Nitrogen-containing multi-component copolymer and preparation method therefor, anion resin, and anion exchange membrane

Abstract

The present application provides a nitrogen-containing multi-component copolymer. The multi-component copolymer comprises at least two of a chain segment I, a chain segment II, and a chain segment III; the chain segment I is formula I, wherein Ar1 is an aryl structural unit; the chain segment II is formula II, wherein Ar2 is an aryl structural unit; and the chain segment III is formula III, wherein Ar3 is an aryl structural unit.

Description

Nitrogen-containing multi-component copolymer and preparation method thereof, anion resin, and anion exchange membrane

[0001] This application claims priority to the Chinese patent application filed with the China Patent Office on January 29, 2024, with application number 2024101268158. The entire contents of the above application are incorporated by reference into this application. Technical Field

[0002] The present application belongs to the field of battery technology, and specifically relates to a nitrogen-containing multi-component copolymer and a preparation method thereof, an anion resin, and an anion exchange membrane. Background Art

[0003] Anion exchange membranes are widely used in electrolyzers, fuel cells, carbon dioxide reduction, hard water softening, desalinated water, pure water production, hydrometallurgy, rare element separation, pharmaceuticals, sugar production, and amino acid adsorption. In the field of hydrogen production from water electrolysis, anion exchange membranes (AEMs) are often used to separate hydrogen between the anode and cathode and provide a pathway for anion transport. The active component of anion exchange membranes is the anion resin, which typically consists of a polymer backbone and charged ion-conducting groups connected by long or short side chains. Reported anion resins with backbones such as polyphenylene ether, polyarylene ether, polysulfone, and polybenzimidazole suffer from the drawbacks of high rigidity and difficulty in membrane formation. Anion exchange membranes with quaternary ammonium cations, quaternary phosphonium cations, imidazolium cations, and guanidinium cations as functional side chains are susceptible to degradation in alkaline, high-temperature environments, resulting in a significant decrease in ion conductivity and a reduction in the service life of the fuel cell. Technical issues

[0004] How to improve the flexibility and alkali resistance of anion resin. Technical Solutions

[0005] In the first aspect, the present application provides a nitrogen-containing multi-polymer, the multi-polymer comprising at least two of segment I, segment II, and segment III; segment I is Among them, Ar1 is an aromatic structural unit; segment II is Among them, Ar2 is an aromatic structural unit; segment III is Wherein, Ar3 is an aromatic structural unit.

[0006] In a second aspect, the present application provides a method for preparing a multi-polymer as described above, comprising the following steps: S1. preparing monomer raw materials, selecting corresponding aromatic monomers according to the aromatic structural units contained in the main chain of the multi-polymer, using the aromatic monomers as the main chain monomer raw materials, and selecting branched monomer raw materials according to the types of segments included in the multi-polymer; when the multi-polymer includes segment I, the branched monomer raw materials include the general formula Acetal monomer; when the multi-polymer includes segment II, the branched monomer raw materials include the general formula When the multi-polymer includes segment III, the branched monomer raw materials include the general formula quinuclidine monomer; S2. adding the monomer raw material into an alkyl organic solvent and fully dispersing it to obtain a reaction base liquid; S3. adding an organic acid catalyst to the reaction base liquid to cause the aromatic raw material and the nitrogen-containing acetal monomer in the reaction base liquid to undergo polymerization reaction under the action of the organic acid catalyst; S4. discharging the polymerization reaction product into pure water or alkaline solution to wash away the residual organic acid catalyst, and after washing and drying, obtaining a multi-polymer.

[0007] In a third aspect, the present application provides an anionic resin, wherein the multi-component copolymer comprises at least two of segment I, segment IV, and segment V; segment I is Wherein, Ar1 is an aromatic structural unit, R1 is H, a hydrocarbon group or a substituted hydrocarbon group; segment IV is Among them, Ar2 is an aromatic structural unit, Z1 － represents an anion; segment V is Among them, Ar3 is an aromatic structural unit, Z2 － Indicates anion.

[0008] In a fourth aspect, the present application provides a method for preparing an anion resin: the multi-component copolymer is subjected to a quaternization reaction with a quaternizing agent to prepare an anion resin, wherein the quaternizing agent includes iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromocyclohexane, bromocyclopentane, bromocyclohexane, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, methyl ... At least one of butyl sulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allylsulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, or cyclohexyl p-toluenesulfonate.

