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

Abstract

To solve the technical problem of enhancing flexibility of an anion exchange membrane while also increasing both its tensile strength and elongation at break.SOLUTION: The present application provides a nitrogen-containing compound, which includes a segment I, the segment I represented by the following formula, wherein a represents the number of methylene groups, a is a positive integer, Ar1 is an aryl structural unit, and R1, R2 are each independently selected from H, a hydrocarbyl group, or a substituted hydrocarbyl group, or, R1, R2 are connected and form a poly-membered ring together with the N atom to which they are connected.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This application claims priority from a Chinese patent application filed with the China Patent Office on January 29, 2024, bearing application number 2024101267846, the entire contents of which are incorporated herein by reference.

[0002] The present application belongs to the field of battery technology, and specifically relates to a nitrogen-containing compound and a method for producing the same, 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, hard water softening, desalting, pure water production, hydrometallurgy, rare element separation, pharmaceuticals, sugar refining, and amino acid adsorption. In the field of water electrolysis, anion exchange membranes (AEMs) are often used to separate hydrogen gas between the anode and cathode and provide anion transport channels. The effective active component of anion exchange membranes is an anion resin, which generally consists of a polymer backbone and charged ion-conducting groups, connected by long or short side chains. Previously reported anion exchange resins with backbones such as polyphenylene ether, polyarylene ether, polysulfone, and polybenzimidazole have the disadvantage of being relatively rigid and difficult to form into membranes. Summary of the Invention [Problem to be solved by the invention]

[0004] The present application aims to solve the technical problem of how to improve the flexibility of an anion exchange membrane and increase both its tensile strength and breaking elongation. [Means for solving the problem]

[0005] According to a first aspect, the present application provides a nitrogen-containing compound, the nitrogen-containing compound comprising Segment I, [ka] wherein a represents the number of methylene groups, a is a positive integer, Ar1 is an aryl structural unit, R1 and R2 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, or R1 and R2 are linked to form a multi-membered ring together with the N atom to which they are attached.

[0006] According to a second aspect, the present application provides a method for producing the nitrogen-containing compound described above, the method comprising: preparing a monomer raw material; selecting a corresponding aromatic monomer according to the aryl structural unit contained in the main chain of a multi-component copolymer; and, using the aromatic monomer as the main chain monomer raw material, preparing a multi-component copolymer having a general formula represented by the formula: [ka] The method includes steps S1 (Step 1) of selecting a branched-chain monomer raw material containing an amino acetal monomer represented by the formula: S2 of adding the monomer raw material to an alkyl organic solvent and dispersing it sufficiently to obtain a reaction base solution; S3 of adding an organic acid catalyst to the reaction base solution and polymerizing the aromatic raw material and the nitrogen-containing acetal monomer in the reaction base solution under the action of the organic acid catalyst; and S4 of discharging the product of the polymerization reaction into pure water or an alkaline solution, washing off the remaining organic acid catalyst, and then obtaining a nitrogen-containing compound after washing and drying.

[0007] According to a third aspect, the present application provides an anion exchange resin, the anion exchange resin comprising a segment V, wherein the segment V is [ka] wherein a represents the number of methylene groups, a is a positive integer, Ar1 is an aryl structural unit, R1 and R2 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, or R1 and R2 are linked together to form a multi-membered ring together with the N atom to which they are attached, and R ais one selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group, and Z1 - 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 nitrogen-containing compound with a quaternizing reagent to produce the 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) at least one of the following:

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

[0010] By utilizing a structural unit that conforms to segment I of the general formula to participate in the construction of a large molecule of a nitrogen-containing compound, the flexibility of an anion exchange membrane produced using the nitrogen-containing compound can be improved, and both the tensile strength and the elongation at break can be increased.

[0011] The anion protection membrane of the present application has excellent flexibility, and when applied to an electrolysis channel, it can optimize the interfacial contact between the electrodes. DETAILED DESCRIPTION OF THE INVENTION

[0012] In one embodiment, in segment I, Ar1 is [ka] It contains at least one of the following structural units.

