Anion exchange polymer, anion exchange resin, preparation methods of anion exchange polymer and anion exchange resin, anion exchange membrane and anion exchange equipment

Abstract

The embodiment of the invention discloses an anion exchange polymer, an anion exchange resin and a preparation method thereof, an anion exchange membrane and anion exchange equipment, the anion exchange polymer is a block polymer, and the structural formula of the anion exchange polymer is shown in the specification; wherein Ar1 is an aryl group with a linear structure, Ar2 is an aryl group with a conjugated rigid structure, R1 and R2 are respectively and independently nitrogen-containing heterocyclic groups, x + y is less than or equal to 100, x is more than or equal to 5 and less than or equal to 95, and y is more than or equal to 5 and less than or equal to 95. The anion exchange polymer comprises two blocks, Ar1 is an aryl group with a linear structure, and Ar2 is an aryl group with a conjugated rigid structure, so that the polymer can generate microphase separation, and the anion exchange polymer has the characteristics of developed ion transmission channels, high water content, low swelling rate and high ionic conductivity.

Description

Technical Field

[0001] This application relates to the field of hydrogen production technology through water electrolysis, specifically to an anion exchange polymer and anion exchange resin, their preparation methods, anion exchange membranes, and anion exchange equipment. Background Technology

[0002] Hydrogen production through water electrolysis and fuel cell technologies are developing rapidly. Taking water electrolysis as an example, anion exchange membrane electrolysis (AEM-WE) technology, with its zero-gap and low-cost characteristics, is one of the most promising technologies for realizing a hydrogen economy. Anion exchange membranes (AEMs), as the main component of anion exchange membrane water electrolyzers (AEM-Wes), function to remove OH-... - It conducts from the cathode to the anode, while simultaneously preventing the direct transfer of gas and electrons between the electrodes.

[0003] Anion exchange membranes are mostly random copolymers or homopolymers with randomly distributed hydrophilic / hydrophobic segments, making it difficult to form efficient ion channels. They have the following limitations: low OH⁻ ion conductivity and dependence on high humidity environment; swelling and mechanical imbalance, excessive water absorption in the hydrophilic region leads to membrane deformation and decreased strength, affecting battery life. Therefore, they cannot simultaneously achieve high conductivity, high water content and low swelling rate. Summary of the Invention

[0004] This application provides an anion exchange polymer and anion exchange resin, a method for preparing the same, an anion exchange membrane, and an anion exchange device, which can improve the technical problem that anion exchange membranes cannot simultaneously possess high conductivity, high water content, and low swelling rate.

[0005] This application provides an anion exchange polymer, which is a block polymer, and the structural formula of the anion exchange polymer is as follows: ; Ar1 is an aryl group with a linear structure, Ar2 is an aryl group with a conjugated rigid structure, R1 and R2 are each independently nitrogen-containing heterocyclic groups, x+y≤100, 5≤x≤95, 5≤y≤95.

[0006] Optionally, in some embodiments of this application, the Ar2 includes , , , , , , , , , , , , , and one or more of the following: is a connection point; and / or the Ar1 includes , and one or more of the following: is a connection point; and / or the R1 and the R2 are each independently selected from , , one or more of the following; wherein R3, R4, R5, R6 are each independently selected from hydrogen, hydrocarbyl, alkenyl, aromatic ring, or hydrocarbyl substituted with a substituent including one or more of hydroxyl, alkoxy, phenyl, nitrogen, fluorine, is a connection point.

[0007] Optionally, in some embodiments of the present application, the Ar2 is , or wherein, is a connection point.

[0008] Correspondingly, the present application also provides a preparation method of an anion exchange polymer, comprising: mixing a first aryl-containing monomer and a first nitrogen-containing heterocyclic ketone compound and performing a first polymerization reaction to obtain a first polymer; mixing a second aryl-containing monomer and a second nitrogen-containing heterocyclic ketone compound and performing a second polymerization reaction to obtain a second polymer; mixing the first polymer and the second polymer and performing a third polymerization reaction to obtain an anion exchange polymer; wherein the first aryl-containing monomer is an aryl monomer with a conjugated rigid structure, and the second aryl-containing monomer is an aryl monomer with a linear structure.

[0009] Optionally, in some embodiments of the present application, the reaction time of the first polymerization reaction is 30 min-3 h; and / or the first polymerization reaction is performed under the action of a first catalyst, and the first catalyst includes one or more of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid, and heptafluorobutyric acid; and / or the reaction temperature of the first polymerization reaction is-2℃~5℃; and / or the reaction time of the second polymerization reaction is 30 min-3 h; and / or The second polymerization reaction is carried out under the action of a second catalyst, the second catalyst comprising one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid and heptafluorobutyric acid; and / or The reaction temperature of the second polymerization reaction is -2℃ to 5℃; and / or The reaction temperature of the third polymerization reaction is 0℃ to 24℃; and / or The reaction time of the third polymerization reaction is 4h to 20h.

