Nitrogen-containing compound and preparation method therefor, anion resin, and anion exchange membrane

Abstract

The present application provides a nitrogen-containing compound, the nitrogen-containing compound comprising segment I. Segment I is represented by [Formula I], where a represents the number of methylene groups, a is a positive integer, Ar1 is an aromatic structural unit, R1 and R2 are independently selected from H, hydrocarbon groups or substituted hydrocarbon groups, or R1 and R2 are connected and form, together with the N atom to which same are connected, a polycyclic ring.

Description

Nitrogen-containing compound 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 2024101267846. 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 compound 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, desalted water, pure water production, hydrometallurgy, rare element separation, pharmaceuticals, sugar production, and amino acid adsorption. In the field of water electrolysis, anion exchange membranes (AEMs) are often used to separate hydrogen between the anode and cathode and provide channels for anion transport. The active component of anion exchange membranes is an anion resin, which is typically composed 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 have the disadvantages of being relatively rigid and difficult to form membranes. Technical issues

[0004] The present application aims to solve the following technical problem: how to improve the flexibility of anion exchange membranes so as to increase their tensile strength and elongation at break. Technical Solutions

[0005] In the first aspect, the present application provides a nitrogen-containing compound, which includes segment I, segment I is Wherein, a represents the number of methylene groups, a is a positive integer, Ar1 is an aromatic structural unit, R1 and R2 are independently selected from H, hydrocarbon groups or substituted hydrocarbon groups, or R1 and R2 are connected to form a polycyclic ring together with the N atom to which they are connected.

[0006] In a second aspect, the present application provides a method for preparing the nitrogen-containing compound 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, selecting branched monomer raw materials according to the types of chain segments included in the multi-polymer, and the branched monomer raw materials including the general formula S2. adding the monomer raw materials into an alkyl organic solvent and fully dispersing them to obtain a reaction base liquid; S3. adding an organic acid catalyst to the reaction base liquid to cause the aromatic raw materials and the nitrogen-containing acetal monomers 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 obtaining a nitrogen-containing compound after washing and drying.

[0007] In a third aspect, the present application provides an anion exchange resin comprising a segment V, wherein the segment V is Wherein: a represents the number of methylene groups, and a is a positive integer; Ar1 ​​is an aromatic structural unit; R1 and R2 are independently selected from H, hydrocarbon groups or substituted hydrocarbon groups, or R1 and R2 are connected to form a polycyclic ring together with the nitrogen atoms to which they are connected; R a One selected from aromatic groups, C1-C10 chain alkyl groups, and C3-C10 cycloalkyl groups; Z1 － Indicates anion.

[0008] In a fourth aspect, the present application provides a method for preparing an anion resin: the nitrogen-containing compound as described above is subjected to a quaternization reaction with a quaternizing agent to prepare an anion resin, wherein the quaternizing agent includes methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl iodide, hexyl bromide, cyclohexyl bromide, cyclopentyl bromide, cyclohexyl bromide, 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] By utilizing structural units conforming to the general formula segment I to participate in the construction of nitrogen-containing compound macromolecules, the flexibility of the anion exchange membrane prepared using the nitrogen-containing compound can be improved, and its tensile strength and elongation at break can be improved.

[0011] The anion protective membrane of the present application has excellent flexibility and can be applied in an electrolytic cell to optimize the interface contact between electrodes.

[0012] Implementation Methods of the Application

[0013] In one embodiment, in segment I, Ar1 comprises at least one of the following structural units:

[0014] In one embodiment, in segment I, Ar1 comprises and / or

[0015] In one embodiment, in segment I, R1 and R2 are independently selected from H, methyl, C2-C7 chain alkyl, C3-C10 cycloalkyl, aryl, or substituted aryl; or, R1 and R2 are linked together and together with the nitrogen atom to which they are attached form a polycyclic ring, which is a five-membered ring, a six-membered ring, or a seven-membered ring.

[0016] In one embodiment, in segment I, R1 and R2 are independently selected from methyl or C2-C7 chain alkyl.

[0017] In one embodiment, segment I is

[0018] In one embodiment, in segment I, R1 and R2 are linked together to form a six-membered ring together with the nitrogen atom to which they are attached.

[0019] In one embodiment, the six-membered ring is a piperidine ring or a piperazine ring.