[0013] In one embodiment, in segment I, Ar1 is [ka] Includes:

[0014] In one embodiment, in segment I, R1 and R2 are each independently selected from H, a methyl group, a C2-C7 linear alkyl group, a C3-C10 cycloalkyl group, an aryl group, or a substituted aryl group; or R1 and R2 are linked together to form a multi-membered ring together with the N atom to which they are attached, and the multi-membered ring is a five-, six-, or seven-membered ring.

[0015] In one embodiment, in segment I, R1 and R2 are independently selected from a methyl group or a C2 to C7 linear alkyl group.

[0016] In one embodiment, segment I comprises: [ka] is.

[0017] In one embodiment, in segment I, R1 and R2 are linked to form a six-membered ring with the N atom to which they are attached.

[0018] In one embodiment, the six-membered ring is a piperidine ring or a piperazine ring.

[0019] In one embodiment, segment I comprises: [ka] is.

[0020] In one embodiment, the nitrogen-containing compound further comprises at least one of Segment II, Segment III, and Segment IV, wherein Segment II comprises: [ka] where Ar2 is an aryl structural unit and segment III is [ka] where Ar3 is an aryl structural unit and segment IV is [ka] where Ar4 is an aryl structural unit.

[0021] In one embodiment, Ar2, Ar3, and Ar4 are each independently [ka] It contains at least one of the following structural units.

[0022] In one embodiment, R3, R4, R5, and R6 are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0023] In one embodiment, the nitrogen-containing compound has the general formula: [ka] wherein n1 represents the degree of polymerization of Segment I, n2 represents the degree of polymerization of Segment II, n2 is a non-negative integer, n3 represents the degree of polymerization of Segment III, n3 is a non-negative integer, Ar3 is an aryl structural unit, and n4 represents the degree of polymerization of Segment IV, n4 is a non-negative integer.

[0024] In one embodiment, n1, n2, n3, and n4 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 recited values and other unrecited values within this range also apply. n2 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the recited values and other unrecited values within this range also apply. n3 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the recited values and other unrecited values within this range also apply. n4 may be 10, 500, 2000, 10000, 500000, 1000000, etc., but is not limited to the enumerated values, and other unenumerated values within this range also apply.

[0025] In one embodiment, n1, n2, n3, and n4 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 this range also apply. n2 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply. n3 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply. n4 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply.

[0026] [ka]

[0027] In one embodiment, the aminoacetal monomer is [ka] The monomers include at least one of the following:

[0028] In one embodiment, the branched monomer feedstock further comprises a piperidone monomer, the piperidone monomer having the general structural formula: [ka] is.

[0029] In one embodiment, the piperidone monomer is [ka] The monomers include at least one of the following:

[0030] In one embodiment, the branched monomer material further comprises a quinuclidinone monomer, the quinuclidinone monomer having the general structural formula: [ka] is.

[0031] In one embodiment, the quinuclidinone monomer is [ka] The monomers include at least one of the following:

[0032] In one embodiment, the branched monomer feedstock further comprises an acetal monomer, the acetal monomer having the general structural formula: [ka] is.

[0033] In one embodiment, the acetal monomer is [ka] The monomers include at least one of the following:

[0034] In one embodiment, the organic acid catalyst comprises at least one of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid.

[0035] In one embodiment, the specific procedure for S3 (step 3) involves first lowering the temperature of the reaction base solution to 0-3°C, adding an organic acid catalyst thereto, and then heating the reaction base solution to 5-24°C and polymerizing under these conditions for 2-24 hours. In S3, before adding the organic acid catalyst, the temperature of the reaction base solution may be controlled to 0°C, 1°C, 2°C, 2.5°C, 3°C, etc., but is not limited to the recited values and any other unrecited values within the above range also apply. After adding the organic acid catalyst, the reaction solution may be heated to 5°C, 10°C, 15°C, 20°C, or 24°C, but is not limited to the recited values and any other unrecited values within the above temperature range also apply. The reaction time may be 2 hours, 5 hours, 10 hours, 16 hours, or 24 hours, but is not limited to the recited values and any other unrecited values within the applicable reaction time range also apply.

