Hyperbranched anion exchange resin, preparation method thereof and hyperbranched anion exchange membrane

Abstract

The invention provides hyperbranched anion exchange resin and a preparation method thereof and a hyperbranched anion exchange membrane, and the preparation method of the hyperbranched anion exchange resin comprises the following steps: mixing a branched monomer, a biphenyl monomer, an azacycloketone monomer, a first catalyst and a first solvent, and carrying out a polymerization reaction to obtain a hyperbranched polymer; and mixing the hyperbranched polymer with a second solvent, a quaternization reagent and a second catalyst, and carrying out quaternization reaction to obtain the hyperbranched anion exchange resin. The hyperbranched anion exchange resin is used for preparing the hyperbranched anion exchange membrane. The anion exchange membrane has the advantages of high ionic conductivity, excellent mechanical property, low swelling degree and strong alkali-resistant stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of basic anion exchange membranes, in particular to a hyperbranched anion exchange resin, a preparation method thereof and a hyperbranched anion exchange membrane. BACKGROUND

[0002] As the core component of the electrochemical devices such as water electrolysis hydrogen production and fuel cells, the performance of the anion exchange membrane directly determines the efficiency and service life of the equipment. The ideal anion exchange membrane needs to meet the following technical requirements at the same time: 1. high hydroxyl ion conductivity; 2. excellent mechanical properties; 3. low swelling degree; 4. strong alkali resistance.

[0003] However, the performances of the existing anion exchange membranes are often mutually restricted, which makes it difficult for the anion exchange membrane to meet the above requirements at the same time. For example: the mechanical strength and the swelling degree of the anion exchange membrane are difficult to balance, and under the condition of high ion exchange capacity, excessive swelling easily occurs, which affects the dimensional stability; in addition, the polymer main chain or ion group of part of the membrane material is easily degraded in a strong alkaline environment, which leads to the collapse of the membrane structure and the performance attenuation, and shortens the service life. These defects jointly restrict the application reliability of the anion exchange membrane in the electrochemical devices such as water electrolysis hydrogen production and fuel cells.

[0004] Therefore, it is urgent to develop a new type of anion exchange membrane which can simultaneously realize high ion conductivity, excellent mechanical properties, low swelling degree and strong alkali resistance. SUMMARY

[0005] The purpose of the present application is to provide a hyperbranched anion exchange resin, a preparation method thereof and a hyperbranched anion exchange membrane, so as to solve the above problems.

[0006] In order to achieve the above purpose, the following technical solutions are adopted in the present application: A preparation method of a hyperbranched anion exchange resin, comprising: mixing a branched monomer, a biphenyl monomer, a nitrogen heterocyclic ketone monomer, a first catalyst and a first solvent to perform a polymerization reaction to obtain a hyperbranched polymer; wherein the branched monomer comprises at least one of the following structures: 、 、 ; mixing the hyperbranched polymer with a second solvent, a quaternization reagent and a second catalyst to perform a quaternization reaction to obtain a hyperbranched anion exchange resin.

[0007] According to the embodiments of the present application, the biphenyl monomer comprises at least one of biphenyl, p-terphenyl, m-terphenyl and p-quaterphenyl; And / or, the azacyclic ketone monomers include at least one of N-alkylpiperidinone monomers and quinone monomers, wherein the N-alkylpiperidinone monomers include at least one of N-methyl-4-piperidinone, N-propyl-4-piperidinone, N-isopropyl-4-piperidinone, 1-cyclopropyl-4-piperidinone, 1-cyclopentyl-4-piperidinone, and 1-cyclohexyl-4-piperidinone; and the quinone monomers include at least one of 3-quininecycloone, 2,2-dihydroxymethyl-1-azabicyclo[2.2.2]oct-3-one, 2-(hydroxymethyl)-2-(methoxymethyl)quininecyclo-3-one, 2-diphenylmethylquininecyclo-3-one, and 2-methylene-3-quinone hydrochloride hydrate; And / or, the first catalyst comprises at least one of trifluoropropionic acid, methanesulfonic acid, nonafluorobutyric acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and pentafluoroacetic acid; And / or, the first solvent includes at least one of acetone, dichloromethane, trichloromethane, and acetonitrile.

[0008] According to embodiments of this application, the molar ratio of the biphenyl monomer to the azacyclic ketone monomer and the branched monomer is 1: (1~2.5): (0.01~0.2); And / or, the molar ratio of the biphenyl monomer to the first catalyst is 1: (1~50); And / or, the polymerization reaction temperature is -5℃ to 5℃, and the polymerization reaction time is 2 to 36 hours.

[0009] According to an embodiment of this application, after the polymerization reaction is completed, the method further includes: adding a diluent to the reaction system to obtain a diluted solution, then pouring the diluted solution into a first precipitant to form a precipitate, filtering, washing, and drying to obtain a hyperbranched polymer; And / or, the diluent includes at least one selected from acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, dichloromethane, and chloroform; And / or, the first precipitant includes at least one of ethanol, methanol, isopropanol, water, aqueous sodium hydroxide solution, and aqueous potassium carbonate solution.

[0010] According to embodiments of this application, the second solvent includes at least one of ethanol, dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, benzene, n-hexane, and acetone. And / or, the quaternizing agent includes at least one of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromocyclopropane, bromocyclobutane, bromocyclopentane, and bromocyclohexane. And / or, the second catalyst comprises at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, potassium iodide, and triethylamine.

[0011] According to embodiments of this application, the content ratio of the hyperbranched polymer to the second solvent is 1:5~10 g / ml; And / or, the mass ratio of the hyperbranched polymer to the quaternizing agent is 1:0.2~3; And / or, the mass ratio of the hyperbranched polymer to the second catalyst is 1:0.05~0.3; And / or, the quaternization reaction is carried out under light-protected conditions; And / or, the temperature of the quaternization reaction is 25~70℃, and the time of the quaternization reaction is 6~24h.