[0009] In a fifth aspect, the present application provides an anion exchange membrane comprising the anion resin as described above. Beneficial effects

[0010] The multi-component copolymer provided herein has excellent structural stability, and the different types of chain segments contained therein can be firmly connected. As a result, the anion exchange membrane prepared using the multi-component copolymer has good flexibility and is not easily broken during use. In addition, using the multi-component copolymer provided herein to prepare anion resins and anion exchange membranes can also help improve the alkali resistance of such materials, thereby ensuring that the membrane materials can remain stable and not easily degraded when these anion resins and anion exchange membranes are used in fields such as water electrolysis to produce hydrogen.

[0011] The anion exchange membrane of the present application has excellent flexibility and alkali resistance. When applied to an electrolytic cell, it can not only optimize the interface contact between electrodes but also improve the working stability of the electrolytic cell. Modes for Carrying Out the Invention

[0012] In one embodiment, Ar1, Ar2, and Ar3 each independently comprise at least one of the following structural units:

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

[0014] In one embodiment, the multi-polymer includes a multi-segment I composed of a segment I and a segment II, wherein the multi-segment I is Wherein, 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 multi-polymer includes a multi-segment II composed of segment I and segment III, wherein the multi-segment II is Wherein, 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 multi-polymer includes a multi-segment III composed of a segment II and a segment III, wherein the multi-segment III is Wherein, 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 multi-polymer includes a multi-segment IV composed of segment I, segment II and segment III, wherein the multi-segment IV is Among them, 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 independently selected from integers between 10 and 1,000,000. n1 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n2 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n3 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0019] In one embodiment, n1, n2, and n3 are independently selected from integers between 50 and 300. n1 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n2 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n3 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable. n4 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0020] In one embodiment, the acetal monomer includes at least one of the following monomers:

[0021] In one embodiment, the piperidone monomer comprises at least one of the following monomers:

[0022] In one embodiment, the quinuclidinone monomer comprises at least one of the following monomers:

[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, the specific operation of S3 includes: first lowering the temperature of the reaction base liquid to -5 to 3°C, adding an organic acid catalyst thereto, then heating the reaction base liquid to 5 to 24°C, and polymerizing under this condition for 4 to 48 hours.

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

[0026] In one embodiment, in S4, the alkali solution contains at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, and potassium hydroxide.

[0027] In one embodiment, Ar1, Ar2, and Ar3 each independently comprise at least one of the following structural units:

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

[0029] In one embodiment, the anion resin includes a multi-segment V composed of the segment I and the segment IV, wherein the multi-segment V is 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, R a One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

[0030] In one embodiment, the anion resin includes a multi-segment VI composed of the segment I and the segment V, wherein the multi-segment VI is 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, R b One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

[0031] In one embodiment, the anion resin includes a multi-segment VII composed of the segment IV and the segment V, and the multi-segment VII is Wherein, 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, R a 、R b Each is independently selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

[0032] In one embodiment, the anion resin comprises a multi-segment VIII composed of the segment I, the segment IV and the segment V, wherein the multi-segment VIII is Wherein, 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, R a 、R b Each is independently selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

[0033] In one embodiment, n1, n4, and n5 are independently selected from integers between 10 and 1,000,000. n1 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable. n4 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable. n5 can be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable.

[0034] In one embodiment, n1, n4, and n5 are independently selected from integers between 50 and 300. n1 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable. n4 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable. n5 can be 50, 100, 150, 300, etc., but is not limited to the listed values. Other values ​​not listed within this numerical range are also applicable.

[0035] Products that need to be prepared and characterized in the Examples and Comparative Examples:

[0036] Example 1

[0037] Preparation of segment Ⅰ and segment II The multi-component copolymer is composed of multi-component segments Ⅰ constitute.

[0038] Preparation of copolymer 1-1:

[0039] S1. Take 0.15 mol of m-terphenyl, 0.09 mol of N-methyl-4-piperidone, and 0.09 mol of isobutyraldehyde diethyl acetal respectively;

[0040] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0041] S3. 90 mL of trifluoromethanesulfonic acid was added dropwise to the reaction base solution at -5°C. After the addition was complete, the reaction system was heated to 24°C. The above raw materials underwent hydrocarbon alkylation under this temperature condition for 16 hours. S4. After the reaction in S3 was completed, the product was discharged into pure water and then filtered. The obtained solid was crushed and washed with pure water and dried in sequence to obtain the final product, copolymer 1-1.

