Nitrogen-containing branched polymers, anion exchange resins, anion exchange membranes, and electrochemical devices

Abstract

The present invention provides nitrogen-containing branched polymers, anion exchange resins, anion exchange membranes, and electrochemical devices. [Solution] The nitrogen-containing branched polymer of the present invention contains nitrogen-containing heterocycles, branched structures, and aryl groups in its molecular structure, with each branched structure having 3 or more branching points, and the aryl groups being linked to the branching sites of the branched structures by the nitrogen-containing heterocycles. When the molar ratio of aryl groups in the nitrogen-containing branched polymer is A and the molar ratio of branched structures in the nitrogen-containing branched polymer is B, then A:B = (80-99):(1-20), the polydispersity index PDI of the nitrogen-containing branched polymer is ≤ 2.6, and the weight-average molecular weight of the nitrogen-containing branched polymer is 40,000 g / mol to 500,000 g / mol. The nitrogen-containing branched polymer provided by the present invention has excellent ionic conductivity and mechanical properties, while achieving a low level of water absorption swelling.

Description

[Technical Field]

[0001] This invention belongs to the field of anion exchange membrane technology, and more specifically relates to nitrogen-containing branched polymers, anion exchange resins, anion exchange membranes, and electrochemical devices. [Background technology]

[0002] The trade-off effect, also known as a dichotomy, generally refers to a trade-off choice between two or more parameters. The trade-off effect indicates that, for the same product, prioritizing one performance aspect may compromise the performance of the other, and vice versa. In the field of materials science, the existence of the trade-off effect can hinder the widespread adoption of new materials.

[0003] Anion exchange membranes (AEMs) are core components of alkaline electrochemical apparatuses, functioning to conduct OH- from the cathode to the anode while simultaneously blocking the direct transfer of gases and electrons between electrodes. Key characteristic requirements for AEMs related to alkaline electrochemical apparatuses include high ion conductivity, low swelling, high mechanical strength, and excellent alkali resistance.

[0004] When developing desirable AEMs for alkaline electrochemical apparatuses, both the polymer backbone and cationic groups of the AEMs are important design considerations. Currently, a common strategy to improve the durability of AEMs is to combine the use of a polyaromatic hydrocarbon backbone without aromatic ethers as the polymer backbone of the AEMs with nitrogen-containing heterocycles as the cationic groups. However, the trap-off effect between ionic conductivity and structural stability remains a major problem faced by most AEMs. Sufficient conductive groups are necessary to ensure high ionic conductivity in AEMs, but the introduction of conductive groups inevitably leads to a decrease in the structural stability and mechanical properties of the membrane material. Furthermore, while the mechanical stability of AMEs membrane materials can be improved by crosslinking, this crosslinking operation significantly reduces the ionic conductivity of AMEs, reduces the toughness of the membrane to some extent, and makes the membrane brittle. On the other hand, there is also a trade-off effect between ionic conductivity and water absorption swelling properties. AEMs often achieve high ionic conductivity while simultaneously possessing high water absorption swelling properties. Generally, the greater the water absorption and swelling of AEMs, the more abundant and wider the corresponding hydration channels become. However, this can lead to a deterioration in hydrogen transmembrane penetration in practical use and raises significant safety concerns.

[0005] As described above, trade-off effects are prevalent across various performance metrics during the improvement and development of AEMs. This significantly limits the industrialization of AEMs of this type of material system. [Overview of the project] [Problems that the invention aims to solve]

[0006] To mitigate the trade-off effect between the ionic conductivity, structural stability, and water-absorbing swelling properties of AEMs, thereby improving the ionic conductivity, structural stability, and water-absorbing swelling rate of AEMs, the present invention provides nitrogen-containing branched polymers, anion exchange resins, anion exchange membranes, and electrochemical devices. [Means for solving the problem]

[0007] According to a first aspect of the present invention, a nitrogen-containing branched polymer is provided, which contains nitrogen-containing heterocycles, branched structures, and aryl groups in its molecular structure, wherein the number of branching points of each branched structure is 3 or more, the aryl groups are linked to the branching sites of the branched structures by nitrogen-containing heterocycles, and when the molar ratio of aryl groups in the nitrogen-containing branched polymer is A and the molar ratio of branched structures in the nitrogen-containing branched polymer is B, then A:B = (80-99):(1-20), the polydispersity index PDI of the nitrogen-containing branched polymer is ≤ 2.6, and the weight-average molecular weight of the nitrogen-containing branched polymer is 40,000 g / mol to 500,000 g / mol. By setting the content of aryl groups and branched structures in the polymer within a specific blending ratio range, the basic skeleton of the nitrogen-containing polymer has good structural strength and is rich in conductive groups. Based on the aforementioned skeletal structure, the structural strength of the nitrogen-containing branched polymer is further improved by controlling the weight-average molecular weight and polydispersity index (PDI) of the polymer within a certain range, while simultaneously controlling the corresponding water absorption swelling rate to a relatively low level. This mitigates the trade-off effect between the ionic conductivity, structural stability, and water absorption swelling properties of the nitrogen-containing branched polymer. The nitrogen-containing branched polymer provided by the present invention, while achieving a low water absorption swelling rate, possesses excellent ionic conductivity and mechanical properties, making it suitable for the efficient and stable production of anion exchange resins and anion exchange membranes.

[0008] Preferably, when the molar ratio of the aryl groups in the nitrogen-containing branched polymer is A and the molar ratio of the branched structure in the nitrogen-containing branched polymer is B, then A:B = (85-95):(5-15).

[0009] Preferably, the aryl group includes at least one of a dibiphenyl group, a terphenyl group, and a tetrabiphenyl group.

[0010] Preferably, the branched structure includes a benzene ring structure in which branching portions are provided.

[0011] Preferably, the branched structure includes at least one of the following: 1,3,5-triphenylbenzene structural unit, triphenylmethane structural unit, 9,10-benzophenanthrene structural unit, tetraphenylmethane structural unit, triptycene structural unit, 9,9-diphenylfluorene structural unit, 9,9'-spirobifluorene structural unit, 9,9'-bifluorene structural unit, 9,9'-bicarbazole structural unit, 4,4'-bis(9-carbazol)biphenyl structural unit, 2,2''-bi-9,9'-spirobi[9H-fluorene] structural unit, and triphenylamine structural unit.

[0012] Preferably, the nitrogen-containing heterocycle comprises at least one of a piperidine ring and a quinuclidine ring.

[0013] Preferably, the molecular structure of the nitrogen-containing branched polymer includes segment I and segment II, and the general structural formula of segment I is: The image is JPEG2026050302000002.jpg1231 (where A represents a nitrogen-containing heterocycle, Ar1 represents an aryl group, and X represents the degree of polymerization of segment I). Segment II consists of a nitrogen-containing heterocycle and a branched structure, and in segment II, the nitrogen-containing heterocycle is directly linked to the branched portion of the branched structure.

[0014] Preferably, the nitrogen-containing branched polymer includes a basic structural unit formed by linking segment I and segment II, wherein in the basic structural unit, the linkage between segment I and segment II is such that the aryl group in segment I is linked to the nitrogen-containing heterocycle in segment II.

[0015] Preferably, in the basic structural unit, the number of segments I directly connected to each segment II is three or more.

[0016] Preferably, the weight average molecular weight of the nitrogen-containing branched polymer is from 40,000 g / mol to 250,000 g / mol.

[0017] Preferably, the weight average molecular weight of the nitrogen-containing branched polymer is from 40,000 g / mol to 130,000 g / mol.

[0018] Preferably, the aryl group is a terphenyl group.

[0019] Preferably, the aryl group is a p-terphenyl group.

[0020] Preferably, the nitrogen-containing polymer contains at least one of nitrogen-containing branched polymer A, nitrogen-containing branched polymer B, nitrogen-containing branched polymer C, nitrogen-containing branched polymer D, and nitrogen-containing branched polymer E, and the nitrogen-containing branched polymer A is JPEG2026050302000003.jpg56157, and the nitrogen-containing branched polymer B is JPEG2026050302000004.jpg56154, and the nitrogen-containing branched polymer C is JPEG2026050302000005.jpg59154, and the nitrogen-containing branched polymer D is JPEG2026050302000006.jpg59149, and the nitrogen-containing branched polymer E is JPEG2026050302000007.jpg60146.

[0021] According to a second aspect of the present invention, there is provided a method for producing the nitrogen-containing branched polymer, comprising preparing a reaction monomer mixture containing monomer I, monomer II, and monomer III, adding an acid-based catalyst to the reaction monomer mixture under temperature conditions of -5°C to 0°C to obtain a reaction solution, wherein monomer I is an aryl monomer, monomer II is a monomer containing a branched structure, and monomer III is a monomer containing a nitrogen-containing heterocyclic ring (step S1); subjecting the reaction solution to an oligomerization reaction, and obtaining an oligomer mixture after the completion of the oligomerization reaction, wherein the reaction temperature of the oligomerization reaction is 0°C to 10°C (step S2); subjecting the oligomer mixture to a high polymerization reaction, wherein the reaction temperature of the high polymerization reaction is 0°C to 24°C (step S3); separating a polymer from the product after the completion of the high polymerization reaction, performing an acid removal treatment on the polymer, and converting the polymer into a nitrogen-containing branched polymer after the acid removal treatment (step S4).

