Polyaryl piperidine anion exchange resin, anion exchange membrane and preparation method and application thereof

Abstract

The invention provides polyaryl piperidine anion exchange resin, an anion exchange membrane and a preparation method and application thereof, and relates to the technical field of hydrogen production through water electrolysis. According to the polyaryl piperidine anion exchange resin, the density of functional groups is further improved after side chains are grafted, and the ion exchange capacity and the ion conductivity are remarkably improved when the functional groups are correspondingly applied to an anion exchange membrane; a hydrophobic structure unit is introduced into a main chain, so that a hydrophilic-hydrophobic microphase separation structure is optimized, the swelling degree of the anion exchange membrane is reduced, and the chemical stability is improved; in addition, the molecular weight of a polymer main chain can be controlled by controlling the feeding proportion of the monomers, so that the mechanical property of the diaphragm can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of hydrogen production by electrolysis of water, and in particular to a polyarylpiperidine anion exchange resin, an anion exchange membrane, and a preparation method and application thereof. Background Art

[0002] As global energy demand continues to grow, the consumption of fossil fuels and the production of large amounts of greenhouse gases have threatened the earth's environment. Therefore, sustainable fuel production has been regarded as one of the most important issues worldwide. Hydrogen, as a clean energy source, is a high-quality carrier of renewable energy and will play an important role in future carbon neutrality actions. Hydrogen production by water electrolysis is a method of using an applied electric current to decompose water molecules into high-purity hydrogen and oxygen.

[0003] Water electrolysis technology can be divided into: alkaline water electrolysis hydrogen production, proton exchange membrane (PEM) water electrolysis hydrogen production, anion exchange membrane (AEM) water electrolysis hydrogen production and high-temperature solid oxidation electrolysis water (SOEC) hydrogen production. Anion exchange membrane water electrolysis hydrogen production combines the advantages of alkaline water electrolysis and proton exchange membrane water electrolysis hydrogen production technology. It has the characteristics of high electrolysis efficiency, fast response speed and low cost. It is considered to be one of the most promising renewable green energy hydrogen production technologies. The anion exchange membrane is a key component that provides OH- ion conduction and blocks gas crossover, which directly affects the performance and service life of the anion exchange membrane water electrolysis system. However, the current anion exchange membrane faces the problems of low ion conductivity and poor stability.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a polyaryl piperidine anion exchange resin, anion exchange membrane and a preparation method and application thereof. The present invention solves the technical problems of low ion conductivity, poor chemical stability and high swelling degree of anion exchange membrane in the prior art.

[0006] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0007] In a first aspect, the present invention provides a polyaryl piperidine anion exchange resin, wherein the polyaryl piperidine anion exchange resin comprises a structure as shown in the following formula I:

[0008]

[0009] in,

[0010] 0<x≤1, 0≤y≤1, n is an integer between 1 and 6;

[0011] Ring A is selected from substituted or unsubstituted 5-6-membered nitrogen heterocyclic rings;

[0012] R1 and R2 are each independently selected from substituted or unsubstituted C1-C6 alkyl, or substituted or unsubstituted C3-C6 cycloalkyl;

[0013] R3 is selected from fluorine-containing substituents.

[0014] Preferably, the ring A is selected from any one of the following rings A1, A2 or A3, wherein: The connection position of the representative group:

[0015]

[0016] wherein Ra, Ra' and Ra" are each independently selected from substituted or unsubstituted C1-C6 alkyl, or substituted or unsubstituted C3-C6 cycloalkyl; Represents the attachment position of the group.

[0017] Preferably, the ring A is selected from any one of the following groups:

[0018]

[0019] Preferably, R3 is selected from any one of fluorine-substituted phenyl, fluorine-substituted tolyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted tolyl or trifluoromethyl-substituted C1-C6 bromoalkyl.

[0020] Preferably, the R3 is selected from any one of the following groups: The connection position of the representative group:

[0021]

[0022] In a second aspect, the present invention provides a method for preparing the polyaryl piperidine anion exchange resin as described in the first aspect, wherein the method for preparing the polyaryl piperidine anion exchange resin comprises the following steps:

[0023] Azacyclic alcohol and N-alkylpiperidone monomers are polymerized to obtain a polyarylpiperidine polymer main chain;

[0024] The dibromoalkane and the piperidine monomer react to obtain a polyarylpiperidine polymer side chain;

[0025] The main chain of the polyaryl piperidine polymer and the side chain of the polyaryl piperidine polymer are subjected to a grafting reaction to obtain a polyaryl piperidine polymer with a grafted side chain;

[0026] The polyaryl piperidine polymer grafted with side chains and a quaternizing agent undergo a quaternization reaction to obtain the polyaryl piperidine anion exchange resin.

[0027] Preferably, the molar ratio of the azacyclic alcohol to the N-alkylpiperidone monomer is (1.0-1.2):(1.0-2.5).

[0028] Preferably, in the process of preparing the polyaryl piperidine polymer main chain, a fluorine-containing monomer is also added, and the molar ratio of the azacyclic alcohol, N-alkyl piperidone monomer and the fluorine-containing monomer is (1.0-1.2):(1.0-2.5):(0.5-2.0).

[0029] Preferably, in the process of preparing the polyaryl piperidine polymer main chain, an acid catalyst is also added, and the molar ratio of the nitrogen heterocyclic alcohol, N-alkyl piperidone monomer, fluorine-containing monomer and acid catalyst is (1.0-1.2):(1.0-2.5):(0.5-2.0):(2-30).

[0030] Preferably, the N-alkylpiperidone monomer is selected from any one of N-methyl-4-piperidone, N-propyl-4-piperidone, N-isopropyl-4-piperidone, 1-cyclopropyl-4-piperidone, 1-cyclopentyl-4-piperidone or 1-cyclohexyl-4-piperidone, or a combination of at least two thereof.

[0031] Preferably, the fluorine-containing monomer is selected from any one or a combination of at least two of the following compounds:

[0032]

[0033] Preferably, the acid catalyst is selected from any one of trifluoropropionic acid, methanesulfonic acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or pentafluoroacetic acid, or a combination of at least two thereof.

[0034] Preferably, in the process of preparing the polyaryl piperidine polymer main chain, the polymerization reaction temperature is -5 to 2°C, and the polymerization reaction time is 2 to 48 hours.

[0035] Preferably, the specific steps of preparing the polyaryl piperidine polymer main chain are:

[0036] The nitrogen heterocyclic alcohol and N-alkyl piperidone monomers are dissolved in solvent A, and the fluorine-containing monomer is added or not, and mixed evenly; then an acid catalyst is added to carry out a polymerization reaction, and after the reaction is completed, dilution, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine polymer main chain.

[0037] Preferably, the solvent A is selected from dichloromethane and / or chloroform.

[0038] Preferably, the dilution is: adding a diluent to the system after the polymerization reaction for dilution; wherein the mass ratio of the diluent to the system after the polymerization reaction is (2-8):1.

[0039] Preferably, the diluent is selected from any one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane or chloroform, or a combination of at least two thereof.

[0040] Preferably, the precipitation is: adding the diluted mixed solution into a precipitant for precipitation; wherein the mass ratio of the precipitant to the diluted mixed solution is (5-10):1.

[0041] Preferably, the precipitant is selected from any one of ethanol, methanol, isopropanol, water, aqueous sodium hydroxide solution or aqueous potassium carbonate solution, or a combination of at least two thereof.

[0042] Preferably, the molar ratio of the dibromoalkane to the piperidine monomer is (1.7-2.5):1.

