Anion exchange resin, preparation method thereof and anion exchange membrane

Abstract

The invention provides anion exchange resin, a preparation method thereof and an anion exchange membrane. The anion exchange resin has a structure as shown in a formula (1). Carbonyl is introduced into the formula (1), the carbonyl has strong electronegativity and conjugation ability, the carbonyl can disperse positive charges of nitrogen-containing heterocyclic cations and weaken the electron withdrawing effect of the nitrogen-containing heterocyclic cations on a skeleton structure, the polarization degree of chemical bonds of the skeleton structure is reduced, then the stability of the skeleton structure is improved, and the skeleton structure is not prone to breakage; and the structural stability of the anion exchange resin and the continuity of an ion transmission channel are ensured. Besides, carbonyl is used as a strong polar group, the carbonyl and a skeleton structure form a remarkable polarity difference, and the polarity difference can induce polymer molecules to realize nanoscale phase separation, promote the formation of a high-speed ion transmission channel, reduce the ion transmission resistance and improve the ion transmission performance of the anion exchange membrane.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of hydrogen production by water electrolysis, and particularly relates to an anion exchange resin, a preparation method thereof and an anion exchange membrane. BACKGROUND

[0002] Hydrogen production by water electrolysis and fuel cell technology are rapidly developing, and it is foreseeable that they will become key technologies to support high proportion of new energy development and build hydrogen-electricity collaborative pattern. Taking hydrogen production by water electrolysis technology as an example, anion exchange membrane water electrolysis technology has the characteristics of zero gap and low cost, and is one of the technologies that are most likely to realize hydrogen economy. Among them, the anion exchange membrane, as the main component of the anion exchange membrane water electrolysis system, its role is to conduct hydroxyl ions from the cathode to the anode, while blocking the direct transmission of gas and electrons between the electrodes. However, in the related technology, the polymer molecules of the anion exchange membrane generally include a carbon skeleton backbone and a cationic group, and the cationic group is directly on the backbone or is too close to the backbone. The electron-deficient cationic group is easy to induce the backbone to break, reducing the ion transport performance of the anion exchange membrane, which needs to be further improved. SUMMARY

[0003] Embodiments of the present application provide an anion exchange resin, a preparation method thereof and an anion exchange membrane, aiming to solve the foregoing technical problems.

[0004] In a first aspect, embodiments of the present application provide an anion exchange resin, which comprises a structure as shown in formula (1):

[0005]

[0006] In the formula (1), Ar represents an organic group containing an aromatic ring, and / or, R1 and R3 are independently selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10 and a heteroatom-containing group, wherein the heteroatom includes at least one of halogen, O, N or S, and / or, R2 is selected from a cyclic group or a substituted or unsubstituted alkyl chain of C0-C10, and / or, A represents a substituted or unsubstituted nitrogen-containing heterocyclic cation, and / or, X represents an anion, and / or, n1 and n2 represent the degree of polymerization. -

[0007] In an embodiment, the A comprises at least one of the structures as shown in formula (2) and formula (3):

[0008]

[0009] ​In one embodiment, R4, R5, and R6 are independently selected from at least one of H, substituted or unsubstituted alkyl, substituted or unsubstituted hydrocarbon, substituted or unsubstituted alkenyl, and substituted or unsubstituted aromatic ring.

[0010] In one embodiment, n1 is a positive integer of 10-50, and / or n2 is a positive integer of 50-90; and / or

[0011] The X - including at least one of iodide ion, trifluoroacetate ion, bromide ion, p-toluenesulfonate ion, chloride ion, hydroxide ion, bicarbonate ion, and carbonate ion; and / or

[0012] The R1 is selected from at least one of a halogenated alkyl group and a C1-C2 unsubstituted chain alkyl group, and / or the R2 is selected from a C0 alkyl group, and / or the R3 is selected from at least one of a C1-C3 substituted or unsubstituted chain alkyl group, an alkoxy group, and a halogenated phenyl group; and / or

[0013] The Ar comprises one or more of the following structures:

[0014]

[0015] In one embodiment, the anion exchange resin has a structure as shown in formula (4):

[0016]

[0017] Wherein, n1 is a positive integer of 10-50, and / or n2 and n3 are both positive integers, and the sum of n2 and n3 is 50-90.