[0022] Preferably, in S1, the acid-based catalyst is added to the reaction monomer mixture in a dropping manner, and the dropping rate is 0.3 mL / min to 2 mL / min.

[0023] Preferably, the reaction time of the oligomerization reaction is 1 hour to 5 hours, and the reaction time of the high polymerization reaction is 1 hour to 15 hours.

[0024] Preferably, in S4, the polymer is discharged as a cylindrical extrudate by an extruder, and the cross-sectional diameter in the radial direction of the extrudate is 0.5 mm to 2.5 mm.

[0025] Preferably, in S4, the extrudate is discharged into pure water or an aqueous solution, and the solute in the aqueous solution contains at least one of potassium carbonate, sodium carbonate, sodium chloride, potassium hydroxide, and calcium chloride.

[0026] According to a third aspect of the present invention, an anion exchange resin is provided that includes a quaternization product of the nitrogen-containing branched polymer described above. The anion exchange resin achieves low water absorption and swelling, has excellent ionic conductivity and mechanical properties, and can be used in the efficient and stable production of anion exchange membranes.

[0027] Preferably, the anion exchange resin includes at least one of anion exchange resin A, anion exchange resin B, anion exchange resin C, anion exchange resin D, anion exchange resin E, anion exchange resin F, anion exchange resin G, anion exchange resin H, anion exchange resin I, anion exchange resin J, anion exchange resin K, and anion exchange resin L, wherein anion exchange resin A is The file is JPEG2026050302000008.jpg57149, Anion exchange resin B is, The file is JPEG2026050302000009.jpg66151, Anion exchange resin C is The filename is JPEG2026050302000010.jpg68147. Anion exchange resin D is The file is JPEG2026050302000011.jpg68146, Anion exchange resin E is The file is JPEG2026050302000012.jpg67144, Anion exchange resin F is The file is JPEG2026050302000013.jpg72135, Anion exchange resin G is The filename is JPEG2026050302000014.jpg66147. Anion exchange resin H is The filename is JPEG2026050302000015.jpg76147. Anion exchange resin I is The file is JPEG2026050302000016.jpg65123, Anion exchange resin J is The file is JPEG2026050302000017.jpg64146, Anion exchange resin K is, The filename is JPEG2026050302000018.jpg50147. The anion exchange resin L is The filename is JPEG2026050302000019.jpg72142.

[0028] Preferably, the anion exchange resin includes at least one of anion exchange resin A, anion exchange resin B, anion exchange resin C, anion exchange resin D, and anion exchange resin E.

[0029] A fourth aspect of the present invention provides a method for producing the anion exchange resin, comprising: step S1, which involves preparing a reaction monomer mixture containing monomer I, monomer II, and monomer III; adding an acidic catalyst to the reaction monomer mixture under temperature conditions of -5°C to 0°C to obtain a reaction solution, wherein monomer I is an aryl monomer, monomer II is a monomer containing a branched structure, and monomer III is a monomer containing a nitrogen-containing heterocycle; and oligomerizing the reaction solution, and obtaining an oligomer mixture after the completion of the oligomerization reaction, wherein the reaction temperature of the oligomerization reaction is The method comprises: step S2, which is 0°C to 10°C; step S3, which involves a high polymerization reaction of an oligomer mixture, wherein the reaction temperature of the high polymerization reaction is 0°C to 24°C; step S4, which involves separating the polymer from the product after the high polymerization reaction is complete, subjecting the polymer to an acid removal treatment, and converting the polymer into a nitrogen-containing branched polymer after the acid removal treatment; and step S5, which involves adding the nitrogen-containing branched polymer and the quaternization reagent to solvent B to prepare a quaternization reaction solution, then subjecting the nitrogen-containing branched polymer and the quaternization reagent to a quaternization reaction, and separating the anion exchange resin from the product obtained by the quaternization reaction.

[0030] By producing an anion exchange resin using the method described above, the problem of molecular weight heterogeneity that arises from further increasing the degree of branching of branched materials can be effectively improved, enabling the controllable and stable production of the anion exchange resin of the present invention, effectively improving the solubility of highly branched materials, and ensuring the excellent performance of anion exchange resins containing branched structures.

[0031] Preferably, in S1, the acidic catalyst is added to the reaction monomer mixture by a dropwise method, with a dropping rate of 0.3 mL / min to 2 mL / min.

[0032] Preferably, the reaction time for the oligomerization reaction is 1 to 5 hours, and the reaction time for the high polymerization reaction is 1 to 15 hours.

[0033] Preferably, monomer I comprises at least one of the following aryl monomers: JPEG2026050302000020.jpg49155

[0034] Preferably, monomer II comprises at least one of the following substances:) JPEG2026050302000021.jpg169117

[0035] Preferably, monomer III comprises at least one of piperidone monomer and quinuclidinone monomer.

[0036] Preferably, the general structural formula of the piperidone monomer is: The image is JPEG2026050302000022.jpg1833, where R1 and R2 are independently selected from methyl, ethyl, propyl, butyl, pentyl, and cyclopropyl, respectively.

[0037] Preferably, the general structural formula of the quinuclidinone monomer is: The image is JPEG2026050302000023.jpg1640, where R3 is a hydrogen atom, alkyl, alkenyl, alkynyl, or aromatic ring.

[0038] Preferably, the piperidone monomer comprises at least one of the following substances: JPEG2026050302000024.jpg4397 The quinuclidinone monomer contains at least one of the following substances: JPEG2026050302000025.jpg1764

[0039] Preferably, the acid catalyst comprises at least one of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid, and the amount of acid catalyst added is 4 to 14 eq, based on the equivalent amount of monomer III added.

[0040] Preferably, the acidic catalyst includes trifluoroacetic acid and trifluoromethanesulfonic acid.

[0041] Preferably, using the amount of monomer III added as an equivalent, the amounts of trifluoroacetic acid and trifluoromethanesulfonic acid added satisfy the ratio trifluoroacetic acid:trifluoromethanesulfonic acid = (0.5eq~3eq):(3.5eq~11eq).

[0042] Preferably, in S5, the amounts of nitrogen-containing branched polymer and quaternization reagent added satisfy a molar ratio of nitrogen-containing branched polymer:quaternization reagent = 1:(1~3).

[0043] Preferably, the quaternization reagent is methyl trifluoroacetate, methyl p-toluenesulfonate, iodomethane, bromopropane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromobutane, bromopentane, bromohexane, bromocyclohexane, bromocyclopentane, bromocyclohexane, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethanesulfonic acid It comprises at least one of the following: ethyl, 3-butyne-1-ylmethanesulfonate, allyl allylsulfonate, methyl benzenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentyl benzenesulfonate, tetrahydro-2H-pyran-4-ylmethanesulfonate, or cyclohexyl p-toluenesulfonate.

[0044] Preferably, preparing the reaction monomer mixture involves mixing monomer I, monomer II, and monomer III in solvent A, which consists of at least one of dichloromethane, trichloromethane, chloroform, or tetrahydrofuran.

[0045] Preferably, the reaction temperature for the quaternization reaction is 10°C to 100°C.

[0046] Preferably, the reaction time for the quaternization reaction is 4 to 36 hours.

[0047] Preferably, solvent B consists of at least one of dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, and acetonitrile.

[0048] Preferably, in S5, separating the anion exchange resin from the product obtained by the quaternization reaction includes, specifically, adding a precipitating agent to the product obtained by the quaternization reaction, washing and drying the precipitate formed from the product, and then obtaining the anion exchange resin by ion exchange treatment, wherein the precipitating agent includes at least one of ethanol, ethyl acetate, ethylene glycol, diethyl ether, tetrahydrofuran, acetone, or water.

[0049] According to a fifth aspect of the present invention, an anion exchange membrane containing the above-described anion exchange resin is provided. The anion exchange membrane provided by the present invention not only has good mechanical properties but can also achieve relatively high ionic conductivity. When this anion exchange membrane is applied to an electrochemical apparatus, the electrochemical performance and structural stability of the electrochemical apparatus can be significantly improved. Furthermore, because the anion exchange membrane has a low water absorption swelling rate, the volume of hydration channels can be reduced, thereby allowing the electrochemical apparatus using this anion exchange membrane to maintain a low permeable hydrogen penetration rate.