[0043] Preferably, the dibromoalkane is selected from any one or a combination of at least two of 1,6-dibromohexane, 1,5-dibromopentane, 1,4-dibromobutane, 1,3-dibromopropane, 1,2-dibromoethane or dibromomethane.

[0044] Preferably, the piperidine monomer is selected from any one or a combination of at least two of N-methylpiperidine, N-ethylpiperidine, 1-methylpyrrolidine, 2,3-dimethylpiperidine or N-cyclohexylpiperidine.

[0045] Preferably, in the process of preparing the polyaryl piperidine polymer side chain, the reaction temperature is 40 to 80° C., and the reaction time is 12 to 48 hours.

[0046] Preferably, the specific steps for preparing the polyaryl piperidine polymer side chain are:

[0047] Dissolving a dibromoalkane and a piperidine monomer in a solvent B to react, and then sequentially performing precipitation, filtering, washing and drying after the reaction to obtain the polyaryl piperidine polymer side chain;

[0048] Preferably, the precipitation is: adding the system obtained by the reaction into solvent B for precipitation; wherein the mass ratio of the solvent B to the system obtained by the reaction is (5-10):1.

[0049] Preferably, the solvent B is selected from ethyl acetate and / or acetonitrile.

[0050] Preferably, the mass ratio of the polyaryl piperidine polymer main chain to the polyaryl piperidine polymer side chain is 1:(0.2-5).

[0051] Preferably, the temperature of the grafting reaction is 60 to 80° C., and the time of the grafting reaction is 12 to 48 hours.

[0052] Preferably, the specific steps for preparing the polyaryl piperidine polymer grafted with side chains are:

[0053] The polyaryl piperidine polymer main chain and the polyaryl piperidine polymer side chain are respectively dissolved in solvent C to obtain a solution containing the main chain and a solution containing the side chain; the solution containing the side chain is added to the solution containing the main chain to carry out a grafting reaction, and after the reaction is completed, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine polymer with grafted side chains.

[0054] Preferably, the solvent C is selected from any one of dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide, or a combination of at least two thereof.

[0055] Preferably, the dissolving temperature is 50-70°C.

[0056] Preferably, the precipitation is: adding the system obtained by the grafting reaction into a precipitant for precipitation; wherein the mass ratio of the precipitant to the system obtained by the grafting reaction is (5-10):1.

[0057] Preferably, the precipitating agent is selected from ethyl acetate and / or acetonitrile.

[0058] Preferably, the mass ratio of the polyaryl piperidine polymer with grafted side chains to the quaternizing agent is 1:(0.2-2.7).

[0059] Preferably, the quaternization reaction is carried out in the presence of an alkali catalyst, and the mass ratio of the polyaryl piperidine polymer grafted with a side chain to the alkali catalyst is 1:(0.02-0.2).

[0060] Preferably, the quaternization reaction is carried out in the presence of a solvent D, and the mass ratio of the polyaryl piperidine polymer grafted with side chains to the solvent D is 1:(5-10).

[0061] Preferably, the quaternizing agent is selected from halogen-substituted C1-C6 alkyl and / or halogen-substituted C3-C6 cycloalkyl, preferably any one of iodomethane, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, cyclopropane bromide, cyclobutane bromide, cyclopentane bromide or any one of cyclohexane bromide or a combination of at least two thereof.

[0062] Preferably, the base catalyst is selected from any one of sodium hydroxide, potassium carbonate, potassium iodide or triethylamine, or a combination of at least two thereof.

[0063] Preferably, the solvent D is selected from any one or a combination of at least two of ethanol, dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, benzene, n-hexane or acetone.

[0064] Preferably, the temperature of the quaternization reaction is 30 to 80° C., and the time of the quaternization reaction is 2 to 48 hours.

[0065] Preferably, the specific steps for preparing the polyaryl piperidine polymer grafted with side chains are:

[0066] The polyaryl piperidine polymer grafted with side chains is dissolved in solvent D, and a quaternizing agent and a base catalyst are added to carry out a quaternization reaction. After the reaction is completed, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine anion exchange resin.

[0067] Preferably, the precipitation is: adding the system obtained by quaternization reaction into a precipitant for precipitation; wherein the mass ratio of the precipitant to the system obtained by quaternization reaction is (2-10):1.

[0068] Preferably, the precipitant is selected from any one of diethyl ether, n-butyl ether, isobutyl ether, ethylene oxide, diisopropyl ether or methyl tert-butyl ether, or a combination of at least two thereof.

[0069] In a third aspect, the present invention provides an anion exchange membrane, wherein the anion exchange membrane is prepared using the polyarylpiperidine anion exchange resin as described in the first aspect.

[0070] In a fourth aspect, the present invention provides a method for preparing the anion exchange membrane, the method for preparing the anion exchange membrane comprising the following steps:

[0071] Dissolving the polyarylpiperidine anion exchange resin in a solvent to prepare a casting solution;

[0072] After coating the casting solution into a film, drying is performed to obtain a film sheet;

[0073] The membrane sheet is placed in an alkaline solution for soaking to obtain the anion exchange membrane.

[0074] Preferably, the solvent is selected from dimethyl sulfoxide and / or N,N-dimethylformamide.

[0075] Preferably, the solid content of the casting solution is 5 to 35 wt %.

[0076] Preferably, the alkaline solution is a 0.5-2 mol / L sodium hydroxide solution.

[0077] Preferably, the soaking time is 12 to 36 hours.

[0078] Preferably, the drying temperature is 50 to 180° C., and the drying time is 0.5 to 24 hours.

[0079] Preferably, the anion exchange membrane has a thickness of 25 to 200 μm.

[0080] In a fifth aspect, the present invention provides a use of the polyaryl piperidine anion exchange resin as described in the first aspect, or the anion exchange membrane as described in the third aspect, in the preparation of a water electrolysis hydrogen production device.

[0081] [Term explanation]

[0082] Various aspects and features of the present invention are further described below.

[0083] As mentioned in the present invention, the term "5- to 6-membered nitrogen heterocycle" refers to an aromatic heterocycle (containing 5 to 6 atoms in the ring) or an aliphatic ring (containing 5 to 6 atoms in the ring) having at least one N atom ring member, and specific groups include pyrrolyl, imidazolyl, imidazolinyl, pyrazolyl, pyridinyl, piperidinyl, piperazinyl, and the like.

[0084] As mentioned in the present invention, the term "alkyl" refers to an alkyl group having a specified number of carbon atoms, which can be a straight-chain alkyl group or a branched alkyl group. For example, the "C1-C6 alkyl group" refers to a straight-chain alkyl group or a branched alkyl group having 1 to 6 carbon atoms, and specific groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc., and similar groups.

[0085] As mentioned in the present invention, the term "cycloalkyl" refers to a cyclic alkyl group having a specified number of ring carbon atoms. For example, when "C3-C6 cycloalkyl" is mentioned, it refers to a cycloalkyl group having 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0086] As mentioned in the present invention, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0087] Compared with the prior art, the present invention has the following beneficial effects:

[0088] (1) The functional group density of the polyarylpiperidine anion exchange resin of the present invention is further improved after the side chain is grafted, which corresponds to a significant improvement in the ion exchange capacity and ion conductivity of the anion exchange membrane;

[0089] (2) The polyarylpiperidine anion exchange resin of the present invention introduces a hydrophobic structural unit into the main chain to optimize the hydrophilic-hydrophobic microphase separation structure, reduce the swelling degree of the anion exchange membrane and improve the chemical stability;

[0090] (3) The present invention can control the molecular weight of the polymer main chain by controlling the feeding ratio of the monomers, thereby improving the mechanical properties of the membrane. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0092] Figure 1 This is a physical picture of the anion exchange membrane provided in Example 1. DETAILED DESCRIPTION

[0093] Unless otherwise defined herein, scientific and technological terms used in conjunction with the present invention shall have the meanings commonly understood by those of ordinary skill in the art. The meaning and scope of the terms should be clear, however, in the case of any potential ambiguity, the definitions provided herein take precedence over any dictionary or external definitions. In this application, unless otherwise stated, the use of "or" means "and / or". In addition, the use of the term "including" and other forms is non-limiting.

