, hydrocarbon or substituted hydrocarbon groups; segment III is Wherein, n3 represents the degree of polymerization of segment III, Ar3 is an aromatic structural unit, and R5 and R6 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group.

[0006] In the second aspect, the present application provides a sulfonic acid type anion exchange resin, which includes at least one of segment V, segment VI, and segment VII; segment V is Wherein, n4 represents the degree of polymerization of segment V, Ar1 is an aromatic structural unit, a represents the number of methylene groups, a is a positive integer, R1 and R2 are independently selected from H, hydrocarbon groups or substituted hydrocarbon groups, or R1 and R2 are connected to form a polycyclic ring together with the nitrogen atoms to which they are connected; segment VI is Wherein, n5 represents the degree of polymerization of segment VI, Ar2 is an aromatic structural unit, R3 and R4 are independently selected from H, hydrocarbon group or substituted hydrocarbon group; segment VII is Wherein, n6 represents the degree of polymerization of segment VII, Ar3 is an aromatic structural unit, and R5 and R6 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group.

[0007] In a third aspect, the present application provides a method for preparing an anion exchange membrane: the membrane is prepared using the sulfonic acid type anion resin as described above. Beneficial effects

[0008] The method for preparing a sulfonic acid anion resin provided herein utilizes a nitrogen-containing compound having a specific chain segment as a reaction raw material. The nitrogen-containing compound undergoes a quaternization reaction with a sulfonate compound, achieving a high quaternization efficiency (the quaternization efficiency can be as high as 95% or more), thereby efficiently producing a sulfonic acid anion exchange resin. Furthermore, the method eliminates the need for highly toxic quaternization agents such as alkyl halides and dimethyl sulfate, significantly improving the safety of the anion exchange resin preparation. Furthermore, the method utilizes inexpensive raw materials, is simple to operate, and operates under mild reaction conditions, thus possessing significant economic value.

[0009] The sulfonic acid anion exchange resin provided herein does not contain halogens. When used in an electrolytic cell, it does not introduce halogens into the cell, thereby maintaining good electrochemical performance. Furthermore, the sulfonic acid anion exchange resin exhibits excellent film-forming properties, enabling the production of smooth, transparent anion exchange membranes.

[0010] The anion exchange membrane provided in the present application has good mechanical properties. At the same time, during the application process, it will not introduce halogen into the electrolytic cell, so that the electrolytic cell using the anion exchange membrane maintains good electrochemical properties. Modes for Carrying Out the Invention

[0011] In one embodiment, n1, n2, and n3 are independently selected from integers between 10 and 1,000,000. n1 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n2 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n3 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0012] In one embodiment, n1, n2, and n3 are each independently selected from integers between 50 and 300. n1 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable. n2 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable. n3 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable.

[0013] In one embodiment, the structure of the sulfonate compound conforms to the general formula IV, which is Among them, R x is selected from one of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl, R y is selected from one of an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group. x The choice of R will have a certain impact on the quaternization efficiency. x The sulfonate compounds containing R y The choice of R will have a certain influence on the water absorption of the anion exchange membrane. y The sulfonate compounds containing the sulfonate group can make the prepared anion exchange membrane have good water absorption.

[0014] In one embodiment, in Formula IV, R y is selected from phenyl, o-tolyl, naphthyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0015] In one embodiment, the sulfonate compound includes at least one of methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allylsulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, or cyclohexyl p-toluenesulfonate.

[0016] In one embodiment, the reaction temperature of the quaternization reaction is 70-120°C, and the reaction time is 8-36 hours. The reaction temperature of the quaternization reaction can be 70°C, 80°C, 90°C, 100°C, 110°C, or 120°C, but is not limited to the values ​​listed above. Other values ​​not listed within the numerical range of the reaction temperature are also applicable. The reaction time of the quaternization reaction can be 8 hours, 16 hours, 24 hours, 32 hours, or 36 hours, but is not limited to the values ​​listed above. Other values ​​not listed within the numerical range of the reaction time are also applicable.