[0020] In one embodiment, segment I is

[0021] In one embodiment, the nitrogen-containing compound further comprises at least one of segment II, segment III, and segment IV; segment II is Among them, Ar2 is an aromatic structural unit; segment III is Among them, Ar3 is an aromatic structural unit; segment IV is Wherein, Ar4 is an aromatic structural unit.

[0022] In one embodiment, Ar2, Ar3, and Ar4 each independently comprise at least one of the following structural units:

[0023] In one embodiment, Ar2, Ar3, and Ar4 each independently comprise at least one of the following structural units:

[0024] In one embodiment, R3, R4, R5, and R6 are independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0025] In one embodiment, the nitrogen-containing compound comprises the following general structure

[0026] 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 aromatic structural unit, n4 represents the degree of polymerization of segment IV, n4 is a non-negative integer.

[0027] In one embodiment, n1, n2, n3, and n4 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. n4 can be 10, 500, 2000, 10000, 500000, 1000000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0028] In one embodiment, n1, n2, n3, and n4 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.

[0029] In one embodiment, R3, R4, R5, and R6 are independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

[0030] In one embodiment, the nitrogen-containing compound comprises the following general structure

[0031] 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 aromatic structural unit, n4 represents the degree of polymerization of segment IV, n4 is a non-negative integer.

[0032] In one embodiment, n1, n2, n3, and n4 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. n4 can be 10, 500, 2000, 10000, 500000, 1000000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0033] In one embodiment, n1, n2, n3, and n4 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.

[0034] In one embodiment, the aminoacetal monomer includes at least one of the following monomers:

[0035] In one embodiment, the branched monomer raw material further comprises a piperidone monomer, and the piperidone monomer has the general structural formula:

[0036] In one embodiment, the piperidone monomer comprises at least one of the following monomers:

[0037] In one embodiment, the branched monomer raw material further comprises a quinuclidine monomer, and the general structural formula of the quinuclidine monomer is

[0038] In one embodiment, the quinuclidinone monomer comprises at least one of the following monomers:

[0039] In one embodiment, the branched monomer raw material further comprises an acetal monomer, and the general structural formula of the acetal monomer is

[0040] In one embodiment, the acetal monomer includes at least one of the following monomers:

[0041] In one embodiment, the organic acid catalyst includes at least one of methanesulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid.

[0042] In one embodiment, the specific operation of S3 includes: first lowering the temperature of the reaction base liquid to 0-3°C, adding an organic acid catalyst thereto, and then heating the reaction base liquid 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 liquid can be controlled at 0°C, 1°C, 2°C, 2.5°C, 3°C, etc., but is not limited to the listed values, and other values ​​not listed within the above numerical range are also applicable; after adding the organic acid catalyst, the reaction liquid can be heated to 5°C, 10°C, 15°C, 20°C, 24°C, but is not limited to the listed values, and other values ​​not listed within the above temperature range are also applicable. The reaction time can be 2 hours, 5 hours, 10 hours, 16 hours, or 24 hours, and other values ​​not listed within the applicable numerical range of the reaction time are also applicable.

[0043] In one embodiment, the alkyl organic solvent includes at least one of dichloromethane, chloroform, chloroform, and tetrahydrofuran.

[0044] 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.

[0045] In one embodiment, in segment V, Ar1 comprises at least one of the following structural units:

[0046] In one embodiment, the anion resin further comprises at least one of segment VI, segment VII, and segment IV; segment VI is Wherein, Ar2 is an aromatic structural unit, Z2 － represents anion, R b One selected from aromatic groups, C1-C10 chain alkyl groups, and C3-C10 cycloalkyl groups; segment VII is Among them, Ar3 is an aromatic structural unit, Z3 － represents anion, R c One selected from aromatic groups, C1-C10 chain alkyl groups, and C3-C10 cycloalkyl groups; segment IV is Wherein, Ar4 is an aromatic structural unit.

[0047] In one embodiment, the anion resin comprises the following general structure:

[0048] Among them, 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, n8 represents the degree of polymerization of segment IV, n8 is a non-negative integer.

[0049] In one embodiment, n5, n6, n7, and n8 are independently selected from integers between 10 and 1,000,000. 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. n6 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. n7 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. n8 can be 10, 500, 2000, 10000, 500000, 1000000, etc., but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable.

[0050] In one embodiment, n5, n6, n7, and n8 are independently selected from integers between 50 and 300. n5 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. n6 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. n7 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. n8 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.

