Nitrogen-containing multicomponent copolymer and preparation method thereof, anionic resin, and anionic exchange membrane

Abstract

To enhance flexibility and alkali stability of an anionic resin.SOLUTION: The present application provides a nitrogen-containing multicomponent copolymer, which includes at least two of three segments represented by the following structures. Here, Ar1, Ar2, and Ar3 are aryl structural units, n1 represents the degree of polymerization of segment I and is 0 or a positive integer, n2 represents the degree of polymerization of segment II and is 0 or a positive integer, and n3 represents the degree of polymerization of segment III and is 0 or a positive integer, provided that two of n1 to n3 are not 0.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority from a Chinese patent application bearing application number 2024101268158, 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 nitrogen-containing multicomponent copolymer and its preparation method, an anion resin, and an anion exchange membrane. [Background technology]

[0003] Anion exchange membranes are widely used in fields such as electrolysis, fuel cells, carbon dioxide reduction, water softening, demineralization, pure water production, hydrometallurgy, rare element separation, pharmaceuticals, sugar refining, and amino acid adsorption. In the field of hydrogen production using electrolyzed water, anion exchange membranes (AEMs) are often used to separate hydrogen gas between the anode and cathode and provide an anion transport pathway. The active component of anion exchange membranes is an anion resin, which generally consists of a polymer backbone and charged ion-conducting groups, connected via long or short side chains. Reported anion exchange resins with backbones such as polyphenylene ether, polyarylene ether, polysulfone, and polybenzimidazole have drawbacks such as high rigidity and difficulty in membrane formation. Anion exchange membranes with functional side chains of quaternary ammonium cations, quaternary phosphonium cations, imidazolium cations, and guanidino cations are prone to decomposition in alkaline high-temperature environments, resulting in a significant decrease in ion conductivity and affecting the service life of fuel cells. Summary of the Invention [Problem to be solved by the invention]

[0004] The object of the present invention is to improve the flexibility and alkali resistance stability of an anionic resin. [Means for solving the problem]

[0005] According to a first aspect, the present application provides a nitrogen-containing multicomponent copolymer, the multicomponent copolymer comprising at least two of a segment I, a segment II, and a segment III, wherein segment I comprises: [ka] where Ar1 is an aryl structural unit and segment II is [ka] where Ar2 is an aryl structural unit and segment III is [ka] where Ar3 is an aryl structural unit.

[0006] According to a second aspect, the present application provides a method for producing the nitrogen-containing multicomponent copolymer described above, the method comprising the steps of: preparing a monomer raw material; selecting a corresponding aromatic monomer according to the aryl structural unit contained in the main chain of the multicomponent copolymer; using the aromatic monomer as the main chain monomer raw material; and selecting a branched-chain monomer raw material according to the type of segment contained in the multicomponent copolymer, wherein when the multicomponent copolymer contains segment I, the branched-chain monomer raw material is selected from the general formula: [ka] and when the multicomponent copolymer comprises segment II, the branched chain monomer raw material comprises an acetal monomer having the general formula [ka] and when the multicomponent copolymer comprises segment III, the branched chain monomer raw material comprises a piperidone monomer having the general formula [ka] the step of adding a quinuclidinone monomer represented by the formula (I) to an alkyl organic solvent and dispersing the monomer raw material therein to obtain a reaction base solution; the step of adding an organic acid catalyst to the reaction base solution and polymerizing at least two of the aromatic monomer, acetal monomer, piperidone monomer, and quinuclidinone monomer in the reaction base solution under the action of the organic acid catalyst; and the step of discharging the product of the polymerization reaction into pure water or an alkaline solution to wash off the remaining organic acid catalyst, and then obtaining a multicomponent copolymer after washing and drying.

[0007] According to a third aspect, the present application provides an anionic resin, the multicomponent copolymer comprising at least two of Segment I, Segment IV, and Segment V, wherein Segment I is [ka] wherein Ar1 is an aryl structural unit, R1 is H, a hydrocarbon group or a substituted hydrocarbon group, and segment IV is [ka] where Ar2 is an aryl structural unit and Z1 - represents an anion, and segment V is [ka] where Ar3 is an aryl structural unit and Z2 - represents an anion.

[0008] According to a fourth aspect, the present application provides a method for producing an anion resin, the method comprising quaternizing the above-described multicomponent copolymer with a quaternizing reagent to obtain an anion resin, the quaternizing reagent being selected from the group consisting of iodomethane, iodoethane, 1-iodopropane, iodobutane, 1-iodopentane, iodohexane, bromoethane, 1-bromopropane, bromobutane, 1-bromopentane, 1-bromohexane, bromocyclohexane, bromocyclopentane, methyl methanesulfonate, ethyl methanesulfonate, and propyl methanesulfonate. methanesulfonate, butyl methanesulfonate, N-propyl ethyl sulfonate, ethanesulfonic acid ethyl ester, 3-butynyl methanesulfonate, allyl ethenesulfonic acid,2-propenyl ester, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl p-toluenesulfonate, toluene-4-sulfonic acid cyclobutyl ester, p-toluenesulfonic acid n-butyl ester, benzenesulfonic acid neopentyl ester, tetrahydro-2H-pyran-4-yl methanesulfonate, or p-toluenesulfonic acid cyclohexyl ester) and at least one of them.