[0010] Optionally, in some embodiments of the present application, the anion exchange resin has a structural formula of ; wherein Ar1 is an aryl group with a linear structure, Ar2 is an aryl group with a conjugated rigid structure, R1 and R2 are independently a nitrogen-containing heterocyclic group, Z - represents an anion, x+y≤100, 5≤x≤95, 5≤y≤95.

[0011] Optionally, in some embodiments of the present application, the anion comprises one or more of iodide, bromide, methanesulfonate, ethanesulfonate, but-3-yn-1-ylmethanesulfonate, allylsulfonic acid anion, benzenesulfonate, nitrobenzenesulfonate, triflic anion, trifluoroacetate, toluenesulfonate, toluene-4-sulfonic acid ring anion, tosylate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-ylmethanesulfonate and p-toluenesulfonate.

[0012] Correspondingly, the present application also provides a preparation method of an anion exchange resin, comprising: quaternizing the anion exchange polymer with a quaternizing agent, and after the quaternization reaction is completed, adding a precipitant to perform a precipitation reaction to obtain the anion exchange resin; wherein the anion exchange polymer comprises the anion exchange polymer described above or the anion exchange polymer prepared by the preparation method of the anion exchange polymer described above.

[0013] Optionally, in some embodiments of this application, the quaternizing agent includes one or more of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromocyclohexane, bromocyclopentane, bromocyclohexane, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl sulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl trifluoroacetate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, and cyclohexyl p-toluenesulfonate; and / or The solvent used in the quaternization reaction includes one or more of dichloromethane, trichloromethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide and acetonitrile; and / or The precipitant includes one or more of ethanol, ethyl acetate, ethylene glycol, diethyl ether, tetrahydrofuran, acetone, and water.

[0014] Optionally, in some embodiments of this application, the molar ratio of the anion exchange polymer to the quaternizing agent is 1:(1~3); and / or The quaternization reaction is carried out at a temperature of 10℃ to 100℃ and for a time of 4h to 36h.

[0015] Accordingly, this application also provides an anion exchange membrane, comprising the anion exchange resin described above, or anion exchange resin prepared by the method described above.

[0016] Accordingly, this application also provides an anion exchange device, including the anion exchange membrane described above.

[0017] The anion exchange polymers provided in this application include and The two blocks, Ar1 being an aryl group with a linear structure and Ar2 being an aryl group with a conjugated rigid structure, enable the polymer to produce microphase separation, thereby exhibiting well-developed ion transport channels, high water content, low swelling ratio, and high ionic conductivity. Attached Figure Description

[0018] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0019] Figure 1 is a structural formula of an anion exchange polymer provided in the present application; Figure 2 is a preparation flow chart of an anion exchange resin in Example 1 of the present application; Figure 3 is a preparation flow chart of an anion exchange resin in Example 2 of the present application; Figure 4 is a thermogravimetric curve of an anion exchange polymer in Example 1 and Comparative Example 1 of the present application. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by a person skilled in the art without creative work fall within the scope of protection of the present application.

[0021] The present application provides an anion exchange polymer. The following are described in detail respectively. It should be noted that the description order of the following embodiments is not intended to limit the preferred order of the embodiments. In addition, in the description of the present application, the term "comprising" means "including but not limited to". The terms first, second, third, etc. are only used as labels and do not impose numerical requirements or establish an order. Various embodiments of the present application can exist in a range of forms; it should be understood that the description in a range of forms is only for the convenience and brevity, and should not be understood as a hard limit to the scope of the present application; therefore, it should be considered that the described range has been specifically disclosed all possible sub-ranges and single values in the range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers in the range, such as 1, 2, 3, 4, 5 and 6, regardless of the range. In addition, whenever a numerical range is indicated in this text, it means that any cited number (fraction or integer) in the indicated range is included.

[0022] The present application provides an anion exchange polymer, which is a block polymer, and the structural formula of the anion exchange polymer is ; wherein Ar1 is an aryl group having a linear structure, Ar2 is an aryl group having a conjugated rigid structure, R1 and R2 are independently a nitrogen-containing heterocyclic group, x+y≤100, 5≤x≤95, 5≤y≤95, for example, x is 5, y is 5, 15, 25, 35, 45, 55, 65, 75, 85, 95; x is 15, y is 5, 15, 25, 35, 45, 55, 65, 75, 85; x is 25, y is 5, 15, 25, 35, 45, 55, 65, 75; x is 35, y is 5, 15, 25, 35, 45, 55, 65; x is 45, y is 5, 15, 25, 35, 45, 55; x is 55, y is 5, 15, 25, 35, 45; x is 65, y is 5, 15, 25, 35; x is 75, y is 5, 15, 25; x is 85, y is 5, 15; x is 95, y is 5, etc.