[0042] The structure of copolymer 1-1 is shown below:

[0043] Preparation of copolymer 1-2

[0044] S1. Take 0.15 mol of p-terphenyl, 0.09 mol of N-methyl-4-piperidone, and 0.09 mol of isobutyraldehyde diethyl acetal respectively;

[0045] S2. The raw materials weighed in S1 were added to 60 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0046] S3. 90 mL of trifluoromethanesulfonic acid was added dropwise to the reaction base solution at 3°C. After the addition was complete, the reaction system was heated to 13°C. The above raw materials underwent hydrocarbon alkylation under this temperature condition for 24 hours. S4. After the reaction in S3 was completed, the product was discharged into pure water and then filtered. The obtained solid was crushed and washed with pure water and dried in sequence to obtain the final product, copolymer 1-2.

[0047] The structure of copolymer 1-2 is shown below:

[0048] Example 2

[0049] Preparation of segment Ⅰ and segment III The multi-component copolymer is composed of multi-component segments II constitute.

[0050] Preparation of copolymer 2-1:

[0051] S1. Take 0.15 mol of m-terphenyl, 0.12 mol of 3-quinuclidinone hydrochloride, and 0.05 mol of isobutyraldehyde diethyl acetal respectively;

[0052] S2. The raw materials weighed in S1 were added to 45 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0053] S3 at 0 ° C, the reaction mixture was added dropwise to 120mL of trifluoromethanesulfonic acid, after completion of the addition, the reaction system was heated to 24 ° C, the above raw materials under this temperature conditions alkylation reaction, the reaction time is 36 hours;

[0054] After the reaction in S4.S3 is completed, the product is discharged into pure water and then filtered. The obtained solid is crushed, washed with pure water and dried in sequence to obtain the final product, copolymer 2-1.

[0055] The structure of copolymer 2-1 is shown below:

[0056] Preparation of copolymer 2-2:

[0057] S1. Take 0.15 mol of biphenyl, 0.12 mol of 3-quinuclidinone hydrochloride, and 0.05 mol of isobutyraldehyde diethyl acetal respectively;

[0058] S2. The raw materials weighed in S1 were added to 45 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0059] S3 at 0 ° C, the reaction mixture was added dropwise to 100mL trifluoromethanesulfonic acid, after completion of the addition, the reaction system was heated to 13 ° C, the above raw materials under this temperature conditions hydrocarbon alkylation reaction, the reaction time is 12 hours;

[0060] After the reaction in S4.S3 is completed, the product is discharged into pure water and then filtered. The obtained solid is crushed, washed with pure water and dried in sequence to obtain the final product, copolymer 2-2.

[0061] The structure of copolymer 2-2 is shown below:

[0062] Example 3

[0063] Preparation of segment II and segment III The multi-component copolymer is composed of multi-component segments III constitute.

[0064] Preparation of copolymer 3-1:

[0065] S1. Take 0.15 mol of p-terphenyl, 0.09 mol of 3-quinuclidinone hydrochloride, and 0.09 mol of N-methyl-4-piperidone respectively;

[0066] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0067] S3 at 0 ° C, the reaction mixture was added dropwise to 120mL trifluoromethanesulfonic acid, after completion of the addition, the reaction system was heated to 13 ° C, the above raw materials under this temperature conditions alkylation reaction, the reaction time is 8 hours;

[0068] After the reaction in S4.S3 is completed, the product is discharged into pure water and then filtered. The obtained solid is crushed, washed with pure water and dried in sequence to obtain the final product, copolymer 3-1.

[0069] The structure of copolymer 3-1 is shown below:

[0070] Preparation of copolymer 3-2:

[0071] S1. Take 0.15 mol of m-terphenyl, 0.09 mol of 3-quinuclidinone hydrochloride, and 0.09 mol of N-ethyl-4-piperidone respectively;

[0072] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0073] S3 at 0 ° C, the reaction mixture was added dropwise to 120mL trifluoromethanesulfonic acid, after completion of the addition, the reaction system was heated to 8 ° C, the above raw materials under this temperature conditions alkylation reaction, the reaction time is 14 hours;

[0074] After the reaction in S4.S3 is completed, the product is discharged into pure water and then filtered. The obtained solid is crushed, washed with pure water and dried in sequence to obtain the final product, copolymer 3-2.

