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

Abstract

To provide a method for producing a sulfonic acid-type anion resin, a sulfonic acid-type anion resin, and an anion exchange membrane, which can eliminate the use of highly toxic quaternizing agent in the preparation of anion exchange resins, improve the safety during the preparation thereof, and prevent the residual of the quaternizing agent from adversely affecting the performance of the electrolyzer.SOLUTION: Sulfonic acid ester compounds are used as quaternizing agents, and nitrogen-containing compounds are subjected to a quaternization reaction to produce sulfonic acid-type anion resins. The reaction temperature ranges from 25 to 120°C, and the reaction time is 3 to 72 hours. The nitrogen-containing compound includes at least one of the three segments obtained by polycondensation of aromatic hydrocarbons and aldehydes having dialkylamino groups, 4-piperidone derivatives, or indole-2,3-dione.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority from a Chinese patent application bearing application number 2024101234039, filed with the China Patent Office on January 29, 2024, the entire contents of which are incorporated herein by reference.

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

[0003] Anion exchange membrane is an important component of the electrolytic cell, and its function is to - The objective of an anion exchange membrane is to conduct charged ions from the cathode to the anode while preventing the direct transfer of gases and electrons between the electrodes. Anion exchange membranes generally consist of a polymer backbone and charged ion-conducting groups, which are connected via long or short branched chains. In the prior art, anion exchange resins are typically prepared by quaternizing a polymer containing tertiary amine nitrogen with a halogenated hydrocarbon. Common alkyl halides include iodomethane, bromomethane, bromopropane, dibromopentane, chloromethane, and benzyl chloride. While these reagents offer high alkylation activity, they are all toxic. Furthermore, the halogen ions present can poison the electrolysis water catalyst, thereby affecting the performance of the electrolysis cell. Summary of the Invention [Problem to be solved by the invention]

[0004] The present application provides a method for producing a sulfonic acid type anion resin, a sulfonic acid type anion resin, and an anion exchange membrane, which reduce the use of highly toxic quaternization reagents in the production of anion exchange resins, improve the safety of the anion exchange resin production process, and mitigate the adverse effects of residual quaternization reagents on electrolytic cell performance. [Means for solving the problem]

[0005] According to a first aspect, the present application provides a method for producing a sulfonic acid type anionic resin, using a sulfonic acid ester compound as a quaternizing reagent, and subjecting a nitrogen-containing compound to a quaternization reaction to obtain a sulfonic acid type anionic resin, the reaction temperature being 25 to 120°C, the reaction time being 3 to 72 hours, and the nitrogen-containing compound comprising at least one of Segment I, Segment II, and Segment III, wherein Segment I is: [ka] wherein n1 represents the degree of polymerization of Segment I, and n1 is selected from integers between 10 and 1,000,000; Ar1 is an aryl structural unit; a represents the number of methylene groups, and a is a positive integer; R1 and R2 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group; or R1 and R2 are connected to each other and form a multi-membered ring together with the N atom connected thereto; and Segment II is [ka] where n2 represents the degree of polymerization of Segment II, Ar2 is an aryl structural unit, R3 and R4 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, and Segment III is [ka] where n3 represents the degree of polymerization of segment III, Ar3 is an aryl structural unit, and R5 and R6 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0006] According to a second aspect, the present application provides a sulfonic acid type anionic resin, the anionic resin comprising at least one of Segment V, Segment VI, and Segment VII, wherein Segment V is: [ka] wherein n4 represents the degree of polymerization of the segment V; Ar1 is an aryl structural unit; a represents the number of methylene groups, and a is a positive integer; R1 and R2 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group; or R1 and R2 are connected to each other and form a multi-membered ring together with the N atom connected thereto; Segment VI is [ka] where n5 represents the degree of polymerization of segment VI, Ar2 is an aryl structural unit, R3 and R4 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group; Segment VII is [ka] where n6 represents the degree of polymerization of segment VII, Ar3 is an aryl structural unit, and R5 and R6 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0007] According to a third aspect, the present application provides an anion exchange membrane, which is manufactured using the sulfonic acid type anion resin described above. [Effects of the Invention]

[0008] The method for producing sulfonic acid-type anion exchange resins according to the present invention employs a nitrogen-containing compound having a specific segment as a reaction raw material, and the nitrogen-containing compound and a sulfonic acid ester compound undergo a quaternization reaction, achieving a high quaternization efficiency (a quaternization efficiency of 95% or more), thereby enabling the efficient production of sulfonic acid-type anion exchange resins. Furthermore, the production of anion exchange resins using this method does not require the use of highly toxic quaternization reagents such as alkyl halides or dimethyl sulfate, significantly improving the safety of anion exchange resin production. Furthermore, the raw materials are inexpensive, the operation is simple, and the reaction conditions are mild, making the method highly economical.