[0017] In one embodiment, the method for preparing a sulfonic acid anion resin comprises the following steps: Step 1. Mixing a nitrogen-containing compound, a sulfonic acid ester compound, and an organic solvent to obtain a reaction solution; then subjecting the nitrogen-containing compound and the sulfonic acid ester in the reaction solution to a quaternization reaction to obtain a product solution; Step 2. Mixing the product solution with a precipitant, separating, collecting, washing, and drying the resulting precipitate to obtain a solid, which is a sulfonic acid anion resin.

[0018] In one embodiment, the organic solvent includes at least one of chloroform, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.

[0019] In one embodiment, the precipitant includes at least one of ethanol, ethyl acetate, ethylene glycol, diethyl ether, tetrahydrofuran, acetone, and water.

[0020] In one embodiment, n4, n5, and n6 are independently selected from integers between 10 and 1,000,000.

[0021] In one embodiment, n4, n5, and n6 are independently selected from integers between 10 and 300.

[0022] In one embodiment, R a 、R c 、R e are independently selected from one of an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group, Rb 、R d 、R f Each is independently selected from one of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl.

[0023] In one embodiment, R a 、R c 、R e Each is independently selected from phenyl, o-tolyl, naphthyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0024] In one embodiment, Ar1, Ar2, and Ar3 are independently selected from By selecting the above aromatic structural units to construct the main chain of the sulfonic acid group anion resin, the obtained sulfonic acid group anion resin has excellent alkali resistance and stability.

[0025] In one embodiment, in segment V, Ar1 is

[0026] In one embodiment, segment V is

[0027] In one embodiment, in segment VI, Ar2 is

[0028] In one embodiment, segment VI is

[0029] In one embodiment, in segment VII, Ar3 is

[0030] In one embodiment, segment VII is

[0031] In one embodiment, the preparation method includes the following operations: S1. dissolving a sulfonic acid anion resin to prepare an anion exchange resin solution, wherein the content of the sulfonic acid anion resin in the anion exchange resin solution is 5 to 40 wt %; S2. scraping the anion exchange resin solution to obtain an anion exchange membrane.

[0032] In one embodiment, in S2, the scraping film temperature is 40-120° C. The scraping film temperature may be 40° C., 70° C., 80° C., 100° C., or 120° C., but is not limited to the listed values. Other values ​​not listed within the above scraping film temperature range are also applicable.

[0033] In one embodiment, the sulfonate content in the anion exchange membrane is greater than 50 ppm. The sulfonate content in the anion exchange membrane may be 55 ppm, 70 ppm, 90 ppm, 120 ppm, or 180 ppm, but is not limited to the values ​​listed above. Other values ​​not listed within the above range of sulfonate content are also applicable.

[0034] In the following examples and comparative examples, the test and calculation methods of the "quaternization efficiency" involved are as follows:

[0035] a. Determination of ion exchange capacity (IEC)

[0036] Anion exchange membranes were prepared using anion resins obtained through quaternization. Membrane samples were then cut into 50×50 mm sections and immersed in a 1 mol / L potassium hydroxide solution at 80°C for 24 hours to exchange anions with hydroxide, resulting in a hydroxide-type membrane sample. The hydroxide-type membrane sample was then immersed in a 1 mol / L NaCl solution at 60°C for 48 hours to exchange hydroxides with chloride ions, resulting in a chloride-type membrane sample. The chloride-type membrane sample was then washed thoroughly with deionized water to ensure that all NaCl adsorbed on the membrane was completely washed away. The surface moisture of the chloride-type membrane sample was then absorbed with filter paper and placed in 50 mL of a 0.1 mol / L NaNO₃ solution at 60°C for 48 hours to completely exchange chloride ions. The amount of chloride ions exchanged from the NaNO3 solution is equal to the amount of anions to be measured in the anion exchange membrane made from the anion resin obtained through the quaternization reaction. To titrate the chloride ion content in the membrane: add 10 mL of NaNO3 solution that has been fully soaked in the chloride-type membrane sample to a conical flask, and add two drops of K2CrO4 as an indicator. Titrate the NaNO3 solution with a calibrated 0.01 mol / L AgNO3 until a brick-red precipitate is produced. Record the volume of the consumed AgNO3 solution, which is recorded as V. AgNO3 Titrate in parallel 3 times and take the average value to calculate the chloride ion content in the chloride-type membrane sample. Finally, take out the membrane sample and wash it thoroughly with deionized water. After it is fully dried in the oven, take it out quickly and weigh the mass of the dry membrane, which is recorded as m dry The ion exchange capacity of the membrane sample can be calculated by the formula: IEC = 5 × C AgNO3 ×V AgNO3 / m dry , where: IEC is the ion exchange capacity of the membrane sample, in mol / g; C AgNO3 V is the concentration of the calibrated AgNO3 solution, in mol / L, and the average value of three titration results is taken; AgNO3The volume of AgNO3 solution consumed in titration is L, and the average of three titrations is taken; m dry It is the mass of the dry membrane sample after titration and drying, and the unit is g.