[0051] Example 1

[0052] This example prepares the chain segment I Nitrogen-containing compounds.

[0053] (1) Preparation of nitrogen-containing compound A1:

[0054] S1. Take 0.15 mol of 9,9-dimethylfluorene and 0.18 mol of dimethylaminoacetaldehyde diethyl acetal respectively;

[0055] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0056] 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 3 hours;

[0057] 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, nitrogen-containing compound A1.

[0058] The general structural formula of the nitrogen-containing compound A1 thus obtained is

[0059] (2) Preparation of nitrogen-containing compound A2:

[0060] S1. Take 0.15 mol of 9,9-dimethylfluorene and 0.18 mol of 1-(2,2-diethoxyethyl)piperidine respectively;

[0061] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0062] S3 at -3 ℃, to the reaction bottom solution was added dropwise 100mL trifluoromethanesulfonic acid, after completion of the addition, the reaction system was warmed to 5 ℃, the above raw materials under this temperature conditions alkylation reaction, the reaction time is 6 hours;

[0063] 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, nitrogen-containing compound A2.

[0064] The general structural formula of the nitrogen-containing compound A2 prepared in this way is

[0065] (3) Preparation of nitrogen-containing compound A3:

[0066] S1. Take 0.15 mol of m-terphenyl and 0.18 mol of dimethylaminoacetaldehyde diethyl acetal respectively;

[0067] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0068] S3 at 3 ° C, the reaction mixture was added dropwise to 60mL 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 3 hours;

[0069] 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, nitrogen-containing compound A3.

[0070] The general structural formula of the nitrogen-containing compound A3 thus prepared is

[0071] (4) Preparation of nitrogen-containing compound A4:

[0072] S1. Take 0.15 mol of m-terphenyl, 0.18 mol of dimethylaminoacetaldehyde diethanol acetal, and 0.05 mol of 1-(dimethoxymethyl)piperidine respectively;

[0073] S2. The raw materials weighed in S1 were added to 45 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0074] 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 6 hours;

[0075] 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, nitrogen-containing compound A4.

[0076] The general structural formula of the nitrogen-containing compound A4 thus obtained is

[0077] Example 2

[0078] This example prepares the chain segment I and segment II Nitrogen-containing compounds.

[0079] Preparation of nitrogen-containing compound B:

[0080] S1. Take 0.15 mol of p-terphenyl, 0.14 mol of N-methyl-4-piperidone, and 0.04 mol of dimethylaminoacetaldehyde diethyl acetal respectively;

[0081] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0082] 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 10 hours;

[0083] 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, nitrogen-containing compound B.

[0084] The general structural formula of the nitrogen-containing compound B thus obtained is

[0085] Example 3

[0086] This example prepares the chain segment I and segment III Nitrogen-containing compounds.

[0087] Preparation of nitrogen-containing compound C:

[0088] S1. Take 0.15 mol of p-terphenyl, 0.12 mol of 3-quinuclidinone hydrochloride, and 0.06 mol of 1-(dimethoxymethyl)piperidine respectively;

[0089] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0090] S3 at 3 ° C, 120mL of trifluoromethanesulfonic acid was added dropwise to the reaction bottom solution. After completion of the addition, the reaction system was heated to 13 ° C. The above raw materials under this temperature condition undergo hydrocarbon alkylation reaction, and the reaction time was 18 hours;

[0091] 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, nitrogen-containing compound C.

[0092] The general structural formula of the nitrogen-containing compound C thus obtained is

[0093] Example 4

[0094] This example prepares the chain segment I and segment IV Nitrogen-containing compounds.

[0095] Preparation of nitrogen-containing compound D:

[0096] S1. Take 0.15 mol of p-terphenyl, 0.12 mol of 1-(dimethoxymethyl)piperidine, and 0.06 mol of isobutyraldehyde diethyl acetal respectively;

[0097] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0098] S3 at 3 ° C, 120mL of trifluoromethanesulfonic acid was added dropwise to the reaction bottom solution. After completion of the addition, the reaction system was heated to 8 ° C. The above raw materials under this temperature condition undergo hydrocarbon alkylation reaction, and the reaction time was 12 hours;

[0099] 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, nitrogen-containing compound D.