[0012] According to an embodiment of this application, after the quaternization reaction is completed, the preparation method further includes: pouring the reaction solution into a second precipitant to form a precipitate, filtering, washing, and drying to obtain a hyperbranched anion exchange resin; And / or, the second precipitant includes at least one of diethyl ether, n-butyl ether, isobutyl ether, ethylene oxide, diisopropyl ether, and methyl tert-butyl ether.

[0013] This application also provides a hyperbranched anion exchange resin, which is prepared by the preparation method described above.

[0014] This application also provides a hyperbranched anion exchange membrane, which is prepared from a hyperbranched anion exchange resin, wherein the hyperbranched anion exchange resin is either the hyperbranched anion exchange resin prepared by the preparation method described above or the hyperbranched anion exchange resin described above.

[0015] According to an embodiment of this application, the hyperbranched anion exchange membrane is prepared by the following method: performing film-forming treatment and ion exchange treatment on the hyperbranched anion exchange resin to obtain the hyperbranched anion exchange membrane; And / or, the film-forming process includes: dissolving the hyperbranched anion exchange resin in a third solvent to prepare a casting solution, coating the casting solution to form a film, and drying it to obtain a halogen-type anion exchange membrane; And / or, the third solvent includes at least one of dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, the temperature at which the hyperbranched anion exchange resin dissolves in the third solvent is 25~80℃; And / or, the solid content of the casting solution is 5-50%; And / or, when performing film-forming treatment, the drying temperature is 50~200℃, and the drying time is 0.5~24h; And / or, the ion exchange treatment includes: immersing the halogen-type anion exchange membrane in an alkaline solution, the alkaline solution including a sodium hydroxide solution, for a soaking time of 12-24 hours.

[0016] Compared with the prior art, the beneficial effects of this application include: This application introduces a large-volume three-dimensional structure into the synthesis of anion exchange resins, resulting in the synthesis of hyperbranched polymers. These hyperbranched anion exchange resins are used to prepare hyperbranched anion exchange membranes. Compared to traditional linear structures, the free volume energy of the branched structure is OH⁻¹. - The conduction provides sufficient channels, reduces mass transfer resistance, and is beneficial to improving the ionic conductivity of anion exchange membranes; in addition, the mutual entanglement or cross-linking between branched molecular chains can enhance the internal structural stability of the membrane, effectively inhibit excessive swelling of the membrane, and ensure the dimensional stability of the membrane.

[0017] Moreover, the method of this application has the advantages of inexpensive and readily available raw materials, mild reaction conditions, no need for complicated post-processing steps, simple operation, and low production cost, which is conducive to large-scale promotion and application.

[0018] The anion exchange membrane of this application has the advantages of high ionic conductivity, excellent mechanical properties, low swelling degree and strong alkali resistance. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0020] Figure 1 Photograph of the hyperbranched anion exchange membrane prepared in Example 1. Detailed Implementation

[0021] As used in this article: "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0022] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0023] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0024] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0025] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0026] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0027] A method for preparing a hyperbranched anion exchange resin, comprising: A branched monomer, a biphenyl monomer, a nitrogen-containing ketone monomer, a first catalyst, and a first solvent are mixed and polymerized to obtain a hyperbranched polymer; wherein the branched monomer comprises at least one of the following structures: (Branched monomer 1) (Branched monomer 2) (Branched monomer 3); The hyperbranched polymer is mixed with a second solvent, a quaternizing agent, and a second catalyst to carry out a quaternization reaction, thereby obtaining a hyperbranched anion exchange resin.

[0028] According to embodiments of this application, the biphenyl monomers include at least one of biphenyl, para-terphenyl, meta-terphenyl, and para-tetraphenyl; The structural formula of biphenyl is: The structural formula of terphenyl is: The structural formula of meta-terphenyl is: The structural formula of p-tetraphenyl is: .

[0029] And / or, the azacyclic ketone monomers include at least one of N-alkylpiperidinone monomers and quinone monomers, wherein the N-alkylpiperidinone monomers include at least one of N-methyl-4-piperidinone, N-propyl-4-piperidinone, N-isopropyl-4-piperidinone, 1-cyclopropyl-4-piperidinone, 1-cyclopentyl-4-piperidinone, and 1-cyclohexyl-4-piperidinone; and the quinone monomers include at least one of 3-quininecycloone, 2,2-dihydroxymethyl-1-azabicyclo[2.2.2]oct-3-one, 2-(hydroxymethyl)-2-(methoxymethyl)quininecyclo-3-one, 2-diphenylmethylquininecyclo-3-one, and 2-methylene-3-quinone hydrochloride hydrate; And / or, the first catalyst comprises at least one of trifluoropropionic acid, methanesulfonic acid, nonafluorobutyric acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and pentafluoroacetic acid; And / or, the first solvent includes at least one of acetone, dichloromethane, trichloromethane, and acetonitrile.

[0030] According to embodiments of this application, the molar ratio of the biphenyl monomer to the azacyclic ketone monomer and the branched monomer is 1: (1~2.5): (0.01~0.2); For example, the molar ratio of biphenyl monomers to azacyclic ketone monomers and branched monomers can be any value between 1:1:0.01, 1:1:0.1, 1:1:0.15, 1:1:0.2, 1:1.5:0.01, 1:1.5:0.1, 1:1.5:0.15, 1:1.5:0.2, 1:2:0.01, 1:2:0.1, 1:2:0.15, 1:2:0.2, 1:2.5:0.01, 1:2.5:0.1, 1:2.5:0.15, 1:2.5:0.2, or 1: (1~2.5) : (0.01~0.2).

[0031] And / or, the molar ratio of the biphenyl monomer to the first catalyst is 1: (1~50); For example, the molar ratio of biphenyl monomers to the first catalyst is any value between 1:1, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50 or 1: (1~50).

[0032] And / or, the polymerization reaction temperature is -5℃ to 5℃, and the polymerization reaction time is 2 to 36 hours.

[0033] For example, the polymerization temperature is any value between -5℃, -4℃, -3℃, -2℃, -1℃, 0℃, 1℃, 2℃, 3℃, 4℃, 5℃, or -5℃ to 5℃, and the polymerization time is any value between 2 hours, 5 hours, 7 hours, 10 hours, 12 hours, 15 hours, 17 hours, 20 hours, 22 hours, 25 hours, 27 hours, 30 hours, 32 hours, 35 hours, 36 hours, or 2 to 36 hours.