[0009] The sulfonic acid type anion exchange resin according to the present application does not contain halogen, and when it is applied to an electrolytic cell, no halogen is introduced into the electrolytic cell, thereby enabling the electrolytic cell to maintain good electrochemical performance. Furthermore, the sulfonic acid type anion exchange resin has good membrane-forming properties, and can be used to produce anion exchange membranes with smooth surfaces and transparency.

[0010] The anion exchange membrane according to the present application has good mechanical properties and does not introduce halogens into the electrolytic cell when applied, so that the electrolytic cell applying the anion exchange membrane maintains good electrochemical properties. DETAILED DESCRIPTION OF THE INVENTION

[0011] In one embodiment, n1, n2, and n3 are each independently selected from integers between 10 and 1,000,000. n1 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the enumerated values, and other unenumerated values within the range are also suitable. n2 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the enumerated values, and other unenumerated values within the range are also suitable. n3 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the enumerated values, and other unenumerated values within the range are also suitable.

[0012] In one embodiment, n1, n2, and n3 are each independently selected from integers between 50 and 300. n1 may be 50, 100, 150, 300, etc., but is not limited to the enumerated values, and other unenumerated values within the range are also suitable. n2 may be 50, 100, 150, 300, etc., but is not limited to the enumerated values, and other unenumerated values within the range are also suitable. n3 may be 50, 100, 150, 300, etc., but is not limited to the enumerated values, and other unenumerated values within the range are also suitable.

[0013] In one embodiment, the structure of the sulfonate ester compound conforms to general formula IV, which is: [ka] where R x is selected from the group consisting of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl, and benzyl; R y is selected from the group consisting of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group. x The choice of R has a certain effect on the quaternization efficiency and x By using the sulfonate ester compound having the R group, the quaternization efficiency of the quaternization reaction can be further increased. y The selection of R has a certain effect on the water absorption of the resulting anion exchange membrane, y By using the sulfonate ester compound having a group, the resulting anion exchange membrane can be endowed with good water absorbency.

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

[0015] In one embodiment, the sulfonate ester compound is 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 trifluoromethane ... benzenesulfonate, methyl trifluoromethanesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl trifluoromethanesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl benzenesulfonate, methyl benzenesulfonate, methyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentyl benzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, or cyclohexyl paratoluenesulfonate ().

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

[0017] In one embodiment, the method for producing the sulfonic acid type anion resin includes the steps of: Step 1: mixing a nitrogen-containing compound, a sulfonic acid ester compound, and an organic solvent to obtain a reaction solution; then completing a quaternization reaction between the nitrogen-containing compound and the sulfonic acid ester in the reaction solution to obtain a product solution; and Step 2: mixing the product solution with a precipitant; separating, collecting, washing, and drying the resulting precipitate; and converting the resulting solid into a sulfonic acid type anion resin.

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

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

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

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

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

[0023] In one embodiment, R a and R c and R e are each independently selected from a phenyl group, an orthotolyl group, a naphthyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0024] In one embodiment, Ar1, Ar2, and Ar3 are each independently [ka] By using the aromatic structural unit to construct the main chain of the sulfonic acid type anionic resin, the resulting sulfonic acid type anionic resin has excellent alkali resistance stability.

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

[0026] In one embodiment, segment V is [ka] , or [ka] is.

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

[0028] In one embodiment, segment VI comprises: [ka] is.

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

[0030] In one embodiment, segment VII comprises: [ka] is.

[0031] In one embodiment, the manufacturing method includes steps S1 of dissolving a sulfonic acid type anion resin to prepare an anion exchange resin solution and adjusting the content of the sulfonic acid type anion resin in the anion exchange resin solution to 5 to 40 wt %, and S2 of wiping the membrane using the anion exchange resin solution to obtain an anion exchange membrane.

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

[0033] In one embodiment, the anion exchange membrane has a sulfonate content of >50 ppm, and may have a sulfonate content of 55 ppm, 70 ppm, 90 ppm, 120 ppm, or 180 ppm, but is not limited to the listed values. Other values within the above range of sulfonate content that are not listed are also suitable.