[0023] In the present application, the anion exchange polymer includes and two blocks, and Ar1 is an aryl group having a linear structure, and Ar2 is an aryl group having a conjugated rigid structure, so that the polymer can generate micro-phase separation, thereby having developed ion transmission channels, high water content, low swelling rate characteristics, and high ionic conductivity, while having excellent durability, and having a broad application prospect in the field of electrolytic water.

[0024] It can be understood that the anion exchange polymer of the present application is connected by two different polymer segments. The monomers of the anion exchange polymer of the present application are arranged in a specific order (-Ar1-R1-Ar1-R1-Ar1-R1-Ar1-R1-Ar1-R1-Ar1-R1-Ar1-R1-Ar1-R1-Ar2-R2-Ar2-R2-Ar2-R2-Ar2-R2-Ar2-R2-Ar2-R2-).

[0025] It can be understood that the conjugated structure refers to a structure having alternating single and double bonds, such as a conjugated double bond or a conjugated ring, which can enhance the rigidity of the molecule and improve its thermal stability and ordered arrangement ability.

[0026] Optionally, in some embodiments of the present application, the Ar2 includes , , , , , , , , , , , , , and one or more of Ar1, Ar2, R1, R2, R3, R4, R5, and R6, wherein, is a connection point.

[0027] Optionally, in some embodiments of the present application, Ar1 includes one or more of , and wherein, is a connection point.

[0028] Optionally, in some embodiments of the present application, Ar2 is , or wherein, is a connection point.

[0029] Optionally, in some embodiments of the present application, R1 and R2 are independently selected from one or more of , , ; wherein R3, R4, R5, and R6 are independently selected from hydrogen, hydrocarbon group, alkenyl group, aromatic ring, or hydrocarbon group substituted by a substituent including one or more of hydroxyl group, alkoxy group, phenyl group, nitrogen, and fluorine, is a connection point.

[0030] Optionally, in some embodiments of the present application, R1 and R2 are formed by one or more of the following structures: .

[0031] Optionally, in some embodiments of the present application, the anion exchange polymer has a structure of , or .

[0032] The present application provides a preparation method of an anion exchange polymer, comprising: mixing a first aryl-containing monomer and a first nitrogen-containing heterocyclic ketone compound and performing a first polymerization reaction to obtain a first polymer; mixing a second aryl-containing monomer and a second nitrogen-containing heterocyclic ketone compound and performing a second polymerization reaction to obtain a second polymer; mixing the first polymer and the second polymer and performing a third polymerization reaction to obtain an anion exchange polymer; wherein the first aryl-containing monomer is an aryl monomer having a conjugated rigid structure, and the second aryl-containing monomer is an aryl monomer having a linear structure.

[0033] In the present application, the first polymer is obtained by polymerizing the first aryl-containing monomer with the first nitrogen-containing heterocyclic ketone compound, the second polymer is obtained by polymerizing the second aryl-containing monomer with the second nitrogen-containing heterocyclic ketone compound, and then the first polymer and the second polymer are reacted to form the anion exchange polymer, so that the anion exchange polymer has a two-block structure. The one-pot method is used to synthesize the anion exchange polymer, without the need for purifying the block intermediate oligomer (the first polymer and the second polymer), and the anion exchange polymer can be prepared by using the existing equipment for preparing the anion exchange polymer, which is suitable for industrialized production and application.

[0034] Optionally, in some embodiments of the present application, the reaction time of the first polymerization reaction is 30 min to 3 h, for example, it can be 30 min, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, etc. In this way, the first aryl-containing monomer and the first nitrogen-containing heterocyclic ketone compound can be fully polymerized to form a binary oligomer.

[0035] Optionally, in some embodiments of the present application, the reaction time of the second polymerization reaction is 30 min to 3 h, for example, it can be 30 min, 1 h, 1.5 h, 2 h, 2.5 h, 3 h, etc. In this way, the second aryl-containing monomer and the second nitrogen-containing heterocyclic ketone compound can be fully polymerized to form a binary oligomer.

[0036] Optionally, in some embodiments of the present application, the first polymerization reaction is carried out under the action of a first catalyst, and the first catalyst comprises one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid and heptafluorobutyric acid.

[0037] Optionally, in some embodiments of the present application, the reaction temperature of the first polymerization reaction is -2°C to 5°C, for example, it can be -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, etc.

[0038] Optionally, in some embodiments of the present application, the second polymerization reaction is carried out under the action of a second catalyst, and the second catalyst comprises one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid and heptafluorobutyric acid.

[0039] Optionally, in some embodiments of the present application, the reaction temperature of the second polymerization reaction is -2°C to 5°C, for example, it can be -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C, 5°C, etc.

[0040] Optionally, in some embodiments of the present application, the reaction temperature of the third polymerization reaction is 0°C to 24°C, for example, it can be 0°C, 2°C, 4°C, 6°C, 8°C, 10°C, 12°C, 14°C, 16°C, 18°C, 20°C, 22°C, 24°C, etc.