[0100] The general structural formula of the nitrogen-containing compound D thus obtained is

[0101] Example 5

[0102] This example prepares the chain segment I Segment II Segment III and segment IV Nitrogen-containing compounds.

[0103] Preparation of nitrogen-containing compound E:

[0104] S1. Take 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 diethyl acetal, and 0.02 mol of isobutyraldehyde diethyl acetal respectively;

[0105] S2. The raw materials weighed in S1 were added to 70 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0106] S3 at 3 ° C, the reaction mixture was added dropwise to 135mL trifluoromethanesulfonic acid, after completion of the addition, the reaction system was heated to 24 ° C, the above raw materials under this temperature conditions hydrocarbon alkylation reaction, the reaction time is 20 hours;

[0107] 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, nitrogen-containing compound E.

[0108] The general structural formula E of the nitrogen-containing compound thus prepared is

[0109] Comparative Example 1

[0110] This comparative example is prepared by segment II Nitrogen-containing compounds.

[0111] Preparation of nitrogen-containing compound F:

[0112] S1. Take 0.15 mol of p-terphenyl monomer and 0.18 mol of 3-quinuclidinone hydrochloride respectively;

[0113] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0114] 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;

[0115] 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, nitrogen-containing compound F.

[0116] The general structural formula of the nitrogen-containing compound F thus obtained is

[0117] Comparative Example 2

[0118] This comparative example is prepared by segment III Nitrogen-containing compounds.

[0119] Preparation of nitrogen-containing compound G:

[0120] S1. Take 0.15 mol of p-terphenyl monomer and 0.18 mol of N-methyl-4-piperidone respectively;

[0121] S2. The raw materials weighed in S1 were added to 50 mL of dichloromethane, mixed and fully dispersed to obtain a reaction bottom liquid;

[0122] 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;

[0123] 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, nitrogen-containing compound G.

[0124] The general structural formula of the nitrogen-containing compound G thus obtained is

[0125] Example 6

[0126] In this example, the raw materials for the chloride ion type anion resin were prepared using 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, and nitrogen-containing compound F and nitrogen-containing compound G prepared in the above comparative example, respectively. Iodomethane was used as a quaternizing agent to prepare the chloride ion type anion resin through quaternization reaction and ion exchange.

[0127] Preparation of chloride ion type anion resin:

[0128] Step 1. The nitrogen-containing compound and methyl iodide are dissolved in dimethyl sulfoxide to obtain a reaction solution, and then the nitrogen-containing compound 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 ion-type anion resin is obtained;

[0129] 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.

[0130] According to the different nitrogen-containing compound raw materials used, the 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 specifically shown in Table 1.

[0131] Table 1. Reaction conditions for the quaternization reaction in Example 6

[0132] Example 7

[0133] In this example, the 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 the nitrogen-containing compound F and nitrogen-containing compound G prepared in the above comparative example are used as raw materials for preparing sulfonic acid type anion resins, and sulfonic acid ester compounds are used as quaternizing agents to prepare sulfonic acid type anion resins through quaternization reaction.

[0134] Preparation of sulfonic acid type anion resin:

[0135] Step 1. The nitrogen-containing compound and the sulfonate compound are dissolved in dimethyl sulfoxide to obtain a reaction solution, and then the nitrogen-containing compound 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 group-type anion resin is obtained;

[0136] 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 to obtain a solid which is a sulfonic acid anion resin obtained by the above-mentioned quaternization reaction.

[0137] According to the different nitrogen-containing compound raw materials 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.

[0138] Table 2. Reaction conditions for the quaternization reaction in Example 7

[0139] Test Example 1

[0140] 1. Test subjects

[0141] Anion exchange membranes were further prepared using the anion resins prepared in Examples 6 and 7, and the anion exchange membranes thus prepared were used as test objects.

[0142] 2. Test items

[0143] (1) Mechanical properties test

[0144] Refer to GB T 20042.3 and apply pure tensile force to the test object to make it break.

[0145] 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.

[0146] 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.