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

[0035] a. Measurement of ion exchange capacity (IEC) Anion exchange membranes were prepared using the anion resin obtained through the quaternization reaction. 50 x 50 mm membrane samples were then cut. The membrane samples were immersed in 1 mol / L potassium hydroxide solution at 80°C for 24 hours to exchange the anions in the membrane samples with hydroxyl groups, resulting in hydroxide-type membrane samples. The hydroxide-type membrane samples were then immersed in 1 mol / L NaCl solution at 60°C for 48 hours to exchange the hydroxyl groups in the hydroxide-type membrane samples with chloride ions, resulting in chloride-type membrane samples. The chloride-type membrane samples were thoroughly washed with deionized water to ensure that the NaCl adsorbed on the chloride-type membrane samples was completely removed. The surface of the chloride-type membrane samples was then absorbed with filter paper and placed in 50 mL of 0.1 mol / L NaNO3 solution for 48 hours at 60°C to completely exchange the chloride ions in the membrane samples with NaNO3 solution. The amount of chloride ions exchanged in the NaNO3 solution is equal to the amount of anions to be measured in the anion exchange membrane produced with the anion resin obtained through the above quaternization reaction. To titrate the chloride ion content in the membrane, add 10 mL of NaNO3 solution to a conical flask in which the chloride-type membrane sample has been thoroughly immersed, add two drops of K2CrO4 as an indicator, and titrate the above NaNO3 solution using the already standardized 0.01 mol / L AgNO3 until a brick-colored precipitate appears. Record the volume of the consumed AgNO3 solution and calculate V. AgNO3The parallel titration is carried out three times, and the average value is taken to calculate the chloride ion content in the chloride-type membrane sample. Finally, the membrane sample is taken out and thoroughly washed with deionized water, and then thoroughly dried in a drying box. The dry membrane is quickly taken out and weighed, and the mass of the membrane is calculated. dry The ion exchange capacity of the membrane sample is expressed as IEC = 5 × C AgNO3 ×V AgNO3 / m dry where IEC is the ion exchange capacity of the membrane sample in mol / g, and C AgNO3 is the concentration of the standardized AgNO3 solution, and its unit is mol / L. The average value of the three titration results is taken, and V AgNO3 is the volume of AgNO3 solution consumed in the titration, in L, and is the average of three titration volumes, m dry is the mass of the dry membrane sample after titration drying, and its unit is g.

[0036] b. Graft rate calculation formula The grafting rate is the ratio of the actual grafting rate to the theoretical grafting rate, i.e., grafting rate = (IEC 実際 / IEC 理論 )*100%.

[0037] Example 1 In this example, four treatment groups were set up, designated as treatment group 1, treatment group 2, treatment group 3, and treatment group 4, respectively. Each treatment group selected a different raw material monomer to produce a nitrogen-containing compound. Here, treatment group 1 and treatment group 2 were selected from the general formula segment I [ka] In the treatment group 3, a nitrogen-containing compound having the general formula segment II was prepared. [ka] In the treatment group 4, a nitrogen-containing compound having the general formula segment III was prepared. [ka] A nitrogen-containing compound is produced.

[0038] (1) Treatment group 1 S1 is 9,9-dimethylfluorene as an aromatic monomer. [ka] The monomer raw material is prepared by adopting dimethylaminoacetal ethylene glycol as the branched chain monomer raw material. [ka] 0.15 mol of 9,9-dimethylfluorene and 0.18 mol of dimethylaminoacetal ethylene glycol were quantitatively weighed out, S2 is prepared by adding quantitatively weighed 9,9-dimethylfluorene and dimethylaminoacetalethylene glycol to 50 mL of dichloromethane and dispersing them thoroughly to obtain a reaction base solution. In S3, the temperature of the reaction base solution was first lowered to 0°C, 120 mL of trifluoromethanesulfonic acid was added thereto, and the mixture was thoroughly stirred. The temperature of the reaction base solution was then raised to 13°C, and polymerization was carried out under this temperature condition for 36 hours. The reaction solution thus obtained was poured into water and immersed for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound produced in this treatment group is: [ka] where the degree of polymerization n1=65.