[0094] It should be noted that specific details are described in the following description to facilitate a full understanding of the present invention. However, the present invention can be implemented in a variety of other ways different from those described herein, and those skilled in the art can make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0095] The embodiments of the present invention will be described in detail below in conjunction with the embodiments and examples, but it will be appreciated by those skilled in the art that the following embodiments and examples are only used to illustrate the present invention and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified, proceed according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0096] In a first aspect, the present invention provides a polyaryl piperidine anion exchange resin, wherein the polyaryl piperidine anion exchange resin comprises a structure as shown in the following formula I:

[0097]

[0098] in,

[0099] 0<x≤1, 0≤y≤1, n is an integer between 1 and 6;

[0100] Ring A is selected from substituted or unsubstituted 5-6-membered nitrogen heterocyclic rings;

[0101] R1 and R2 are each independently selected from a substituted or unsubstituted C1-C6 alkyl group (for example, a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group), or a substituted or unsubstituted C3-C6 cycloalkyl group (for example, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group);

[0102] R3 is selected from fluorine-containing substituents.

[0103] In the present invention, the polyaryl piperidine anion exchange resin is prepared by synthesizing a polyaryl piperidine main chain by using azacyclic alcohol and N-alkyl piperidone monomers, wherein the azacyclic alcohol contains both an aromatic structure and a piperidine structure, and after polymerization with the N-alkyl piperidone monomer, a functional group-rich structure is formed. Furthermore, the polyarylpiperidine anion exchange resin grafted side chain of the present invention The functional group density is further improved, which corresponds to a significant improvement in the ion exchange capacity and ion conductivity of the anion exchange membrane; further, in order to avoid the high swelling degree caused by the high ion exchange capacity, the polyaryl piperidine anion exchange resin of the present invention introduces a hydrophobic monomer (selected from R3 containing fluorine substituents) into the main chain, optimizes the hydrophilic-hydrophobic microphase separation structure, reduces the swelling degree of the anion exchange membrane and improves the chemical stability. In addition, the present invention can control the molecular weight of the polymer main chain by controlling the feeding ratio of the monomers to improve the mechanical properties of the membrane.

[0104] As an optional embodiment, the ring A is selected from any one of the following rings A1, A2 or A3, wherein: The connection position of the representative group:

[0105]

[0106] wherein Ra, Ra' and Ra" are each independently selected from substituted or unsubstituted C1-C6 alkyl, or substituted or unsubstituted C3-C6 cycloalkyl; Represents the attachment position of the group.

[0107] As an optional embodiment, the ring A is selected from any one of the following groups:

[0108]

[0109] As an optional embodiment, R3 is selected from any one of fluorine-substituted phenyl, fluorine-substituted tolyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted tolyl or trifluoromethyl-substituted C1-C6 bromoalkyl.

[0110] As an optional embodiment, the R3 is selected from any one of the following groups: wherein, The connection position of the representative group:

[0111]

[0112] In a second aspect, the present invention provides a method for preparing the polyaryl piperidine anion exchange resin as described in the first aspect, wherein the method for preparing the polyaryl piperidine anion exchange resin comprises the following steps:

[0113] Azacyclic alcohol and N-alkylpiperidone monomers are polymerized to obtain a polyarylpiperidine polymer main chain;

[0114] The dibromoalkane and the piperidine monomer react to obtain a polyarylpiperidine polymer side chain;

[0115] The main chain of the polyaryl piperidine polymer and the side chain of the polyaryl piperidine polymer are subjected to a grafting reaction to obtain a polyaryl piperidine polymer with a grafted side chain;

[0116] The polyaryl piperidine polymer grafted with side chains and a quaternizing agent undergo a quaternization reaction to obtain the polyaryl piperidine anion exchange resin.

[0117] As an optional embodiment, the molar ratio of the azacyclic alcohol and the N-alkylpiperidone monomer is (1.0-1.2):(1.0-2.5);

[0118] Here, “1.0-1.2” may be, for example, 1.0, 1.05, 1.1, 1.15, 1.2, etc.;

[0119] Here, “1.0-2.5” can be, for example, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, etc.

[0120] As an optional embodiment, in the process of preparing the polyaryl piperidine polymer main chain, a fluorine-containing monomer is also added, and the molar ratio of the azacyclic alcohol, the N-alkyl piperidone monomer and the fluorine-containing monomer is (1.0-1.2): (1.0-2.5): (0.5-2.0);

[0121] Here, “1.0-1.2” may be, for example, 1.0, 1.05, 1.1, 1.15, 1.2, etc.;

[0122] Here, “1.0-2.5” may be, for example, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, etc.;

[0123] Here, “0.5-2.0” can be, for example, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, etc.

[0124] As an optional embodiment, in the process of preparing the polyaryl piperidine polymer main chain, an acid catalyst is also added, and the molar ratio of the azacyclic alcohol, N-alkyl piperidone monomer, fluorine-containing monomer and acid catalyst is (1.0-1.2):(1.0-2.5):(0.5-2.0):(2-30);

[0125] Here, “1.0-1.2” may be, for example, 1.0, 1.05, 1.1, 1.15, 1.2, etc.;

[0126] Here, “1.0-2.5” may be, for example, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, 2.2, 2.4, 2.5, etc.;

[0127] Here, “0.5-2.0” can be, for example, 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5, 1.6, 1.8, 2.0, etc.

[0128] Here, “2-30” can be, for example, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, etc.

[0129] As an optional embodiment, the N-alkyl piperidone monomer is selected from any one of N-methyl-4-piperidone, N-propyl-4-piperidone, N-isopropyl-4-piperidone, 1-cyclopropyl-4-piperidone, 1-cyclopentyl-4-piperidone or 1-cyclohexyl-4-piperidone, or a combination of at least two thereof.

[0130] As an optional embodiment, the fluorine-containing monomer is selected from any one or a combination of at least two of the following compounds:

[0131]

[0132] As an optional embodiment, the acid catalyst is selected from any one of trifluoropropionic acid, methanesulfonic acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or pentafluoroacetic acid, or a combination of at least two thereof.

[0133] As an optional embodiment, in the process of preparing the polyaryl piperidine polymer main chain, the temperature of the polymerization reaction is -5 to 2°C, for example, it can be -5°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, etc., and the time of the polymerization reaction is 2 to 48h, for example, it can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, etc.

[0134] As an optional embodiment, the specific steps for preparing the polyaryl piperidine polymer main chain are:

[0135] The nitrogen heterocyclic alcohol and N-alkyl piperidone monomers are dissolved in solvent A, and the fluorine-containing monomer is added or not, and mixed evenly; then an acid catalyst is added to carry out a polymerization reaction, and after the reaction is completed, dilution, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine polymer main chain.

[0136] As an optional embodiment, the solvent A is selected from dichloromethane and / or chloroform.