[0147] 3. Test results

[0148] The test results of this test example are shown in Table 3 and Table 4. Among the test objects, the nitrogen-containing compound A1, nitrogen-containing compound A2, nitrogen-containing compound A3, and nitrogen-containing compound A4 prepared in Example 1 are all composed of a chain segment conforming to the general formula Similarly, the molecular structure of the nitrogen-containing compound D prepared in Example 4 also includes the structural unit that conforms to the general formula segment Ⅰ, while the nitrogen-containing compound F and the nitrogen-containing compound G prepared in Comparative Example 1 and Comparative Example 2 are respectively composed of the structural unit that conforms to the general formula segment Ⅱ Segment III The test results of this test example clearly show that when the types of anions contained in the anion resin are the same, compared with the anion exchange membranes prepared by using nitrogen-containing compound F and nitrogen-containing compound G, the anion exchange membranes prepared by using nitrogen-containing compound A1, nitrogen-containing compound A2, nitrogen-containing compound A3, nitrogen-containing compound A4, and nitrogen-containing compound D respectively have higher measured tensile strength and elongation at break.

[0149] The nitrogen-containing compound B prepared in Example 2 is similar to the nitrogen-containing compound F. The molecular structure of the nitrogen-containing compound B also includes structural units that conform to the general formula segment II. However, it is different from the nitrogen-containing compound F in that the molecular structure of the nitrogen-containing compound B also includes structural units that conform to the general formula segment I. Based on this difference, when the types of anions contained in the anion resin are the same, the anion exchange membrane prepared using the nitrogen-containing compound B has a higher measured tensile strength and a higher elongation at break than the anion exchange membrane prepared using the nitrogen-containing compound F.

[0150] The nitrogen-containing compound C prepared in Example 3 is similar to the nitrogen-containing compound G. The molecular structure of the nitrogen-containing compound B also includes structural units that conform to the general formula segment III. However, it is different from the nitrogen-containing compound G in that the molecular structure of the nitrogen-containing compound C also includes structural units that conform to the general formula segment I. Based on this difference, when the types of anions contained in the anion resin are the same, the anion exchange membrane prepared using the nitrogen-containing compound C has a higher measured tensile strength and a higher elongation at break than the anion exchange membrane prepared using the nitrogen-containing compound G.

[0151] The molecular structure of the nitrogen-containing compound E prepared in Example 5 includes structural units conforming to the general formula segment II and structural units conforming to the general formula segment III. Furthermore, the molecular structure of the nitrogen-containing compound E also includes structural units conforming to the general formula segment I. The test results of this test example show that the anion exchange membrane prepared using the nitrogen-containing compound E exhibits higher tensile strength and elongation at break than the nitrogen-containing compound F, whose molecular structure includes structural units conforming to the general formula segment II, and the nitrogen-containing compound G, whose molecular structure includes structural units conforming to the general formula segment III.

[0152] Based on the test results of this test example, it can be shown that by utilizing structural units conforming to the general formula segment I to participate in the construction of nitrogen-containing compound macromolecules, the flexibility of the anion exchange membrane prepared using the nitrogen-containing compound can be improved, and its tensile strength and elongation at break can be improved. Applying such an anion exchange membrane to an electrolytic cell can optimize the interface contact between the electrodes.

[0153] Table 3. Mechanical properties test of the test object of the chloride ion anion resin provided by Example 6

[0154] Table 4. Mechanical properties test of the test object using the sulfonic acid anion resin provided in Example 7

Claims

1. A nitrogen-containing compound, The nitrogen-containing compound includes segment I, and the segment I is in, a represents the number of methylene groups, a is a positive integer, Ar1 is an aromatic structural unit, R1 and R2 are independently selected from H, a hydrocarbon group or a substituted hydrocarbon group, or R1 and R2 are connected to form a polycyclic ring together with the N atom to which they are connected.

2. The nitrogen-containing compound according to claim 1, wherein: In the segment I, the Ar1 comprises at least one of the following structural units:

3. The nitrogen-containing compound according to claim 2, wherein: In the segment I, the Ar1 comprises 4. The nitrogen-containing compound according to claim 2, wherein: In the segment I, the R1 and the R2 are independently selected from H, methyl, C2-C7 chain alkyl, C3-C10 cycloalkyl, aryl or substituted aryl; or, the R1 and the R2 are connected and together with the N atom to which they are connected form a polycyclic ring, and the polycyclic ring is a five-membered ring, a six-membered ring or a seven-membered ring.

5. The nitrogen-containing compound according to claim 4, wherein: In the segment I, the R1 and R2 are independently selected from a methyl group or a C2-C7 chain alkyl group.

6. The nitrogen-containing compound according to claim 5, wherein: The segment I is 7. The nitrogen-containing compound according to claim 4, wherein: In the segment I, the R1 and the R2 are connected to form a six-membered ring together with the N atom to which they are connected.