[0009] According to a fifth aspect, the present application provides an anion exchange membrane, the anion exchange membrane containing the anion resin described above. [Effects of the Invention]

[0010] The multicomponent copolymer of the present application has excellent structural stability, and the different types of segments contained therein can be firmly linked, so that the anion exchange membrane produced using the multicomponent copolymer has good flexibility and is less likely to rupture during application.In addition, using the multicomponent copolymer of the present application to produce anion resins and anion exchange membranes can improve the alkali resistance of such materials, so that when these anion resins and anion exchange membranes are used in fields such as hydrogen production using electrolyzed water, the membrane materials can maintain stability and be less likely to decompose.

[0011] The anion exchange membrane of the present application has excellent flexibility and alkali resistance, and when applied to an electrolytic cell, it can not only optimize the interfacial contact between electrodes, but also improve the operational stability of the electrolytic cell. DETAILED DESCRIPTION OF THE INVENTION

[0012] In one embodiment, Ar1, Ar2, and Ar3 are each independently [ka] It contains at least one of the following structural units.

[0013] In one embodiment, R1, R2, R3, and R4 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0014] In one embodiment, the multicomponent copolymer comprises a multicomponent segment I collectively composed of a segment I and a segment II, wherein the multicomponent segment I is [ka] where n1 represents the degree of polymerization of segment I, n1 is a positive integer, and n2 represents the degree of polymerization of segment II, n2 is a positive integer.

[0015] In one embodiment, the multicomponent copolymer comprises a multicomponent segment II collectively composed of segment I and segment III, wherein the multicomponent segment II comprises: [ka] where n1 represents the degree of polymerization of segment I, n1 is a positive integer, and n3 represents the degree of polymerization of segment III, n3 is a positive integer.

[0016] In one embodiment, the multicomponent copolymer comprises a multicomponent segment III jointly composed of segment II and segment III, wherein the multicomponent segment III is [ka] where n2 represents the degree of polymerization of segment II, n2 is a positive integer, and n3 represents the degree of polymerization of segment III, n3 is a positive integer.

[0017] In one embodiment, the multicomponent copolymer comprises a multicomponent segment IV collectively composed of segment I, segment II, and segment III, wherein the multicomponent segment IV is [ka] where n1 represents the degree of polymerization of segment I, n1 is a positive integer, n2 represents the degree of polymerization of segment II, n2 is a positive integer, and n3 represents the degree of polymerization of segment III, n3 is a positive integer.

[0018] 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.

[0019] 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. n4 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.

[0020] In one embodiment, the acetal monomer is [ka] The monomers include at least one of the following:

[0021] In one embodiment, the piperidone monomer is [ka] The monomers include at least one of the following:

[0022] In one embodiment, the quinuclidinone monomer is [ka] The monomers include at least one of the following:

[0023] In one embodiment, the organic acid catalyst includes at least one of methanesulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid.

[0024] In one embodiment, a method for producing a nitrogen-containing multicomponent copolymer includes lowering the temperature of the reaction base solution to -5 to 3°C before adding an organic acid catalyst to the reaction base solution, and adding the organic acid catalyst to the reaction base solution to polymerize at least two of the aromatic monomer, acetal monomer, piperidone monomer, and quinuclidinone monomer in the reaction base solution under the action of the organic acid catalyst, and then raising the temperature of the reaction base solution to 5 to 24°C and polymerizing at least two of the aromatic monomer, acetal monomer, piperidone monomer, and quinuclidinone monomer under these conditions for 4 to 48 hours.

[0025] In one embodiment, the alkyl organic solvent includes at least one of dichloromethane, trichloromethane, chloroform, and tetrahydrofuran.

[0026] In one embodiment, the alkaline solution includes at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, and potassium hydroxide.

[0027] In one embodiment, Ar1, the Ar2, and the Ar3 are each independently [ka] It contains at least one of the following structural units.

[0028] In one embodiment, R1, R2, R3, and R4 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0029] In one embodiment, the anion resin comprises a multi-segment V collectively composed of the segment I and the segment IV, the multi-segment V comprising: [ka] where n1 represents the degree of polymerization of segment I, n1 is a positive integer, n4 represents the degree of polymerization of segment IV, n4 is a positive integer, and R a is selected from one of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group.