[0037] b. Grafting rate calculation formula

[0038] The grafting rate is the ratio of the grafting rate to the theoretical grafting rate, that is, the grafting rate = (IEC 实际 / IEC 理论 )*100%.

[0039] Example 1

[0040] In this embodiment, four treatment groups are set, which are marked as treatment group 1, treatment group 2, treatment group 3 and treatment group 4. Each treatment group selects different raw material monomers to prepare nitrogen-containing compounds. Among them, treatment group 1 and treatment group 2 prepare the general chain segment I The nitrogen-containing compound composed of the general chain segment II is prepared by processing group 3 The nitrogen-containing compound composed of the general chain segment Ⅲ is prepared by processing group 4 Nitrogen-containing compounds.

[0041] (1) Treatment group 1:

[0042] S1. Using 9,9-dimethylfluorene As the aromatic monomer to prepare the monomer raw material, dimethylamino acetal ethylene glycol is used As the branched monomer raw materials, 0.15 mol of 9,9-dimethylfluorene and 0.18 mol of dimethylamino acetal ethylene glycol were weighed respectively;

[0043] S2. The weighed 9,9-dimethylfluorene and dimethylamino acetal ethylene glycol were added into 50 mL of dichloromethane and fully dispersed to obtain a reaction bottom liquid;

[0044] S3. First, the temperature of the reaction liquid was lowered to 0°C, 120 mL of trifluoromethanesulfonic acid was added thereto, and the mixture was stirred thoroughly. Then, the temperature of the reaction liquid was raised to 13°C, and the polymerization was carried out under this temperature condition for 36 hours. The resulting reaction liquid was discharged from the mixture and soaked in water for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound obtained in this treatment group is Wherein, degree of polymerization n1=65.

[0045] (2) Treatment Group 2:

[0046] S1. Using 9,9-dimethylfluorene As the aromatic monomer, 1-piperidinyl acetaldehyde diethyl acetal was used to prepare the monomer raw material. As branched monomer raw materials, 0.16 mol of 9,9-dimethylfluorene and 0.18 mol of 1-piperidineacetaldehyde diethyl acetal were weighed respectively;

[0047] S2. The weighed 9,9-dimethylfluorene and dimethylamino acetal ethylene glycol were put into 50 mL of dichloromethane and fully dispersed to obtain a reaction bottom liquid;

[0048] S3. First, the temperature of the reaction liquid was lowered to 0°C, 120 mL of trifluoromethanesulfonic acid was added thereto, and the mixture was stirred thoroughly. Then, the temperature of the reaction liquid was raised to 13°C, and the polymerization was carried out under this temperature condition for 24 hours. The resulting material was immersed in water for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound obtained in this treatment group is Wherein, degree of polymerization n1=80.