[0050] According to a sixth aspect of the present invention, a method for producing the anion exchange membrane is provided, comprising: step S1, which involves preparing a reaction monomer mixture containing monomer I, monomer II, and monomer III; adding an acidic catalyst to the reaction monomer mixture at a temperature of -5°C to 0°C to obtain a reaction solution, wherein monomer I is an aryl monomer, monomer II is a monomer containing a branched structure, and monomer III is a monomer containing a nitrogen-containing heterocycle; step S2, which involves oligomerizing the reaction solution and obtaining an oligomer mixture after the oligomerization reaction is completed, wherein the reaction temperature of the oligomerization reaction is 0°C to 10°C; and step S2, which involves highly polymerizing the oligomer mixture. The method comprises: step S3, in which the reaction temperature of the high polymerization reaction is 0°C to 24°C; step S4, in which the polymer is separated from the product after the completion of the high polymerization reaction, the polymer is subjected to an acid removal treatment, and after the acid removal treatment the polymer is converted into a nitrogen-containing branched polymer; step S5, in which the nitrogen-containing branched polymer and the quaternization reagent are added to solvent B to prepare a quaternization reaction solution, then the nitrogen-containing branched polymer and the quaternization reagent are subjected to a quaternization reaction, and the anion exchange resin is separated from the product obtained by the quaternization reaction; and step S6, in which a homogeneous phase solution containing the anion exchange resin in the solute is prepared, and then the homogeneous phase solution is applied to a film substrate and dried to produce an anion exchange membrane.

[0051] Preferably, in S1, the acidic catalyst is added to the reaction monomer mixture by a dropwise method, with a dropping rate of 0.3 mL / min to 2 mL / min.

[0052] Preferably, the reaction time for the oligomerization reaction is 1 to 5 hours, and the reaction time for the high polymerization reaction is 1 to 15 hours.

[0053] Preferably, the reaction temperature for the quaternization reaction is 10°C to 100°C.

[0054] Preferably, the reaction time for the quaternization reaction is 4 to 36 hours.

[0055] Preferably, S6 specifically includes dissolving an anion exchange resin in solvent C, filtering the resulting mixed solution through a diaphragm with a mesh count of 2000 to 6000, applying the homogeneous phase solution, which is the filtrate filtered through the diaphragm, to a film substrate to obtain a semi-finished product, and drying the semi-finished product at 60°C for 8 to 12 hours.

[0056] Preferably, solvent C consists of at least one of dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, and acetonitrile.

[0057] According to a seventh aspect of the present invention, an electrochemical apparatus including the anion exchange membrane described above is provided. Based on the use of the anion exchange membrane provided by the present invention, hydrogen in oxygen in the electrochemical apparatus can remain within a safe control range for a long period of time. This gives the electrochemical apparatus good safety. Furthermore, because the ionic conductivity of the anion exchange membrane is relatively high, efficient ion movement within the electrochemical apparatus is ensured. This gives the electrochemical apparatus excellent electrochemical performance. [Brief explanation of the drawing]

[0058] [Figure 1] This is a device for measuring ionic conductivity. [Figure 2] This is a statistical chart showing the test results for tensile strength and elongation at break measured for the test subject in Test Example 1. [Figure 3] This is a statistical chart showing the test results for ionic conductivity, water absorption, and swelling rate measured for the test subject in Test Example 1. [Figure 4] This is a statistical chart showing the test results for the hydrogen content in oxygen and polarization performance of a single cell of an alkaline membrane, using the test subject from Test Example 1. [Figure 5] This is a statistical chart showing the test results for tensile strength and elongation at break measured for the test subject in Test Example 2. [Figure 6] This is a statistical chart showing the test results for ionic conductivity, water absorption, and swelling rate measured for the test subject in Test Example 2. [Figure 7] This is a statistical chart showing the test results for the hydrogen content in oxygen and polarization performance of a single cell of an alkaline membrane, using the test subject from Test Example 2. [Figure 8] This is a statistical chart showing the test results for tensile strength and elongation at break measured for the test subject in Test Example 3. [Figure 9] This is a statistical chart showing the test results for ionic conductivity, water absorption, and swelling rate measured for the test subject in Test Example 3. [Figure 10] This is a statistical chart showing the test results for the hydrogen content in oxygen and polarization performance of a single cell of an alkaline membrane, using the test subject from Test Example 3. [Figure 11] This is a statistical chart showing the test results for tensile strength and elongation at break measured for the test subject in Test Example 4. [Figure 12] This is a statistical chart showing the test results for ionic conductivity, water absorption, and swelling rate measured for the test subject in Test Example 4. [Figure 13] This is a statistical chart showing the test results for the hydrogen content in oxygen and polarization performance of a single cell of an alkaline membrane, using the test subject from Test Example 4. [Modes for carrying out the invention]

[0059] To help those skilled in the art better understand the technical concept of the present invention, the technical concept in embodiments of the present invention will be described below clearly and completely, although it will be clear that the embodiments described are only some embodiments of the present invention and not all embodiments.

[0060] Examples 1-10 The manufacturing methods for the anion exchange membranes of Examples 1 to 10 are as follows. S1.0.27 mol of monomer I, 0.03 mol of monomer II, and 0.36 mol of monomer III were added to 100 mL of dichloromethane and mixed thoroughly to obtain a reaction monomer mixture. Then, at 0°C, an acidic catalyst (specifically, the acidic catalyst contained 22.8 mL of trifluoroacetic acid and 240 mL of trifluoromethanesulfonic acid) was added dropwise to the reaction monomer solution at a rate of 1 mL / min. The solution obtained after the addition was completed was used as the reaction solution (wherein monomer I is an aryl monomer, monomer II is a monomer containing a branched structure, and monomer III is a monomer containing a nitrogen-containing heterocycle). S2. The reaction solution was incubated at the reaction temperature for the oligomerization reaction for 1 to 1.5 hours. During this process, the reaction monomers in the reaction solution underwent oligomerization by the action of an acidic catalyst. The product obtained after the completion of the oligomerization reaction was an oligomer mixture. S3. Next, the oligomer mixture was heated to the reaction temperature for high polymerization and kept warm for 2 to 5.5 hours. During this process, high polymerization occurred in the oligomer mixture. S4. After the reaction was complete, the polymer was discharged into pure water using an extruder, filtered, washed with pure water, and dried. Then, the resulting polymer was dissolved in an alkaline solution to remove acid. After sufficient acid removal, the precipitate was washed and dried to obtain a nitrogen-containing branched polymer. After completion of steps S5 and S4, 0.1 mol of nitrogen-containing branched polymer and 0.15 mol of p-toluenesulfonate were added to 200 mL of dimethyl sulfoxide and mixed well to obtain a quaternization reaction solution. The quaternization reaction solution was then heated to 80°C and kept warm for 15 hours. Subsequently, ethyl acetate (2 L) was added to the obtained product solution to precipitate a precipitate, and the precipitate from the product solution was then obtained by filtration. After washing the precipitate with ethyl acetate, ion exchange was performed using 1 L of 1 M KBr aqueous solution, and the solution was dried to obtain an anion exchange resin. S6. An anion exchange resin was dissolved in dimethyl sulfoxide (DMSO) to obtain a homogeneous phase solution with a solid content of 20 wt%. The homogeneous phase solution was cast into a coating machine to obtain a semi-finished product. The obtained semi-finished product was dried at 60°C for 8 hours, and then the dried film was placed in 1 M KOH and immersed at 60°C for 48 hours to obtain an anion exchange film.

[0061] In this example, different experimental groups were established using the types of monomers I, II, and III in the raw materials as variables. Based on the specific monomers I and II selected between the different experimental groups, the reaction temperature and reaction time for the oligomerization reaction involving S2 and S3, and the reaction temperature and reaction time for the high polymerization reaction in the production of the anion exchange membrane were adaptively adjusted. Table 1 shows the variable settings between each experimental group. Except for the variables shown in Table 1, all other experimental procedures and the use of raw materials were strictly identical across all experimental groups in this example.

[0062] Table 1: Examples 1-10 and variable settings between each example JPEG2026050302000026.jpg114116

[0063] The numbers of the anion exchange resins obtained in the above experimental groups are specifically shown in Table 2. Table 2 shows the weight-average molecular weight and polydispersity index (PDI) corresponding to the nitrogen-containing branched polymer obtained after the completion of step S4 in the manufacturing process of the anion exchange resin for each experimental group.

[0064] Table 2: Nitrogen-containing branched polymers and anion exchange resins produced in Examples 1-10 JPEG2026050302000027.jpg77110

[0065] The anion exchange resins and their corresponding chemical structures shown in Table 2 are specifically as follows:

[0066] Anion exchange resin A is The file is JPEG2026050302000028.jpg3692, Anion exchange resin B is, The file is JPEG2026050302000029.jpg4395, Anion exchange resin C is The file is JPEG2026050302000030.jpg4394, Anion exchange resin D is The file is JPEG2026050302000031.jpg4291, Anion exchange resin E is The file is JPEG2026050302000032.jpg4489, Anion exchange resin F is The file is JPEG2026050302000033.jpg4481, Anion exchange resin G is The filename is JPEG2026050302000034.jpg4190. Anion exchange resin H is The file is JPEG2026050302000035.jpg4584, Anion exchange resin I is The file is JPEG2026050302000036.jpg4076, Anion exchange resin J is The filename is JPEG2026050302000037.jpg4090.