[0039] (2) Treatment group 2 S1 is 9,9-dimethylfluorene as an aromatic monomer. [ka] The monomer raw material was prepared using 1-piperidineacetaldehyde diethyl acetal as the branched chain monomer raw material. [ka] 0.16 mol of 9,9-dimethylfluorene and 0.18 mol of 1-piperidineacetaldehyde diethyl acetal were quantitatively weighed out, For S2, quantitatively weighed 9,9-dimethylfluorene and 1-piperidineacetaldehyde diethyl acetal were added to 50 mL of dichloromethane and thoroughly dispersed to obtain a reaction base solution. In S3, the temperature of the reaction base solution is first lowered to 0°C, 120 mL of trifluoromethanesulfonic acid is added thereto, and the mixture is thoroughly stirred. The temperature of the reaction base solution is then raised to 13°C, and polymerization is carried out under this temperature condition for 24 hours. The reaction solution thus obtained is poured into water and immersed for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound produced in this treatment group is: [ka] where the degree of polymerization n1=80.

[0040] (3) Treatment group 3 S1 is terphenyl as the aromatic monomer. [ka] The monomer raw material was prepared using N-methyl-4-piperidone as the branched chain monomer raw material. [ka] 0.005 mol of terphenyl and 0.005 mol of N-methyl-4-piperidone were quantitatively weighed out, For S2, quantitatively weighed terphenyl and N-methyl-4-piperidone were added to 20 mL of dichloromethane and thoroughly dispersed to obtain a reaction base solution. In S3, the temperature of the reaction base solution was first lowered to 0°C, 3.6 mL of trifluoroacetic acid was added thereto, and the mixture was stirred for 30 minutes. Then, 45 mL of trifluoromethanesulfonic acid was further added thereto. The reaction base solution was then heated to 13°C and polymerized under this temperature condition for 13 hours. The reaction solution thus obtained was poured into water and immersed for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound produced in this treatment group is: [ka] where the degree of polymerization n2=92.

[0041] (4) Treatment group 4 S1 is a stilbene aromatic monomer. [ka] The monomer raw material was prepared using indole-2,3-dione as the branched chain monomer raw material. [ka] 0.005 mol of stilbene and 0.006 mol of indole-2,3-dione were quantitatively weighed out, For S2, quantitatively weighed stilbene and indole-2,3-dione were added to 15 mL of dichloromethane and thoroughly dispersed to obtain a reaction base solution. In S3, the temperature of the reaction base solution was first lowered to 0°C, 3.6 mL of trifluoroacetic acid was added thereto, and the mixture was stirred for 30 minutes. Then, 50 mL of trifluoromethanesulfonic acid was further added thereto. The reaction base solution was then heated to 13°C and polymerized under this temperature condition for 8 hours. The reaction solution thus obtained was poured into water and immersed for 12 hours, filtered, and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound produced in this treatment group is: [ka] where the degree of polymerization n3=145.

[0042] Example 2 Based on the nitrogen-containing compound prepared in Example 1, this example further employs the nitrogen-containing compound as the raw material for preparing a sulfonic acid-type anionic resin, and employs a sulfonic acid ester compound as the quaternizing reagent to quaternize the nitrogen-containing compound to prepare a sulfonic acid-type anionic resin. The structure of the sulfonic acid ester compound corresponds to general formula IV, which is: [ka] and the specifically selected sulfonate ester compounds are shown in Tables 1 to 4. In some other specific embodiments, a sulfonate ester compound conforming to general formula IV is selected as the quaternizing reagent, and R in the formula is selected according to the specific situation. x is selected from the group consisting of methyl, ethyl, vinyl, cyclopropyl, trifluoromethyl, phenyl, tolyl, nitrophenyl, and benzyl; R y may be selected from one of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group.

[0043] This example is divided into different treatment groups depending on the nitrogen-containing compound used to produce the sulfonic acid type anionic resin, specifically designated as treatment group 1, treatment group 2, treatment group 3, and treatment group 4. The specific procedures for producing the sulfonic acid type anionic resin in these treatment groups are as follows:

[0044] In step 1, a nitrogen-containing compound and the sulfonate ester compound are dissolved in N-methylpyrrolidone to obtain a reaction solution, and then the nitrogen-containing compound and the sulfonate ester compound in the reaction solution are subjected to a quaternization reaction at 25 to 120°C for a reaction time of 3 to 72 hours. After completion of the reaction, a product solution containing a sulfonic acid type anion resin is obtained, In step 2, a precipitant is added to the product solution, in this example, deionized water is used as the precipitant, and the mixture is allowed to stand to obtain a mixed liquid system, which is then allowed to fully precipitate. The precipitate is then filtered, washed, and dried, and the resulting solid is the sulfonic acid type anion resin produced by the quaternization reaction.