[0036] In one embodiment, the alkyl organic solvent comprises at least one of dichloromethane, trichloromethane, chloroform, and tetrahydrofuran.

[0037] In one embodiment, in S4 (step 4), the alkaline solution contains at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, and potassium hydroxide.

[0038] In one embodiment, in segment V, Ar1 is: [ka] It contains at least one of the following structural units.

[0039] In one embodiment, the anion resin further comprises at least one of segment VI, segment VII, and segment IV, wherein segment VI comprises: [ka] where Ar2 is an aryl structural unit and Z2 - represents an anion, and R b is one selected from an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group, and segment VII is [ka] where Ar3 is an aryl structural unit and Z3 - represents an anion, and R c is one selected from an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group, and segment IV is [ka] where Ar4 is an aryl structural unit.

[0040] In one embodiment, the anion resin has the general formula: [ka] wherein n5 represents the degree of polymerization of segment V, n5 being a positive integer, n6 represents the degree of polymerization of segment VI, n6 being a non-negative integer, n7 represents the degree of polymerization of segment VII, n7 being a non-negative integer, and n8 represents the degree of polymerization of segment IV, n8 being a non-negative integer.

[0041] In one embodiment, n5, n6, n7, and n8 are each independently selected from integers between 10 and 1,000,000. n5 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the recited values and other unrecited values within this range also apply. n6 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the recited values and other unrecited values within this range also apply. n7 may be 10, 500, 2,000, 10,000, 500,000, 1,000,000, etc., but is not limited to the recited values and other unrecited values within this range also apply. n8 may be 10, 500, 2000, 10000, 500000, 1000000, etc., but is not limited to the enumerated values, and other unenumerated values within this range apply as well.

[0042] In one embodiment, n5, n6, n7, and n8 are each independently selected from integers between 50 and 300. n5 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply. n6 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply. n7 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply. n8 may be 50, 100, 150, 300, etc., but is not limited to the recited values and other unrecited values within this range also apply. [Example]

[0043] Example 1 In this embodiment, segment I [ka] A nitrogen-containing compound consisting of the following was produced.

[0044] (1) The production of nitrogen-containing compound A1 is as follows: In S1 (step 1), 0.15 mol of 9,9-dimethylfluorene and 0.18 mol of dimethylaminoacetaldehyde diethanol were taken. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C. After the addition is completed, the reaction system is heated to 8°C. Under this temperature condition, a hydrocarbon alkylation reaction occurs in the raw material, and the reaction time is set to 3 hours. In S4 (step 4), after the reaction of 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, nitrogen-containing compound A1.

[0045] The general structural formula of the nitrogen-containing compound A1 thus produced is: [ka] is.

[0046] (2) The nitrogen-containing compound A2 is produced as follows. In S1 (step 1), 0.15 mol of 9,9-dimethylfluorene and 0.18 mol of 1-(2,2-diethoxyethyl)piperidine were taken. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 100 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at -3°C. After the addition is completed, the reaction system is heated to 5°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is set to 6 hours. In S4 (step 4), after the reaction of 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, nitrogen-containing compound A2.

[0047] The general structural formula of the nitrogen-containing compound A2 thus produced is: [ka] is.

[0048] (3) The production of nitrogen-containing compound A3 is as follows: In S1 (Step 1), 0.15 mol of terphenyl and 0.18 mol of dimethylaminoacetaldehyde diethanol were taken. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 60 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 3°C, and after the addition is completed, the reaction system is heated to 13°C, and the hydrocarbon alkylation reaction of the raw material is caused to occur under this temperature condition, and the reaction time is 3 hours. In S4 (step 4), after the reaction of 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, nitrogen-containing compound A3.