[0049] (3) Treatment group 3

[0050] S1. Using terphenyl As the aromatic monomer, N-methyl-4-piperidone was used to prepare the monomer raw material. As the branched monomer raw materials, 0.005 mol of p-terphenyl and 0.005 mol of N-methyl-4-piperidone were weighed respectively;

[0051] S2. The weighed terphenyl and N-methyl-4-piperidone were added to 20 mL of dichloromethane and fully dispersed to obtain a reaction bottom solution;

[0052] S3. The temperature of the reaction liquid was first lowered to 0°C, 3.6 mL of trifluoroacetic acid was added thereto, and after stirring for 30 minutes, 45 mL of trifluoromethanesulfonic acid was added thereto. The reaction liquid was then heated to 13°C and polymerized under this temperature for 13 hours. The resulting product was immersed in water for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical formula of the nitrogen-containing compound obtained in this treatment group is Wherein, degree of polymerization n2=92.

[0053] (4) Treatment group 4

[0054] S1. Using diphenylethylene As an aromatic monomer, indole-2,3-dione was used to prepare the monomer raw material. As the branched monomer raw materials, 0.005 mol of stilbene and 0.006 mol of indole-2,3-dione were weighed respectively;

[0055] S2. The weighed stilbene and indole-2,3-dione were added to 15 mL of dichloromethane and fully dispersed to obtain a reaction base solution;

[0056] S3. The temperature of the reaction liquid was first lowered to 0°C, 3.6 mL of trifluoroacetic acid was added thereto, and after stirring for 30 minutes, 50 mL of trifluoromethanesulfonic acid was added thereto. The reaction liquid was then heated to 13°C and polymerized under this temperature for 8 hours. The resulting material was immersed in water for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical formula of the nitrogen-containing compound obtained in this treatment group is Wherein, degree of polymerization n3=145.

[0057] Example 2

[0058] Based on the nitrogen-containing compound prepared in Example 1, this example further uses the above nitrogen-containing compound as a raw material for preparing a sulfonic acid anion resin, and uses a sulfonic acid ester compound as a quaternizing agent to cause the nitrogen-containing compound to undergo a quaternization reaction to prepare a sulfonic acid anion resin. The structure of the above sulfonic acid ester compound conforms to the general formula IV, which is The specific sulfonate compounds selected are clearly shown in Tables 1 to 4. In other embodiments, sulfonate compounds conforming to the general formula IV are selected as quaternary ammonium agents. According to the specific circumstances, R x is selected from one of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl, R y One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

[0059] This example is divided into different treatment groups according to the different nitrogen-containing compounds used to prepare the sulfonic acid anion resin, specifically labeled as treatment group 1, treatment group 2, treatment group 3, and treatment group 4. The specific operations for preparing the sulfonic acid anion resin in these treatment groups are as follows:

[0060] Step 1. The nitrogen-containing compound and the sulfonate compound are dissolved in N-methylpyrrolidone to obtain a reaction solution, and then the nitrogen-containing compound and the sulfonate in the reaction solution are quaternized at 25 to 120 ° C for 3 to 72 hours. After completion of the reaction, a product solution containing a sulfonic acid group-type anion resin is obtained;

[0061] Step 2. A precipitant is added to the product solution. In this embodiment, deionized water is used as the precipitant. The resulting mixed liquid system is allowed to stand to allow the precipitate to fully precipitate. The precipitate is then filtered out and washed and dried. The solid obtained is the sulfonic acid anion resin obtained by the above-mentioned quaternization reaction.

[0062] (1) Treatment group 1

[0063] This treatment group used the As the nitrogen-containing compound in the reactant for preparing the sulfonic acid type anion exchange resin, different sulfonate compounds are used as quaternary ammonium reagents. Different groups are further set based on the different sulfonate compounds, marked as treatment group 1-1, treatment group 1-2, and treatment group 1-3. Table 1 shows the use of The optimal reaction conditions for the quaternization reaction with different sulfonate compounds are as follows. When the specific material types of the nitrogen-containing compound and the sulfonate compound are determined, the quaternization reaction completed according to the reaction conditions shown in Table 1 has the highest quaternization efficiency. The general structural formula of the sulfonic acid type anion resin prepared in treatment group 1 of this embodiment meets the requirements of

[0064] Table 1. Optimal quaternization conditions corresponding to the material combinations involved in each group of treatment group 1 in Example 2