[0030] In one embodiment, the anion resin comprises a multi-component segment VI collectively composed of the segment I and the segment V, wherein the multi-component segment VI is [ka] where n1 represents the degree of polymerization of segment I, n1 is a positive integer, n5 represents the degree of polymerization of segment V, n5 is a positive integer, and R b is selected from one of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group.

[0031] In one embodiment, the anion resin comprises a multi-component segment VII collectively composed of the segment IV and the segment V, wherein the multi-component segment VII comprises: [ka] where n4 represents the degree of polymerization of segment IV, n4 is a positive integer, n5 represents the degree of polymerization of segment V, n5 is a positive integer, and R a , R b are each independently selected from one of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group.

[0032] In one embodiment, the anion resin comprises a multi-component segment VIII collectively composed of the segment I, the segment IV, and the segment V, wherein the multi-component segment VIII comprises: [ka] where n1 represents the degree of polymerization of segment I, n1 is a positive integer, n4 represents the degree of polymerization of segment IV, n4 is a positive integer, n5 represents the degree of polymerization of segment V, n5 is a positive integer, and R a , R b are each independently selected from one of an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group.

[0033] In one embodiment, n1, n4, and n5 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. n4 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. n5 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.

[0034] In one embodiment, n1, n4, and n5 are each independently selected from integers between 50 and 300. n1 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within the range are also suitable. n4 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within the range are also suitable. n5 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within the range are also suitable.

[0035] The products whose manufacture and performance require analysis in the examples and comparative examples are as follows: Example 1 Segment I [ka] and Segment II [ka] The multicomponent copolymer is prepared by the multicomponent segment I. [ka] It consists of:

[0036] The preparation of copolymer 1-1 involves the following: S1 contains 0.15 mol of m-terphenyl (1,3-diphenylbenzene), 0.09 mol of N-methyl-4-piperidone, and 0.09 mol of isobutyraldehyde diethyl acetal. In step S2, the raw materials weighed in step S1 are added to 50 mL of dichloromethane, and the raw materials are mixed with dichloromethane and thoroughly dispersed to obtain a reaction base solution. In S3, 90 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at -5°C, and after the addition is complete, the reaction system is heated to 24°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 16 hours. After the reaction of S3 was completed, S4 was prepared by discharging the product into pure water, filtering the product, pulverizing the solid matter obtained, washing it with pure water, and drying it to obtain the final product, Copolymer 1-1.

[0037] The structure of copolymer 1-1 was as shown below in [Chemical Formula 26]. [ka]

[0038] The preparation of copolymer 1-2 involves the following: S1, 0.15 mol of p-terphenyl, 0.09 mol of N-methyl-4-piperidone, and 0.09 mol of isobutyraldehyde diethyl acetal were taken, S2: The raw materials weighed in S1 are added to 60 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. S3: At 3°C, 90 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution. After the addition is complete, the reaction system is heated to 13°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 24 hours. After the reaction of S4 and S3 was completed, the product was poured into pure water and then filtered. The resulting solid was crushed, washed with pure water, and dried to obtain the final product, Copolymer 1-2.

[0039] The structure of copolymer 1-2 was as shown below in [Chemical Formula 27]. [ka]

[0040] Example 2 Segment I [ka] and Segment III [ka] and the multicomponent copolymer is prepared by the multicomponent segment II. [ka] It consists of:

[0041] The preparation of copolymer 2-1 involves the following: S1 contains 0.15 mol of m-terphenyl, 0.12 mol of 3-quinuclidinone hydrochloride, and 0.05 mol of isobutyraldehyde diethyl acetal. In S2, the raw materials weighed in S1 are added to 45 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 24°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 36 hours. After the reaction of S3 was completed, S4 was prepared by discharging the product into pure water, filtering the product, pulverizing the resulting solid, washing it with pure water, and drying it to obtain the final product, Copolymer 2-1.

[0042] The structure of copolymer 2-1 was as shown below in [Chemical Formula 31]. [ka]

[0043] The preparation of copolymer 2-2 involves the following: S1 takes 0.15 mol of biphenyl, 0.12 mol of 3-quinuclidinone hydrochloride, and 0.05 mol of isobutyraldehyde diethyl acetal, In S2, the raw materials weighed in S1 are added to 45 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 100 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 13°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 12 hours. After the reaction of S3 was completed, the product of S4 was poured into pure water, filtered, and the resulting solid was crushed, washed with pure water, and dried to obtain the final product, copolymer 2-2.