[0034] According to an embodiment of this application, after the polymerization reaction is completed, the method further includes: adding a diluent to the reaction system to obtain a diluted solution, then pouring the diluted solution into a first precipitant to form a precipitate, filtering, washing, and drying to obtain a hyperbranched polymer; And / or, the diluent includes at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, dichloromethane, and chloroform; And / or, the first precipitant includes at least one of ethanol, methanol, isopropanol, water, aqueous sodium hydroxide solution, and aqueous potassium carbonate solution.

[0035] According to embodiments of this application, the second solvent includes at least one of ethanol, dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, benzene, n-hexane, and acetone. And / or, the quaternizing agent includes at least one of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromocyclopropane, bromocyclobutane, bromocyclopentane, and bromocyclohexane. And / or, the second catalyst comprises at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, potassium iodide, and triethylamine.

[0036] According to embodiments of this application, the ratio of the hyperbranched polymer to the second solvent is 1:5~10 g / ml; For example, the ratio of the hyperbranched polymer to the second solvent is 1:5 g / ml, 1:6 g / ml, 1:7 g / ml, 1:8 g / ml, 1:9 g / ml, 1:10 g / ml or any value between 1:5 and 10 g / ml; And / or, the mass ratio of the hyperbranched polymer to the quaternizing agent is 1:0.2~3; For example, the mass ratio of the hyperbranched polymer to the quaternizing agent is 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3 or any value between 1:0.2 and 3; And / or, the mass ratio of the hyperbranched polymer to the second catalyst is 1:0.05~0.3; For example, the mass ratio of the hyperbranched polymer to the second catalyst is any value between 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3 or 1:0.05 to 0.3.

[0037] And / or, the quaternization reaction is carried out under light-protected conditions; And / or, the temperature of the quaternization reaction is 25~70℃, and the time of the quaternization reaction is 6~24h.

[0038] For example, the temperature of the quaternization reaction is any value between 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃ or 25~70℃, and the time of the quaternization reaction is any value between 6h, 8h, 10h, 12h, 15h, 17h, 20h, 22h, 24h or 6~24h.

[0039] According to an embodiment of this application, after the quaternization reaction is completed, the preparation method further includes: pouring the reaction solution into a second precipitant to form a precipitate, filtering, washing, and drying to obtain a hyperbranched anion exchange resin; And / or, the second precipitant includes at least one of diethyl ether, n-butyl ether, isobutyl ether, ethylene oxide, diisopropyl ether, and methyl tert-butyl ether.

[0040] This application also provides a hyperbranched anion exchange resin, which is prepared by the preparation method described above.

[0041] In some embodiments, the hyperbranched anion exchange resin includes the following repeating units: Where E is , Representing the connection sites, x1, x2, x3, and y are the molar proportions of the structural units in the hyperbranched anion exchange resin, where x = x1 + x2 + x3, x + y = 1, y = 0.01~0.2, x = 0.8~0.99, A includes at least one of CH, B, and P, and D is... or R1, R2, R3, R4, and R5 are independently selected from H, are unsubstituted, or are replaced by one, two, or more Rs. a Substituted alkyl, cycloalkyl, alkenyl, R a It is at least one of hydroxyl, alkoxy, and aryl, where Ar is aryl and X is Br or I.

[0042] This application also provides a hyperbranched anion exchange membrane, which is prepared from a hyperbranched anion exchange resin, wherein the hyperbranched anion exchange resin is either the hyperbranched anion exchange resin prepared by the preparation method described above or the hyperbranched anion exchange resin described above.

[0043] According to an embodiment of this application, the hyperbranched anion exchange membrane is prepared by the following method: performing film-forming treatment and ion exchange treatment on the hyperbranched anion exchange resin to obtain the hyperbranched anion exchange membrane; And / or, the film-forming process includes: dissolving the hyperbranched anion exchange resin in a third solvent to prepare a casting solution, coating the casting solution to form a film, and drying it to obtain a halogen-type anion exchange membrane; And / or, the third solvent includes at least one of dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, the temperature at which the hyperbranched anion exchange resin dissolves in the third solvent is 25~80℃; For example, the temperature at which the hyperbranched anion exchange resin dissolves in the third solvent is any value between 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, or 25°C to 80°C.

[0044] And / or, the solid content of the casting solution is 5-50%; For example, the solid content of the casting solution is 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or any value between 5% and 50%.

[0045] And / or, when performing film-forming treatment, the drying temperature is 50~200℃, and the drying time is 0.5~24h; For example, during film formation, the drying temperature is any value between 50℃, 70℃, 100℃, 120℃, 150℃, 170℃, 200℃, or 50~200℃, and the drying time is any value between 0.5h, 1h, 3h, 5h, 7h, 10h, 12h, 15h, 17h, 20h, 22h, 24h, or 0.5~24h.

[0046] And / or, the ion exchange treatment includes: immersing the halogen-type anion exchange membrane in an alkaline solution, the alkaline solution including a sodium hydroxide solution, for a soaking time of 12 to 24 hours. For example, the soaking time can be any value between 12 hours, 15 hours, 17 hours, 20 hours, 22 hours, 24 hours, or 12 to 24 hours.

[0047] In some embodiments, the concentration of the alkaline solution is 0.5-2 mol / L, for example, the concentration of the alkaline solution is 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L or any value between 0.5-2 mol / L.

[0048] In some embodiments, when the halogen-type anion exchange membrane is immersed in an alkaline solution for a set time, the preparation method further includes: taking the membrane immersed in the alkaline solution out of the alkaline solution, washing the membrane immersed in the alkaline solution with water, immersing the washed membrane in water until the washing solution is neutral, and obtaining a hyperbranched anion exchange membrane.