[0137] As an optional embodiment, the dilution is: adding a diluent to the system after the polymerization reaction for dilution; wherein the mass ratio of the diluent to the system after the polymerization reaction is (2-8):1, for example, it can be 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, etc.

[0138] As an optional embodiment, the diluent is selected from any one of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane or chloroform, or a combination of at least two thereof.

[0139] As an optional embodiment, the precipitation is: adding the diluted mixed solution to a precipitant for precipitation; wherein the mass ratio of the precipitant to the diluted mixed solution is (5-10):1, for example, it can be 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc.

[0140] As an optional embodiment, the precipitant is selected from any one of ethanol, methanol, isopropanol, water, sodium hydroxide aqueous solution or potassium carbonate aqueous solution, or a combination of at least two thereof.

[0141] As an optional embodiment, the molar ratio of the dibromoalkane to the piperidine monomer is (1.7-2.5):1, for example, it can be 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, etc.

[0142] As an optional embodiment, the dibromoalkane is selected from any one or a combination of at least two of 1,6-dibromohexane, 1,5-dibromopentane, 1,4-dibromobutane, 1,3-dibromopropane, 1,2-dibromoethane or dibromomethane.

[0143] As an optional embodiment, the piperidine monomer is selected from any one or a combination of at least two of N-methylpiperidine, N-ethylpiperidine, 1-methylpyrrolidine, 2,3-dimethylpiperidine or N-cyclohexylpiperidine.

[0144] As an optional embodiment, in the process of preparing the polyaryl piperidine polymer side chain, the reaction temperature is 40-80°C, for example, it can be 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc., and the reaction time is 12-48h, for example, it can be 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, etc.

[0145] As an optional embodiment, the specific steps for preparing the polyaryl piperidine polymer side chain are:

[0146] The dibromoalkane and the piperidine monomer are dissolved in solvent B to react, and after the reaction is completed, precipitation, filtration, washing and drying are performed in sequence to obtain the polyaryl piperidine polymer side chain.

[0147] As an optional embodiment, the precipitation is: adding the system obtained by the reaction into solvent B for precipitation; wherein the mass ratio of the solvent B to the system obtained by the reaction is (5-10):1, for example, it can be 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, etc.

[0148] As an optional embodiment, the solvent B is selected from ethyl acetate and / or acetonitrile.

[0149] As an optional embodiment, the mass ratio of the polyaryl piperidine polymer main chain to the polyaryl piperidine polymer side chain is 1:(0.2-5), for example, it can be 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, etc.

[0150] As an optional embodiment, the temperature of the grafting reaction is 60-80°C, for example, it can be 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, etc., the time of the grafting reaction is 12-48h, and the time of the reaction is 12-48h, for example, it can be 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, etc.

[0151] As an optional embodiment, the specific steps for preparing the polyaryl piperidine polymer grafted with side chains are:

[0152] The polyaryl piperidine polymer main chain and the polyaryl piperidine polymer side chain are respectively dissolved in solvent C to obtain a solution containing the main chain and a solution containing the side chain; the solution containing the side chain is added to the solution containing the main chain to carry out a grafting reaction, and after the reaction is completed, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine polymer with grafted side chains.

[0153] As an optional embodiment, the solvent C is selected from any one of dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide, or a combination of at least two thereof.

[0154] As an optional embodiment, the dissolution temperature is 50-70°C, for example, it can be 50°C, 52°C, 54°C, 56°C, 58°C, 60°C, 62°C, 64°C, 66°C, 68°C, 70°C, etc.

[0155] As an optional embodiment, the precipitation is: adding the system obtained by the grafting reaction into a precipitant for precipitation; wherein the mass ratio of the precipitant to the system obtained by the grafting reaction is (5-10):1, for example, it can be 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, etc.

[0156] As an optional embodiment, the precipitant is selected from ethyl acetate and / or acetonitrile.

[0157] As an optional embodiment, the mass ratio of the polyaryl piperidine polymer with grafted side chains to the quaternizing agent is 1:(0.2-2.7), for example, it can be 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1.0, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2.0, 1:2.2, 1:2.4, 1:2.6, 1:2.7, etc.

[0158] As an optional embodiment, the quaternization reaction is carried out in the presence of an alkaline catalyst, and the mass ratio of the polyaryl piperidine polymer with grafted side chains to the alkaline catalyst is 1:(0.02-0.2), for example, it can be 1:0.02, 1:0.04, 1:0.06, 1:0.08, 1:0.1, 1:0.12, 1:0.14, 1:0.16, 1:0.18, 1:0.2, etc.

[0159] As an optional embodiment, the quaternization reaction is carried out in the presence of solvent D, and the mass ratio of the polyaryl piperidine polymer with grafted side chains to solvent D is 1:(5-10), for example, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.

[0160] As an optional embodiment, the quaternizing agent is selected from halogen-substituted C1-C6 alkyl and / or halogen-substituted C3-C6 cycloalkyl, preferably any one of iodomethane, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, cyclopropane bromide, cyclobutane bromide, cyclopentane bromide or cyclohexane bromide, or a combination of at least two thereof.

[0161] As an optional embodiment, the base catalyst is selected from any one of sodium hydroxide, potassium carbonate, potassium iodide or triethylamine, or a combination of at least two thereof.

[0162] As an optional embodiment, the solvent D is selected from any one or a combination of at least two of ethanol, dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, benzene, n-hexane or acetone.

[0163] As an optional embodiment, the temperature of the quaternization reaction is 30-80°C, for example, it can be 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, etc., and the time of the quaternization reaction is 2-48h, for example, it can be 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, etc.

[0164] As an optional embodiment, the specific steps for preparing the polyaryl piperidine polymer grafted with side chains are:

[0165] The polyaryl piperidine polymer grafted with side chains is dissolved in solvent D, and a quaternizing agent and a base catalyst are added to carry out a quaternization reaction. After the reaction is completed, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine anion exchange resin.

[0166] As an optional embodiment, the precipitation is: adding the system obtained by the quaternary ammonium reaction to a precipitant for precipitation; wherein the mass ratio of the precipitant to the system obtained by the quaternary ammonium reaction is (2 to 10):1, for example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.

[0167] As an optional embodiment, the precipitant is selected from any one of diethyl ether, n-butyl ether, isobutyl ether, ethylene oxide, diisopropyl ether or methyl tert-butyl ether, or a combination of at least two thereof.

[0168] In a third aspect, the present invention provides an anion exchange membrane, wherein the anion exchange membrane is prepared using the polyarylpiperidine anion exchange resin as described in the first aspect.

[0169] In a fourth aspect, the present invention provides a method for preparing the anion exchange membrane, the method for preparing the anion exchange membrane comprising the following steps:

[0170] Dissolving the polyarylpiperidine anion exchange resin in a solvent to prepare a casting solution;

[0171] After coating the casting solution into a film, drying is performed to obtain a film sheet;

[0172] The membrane sheet is placed in an alkaline solution for soaking to obtain the anion exchange membrane.

[0173] As an optional embodiment, the solvent is selected from dimethyl sulfoxide and / or N,N-dimethylformamide.

[0174] As an optional embodiment, the solid content of the casting liquid is 5 to 35wt%, for example, it can be 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt% and the like.

[0175] As an optional embodiment, the coating and film formation is performed by coating with a coater.

[0176] As an optional embodiment, the drying temperature is 50-180°C, for example, it can be 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, etc., and the drying time is 0.5-24h, for example, it can be 0.5h, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h.