[0044] The structure of copolymer 2-2 was as shown below in [Chemical Formula 32]. [ka]

[0045] Example 3 Segment II [ka] and Segment III [ka] and the multicomponent copolymer is prepared by the multicomponent segment III. [ka] It consists of:

[0046] The preparation of copolymer 3-1 involves the following: S1 takes 0.15 mol of p-terphenyl, 0.09 mol of 3-quinuclidinone hydrochloride, and 0.09 mol of N-methyl-4-piperidone, In S2, the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 13°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 8 hours. After the reaction of S3 was completed, the product of S4 was poured into pure water, filtered, and the resulting solid was crushed, washed with pure water, and dried to obtain the final product, copolymer 3-1.

[0047] The structure of copolymer 3-1 was as shown below in [Chemical Formula 36]. [ka]

[0048] The preparation of copolymer 3-2 involves the following: S1 takes 0.15 mol of m-terphenyl, 0.09 mol of 3-quinuclidinone hydrochloride, and 0.09 mol of N-ethyl-4-piperidone, In S2, the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 8°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 14 hours. After the reaction of S3 was completed, the product of S4 was poured into pure water, filtered, and the resulting solid was crushed, washed with pure water, and dried to obtain the final product, copolymer 3-2.

[0049] The structure of copolymer 3-2 was as shown below in [Chemical Formula 37]. [ka]

[0050] Example 4 Segment I [ka] , Segment II [ka] and Segment III [ka] and the multicomponent copolymer is prepared by multicomponent segment IV. [ka] It consists of:

[0051] The preparation of copolymer 4-1 involves the following: S1 takes 0.15 mol of p-terphenyl, 0.05 mol of 3-quinuclidinone hydrochloride, 0.10 mol of N-methyl-4-piperidone, and 0.03 mol of isobutyraldehyde diethyl acetal, In S2, the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 13°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 36 hours. After the reaction of S3 was completed, the product of S4 was poured into pure water, filtered, and the resulting solid was crushed, washed with pure water, and dried to obtain the final product, Copolymer 4-1.

[0052] The structure of copolymer 4-1 was as shown below in [Chemical Formula 42]. [ka]

[0053] The preparation of copolymer 4-2 involves the following: S1 takes 0.15 mol of m-terphenyl, 0.06 mol of 3-quinuclidinone hydrochloride, 0.80 mol of N-methyl-4-piperidone, and 0.04 mol of isobutyraldehyde diethyl acetal, In S2, the raw materials weighed in S1 are added to 80 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 3°C, and after the addition is complete, the reaction system is heated to 13°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 48 hours. After the reaction of S3 was completed, the product of S4 was poured into pure water, filtered, and the resulting solid was crushed, washed with pure water, and dried to obtain the final product, copolymer 4-2.

[0054] The structure of copolymer 4-2 was as shown below in [Chemical Formula 43]. [ka]

[0055] Comparative Example 1 Segment I [ka] The general formula for this class of polymers is: [ka] is.

[0056] The preparation of polymer 5-1 involves the following: S1 takes 0.15 mol of m-terphenyl and 0.17 mol of isobutyraldehyde diethyl acetal, In S2, the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 90 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at -3°C, and after the addition is complete, the reaction system is heated to 18°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 24 hours. After the reaction of S3 was completed, S4 was prepared by discharging the product into pure water, filtering the product, pulverizing the solid matter obtained, washing it with pure water, and drying it to obtain the final product polymer 5-1.

[0057] The structure of polymer 5-1 was as shown below in [Chemical Formula 46]. [ka]

[0058] Comparative Example 2 Segment II [ka] The general formula for this class of polymers is: [ka] is.

[0059] The preparation of polymer 6-1 involves the following: S1 takes 0.15 mol of p-terphenyl monomer and 0.18 mol of 3-quinuclidinone hydrochloride, In S2, the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 24°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 36 hours. After the reaction of S3 was completed, S4 was prepared by discharging the product into pure water, filtering, pulverizing the resulting solid, washing it with pure water, and drying it to obtain the final product polymer 6-1.

[0060] The structure of polymer 6-1 was as shown below in [Chemical Formula 49]. [ka]

[0061] Comparative Example 3 Segment III [ka] The general formula for this class of polymers is: [ka] is.

[0062] The preparation of polymer 7-1 involves the following: S1 takes 0.15 mol of m-terphenyl and 0.18 mol of N-methyl-4-piperidone, In S2, the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed and thoroughly dispersed to obtain a reaction base solution. In S3, 90 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C, and after the addition is complete, the reaction system is heated to 13°C, and the raw materials are subjected to a hydrocarbon alkylation reaction at this temperature for 6 hours. After the reaction of S3 was completed, S4 was prepared by discharging the product into pure water, filtering, pulverizing the resulting solid, washing it with pure water, and drying it to obtain the final product, polymer 7-1.