[0041] Optionally, in some embodiments of this application, the reaction time of the third polymerization reaction is 4h to 20h, for example, it can be 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, etc.

[0042] Optionally, in some embodiments of this application, after the third polymerization reaction, the process further includes: extruding the anion exchange polymer into water, followed by filtration, washing, drying, acid removal, washing, and drying.

[0043] As an example, the solution used for acid removal is an alkaline solution.

[0044] As an example, the water used for extrusion can be one or more of the following: pure water, potassium carbonate aqueous solution, sodium carbonate aqueous solution, sodium chloride aqueous solution, potassium hydroxide aqueous solution, and calcium chloride aqueous solution.

[0045] This application also provides an anion exchange resin, the structural formula of which is as follows: ; Wherein, Ar1 is an aryl group with a linear structure, Ar2 is an aryl group with a conjugated rigid structure, R1 and R2 are each independently a nitrogen-containing heterocyclic group, Z - This indicates anion, where x + y ≤ 100, 5 ≤ x ≤ 95, and 5 ≤ y ≤ 95. For example, if x is 5, y can be 5, 15, 25, 35, 45, 55, 65, 75, 85, or 95; if x is 15, y can be 5, 15, 25, 35, 45, 55, 65, 75, or 85; if x is 25, y can be 5, 15, 25, 35, 45, 55, 65, or 75. x is 35, y is 5, 15, 25, 35, 45, 55, 65; x is 45, y is 5, 15, 25, 35, 45, 55; x is 55, y is 5, 15, 25, 35, 45; x is 65, y is 5, 15, 25, 35; x is 75, y is 5, 15, 25; x is 85, y is 5, 15; x is 95, y is 5, etc.

[0046] Optionally, in some embodiments of this application, the anion includes one or more of the following: iodide ion, bromide ion, methanesulfonate ion, ethanesulfonate ion, but-3-yn-1-ylmethanesulfonate ion, allyl sulfonate ion, benzenesulfonate ion, nitrobenzenesulfonate ion, trifluoromethanesulfonate ion, trifluoroacetic acid ion, toluenesulfonate ion, toluene-4-sulfonic acid ring ion, toluenesulfonate ion, neopentylbenzenesulfonate ion, tetrahydro-2H-pyran-4-ylmethanesulfonate ion, and p-toluenesulfonate ion.

[0047] This application also provides a method for preparing anion exchange resin, comprising: The anion exchange polymer is subjected to a quaternization reaction with a quaternization reagent, and after the quaternization reaction is completed, a precipitant is added to perform a precipitation reaction to obtain an anion exchange resin. The anion exchange polymer includes the anion exchange polymer described above.

[0048] Optionally, in some embodiments of the present application, the molar ratio of the anion exchange polymer to the quaternization reagent is 1:(1-3), which can be 1:1, 1:1.5, 1:2, 1:1, 1:2.5, 1:3, etc. In this way, the anion exchange resin can have good electrochemical performance and stability.

[0049] It can be understood that if the molar ratio of the anion exchange polymer to the quaternization reagent is too small, the electrochemical performance of the obtained anion exchange resin is poor, and if the molar ratio of the anion exchange polymer to the quaternization reagent is too large, the stability of the obtained anion exchange resin is poor.

[0050] Optionally, in some embodiments of the present application, the temperature of the quaternization reaction is 10-100°C, which can be 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, etc., and the time of the quaternization reaction is 4-36h, which can be 4h, 10h, 15h, 20h, 25h, 30h, 35h, 36h, etc.

[0051] Optionally, in some embodiments of the present application, the quaternization reagent includes one or more of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, bromocyclohexane, bromocyclopentane, methyl methanesulfonate, methyl ethanesulfonate, methyl propylsulfonate, methyl butylsulfonate, ethyl propylsulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allyl sulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl trifluoroacetate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentyl benzene sulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, and cyclohexyl p-toluenesulfonate.

[0052] Optionally, in some embodiments of the present application, the solvent used in the quaternization reaction includes dichloromethane, chloroform, chloroform, tetrahydrofuran, one or more selected from dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, and acetonitrile.

[0053] Optionally, in some embodiments of the present application, the precipitant includes one or more of ethanol, ethyl acetate, ethylene glycol, diethyl ether, tetrahydrofuran, acetone, and water.

[0054] Optionally, in some embodiments of the present application, after the precipitation reaction, the method further comprises: crushing, washing and drying the anion exchange resin.

[0055] The present application also provides an anion exchange membrane comprising the anion exchange resin described above.

[0056] The present application also provides a method for preparing an anion exchange membrane, comprising: The anion exchange resin described above is dissolved in a solvent to obtain a homogeneous solution, and then the homogeneous solution is subjected to film forming treatment to obtain an anion exchange membrane.