[0049] The general structural formula of the nitrogen-containing compound A3 thus produced is: [ka] is.

[0050] (4) The production of nitrogen-containing compound A4 is as follows: In S1 (step 1), 0.15 mol of m-terphenyl, 0.18 mol of dimethylaminoacetaldehyde diethanol, and 0.05 mol of 1-(dimethoxymethyl)piperidine were taken. In S2 (step 2), the raw materials weighed in S1 are added to 45 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C. After the addition is completed, the reaction system is heated to 13°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is set to 6 hours. In step S4 (step 4), after the reaction in step S3 was completed, the product was poured into pure water, filtered, and the resulting solid was crushed, washed with pure water, and dried to obtain the final product, nitrogen-containing compound A4.

[0051] The general structural formula of the nitrogen-containing compound A4 thus produced is: [ka] is.

[0052] <Example 2> In this embodiment, segment I [ka] and Segment II [ka] A nitrogen-containing compound was produced by the joint production of

[0053] The nitrogen-containing compound B is prepared as follows. In S1 (step 1), 0.15 mol of p-terphenyl, 0.14 mol of N-methyl-4-piperidone, and 0.04 mol of dimethylaminoacetaldehyde diethanol were taken, respectively. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C. After the addition is completed, the reaction system is heated to 13°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is set to 10 hours. In S4 (step 4), after the reaction in 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, nitrogen-containing compound B.

[0054] The general structural formula of the nitrogen-containing compound B produced thereby is: [ka] is.

[0055] Example 3 In this embodiment, segment I [ka] and Segment III [ka] A nitrogen-containing compound was produced by the joint production of

[0056] The preparation of nitrogen-containing compound C is as follows. In S1 (Step 1), 0.15 mol of p-terphenyl, 0.12 mol of 3-quinuclidinone hydrochloride, and 0.06 mol of 1-(dimethoxymethyl)piperidine were taken, respectively. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 3°C. After the addition is completed, the reaction system is heated to 13°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is 18 hours. In S4 (step 4), after the reaction in 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, nitrogen-containing compound C.

[0057] The general structural formula of the nitrogen-containing compound C produced thereby is: [ka] is.

[0058] Example 4 In this embodiment, segment I [ka] and segment IV [ka] A nitrogen-containing compound was produced by the joint production of

[0059] The preparation of nitrogen-containing compound D is as follows. In S1 (Step 1), 0.15 mol of p-terphenyl, 0.12 mol of 1-(dimethoxymethyl)piperidine, and 0.06 mol of isobutyraldehyde diethyl acetal were taken, respectively. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 3°C. After the addition is completed, the reaction system is heated to 8°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is set to 12 hours. In S4 (step 4), after the reaction in 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, nitrogen-containing compound D.

[0060] The general structural formula of the nitrogen-containing compound D produced thereby is: [ka] is.

[0061] <Example 5> In this embodiment, segment I [ka] and Segment II [ka] and Segment III [ka] and Segment IV [ka] A nitrogen-containing compound was produced by the joint production of

[0062] The nitrogen-containing compound E is prepared as follows. In S1 (step 1), 0.15 mol of p-terphenyl, 0.08 mol of N-methyl-4-piperidone, 0.06 mol of 3-quinuclidinone hydrochloride, 0.02 mol of dimethylaminoacetaldehyde diethanol, and 0.02 mol of isobutyraldehyde diethyl acetal were taken, respectively. In S2 (step 2), the raw materials weighed in S1 are added to 70 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 135 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 3°C. After the addition is completed, the reaction system is heated to 24°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is set to 20 hours. In S4 (step 4), after the reaction in 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, nitrogen-containing compound E.

[0063] The nitrogen-containing compound produced thereby has the general structural formula E: [ka] is.

[0064] <Comparative Example 1> This comparative example is segment II [ka] A nitrogen-containing compound consisting of the following was produced.