[0177] As an optional embodiment, the alkaline solution is a 0.5-2 mol / L sodium hydroxide solution, and the concentration of the sodium hydroxide solution can be, for example, 0.5 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.5 mol / L, 1.6 mol / L, 1.8 mol / L, 2 mol / L, etc.

[0178] As an optional embodiment, the soaking time is 12 to 36 hours, for example, it can be 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, etc.

[0179] As an optional embodiment, after the soaking, the step of washing in deionized water and soaking until neutral is also included.

[0180] As an optional embodiment, the thickness of the anion exchange membrane is 25 to 200 μm, for example, it can be 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, etc.

[0181] In a fifth aspect, the present invention provides a use of the polyaryl piperidine anion exchange resin as described in the first aspect, or the anion exchange membrane as described in the third aspect, in the preparation of a water electrolysis hydrogen production device.

[0182] The present invention is further described below by means of specific examples and comparative examples. However, it should be understood that these examples are only used for more detailed description and should not be construed as limiting the present invention in any form.

[0183] Example 1

[0184] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, wherein the anion exchange membrane is prepared by the following steps:

[0185] S1. Preparation of polyarylpiperidine polymer main chain:

[0186] Under ice-water bath conditions, 5 g (18.70 mmol) of azacyclic alcohol and 3.43 g (24.30 mmol) of N-isopropyl-4-piperidone were dissolved in 12 mL of dichloromethane, and then 1.64 g (9.35 mmol) of 2,2,2-trifluoroacetophenone was added. After mixing evenly, 30 mL of trifluoromethanesulfonic acid was added and reacted at 0°C for 6 h until the reaction system became viscous. Finally, the viscous reaction system was diluted with DMSO (100 mL), and finally poured into anhydrous ethanol (1200 mL) for precipitation. After filtering, washing and drying, the polyaryl piperidine polymer main chain was obtained.

[0187] S2. Preparation of functionalized polyarylpiperidine polymer side chains:

[0188] 10 g (40.98 mmol) of 1,6-dibromohexane and 2.03 g (20.50 mmol) of 1-methylpiperidine were dissolved in 20 mL of ethyl acetate and reacted at 40 °C for 48 h. After the reaction, the reaction system was poured into ethyl acetate (210 mL) for precipitation, filtered and washed 3 times, and vacuum dried to obtain a functionalized polyaryl piperidine polymer side chain.

[0189] S3, polyaryl piperidine main chain grafted side chain:

[0190] At 60°C, 5 g of the main chain of the polyaryl piperidine polymer was dissolved in 50 mL of DMSO, and 2.33 g of the side chain of the functionalized polyaryl piperidine polymer was dissolved in 10 mL of DMSO. The two were added to the reaction system and the temperature was raised to 80°C for reaction for 12 h. After the reaction, the reaction system was poured into precipitant ethyl acetate (450 mL), filtered, washed, and dried to obtain a polyaryl piperidine polymer with grafted side chains.

[0191] S4, quaternization of polyaryl piperidine polymer:

[0192] 4 g of the grafted side chain polyaryl piperidine polymer was dissolved in 30 mL of N, N-dimethylformamide, and then 2 mL of iodomethane and 0.5 g of potassium carbonate were added. After reacting for 24 h at room temperature and away from light, the reaction system was poured into ether (270 mL) for precipitation, filtered, washed, and dried to obtain the quaternized polyaryl piperidine anion exchange resin without ether bond.

[0193] S5. Preparation of polyarylpiperidine anion exchange membrane:

[0194] At 40°C, 3 g of the polyarylpiperidine anion exchange resin was dissolved in 12 mL of DMSO to prepare a casting solution, which was then coated with a coating machine (0.05 mL / cm 2), the dried membrane was immersed in 1 mol / L sodium hydroxide solution for 24 h, washed and immersed in deionized water until neutral, and an OH-type ether-free polyaryl piperidine anion exchange membrane (thickness of 50 μm) was obtained (such as Figure 1 shown).

[0195] Example 2

[0196] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, wherein the anion exchange membrane is prepared by the following steps:

[0197] S1. Preparation of polyarylpiperidine polymer main chain:

[0198] Under ice-water bath conditions, 8 g (29.96 mmol) of azacyclic alcohol and 7 g (41.94 mmol) of 1-cyclopentyl-4-piperidone were dissolved in 19.2 mL of dichloromethane, and then 2.62 g (9.35 mmol) of 2,2,2-trifluoroacetophenone was added. After mixing evenly, 30 mL of trifluoroacetic acid was added, and the mixture was reacted at -2°C for 6 h until the reaction system became viscous. Finally, the viscous reaction system was diluted with 180 mL of DMSO, and finally poured into anhydrous ethanol (1800 mL) for precipitation, filtration, washing, and drying to obtain a polyaryl piperidine polymer main chain.

[0199] S2. Preparation of functionalized polyarylpiperidine polymer side chains:

[0200] 15 g (65.50 mmol) of 1,4-dibromopentane and 4.97 g (29.76 mmol) of N-cyclohexylpiperidine were dissolved in 30 mL of ethyl acetate and reacted at 40 °C for 36 h. After the reaction, the reaction system was poured into ethyl acetate (300 mL) for precipitation, filtered and washed 3 times, and vacuum dried to obtain a functionalized polyaryl piperidine polymer side chain.

[0201] S3, polyaryl piperidine main chain grafted side chain:

[0202] At 60°C, 5 g of the main chain of the polyaryl piperidine polymer was dissolved in 50 mL of DMSO, and 11.79 g of the functionalized polyaryl piperidine polymer side chain was dissolved in 20 mL of DMSO and added to the reaction system. The temperature was raised to 80°C and the reaction was carried out for 12 hours. After the reaction, the reaction system was poured into 650 mL of precipitant ethyl acetate, filtered, washed and dried to obtain a polyaryl piperidine polymer with grafted side chains.

[0203] S4, quaternization of polyaryl piperidine polymer:

[0204] 5 g of the grafted side chain polyaryl piperidine polymer was dissolved in 37.5 mL of N, N-dimethylformamide, and then 2.5 mL of iodine hexane and 0.5 g of potassium carbonate were added. After reacting for 24 h at room temperature and away from light, the reaction system was poured into methyl tert-butyl ether (380 mL) for precipitation, filtered, washed, and dried to obtain the quaternized polyaryl piperidine anion exchange resin without ether bond.

[0205] S5. Preparation of polyarylpiperidine anion exchange membrane:

[0206] At 50°C, 5 g of the polyarylpiperidine anion exchange resin was dissolved in 15 mL of DMSO to prepare a casting solution, which was then coated with a coating machine to form a film (0.1 mL / cm 2 ), the dried membrane was immersed in a 1 mol / L sodium hydroxide solution for 24 h, washed and immersed in deionized water until neutral, thereby obtaining an OH-type ether-free polyaryl piperidine anion exchange membrane (thickness of 100 μm).

[0207] Example 3

[0208] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, wherein the anion exchange membrane is prepared by the following steps:

[0209] S1. Preparation of polyarylpiperidine polymer main chain:

[0210] Under ice-water bath conditions, 15 g (56.18 mmol) of azacyclic alcohol and 6.35 g (56.18 mmol) of N-methyl-4-piperidone were dissolved in 36 mL of dichloromethane, and then 13.87 g (28.09 mmol) of 7-bromo-1,1,1-trifluoroheptan-2-one was added. After mixing evenly, 30 mL of pentafluoropropionic acid was added, and the mixture was reacted at 2°C for 12 h until the reaction system became viscous. Finally, the viscous reaction system was diluted with 240 mL of DMSO, and finally poured into anhydrous ethanol (2500 mL) for precipitation. After filtering, washing, and drying, the polyaryl piperidine polymer main chain was obtained.