[0049] In some embodiments, the hyperbranched anion exchange membrane includes the following repeating units: Where E is , Representing the connection site, x1, x2, x3, and y are the molar proportions of the structural units in the hyperbranched anion exchange membrane, x = x1 + x2 + x3, x + y = 1, y = 0.01~0.2, x = 0.8~0.99, A includes at least one of CH, B, and P, and D is... or R1, R2, R3, R4, and R5 are independently selected from H, are unsubstituted, or are replaced by one, two, or more Rs. a Substituted alkyl, cycloalkyl, alkenyl, R a Ar is at least one of hydroxyl, alkoxy, and aryl, and Ar is aryl.

[0050] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0051] Example 1 Example 1 provides a hyperbranched anion exchange membrane, the preparation method of which includes: (1) Synthesis of hyperbranched polymers Under ice-water bath conditions (temperature 0℃), 10 mmol of biphenyl, 12 mmol of N-methyl-4-piperidinone, and 0.5 mmol of branched monomer 1 were dissolved in 50 mL of acetone (first solvent) at a molar ratio of biphenyl:N-methyl-4-piperidinone:branched monomer 1:trifluoromethanesulfonic acid = 1:1.2:0.05:5. After mixing thoroughly, 50 mmol of trifluoromethanesulfonic acid (first catalyst) was added, and the reaction was carried out at a constant temperature for 8 h until the reaction system became viscous. Subsequently, acetonitrile (diluent) was added at a volume ratio of 1:6 to dilute the viscous system. After stirring thoroughly, the solution was slowly poured into 100 mL of ethanol (first precipitant), and the mixture was allowed to stand for 2 h to precipitate. The precipitate was collected by filtration, washed three times with ethanol, and dried under vacuum at 60℃ for 12 h to obtain the hyperbranched polymer.

[0052] The structural formula of branched monomer 1 is: .

[0053] (2) Preparation of hyperbranched anion exchange resins Take 5g of the synthesized hyperbranched polymer and add 30mL of dichloromethane (second solvent) at a polymer-to-dichloromethane mass-to-volume ratio of 1:6g / mL. Stir until completely dissolved, then add 2.5g of iodomethane (quaternizing agent, polymer-to-quaternizing agent mass ratio of 1:0.5) and 0.3g of potassium iodide (second catalyst). React at 30℃ for 8 hours under light-protected conditions. After the reaction is complete, slowly pour the reaction system into 50mL of diethyl ether (second precipitant). After precipitation, filter, wash twice with diethyl ether, and dry under vacuum at 50℃ for 8 hours to obtain the quaternized hyperbranched anion exchange resin.

[0054] (3) Preparation of hyperbranched anion exchange membranes At 30℃, 8g of the quaternized hyperbranched anion exchange resin prepared in step (2) was dissolved in 72mL of dimethyl sulfoxide (third solvent) to prepare a casting solution with a solid content of 10%. The solution was stirred for 3h until the system was homogeneous and transparent. The casting solution was uniformly coated onto a clean glass plate using a coating machine and dried in an oven at 80℃ for 2h. The dried membrane was then removed and immersed in a 1mol / L sodium hydroxide solution for 16h, followed by repeated washing and immersion in deionized water until the washing solution was neutral, yielding OH... - Hyperbranched anion exchange membrane.

[0055] A photograph of the hyperbranched anion exchange membrane prepared in Example 1 is shown below. Figure 1 As shown.

[0056] Example 2 Example 2 provides a hyperbranched anion exchange membrane, the preparation method of which includes: (1) Synthesis of hyperbranched polymers Under ice-water bath conditions (2°C), 8 mmol of p-terphenyl, 12 mmol of 3-quinine cycloketone, and 0.8 mmol of branched monomer 2 were dissolved in 40 mL of dichloromethane (the primary solvent) at a molar ratio of p-terphenyl: 3-quinine cycloketone: branched monomer 2: methanesulfonic acid = 1:1.5:0.1:10. After thorough mixing, 80 mmol of methanesulfonic acid (the primary catalyst) was added, and the mixture was reacted at a constant temperature for 12 h until the system became viscous. The mixture was then diluted with N,N-dimethylformamide (a diluent) at a volume ratio of 1:5, stirred thoroughly, and poured into 80 mL of methanol (the primary precipitant) to precipitate. After filtration, the precipitate was washed three times with methanol and dried under vacuum at 70°C for 10 h to obtain the hyperbranched polymer.

[0057] The structural formula of branched monomer 2 is: .

[0058] (2) Preparation of hyperbranched anion exchange resins Take 4g of the above polymer and add 20mL of acetonitrile (second solvent) at a polymer-to-second solvent mass-volume ratio of 1:5g / ml. After dissolving, add 4g of bromoethane (quaternizing reagent, polymer-to-quaternizing reagent mass ratio 1:1.0) and 0.5g of sodium hydroxide (second catalyst). React at 40℃ for 12h in the dark. Pour the reaction solution into 60mL of n-butyl ether (second precipitant), allow it to stand to precipitate, filter, wash twice with n-butyl ether, and dry under vacuum at 60℃ for 6h to obtain the anion exchange resin.

[0059] (3) Preparation of hyperbranched anion exchange membranes At 40℃, 9g of the anion exchange resin obtained in step (2) was dissolved in 51mL of N,N-dimethylformamide (third solvent) to prepare a casting solution with a solid content of 15%, and stirred for 4h until no particles were present. After coating with a coating machine, the membrane was dried in an oven at 100℃ for 4h. The membrane was then removed and immersed in a 1mol / L sodium hydroxide solution for 18h, and washed with deionized water until neutral to obtain OH. - Type of anion exchange membrane.

[0060] Example 3 Example 3 provides a hyperbranched anion exchange membrane, the preparation method of which includes: (1) Synthesis of hyperbranched polymers Under ice-water bath conditions (temperature -2℃), 6 mmol of m-terphenyl, 10.8 mmol of N-propyl-4-piperidinone, and 0.9 mmol of branched monomer 3 were dissolved in 35 mL of chloroform (first solvent) at a molar ratio of m-terphenyl: N-propyl-4-piperidinone: branched monomer 3: trifluoropropionic acid = 1:1.8:0.15:15. After thorough mixing, 90 mmol of trifluoropropionic acid (first catalyst) was added, and the reaction was carried out at a constant temperature for 16 h until the system became viscous. Tetrahydrofuran (diluent) was added at a volume ratio of 1:7 to dilute the mixture, and the solution was slowly poured into 90 mL of deionized water (first precipitant). After precipitation, the mixture was filtered, washed three times with water, and dried under vacuum at 65℃ for 14 h to obtain the hyperbranched polymer.