[0075] The structure of copolymer 3-2 is shown below:

[0076] Example 4

[0077] Preparation of segment Ⅰ Segment II and segment III The multi-component copolymer is composed of multi-component segments IV constitute.

[0078] Preparation of copolymer 4-1:

[0079] S1. Take 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 respectively;

[0080] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0081] S3. At 0°C, 120 mL of trifluoromethanesulfonic acid was added dropwise to the reaction base solution. After the addition was complete, the reaction system was heated to 13°C. The above raw materials underwent hydrocarbon alkylation under this temperature condition for 36 hours. S4. After the reaction in S3 was completed, the product was discharged into pure water and then filtered. The obtained solid was crushed and washed with pure water and dried in sequence to obtain the final product, copolymer 4-1.

[0082] The structure of copolymer 4-1 is shown below:

[0083] Preparation of copolymer 4-2:

[0084] S1. Take 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 respectively;

[0085] S2. The raw materials weighed in S1 were added to 80 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0086] S3. 120 mL of trifluoromethanesulfonic acid was added dropwise to the reaction base solution at 3°C. After the addition was complete, the reaction system was heated to 13°C. The above raw materials underwent hydrocarbon alkylation under this temperature condition for 48 hours. S4. After the reaction in S3 was completed, the product was discharged into pure water and then filtered. The obtained solid was crushed and washed with pure water and dried in sequence to obtain the final product, copolymer 4-2.

[0087] The structure of copolymer 4-2 is shown below:

[0088] Comparative Example 1

[0089] Preparation of segment Ⅰ The polymer is composed of the general formula of

[0090] Preparation of polymer 5-1:

[0091] S1. Take 0.15 mol of m-terphenyl and 0.17 mol of isobutyraldehyde diethyl acetal respectively;

[0092] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0093] S3. 90 mL of trifluoromethanesulfonic acid was added dropwise to the reaction base solution at -3°C. After the addition was complete, the reaction system was heated to 18°C. The above raw materials underwent hydrocarbon alkylation under this temperature condition for 24 hours. S4. After the reaction in S3 was completed, the product was discharged into pure water and then filtered. The obtained solid was pulverized, washed with pure water, and dried to obtain the final product, polymer 5-1.

[0094] The structure of polymer 5-1 is shown below:

[0095] Comparative Example 2

[0096] Preparation of segment II The polymer is composed of the general formula of

[0097] Preparation of polymer 6-1:

[0098] S1. Take 0.15 mol of p-terphenyl monomer and 0.18 mol of 3-quinuclidinone hydrochloride respectively;

[0099] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0100] S3. At 0°C, 120 mL of trifluoromethanesulfonic acid was added dropwise to the reaction base solution. After the addition was complete, the reaction system was heated to 24°C. The above raw materials underwent hydrocarbon alkylation under this temperature condition for 36 hours. S4. After the reaction in S3 was completed, the product was discharged into pure water and then filtered. The obtained solid was pulverized, washed with pure water, and dried to obtain the final product, polymer 6-1.

[0101] The structure of polymer 6-1 is shown below:

[0102] Comparative Example 3

[0103] Preparation of segment III The polymer is composed of the general formula of

[0104] Preparation of polymer 7-1:

[0105] S1. Take 0.15 mol of m-terphenyl and 0.18 mol of N-methyl-4-piperidone respectively;

[0106] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0107] S3 at 0 ℃, to the reaction bottom solution was added dropwise 90mL trifluoromethanesulfonic acid, after completion of the addition, the reaction system was heated to 13 ℃, the above raw materials under this temperature conditions alkylation reaction, the reaction time is 6 hours;

[0108] After the reaction of S4.S3 is completed, the product is discharged into pure water and then filtered. The obtained solid is crushed, washed with pure water and dried in sequence to obtain the final product, polymer 7-1.