[0211] S2. Preparation of functionalized polyarylpiperidine polymer side chains:

[0212] 10 g (49.75 mmol) of 1,3-dibromopropane and 1.69 g (19.90 mmol) of 1-methylpyrrolidine were dissolved in 30 mL of ethyl acetate and reacted at 40 °C for 24 h. After the reaction, the reaction system was poured into ethyl acetate (350 mL) for precipitation, filtered and washed three times, and vacuum dried to obtain a functionalized polyaryl piperidine polymer side chain.

[0213] S3, polyaryl piperidine main chain grafted side chain:

[0214] Under the temperature condition of 60°C, 5g of polyaryl piperidine polymer main chain was dissolved in 50mL of DMSO, 8.03g of functionalized ionic polymer side chain was dissolved in 20mL of DMSO and added into the reaction system, and the temperature was raised to 80°C for reaction for 36h; after the reaction, the reaction system was poured into precipitant ethyl acetate (700mL), filtered, washed and dried to obtain polyaryl piperidine polymer with grafted side chains.

[0215] S4, quaternization of polyaryl piperidine polymer:

[0216] 8 g of the grafted side chain polyaryl piperidine polymer was dissolved in 60 mL of N, N-dimethylformamide, and then 4 mL of iodomethane and 1.2 g of potassium carbonate were added. After reacting for 24 h at room temperature and away from light, the reaction system was poured into methyl tert-butyl ether (450 mL) for precipitation, filtered, washed, and dried to obtain the quaternized polyaryl piperidine anion exchange resin without ether bond.

[0217] S5. Preparation of polyarylpiperidine anion exchange membrane:

[0218] At 50°C, 5 g of ether-free polyaryl piperidine anion exchange resin was dissolved in 15 mL of DMSO to prepare a casting solution, which was then coated with a coating machine (0.075 mL / cm 2 ), the dried membrane was immersed in a 1 mol / L sodium hydroxide solution for 24 h, washed and immersed in deionized water until neutral, thereby obtaining an OH-type ether-free polyaryl piperidine anion exchange membrane (thickness of 95 μm).

[0219] Example 4

[0220] This comparative example provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Example 1 only in that the amount of N-isopropyl-4-piperidone added in S1 is 4.22 g (29.92 mmol), and the rest is the same as Example 1.

[0221] Example 5

[0222] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, wherein the anion exchange membrane is prepared by the following steps:

[0223] S1. Preparation of polyarylpiperidine polymer main chain:

[0224] In an ice-water bath, 5 g (18.70 mmol) of azacyclic alcohol and 3.43 g (24.30 mmol) of N-isopropyl-4-piperidone were dissolved in 12 mL of dichloromethane, mixed evenly, and 30 mL of trifluoromethanesulfonic acid was added. The mixture was reacted at 0°C for 6 h until the reaction system became viscous. Finally, the viscous reaction system was diluted with DMSO (100 mL), and finally poured into anhydrous ethanol (1200 mL) for precipitation. After filtering, washing, and drying, the polyaryl piperidine polymer main chain was obtained.

[0225] S2. Preparation of functionalized polyarylpiperidine polymer side chains:

[0226] 10 g (40.98 mmol) of 1,6-dibromohexane and 2.03 g (20.50 mmol) of 1-methylpiperidine were dissolved in 20 mL of ethyl acetate and reacted at 40 °C for 48 h. After the reaction, the reaction system was poured into ethyl acetate (210 mL) for precipitation, filtered and washed 3 times, and vacuum dried to obtain a functionalized polyaryl piperidine polymer side chain.

[0227] S3, polyaryl piperidine main chain grafted side chain:

[0228] At 60°C, 5 g of the main chain of the polyaryl piperidine polymer was dissolved in 50 mL of DMSO, and 2.33 g of the side chain of the functionalized polyaryl piperidine polymer was dissolved in 10 mL of DMSO. The two were added to the reaction system and the temperature was raised to 80°C for reaction for 12 h. After the reaction, the reaction system was poured into precipitant ethyl acetate (450 mL), filtered, washed, and dried to obtain a polyaryl piperidine polymer with grafted side chains.

[0229] S4, quaternization of polyaryl piperidine polymer:

[0230] 4 g of the grafted side chain polyaryl piperidine polymer was dissolved in 30 mL of N, N-dimethylformamide, and then 2 mL of iodomethane and 0.5 g of potassium carbonate were added. After reacting for 24 h at room temperature and away from light, the reaction system was poured into ether (270 mL) for precipitation, filtered, washed, and dried to obtain the quaternized polyaryl piperidine anion exchange resin without ether bond.

[0231] S5. Preparation of polyarylpiperidine anion exchange membrane:

[0232] At 40°C, 3 g of the polyarylpiperidine anion exchange resin was dissolved in 12 mL of DMSO to prepare a casting solution, which was then coated with a coating machine (0.085 mL / cm 2 ), the dried membrane was immersed in a 1 mol / L sodium hydroxide solution for 24 h, washed and immersed in deionized water until neutral, thereby obtaining an OH-type ether-free polyaryl piperidine anion exchange membrane (thickness of 100 μm).

[0233] Example 6

[0234] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Embodiment 1 only in that 2,2,2-trifluoroacetophenone in S1 is replaced by an equal molar amount of 3,4,5-trifluorobenzaldehyde, and the rest is the same as Embodiment 1.

[0235] Example 7

[0236] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Embodiment 1 only in that the content of 2,2,2-trifluoroacetophenone in S1 is adjusted to 3.28 g (18.70 mmol), and the rest is the same as Embodiment 1.

[0237] Example 8

[0238] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Embodiment 1 only in that the content of 2,2,2-trifluoroacetophenone in S1 is adjusted to 6.56 g (37.4 mmol), and the rest is the same as Embodiment 1.

[0239] Example 9

[0240] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Example 1 only in that the content of the polyaryl piperidine polymer main chain is adjusted to 4 g, and the content of the functionalized polyaryl piperidine polymer side chain is adjusted to 3.33 g, and the rest is the same as Example 1.

[0241] Example 10

[0242] This embodiment provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Example 1 only in that the content of the polyaryl piperidine polymer main chain is adjusted to 6 g, and the content of the functionalized polyaryl piperidine polymer side chain is adjusted to 1.33 g, and the rest is the same as Example 1.

[0243] Comparative Example 1

[0244] This comparative example provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, which is different from Example 1 only in that the nitrogen heterocyclic alcohol in S1 is replaced by terphenyl in an amount of 4.09 g (17.8 mmol), and the rest is the same as Example 1.

[0245] Comparative Example 2

[0246] This comparative example provides a polyaryl piperidine anion exchange resin and an anion exchange membrane prepared therefrom, wherein the anion exchange membrane is prepared by the following steps:

[0247] S1. Preparation of polyarylpiperidine polymer main chain:

[0248] Under ice-water bath conditions, 5 g (18.7 mmol) of azacyclic alcohol and 3.43 g (24.3 mmol) of N-isopropyl-4-piperidone were dissolved in 12 mL of dichloromethane, and then 1.64 g (9.35 mmol) of 2,2,2-trifluoroacetophenone was added. After mixing evenly, 30 mL of trifluoromethanesulfonic acid was added and reacted at 1 ° C for 6 h until the reaction system became viscous. Finally, the viscous reaction system was diluted with DMSO (350 mL), and finally anhydrous ethanol (3200 mL) was poured into it for precipitation. After filtering, washing and drying, a polyaryl piperidine polymer was obtained.