[0057] For example, the film forming treatment can be pouring the homogeneous solution onto a film coating machine and then drying at 60°C for 8-12h, such as 8h, 9h, 10h, 11h, 12h, etc.

[0058] Optionally, in some embodiments of the present application, the anion exchange resin described above is dissolved in a solvent to obtain a homogeneous solution, comprising: The anion exchange resin described above is dissolved in a solvent and then filtered to obtain a homogeneous solution.

[0059] Optionally, in some embodiments of the present application, the mesh size of the filter screen used for filtering is 2000-6000 mesh, such as 2000 mesh, 3000 mesh, 4000 mesh, 5000 mesh, 6000 mesh, etc.

[0060] For example, the filter screen is a polyphenylene sulfide (PPS) diaphragm.

[0061] Optionally, in some embodiments of the present application, the solvent comprises dichloromethane, trichloromethane, chloroform, tetrahydrofuran, one or more selected from dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide and acetonitrile.

[0062] The present application also provides an anion exchange device comprising the anion exchange membrane described above.

[0063] It can be understood that the anion exchange device of the present application is a device comprising an anion exchange membrane, such as an anion exchange membrane fuel cell (AEMFC) and an anion exchange membrane water electrolyzer (AEM-Wes).

[0064] Example 1 An anion exchange membrane and a method for preparing the same, comprising: (1) mixed p-terphenyl (0.24 mol) and N-methyl-4-piperidone (0.288 mol) in dichloromethane (70 mL), then added trifluoroacetic acid (22.8 mL) and trifluoromethanesulfonic acid (192 mL) dropwise into the solution at 0°C, and carried out oligomerization reaction at 0°C for 1 h to obtain a first mixed solution; (2) mixed 9,9-dimethylfluorene (0.06 mol) and N-methyl-4-piperidone (0.072 mol) in dichloromethane (30 mL), then added trifluoromethanesulfonic acid (48 mL) into the solution at 0°C, and carried out oligomerization reaction at 0°C for 0.5 h to obtain a second mixed solution; (3) mixed the first mixed solution and the second mixed solution, and carried out polymerization reaction at 10°C for 4 h, then discharged the polymer from an extruder into pure water, followed by filtration, washing with pure water, and drying to obtain an anion exchange polymer; (4) mixed the anion exchange polymer (0.1 mol) and iodomethane (0.15 mol) in dimethyl sulfoxide (200 mL), and reacted at 80°C for 15 h, then added ethyl acetate (2 L) to precipitate the product, followed by filtration, washing with ethyl acetate, and drying to obtain an anion exchange resin (the preparation process thereof is shown in Figure 2 , and the structural formula of the anion exchange resin is shown in the figure, wherein x is 80 and y is 20); (5) dissolved the anion exchange resin in dimethyl sulfoxide (DMSO) to obtain a homogeneous solution with a solid content of 20 wt%, then cast the homogeneous solution on a film coating machine, and dried at 60°C for 8 h to obtain an anion exchange membrane.

[0065] Example 2 This example is basically the same as Example 1, except that N-methyl-4-piperidone in steps (1) and (2) is replaced by quinuclidone (the preparation process of the anion exchange resin is shown in Figure 3 , and the structural formula of the obtained anion exchange resin is shown in the figure, wherein x is 80 and y is 20).

[0066] Example 3 This example is basically the same as Example 1, except that p-terphenyl is replaced by biphenyl (the structural formula of the obtained anion exchange resin is shown in the figure, wherein x is 80 and y is 20).

[0067] Example 4 This example is basically the same as Example 1, except that p-terphenyl is replaced by quaterphenyl (the structural formula of the obtained anion exchange resin is shown in the figure, wherein x is 80 and y is 20).

[0068] Example 5 This example is basically the same as Example 1, except that in this example, 9,9-dimethylfluorene is replaced by m-terphenyl (in the structural formula of the obtained anion exchange resin, x is 80, and y is 20).

[0069] Example 6 This example is basically the same as Example 1, except that in this example, 9,9-dimethylfluorene is replaced by (perfluoropropane-2,2-diyl)diphenyl (in the structural formula of the obtained anion exchange resin, x is 80, and y is 20).

[0070] The preparation method of the anion exchange polymer of Formula (I) is as follows: p-terphenyl (0.24 mol), 9,9-dimethylfluorene (0.06 mol), and N-methyl-4-piperidone (0.36 mol) are mixed in dichloromethane (100 mL), then trifluoroacetic acid (22.8 mL) and triflic acid (240 mL) are added dropwise to the solution at 0°C, after the dropwise addition is completed, oligomerization is carried out at 0°C, and then polymerization is carried out at 10°C, the reaction is carried out for 4 h, after the reaction is completed, the polymer is discharged into pure water through an extruder, then filtered, washed with pure water, and dried to obtain the anion exchange polymer.