[0061] The structural formula of branched monomer 3 is: .

[0062] (2) Preparation of hyperbranched anion exchange resins Take 3g of the above polymer and add 21mL of tetrahydrofuran (second solvent) at a polymer-to-tetrahydrofuran mass-to-volume ratio of 1:7g / ml. After dissolving, add 4.5g of iodopropane (quaternizing agent, polymer-to-quaternizing agent mass ratio of 1:1.5) and 0.4g of potassium carbonate (second catalyst). React at 50℃ for 16h in the dark. Pour the reaction solution into 70mL of isobutyl ether (second precipitant), filter, wash twice with isobutyl ether, and dry under vacuum at 55℃ for 7h to obtain the anion exchange resin.

[0063] (3) Preparation of hyperbranched anion exchange membranes At 50℃, 10g of the anion exchange resin prepared in step (2) was dissolved in 40mL of dimethyl sulfoxide (third solvent) to prepare a casting solution with a solid content of 20%, and stirred for 5h until homogeneous. After coating, the membrane was placed in an oven at 120℃ and dried for 6h. The membrane was then immersed in 1mol / L sodium hydroxide solution for 20h and washed with deionized water until neutral to obtain a hyperbranched anion exchange membrane.

[0064] Example 4 Example 4 provides a hyperbranched anion exchange membrane, the preparation method of which includes: (1) Synthesis of hyperbranched polymers Under ice-water bath conditions (temperature 5℃), 5 mmol of p-tetraphenyl, 10 mmol of 2,2-dihydroxymethyl-1-azabicyclo[2.2.2]oct-3-one, and 0.4 mmol of branched monomer 3 were dissolved in 30 mL of acetonitrile (first solvent) at a molar ratio of p-tetraphenyl: 2,2-dihydroxymethyl-1-azabicyclo[2.2.2]oct-3-one: branched monomer 3: pentafluoroacetic acid = 1:2.0:0.08:20. After mixing thoroughly, 100 mmol of pentafluoroacetic acid (first catalyst) was added, and the mixture was reacted at a constant temperature for 20 h until the system became viscous. Diluted with dimethyl sulfoxide (diluent) at a volume ratio of 1:8, the solution was poured into 100 mL of 0.5 mol / L sodium hydroxide aqueous solution (first precipitant), filtered after precipitation, washed 4 times with water, and dried under vacuum at 75℃ for 8 h to obtain the hyperbranched polymer.

[0065] The structural formula of branched monomer 3 is: .

[0066] (2) Preparation of hyperbranched anion exchange resins Take 2.5 g of the above polymer and add 20 mL of N,N-dimethylformamide (second solvent) at a polymer-to-second solvent mass-to-volume ratio of 1:8 g / mL. After dissolving, add 5 g of bromobutane (quaternizing agent, polymer-to-quaternizing agent mass ratio of 1:2.0) and 0.6 g of triethylamine (second catalyst). React at 60°C for 20 h in the dark. Pour the reaction solution into 80 mL of diisopropyl ether (second precipitant), filter, wash three times with diisopropyl ether, and dry under vacuum at 60°C for 9 h to obtain the anion exchange resin.

[0067] (3) Preparation of hyperbranched anion exchange membranes At 60℃, 12.5g of the anion exchange resin prepared in step (2) was dissolved in 37.5mL of N,N-dimethylformamide (third solvent) to prepare a casting solution with a solid content of 25%, and stirred for 6h until transparent. After coating, it was placed in an oven at 150℃ and dried for 8h. The membrane was then immersed in 1mol / L sodium hydroxide solution for 22h, washed with deionized water until neutral, and OH was obtained. - Type of anion exchange membrane.

[0068] Example 5 Example 5 provides a hyperbranched anion exchange membrane, the preparation method of which includes: (1) Synthesis of hyperbranched polymers Under ice-water bath conditions (temperature -5℃), with a molar ratio of biphenyl: 1-cyclohexyl-4-piperidinone: branched monomer 2: nonafluorobutyric acid pentafluoropropionic acid = 1:2.2:0.12:30, 7 mmol of biphenyl, 15.4 mmol of 1-cyclohexyl-4-piperidinone, and 0.84 mmol of branched monomer 2 were dissolved in 45 mL of a mixed solvent of acetone and dichloromethane (volume ratio 1:1, first solvent). After thorough mixing, nonafluorobutyric acid and pentafluoropropionic acid (first catalyst) were added. The molar ratio of nonafluorobutyric acid to pentafluoropropionic acid was 6:1, and the total molar amount of nonafluorobutyric acid and pentafluoropropionic acid was 210 mmol. The reaction was carried out at a constant temperature for 24 h until the system became viscous. Dilute with ethyl acetate (diluent) at a volume ratio of 1:6.5, slowly pour into 110 mL of 2 mol / L potassium carbonate aqueous solution (first precipitant), filter after precipitation, wash with water 3 times, and vacuum dry at 80℃ for 10 h to obtain hyperbranched polymer.

[0069] The structural formula of branched monomer 2 is: .

[0070] (2) Preparation of hyperbranched anion exchange resins Take 4.5 g of the above polymer and add 40.5 mL of dimethyl sulfoxide (second solvent) at a polymer-to-second solvent mass-volume ratio of 1:9 g / mL. After dissolving, add 11.25 g of iodopentane (quaternizing agent, polymer-to-quaternizing agent mass ratio 1:2.5) and 0.5 g of potassium iodide / 0.3 g of sodium hydroxide mixed catalyst (second catalyst). React at 25°C for 6 h in the dark. Pour the reaction solution into 90 mL of methyl tert-butyl ether (second precipitant), filter, wash twice with methyl tert-butyl ether, and dry under vacuum at 55°C for 10 h to obtain the anion exchange resin.