[0065] (2) Treatment group 2

[0066] This treatment group used the As the nitrogen-containing compound in the reactant for preparing the sulfonic acid type anion exchange resin, different sulfonate compounds were used as quaternary ammonium reagents. Different groups were further set based on the different sulfonate compounds, and marked as treatment group 2-1, treatment group 2-2, and treatment group 2-3. Table 2 shows the use of The optimal reaction conditions for quaternization reaction with different sulfonate compounds are as follows. When the specific material types of nitrogen-containing compounds and sulfonate compounds are determined, the quaternization reaction completed according to the reaction conditions shown in Table 2 has the highest quaternization efficiency. The general structural formula of the sulfonic acid type anion resin prepared in treatment group 2 of this embodiment meets the requirements of

[0067] Table 2. Optimal quaternization conditions corresponding to the material combinations involved in each group of treatment group 2 in Example 2

[0068] (3) Treatment group 3

[0069] This treatment group used the As the nitrogen-containing compound in the reactant for preparing the sulfonic acid type anion exchange resin, different sulfonate compounds were used as quaternary ammonium reagents. Different groups were further set based on the different sulfonate compounds, and marked as treatment group 3-1, treatment group 3-2, and treatment group 3-3. Table 3 shows the use of The optimal reaction conditions for quaternization reaction with different sulfonate compounds are as follows. When the specific material types of nitrogen-containing compounds and sulfonate compounds are determined, the quaternization reaction completed according to the reaction conditions shown in Table 3 has the highest quaternization efficiency. The general structural formula of the sulfonic acid type anion resin prepared in treatment group 3 of this embodiment meets the requirements of

[0070] Table 3. Optimal quaternization conditions corresponding to the material combinations involved in each group of treatment group 3 in Example 2

[0071] (4) Treatment group 4

[0072] Treatment group 4, this treatment group was prepared using Example 1 As the nitrogen-containing compound in the reactant for preparing the sulfonic acid type anion exchange resin, different sulfonate compounds were used as quaternary ammonium reagents. Different groups were further set based on the different sulfonate compounds, and marked as treatment group 4-1, treatment group 4-2, and treatment group 4-3. Table 4 shows the use of The optimal reaction conditions for the quaternization reaction with different sulfonate compounds are as follows. When the specific material types of the nitrogen-containing compound and the sulfonate compound are determined, the quaternization reaction completed according to the reaction conditions shown in Table 4 has the highest quaternization efficiency. The general structural formula of the sulfonic acid type anion resin prepared in treatment group 4 of this embodiment meets the requirements of

[0073] Table 4. Optimal quaternization conditions corresponding to the material combinations involved in each group of treatment group 4 in Example 2

[0074] Comparative Example 1

[0075] 1. Preparation of nitrogen-containing compounds

[0076] S1. Prepare the monomer raw material using p-terphenyl as the aromatic monomer and 3-quinine brass hydrochloride as the branched monomer raw material, and weigh 0.005 mol p-terphenyl and 0.006 mol 3-quinine brass hydrochloride respectively;

[0077] S2. The weighed amount of p-terphenyl and 3-quinine brass hydrochloride was added to 20 mL of dichloromethane and fully dispersed to obtain a reaction base solution;

[0078] S3. First, the temperature of the reaction liquid was lowered to 0°C, 50 mL of trifluoromethanesulfonic acid was added thereto, and then the reaction liquid was heated to 60°C and polymerized under this temperature condition for 16 hours. The resulting product was immersed in water and soaked for 12 hours, filtered and dried to obtain the product of this treatment group. The product was washed and dried in pure water or aqueous solution to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound obtained in this treatment group is Wherein, the degree of polymerization n3=75.

[0079] 2. Quaternization reaction

[0080] The nitrogen-containing compound prepared in this comparative example is used as a raw material for preparing a sulfonic acid anion resin, and a sulfonic acid ester compound is used as a quaternizing agent to cause the nitrogen-containing compound to undergo a quaternization reaction to prepare a sulfonic acid anion resin. This comparative example utilizes the above-mentioned nitrogen-containing compound and different sulfonic acid ester compounds to be matched as raw materials, and the preparation of the sulfonic acid anion resin is completed with reference to the specific operation of preparing the sulfonic acid anion resin recorded in Example 2. Different groups are further set according to the different sulfonic acid ester compounds, marked as comparative group 1-1, comparative group 1-2, comparative group 1-3, and comparative group 1-4. Table 5 shows the optimal reaction conditions corresponding to the different reactant material combinations in this comparative example. When the specific material types of the nitrogen-containing compound and the sulfonic acid ester compound are matched, the quaternization reaction completed according to the reaction conditions shown in Table 5 has the highest corresponding quaternization efficiency.