[0065] The nitrogen-containing compound F is prepared as follows. In S1 (Step 1), 0.15 mol of p-terphenyl monomer and 0.18 mol of 3-quinuclidinone hydrochloride were taken. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 120 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C. After the addition is completed, the reaction system is heated to 24°C. Under this temperature condition, the hydrocarbon alkylation reaction of the raw material is caused to occur, and the reaction time is 36 hours. In S4 (step 4), after the reaction of 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, nitrogen-containing compound F.

[0066] The general structural formula of the nitrogen-containing compound F produced thereby is: [ka] is.

[0067] <Comparative Example 2> This comparative example is segment III [ka] A nitrogen-containing compound consisting of the following was produced.

[0068] The nitrogen-containing compound G is produced as follows. In S1 (Step 1), 0.15 mol of p-terphenyl monomer and 0.18 mol of N-methyl-4-piperidone were taken. In S2 (step 2), the raw materials weighed in S1 are added to 50 mL of dichloromethane, mixed, and then thoroughly dispersed to obtain a reaction base solution. In S3 (step 3), 90 mL of trifluoromethanesulfonic acid is added dropwise to the reaction base solution at 0°C. After the addition is completed, the reaction system is heated to 13°C. Under this temperature condition, a hydrocarbon alkylation reaction occurs in the raw material, and the reaction time is set to 6 hours. In S4 (step 4), after the reaction in S3 was completed, the product was poured into pure water and then filtered. The resulting solid was pulverized, washed with pure water, and dried to obtain the final product, nitrogen-containing compound G.

[0069] The general structural formula of the nitrogen-containing compound G produced thereby is: [ka] is.

[0070] Example 6 In this example, nitrogen-containing compound A1, nitrogen-containing compound A2, nitrogen-containing compound A3, nitrogen-containing compound A4, nitrogen-containing compound B, nitrogen-containing compound C, nitrogen-containing compound D, and nitrogen-containing compound E produced in the above examples, and nitrogen-containing compound F and nitrogen-containing compound G produced in the above comparative examples were used to produce raw materials for chloride ion-type anion resins. Using iodomethane as a quaternizing reagent, chloride ion-type anion resins were produced by quaternization reaction and ion exchange.

[0071] The chloride ion type anion resin is produced as follows. Step 1: dissolving a nitrogen-containing compound and iodomethane in dimethyl sulfoxide to obtain a reaction solution; then, the nitrogen-containing compound and iodomethane in the reaction solution are subjected to a quaternization reaction at 50-100°C for 3-36 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 is used as the precipitant, to fully precipitate the precipitate, then filter the resulting precipitate, and then ion-exchange the precipitate with an aqueous solution of KOH and NaCl, wash, and dry. The resulting solid is the chloride ion type anion resin produced by the above quaternization reaction.

[0072] Depending on the nitrogen-containing compound used as raw material, the conditions for the quaternization reaction are optimized to maximize the conversion rate of the quaternization reaction as the optimization criterion. The optimized reaction conditions are specifically shown in Table 1.

[0073] [Table 1]

[0074] Example 7 In this example, nitrogen-containing compound A1, nitrogen-containing compound A2, nitrogen-containing compound A3, nitrogen-containing compound A4, nitrogen-containing compound B, nitrogen-containing compound C, nitrogen-containing compound D, nitrogen-containing compound E prepared in the above examples, and nitrogen-containing compound F and nitrogen-containing compound G prepared in the above comparative examples were used as raw materials for preparing sulfonic acid group-type anion resins, and sulfonate ester compounds were used as quaternizing reagents to prepare sulfonic acid group-type anion resins by quaternization reaction.