[0071] Comparative Example 1 This comparative example is basically the same as Example 1, except that in this comparative example, the preparation method of the anion exchange polymer is as follows: p-terphenyl (0.24 mol), 9,9-dimethylfluorene (0.06 mol), and N-methyl-4-piperidone (0.36 mol) are mixed in dichloromethane (100 mL), then trifluoroacetic acid (22.8 mL) and triflic acid (240 mL) are added dropwise to the solution at 0°C, after the dropwise addition is completed, oligomerization is carried out at 0°C, and then polymerization is carried out at 10°C, the reaction is carried out for 4 h, after the reaction is completed, the polymer is discharged into pure water through an extruder, then filtered, washed with pure water, and dried to obtain the anion exchange polymer.

[0072] Comparative Example 2 This comparative example is basically the same as Example 2, except that in this comparative example, the preparation method of the anion exchange polymer is as follows: p-terphenyl (0.24 mol), 9,9-dimethylfluorene (0.06 mol), and quinuclidone (0.36 mol) are mixed in dichloromethane (100 mL), then trifluoroacetic acid (22.8 mL) and triflic acid (240 mL) are added dropwise to the solution at 0°C, after the dropwise addition is completed, oligomerization is carried out at 0°C, and then polymerization is carried out at 10°C, the reaction is carried out for 4 h, after the reaction is completed, the polymer is discharged into pure water through an extruder, then filtered, washed with pure water, and dried to obtain the anion exchange polymer.

[0073] Comparative Example 3 This comparative example is substantially the same as Example 1, except that in this comparative example, 9,9-dimethylfluorene is replaced by 1,2-diphenylethane.

[0074] Comparative Example 4 This comparative example is substantially the same as Example 1, except that in this comparative example, p-terphenyl is replaced by (perfluoropropane-2,2-diyl)diphenyl.

[0075] Test Example: The anion exchange polymers obtained in Examples and Comparative Examples are subjected to solubility test and thermal gravimetric test, and the anion exchange membranes obtained in Examples and Comparative Examples are subjected to mechanical property test, water absorption and swelling test, OH - ion conductivity performance test, and polarization performance test, and the test results are shown in Table 1 and Table 2.

[0076] 1. Solubility test: The anion exchange polymer is dissolved in dimethyl sulfoxide, and the solubility within 24 hours at 80°C is observed.

[0077] 2. Thermal gravimetric test: a. Sampling: 10 mg of powder or film, accurate to 0.01 mg, evenly spread on an alumina crucible; b. Atmosphere: dry nitrogen is introduced at a flow rate of 70 mL / min; c. Temperature rise: linearly raised to the target temperature at a rate of 8°C / min, and the mass-temperature data are recorded synchronously; d. Analysis: the first downward inflection point of the TG curve is taken as the initial decomposition temperature, the TG curve is differentiated once to obtain the DTG curve, the DTG peak value corresponds to the maximum weight loss rate temperature, and the residual mass fraction is used to quantify the amount of inorganic filler or carbon residue.

[0078] 3. Mechanical property test Test method: according to GB T 20042.3, the sample thickness and width are measured under constant temperature and humidity conditions of temperature 23°C±2°C and relative humidity 50%±10%.

[0079] The sample is placed in the test fixture, and different tensile speeds can be used when measuring tensile strength and elongation at break, selected within the range of 100 mm / min. For each tensile speed, a separate sample should be used. After the sample breaks, the corresponding load value is read.

[0080] a. Tensile strength: the maximum load that the anion exchange membrane can withstand under the action of pure tensile force when it breaks, and the ratio of the tensile film width, divided into transverse and longitudinal tensile strength, is used to evaluate the mechanical strength of the membrane; b. Elongation at break: The ratio of the distance between two points at the time of breakage to the original length under the maximum load before the anion exchange membrane breaks. It represents the maximum deformation that the alkaline membrane can withstand before breaking, and is used to represent the flexibility of the membrane.

[0081] 4. Water absorption and swelling performance test Test method: a: Cut the anion exchange membrane into 1 cm * 4 cm, and put it into 1M KOH for three times of alkali exchange, and test the swelling performance in 80℃ deionized water; b: Cut the anion exchange membrane into 5cm*5cm, put it into 1M KOH for three times of alkali exchange, and test the water absorption performance in 80℃ deionized water.

[0082] 5. OH - Ion conductivity performance Cut 10mm×45mm anion exchange membrane as sample. Put the sample into 1M KOH aqueous solution, and ion exchange at 80℃ for 24h. After completion, wash with deionized water to neutral, and save in deionized water. Before testing, measure the thickness and width of the anion exchange membrane with thickness gauge and ruler respectively, and take the average value of three tests as the width a , thickness b . At least 3 points are taken for each sample.