[0067] Test Example 1 1. Subjects of the Examination This test example uses the anion exchange resins and anion exchange membranes manufactured in Examples 1 to 10 as test subjects. 2. Test items and test methods (1) Solubility test Each anion exchange resin was dissolved separately in a fixed amount of dimethyl sulfoxide, and its solubility was observed at 80°C for up to 24 hours. Solubility evaluation criteria: "++" indicates good solubility, "-+" indicates slight solubility, and "-" indicates no solubility.

[0068] (2) Mechanical performance test Test method: The thickness and width of the anion exchange membrane were measured under constant temperature and humidity conditions of 23°C ± 2°C and relative humidity of 50% ± 10%. When measuring the tensile strength and elongation at break of the anion exchange membrane under test, different tensile speeds selected from the range of 50 mm / min to 200 mm / min were used. A separate sample should be applied to each tensile speed. After breaking the sample, the corresponding load value was read. a. Tensile Strength: The ratio of the maximum load an anion exchange membrane can withstand when it breaks under pure tensile force to the width of the stretched membrane material is used to evaluate the mechanical strength of the membrane, by separating it into transverse tensile strength and longitudinal tensile strength. b. Elongation at Break: This is the ratio of the distance between two points to the original length at which the anion exchange membrane breaks under the maximum load it has been subjected to. This represents the maximum amount of deformation that an alkaline membrane can withstand before being stretched and breaking, and is used to indicate the flexibility of the anion exchange membrane.

[0069] (3) Water absorption and swelling performance test Test method: a. The anion exchange membrane was cut into 1cm x 4cm pieces, placed in 1M KOH, underwent three base exchanges, and then subjected to a swelling performance test in deionized water at 80°C. b. The anion exchange membrane was cut into 5cm x 5cm pieces, placed in 1M KOH, and subjected to three base exchanges. A water absorption performance test was then conducted in deionized water at 80°C.

[0070] (4)OH - Ionic conductivity performance (In electrical conductivity tests, the film state is OH) - (80℃, pure water) A 10 mm x 45 mm anion exchange membrane was cut as a sample. The sample was placed in a 1 M KOH aqueous solution and ion exchange was performed at 80°C for 24 hours. After ion exchange was complete, the sample was washed with deionized water until neutral and stored in deionized water. Before the test, the thickness and width of the anion exchange membrane were measured using a thickness gauge and a ruler, respectively. The average values ​​of three measurements were taken as width a and thickness b, and at least three points were collected for each sample group. The ionic conductivity test apparatus was tested using a four-electrode probe method, as shown in Figure 1. First, the sample was placed flat and wrinkle-free on the platinum wire electrode, and after confirming that the sample and the platinum wire electrode were in firm contact, the lid was lightly placed on top and the screw was tightened with a wrench. After ensuring that there were no protrusions on the sample after tightening, the assembly of the test module was completed. The test fixture was connected to the temperature and humidity control system. After connection, it was purged with N2 (99.999%, the same applies hereafter), and the flow rates on both sides were set to 500 sccm. The humidification condition was set to 100% RH, and it was ensured that the line temperature was 5°C higher than the temperature of the test apparatus. The actual test temperature was set as needed. Subsequently, the temperature and humidity device was started, and the electrolysis process was initiated after the set conditions were reached. Throughout the entire process, the N2 purging was maintained without changing the gas flow rate.

[0071] (5) Electrolyzed water test The anion exchange membrane under test was electrolytically treated using a constant current method. The electrolytic current value can be adjusted within an electrolytic potential of 2V to meet the actual test requirements. During the electrolysis process, an electrochemical reaction occurs at the electrodes, and all anions in the anion exchange membrane are converted to OH in place. - Carbonate (hydrogen) ions in the anion exchange membrane were released in the form of CO2 gas until they were replaced. Whether electrolysis had reached equilibrium was determined based on the change in overpotential during the test process. Generally, when electrolysis continues until the potential fluctuation value is less than 1%, the electrolysis process is considered complete and the system is judged to have reached equilibrium. a. EIS Examination Process After electrolytic equilibrium, an EIS test was performed and the current perturbation mode was selected. The frequency range was 0.1 Hz to 1.0 MHz. The perturbation width was 1 mA. An impedance spectrum was obtained. The impedance value R of the anion exchange membrane was read from the intersection of the low-frequency portion of the spectral line with the real axis. The in-plane ionic conductivity of the sample was calculated using the following formula. σ = l / (a ​​× b × R) During the ceremony, σ -- This is the in-plane ionic conductivity of the sample (unit: millisiemen / centimeter (mS / cm)). l -- This is the distance between electrodes (in centimeters (cm)). a--This is the width of the membrane sample (in centimeters (cm)). b -- The thickness of the membrane sample (in centimeters (cm)). R -- This is the measured impedance value of the membrane sample (unit: ohms (Ω)). b. Polarization performance test In a catalyst system with nickel ferrite as the anode and platinum-carbon as the cathode, the polarization curve of a single-cell alkaline film was tested at 60°C @ 1M KOH. c. Testing hydrogen in oxygen A GC online test was performed on the oxygen at the anode to obtain data on the hydrogen content of the oxygen.

[0072] 3. Test Results The test results for this example are recorded in Tables 3 and 4. Based on the data in Table 3, Figure 2 was created. Figure 2 shows a comparison of the test results for tensile strength and elongation at break of the test subjects in this example. Based on the data in Table 4, Figures 3 and 4 were created. Figure 3 shows a comparison of the test results for ionic conductivity, water absorption, and swelling rate of the test subjects in this example. Figure 4 shows a comparison of the test results for hydrogen content in oxygen and polarization characteristics of a single cell of an alkaline film using the test subjects in this example. As can be seen from the test results, all of the anion exchange resins produced in Example 1 simultaneously satisfy the following conditions: both the measured tensile strength and elongation at break are at relatively high levels, the measured swelling rate is at a relatively low level, and the measured conductivity is at a relatively high level. From this, it can be seen that all of the anion exchange resins obtained in Example 1 simultaneously possess good structural stability, conductivity, and swelling resistance. By further applying the anion exchange resin to electrolytic water testing, based on the excellent performance of the anion exchange resin, it is possible to suppress the transmembrane transport of hydrogen gas generated during operation of the electrolytic water system using the anion exchange resin. This makes it possible to control the hydrogen in the oxygen of the electrolytic water system to a relatively low level, ensuring the safety of operation of the electrolytic water system, maintaining the good ion transport effect of the electrolytic water system, and ensuring electrochemical work efficiency. Further comparison of the test results of this test example reveals that, in terms of the selection of reaction raw materials, Examples 2 and 7, Examples 3 and 8, and Examples 4 and 9 form pairs of contrasting examples, and the difference between these contrasting examples lies in the type of material used for the selected monomer I. The comparison shows that, among the above contrasting examples, when p-terphenyl is used as monomer I for producing the anion exchange resin, the performance of the produced anion exchange resin is superior.

[0073] Table 3: Statistical results of performance measurements of the anion exchange resin and anion exchange membrane tested in this example. JPEG2026050302000038.jpg64102

[0074] Table 4: Statistics of the performance test results for anion exchange membranes using electrolyzed water. JPEG2026050302000039.jpg77109

[0075] Examples 11-16, Comparative Example 1, Comparative Example 2 Referring to Examples 1 and 4, the experiments were designed to show the effect of the dose ratio of raw material monomers on the product performance of the anionic resin and anion exchange membrane, with the dose ratio of monomers used in the production of the anion exchange membrane as a variable. (1) Refer to Example 1 Examples 11, 12, 13, and 14 were established based on Example 1. The variable between each of the above examples is the amount of p-terphenyl and 1,3,5-triphenylbenzene used in the production of the anion exchange membrane. The amounts of p-terphenyl and 1,3,5-triphenylbenzene used for each experimental group are shown in Table 5. Except for the variable shown in Table 5, all other experimental procedures and raw material usage in each of the above examples were in exact agreement with Example 1.

[0076] Table 5: Amounts of p-terphenyl and 1,3,5-triphenylbenzene added corresponding to Examples 1 and 11-14 JPEG2026050302000040.jpg4892

[0077] (2) Refer to Example 4 Based on Example 4, Examples 15, 16, Comparative Example 1, and Comparative Example 2 were established. The variable between the Examples and Comparative Examples is the amount of p-terphenyl and triphenylamine used in the production of the anion exchange membrane. The amounts of p-terphenyl and triphenylamine used corresponding to each Example and Comparative Example are shown in Table 6. Except for the variable shown in Table 6, the other experimental procedures and the use of raw materials in each Example and Comparative Example were strictly identical.