[0109] The structure of polymer 7-1 is shown below:

[0110] Example 5

[0111] 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 prepared in Examples 1 to 4 and Comparative Examples 1 to 3 are used as nitrogen-containing high molecular weight polymers for preparing chloride ion anion resin, and iodomethane is used as a quaternizing agent to prepare chloride ion anion resin through quaternization reaction and ion exchange.

[0112] Preparation of chloride ion type anion resin:

[0113] Step 1. A nitrogen-containing polymer and methyl iodide are dissolved in dimethyl sulfoxide to obtain a reaction solution, and then the nitrogen-containing polymer and methyl iodide in the reaction solution are subjected to a quaternization reaction at 50 to 100 ° C. The reaction time is 3 to 36 hours. After completion of the reaction, a product solution containing an iodide-type anion resin is obtained;

[0114] Step 2. A precipitant is added to the product solution. In this embodiment, deionized water is used as the precipitant to allow the precipitate to fully precipitate. The precipitate is then filtered out, and the precipitate is ion exchanged with KOH and NaCl aqueous solutions, washed, and dried to obtain a solid, which is a chloride ion anion resin obtained by the above-mentioned quaternization reaction.

[0115] According to the different nitrogen-containing polymers used, the conditions of the quaternization reaction were optimized with the highest conversion rate of the quaternization reaction as the optimization standard. The optimized reaction conditions are specifically shown in Table 1.

[0116] Table 1. Reaction conditions for the quaternization reaction in Example 5

[0117] Example 6

[0118] In this example, copolymers 1-1, 1-2, 2-1, 2-2, 3-1, 3-2, 4-1, 4-2, 5-1, 6-1, and 7-1 prepared in Examples 1 to 4 and Comparative Examples 1 to 3 were used as nitrogen-containing polymers for preparing sulfonic acid anion resins, and sulfonic acid ester compounds were used as quaternizing agents to prepare sulfonic acid anion resins through a quaternization reaction.

[0119] Preparation of sulfonic acid anion resin:

[0120] Step 1. The nitrogen-containing polymer and the sulfonate compound are dissolved in dimethyl sulfoxide to obtain a reaction solution, and then the nitrogen-containing polymer and the sulfonate compound in the reaction solution are quaternized at 70 to 120 ° C for 3 to 72 hours. After completion of the reaction, a product solution containing a sulfonic acid anion resin is obtained;

[0121] Step 2. A precipitant is added to the product solution. In this embodiment, deionized water is used as the precipitant to allow the precipitate to fully precipitate. The precipitate thus obtained is then filtered out, washed, and dried. The solid thus obtained is the sulfonic acid anion resin obtained by the above-mentioned quaternization reaction.

[0122] According to the different nitrogen-containing polymers used, the type of quaternizing agent and reaction conditions of the quaternization reaction were optimized respectively with the highest conversion rate of the quaternization reaction as the optimization standard. The optimized reaction conditions are shown in Table 2.

[0123] Table 2. Reaction conditions for the quaternization reaction in Example 6

[0124] Test Example 1

[0125] 1. Test subjects

[0126] Anion exchange membranes were further prepared using the anion resins prepared in Examples 5 and 6, and the anion exchange membranes thus prepared were used as test objects.

[0127] 2. Test items

[0128] (1) Mechanical properties test

[0129] Refer to GB T 20042.3 and apply pure tensile force to the test object to make it break.

[0130] a. Tensile strength: This measures the ratio of the maximum load a test object can withstand when breaking under pure tensile force to the width of the stretched membrane. It is divided into transverse and longitudinal tensile strengths and is used to evaluate the mechanical strength of the membrane.

[0131] b. Elongation at break: This value is the ratio of the distance between two points at break to the original length under the maximum load applied to the test object before breaking. This value indicates the maximum deformation that the alkaline membrane can withstand before breaking and serves as an indicator of membrane flexibility.

[0132] 3. Test results

[0133] The test results of this test case are shown in Table 3 and Table 4.

[0134] The structural units constituting polymer 5-1 are The molecular structures of polymers 1-1, 2-1, and 4-2 also contain the above structural units. However, compared with the test objects prepared using polymer 5-1, when the anion types contained in the anion resin are the same, the test objects prepared using polymers 1-1, 2-1, and 4-2 respectively have higher tensile strength and elongation at break. Although the molecular structures of polymers 1-2, 2-2, and 4-1 do not contain the same chain segments as the structural units constituting polymer 5-1, the structural units constituting polymer 5-1 conform to the general formula: Segment I Similarly, the molecular structures of polymers 1-2, 2-2, and 4-1 also include structural units that conform to the above-mentioned general formula segment I. However, compared with the test objects prepared using polymers 1-1, 2-1, and 4-2, respectively, when the types of anions contained in the anion resin are the same, the tensile strength and elongation at break measured by the test objects prepared using polymer 5-1 are still relatively low.