[0083] Four-electrode probe method ion conductivity test device is used to test ion conductivity. First, lay the sample on the platinum wire electrode without wrinkles, ensure good contact between the sample and the platinum wire electrode, then gently place the cover, and tighten the screw with wrench. After tightening, the sample should have no protrusion phenomenon, and the assembly of the test module is completed.

[0084] The test fixture is connected to the temperature and humidity control system. After connection, N2 (99.999%, same below) is blown, and the flow rate on both sides is set to 500sccm. The humidification condition is set to 100%RH, and the temperature of the pipeline is guaranteed to be 5℃ higher than the temperature of the test device; The actual test temperature is set according to the requirements. Then start the temperature and humidity device, and start the electrolysis process after reaching the set conditions, and keep N2 blowing throughout the process with constant gas flow.

[0085] EIS test: Electrolysis process: constant current method is used to electrolyze the anion exchange membrane to be tested. The electrolysis current value can be adjusted within 2V electrolysis potential to meet the actual test requirements. During the electrolysis process, the electrode undergoes an electrochemical reaction, and the carbonate (hydrogen) ion in the anion exchange membrane is discharged in the form of CO2 gas, until all the anions in the membrane are exchanged in situ to OH -The balance of electrolysis is determined by the change of overpotential during the test process. Generally, when the potential fluctuation value is less than 1%, the electrolysis process is determined to be completed, and the system reaches a balanced state.

[0086] After the electrolysis is balanced, EIS test is performed. The current perturbation mode is selected, the frequency range is 0.1 Hz-1.0 MHz, the perturbation amplitude is 1 mA, and the impedance spectrum is obtained. The impedance value R of the film sample is read from the intersection of the low-frequency part of the spectrum line and the real axis, and the in-plane ion conductivity of the sample is calculated according to the following formula: σ = 1 / (a x b x R); In the formula: σ is the in-plane ion conductivity of the sample, in units of millisiemens per centimeter (mS / cm); l is the distance between the electrodes, in units of centimeters (cm); a is the width of the film sample, in units of centimeters (cm); b is the thickness of the film sample, in units of centimeters (cm); R is the measured impedance of the film sample, in units of ohms (Ω).

[0087] 6. Polarization performance test: The polarization performance of the anion exchange membrane single cell is tested under the anode bare film-cathode platinum carbon catalytic system 70°C @ 2M KOH.

[0088] Table 1 test results

[0089] Table 2 test results

[0090] From Tables 1 and 2, it can be seen that: Compared with Comparative Example 1, and compared with Comparative Example 2, the anion exchange membrane of Example 1 and Example 2 has greater tensile strength, greater elongation at break, higher conductivity, lower swelling rate, lower water absorption rate, lower constant-frequency impedance, and lower cell voltage. The reason is that the anion exchange polymer of the present application has a block structure, and the anion exchange polymer of Comparative Example 1 and Comparative Example 2 has a random arrangement of polymerized monomers. It can be seen that the anion exchange polymer with a double block structure of the present application has developed ion transmission channels, low swelling rate characteristics, high mechanical properties, and high ion conductivity, thereby improving the electrochemical performance of the anion exchange membrane.

[0091] Compared with Comparative Examples 3 and 4, the anion exchange membrane of Example 1 has a higher elongation at break, higher conductivity, lower swelling rate, lower water absorption rate, lower constant frequency impedance, and lower cell voltage. This is because the anion exchange polymer of this application has linear aryl groups and conjugated rigid aryl groups, which can enable the polymer to produce microphase separation, thereby having well-developed ion transport channels, high water content, low swelling rate, and high ionic conductivity, which can improve the electrochemical performance of the anion exchange membrane.

[0092] Compared with Examples 1 and 5, the anion exchange membrane of Example 6 has greater tensile strength, greater elongation at break, higher conductivity, lower swelling rate, and lower water absorption rate. It can be seen that the structure of aryl monomers with conjugated rigid structures affects the performance of anion exchange polymers.

[0093] Figure 4 The thermogravimetric diagrams of the anion exchange polymers in Example 1 and Comparative Example 1 are shown below. Figure 4 It can be seen that the thermodynamic properties of the anion exchange polymers obtained in Example 1 and Comparative Example 1 are different. The reason is that the methods for preparing the anion exchange polymers in Example 1 and Comparative Example 1 are different, and the structures of the anion exchange polymers obtained from the reaction are different. The anion exchange polymer in Example 1 is a block polymer, while the anion exchange polymer in Comparative Example 1 is a random polymer.

[0094] The foregoing has provided a detailed description of anion exchange polymer and anion exchange resin, their preparation methods, anion exchange membranes, and anion exchange devices provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. An anion exchange polymer, characterized in that, The anion exchange polymer is a block polymer, and the structural formula of the anion exchange polymer is ; Ar1 is an aryl group having a linear structure, Ar2 is an aryl group having a conjugated rigid structure, R1 and R2 are independently a nitrogen-containing heterocyclic group, x+y≤100, 5≤x≤95, and 5≤y≤95.