[0063] The structure of polymer 7-1 was as shown below in [Chemical Formula 52]. [ka]

[0064] Example 5 In this example, the nitrogen-containing polymers used to produce chloride ion type anion resins were Copolymer 1-1, Copolymer 1-2, Copolymer 2-1, Copolymer 2-2, Copolymer 3-1, Copolymer 3-2, Copolymer 4-1, Copolymer 4-2, Polymer 5-1, Polymer 6-1, and Polymer 7-1 produced in Examples 1 to 4 and Comparative Examples 1 to 3, respectively, and chloride ion type anion resins were produced by quaternization reaction and ion exchange using iodomethane as a quaternization reagent.

[0065] The preparation of chloride ion type anion resins includes the following: Step 1: dissolving a nitrogen-containing polymer and iodomethane in dimethyl sulfoxide to obtain a reaction solution; then, the nitrogen-containing polymer and iodomethane in the reaction solution are subjected to a quaternization reaction at 50 to 100°C, the reaction time is 3 to 36 hours; and after the reaction is completed, a product solution containing an iodine ion type anion resin is obtained; Step 2: Add a precipitant to the product solution. In this example, deionized water was used as the precipitant, and the precipitate was allowed to precipitate sufficiently. The precipitate was then filtered, ion-exchanged with an aqueous solution of KOH and NaCl, washed, and dried. The resulting solid was the chloride ion-type anion resin produced by the quaternization reaction.

[0066] The conditions for the quaternization reaction were optimized based on the nitrogen-containing polymer used, with the highest conversion rate of the quaternization reaction being the optimization criterion. The optimized reaction conditions were as shown in Table 1.

[0067] [Table 1]

[0068] Example 6 In this example, Copolymer 1-1, Copolymer 1-2, Copolymer 2-1, Copolymer 2-2, Copolymer 3-1, Copolymer 3-2, Copolymer 4-1, Copolymer 4-2, Polymer 5-1, Polymer 6-1, and Polymer 7-1 produced in Examples 1 to 4 and Comparative Examples 1 to 3 were used as nitrogen-containing polymers for producing sulfonic acid type anionic resins, and sulfonic acid ester compounds were used as quaternizing reagents to produce sulfonic acid type anionic resins by quaternization reaction.

[0069] The preparation of sulfonic acid anion resins involves the following: Step 1: dissolving a nitrogen-containing polymer and a sulfonate ester compound in dimethyl sulfoxide to obtain a reaction solution; then, the nitrogen-containing polymer and the sulfonate ester compound in the reaction solution are subjected to a quaternization reaction at 70 to 120°C, the reaction time is 3 to 72 hours; and after the reaction is completed, a product solution containing a sulfonate anion resin is obtained; Step 2: Add a precipitant to the product solution. In this example, deionized water was used as the precipitant, and the precipitate was thoroughly precipitated. The precipitate was then filtered, washed, and dried. The resulting solid was the sulfonic acid anion resin produced by the quaternization reaction.

[0070] The type of quaternization reagent and reaction conditions for the quaternization reaction were optimized based on the nitrogen-containing polymer used, with the highest conversion rate of the quaternization reaction being the optimization criterion. The optimized conditions are shown in Table 2.

[0071] [Table 2]

[0072] Test Example 1 1. Test subjects Further anion exchange membranes were produced using the anion resins produced in Examples 5 and 6, and the anion exchange membranes thus produced were used as test subjects.

[0073] 2. Test items (1) Mechanical performance test Referring to GB T 20042.3, the test object was subjected to a pure tensile force until it broke.

[0074] a. The tensile strength is recorded as the ratio of the maximum load that the test object can withstand when it breaks under the action of pure tensile force to the width of the stretched membrane material, and is used to evaluate the mechanical strength of the membrane, divided into transverse and longitudinal tensile strength. b. The breaking elongation was recorded as the ratio of the distance between two points on the test object when the test object broke under the maximum load it received before breaking to the original length between those two points. This indicates the maximum deformation that the alkaline membrane can withstand before breaking, and was used to evaluate the flexibility of the membrane.

[0075] 3. Test Results The test results of this test example are shown in Tables 3 and 4.

[0076] The structural units constituting polymer 5-1 are: [ka] The molecular structures of polymers 1-1, 2-1, and 4-2 also contain the above structural units, but the test specimens produced using polymers 1-1, 2-1, and 4-2, respectively, had higher measured tensile strengths and higher elongations at break than the test specimens produced using polymer 5-1, when the types of anions contained in the anionic resins were the same. On the other hand, the molecular structures of polymers 1-2, 2-2, and 4-1 do not contain the exact same segment as the structural unit constituting polymer 5-1, but the structural unit constituting polymer 5-1 is represented by the general formula segment I [ka] Similarly, the molecular structures of Polymer 1-2, Polymer 2-2, and Polymer 4-1 also contain structural units conforming to the general formula Segment I. However, the test specimens prepared using Polymer 5-1 still had lower measured tensile strengths and elongations at break than the test specimens prepared using Polymer 1-1, Polymer 2-1, and Polymer 4-2, respectively, when the types of anions contained in the anion resins were the same.