[0081] Table 5. Optimal quaternization conditions corresponding to the material combinations involved in each group of Comparative Example 1

[0082] In each group of this comparative example: the quaternizing agent used in comparative group 1-1 is the same as the quaternizing agent used in treatment group 1-1 of Example 2; the quaternizing agent used in comparative group 1-2 is the same as the quaternizing agent used in treatment group 2-1 of Example 2; the quaternizing agent used in comparative group 1-3 is the same as the quaternizing agent used in treatment group 3-1 of Example 2; and the quaternizing agent used in comparative group 4-1 is the same as the quaternizing agent used in treatment group 4-1 of Example 2. By comparing the above, it can be found that when a nitrogen-containing compound undergoes a quaternization reaction under the action of a sulfonate compound, when the type of sulfonate compound selected is the same, the type of nitrogen-containing compound has a significant impact on the quaternization efficiency. Compared with the nitrogen-containing polymer used in this comparative example, the several nitrogen-containing compounds prepared in Example 1 have less steric hindrance, resulting in a significantly higher quaternization efficiency when the several nitrogen-containing compounds prepared in Example 1 interact with the sulfonate compound.

[0083] Comparative Example 2

[0084] In this comparative example, methyl iodide was used as a quaternizing agent, and different nitrogen-containing compounds prepared in Example 1 were subjected to quaternization reaction with methyl iodide to prepare halogen-type anion resins. Different groups were set according to the types of nitrogen-containing compounds selected, specifically marked as comparative group 2-1, comparative group 2-2, comparative group 2-3, and comparative group 2-4. The specific grouping of each group is shown in Table 6.

[0085] Table 6. Comparative Example 2: Reactant Matching of Each Comparative Group

[0086] The specific operations of each group for preparing halogen-type anion resin are as follows:

[0087] S1. Dissolve the nitrogen-containing compound in DMSO solution (the mass volume ratio of nitrogen-containing polymer to DMSO is 1 g:5 mL), and add 3 eqv of iodomethane at room temperature;

[0088] S2. The reaction solution obtained in S1 was reacted at 80°C for 24 hours, and then the reaction solution was poured into ethyl acetate to precipitate a solid, which was filtered and washed with ethanol. The prepared resin was then exchanged for alkali and chlorine with 3 L of 1 M KOH and 1 M NaC aqueous solutions at 80°C, filtered, and washed with water to obtain a halogen-type anion exchange resin.

[0089] Example 3

[0090] Anion exchange membranes were prepared using the sulfonic acid anion resins prepared in Example 2 according to the following method:

[0091] S1. The sulfonic acid type anion exchange resin was dissolved in dimethyl sulfoxide at 80 ° C to obtain an anion exchange resin solution having a sulfonic acid type anion exchange resin content of 20 wt%;

[0092] S2. Pour the anion exchange resin solution prepared in S1 onto an automatic film scraping machine. Adjust the scraper height according to actual needs. Scrape out films of different thicknesses at 60°C and dry them at high temperature to obtain an anion exchange membrane.

[0093] Comparative Example 3

[0094] Anion exchange membranes were prepared using the anion resins prepared in Comparative Example 2 according to the following method:

[0095] S1. The anion exchange resin was dissolved in dimethyl sulfoxide at 80 ° C to obtain an anion exchange resin solution having an anion exchange resin content of 20 wt%;

[0096] S2. Pour the anion exchange resin solution prepared in S1 onto an automatic film scraping machine. Adjust the scraper height according to actual needs. Scrape out films of different thicknesses at 60°C and dry them at high temperature to obtain an anion exchange membrane.