[0045] (1) Treatment group 1 This treatment group used the nitrogen-containing compound produced in Example 1 as the reactant for producing a sulfonic acid type anion exchange resin. [ka] The method was applied, and different sulfonate ester compounds were used as quaternizing agents. Different groups were further divided depending on the sulfonate ester compounds, and these were designated as treatment group 1-1, treatment group 1-2, and treatment group 1-3. [ka] The best reaction conditions are shown for when a quaternization reaction is carried out by combining different sulfonate ester compounds using the nitrogen-containing compound, and when the specific material combination of the nitrogen-containing compound and the sulfonate ester compound is determined, the quaternization efficiency corresponding to the quaternization reaction completed according to the reaction conditions shown in Table 1 is the highest. The general structural formula of the sulfonic acid type anion resin produced in treatment group 1 of this example is: [ka] matches.

[0046] [Table 1]

[0047] (2) Treatment group 2 This treatment group used the nitrogen-containing compound produced in Example 1 as the reactant for producing a sulfonic acid type anion exchange resin. [ka] The method was applied, and different sulfonate ester compounds were used as quaternizing agents. Different groups were further divided depending on the sulfonate ester compounds, and these were designated as treatment group 2-1, treatment group 2-2, and treatment group 2-3. [ka] The best reaction conditions are shown for when the nitrogen-containing compound is used in combination with different sulfonate ester compounds to carry out a quaternization reaction, and when the specific material combination of the nitrogen-containing compound and the sulfonate ester compound is determined, the quaternization efficiency corresponding to the quaternization reaction completed according to the reaction conditions shown in Table 2 is the highest. The general structural formula of the sulfonic acid type anion resin produced in treatment group 2 of this example is: [ka] matches.

[0048] [Table 2]

[0049] (3) Treatment group 3 This treatment group used the nitrogen-containing compound produced in Example 1 as the reactant for producing a sulfonic acid type anion exchange resin. [ka] The method was applied, and different sulfonate ester compounds were used as quaternizing agents. Different groups were further divided depending on the sulfonate ester compounds, and the groups were designated as treatment group 3-1, treatment group 3-2, and treatment group 3-3. [ka] The best reaction conditions are shown for the quaternization reaction when the nitrogen-containing compound is used in combination with different sulfonate ester compounds, and when the specific material combination of the nitrogen-containing compound and the sulfonate ester compound is 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 produced in treatment group 3 of this example is: [ka] matches.

[0050] [Table 3]

[0051] (4) Treatment group 4 This treatment group used the nitrogen-containing compound produced in Example 1 as the reactant for producing a sulfonic acid type anion exchange resin. [ka] The method was applied, and different sulfonate ester compounds were used as quaternizing agents. Different groups were further divided depending on the sulfonate ester compounds, and the groups were designated as treatment group 4-1, treatment group 4-2, and treatment group 4-3. [ka] The best reaction conditions are shown for the quaternization reaction when the nitrogen-containing compound is used in combination with different sulfonate ester compounds, and when the specific material combination of the nitrogen-containing compound and the sulfonate ester compound is 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 produced in treatment group 4 of this example is: [ka] matches.

[0052] [Table 4]

[0053] Comparative Example 1 1. Production of nitrogen-containing compounds S1 uses terphenyl as the aromatic monomer to prepare the monomer raw material, and 3-quinuclidinone hydrochloride as the branched-chain monomer raw material. 0.005 mol of terphenyl and 0.006 mol of 3-quinuclidinone hydrochloride are quantitatively weighed out. For S2, quantitatively weighed terphenyl and 3-quinuclidinone hydrochloride were added to 20 mL of dichloromethane and thoroughly dispersed to obtain a reaction base solution. In S3, the temperature of the reaction base solution was first lowered to 0°C, 50 mL of trifluoromethanesulfonic acid was added thereto, and the reaction base solution was then heated to 60°C and polymerized under this temperature condition for 16 hours. The reaction solution thus obtained was poured into water and immersed for 12 hours, filtered and dried to obtain a nitrogen-containing compound. The chemical structure of the nitrogen-containing compound produced in this treatment group is: [ka] where the degree of polymerization n3=75.