[0078] Table 6: Amounts of p-terphenyl and triphenylamine added corresponding to Example 4, Example 15, Example 16, Comparative Example 1, and Comparative Example 2. JPEG2026050302000041.jpg4884

[0079] Table 7 shows the weight-average molecular weight and polydispersity index (PDI) corresponding to the nitrogen-containing branched polymer obtained after the completion of step S4 in the manufacturing process of the anion exchange resins of each of the above examples and comparative examples. For ease of comparison, Table 7 also includes the weight-average molecular weight and polydispersity index (PDI) of the nitrogen-containing branched polymers obtained in Example 1 and Example 4.

[0080] Table 7: Weight-average molecular weight and PDI of nitrogen-containing branched polymers obtained in each example and comparative example. JPEG2026050302000042.jpg82108

[0081] Test Example 2

[0082] 1. Subjects of the Examination This test example uses the anion exchange resins and anion exchange membranes obtained in Examples 11-16, Comparative Example 1, and Comparative Example 2 as test subjects.

[0083] 2. Test items and test methods The specific test items for this example are as follows. The test methods for each test item in this example were identical to the test methods for the corresponding test items in Example 1. (1) Solubility test (2) Mechanical performance test a. Tensile strength b. Elongation at break (3) Water absorption and swelling performance test (4)OH - Ionic conductivity performance (In electrical conductivity tests, the film state is OH) - (80℃, pure water) (5) Electrolyzed water test a. EIS Examination Process

[0084] 3. Test Results The test results for this example are recorded in Tables 8 and 9. Based on the data in Table 8, Figure 5 was created. Figure 5 shows a comparison of the test results for tensile strength and elongation at break of the test subjects in this example. Based on the data in Table 9, Figures 6 and 7 were created. Figure 6 shows a comparison of the test results for ionic conductivity, water absorption, and swelling rate of the test subjects in this example. Figure 7 shows a comparison of the test results for hydrogen content in oxygen and polarization characteristics of a single cell of an alkaline film using the test subjects in this example. By comparing the test results of the test subject provided in Example 1 with those of the test subjects provided in Examples 11, 12, 13, and 14, and by comparing the test results of the test subject provided in Example 4 with those of the test subjects provided in Examples 15, 16, Comparative Example 1, and Comparative Example 2, it is possible to demonstrate the effect of the mixing ratio of monomer I and monomer II on the product performance of the anion exchange resin during the manufacturing process. Considering the contents shown in Table 7 of this specification, it can be seen that, assuming the same type of reaction raw materials are used, the weight-average molecular weight and polydispersity index (PDI) of the nitrogen-containing branched polymer change depending on the mixing ratio of monomer I and monomer II. In Examples 11-16, Comparative Example 1, and Comparative Example 2, the weight-average molecular weight of the nitrogen-containing branched polymer produced in Comparative Example 1 is relatively low, less than 40,000 g / mol. The polydispersity index (PDI) corresponding to the nitrogen-containing branched polymer produced in Comparative Example 2 is relatively high, higher than 2.6. Furthermore, considering the test results shown in Table 8, the anion exchange resin produced in Comparative Example 1 has relatively low electrical conductivity. The anion exchange resin produced in Comparative Example 2 has problems with relatively low tensile strength, relatively low elongation at break, and relatively high swelling rate. The anion exchange resins produced in Examples 11 to 16 all have high tensile strength, large elongation at break, low swelling rate, and high electrical conductivity. From this, it can be explained that if the nitrogen-containing branched polymer used to produce the anion exchange resin has a weight-average molecular weight of 40,000 g / mol or more and cannot simultaneously satisfy the polydispersity index PDI ≤ 2.6, the anion exchange resin cannot overcome the trade-off effect between ionic conductivity, structural stability, and water absorption swelling characteristics. Analysis of the above experimental results shows that the anion exchange resins produced in Examples 11, 12, 13, 14, Comparative Example 1, and Comparative Example 2 all possess relatively high ionic conductivity, good structural stability, and relatively low water absorption swelling characteristics. Based on this, comparing the test results of the experimental groups with the test results of the experimental group of Example 1, which is the set standard, it is possible to easily produce a nitrogen-containing branched polymer with a weight-average molecular weight of 40,000 g / mol or more and simultaneously satisfying a polydispersity index PDI ≤ 2.6 by controlling the molar ratio of monomer I to monomer II in the manufacturing process of the anion exchange resin to monomer I:monomer II = (85-95):(5-15).

[0085] Table 8: Statistical results of performance measurements of the anion exchange resin and anion exchange membrane tested in this example. JPEG2026050302000043.jpg64113

[0086] Table 9: Statistics of the performance test results for anion exchange membranes using electrolyzed water. JPEG2026050302000044.jpg78112

[0087] Example 17, Comparative Examples 3-6 In this example, anion exchange membranes were manufactured by providing examples and comparative examples, with Examples 1, 2, 3, 4, and 5 serving as controls for each. The types of monomer I and monomer II used to manufacture the anion exchange membranes were the same across the corresponding experimental groups. The control conditions for each experimental group and the specific methods used to manufacture the anion exchange membranes are described below in detail.

[0088] (1) Example 17 Referring to Example 1, the method for producing the anion exchange membrane in Example 17 is as follows: S1.0.27 mol of p-terphenyl, 0.03 mol of 1,3,5-triphenylbenzene, and 0.36 mol of 3-quinuclidinone hydrochloride were dissolved in 100 mL of dichloromethane, and 240 mL of trifluoromethanesulfonic acid and 22.8 mL of trifluoroacetic acid were slowly added dropwise while stirring at 0°C. After the addition was complete, the mixture was stirred for 72 hours to obtain a viscous solution. The viscous solution was sequentially washed with pure water, 1 mol of NaOH aqueous solution, and pure water, and dried at 100°C for 30 hours to obtain a pale yellow powdery nitrogen-containing branched polymer. 0.1 mol of nitrogen-containing branched polymer and 0.15 mol of iodomethane were dissolved in dimethyl sulfoxide and stirred at 60°C for 10 hours. After the reaction was complete, the resulting product was washed three times with pure water and dried at 100°C for 30 hours to obtain a pale yellow powdered anion exchange resin. S3. An anion exchange resin was dissolved in N,N-dimethylacetamide to obtain a polymer solution. The polymer solution was coated onto a glass plate, dried in an oven at 80°C for 5 hours, and then the temperature was raised to 120°C and drying continued for 20 hours to obtain an iodine ion exchange membrane. S4. The iodine ion exchange membrane was immersed in a 1M NaOH aqueous solution at room temperature for 5 hours. After removing the film, it was washed with pure water and dried in a 100°C oven under a nitrogen atmosphere for 5 hours to obtain an anion exchange membrane.

[0089] (2) Comparative Example 3 Referring to Example 2, the method for producing the anion exchange membrane of Comparative Example 3 is as follows: 0.27 mol of p-terphenyl, 0.03 mol of triptycene, and 0.36 mol of 3-quinuclidinone were added to 100 mL of dichloromethane and stirred for 10 minutes in an ice bath under an air atmosphere using a magnetic stirrer to obtain a pale yellow mixed solution. Then, 240 mL of tetrafluoromethanesulfonic anhydride (TFSA) was added dropwise to the above mixed solution. After the addition was complete, the reaction was stirred for 36 hours. The resulting viscous solution was poured into a mixture of 200 mL + 200 mL of water and methanol to precipitate a yellow polymer. The above yellow polymer was stirred and ground, then filtered and collected, and washed with 1 M K2CO3 solution at room temperature for 12 hours with stirring to neutralize any residual acid from the reaction. Then, it was washed three times with deionized water and dried in a vacuum oven at 80°C for 12 hours to obtain a nitrogen-containing branched polymer. The polymer obtained from S2, 0.1 mol of S1 was dissolved in 30 mL of DMSO and stirred at room temperature for 30 minutes. Then, K2CO3 and 0.15 mol of iodomethane were added, and the mixture was stirred at room temperature in the dark for 12 hours, followed by heating to 60°C and stirring for 6 hours. 200 mL of diethyl ether was added to the resulting viscous solution, the yellow precipitate was filtered, rinsed three times with deionized water, and dried in a vacuum oven at 80°C for 12 hours to obtain an anion exchange resin. The anion exchange resin obtained in S3 and S2 was dissolved in 15 mL of DMSO, and the polymer solution was filtered through a 0.45 μm polytetrafluoroethylene (PTFE) filter and cast onto a glass plate. The solution was then dried on a solvent evaporation heating plate at 120°C for 6 hours to completely remove any remaining solvent, resulting in a 40 μm thick I-type polymer film. S4. An I-type polymer membrane was immersed in a 1M KOH solution to obtain an OH-type membrane, which was then washed three times with deionized water to finally obtain an anion exchange membrane.