[0077] The structural units constituting polymer 6-1 are: [ka] Although the molecular structures of polymers 1-2, 3-1, and 4-1 also contain the above structural unit, the test specimens produced using polymers 1-2, 3-1, and 4-1, respectively, had higher measured tensile strengths and higher elongations at break than the test specimens produced using polymer 6-1, when the types of anions contained in the anionic resins were the same. On the other hand, the molecular structures of polymers 1-1, 3-2, and 4-2 do not contain exactly the same segment as the structural unit constituting polymer 6-1, but the structural unit constituting polymer 6-1 is represented by the general formula segment II [ka] Similarly, the molecular structures of Polymer 1-1, Polymer 3-2, and Polymer 4-2 also contain structural units conforming to the general formula Segment II. However, the test specimens prepared using Polymer 6-1 still had lower tensile strengths and elongations at break than the test specimens prepared using Polymer 1-1, Polymer 3-2, and Polymer 4-2, respectively, when the anion resins contained the same type of anion.

[0078] The structural units constituting polymer 7-1 are: [ka] The molecular structures of polymers 2-1, 3-2, and 4-2 also contain the above structural unit, but the test specimens produced using polymers 2-1, 3-2, and 4-2, respectively, had higher measured tensile strengths and higher elongations at break than the test specimens produced using polymer 7-1, when the type of anion contained in the anionic resin was the same. On the other hand, the molecular structures of polymers 2-2, 3-1, and 4-1 do not contain exactly the same segment as the structural unit constituting polymer 7-1, but the structural unit constituting polymer 7-1 is represented by the general formula segment III [ka] Similarly, the molecular structures of Polymer 2-2, Polymer 3-1, and Polymer 4-1 also contain structural units conforming to the general formula Segment III. However, the test specimens prepared using Polymer 7-1 still had lower tensile strengths and elongations at break than the test specimens prepared using Polymer 2-2, Polymer 3-1, and Polymer 4-1, respectively, when the anion resins contained the same type of anion.

[0079] In summary, the test results of this test example showed that, in contrast to nitrogen-containing polymers constructed using only one structural unit of Segment I, Segment II, or Segment III, nitrogen-containing multicomponent copolymers constructed jointly by selecting and combining two or more of the above segments, and ultimately anion resins and anion exchange membranes produced using these nitrogen-containing multicomponent copolymers, can increase the flexibility of the anion exchange membrane of the present application and have higher tensile strength and breaking elongation. It was also shown that when such anion exchange membrane is applied to an electrolytic cell, the interfacial contact between the electrodes can be optimized.

[0080] [Table 3]

[0081] [Table 4]

[0082] Test Example 2 1. Test subjects An anion exchange membrane was further produced using the anion resin produced in Example 5, and the anion exchange membrane thus produced was used as the test subject.

[0083] 2. Stability testing The test method is to cut the test object into membrane samples of 2cm x 2cm size, immerse them in 1M NaOH aqueous solution and seal them, put the solution in a drying box at 80°C for 2000 hours, remove the membrane sample, 1 HNMR test was performed to calculate the decomposition rate of the membrane sample, the grafting rate of the original membrane material was denoted as G0, the grafting rate of the membrane material immersed in NaOH aqueous solution was denoted as G1, and the calculation formula for the decomposition rate was [(G0-G1) / G0]*100%.

[0084] The graft rate is calculated as follows: a. Measurement of ion exchange capacity (IEC) The test specimen was cut into pieces, and 50mm x 50mm membrane samples were cut. The membrane samples were immersed in 1 mol / L KOH solution at 80°C for 24 hours to exchange the anions in the membrane samples with hydroxyl groups, yielding hydroxide-type membrane samples. The hydroxide-type membrane samples were 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, yielding chloride-type membrane samples. The chloride-type membrane samples were thoroughly washed with deionized water to ensure complete removal of NaCl adsorbed on the chloride-type membrane samples. The surface of the chloride-type membrane samples was absorbed with filter paper and then 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 the NaNO3 solution. The amount of chloride ions exchanged into the NaNO3 solution was equal to the amount of anions to be measured in the test specimen obtained through the quaternization reaction. The titration of the chloride ion content in the membrane is carried out by adding 10 mL of NaNO3 solution to an Erlenmeyer flask in which the chloride type membrane sample has been thoroughly immersed, adding two drops of K2CrO4 as an indicator, and titrating the 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. AgNO3 The parallel titration was performed three times, and the average value was taken to calculate the chloride ion content in the chloride-type membrane sample. Finally, the membrane sample was taken out and thoroughly washed with deionized water, and then thoroughly dried in a drying box. The dry membrane was quickly taken out and weighed, and the mass of the membrane was calculated. dry The ion exchange capacity of the membrane sample was calculated using the formula 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, the unit is mol / L, and the average value of the three titration results is taken. 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.