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

9. The nitrogen-containing compound according to claim 8, wherein: The segment I is 10. The nitrogen-containing compound according to any one of claims 1 to 9, wherein: The nitrogen-containing compound further comprises at least one of segment II, segment III, and segment IV; The segment II is Wherein, Ar2 is an aromatic structural unit; The segment III is Wherein, Ar3 is an aromatic structural unit; The segment IV is Wherein, Ar4 is an aromatic structural unit.

11. The nitrogen-containing compound according to claim 10, wherein: The Ar2, the Ar3, and the Ar4 each independently comprise at least one of the following structural units:

12. The nitrogen-containing compound according to claim 10, wherein: The R3, R4, R5, and R6 are independently selected from H, a hydrocarbon group, or a substituted hydrocarbon group.

13. The nitrogen-containing compound according to claim 10, wherein: The nitrogen-containing compound includes the following general structure 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, Ar3 is an aromatic structural unit, n4 represents the degree of polymerization of the segment IV, n4 is a non-negative integer.

14. A method for preparing the nitrogen-containing compound according to any one of claims 1 to 13, 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, select branched monomer raw materials according to the types of chain segments included in the multi-polymer, and the branched monomer raw materials include the general formula Aminoacetal 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, and after washing and drying, the nitrogen-containing compound is obtained.

15. The method of claim 14, wherein: The aminoacetal monomer comprises at least one of the following monomers:

16. The method of claim 14, wherein: The branched monomer raw material also includes a piperidone monomer, and the piperidone monomer has the general structural formula:

17. The method of claim 16, wherein: The piperidone monomer comprises at least one of the following monomers:

18. The method of claim 14, wherein: The branched monomer raw material also includes quinuclidine monomer, and the general structural formula of the quinuclidine monomer is 19. The method of claim 18, wherein: The quinuclidine monomer comprises at least one of the following monomers:

20. The method of claim 14, wherein: The branched monomer raw material also includes an acetal monomer, and the general structural formula of the acetal monomer is 21. The method of claim 20, wherein: The acetal monomer includes at least one of the following monomers:

22. The method of claim 14, wherein: The organic acid catalyst includes at least one of methanesulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid.

23. The method of claim 22, wherein: The specific operation of S3 includes: firstly lowering the temperature of the reaction base liquid to 0-3°C, adding the organic acid catalyst thereto, then raising the temperature of the reaction base liquid to 5-24°C, and polymerizing under this condition for 2-24 hours.

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

25. The method of claim 14, wherein: In S4, the alkali solution contains at least one of sodium hydroxide, sodium bicarbonate, potassium bicarbonate, potassium carbonate, sodium carbonate, and potassium hydroxide.

26. An anion exchange resin comprising a segment V, wherein the segment V is in: a represents the number of methylene groups, and a is a positive integer; Ar1 is an aromatic structural unit; R1 and R2 are independently selected from H, hydrocarbon groups or substituted hydrocarbon groups, or R1 and R2 are connected to form a polycyclic ring together with the N atom to which they are connected; R a is selected from one of an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group; said Z1 － Indicates anion.

27. The anionic resin of claim 26, wherein: In the segment V, the Ar1 comprises at least one of the following structural units:

28. The anionic resin according to claim 26 or 27, wherein: The anionic resin further comprises at least one of segment VI, segment VII, and segment IV; The segment VI is Wherein, Ar2 is an aromatic structural unit, Z2 － represents an anion, the R b One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group; The segment VII is Among them, Ar3 is an aromatic structural unit, Z3 － represents an anion, the R c One selected from an aromatic group, a C1-C10 chain alkyl group, and a C3-C10 cycloalkyl group; The segment IV is Wherein Ar4 is an aromatic structural unit.

29. The anionic resin of claim 28, wherein: The anion resin includes the following general structure Among them, n5 represents the degree of polymerization of the segment V, n5 is a positive integer, n6 represents the degree of polymerization of the segment VI, n6 is a non-negative integer, n7 represents the degree of polymerization of the segment VII, n7 is a non-negative integer, n8 represents the degree of polymerization of the segment IV, n8 is a non-negative integer.

30. A method for preparing an anion resin, comprising reacting the nitrogen-containing compound according to any one of claims 1 to 13 with a quaternizing agent to produce 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.

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

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