[0054] 2. Quaternization Reaction The nitrogen-containing compound prepared in this comparative example was used as the raw material for the production of sulfonic acid-type anionic resins. A sulfonic acid ester compound was used as the quaternizing reagent, and the nitrogen-containing compound was quaternized to produce sulfonic acid-type anionic resins. In this comparative example, the above nitrogen-containing compound was blended with different sulfonic acid ester compounds as raw materials, and the sulfonic acid-type anionic resins were produced by following the specific procedure for producing sulfonic acid-type anionic resins described in Example 2. Different groups were established based on the sulfonic acid ester compounds blended, designated Comparative Groups 1-1, 1-2, 1-3, and 1-4. Table 5 lists the optimal reaction conditions for the different reactant combinations used in this comparative example. Given the specific blends of nitrogen-containing compound and sulfonic acid ester compounds, the quaternization efficiency corresponding to the quaternization reaction completed under the reaction conditions listed in Table 5 was highest.

[0055] [Table 5]

[0056] In each group of this Comparative Example, the quaternization reagent used in Comparative Group 1-1 was the same as that used in Treatment Group 1-1 of Example 2; the quaternization reagent used in Comparative Group 1-2 was the same as that used in Treatment Group 2-1 of Example 2; the quaternization reagent used in Comparative Group 1-3 was the same as that used in Treatment Group 3-1 of Example 2; and the quaternization reagent used in Comparative Group 4-1 was the same as that used in Treatment Group 4-1 of Example 2. As can be seen from the above, when a nitrogen-containing compound is quaternized under the action of a sulfonate ester compound, even if the type of sulfonate ester compound selected is the same, the type of nitrogen-containing compound has a significant impact on the quaternization efficiency. Compared to the nitrogen-containing polymer used in this Comparative Example, some of the nitrogen-containing compounds prepared in Example 1 have smaller steric hindrance, which significantly increases the quaternization efficiency when some of the nitrogen-containing compounds prepared in Example 1 are used to interact with sulfonate ester compounds.

[0057] Comparative Example 2 In this comparative example, methyl iodide was used as the quaternizing reagent, and the different nitrogen-containing compounds prepared in Example 1 were each subjected to a quaternization reaction with methyl iodide to prepare halogen-type anion resins. Different groups were set according to the type of nitrogen-containing compound selected, specifically designated as Comparative Group 2-1, Comparative Group 2-2, Comparative Group 2-3, and Comparative Group 2-4. The specific grouping status of each group is as shown in Table 6.

[0058] [Table 6]

[0059] The specific procedures for producing each group of halogen-type anion resins are as follows:

[0060] S1 is prepared by dissolving a nitrogen-containing compound in a DMSO solution (the mass / volume ratio of the nitrogen-containing polymer to DMSO is 1 g:5 mL), and adding 3 eq. of methyl iodide at room temperature. For 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 then filtered and washed with ethanol. The resulting resin was then subjected to alkali exchange and chlorine exchange at 80°C using 3 L of 1 M KOH and 3 L of 1 M NaCl aqueous solution, respectively, and then filtered and washed with water to obtain a halogen-type anion exchange resin.

[0061] Example 3 Using each of the sulfonic acid type anion exchange resins produced in Example 2, anion exchange membranes were produced according to the following method.

[0062] S1 is a method for dissolving a sulfonic acid type anion exchange resin in dimethyl sulfoxide at 80°C to obtain an anion exchange resin solution containing 20 wt% of sulfonic acid type anion exchange resin; In step S2, the anion exchange resin solution obtained in step S1 was poured onto an automatic membrane wiping machine, and the height of the doctor blade was adjusted according to actual needs. Membranes of different thicknesses were processed at 60°C, and then dried at high temperatures to obtain anion exchange membranes.

[0063] Comparative Example 3 Using the anion exchange resins prepared in Comparative Example 2, anion exchange membranes were prepared according to the following method.

[0064] S1 is a method for dissolving an anion exchange resin in dimethyl sulfoxide at 80°C to obtain an anion exchange resin solution containing 20 wt% of anion exchange resin; In step S2, the anion exchange resin solution obtained in step S1 was poured onto an automatic membrane wiping machine, and the height of the doctor blade was adjusted according to actual needs. Membranes of different thicknesses were processed at 60°C, and then dried at high temperatures to obtain anion exchange membranes.