[0085] 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%.

[0086] 3. Test Results The test results of this test example are as shown in Table 5. Among the test subjects, the chloride ion type anion exchange resins produced using copolymers 5-1, 6-1, and 7-1 each had a high decomposition rate. As described above, copolymers 5-1, 6-1, and 7-1 are nitrogen-containing polymers constructed using a single structural unit selected from segment I, segment II, and segment III. However, the experimental results of this test example demonstrate that nitrogen-containing multicomponent copolymers constructed using a combination of two or more of the above segments, as well as anion resins and anion exchange membranes produced using these nitrogen-containing multicomponents, can improve the alkali resistance of the anion exchange membrane and reduce the decomposition rate of the anion exchange membrane in an electrolytic cell. The alkali resistance of an anion resin is mainly determined by the main molecular structure of the anion resin. Although the types of anions contained in the anion resins prepared in Example 6 and those prepared in Example 5 are different, when the alkali resistance test was conducted using the sulfonic acid anion resin prepared in Example 6, the test results were consistent with the results measured in this test example.

[0087] [Table 5]

Claims

1. A nitrogen-containing multicomponent copolymer, The multicomponent copolymer includes at least two of Segment I, Segment II, and Segment III, The segment I is 【Chemical 1】 where Ar １ is an aryl structural unit, The segment II is 【Chemistry 2】 where Ar ２ is an aryl structural unit, The segment III is 【Chemistry 3】 where Ar ３ is a nitrogen-containing multi-component copolymer in which the aryl structural unit is

2. The Ar １ , the Ar ２ , the Ar ３ are each independently 【Chemistry 4】 The nitrogen-containing multicomponent copolymer according to claim 1, comprising at least one of the following structural units:

3. The R １ , the R ２ , the R ３ , the R ４ 3. The nitrogen-containing multicomponent copolymer according to claim 1, wherein each of is independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

4. The multicomponent copolymer includes a multicomponent segment I jointly composed of the segment I and the segment II, and the multicomponent segment I is 【Chemistry 5】 wherein n1 represents the degree of polymerization of the segment I, n1 is a positive integer, and n2 represents the degree of polymerization of the segment II, n2 is a positive integer. The nitrogen-containing multicomponent copolymer according to any one of claims 1 to 3.

5. The multicomponent copolymer includes a multicomponent segment II jointly constituted by the segment I and the segment III, and the multicomponent segment II is 【Chemistry 6】 wherein n1 represents the degree of polymerization of the segment I, n1 is a positive integer, and n3 represents the degree of polymerization of the segment III, n3 is a positive integer. The nitrogen-containing multicomponent copolymer according to any one of claims 1 to 3.

6. The multicomponent copolymer includes a multicomponent segment III jointly constituted by the segment II and the segment III, and the multicomponent segment III is 【Chemistry 7】 wherein n2 represents the degree of polymerization of the segment II, n2 is a positive integer, and n3 represents the degree of polymerization of the segment III, n3 is a positive integer. The nitrogen-containing multicomponent copolymer according to any one of claims 1 to 3.

7. The multicomponent copolymer includes a multicomponent segment IV jointly constituted by the segment I, the segment II, and the segment III, and the multicomponent segment IV is 【Chemistry 8】 wherein n1 represents the degree of polymerization of the segment I, n1 is a positive integer, n2 represents the degree of polymerization of the segment II, n2 is a positive integer, and n3 represents the degree of polymerization of the segment III, n3 is a positive integer. The nitrogen-containing multicomponent copolymer according to any one of claims 1 to 3.

8. A method for producing the nitrogen-containing multicomponent copolymer according to any one of claims 1 to 3, comprising: a step of preparing a monomer raw material, selecting a corresponding aromatic monomer according to the aryl structural unit contained in the main chain of the multicomponent copolymer, using the aromatic monomer as a main chain monomer raw material, and selecting a branched chain monomer raw material according to the type of segment contained in the multicomponent copolymer, wherein when the multicomponent copolymer contains the segment I, the branched chain monomer raw material is selected from the general formula 【Chemistry 9】 and when the multicomponent copolymer contains the segment II, the branched chain monomer raw material contains an acetal monomer represented by the general formula 【Chemistry 10】 and when the multicomponent copolymer comprises the segment III, the branched chain monomer raw material comprises a piperidone monomer represented by the general formula 【Chemistry 11】 and a quinuclidinone monomer comprising: adding the monomer raw material to an alkyl organic solvent and dispersing it sufficiently to obtain a reaction base solution; adding an organic acid catalyst to the reaction base solution, and polymerizing at least two of the aromatic monomer, the acetal monomer, the piperidone monomer, and the quinuclidinone monomer in the reaction base solution under the action of the organic acid catalyst; and discharging the product of the polymerization reaction into pure water or an alkaline solution to wash off any remaining organic acid catalyst, and then obtaining the multicomponent copolymer after the product has been washed and dried.