[0018] In one embodiment, the structure of formula (1) is one or more of the following:

[0019]

[0020]

[0021] In a second aspect, an embodiment of the present application further includes a method for preparing an anion exchange resin, comprising the following steps:

[0022] Providing a first monomer, a second monomer and a ketone monomer, wherein the first monomer is a monomer containing a nitrogen-containing heterocyclic ring, and the second monomer is a monomer containing an aromatic ring;

[0023] causing the first monomer, the second monomer, and the ketone monomer to undergo a polymerization reaction to generate a polymer;

[0024] quaternizing the polymer to obtain the anion exchange resin;

[0025] wherein the anion exchange resin comprises a structure as shown in formula (1):

[0026]

[0027] In the formula (1), Ar represents an organic group containing an aromatic ring, and / or, R1and R3are independently selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom containing group, wherein the heteroatom comprises at least one of halogen, O, N, or S, and / or, R2is selected from a cyclic group or a substituted or unsubstituted alkyl chain of C0-C10, and / or, A represents a substituted or unsubstituted nitrogen containing heterocyclic cation, and / or, X - represents an anion, and / or, n1and n2represent a degree of polymerization.

[0028] In an embodiment, the first monomer comprises at least one of a piperidone monomer and a quinuclidone monomer, the piperidone monomer having a structure as shown in formula (5), and the quinuclidone monomer having a structure as shown in formula (6):

[0029]

[0030] In an embodiment, R4, R5, R6are independently selected from at least one of H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aromatic ring.

[0031] In an embodiment, the piperidone monomer comprises one or more of the following structures:

[0032]

[0033] and / or

[0034] The quinuclidone monomer comprises one or more of the following structures:

[0035]

[0036] In an embodiment, the second monomer comprises one or more of the following structures:

[0037]

[0038] and / or;

[0039] The ketone monomer has a structure as shown in formula (7):

[0040]

[0041] wherein R1 and R3 are independently selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, wherein the heteroatom comprises at least one of halogen, O, N, or S, and / or R2 is selected from a cyclic group or a substituted or unsubstituted alkyl chain of C0-C10.

[0042] In an embodiment, the ketone monomer comprises one or more of the following structures:

[0043]

[0044] In an embodiment, the step of allowing the first monomer, the second monomer, and the ketone monomer to undergo a polymerization reaction to generate a polymer specifically comprises:

[0045] mixing the first monomer and the second monomer to obtain a first mixture;

[0046] adding an acid catalyst to the first mixture at a temperature of -5°C to 5°C to obtain a reaction solution;

[0047] allowing the reaction solution to undergo a polymerization reaction at a temperature of 0°C to 10°C for 2h to 6h to obtain a first mixture;

[0048] adding the ketone monomer to the first mixture and allowing the mixture to undergo a polymerization reaction at a temperature of 5°C to 20°C for 2h to 10h to obtain a second mixture;

[0049] filtering, washing, and drying the second mixture to obtain the polymer.

[0050] In an embodiment, the acid catalyst comprises one or more of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid, and heptafluorobutyric acid; and / or

[0051] the molar ratio of the first monomer to the ketone monomer is (1-9): 1; and / or

[0052] the number of moles of the second monomer is N1, the sum of the number of moles of the first monomer and the number of moles of the ketone monomer is N2, and the ratio of N1 to N2 is 1:(1-5).

[0053] In an embodiment, the step of allowing the polymer to undergo a quaternization treatment specifically comprises:

[0054] adding the polymer and a quaternization reagent to a solvent A to obtain a second mixture;

[0055] The second mixture is subjected to a quaternization reaction at a temperature of 10-100℃ for 4-36h to obtain a third mixture, which is filtered, washed, and dried to obtain the anion exchange resin.

[0056] In an embodiment, 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, 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.

[0057] The solvent A comprises one or more of dichloromethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide, or N,N-dimethylacetamide, acetonitrile.

[0058] In a third aspect, the embodiments of the present application also provide an anion exchange membrane comprising the anion exchange resin as described above or prepared by the method as described above.

[0059] In a fourth aspect, the embodiments of the present application also provide a membrane electrode comprising the anion exchange resin as described above or prepared by the method as described above, or comprising the anion exchange membrane as described above.