[0075] The sulfonic acid group-type anionic resin is produced as follows. Step 1: dissolving a nitrogen-containing compound and a sulfonate ester compound in dimethyl sulfoxide to obtain a reaction solution; then, the nitrogen-containing compound and the sulfonate ester compound in the reaction solution are subjected to a quaternization reaction at 70 to 120°C for 3 to 72 hours; and after the reaction is completed, a product solution containing a sulfonate group-type anion resin is obtained; Step 2: Add a precipitant to the product solution, in this example deionized water, to precipitate the product. Then, filter, wash, and dry the resulting precipitate. The resulting solid is the sulfonic acid group-type anion resin prepared by the quaternization reaction.

[0076] Depending on the nitrogen-containing compound raw material used, the type of quaternization reagent and reaction conditions for the quaternization reaction are optimized to maximize the conversion rate of the quaternization reaction as the optimization criterion. The optimized reaction conditions are specifically shown in Table 2.

[0077] [Table 2]

[0078] <Test Example 1> 1. Test Subjects The anion exchange membranes were further manufactured using the anion exchange resins manufactured in Examples 6 and 7, and the anion exchange membranes were used as test subjects.

[0079] 2. Test items (1) Mechanical performance test Referring to GB T 20042.3, the test specimen was subjected to pure tensile force until it broke.

[0080] a. Tensile strength was recorded as the ratio of the maximum load that the test specimen could withstand when it broke under pure tensile force to the width of the stretched membrane material, and was divided into transverse and longitudinal tensile strength and used to evaluate the mechanical strength of the membrane. b. The breaking elongation was recorded as the ratio of the distance between the two points at which the test object broke under the maximum load received before breaking to its original length. This represents the maximum deformation that the alkaline membrane can withstand when pulled until it breaks, and was used to evaluate the flexibility of the membrane.

[0081] 3. Test Results The test results of this test example are shown in Tables 3 and 4. Of the test subjects, nitrogen-containing compound A1, nitrogen-containing compound A2, nitrogen-containing compound A3, and nitrogen-containing compound A4 produced in Example 1 all have the general formula segment I. [ka] Similarly, the molecular structure of nitrogen-containing compound D prepared in Example 4 also contained a structural unit conforming to segment I of the general formula, while nitrogen-containing compounds F and G prepared in Comparative Examples 1 and 2 each contained a structural unit conforming to segment II of the general formula. [ka] , Segment III [ka] As can be clearly seen from the test results of this test example, when the types of anions contained in the anion resins are the same, the anion exchange membranes produced using nitrogen-containing compound A1, nitrogen-containing compound A2, nitrogen-containing compound A3, nitrogen-containing compound A4, and nitrogen-containing compound D had higher corresponding tensile strengths and higher breaking elongations than the anion exchange membranes produced using nitrogen-containing compound F and nitrogen-containing compound G, respectively.

[0082] The nitrogen-containing compound B prepared in Example 2 is similar to nitrogen-containing compound F, and the molecular structure of nitrogen-containing compound B also contains a structural unit that matches segment II of the general formula. However, the difference between nitrogen-containing compound B and nitrogen-containing compound F is that the molecular structure of nitrogen-containing compound B further contains a structural unit that matches segment I of the general formula. Based on this difference, the anion exchange membrane prepared using nitrogen-containing compound B had a higher tensile strength and a higher elongation at break than the anion exchange membrane prepared using nitrogen-containing compound F, when the types of anions contained in the anion resin were the same.

[0083] The nitrogen-containing compound C prepared in Example 3 is similar to nitrogen-containing compound G, and the molecular structure of nitrogen-containing compound C also contains a structural unit that matches segment III of the general formula. However, the difference between nitrogen-containing compound C and nitrogen-containing compound G is that the molecular structure of nitrogen-containing compound C further contains a structural unit that matches segment I of the general formula. Based on this difference, the anion exchange membrane prepared using nitrogen-containing compound C had a higher tensile strength and a higher elongation at break than the anion exchange membrane prepared using nitrogen-containing compound G when the anion resin contained the same type of anion.