[0090] (3) Comparative Example 4 Referring to Example 3, the method for producing the anion exchange membrane of Comparative Example 4 is as follows: 0.27 mol of p-terphenyl, 0.03 mol of triphenylmethane, and 0.36 mol of N-methyl-4-piperidone were added to 100 mL of dichloromethane and stirred with a magnetic stirrer in an ice bath under an air atmosphere for 10 minutes to obtain a pale yellow mixed solution. Then, 240 mL of TFSA was added dropwise to the mixed solution. After the addition was complete, the mixture was stirred for 1 hour, and the resulting viscous solution was poured into a mixture of 200 mL + 200 mL of water and methanol to precipitate a pale yellow polymer. After stirring and grinding the yellow polymer, these pulverized pieces were collected by filtration and washed with 1 M K2CO3 solution at room temperature for 12 hours with stirring to neutralize any residual acid from the reaction. Subsequently, the mixture was washed three times with deionized water and dried in a vacuum oven at 80°C for 12 hours to obtain a nitrogen-containing branched polymer. 0.1 mol of nitrogen-containing branched polymer was dissolved in DMSO and stirred at room temperature for 30 minutes. Then, K2CO3 and 0.15 mol of iodomethane were added, and the mixture was stirred at room temperature in the dark for 12 hours, followed by heating to 60°C and stirring for 6 hours. 200 mL of diethyl ether was added to the resulting viscous solution, the yellow precipitate was filtered, the mixture was rinsed three times with deionized water, and dried in a vacuum oven at 80°C for 12 hours to obtain an anionic resin. S3. Anionic resin (0.4g) was dissolved in 15mL of DMSO, and the polymer solution was filtered through a 0.45μm polytetrafluoroethylene (PTFE) filter and cast onto a glass plate. The solution was then dried on a solvent evaporation heating plate at 120°C for 6 hours to completely remove any remaining solvent, and a 40μm thick I-type polymer film was obtained. The I-type polymer film was immersed in a 1M KOH solution and ion-exchanged at 60°C for 12 hours to obtain an OH-type film, which was then washed three times with deionized water to finally obtain an anion exchange film.

[0091] (4) Comparative Example 5 Referring to Example 4, the method for producing the anion exchange membrane of Comparative Example 5 is as follows: S1.0.27 mol of p-terphenyl was added to a 250 mL three-necked flask, followed by 100 mL of dichloromethane, then 0.36 mol of N-methyl-4-piperidone and 0.03 mol of triphenylamine. After mechanical stirring for a certain period of time, 22.8 mL of trifluoroacetic acid and 240 mL of trifluoromethanesulfonic acid were slowly added under ice bath conditions, maintaining the ice bath conditions throughout the reaction. The reaction took 4 hours, and after the solution became very viscous, the reaction solution was poured into methanol to precipitate the crude polymer. The solution was then washed with deionized water until neutral, and dried at 60°C for 24 hours to obtain a nitrogen-containing branched polymer. 0.1 mol of nitrogen-containing branched polymer S2 was weighed and dissolved in 200 mL of dimethyl sulfoxide. Then potassium carbonate and 0.15 mol of iodomethane were added, and the reaction was carried out at room temperature in the dark for about 36 hours. After the reaction was complete, the resulting solution was poured into ethyl acetate to precipitate the solid powder product. After filtration and drying, unreacted salts were removed by washing multiple times with deionized water, and the product was dried at 60°C for 24 hours to obtain an anion exchange resin. 0.05 g of S3 anion exchange resin was weighed, dissolved in 5 mL of dimethyl sulfoxide, and the casting solution was centrifuged. The solution was then cast into a glass mold and dried at 60°C for 24 hours to obtain a polymer film. The polymer film was immersed in a 1 mol / L NaOH solution at room temperature for 24 hours, then washed repeatedly with deionized water, and immersed for 24 hours until neutral to obtain an anion exchange film.

[0092] (5) Comparative Example 6 Referring to Example 5, the method for producing the anion exchange membrane of Comparative Example 6 is as follows: 0.27 mol of p-terphenyl, 0.03 mol of 9,9'-spirobifluorene, and 0.36 mol of N-methyl-4-piperidone were added to 100 mL of dichloromethane and stirred with a magnetic stirrer in an ice bath under an air atmosphere for 10 minutes to obtain a pale yellow mixed solution. Then, 240 mL of TFSA was added dropwise to the mixed solution. After the addition was complete, the mixture was stirred for 1 hour, and the resulting viscous solution was poured into a mixture of 200 mL + 200 mL of water and methanol to precipitate a pale yellow polymer. After stirring and grinding the yellow polymer, these pulverized pieces were collected by filtration and washed with 1 M K2CO3 solution at room temperature for 12 hours with stirring to neutralize any residual acid from the reaction. Subsequently, the mixture was washed three times with deionized water and dried in a vacuum oven at 80°C for 12 hours to obtain a nitrogen-containing branched polymer. 0.1 mol of nitrogen-containing branched polymer S2 was dissolved in DMSO and stirred at room temperature for 30 minutes. Then, K2CO3 and 0.15 mol of iodomethane were added, and the mixture was stirred at room temperature in the dark for 12 hours, followed by heating to 60°C and stirring for 6 hours. 200 mL of diethyl ether was added to the resulting viscous solution, the yellow precipitate was filtered, rinsed three times with deionized water, and dried in a vacuum oven at 80°C for 12 hours to obtain a quaternary branched anion exchange resin. S3. Anion exchange resin (0.4g) was dissolved in DMSO (15mL), and the polymer solution was filtered through a 0.45μm polytetrafluoroethylene (PTFE) filter and cast onto a glass plate. The solution was then dried on a solvent evaporation heating plate at 120°C for 6 hours to completely remove any remaining solvent, and a 40μm thick I-type polymer film was obtained. The I-type polymer film was immersed in a 1M KOH solution and ion-exchanged at 60°C for 12 hours to obtain an OH-type film, which was then washed three times with deionized water to finally obtain an anion exchange film.

[0093] Table 10 shows the weight-average molecular weight and polydispersity index (PDI) corresponding to the nitrogen-containing branched polymers obtained during the manufacturing process of the anion exchange resins in Example 17 and Comparative Examples 3-6. Referring to the settings of Example 17 and Comparative Examples 3-6, while using the same monomers I and II as in Example 1, and referencing a specific experimental group in Example 1, nitrogen-containing branched polymers were produced using different synthesis methods. Comparing the data in Table 10 with the data in Table 2, it can be seen that different manufacturing methods can bring about significant changes in the weight-average molecular weight and polydispersity index (PDI) of the nitrogen-containing branched polymers. In this case, Comparative Examples 3-6 produced nitrogen-containing branched polymers with appropriate weight-average molecular weights, but their polydispersity index (PDI) is high at 2.6 or higher.

[0094] Table 10: Weight-average molecular weight and PDI of nitrogen-containing branched polymers obtained in Example 17 and Comparative Examples 3-6 JPEG2026050302000045.jpg48109

[0095] Test Example 3

[0096] 1. Subjects of the Examination This test example uses the anion exchange resin and anion exchange membrane obtained in Example 17 and Comparative Examples 3-6 as test subjects.

[0097] 2. Test items and test methods The specific test items for this example are as follows. The test methods for each test item in this example were identical to the test methods for the corresponding test items in Example 1. (1) Solubility test (2) Mechanical performance test a. Tensile strength b. Elongation at break (3) Water absorption and swelling performance test (4)OH - Ionic conductivity performance (In electrical conductivity tests, the film state is OH) - (80℃, pure water) (5) Electrolyzed water test a. EIS Examination Process b. Polarization characteristics test c. Hydrogen test in oxygen

[0098] 3. Test Results The test results for this example are recorded in Tables 11 and 12. Figure 8 was created based on the data in Table 11. Figure 8 shows a comparison of the test results for tensile strength and elongation at fracture of the test subject in this example. Figures 9 and 10 were created based on the data in Table 12. Figure 9 shows a comparison of the test results for ionic conductivity, water absorption, and swelling rate of the test subject in this example. Figure 10 shows a comparison of the test results for hydrogen content in oxygen and polarization characteristics of a single cell of an alkaline film using the test subject in this example. As described above, when the monomer raw materials for producing nitrogen-containing branched polymers are the same, the production method affects the weight-average molecular weight and polydispersity index (PDI) of the nitrogen-containing branched polymer. As the test results of this example show, among the test subjects in this example, the anion exchange resin provided in Example 17 possesses relatively high ionic conductivity, good structural stability, and relatively low water absorption swelling characteristics, and its overall performance is clearly superior to the anion exchange resins produced in Comparative Examples 3 to 6. However, when comparing the anion exchange resin of Example 17 with the anion exchange resin obtained in Example 1, the anion exchange resin obtained in Example 1 had better overall performance.