[0065] Test Example 1 1. Test Subjects The anion exchange membranes produced in Example 3 and Comparative Example 3 were tested. In this test example, anion exchange membranes with the same anion exchange resin content were tested in order to eliminate performance differences between anion exchange membranes due to differences in anion exchange resin content.

[0066] 2. Test items (1) Performance measurement by proton nuclear magnetic resonance (1H NMR) The performance is measured by nuclear magnetic resonance using a Swiss AV III 500 HD superconducting nuclear magnetic resonance spectrometer, and the structure of the polymer is determined using tetramethylsilane as an internal standard and deuterated DMSO as a solvent.

[0067] (2) Tensile strength and breaking elongation test of anion exchange membrane The Shimadzu AG-I 1 KN universal testing machine was used to test the breaking elongation and tensile strength of the anion exchange membrane. The anion exchange membrane was cut into dumbbell shapes along both the length (X direction) and width (Y direction) of the material. The edges of the sample should be smooth and free of notches. Notches were inspected using a low-power magnifying glass, and samples with defects on the edges could be discarded. The length, width, and thickness of the membrane material were measured before the test, and the tensile speed was 10 mm min -1and the measurement results for each membrane are the average of measurements of at least three samples.

[0068] (3) Ion Residual Test a. The IC test for iodide ion content in anion exchange resin using oxygen bomb was carried out using ion chromatography Ion Pac AS11 analytical column (4mm x 250mm) and Ion Pac AG11 guard column (4mm x 50mm). 30mmol / L potassium hydroxide solution was used as the eluent, the flow rate was 1mL / min, the column temperature was 30℃, and the detection was performed using an electrical conductivity detector.

[0069] b. To detect sulfonic acid radical content (using paratoluenesulfonic acid radical as an example) using a UV-Vis spectrophotometer, a standard curve was constructed. Using a UV-Vis spectrophotometer, spectral scans were performed on aqueous solutions of methyl p-toluenesulfonate at concentrations of 2 mmol / L, 1 mmol / L, and 0.4 mmol / L, respectively, to determine the appearance of the maximum absorption wavelength at 261 nm. At this wavelength, a concentration range of 0.5 to 4 mmol / L was set, and the absorbance was controlled in the range of 0.2 to 0.8. A standard curve was constructed, with a standard curve correlation coefficient r = 0.9999 (>0.99), demonstrating that the standard curve was valid and could be used successfully. The sample solution to be tested was then prepared and the test was performed.

[0070] (4) Water electrolysis single cell performance test (single cell tank pressure) A multi-channel Ivium electrochemical workstation was used to perform battery performance testing, with a current of 0-1A / cm 2 Ten current steps were set under a current of 10 s, and each step was tested for 10 s. One voltage value was recorded every second, and the average voltage value of each current step was recorded.

[0071] 3. Test Results As can be seen from the test results of this test example, the bath pressure of the electrolytic cell using the anion exchange membrane prepared in Example 3 was lower than that of the electrolytic cell using the anion exchange membrane prepared in Comparative Example 3. This indicates that under water electrolysis conditions, anion exchange membranes prepared using sulfonic acid-type anion resins, when used in electrolytic cells, have lower bath pressure and consume less energy during water electrolysis than anion exchange membranes prepared using halogen-type anion resins. Anion exchange membranes prepared using halogen-type anion resins still have a large amount of residual halogen ions in the membrane material even after alkali exchange or chlorine exchange. The residual halogen ions poison the electrode catalyst, affecting its electrocatalytic efficiency, resulting in a higher bath pressure at the same current density.

[0072] [Table 7]

Claims

1. A method for producing a sulfonic acid type anionic resin, comprising: A sulfonate ester compound is used as a quaternizing reagent, and a nitrogen-containing compound is subjected to a quaternization reaction to obtain the sulfonate-type anion resin, the reaction temperature is 25 to 120°C, and the reaction time is 3 to 72 hours; The nitrogen-containing compound includes at least one of Segment I, Segment II, and Segment III, The segment I is 【Chemical 1】 where n1 represents the degree of polymerization of segment I, and Ar １ is an aryl structural unit, a represents the number of methylene groups, and a is a positive integer, and R １ and R ２ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, or １ and the above R ２ are connected together and form a poly-membered ring together with the N atom to which they are attached, The segment II is 【Chemistry 2】 where n2 represents the degree of polymerization of segment II, and Ar ２ is an aryl structural unit, and R ３ and R ４ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group; The segment III is 【Chemistry 3】 where n3 represents the degree of polymerization of segment III, and Ar ３ is an aryl structural unit, and R ５ and R ６ and each independently is selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

2. The structure of the sulfonate ester compound conforms to general formula IV, which is: 【Chemistry 4】 wherein R ｘ is selected from the group consisting of a methyl group, an ethyl group, a vinyl group, a cyclopropyl group, a trifluoromethyl group, a phenyl group, a tolyl group, a nitrophenyl group, and a benzyl group; ｙ is selected from the group consisting of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group.