[0084] The molecular structure of nitrogen-containing compound E prepared in Example 5 included a structural unit conforming to segment II of the general formula and a structural unit conforming to segment III of the general formula, and the molecular structure of nitrogen-containing compound E also included a structural unit conforming to segment I of the general formula. The test results of this test example showed that the anion exchange membrane prepared using nitrogen-containing compound E had a higher measured tensile strength and a higher elongation at break than nitrogen-containing compound F, whose molecular structure includes a structural unit conforming to segment II of the general formula, and nitrogen-containing compound G, whose molecular structure includes a structural unit conforming to segment III of the general formula, respectively.

[0085] Based on the test results of this test example, it was demonstrated that by using a structural unit that conforms to segment I of the general formula to participate in the construction of a large molecule of a nitrogen-containing compound, the flexibility of the anion exchange membrane manufactured using the nitrogen-containing compound can be improved, and both its tensile strength and breaking elongation can be increased. It was also demonstrated that when such an anion exchange membrane is used in an electrolytic chamber, the interfacial contact between the electrodes can be optimized.

[0086] [Table 3]

[0087] [Table 4]

Claims

【Request 1】 【Chemical 1】 A nitrogen-containing compound comprising a segment I of the formula: １ is an aryl structural unit, and the R １ , the R ２ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, or １ , the R ２ are nitrogen-containing compounds that link together to form a multi-membered ring with the N atom to which they are linked.

2. In the segment I, the Ar １ teeth, 【Chemistry 2】 The nitrogen-containing compound according to claim 1, comprising at least one of the following structural units:

3. In the segment I, the Ar １ teeth, 【Chemistry 3】 The nitrogen-containing compound of claim 2, comprising:

4. In the segment I, the R １ , the R ２ are each independently selected from H, a methyl group, a C2 to C7 linear alkyl group, a C3 to C10 cycloalkyl group, an aryl group, or a substituted aryl group, or １ , the R ２ are linked to form a multi-membered ring together with the N atom to which they are attached, and the multi-membered ring is a five-, six-, or seven-membered ring.

5. In the segment I, the R １ and the above R ２ are independently selected from a methyl group or a C2 to C7 linear alkyl group.

6. The segment I is 【Chemistry 4】 The nitrogen-containing compound of claim 5, wherein

7. In the segment I, the R １ , the R ２ are linked to form a six-membered ring together with the N atom to which they are attached.

8. The nitrogen-containing compound according to claim 7 , wherein the six-membered ring is a piperidine ring or a piperazine ring.

9. The segment I is 【Chemistry 5】 9. The nitrogen-containing compound of claim 8, wherein:

10. The nitrogen-containing compound further comprises at least one of Segment II, Segment III, and Segment IV; The segment II is 【Chemistry 6】 where Ar ２ is an aryl structural unit, The segment III is 【Chemistry 7】 where Ar ３ is an aryl structural unit, The segment IV is 【Chemistry 8】 where Ar ４ The nitrogen-containing compound according to any one of claims 1 to 9, wherein is an aryl structural unit.

11. The Ar ２ , the Ar ３ , the Ar ４ are each independently 【Chemistry 9】 The nitrogen-containing compound of claim 10, comprising at least one of the structural units:

12. The R ３ , the R ４ , the R ５ , the R ６ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

13. The nitrogen-containing compound has the following general formula: 【Chemistry 10】 wherein n1 represents the degree of polymerization of the segment I, n2 represents the degree of polymerization of the segment II, n2 is a non-negative integer, n3 represents the degree of polymerization of the segment III, n3 is a non-negative integer, and Ar ３ is an aryl structural unit; n4 represents the degree of polymerization of the segment IV; and n4 is a non-negative integer.