[0135] The structural units constituting polymer 6-1 are The molecular structures of polymers 1-2, 3-1, and 4-1 also contain the above structural units. However, compared with the test objects prepared using polymer 6-1, when the anion types contained in the anion resin are the same, the test objects prepared using polymers 1-2, 3-1, and 4-1 respectively have higher tensile strength and elongation at break. Although the molecular structures of polymers 1-1, 3-2, and 4-2 do not contain the same chain segments as the structural units constituting polymer 6-1, the structural units constituting polymer 6-1 conform to the general formula Segment II Similarly, the molecular structures of polymers 1-1, 3-2, and 4-2 also include structural units that conform to the above-mentioned general formula segment II. However, compared with the test objects prepared using polymers 1-1, 3-2, and 4-2, respectively, when the types of anions contained in the anion resin are the same, the tensile strength and elongation at break measured by the test objects prepared using polymer 6-1 are still relatively low.

[0136] The structural units constituting polymer 7-1 are The molecular structures of polymers 2-1, 3-2, and 4-2 also contain the above-mentioned structural units. However, compared with the test objects prepared using polymer 7-1, when the anion resin contains the same type of anions, the test objects prepared using polymers 2-1, 3-2, and 4-2 respectively have higher tensile strength and elongation at break. Although the molecular structures of polymers 2-2, 3-1, and 4-1 do not contain the same chain segments as the structural units constituting polymer 7-1, the structural units constituting polymer 7-1 conform to the general formula segment III. Similarly, the molecular structures of polymers 2-2, 3-1, and 4-1 also include structural units that conform to the above-mentioned general formula segment III. However, compared with the test objects prepared using polymers 2-2, 3-1, and 4-1, respectively, when the types of anions contained in the anion resin are the same, the tensile strength and elongation at break measured by the test objects prepared using polymer 7-1 are still relatively low.

[0137] In general, the test results of this test example show that compared with nitrogen-containing polymers constructed using only one structural unit from segment I, segment II, and segment III, selecting any two or more of the above segments to combine and jointly construct a nitrogen-containing multipolymer, and further using these nitrogen-containing multipolymers to prepare anion resins and anion exchange membranes, the flexibility of the anion exchange membrane can be improved, and the anion exchange membrane has higher tensile strength and elongation at break. Applying such anion exchange membranes to electrolytic cells can optimize the interfacial contact between the electrodes.

[0138] Table 3. Mechanical properties test of the test object of the chloride ion anion resin provided in Example 5

[0139] Table 4. Mechanical properties test of the test object using the sulfonic acid anion resin provided in Example 6

[0140] Test Example 2

[0141] 1. Test subjects

[0142] An anion exchange membrane was further prepared using the anion resin prepared in Example 5, and the anion exchange membrane thus prepared was used as a test object.

[0143] 2. Stability test

[0144] Test method: Cut the test object into a 2cm*2cm film sample, immerse it in 1M NaOH aqueous solution and seal it. Place the solution in an 80℃ oven for 2000 hours, take out the film sample and test it. 1 The degradation rate of the membrane sample was calculated by HNMR test. The grafting rate of the original membrane material was recorded as G0, and the grafting rate of the membrane material after soaking in NaOH aqueous solution was recorded as G1. The degradation rate was calculated as [(G0-G1) / G0]*100%.