[0071] (3) Preparation of hyperbranched anion exchange membranes At 70℃, 18g of the anion exchange resin prepared in step (2) was dissolved in 42mL of dimethyl sulfoxide (third solvent) to prepare a casting solution with a solid content of 30%, and stirred for 4h until homogeneous. After coating, the membrane was placed in an oven at 180℃ and dried for 12h. The membrane was then immersed in 1mol / L sodium hydroxide solution for 12h and washed with deionized water until neutral to obtain a hyperbranched anion exchange membrane.

[0072] Example 6 Example 6 provides a hyperbranched anion exchange membrane, the preparation method of which includes: (1) Synthesis of hyperbranched polymers Under ice-water bath conditions (3°C), 4 mmol of p-terphenyl, 10 mmol of 2-methylene-3-quinone hydrochloride hydrate, and 0.8 mmol of branched monomer 1 were dissolved in 25 mL of a mixed solvent of chloroform and acetonitrile (volume ratio 2:1, first solvent) at a molar ratio of p-terphenyl: 2-methylene-3-quinone hydrochloride hydrate: branched monomer 1: trifluoroacetic acid = 1:2.5:0.2:40. After thorough mixing, 160 mmol of trifluoroacetic acid (first catalyst) was added, and the mixture was reacted at a constant temperature for 30 h until the system became viscous. The mixture was then diluted with dichloromethane (diluent) at a volume ratio of 1:5.5, poured into 70 mL of isopropanol (first precipitant), precipitated, filtered, washed twice with isopropanol, and dried under vacuum at 60°C for 16 h to obtain the hyperbranched polymer.

[0073] The structural formula of branched monomer 1 is: .

[0074] (2) Preparation of hyperbranched anion exchange resins Take 3.2 g of the above polymer and add 32 mL of benzene (second solvent) at a polymer-to-second solvent mass ratio of 1:10 g / mL. After dissolving, add 8.64 g of bromocyclohexane (quaternizing agent, polymer-to-quaternizing agent mass ratio 1:2.7) and a mixed catalyst consisting of 0.4 g of potassium carbonate and 0.2 g of triethylamine (second catalyst, potassium carbonate-to-triethylamine mass ratio 2:1). React at 70°C for 24 h in the dark. Pour the reaction solution into 100 mL of ethylene oxide (second precipitant), filter, wash twice with ethylene oxide, and dry under vacuum at 50°C for 12 h to obtain the anion exchange resin.

[0075] (3) Preparation of hyperbranched anion exchange membranes At 25℃, 4g of the anion exchange resin prepared in step (2) was dissolved in 46mL of N,N-dimethylformamide (third solvent) to prepare a casting solution with a solid content of 8%, and stirred for 8h until no obvious particles were observed. After coating, the membrane was dried in an oven at 50℃ for 24h, and then immersed in 1mol / L sodium hydroxide solution for 24h. After washing with deionized water until neutral, OH was obtained. - Hyperbranched anion exchange membrane.

[0076] Comparative Example 1 (1) Synthesis of linear polymers Under ice-water bath conditions (temperature 0℃), 10 mmol of biphenyl and 12 mmol of N-methyl-4-piperidinone were dissolved in 50 mL of acetone (first solvent) at a molar ratio of biphenyl: N-methyl-4-piperidinone: trifluoromethanesulfonic acid = 1:1.2:5. After mixing thoroughly, 50 mmol of trifluoromethanesulfonic acid (first catalyst) was added, and the reaction was carried out at a constant temperature for 8 h until the reaction system became viscous. Subsequently, acetonitrile (diluent) was added at a volume ratio of 1:6 to dilute the viscous system. After stirring thoroughly, the solution was slowly poured into 100 mL of ethanol (first precipitant), and the mixture was allowed to stand for 2 h to precipitate. The precipitate was collected by filtration, washed three times with ethanol, and dried under vacuum at 60℃ for 12 h to obtain the linear polymer.

[0077] (2) Preparation of linear anion exchange resin Take 5g of the synthesized linear polymer and add 30mL of dichloromethane (second solvent) at a polymer-to-second solvent mass-volume ratio of 1:6 g / mL. Stir until completely dissolved, then add 2.5g of iodomethane (quaternizing agent, polymer-to-quaternizing agent mass ratio 1:0.5) and 0.3g of potassium iodide (second catalyst). React at 30℃ for 8 hours under light-protected conditions. After the reaction is complete, slowly pour the reaction system into 50mL of diethyl ether (second precipitant). After precipitation, filter, wash twice with diethyl ether, and dry under vacuum at 50℃ for 8 hours to obtain the quaternized linear anion exchange resin.

[0078] (3) Preparation of linear anion exchange membranes At 30℃, 8g of the anion exchange resin prepared in step (2) was dissolved in 72mL of dimethyl sulfoxide (third solvent) to prepare a casting solution with a solid content of 10%, and stirred for 3h until the system was homogeneous and transparent. The casting solution was uniformly coated onto a clean glass plate using a coating machine and dried in an oven at 80℃ for 2h. The dried membrane was taken out and immersed in 1mol / L sodium hydroxide solution for 16h, and then repeatedly washed and immersed in deionized water until the washing solution was neutral to obtain OH - Linear anion exchange membrane.

[0079] Comparative Example 2 S1: Add 80 mmol of branched monomer, 20 mmol of biphenyl, and 40 mmol of N-methyl-4-piperidinone to a round-bottom flask. The structure of the branched monomer is: .