[0099] Table 11: Statistical results of performance measurements of oxidized anion exchange resins and anion exchange membranes in this test example. JPEG2026050302000046.jpg39112

[0100] Table 12: Statistics of the performance test results for anion exchange membranes using electrolyzed water. JPEG2026050302000047.jpg49111

[0101] Examples 18-21, Comparative Example 7, Comparative Example 8 Based on Example 1, Examples 18, 19, 20, 21, Comparative Example 7, and Comparative Example 8 were established. The experiment was designed to show the effect of the use of an acid-based catalyst on the product performance of the anionic resin and anion exchange membrane, with the acid-based catalyst used in the production of the anion exchange membrane as a variable. The variables between Examples 18-21, Comparative Example 7, and Comparative Example 8 are the type and amount of acid-based catalyst used during the production of the anion exchange membrane. Table 13 shows the usage of acid-based catalysts during the production of the anion exchange membranes in the above examples and comparative examples. In Examples 1, 18, 19, Comparative Example 7, and 8, the acid-based catalysts used were all blended from trifluoroacetic acid and trifluoromethanesulfonic acid in a volume ratio of trifluoroacetic acid:trifluoromethanesulfonic acid = 22.8:240. However, the acid-based catalyst used in Example 20 was trifluoroacetic acid, and the acid-based catalyst used in Example 21 was trifluoromethanesulfonic acid. The equivalent amounts of acid-based catalysts shown in Table 13 are based on the amount of monomer III added. Except for the variables shown in Table 13, the other experimental procedures and raw material usage in Examples 18-21, Comparative Example 7, and Comparative Example 8 were all in exact agreement with those in Example 1.

[0102] Table 13: Usage of acid-based catalysts corresponding to Examples 18-21, Comparative Example 7, and Comparative Example 8. JPEG2026050302000048.jpg5495

[0103] Table 14 shows the weight-average molecular weight and polydispersity index (PDI) corresponding to the nitrogen-containing branched polymer obtained after the completion of step S4 in the manufacturing process of the anion exchange resins of Examples 18-21, Comparative Example 7, and Comparative Example 8. For ease of comparison, Table 14 also includes the weight-average molecular weight and polydispersity index (PDI) of the nitrogen-containing branched polymer obtained in Example 1. In Comparative Example 7, the molecular weight of the obtained nitrogen-containing branched polymer was too low because the polymerization reaction failed during the manufacturing process of the nitrogen-containing branched polymer, while in Comparative Example 8, the molecular weight of the obtained nitrogen-containing branched polymer was non-uniform because rapid polymerization occurred during the manufacturing process of the nitrogen-containing branched polymer. From the manufacturing conditions of the nitrogen-containing branched polymers in Examples 1, 18, 19, 20, and 21, it can be seen that by using either trifluoroacetic acid, trifluoromethanesulfonic acid, or a combination of both as an acid-based catalyst for manufacturing nitrogen-containing branched polymers, it is possible to successfully catalyze the polymerization reaction of the raw material monomers and successfully manufacture nitrogen-containing branched polymers.

[0104] Table 14: Weight-average molecular weight and PDI of nitrogen-containing branched polymers obtained in Examples 18-21, Comparative Example 7, and Comparative Example 8. JPEG2026050302000049.jpg61103 Note: " / " means that during the polymerization reaction to produce the nitrogen-containing branched polymer, the reaction failed, making it impossible to obtain performance data for the film material, or that rapid polymerization resulted in non-uniform molecular weight, preventing the polymer from dissolving and thus making it impossible to obtain performance data for the film material.

[0105] 1. Subjects of the Examination This test example uses the anion exchange resins and anion exchange membranes obtained in Examples 18-21, Comparative Example 7, and Comparative Example 8.

[0106] 2. Test items and test methods The specific test items for this example are as follows. The test methods for each test item in this example were identical to the test methods for the corresponding test items in Example 1. (1) Solubility test (2) Mechanical performance test a. Tensile strength b. Elongation at break (3) Water absorption and swelling performance test (4) OH - Ion conductivity performance (in the electrical conductivity test, the membrane state is OH - @80°C@ pure water) (5) Electrolyzed water test a. EIS test process b. Polarization characteristic test c. Hydrogen in oxygen test

[0107] 3. Test results The test results of this test example are recorded in Tables 15 and 16. Based on the data in Table 15, Figure 11 was created. In Figure 11, the comparison of the test results of the tensile strength and elongation at break of the test object in this test example is shown. Based on the data in Table 16, Figures 12 and 13 were created. In Figure 12, the comparison of the test results of the ion conductivity, water absorption rate and swelling rate of the test object in this test example is shown. In Figure 13, the comparison of the test results of the hydrogen content and polarization characteristics of the alkaline membrane single cell applied with the test object in this test example is shown. The anion exchange resins provided in Comparative Example 7 and Comparative Example 8 did not dissolve, and therefore, the product performance corresponding to the test subjects provided in Comparative Example 7 and Comparative Example 8 could not be measured. Except for Comparative Example 7 and Comparative Example 8, the remaining test subjects in this test example all exhibited good overall performance. Among these, Examples 1, 20, and 21 used the same equivalent amount of acid catalyst in the polymerization reaction to produce the nitrogen-containing branched polymer. Under these conditions, the product performance corresponding to the anion exchange resin and anion exchange membrane produced in Example 1 showed clear overall superiority. As can be seen from this, compared to using either trifluoroacetic acid or trifluoromethanesulfonic acid individually as the acid catalyst for producing the nitrogen-containing branched polymer, using a combination of both trifluoroacetic acid and trifluoromethanesulfonic acid as the acid catalyst for producing the nitrogen-containing branched polymer exhibits a synergistic effect, further improving the overall performance of the anion exchange resin and anion exchange membrane produced thereafter.

[0108] Table 15: Statistical results of performance measurements of the anion exchange resin and anion exchange membrane tested in this example. JPEG2026050302000050.jpg51111 Note: " / " means that during the polymerization reaction to produce the nitrogen-containing branched polymer, the reaction failed, making it impossible to obtain performance data for the film material, or that rapid polymerization resulted in non-uniform molecular weight, preventing the polymer from dissolving and thus making it impossible to obtain performance data for the film material.

[0109] Table 16: Statistics of the performance test results for anion exchange membranes using electrolyzed water. JPEG2026050302000051.jpg63107 Note: " / " means that during the polymerization reaction to produce the nitrogen-containing branched polymer, the reaction failed, making it impossible to obtain performance data for the film material, or that rapid polymerization resulted in non-uniform molecular weight, preventing the polymer from dissolving and thus making it impossible to obtain performance data for the film material.

[0110] Examples 22, 23 Examples 22 and 23 each produced anion exchange membranes based on the method for producing anion exchange membranes in Example 1. The difference between Examples 22 and 23 and Example 1 is that in the manufacturing process of the anion exchange membranes in Examples 22 and 23, the types of materials for monomer I, monomer II, and monomer III in the raw materials were replaced, and the reaction temperature and reaction time of the oligomerization reaction S2 and S3, and the reaction temperature and reaction time of the high polymerization reaction for producing the anion exchange membrane were adaptively adjusted based on the specific monomer I and monomer II selected. The specific details are shown in Table 17. Aside from the above distinction, the other experimental procedures and the use of raw materials in Examples 22 and 23 were in exact agreement with Example 1.

[0111] Table 17: Experimental groups and intermediate variables set for each group in Examples 22 and 23 JPEG2026050302000052.jpg37106

[0112] In Example 22, the anion exchange resin obtained during the production of the anion exchange membrane was marked as anion exchange resin K, and in Example 23, the anion exchange resin obtained during the production of the anion exchange membrane was marked as anion exchange resin L.

[0113] Anion exchange resin K is, The file is JPEG2026050302000053.jpg3193, The anion exchange resin L is The filename is JPEG2026050302000054.jpg4590.

[0114] The above embodiments are merely for illustrative purposes and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that the technical aspects of the present invention can be modified or replaced with equivalents, and all such modifications or replacements fall within the scope of protection of the present invention.

Claims

1. A nitrogen-containing branched polymer, The molecular structure of the nitrogen-containing branched polymer contains a nitrogen-containing heterocycle, a branched structure, and an aryl group, wherein the number of branching points of each branched structure is three or more, and the aryl group is linked to the branching portion of the branched structure by the nitrogen-containing heterocycle. When the molar ratio of the aryl groups in the nitrogen-containing branched polymer is A, and the molar ratio of the branched structure in the nitrogen-containing branched polymer is B, then A:B = (80-99):(1-20), The polydispersity index PDI of the nitrogen-containing branched polymer is ≤ 2.6, and the weight-average molecular weight of the nitrogen-containing branched polymer is 40,000 g / mol to 500,000 g / mol. A nitrogen-containing branched polymer characterized by the following features.

2. The aryl group comprises at least one of a dibiphenyl group, a terphenyl group, and a tetrabiphenyl group. The nitrogen-containing branched polymer according to feature 1.

3. The aforementioned branched structure includes a benzene ring structure in which branched portions are provided. The nitrogen-containing branched polymer according to feature 1.