[0249] S2. Quaternization of polyarylpiperidine polymers:

[0250] 4 g of polyaryl piperidine polymer was dissolved in 30 mL of N,N-dimethylformamide, and then 2 mL of iodomethane and 0.5 g of potassium carbonate were added. After reacting for 24 h at room temperature and away from light, the reaction system was poured into ether (300 mL) for precipitation, filtered, washed, and dried to obtain a quaternized polyaryl piperidine anion exchange resin without ether bonds.

[0251] S3. Preparation of ether-free polyarylpiperidine anion exchange membrane:

[0252] At 40°C, 3 g of the polyarylpiperidine anion exchange resin was dissolved in 12 mL of DMSO to prepare a casting solution, which was then coated with a coating machine (0.025 mL / cm 2 ), the dried membrane was immersed in a 1 mol / L sodium hydroxide solution for 24 h, washed and immersed in deionized water until neutral, and an OH-type ether-free polyaryl piperidine anion exchange membrane (thickness of 25 μm) was obtained.

[0253] Test Example 1

[0254] Test samples: anion exchange membranes provided in Examples 1 to 10 and anion exchange membranes provided in Comparative Examples 1 to 2.

[0255] Test method:

[0256] (1) Ion exchange capacity:

[0257] The ion exchange capacity (IEC) is determined by back titration. The OH-type anion exchange membrane is dried and the dry membrane weight is recorded as m dryThen, the membrane was immersed in 0.01M HCl for 24h, and phenolphthalein was used as an indicator, and 0.01M NaOH was used to titrate to the end point, and the volume of NaOH solution V1 and V2 at the start and end points were recorded. The ion exchange capacity was calculated as follows:

[0258]

[0259] (2) Ionic conductivity:

[0260] The ionic conductivity of anion exchange membranes is 10 -1 Hz to 10 5 The four-probe method (AC) of Hz was measured on a Chenhua CHI604F electrochemical workstation. A fully hydrated sample of 2 cm × 2 cm size was installed in a tetrafluoroethylene mold, with a distance of 1 cm between the reference electrodes. It was rinsed with deionized water, immersed in a beaker filled with deionized water, and tested in a constant temperature water bath at 80°C. Hydroxide conductivity (σ, mS·cm -1 ) is calculated as follows:

[0261]

[0262] Where A (cm2) refers to the cross-sectional area of ​​the test film sample and L (cm) is the distance between the die electrodes.

[0263] (3) Tensile strength and elongation at break:

[0264] The tensile strength and elongation at break were tested by an electronic universal testing machine. The film was cut into 1 cm × 10 cm strips and subjected to a tensile test at a speed of 10 mm / min under 100% relative humidity. The average value was obtained by measuring three times.

[0265] (4) Swelling degree:

[0266] After the film is dried, the length, width and thickness of the film are measured and recorded as l dry 、w dry and d dry Soak the sample in deionized water at 80℃ for 24 hours, and then wipe off the water attached to the surface. Record the length, width and thickness of the film at this time. wet 、w wet and d wet The calculation formula of swelling ratio (SR) is as follows:

[0267]

[0268] (5) Alkali resistance: It is expressed by the decrease in ion exchange capacity after immersion in 80°C, 1 mol / L potassium hydroxide solution for 1000 h.

[0269] The specific test results are shown in Table 1 below:

[0270] Table 1

[0271]

[0272]

[0273] As shown in Table 1, the ion exchange capacity of the anion exchange membrane prepared by the polyaryl piperidine anion exchange resin of the present invention can reach more than 1.80mmol / g, the ion conductivity can reach more than 86mS / cm, the tensile strength is more than 32MPa, the elongation at break is more than 18%, the swelling degree can be controlled within 2.6-3.5%, and the alkali resistance can be controlled within 4.7-7.3%. This shows that the ion exchange capacity of the ether-free polyaryl piperidine polymer provided by the present invention is significantly improved after the side chain is grafted, and the swelling degree is also increased.

[0274] The test results of Examples 1 and 4 show that the present invention can effectively improve the mechanical properties of anion exchange membranes by adjusting the monomer ratio. The test results of Examples 1 and 5 show that the present invention can effectively suppress the swelling degree and improve the chemical stability by introducing hydrophobic structural units and optimizing microphase separation.

[0275] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A polyarylpiperidine anion exchange resin, characterized in that The polyarylpiperidine anion exchange resin comprises a structure as shown in the following formula I: in, 0<x≤1, 0≤y≤1, n is an integer between 1 and 6; Ring A is selected from substituted or unsubstituted 5-6-membered nitrogen heterocyclic rings; R1 and R2 are each independently selected from substituted or unsubstituted C1-C6 alkyl, or substituted or unsubstituted C3-C6 cycloalkyl; R3 is selected from fluorine-containing substituents.

2. The polyarylpiperidine anion exchange resin according to claim 1, characterized in that The ring A is selected from any one of the following rings A1, A2 or A3, wherein: The connection position of the representative group: wherein Ra, Ra' and Ra" are each independently selected from substituted or unsubstituted C1-C6 alkyl, or substituted or unsubstituted C3-C6 cycloalkyl; The attachment position of the representative group; Preferably, the ring A is selected from any one of the following groups: Preferably, R3 is selected from any one of fluorine-substituted phenyl, fluorine-substituted tolyl, trifluoromethyl-substituted phenyl, trifluoromethyl-substituted tolyl or trifluoromethyl-substituted C1-C6 bromoalkyl; Preferably, the R3 is selected from any one of the following groups: The connection position of the representative group:

3. A method for preparing a polyarylpiperidine anion exchange resin according to claim 1 or 2, characterized in that: The preparation method comprises the following steps: Azacyclic alcohol and N-alkylpiperidone monomers are polymerized to obtain a polyarylpiperidine polymer main chain; The dibromoalkane and the piperidine monomer react to obtain a polyarylpiperidine polymer side chain; The main chain of the polyaryl piperidine polymer and the side chain of the polyaryl piperidine polymer are subjected to a grafting reaction to obtain a polyaryl piperidine polymer with a grafted side chain; The polyaryl piperidine polymer grafted with side chains and a quaternizing agent undergo a quaternization reaction to obtain the polyaryl piperidine anion exchange resin.