[0080] The round-bottom flask was fixed on a magnetic stirrer, and 10 mL of dichloromethane was added. The mixture was stirred to dissolve the monomers. The round-bottom flask was then placed in a glass dish containing ice water. The temperature of the solution in the round-bottom flask was monitored with a thermometer. At 0 °C, 1 mL of trifluoroacetic acid and 5 mL of trifluoromethanesulfonic acid were added dropwise to the solution. The mixture was then kept at this temperature for 5 hours. The reaction solution was then added to a potassium hydroxide aqueous solution. After precipitation and filtration, the polymer solid was obtained. S2: Wash the polymer solid with pure water until its pH is neutral, and then dry it at 60°C for 8 hours; add 1g of the dried polymer solid and tetrahydrofuran to another round-bottom flask, stir and dissolve at 40°C to obtain a polymer solution with a concentration of 3wt%; when the polymer solution is cooled to room temperature, add 0.5g of potassium hydroxide to the polymer solution, and then stir and keep it at 70°C for 48 hours; after the reaction solution is cooled to room temperature, add 1g of iodomethane, and stir and react at room temperature for 12 hours to obtain a hyperbranched polyarylpiperidine polymer solution; S3: The hyperbranched polyarylpiperidine polymer solution from step S2 is added dropwise to pure water to precipitate. After filtration, the solid is washed with pure water until its pH is neutral. Then, it is dried at 55°C for 10 hours to obtain the hyperbranched polyarylpiperidine polymer. S4: Take 1g of the branched polyarylpiperidine polyelectrolyte resin obtained in step S3 and dissolve it in N,N Dimethylformamide was used to obtain a 3 wt% polyelectrolyte resin solution. This solution was then cast onto a glass plate and dried at 50°C for 24 hours to form a film. The dried film was then immersed in a 1 mol / L potassium hydroxide aqueous solution at 60°C for 12 hours. After removal, the film was washed with pure water to remove residual potassium hydroxide. Finally, the film was dried in a vacuum drying oven at 45°C and a vacuum degree of [missing information]. The drying pressure was 0.1 MPa, and the drying time was 10 h. After drying, the hyperbranched polyarylpiperidine anion exchange membrane was obtained.

[0081] Comparative Example 3 A method for preparing a high molecular weight hyperbranched polyarylpiperidine anion exchange membrane, the method comprising the following steps: S1: Add 100 mmol of the branched monomer to a 50 mL round-bottom flask. The structure of the branched monomer is as follows: .

[0082] The round-bottom flask was fixed on a magnetic stirrer, and 5 mL of dichloromethane was added. The mixture was stirred to dissolve the monomers. The round-bottom flask was then placed in a glass dish containing ice water. The temperature of the solution in the round-bottom flask was monitored with a thermometer. At 0°C, 2 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid were added dropwise to the solution. The mixture was then kept at this temperature for 10 hours. The reaction solution was then added to an aqueous sodium hydroxide solution. After precipitation and filtration, the polymer solid was obtained. S2: Wash the polymer solid with pure water until its pH is neutral, and then dry it at 60°C for 8 hours; add 1g of the dried polymer solid and acetonitrile to another round-bottom flask, stir and dissolve at 40°C to obtain a polymer solution with a concentration of 15wt%; when the polymer solution is cooled to room temperature, add 1g of sodium hydroxide to the polymer solution, and then stir and keep it at 80°C for 36 hours; after the reaction solution is cooled to room temperature, add 2g of iodomethane, and stir and react at room temperature for 24 hours to obtain a hyperbranched polyarylpiperidine polymer solution; S3: The hyperbranched polyarylpiperidine polymer solution from step S2 is added dropwise to pure water to precipitate. After filtration, the solid is washed with pure water until its pH is neutral. Then, it is dried at 55°C for 10 hours to obtain the hyperbranched polyarylpiperidine polymer. S4: Take 1g of the hyperbranched polyarylpiperidine polyelectrolyte resin obtained in step S3 and dissolve it in N,N Dimethylformamide was used to obtain a 15 wt% polyelectrolyte resin solution. This solution was then cast onto a glass plate and dried at 65°C for 16 hours to form a film. The dried film was then immersed in a 1 mol / L potassium hydroxide aqueous solution at 60°C for 12 hours. After removal, the film was washed with pure water to remove residual potassium hydroxide. Finally, the film was dried in a vacuum drying oven at 50°C and a vacuum degree of [missing information]. The drying pressure was 0.1 MPa, and the drying time was 9 h. After drying, the hyperbranched polyarylpiperidine anion exchange membrane was obtained.

[0083] The anion exchange membranes prepared in Examples 1-6 and Comparative Examples 1-3 were subjected to performance tests under the same conditions. The test methods included: (1) Ionic conductivity The ionic conductivity of the anion exchange membrane is obtained through 10 -1 Hz to 10 5 The four-probe method (AC) for Hz was measured on a Chenhua CHI604F electrochemical workstation. A fully hydrated sample measuring 1 cm × 5 cm was mounted in a tetrafluoroethylene mold, with a 1 cm distance between the reference electrodes. The sample was rinsed with deionized water, immersed in a beaker filled with deionized water, and tested in a constant temperature water bath at 80°C. Ionic conductivity (σ, mS·cm) was measured. -1 The calculation is as follows:

[0084] Where A (cm) 2 ) refers to the cross-sectional area of ​​the test membrane sample, L (cm) is the distance between the mold electrodes, and R represents the ohmic resistance of the membrane sample.

[0085] (2) Tensile strength and elongation at break Tensile strength and elongation at break were tested using an electronic universal testing machine (PT-305B, Guangdong Beidou Precision Instruments Co., Ltd.). The diaphragm was cut into strips of 1cm × 10cm and subjected to tensile testing at a speed of 50mm / min under 100% relative humidity. Three measurements were taken and the average value was recorded.

[0086] (3) Swelling degree After the membrane is dried, its length, width, and thickness are measured and recorded as l. dry w dry and d dry After immersing the sample in deionized water at 80℃ for 24 hours, wipe off the water adhering to the surface. Record the length, width, and thickness of the membrane at this point. wet w wet and d wet The formula for calculating the degree of swelling (SR) is as follows:

[0087] (4) Alkali resistance The prepared anion exchange membrane was immersed in a 1 mol / L KOH solution at 80℃, and the time it took for the ionic conductivity to decrease by 10% was recorded as an evaluation index of alkali resistance stability.