3. In the general formula IV, the R ｙ is selected from the group consisting of a phenyl group, an orthotolyl group, a naphthyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

4. The method for producing a sulfonic acid type anionic resin according to claim 3, wherein the sulfonic acid ester compound comprises at least one of methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allyl sulfonate, 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, and cyclohexyl paratoluenesulfonate.

5. 2. The method for producing a sulfonic acid type anionic resin according to 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. Step 1: Mixing the nitrogen-containing compound, the sulfonate ester compound, and an organic solvent to obtain a reaction solution, and then completing the quaternization reaction between the nitrogen-containing compound and the sulfonate ester in the reaction solution to obtain a product solution; and step 2 of mixing the product solution with a precipitant, separating, collecting, washing, and drying the resulting precipitate, thereby obtaining a solid as the sulfonate type anion resin.

7. 7. The method for producing a sulfonic acid type anionic resin according to claim 6, wherein the organic solvent contains at least one of chloroform, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and dimethyl sulfoxide.

8. 7. The method for producing a sulfonic acid type anionic resin according to claim 6, wherein the precipitating agent contains at least one of ethanol, ethyl acetate, ethylene glycol, ethyl ether, tetrahydrofuran, acetone, and water.

9. A sulfonic acid type anionic resin, The anionic resin contains at least one of Segment V, Segment VI, and Segment VII, The segment V is 【Chemistry 5】 where n4 represents the degree of polymerization of segment V, and Ar １ is an aryl structural unit, a represents the number of methylene groups, a is a positive integer, and R １ and R ２ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, or １ and the above R ２ are connected together and form a poly-membered ring together with the N atom to which they are attached, The segment VI is 【Chemistry 6】 where n5 represents the degree of polymerization of segment VI, and Ar ２ is an aryl structural unit, and R ３ and R ４ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group; The segment VII is 【Chemistry 7】 where n6 represents the degree of polymerization of segment VII, and Ar ３ is an aryl structural unit, and R ５ and R ６ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

10. The R ａ and the above R ｃ and the above R ｅ are each independently selected from the group consisting of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group, ｂ and the above R ｄ and the above R ｆ are each independently selected from the group consisting of a methyl group, an ethyl group, a vinyl group, a cyclopropyl group, a trifluoromethyl group, a phenyl group, a tolyl group, a nitrophenyl group, and a benzyl group.

11. The R ａ and the above R ｃ and the above R ｅ are each independently selected from a phenyl group, an orthotolyl group, a naphthyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

12. The Ar １ and the Ar ２ and the Ar ３ are each independently 【Chemistry 8】 The sulfonic acid type anionic resin according to claim 9, selected from the group consisting of:

13. In the segment V, the Ar １ teeth, 【Chemistry 9】 The sulfonic acid type anionic resin according to claim 12, wherein

14. The segment V is 【Chemistry 10】 , or 【Chemistry 11】 The sulfonic acid type anionic resin according to claim 12, wherein

15. In the segment VI, the Ar ２ teeth, 【Chemistry 12】 The sulfonic acid type anionic resin according to claim 12, wherein

16. In the segment VII, the Ar ３ teeth, 【Chemistry 13】 The sulfonic acid type anionic resin according to claim 12, wherein

17. An anion exchange membrane produced by using the sulfonic acid type anion resin according to any one of claims 9 to 16.

18. The method for producing the anion exchange membrane includes: S1 is a step of dissolving the sulfonic acid type anion exchange resin to prepare an anion exchange resin solution, in which the content of the sulfonic acid type anion exchange resin in the anion exchange resin solution is 5 to 40 wt %; and S2. performing membrane wiping using the anion exchange resin solution to obtain the anion exchange membrane.

19. The anion exchange membrane according to claim 18, wherein in S2, the membrane wiping temperature is 40 to 120°C.

20. 18. The anion exchange membrane according to claim 17, wherein the content of sulfonic acid groups in the anion exchange membrane is >50 ppm.

Images