[0060] In a fifth aspect, the embodiments of the present application also provide a water electrolysis hydrogen production system comprising the anion exchange resin as described above or prepared by the method as described above, or comprising the anion exchange membrane as described above, or comprising the membrane electrode as described above.

[0061] The beneficial effects of the embodiments of the present application are as follows:

[0062] The anion exchange resin of the embodiment of the present application comprises a structure as shown in formula (1). On the one hand, Ar contains an aromatic ring, A has a nitrogen-containing heterocyclic cation, and Ar and A can form a skeleton structure with a certain supporting effect after being connected, thereby improving the mechanical strength of the anion exchange resin and ensuring the structural stability of the anion exchange resin. In addition, a carbonyl group is introduced in formula (1), the carbonyl group has strong electronegativity and conjugation ability, the carbonyl group can disperse the positive charge of the nitrogen-containing heterocyclic cation, weaken the electron-withdrawing effect of the nitrogen-containing heterocyclic cation on the skeleton structure, reduce the polarization degree of the chemical bond of the skeleton structure, and further improve the stability of the skeleton structure, so that the skeleton structure is not easy to break, and the structural stability of the anion exchange resin and the continuity of the ion transmission channel are ensured. On the other hand, the carbonyl group is a strong polar group, and the carbonyl group and the skeleton structure form a significant polarity difference, which can induce the nanoscale phase separation of the polymer molecules, promote the formation of high-speed ion transmission channels, reduce the ion transmission resistance, and improve the ion transmission performance of the anion exchange membrane. DETAILED DESCRIPTION

[0063] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with 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 those skilled in the art without creative labor fall within the scope of protection of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application. In the present application, the orientation words such as "upper" and "lower" generally refer to the upper and lower in the actual use or working state of the device, and "inner" and "outer" refer to the outline of the device.

[0064] In the related art, the polymer molecules of the anion exchange membrane generally comprise a carbon skeleton main chain and a cationic group, and the cationic group is directly on the main chain or is too close to the main chain. The electron-deficient cationic group is easy to induce the main chain to break, thereby reducing the ion transmission performance of the anion exchange membrane, which needs to be further improved.

[0065] The present application provides an anion exchange resin, which comprises a structure as shown in formula (1):

[0066]

[0067] In the formula (1), Ar represents an organic group containing an aromatic ring, and / or, R1 and R3 are independently selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, wherein the heteroatom includes at least one of halogen, O, N, or S, and / or, R2 is selected from a cyclic group or a substituted or unsubstituted alkyl chain of C0-C10, and / or, A represents a substituted or unsubstituted nitrogen-containing heterocyclic cation, and / or, X - represents an anion, and / or, n1 and n2 represent a degree of polymerization.

[0068] In the present embodiment, the anion exchange resin comprises a structure as shown in formula (1). On the one hand, Ar contains an aromatic ring, A has a nitrogen-containing heterocyclic cation, and Ar and A can form a skeleton structure with certain support after being connected, thereby improving the mechanical strength of the anion exchange resin and ensuring the structural stability of the anion exchange resin. In addition, a carbonyl group is introduced in formula (1), the carbonyl group has strong electronegativity and conjugation ability, the carbonyl group can disperse the positive charge of the nitrogen-containing heterocyclic cation, weaken the electron-withdrawing effect of the nitrogen-containing heterocyclic cation on the skeleton structure, reduce the polarization degree of the chemical bond of the skeleton structure, and further improve the stability of the skeleton structure, so that the skeleton structure is not easy to break, and the structural stability of the anion exchange resin and the continuity of the ion transmission channel are ensured. On the other hand, the carbonyl group is a strong polar group, and the carbonyl group and the skeleton structure form a significant polarity difference. This polarity difference can induce the polymer molecules to realize nanoscale phase separation, promote the formation of high-speed ion transmission channels, reduce the ion transmission resistance, and improve the ion transmission performance of the anion exchange membrane.