2. The anion exchange polymer of claim 1, wherein, The Ar2 includes one or more of , , , , , , , , , , , , , and wherein, is a point of attachment; and / or The Ar1includes , and one or more of is a point of attachment; and / or said R1and said R2are each independently selected from one or more of , , ; wherein R3, R4, R5, R6 are each independently selected from hydrogen, hydrocarbyl, alkenyl, aromatic ring, or hydrocarbyl substituted with a substituent including one or more of hydroxyl, alkoxy, phenyl, nitrogen, fluorine, is a connection point.

3. The anion exchange polymer of claim 1, wherein, Ar2is , or wherein, is a point of attachment.

4. A method for producing an anion exchange polymer, characterized by, The method comprises the following steps: mixing a first aryl-containing monomer with a first nitrogen-containing heterocyclic ketone compound and performing a first polymerization reaction to obtain a first polymer; mixing a second aryl-containing monomer with a second nitrogen-containing heterocyclic ketone compound and performing a second polymerization reaction to obtain a second polymer; mixing the first polymer and the second polymer and performing a third polymerization reaction to obtain an anion exchange polymer; The first aryl-containing monomer is an aryl monomer having a conjugated rigid structure, and the second aryl-containing monomer is an aryl monomer having a linear structure.

5. The method for preparing an anion exchange polymer according to claim 4, characterized by, The reaction time of the first polymerization reaction is 30 min to 3 h; and / or The first polymerization reaction is performed in the presence of a first catalyst, and the first catalyst comprises one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid, and heptafluorobutyric acid; and / or The reaction temperature of the first polymerization reaction is -2℃ to 5℃; and / or The reaction time of the second polymerization reaction is 30 min to 3 h; and / or The second polymerization reaction is performed in the presence of a second catalyst, and the second catalyst comprises one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid, and heptafluorobutyric acid; and / or The reaction temperature of the second polymerization reaction is -2℃ to 5℃; and / or The reaction temperature of the third polymerization reaction is 0℃ to 24℃; and / or The reaction time of the third polymerization reaction is 4 h to 20 h.

6. An anion exchange resin characterized in that, The anion exchange resin has a structural formula of ; wherein Ar1 is an aryl group having a linear structure, Ar2 is an aryl group having a conjugated rigid structure, R1 and R2 are each independently a nitrogen-containing heterocyclic group, Z - represents an anion, x + y < 100, 5 < x < 95, 5 < y < 95.

7. The anion exchange resin according to claim 6, characterized in that, The anion comprises one or more of iodide, bromide, methanesulfonate, ethanesulfonate, but-3-yn-1-yl methanesulfonate, allylsulfonic acid anion, benzenesulfonate, nitrobenzenesulfonate, triflate, trifluoroacetate, toluenesulfonate, toluene-4-sulfonic acid ring, toluenesulfonate, neopentylbenzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, and p-toluenesulfonate.

8. A method for producing an anion exchange resin, characterized by, The method comprises the following steps: mixing the anion exchange polymer with a quaternary ammonium reagent to perform a quaternary ammonium reaction, and after the quaternary ammonium reaction is completed, adding a precipitant to perform a precipitation reaction to obtain an anion exchange resin; The anion exchange polymer comprises the anion exchange polymer of any one of claims 1-3 or the anion exchange polymer prepared by the method of claims 4-5.

9. The method of producing an anion exchange resin according to claim 8, characterized by, The quaternization reagent comprises one or more of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, bromocyclohexane, bromocyclopentane, bromocyclohexane, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allyl sulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl trifluoromethanesulfonate, ethyl trifluoromethanesulfonate, methyl trifluoroacetate, ethyl toluenesulfonate, cyclobutyl toluene-4-sulfonate, butyl toluenesulfonate, neopentyl benzene sulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, and cyclohexyl p-toluenesulfonate; and / or The solvent used in the quaternization reaction comprises dichloromethane, chloroform, chloroform, tetrahydrofuran, one or more of dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, and acetonitrile; and / or The precipitant comprises one or more of ethanol, ethyl acetate, ethylene glycol, diethyl ether, tetrahydrofuran, acetone, and water.

10. The method of preparing an anion exchange resin according to claim 8, characterized in that, The molar ratio of the anion exchange polymer to the quaternization reagent is 1:(1~3); and / or The temperature of the quaternization reaction is 10℃~100℃, and the time of the quaternization reaction is 4h~36h.

11. An anion exchange membrane, characterized by, The anion exchange resin comprises the anion exchange resin according to claim 6 or 7, or the anion exchange resin prepared by the preparation method of the anion exchange resin according to any one of claims 8-10.

12. An anion exchange device characterized by, The anion exchange membrane comprises the anion exchange membrane according to claim 11.

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