[0145] Grafting rate calculation method:

[0146] a. Determination of ion exchange capacity (IEC)

[0147] The test object was cut into 50 mm x 50 mm membrane samples. The membrane samples were immersed in a 1 mol / L KOH solution at 80°C for 24 hours to exchange the anions in the membrane sample with hydroxide ions, resulting in a hydroxide-type membrane sample. The hydroxide-type membrane sample was then immersed in a 1 mol / L NaCl solution at 60°C and allowed to stand for 48 hours to perform ion exchange, exchanging the hydroxide ions in the hydroxide-type membrane sample with chloride ions, resulting in a chloride-type membrane sample. The chloride-type membrane sample was thoroughly washed with deionized water to ensure that all NaCl adsorbed on the chloride-type membrane sample was completely washed away. The chloride-type membrane sample was then dried with filter paper and placed in 50 mL of a 0.1 mol / L NaNO₃ solution at 60°C for 48 hours to completely exchange the chloride ions in the membrane sample with the NaNO₃ solution. The amount of chloride ions exchanged into the NaNO₃ solution was equivalent to the amount of anions to be measured in the test object obtained through the quaternization reaction described above. Titrate the chloride ion content in the membrane: add 10mL of NaNO3 solution that has been fully soaked with the chloride-type membrane sample to the conical flask, and add two drops of K2CrO4 as an indicator. Titrate the above NaNO3 solution with a calibrated 0.01mol / L AgNO3 until a brick-red precipitate is produced. Record the volume of AgNO3 solution consumed, which is recorded as V AgNO3 Titrate in parallel 3 times and take the average value to calculate the chloride ion content in the chloride-type membrane sample. Finally, take out the membrane sample and wash it thoroughly with deionized water. After it is fully dried in the oven, take it out quickly and weigh the mass of the dry membrane, which is recorded as m dry The ion exchange capacity of the membrane sample can be calculated by the formula: IEC = 5 × C AgNO3 ×V AgNO3 / m dry , where: IEC is the ion exchange capacity of the membrane sample, in mol / g; C AgNO3 is the concentration of the calibrated AgNO3 solution, the unit is mol / L, and the average value of three titration results is taken; V AgNO3The volume of AgNO3 solution consumed in titration is L, and the average of three titrations is taken; m dry It is the mass of the dry membrane sample after titration and drying, and the unit is g.

[0148] b. Grafting rate calculation formula

[0149] The grafting rate is the ratio of the actual grafting rate to the theoretical grafting rate, that is:

[0150] Grafting rate = (IEC 实际 / IEC 理论 )*100%.

[0151] 3. Test results

[0152] The test results of this test example are shown in Table 5. Among the test subjects, the chloride-type anion exchange resins prepared using copolymers 5-1, 6-1, and 7-1, respectively, exhibited relatively high degradation rates. As mentioned above, copolymers 5-1, 6-1, and 7-1 are nitrogen-containing polymers constructed using a single structural unit from segment I, segment II, and segment III, respectively. The experimental results of this test example demonstrate that combining any two or more of these segments to construct nitrogen-containing multi-component copolymers, and further utilizing these nitrogen-containing multi-component copolymers to prepare anion resins and anion exchange membranes, can improve the alkali resistance of the anion exchange membranes and reduce their degradation rate in electrolytic cells. In addition, the alkali resistance of the anion resin is mainly determined by the main molecular structure of the anion resin. Although the anion resin prepared in Example 6 and the anion resin prepared in Example 5 have different anion types, when the sulfonic acid anion resin prepared in Example 6 is used to perform an alkali resistance test, the test results are consistent with the results measured in this test example.

[0153] Table 5. Alkali resistance test of the test objects of the chloride ion anion resin provided in Example 5

Claims

1. A nitrogen-containing multi-component copolymer, The multi-component copolymer includes at least two of segment I, segment II, and segment III; The segment I is in, Ar1 is an aromatic structural unit; The segment II is Wherein, Ar2 is an aromatic structural unit; The segment III is Wherein, Ar3 is an aromatic structural unit.

2. The nitrogen-containing multi-component copolymer according to claim 1, wherein The Ar1, Ar2, and Ar3 each independently comprise at least one of the following structural units:

3. The nitrogen-containing multi-polymer according to claim 1, wherein: The R1, R2, R3, and R4 are independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

4. The nitrogen-containing multi-component copolymer according to any one of claims 1 to 3, wherein: The multi-component copolymer includes a multi-component segment I composed of the segment I and the segment II, wherein the multi-component segment I is 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.

5. The nitrogen-containing multi-component copolymer according to any one of claims 1 to 3, wherein: The multi-component copolymer includes a multi-component segment II composed of the segment I and the segment III, wherein the multi-component segment II is 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.