4. The branched structure includes at least one of the following: 1,3,5-triphenylbenzene structural unit, triphenylmethane structural unit, 9,10-benzophenanthrene structural unit, tetraphenylmethane structural unit, triptycene structural unit, 9,9-diphenylfluorene structural unit, 9,9'-spirobifluorene structural unit, 9,9'-bifluorene structural unit, 9,9'-bicarbazole structural unit, 4,4'-bis(9-carbazol)biphenyl structural unit, 2,2''-bi-9,9'-spirobi[9H-fluorene] structural unit, and triphenylamine structural unit. The nitrogen-containing branched polymer according to feature 3.

5. The nitrogen-containing heterocycle comprises at least one of a piperidine ring and a quinuclidine ring. The nitrogen-containing branched polymer according to feature 1.

6. The molecular structure of the nitrogen-containing branched polymer includes segment I and segment II. The general structural formula of segment I is: (wherein A represents the nitrogen-containing heterocycle, Ar １ (wherein X represents the aryl group, and X represents the degree of polymerization of segment I.) The segment II consists of the nitrogen-containing heterocycle and the branched structure, and in the segment II, the nitrogen-containing heterocycle is directly connected to the branched portion of the branched structure. The nitrogen-containing branched polymer according to feature 1.

7. The nitrogen-containing branched polymer includes a basic structural unit formed by linking segment I and segment II. In the basic structural unit, the connection between segment I and segment II is such that the aryl group in segment I is connected to the nitrogen-containing heterocycle in segment II. The nitrogen-containing branched polymer according to feature 6.

8. In the aforementioned basic structural unit, the number of segments I directly connected to each segment II is three or more. The nitrogen-containing branched polymer according to feature 7.

9. The weight-average molecular weight of the nitrogen-containing branched polymer is between 40,000 g / mol and 250,000 g / mol. The nitrogen-containing branched polymer according to feature 1.

10. The aforementioned aryl group is a terphenyl group. The nitrogen-containing branched polymer according to feature 1.

11. The nitrogen-containing branched polymer comprises at least one of nitrogen-containing branched polymer A, nitrogen-containing branched polymer B, nitrogen-containing branched polymer C, nitrogen-containing branched polymer D, and nitrogen-containing branched polymer E. The nitrogen-containing branched polymer A is And, The aforementioned nitrogen-containing branched polymer B is And, The nitrogen-containing branched polymer C is And, The aforementioned nitrogen-containing branched polymer D is And, The nitrogen-containing branched polymer E is That is, The nitrogen-containing branched polymer according to feature 10.

12. A method for producing a nitrogen-containing branched polymer according to any one of claims 1 to 11, Step S1 involves preparing a reaction monomer mixture containing monomer I, monomer II, and monomer III, adding an acidic catalyst to the reaction monomer mixture at a temperature of -5°C to 0°C, wherein monomer I is an aryl monomer, monomer II is a monomer containing the branched structure, and monomer III is a monomer containing a nitrogen-containing heterocycle. Step S2 involves oligomerizing the reaction solution, and obtaining an oligomer mixture after the oligomerization reaction is completed, wherein the reaction temperature of the oligomerization reaction is 0°C to 10°C. Step S3 involves carrying out a high polymerization reaction of the oligomer mixture, wherein the reaction temperature of the high polymerization reaction is 0°C to 24°C. Step S4 includes separating the polymer from the product after the completion of the high polymerization reaction, subjecting the polymer to an acid removal treatment, and converting the polymer after the acid removal treatment to the nitrogen-containing branched polymer. A method for producing a nitrogen-containing branched polymer, characterized by the above.

13. The quaternization product of the nitrogen-containing branched polymer described in any one of claims 1 to 11 is included. An anion exchange resin characterized by the following features.

14. A method for producing an anion exchange resin according to claim 13, Step S1 involves preparing a reaction monomer mixture containing monomer I, monomer II, and monomer III, adding an acidic catalyst to the reaction monomer mixture at a temperature of -5°C to 0°C, wherein monomer I is an aryl monomer, monomer II is a monomer containing the branched structure, and monomer III is a monomer containing a nitrogen-containing heterocycle. Step S2 involves oligomerizing the reaction solution, and obtaining an oligomer mixture after the oligomerization reaction is completed, wherein the reaction temperature of the oligomerization reaction is 0°C to 10°C. Step S3 involves carrying out a high polymerization reaction of the oligomer mixture, wherein the reaction temperature of the high polymerization reaction is 0°C to 24°C. Step S4 involves separating the polymer from the product after the completion of the high polymerization reaction, subjecting the polymer to an acid removal treatment, and converting the polymer after the acid removal treatment into the nitrogen-containing branched polymer. The process includes S5, which involves adding the nitrogen-containing branched polymer and quaternization reagent to solvent B to prepare a quaternization reaction solution, then carrying out a quaternization reaction between the nitrogen-containing branched polymer and the quaternization reagent, and separating the anion exchange resin from the product obtained by the quaternization reaction. A method for producing an anion exchange resin characterized by the above.

15. The monomer I comprises at least one of the following aryl monomers: A method for producing an anion exchange resin according to feature 14.

16. The monomer II comprises at least one of the following substances: A method for producing an anion exchange resin according to feature 14.

17. The monomer III comprises at least one of piperidone monomer and quinuclidinone monomer. A method for producing an anion exchange resin according to feature 14.

18. The piperidone monomer comprises at least one of the following substances: The quinuclidinone monomer comprises at least one of the following substances: A method for producing an anion exchange resin according to feature 17.

19. The acid-based catalyst comprises at least one of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, and heptafluorobutyric acid. The amount of the acid-based catalyst added is such that it satisfies 4 to 14 eq, with the amount of monomer III added as the equivalent. A method for producing an anion exchange resin according to feature 14.

20. The quaternization reagents include methyl trifluoroacetate, methyl p-toluenesulfonate, iodomethane, bromopropane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromobutane, bromopentane, bromohexane, bromocyclohexane, bromocyclopentane, bromocyclohexane, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, and ethyl ethanesulfonate. The following are included: 3-butyne-1-ylmethanesulfonate, allyl allylsulfonate, methyl benzenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentyl benzenesulfonate, tetrahydro-2H-pyran-4-ylmethanesulfonate, or cyclohexyl p-toluenesulfonate. A method for producing an anion exchange resin according to feature 14.

21. The preparation of the reaction monomer mixture includes mixing monomer I, monomer II, and monomer III in solvent A, which consists of at least one of dichloromethane, trichloromethane, chloroform, or tetrahydrofuran. A method for producing an anion exchange resin according to feature 14.

22. The reaction temperature for the quaternization reaction is 10°C to 100°C. A method for producing an anion exchange resin according to feature 14.

23. The solvent B consists of at least one of dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, and acetonitrile. A method for producing an anion exchange resin according to feature 14.

24. In step S5, separating the anion exchange resin from the product obtained by the quaternization reaction specifically includes adding a precipitating agent to the product obtained by the quaternization reaction, washing the precipitate formed from the product, drying it, and then obtaining the anion exchange resin. The precipitating agent comprises at least one of ethanol, ethyl acetate, ethylene glycol, diethyl ether, tetrahydrofuran, acetone, or water. A method for producing an anion exchange resin according to feature 14.

25. An anion exchange membrane characterized by comprising the anion exchange resin described in claim 13.

26. A method for producing an anion exchange membrane according to claim 25, Step S1 involves preparing a reaction monomer mixture containing monomer I, monomer II, and monomer III, adding an acidic catalyst to the reaction monomer mixture under temperature conditions of -5°C to 0°C, wherein monomer I is an aryl monomer, monomer II is a monomer containing the branched structure, and monomer III is a monomer containing a nitrogen-containing heterocycle. Step S2 involves oligomerizing the reaction solution, and obtaining an oligomer mixture after the oligomerization reaction is completed, wherein the reaction temperature of the oligomerization reaction is 0°C to 10°C. Step S3 involves carrying out a high polymerization reaction of the oligomer mixture, wherein the reaction temperature of the high polymerization reaction is 0°C to 24°C. Step S4 involves separating the polymer from the product after the completion of the high polymerization reaction, subjecting the polymer to an acid removal treatment, and converting the polymer after the acid removal treatment into the nitrogen-containing branched polymer. Step S5 involves adding the nitrogen-containing branched polymer and quaternization reagent to solvent B to prepare a quaternization reaction solution, then carrying out a quaternization reaction between the nitrogen-containing branched polymer and the quaternization reagent, and separating the anion exchange resin from the product obtained by the quaternization reaction. The process includes step S6, which involves preparing a homogeneous phase solution containing the anion exchange resin in a solute, then applying the homogeneous phase solution to a film substrate and drying it to produce the anion exchange membrane. A method for producing an anion exchange membrane, characterized by the above.

27. An electrochemical apparatus characterized by comprising the anion exchange membrane described in claim 25.

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