14. A method for producing the nitrogen-containing compound according to any one of claims 1 to 9, comprising: A monomer raw material is prepared, and a corresponding aromatic monomer is selected depending on the aryl structural unit contained in the main chain of the nitrogen-containing compound. The aromatic monomer is used as a main chain monomer raw material, and a compound represented by the general formula: 【Chemistry 11】 S1 (Step 1) selecting a branched monomer raw material containing an amino acetal monomer of S2 (step 2) of adding the monomer raw material to an alkyl organic solvent and dispersing it sufficiently to obtain a reaction base solution; S3 (step 3) of adding an organic acid catalyst to the reaction base solution and polymerizing the aromatic monomer and the aminoacetal monomer in the reaction base solution under the action of the organic acid catalyst; and S4 (step 4) discharging the product of the polymerization reaction into pure water or an alkaline solution, washing, and drying the product, and then obtaining the nitrogen-containing compound.

15. The aminoacetal monomer is 【Chemistry 12】 The method of claim 14 , comprising at least one of the following monomers:

16. The branched monomer raw material further includes a piperidone monomer, and the piperidone monomer has the general structural formula: 【Chemistry 13】 The method of claim 14, wherein

17. The piperidone monomer is 【Chemistry 14】 17. The method of claim 16, comprising at least one of the monomers:

18. The branched monomer raw material further includes a quinuclidinone monomer, and the quinuclidinone monomer has the general structural formula: 【Chemistry 15】 The method of claim 14, wherein

19. The quinuclidinone monomer is 【Chemistry 16】 20. The method of claim 18, comprising at least one of the following monomers:

20. The branched monomer raw material further includes an acetal monomer, and the acetal monomer has the general structural formula: 【Chemistry 17】 The method of claim 14, wherein

21. The acetal monomer is 【Chemistry 18】 21. The method of claim 20, comprising at least one of the monomers:

22. 15. The method of claim 14, wherein the organic acid catalyst comprises at least one of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid.

23. The method according to claim 22, wherein the specific operation of S3 (step 3) comprises: first lowering the temperature of the reaction base solution to 0-3°C, adding the organic acid catalyst thereto, and then raising the temperature of the reaction base solution to 5-24°C, and polymerizing under these conditions for 2-24 hours.

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

25. 15. The method according to claim 14, wherein in step S4 (step 4), the alkaline solution contains at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, and potassium hydroxide.

26. 【Catalog 19】 An anionic resin comprising a segment V of the formula: １ is an aryl structural unit, and the R １ , the R ２ are each independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group, or １ , the R ２ are linked to form a poly-membered ring together with the N atom to which they are linked, and ａ is one selected from an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group, １ － represents anion, anion resin.

27. In the segment V, the Ar １ teeth, 【Chemistry 20】 27. The anion resin of claim 26, comprising at least one of the structural units:

28. the anion resin further comprises at least one of segment VI, segment VII, and segment IV; The segment VI is 【Chemical 21】 where Ar ２ is an aryl structural unit, and Z ２ － represents an anion, and the R ｂ is one selected from an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group, The segment VII is 【Chemical 22】 where Ar ３ is an aryl structural unit, and Z ３ － represents an anion, and the R ｃ is one selected from an aromatic group, a C1 to C10 chain alkyl group, and a C3 to C10 cycloalkyl group, The segment IV is 【Chemical 23】 where Ar ４ 27. The anion resin of claim 26, wherein is an aryl structural unit.

29. The anionic resin has the following general formula: 【Chemistry 24】 wherein n5 represents the degree of polymerization of segment V, n5 is a positive integer, n6 represents the degree of polymerization of segment VI, n6 is a non-negative integer, n7 represents the degree of polymerization of segment VII, n7 is a non-negative integer, and n8 represents the degree of polymerization of segment IV, n8 is a non-negative integer.

30. A method for producing an anion resin, comprising: subjecting the nitrogen-containing compound according to any one of claims 1 to 9 to a quaternization reaction with a quaternizing reagent to produce the anion resin; and the quaternizing 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, and ethanesulfonate. ethyl benzoate, 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-ylmethanesulfonate, or cyclohexyl paratoluenesulfonate.

31. An anion exchange membrane comprising the anion resin according to any one of claims 26 to 29.

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