[0069] It should be noted that in the present embodiment, when R2 is selected from a substituted or unsubstituted alkyl chain of C0, the anion exchange resin comprises a structure as shown in formula (1-1):

[0070]

[0071] In an embodiment, A comprises at least one of the structures shown in formula (2) and formula (3):

[0072]

[0073] In an embodiment, R4, R5, and R6 are independently selected from at least one of H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aromatic ring. In the present embodiment, both formula (2) and formula (3) are relatively large cations, which can naturally limit the water absorption of the anion exchange resin and reduce excessive swelling. In addition, the six-membered ring structure can enhance the mechanical strength and stability of the anion exchange resin.

[0074] In an embodiment, n1 is a positive integer from 10 to 50. Alternatively, n1 can be any one of 10, 20, 30, 40, 50, or a range between any two of them, without limitation. In the present embodiment, when n1 is less than 10, the effect of the structure of formula (1) on improving the ion transport performance of the improved anion exchange membrane of the anion exchange resin is not ideal; when n1 is greater than 50, it is easy to cause the anion exchange resin to be too soft, which is not conducive to improving the overall mechanical strength of the anion exchange resin.

[0075] In an embodiment, n2 is a positive integer from 50 to 90. Alternatively, n2 can be any one of 50, 60, 70, 80, 90, or a range between any two of them, without limitation. In the present embodiment, when n2 is less than 50, it is easy to reduce the mechanical strength and exchange capacity of the anion exchange resin; when n2 is greater than 90, it is easy to cause the ion exchange sites to be crowded, the diffusion rate of anions in the anion exchange resin to be reduced, and the mass transfer resistance to be increased.

[0076] In an embodiment, the X- includes at least one of iodide ion, trifluoroacetate ion, bromide ion, p-toluenesulfonate ion, chloride ion, hydroxide ion, bicarbonate ion, carbonate ion.

[0077] In an embodiment, R1 is selected from at least one of halogenated alkyl, C1-C2 unsubstituted chain alkyl, and / or, R2 is selected from C0 alkyl, and / or, R3 is selected from at least one of C1-C3 substituted or unsubstituted chain alkyl, alkoxy, halogenated phenyl.

[0078] In the present embodiment, when R3 is selected from alkoxy, the carbonyl group as a strong hydrogen bond acceptor forms stable hydrogen bonds with water molecules, significantly improving the hydrophilicity of the anion exchange resin, and the steric hindrance effect of the alkoxy group moderately limits the hydrophilicity of the carbonyl group, avoiding swelling caused by excessive water absorption, and maintaining the hydrophilic-hydrophobic balance; in addition, the rigid structure of the carbonyl group combined with the flexible chain segment of the alkoxy group balances the chain segment movement and rigidity, reducing the swelling deformation of the anion exchange resin. Therefore, when R3 is selected from alkoxy, the carbonyl group and the alkoxy group can synergistically act to avoid swelling caused by excessive water absorption, and further improve the ion transport performance and mechanical properties of the anion exchange resin.

[0079] In the embodiment, when R3 is selected from halophenyl, the π electron cloud of the halophenyl can form a conjugated system with the carbonyl group, enhancing the electron delocalization, further promoting the ion adsorption and conduction of the anion exchange resin, meanwhile, the carbonyl group and the halophenyl group synergistically form a hydrophilic-hydrophobic microphase separation structure, constructing a continuous ion transport channel, improving the ion mobility; in addition, the steric hindrance effect of the halophenyl group moderately limits the hydrophilicity of the carbonyl group, avoiding the swelling caused by excessive water absorption; in addition, the dipole-dipole interaction of the carbonyl group and the van der Waals force of the halophenyl group synergistically enhance the interchain force, improving the tensile strength of the anion exchange resin.

[0080] In an embodiment, Ar comprises one or more of the following structures:

[0081]

[0082] In an embodiment, the anion exchange resin has a structure as shown in formula (4):

[0083]

[0084] wherein n1 is a positive integer of 10-50, and / or, n2 and n3 are both positive integers, and the sum of n2 and n3 is 50-90. In the embodiment, the structure shown in formula (4) can further improve the mechanical strength and stability of the anion exchange resin, and reduce the water absorption swelling.