[0097] Test Example 1

[0098] 1. Test subjects

[0099] The anion exchange membranes prepared in Example 3 and Comparative Example 3 were used as test objects. In this test example, anion exchange membranes with the same anion exchange resin content were selected as test objects to eliminate the difference in the performance of the anion exchange membrane caused by different anion exchange resin contents.

[0100] 2. Test items

[0101] (1) Nuclear magnetic resonance (1H NMR) characterization

[0102] The structure of the polymer was characterized by nuclear magnetic resonance (NMR) characterization using a Swiss AVIII 500HD superconducting NMR spectrometer with tetramethylsilane as the internal standard and deuterated DMSO as the solvent.

[0103] (2) Tensile strength and elongation at break test of anion exchange membrane

[0104] A Shimadzu AG-I 1KN universal testing machine was used to test the elongation at break and tensile strength of anion exchange membranes. The membranes were cut into dumbbell shapes along both the length (X-axis) and width (Y-axis). The edges of the samples should be smooth and free of notches. Notches can be inspected with a low-power magnifying glass, and samples with defective edges were discarded. The length, width, and thickness of the membranes were measured before testing. The tensile rate was 10 mm / min. -1 The measurement results of each membrane are the average of at least three samples.

[0105] (3) Ion residue test

[0106] a. Use an oxygen bomb IC to test the iodide ion content in the anion exchange resin: ion chromatography was performed using an Ion Pac AS11 analytical column (4 mm × 250 mm) and an Ion Pac AG11 guard column (4 mm × 50 mm), with 30 mmol / L potassium hydroxide solution as the eluent, a flow rate of 1 mL / min, a column temperature of 30°C, and detection with a conductivity detector.

[0107] b. Use a UV-visible spectrophotometer to detect the sulfonate content (taking p-toluenesulfonate as an example): Configure a standard curve. Use a UV-visible spectrophotometer to scan the spectra of aqueous solutions of methyl p-toluenesulfonate at concentrations of 2 mmol / L, 1 mmol / L, and 0.4 mmol / L, respectively, and determine the maximum absorption wavelength at 261 nm. At this wavelength, set the concentration range to 0.5-4 mmol / L, control the absorbance to the range of 0.2-0.8, and create a standard curve. The correlation coefficient of the standard curve is r = 0.9999 (> 0.99), proving that the standard curve is valid and can be tested normally. Configure the sample solution to be tested.

[0108] (4) Water electrolysis single cell performance test (single cell pressure)

[0109] The battery performance was tested using a multi-channel Ivium electrochemical workstation at 0-1 A / cm 2 Under the current of , set 10 current steps, test each step for 10s, record a voltage value per second, and record the average voltage on each current step.

[0110] 3. Test results

[0111] From the test results of this test example, it can be seen that the electrolytic cell pressure of the anion exchange membrane using the anions prepared in Example 3 is lower than the electrolytic cell pressure of the anion exchange membrane using the anions prepared in Comparative Example 3. This shows that under the conditions of water electrolysis, compared with the anion exchange membrane made by applying a halogen-type anion resin, the anion exchange membrane made by applying a sulfonic acid-type anion resin is applied to the electrolytic cell, and the cell pressure is lower and the energy consumption is lower when electrolyzing water. Even after the anion exchange membrane made by applying a halogen-type anion resin is replaced with alkali and chlorine, there are still more halogen ions remaining in the membrane material. The residual halogen ions will poison the electrode catalyst and affect its electrocatalytic efficiency. At the same current density, it is reflected as a higher cell pressure.

[0112] Table 7. Test result statistics

Claims

1. A method for preparing a sulfonic acid type anionic resin, A sulfonic acid ester compound is used as a quaternizing agent to cause a nitrogen-containing compound to undergo a quaternization reaction at a reaction temperature of 25 to 120° C. for a reaction time of 3 to 72 hours to obtain the sulfonic acid group-type anionic resin; The nitrogen-containing compound includes at least one of segment I, segment II, and segment III; The segment I is in, n1 represents the degree of polymerization of segment I, Ar1 is an aromatic structural unit, a represents the number of methylene groups, said a is a positive integer, R1 and R2 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group, or said R1 and R2 are connected to form a polycyclic ring together with the nitrogen atom to which they are connected; The segment II is wherein n2 represents the degree of polymerization of segment II, Ar2 is an aromatic structural unit, and R3 and R4 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group; The segment III is Wherein, n3 represents the degree of polymerization of segment III, Ar3 is an aromatic structural unit, and R5 and R6 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group.