9. The acetal monomer is 【Chemistry 12】 The method of claim 8 , comprising at least one of the following monomers:

10. The piperidone monomer is 【Chemistry 13】 The method of claim 8 , comprising at least one of the following monomers:

11. The quinuclidinone monomer is 【Chemistry 14】 The method of claim 8 , comprising at least one of the following monomers:

12. 9. The method of claim 8, wherein the organic acid catalyst comprises at least one of methanesulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid.

13. In the method, Before adding the organic acid catalyst to the reaction base solution, the temperature of the reaction base solution is lowered to −5 to 3° C.

13. The method according to claim 12, wherein adding the organic acid catalyst to the base reaction solution and polymerizing at least two of the aromatic monomer, the acetal monomer, the piperidone monomer, and the quinuclidinone monomer in the base reaction solution under the action of the organic acid catalyst comprises raising the temperature of the base reaction solution to 5 to 24°C and polymerizing at least two of the aromatic monomer, the acetal monomer, the piperidone monomer, and the quinuclidinone monomer under these conditions for 4 to 48 hours.

14. 9. The method of claim 8, wherein the alkyl organic solvent comprises at least one of dichloromethane, trichloromethane, chloroform, and tetrahydrofuran.

15. 9. The method of claim 8, wherein the alkaline solution contains at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, or potassium hydroxide.

16. An anionic resin, The anion resin comprises at least two of Segment I, Segment IV, and Segment V; The segment I is 【Chemistry 15】 where Ar １ is an aryl structural unit, The segment IV is 【Chemistry 16】 where Ar ２ is an aryl structural unit, Z １ － represents an anion, The segment V is 【Chemistry 17】 where Ar ３ is an aryl structural unit, Z ２ － represents anion, anion resin.

17. The Ar １ , the Ar ２ , the Ar ３ are each independently 【Chemistry 18】 17. The anion resin of claim 16, comprising at least one of the structural units:

18. The R １ , the R ２ , the R ３ , the R ４ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

19. The anion resin includes a multi-component segment V collectively composed of the segment I and the segment IV, and the multi-component segment V is 【Chemistry 19】 where n1 represents the degree of polymerization of the segment I, n1 is a positive integer, n4 represents the degree of polymerization of the segment IV, n4 is a positive integer, and R ａ is selected from the group consisting of an aromatic group, a C1 to C10 linear alkyl group, and a C3 to C10 cycloalkyl group.

20. The anion resin includes a multiple segment VI jointly constituted by the segment I and the segment V, and the multiple segment VI is 【Chemistry 20】 where n1 represents the degree of polymerization of the segment I, n1 is a positive integer, n5 represents the degree of polymerization of the segment V, n5 is a positive integer, and R ｂ is selected from the group consisting of an aromatic group, a C1 to C10 linear alkyl group, and a C3 to C10 cycloalkyl group.

21. The anion resin comprises a multiple segment VII collectively constituted by the segment IV and the segment V, the multiple segment VII comprising: ​ where n4 represents the degree of polymerization of the segment IV, n4 is a positive integer, n5 represents the degree of polymerization of the segment V, n5 is a positive integer, and R ａ , the R ｂ are each independently selected from the group consisting of an aromatic group, a C1 to C10 linear alkyl group, and a C3 to C10 cycloalkyl group.

22. The anion resin includes a multiple segment VIII collectively composed of the segment I, the segment IV, and the segment V, wherein the multiple segment VIII is 【Chemical 22】 where n1 represents the degree of polymerization of the segment I, n1 is a positive integer, n4 represents the degree of polymerization of the segment IV, n4 is a positive integer, n5 represents the degree of polymerization of the segment V, n5 is a positive integer, and R ａ , the R ｂ are each independently selected from the group consisting of an aromatic group, a C1 to C10 linear alkyl group, and a C3 to C10 cycloalkyl group.

23. A method for producing an anion resin, comprising: subjecting the multicomponent copolymer according to any one of claims 1 to 3 to a quaternization reaction with a quaternization reagent to obtain the anion resin, wherein the quaternization reagent is selected from the group consisting of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromocyclohexane, bromocyclopentane, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, butyl methyl ... A method for producing an anionic resin containing at least one of ter-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-ylmethanesulfonate, and cyclohexyl p-toluenesulfonate.

24. An anion exchange membrane comprising the anion resin according to any one of claims 16 to 18.

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