6. The nitrogen-containing multi-component copolymer according to any one of claims 1 to 3, wherein: The multi-component copolymer includes a multi-component segment III composed of the segment II and the segment III, wherein the multi-component segment III is 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.

7. The nitrogen-containing multi-component copolymer according to any one of claims 1 to 3, wherein: The multi-component copolymer includes a multi-component segment IV composed of the segment I, the segment II and the segment III, wherein the multi-component segment IV is 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.

8. A method for preparing the nitrogen-containing multi-component copolymer according to any one of claims 1 to 7, comprising the following steps: S1. Prepare monomer raw materials, select corresponding aromatic monomers according to the aromatic structural units contained in the main chain of the multi-polymer, use the aromatic monomers as the main chain monomer raw materials, and select branched monomer raw materials according to the types of segments included in the multi-polymer; when the multi-polymer includes the segment I, the branched monomer raw materials include the general formula When the multi-polymer includes the segment II, the branched monomer raw material includes the general formula When the multi-polymer includes the segment III, the branched monomer raw material includes the general formula Quinuclidinone monomer; S2. The monomer raw material is put into an alkyl organic solvent and fully dispersed to obtain a reaction bottom liquid; S3. An organic acid catalyst is added to the reaction base liquid, so that the aromatic raw material and the nitrogen-containing acetal monomer in the reaction base liquid are polymerized under the action of the organic acid catalyst; S4. The product of the polymerization reaction is discharged into pure water or alkaline solution to wash away the residual organic acid catalyst. After washing and drying, the multi-component copolymer is obtained.

9. The method of claim 8, wherein: The acetal monomer includes at least one of the following monomers:

10. The method of claim 8, wherein: The piperidone monomer comprises at least one of the following monomers:

11. The method of claim 8, wherein: The quinuclidine monomer comprises at least one of the following monomers:

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

13. The method of claim 12, wherein: The specific operation of S3 includes: firstly lowering the temperature of the reaction base liquid to -5 to 3°C, adding the organic acid catalyst thereto, then raising the temperature of the reaction base liquid to 5 to 24°C, and polymerizing under this condition for 4 to 48 hours.

14. The method of claim 8, wherein: The alkyl organic solvent includes at least one of dichloromethane, chloroform, chloroform and tetrahydrofuran.

15. The method of claim 8, wherein: In S4, the alkali solution contains at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate or potassium hydroxide.

16. An anionic resin, The anionic resin includes at least two of segment I, segment IV, and segment V; The segment I is in, Ar1 is an aromatic structural unit; The segment IV is Among them, Ar2 is an aromatic structural unit, Z1 － represents anion; The segment V is Among them, Ar3 is an aromatic structural unit, Z2 － Indicates anion.

17. The anionic resin according to claim 16, wherein The Ar1, Ar2, and Ar3 each independently comprise at least one of the following structural units:

18. The anionic resin according to claim 16, wherein: The R1, R2, R3, and R4 are independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

19. The anionic resin according to any one of claims 16 to 18, wherein: The anion resin includes a multi-segment V composed of the segment I and the segment IV, and the multi-segment V is Wherein, 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 the R a One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

20. The anionic resin according to any one of claims 16 to 18, wherein: The anion resin includes a multi-segment VI composed of the segment I and the segment V, and the multi-segment VI is Wherein, 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 the R b One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

21. The anionic resin according to any one of claims 16 to 18, wherein: The anion resin includes a multi-segment VII composed of the segment IV and the segment V, and the multi-segment VII is Wherein, 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 the R a 、The R b Each is independently selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

22. The anionic resin according to any one of claims 16 to 18, wherein: The anion resin includes a multi-segment VIII composed of the segment I, the segment IV and the segment V, and the multi-segment VIII is Wherein, 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 the R a 、The R b Each is independently selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group.

23. A method for preparing an anion resin, comprising subjecting the multi-component copolymer according to any one of claims 1 to 7 to a quaternizing agent to a quaternizing reaction to obtain the anion resin, wherein the quaternizing agent comprises methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, cyclohexyl bromide, cyclopentyl bromide, cyclohexyl bromide, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, At least one of butyl methanesulfonate, butyl ethanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allylsulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, or cyclohexyl p-toluenesulfonate.

24. An anion exchange membrane comprising the anion resin according to any one of claims 16 to 22.

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