4. The method for preparing a polyarylpiperidine anion exchange resin according to claim 3, wherein: The molar ratio of the azacyclic alcohol to the N-alkylpiperidone monomer is (1.0-1.2):(1.0-2.5); Preferably, in the process of preparing the polyaryl piperidine polymer main chain, a fluorine-containing monomer is also added, and the molar ratio of the azacyclic alcohol, the N-alkyl piperidone monomer and the fluorine-containing monomer is (1.0-1.2):(1.0-2.5):(0.5-2.0); Preferably, in the process of preparing the polyaryl piperidine polymer main chain, an acid catalyst is also added, and the molar ratio of the azacyclic alcohol, N-alkyl piperidone monomer, fluorine-containing monomer and acid catalyst is (1.0-1.2):(1.0-2.5):(0.5-2.0):(2-30); Preferably, the N-alkylpiperidone monomer is selected from any one or a combination of at least two of N-methyl-4-piperidone, N-propyl-4-piperidone, N-isopropyl-4-piperidone, 1-cyclopropyl-4-piperidone, 1-cyclopentyl-4-piperidone or 1-cyclohexyl-4-piperidone; Preferably, the fluorine-containing monomer is selected from any one or a combination of at least two of the following compounds: Preferably, the acid catalyst is selected from any one or a combination of at least two of trifluoropropionic acid, methanesulfonic acid, pentafluoropropionic acid, trifluoromethanesulfonic acid, trifluoroacetic acid or pentafluoroacetic acid: Preferably, in the process of preparing the polyaryl piperidine polymer main chain, the polymerization reaction temperature is -5 to 2°C, and the polymerization reaction time is 2 to 48 hours; Preferably, the specific steps of preparing the polyaryl piperidine polymer main chain are: Dissolving an azacyclic alcohol and an N-alkylpiperidone monomer in a solvent A, adding or not adding the fluorine-containing monomer, and mixing evenly; then adding an acid catalyst to carry out a polymerization reaction, and after the reaction is completed, diluting, precipitating, filtering, washing and drying are carried out in sequence to obtain the polyarylpiperidine polymer main chain; Preferably, the solvent A is selected from dichloromethane and / or chloroform; Preferably, the dilution is: adding a diluent to the system after the polymerization reaction for dilution; wherein the mass ratio of the diluent to the system after the polymerization reaction is (2-8):1; Preferably, the diluent is selected from any one or a combination of at least two of acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, tetrahydrofuran, dimethyl sulfoxide, dichloromethane or chloroform; Preferably, the precipitation is: adding the diluted mixed solution into a precipitant for precipitation; wherein the mass ratio of the precipitant to the diluted mixed solution is (5-10):1; Preferably, the precipitant is selected from any one of ethanol, methanol, isopropanol, water, aqueous sodium hydroxide solution or aqueous potassium carbonate solution, or a combination of at least two thereof.

5. The method for preparing a polyarylpiperidine anion exchange resin according to claim 3, wherein: The molar ratio of the dibromoalkane to the piperidine monomer is (1.7-2.5):1; Preferably, the dibromoalkane is selected from any one or a combination of at least two of 1,6-dibromohexane, 1,5-dibromopentane, 1,4-dibromobutane, 1,3-dibromopropane, 1,2-dibromoethane or dibromomethane; Preferably, the piperidine monomer is selected from any one or a combination of at least two of N-methylpiperidine, N-ethylpiperidine, 1-methylpyrrolidine, 2,3-dimethylpiperidine or N-cyclohexylpiperidine; Preferably, in the process of preparing the polyaryl piperidine polymer side chain, the reaction temperature is 40 to 80° C., and the reaction time is 12 to 48 hours; Preferably, the specific steps for preparing the polyaryl piperidine polymer side chain are: Dissolving a dibromoalkane and a piperidine monomer in a solvent B to react, and then sequentially performing precipitation, filtering, washing and drying after the reaction to obtain the polyaryl piperidine polymer side chain; Preferably, the precipitation is: adding the system obtained by the reaction into solvent B for precipitation; wherein the mass ratio of the solvent B to the system obtained by the reaction is (5-10):1; Preferably, the solvent B is selected from ethyl acetate and / or acetonitrile.

6. The method for preparing a polyarylpiperidine anion exchange resin according to claim 3, wherein: The mass ratio of the polyaryl piperidine polymer main chain to the polyaryl piperidine polymer side chain is 1:(0.2-5); Preferably, the temperature of the grafting reaction is 60 to 80° C., and the time of the grafting reaction is 12 to 48 hours; Preferably, the specific steps for preparing the polyaryl piperidine polymer grafted with side chains are: The main chain of the polyaryl piperidine polymer and the side chain of the polyaryl piperidine polymer are dissolved in a solvent C respectively to obtain a solution containing the main chain and a solution containing the side chain; the solution containing the side chain is added to the solution containing the main chain to carry out a grafting reaction, and after the reaction is completed, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine polymer with grafted side chains; Preferably, the solvent C is selected from any one or a combination of at least two of dimethyl sulfoxide, N,N-dimethylformamide or N,N-dimethylacetamide; Preferably, the dissolving temperature is 50-70°C; Preferably, the precipitation is: adding the system obtained by the grafting reaction into a precipitant for precipitation; wherein the mass ratio of the precipitant to the system obtained by the grafting reaction is (5-10):1; Preferably, the precipitating agent is selected from ethyl acetate and / or acetonitrile.

7. The method for preparing a polyarylpiperidine anion exchange resin according to claim 3, characterized in that: The mass ratio of the polyaryl piperidine polymer grafted with side chains to the quaternizing agent is 1:(0.2-2.7); Preferably, the quaternization reaction is carried out in the presence of an alkaline catalyst, and the mass ratio of the polyaryl piperidine polymer grafted with a side chain to the alkaline catalyst is 1:(0.02-0.2); Preferably, the quaternization reaction is carried out in the presence of solvent D, and the mass ratio of the polyaryl piperidine polymer grafted with side chains to solvent D is 1:(5-10); Preferably, the quaternizing agent is selected from halogen-substituted C1-C6 alkyl and / or halogen-substituted C3-C6 cycloalkyl, preferably any one of iodomethane, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, hexyl iodide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, cyclopropane bromide, cyclobutane bromide, cyclopentane bromide or any one of cyclohexane bromide or a combination of at least two thereof; Preferably, the base catalyst is selected from any one or a combination of at least two of sodium hydroxide, potassium carbonate, potassium iodide or triethylamine; Preferably, the solvent D is selected from any one or a combination of at least two of ethanol, dichloromethane, acetonitrile, tetrahydrofuran, N,N-dimethylformamide, dimethyl sulfoxide, benzene, n-hexane or acetone; Preferably, the temperature of the quaternization reaction is 30 to 80° C., and the time of the quaternization reaction is 2 to 48 hours; Preferably, the specific steps for preparing the polyaryl piperidine polymer grafted with side chains are: The polyaryl piperidine polymer grafted with side chains is dissolved in a solvent D, a quaternizing agent and a base catalyst are added to carry out a quaternization reaction, and after the reaction is completed, precipitation, filtration, washing and drying are carried out in sequence to obtain the polyaryl piperidine anion exchange resin; Preferably, the precipitation is: adding the system obtained by quaternization reaction into a precipitant for precipitation; wherein the mass ratio of the precipitant to the system obtained by quaternization reaction is (2-10):1; Preferably, the precipitant is selected from any one of diethyl ether, n-butyl ether, isobutyl ether, ethylene oxide, diisopropyl ether or methyl tert-butyl ether, or a combination of at least two thereof.

8. An anion exchange membrane, characterized in that: The anion exchange membrane is prepared by using the polyaryl piperidine anion exchange resin according to claim 1 or 2.

9. A method for preparing an anion exchange membrane according to claim 8, characterized in that: The preparation method of the anion exchange membrane comprises: Dissolving the polyarylpiperidine anion exchange resin in a solvent to prepare a casting solution; After coating the casting solution into a film, drying is performed to obtain a film sheet; placing the membrane in an alkaline solution for soaking to obtain the anion exchange membrane; Preferably, the solvent is selected from dimethyl sulfoxide and / or N,N-dimethylformamide; Preferably, the solid content of the casting solution is 5 to 35 wt %; Preferably, the drying temperature is 50 to 180° C., and the drying time is 0.5 to 24 hours; Preferably, the alkaline solution is a 0.5-2 mol / L sodium hydroxide solution; Preferably, the soaking time is 12 to 36 hours; Preferably, the anion exchange membrane has a thickness of 25 to 200 μm.

10. Use of the polyarylpiperidine anion exchange resin according to 1 or 2, or the anion exchange membrane according to claim 8, in preparing a water electrolysis hydrogen production device.

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