2. The method of claim 1 , wherein: The structure of the sulfonate compound conforms to the general formula IV, which is: Among them, the R x is selected from one of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl, wherein R y One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

3. The method of claim 2, wherein: In the general formula IV, the R y is selected from phenyl, o-tolyl, naphthyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

4. The method of claim 3 , wherein: The sulfonate compound includes at least one of methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allylsulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate or cyclohexyl p-toluenesulfonate.

5. The method of claim 1 , wherein: The reaction temperature of the quaternization reaction is 70 to 120° C., and the reaction time is 8 to 36 hours.

6. The method of any one of claims 1 to 5, wherein: The following steps are involved: Step 1. mixing the nitrogen-containing compound, the sulfonate compound and an organic solvent to obtain a reaction solution, and then allowing the nitrogen-containing compound and the sulfonate in the reaction solution to complete the quaternization reaction to obtain a product solution; Step 2. Mixing the product solution with a precipitant, separating, collecting, washing, and drying the resulting precipitate, thereby obtaining the solid that is the sulfonic acid type anion resin.

7. The method of claim 6, wherein: The organic solvent includes at least one of chloroform, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.

8. The method of claim 6, wherein: The precipitant comprises at least one of ethanol, ethyl acetate, ethylene glycol, ethyl ether, tetrahydrofuran, acetone and water.

9. A sulfonic acid type anion resin, The anion exchange resin includes at least one of segment V, segment VI, and segment VII; The segment V is in, n4 represents the degree of polymerization of segment V, Ar1 is an aromatic structural unit, a represents the number of methylene groups, a is a positive integer, R1 and R2 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group, or the R1 and R2 are connected to form a polycyclic ring together with the nitrogen atom to which they are connected; The segment VI is wherein n5 represents the degree of polymerization of segment VI, Ar2 is an aromatic structural unit, and R3 and R4 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group; The segment VII is Wherein, n6 represents the degree of polymerization of segment VII, Ar3 is an aromatic structural unit, and R5 and R6 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group.

10. The sulfonic acid type anion resin according to claim 9, wherein: The R a 、The R c 、The R e are independently selected from one of an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group, wherein R b 、The R d 、The R f Each is independently selected from one of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl and benzyl.

11. The sulfonic acid type anion resin according to claim 10, wherein: The R a 、The R c 、The R e Each is independently selected from phenyl, o-tolyl, naphthyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

12. The sulfonic acid type anion resin according to claim 9, wherein: The Ar1, Ar2, and Ar3 are independently selected from 13. The sulfonic acid type anion resin according to claim 12, wherein: In the segment V, Ar1 is 14. The sulfonic acid type anion resin according to claim 12, wherein: The segment V is 15. The sulfonic acid type anion resin according to claim 12, wherein: In the segment VI, the Ar2 is 16. The sulfonic acid type anion resin according to claim 12, wherein: In the segment VII, the Ar3 is 17. A method for preparing an anion exchange membrane, which is prepared using the sulfonic acid type anion resin according to any one of claims 9 to 16.

18. The anion exchange membrane according to claim 17, wherein Preparation method thereof The following operations are included: S1 dissolving the sulfonic acid type anion resin to form an anion exchange resin solution, in the anion exchange resin solution, the content of the sulfonic acid type anion resin is 5 to 40wt%; S2. scraping the anion exchange resin solution to obtain the anion exchange membrane.

19. The anion exchange membrane according to claim 18, wherein: In the step S2, the film scraping temperature is 40-120°C.

20. The anion exchange membrane according to any one of claims 17 to 19, wherein: The sulfonate content in the anion exchange membrane is greater than 50 ppm.

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