[0088] Table 1. Performance Comparison of Examples and Comparative Examples

[0089] As can be seen from Table 1, the anion exchange membranes of Examples 1-6 simultaneously possess high ionic conductivity, excellent mechanical properties, low swelling degree, and strong alkali resistance. The overall performance of the anion exchange membranes of Examples 1-6 is significantly better than that of Comparative Examples 1-3.

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0091] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A method for preparing a hyperbranched anion exchange resin, characterized in that, include: A branched monomer, a biphenyl monomer, a nitrogen-containing ketone monomer, a first catalyst, and a first solvent are mixed and subjected to a polymerization reaction to obtain a hyperbranched polymer; wherein the branched monomer comprises at least one of the following structures: , , ; The hyperbranched polymer is mixed with a second solvent, a quaternizing agent, and a second catalyst to carry out a quaternization reaction, thereby obtaining a hyperbranched anion exchange resin.

2. The method for preparing the hyperbranched anion exchange resin according to claim 1, characterized in that, The biphenyl monomers include at least one of biphenyl, para-terphenyl, meta-terphenyl, and para-tetraphenyl; And / or, the azacyclic ketone monomers include at least one of N-alkylpiperidinone monomers and quinone monomers, wherein the N-alkylpiperidinone monomers include at least one of N-methyl-4-piperidinone, N-propyl-4-piperidinone, N-isopropyl-4-piperidinone, 1-cyclopropyl-4-piperidinone, 1-cyclopentyl-4-piperidinone, and 1-cyclohexyl-4-piperidinone; and the quinone monomers include at least one of 3-quininecycloone, 2,2-dihydroxymethyl-1-azabicyclo[2.2.2]oct-3-one, 2-(hydroxymethyl)-2-(methoxymethyl)quininecyclo-3-one, 2-diphenylmethylquininecyclo-3-one, and 2-methylene-3-quinone hydrochloride hydrate; And / or, the first catalyst comprises at least one of trifluoropropionic acid, methanesulfonic acid, nonafluorobutyric acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and pentafluoroacetic acid; And / or, the first solvent includes at least one of acetone, dichloromethane, trichloromethane, and acetonitrile.

3. The method for preparing the hyperbranched anion exchange resin according to claim 2, characterized in that, The molar ratio of the biphenyl monomer to the azacyclic ketone monomer and the branched monomer is 1: (1~2.5): (0.01~0.2); And / or, the molar ratio of the biphenyl monomer to the first catalyst is 1: (1~50); And / or, the polymerization reaction temperature is -5℃ to 5℃, and the polymerization reaction time is 2 to 36 hours.

4. The method for preparing the hyperbranched anion exchange resin according to any one of claims 1-3, characterized in that, After the polymerization reaction is completed, the method further includes: adding a diluent to the reaction system to obtain a diluted solution, then pouring the diluted solution into a first precipitant to form a precipitate, filtering, washing, and drying to obtain a hyperbranched polymer; And / or, the diluent includes at least one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, ethyl acetate, dichloromethane, and chloroform; And / or, the first precipitant includes at least one of ethanol, methanol, isopropanol, water, aqueous sodium hydroxide solution, and aqueous potassium carbonate solution.

5. The method for preparing the hyperbranched anion exchange resin according to claim 1, characterized in that, The second solvent includes at least one of ethanol, dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, benzene, n-hexane, and acetone; And / or, the quaternizing agent includes at least one of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromocyclopropane, bromocyclobutane, bromocyclopentane, and bromocyclohexane. And / or, the second catalyst comprises at least one of sodium hydroxide, potassium hydroxide, potassium carbonate, potassium iodide, and triethylamine.

6. The method for preparing the hyperbranched anion exchange resin according to claim 5, characterized in that, The content ratio of the hyperbranched polymer to the second solvent is 1:5~10g / ml; And / or, the mass ratio of the hyperbranched polymer to the quaternizing agent is 1:0.2~3; And / or, the mass ratio of the hyperbranched polymer to the second catalyst is 1:0.05~0.3; And / or, the quaternization reaction is carried out under light-protected conditions; And / or, the temperature of the quaternization reaction is 25~70℃, and the time of the quaternization reaction is 6~24h.

7. The method for preparing the hyperbranched anion exchange resin according to claim 6, characterized in that, After the quaternization reaction is completed, the preparation method further includes: pouring the reaction solution into a second precipitant to form a precipitate, filtering, washing, and drying to obtain a hyperbranched anion exchange resin; And / or, the second precipitant includes at least one of diethyl ether, n-butyl ether, isobutyl ether, ethylene oxide, diisopropyl ether, and methyl tert-butyl ether.

8. A hyperbranched anion exchange resin, characterized in that, The hyperbranched anion exchange resin is prepared by the preparation method according to any one of claims 1-7.

9. A hyperbranched anion exchange membrane, characterized in that, The hyperbranched anion exchange membrane is prepared from a hyperbranched anion exchange resin, wherein the hyperbranched anion exchange resin is the hyperbranched anion exchange resin prepared by the preparation method according to any one of claims 1-7 or the hyperbranched anion exchange resin according to claim 8.

10. The hyperbranched anion exchange membrane according to claim 9, characterized in that, The hyperbranched anion exchange membrane is prepared by the following method: the hyperbranched anion exchange resin is subjected to film-forming treatment and ion exchange treatment to obtain the hyperbranched anion exchange membrane; And / or, the film-forming process includes: dissolving the hyperbranched anion exchange resin in a third solvent to prepare a casting solution, coating the casting solution to form a film, and drying it to obtain a halogen-type anion exchange membrane; And / or, the third solvent includes at least one of dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; And / or, the temperature at which the hyperbranched anion exchange resin dissolves in the third solvent is 25~80℃; And / or, the solid content of the casting solution is 5-50%; And / or, when performing film-forming treatment, the drying temperature is 50~200℃, and the drying time is 0.5~24h; And / or, the ion exchange treatment includes: immersing the halogen-type anion exchange membrane in an alkaline solution, the alkaline solution including a sodium hydroxide solution, for a soaking time of 12-24 hours.

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