[0085] In an embodiment, the structure of formula (1) is one or more of the following:

[0086]

[0087] The application also provides a preparation method of the anion exchange resin, comprising the following steps:

[0088] S1, providing a first monomer, a second monomer and a ketone monomer, the first monomer being a monomer containing a nitrogen-containing heterocycle, and the second monomer being a monomer containing an aromatic ring;

[0089] S2, causing the first monomer, the second monomer and the ketone monomer to undergo a polymerization reaction to generate a polymer;

[0090] S3, subjecting the polymer to quaternization treatment to obtain the anion exchange resin;

[0091] wherein the anion exchange resin comprises a structure as shown in formula (1):

[0092]

[0093] In formula (1), Ar represents an organic group containing an aromatic ring, and / or, R1and R3are independently selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, wherein the heteroatom includes at least one of halogen, O, N, or S, and / or, R2is selected from a cyclic group or a substituted or unsubstituted alkyl chain of C0-C10, and / or, A represents a substituted or unsubstituted nitrogen-containing heterocyclic cation, and / or, X - represents an anion, and / or, n1and n2represent a degree of polymerization.

[0094] In the present embodiment, the anion exchange resin comprises a structure as shown in formula (1). On the one hand, Ar contains an aromatic ring, A has a nitrogen-containing heterocyclic cation, and Ar and A can form a skeleton structure with a certain supporting effect after being connected, thereby improving the mechanical strength of the anion exchange resin and ensuring the structural stability of the anion exchange resin. In addition, a carbonyl group is introduced in formula (1), the carbonyl group has strong electronegativity and conjugation ability, the carbonyl group can disperse the positive charge of the nitrogen-containing heterocyclic cation, weaken the electron-withdrawing effect of the nitrogen-containing heterocyclic cation on the skeleton structure, reduce the polarization degree of the chemical bond of the skeleton structure, and further improve the stability of the skeleton structure, so that the skeleton structure is not easy to break, and the structural stability of the anion exchange resin and the continuity of the ion transmission channel are ensured. On the other hand, the carbonyl group is a strong polar group, and the carbonyl group and the skeleton structure form a significant polarity difference. This polarity difference can induce the polymer molecules to realize nanoscale phase separation, promote the formation of high-speed ion transmission channels, reduce the ion transmission resistance, and improve the ion transmission performance of the anion exchange membrane.

[0095] In an embodiment, the first monomer comprises at least one of a piperidone monomer and a quinuclidone monomer, the structure of the piperidone monomer is as shown in formula (5), and the structure of the quinuclidone monomer is as shown in formula (6):

[0096]

[0097] In an embodiment, R4, R5, and R6are independently selected from at least one of H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aromatic ring.

[0098] In an embodiment, the piperidone monomer comprises one or more of the following structures:

[0099]

[0100] and / or

[0101] In an embodiment, the quinuclidone monomer comprises one or more of the following structures:

[0102]

[0103] In an embodiment, the second monomer comprises one or more of the following structures:

[0104]

[0105] In an embodiment, the structure of the ketone monomer is shown in formula (7):

[0106]

[0107] wherein R1and R3are independently selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, wherein the heteroatom comprises at least one of halogen, O, N, or S, and / or R2is selected from a cyclic group or a substituted or unsubstituted alkyl chain of C0-C10.

[0108] In the present embodiment, it is to be noted that when R2is selected from a substituted or unsubstituted alkyl chain of C0, the structure of the ketone monomer is shown in formula (7-1):

[0109]

[0110] In an embodiment, the ketone monomer comprises one or more of the following structures:

[0111]

[0112] In an embodiment, the step S2 specifically comprises:

[0113] S21, mixing the first monomer and the second monomer to obtain a first mixture liquid;

[0114] S22, adding an acid catalyst to the first mixture liquid under a temperature condition of -5-5°C to obtain a reaction liquid;

[0115] S23, performing a polymerization reaction on the reaction liquid under a temperature condition of 0-10°C for 2-6h to obtain a first mixture;

[0116] S24, adding a ketone monomer to the first mixture and performing a polymerization reaction under a temperature condition of 5-20°C for 2-10h to obtain a second mixture;

[0117] S25, filtering, washing, and drying the second mixture to obtain a polymer.

[0118] In the embodiment, the acid catalyst can reduce the activation energy of the polymerization reaction, thereby accelerating the polymerization process between monomers. In addition, the temperature of the polymerization reaction is controlled at 0-20℃, which can reduce the decomposition or deactivation of the acid catalyst at high temperature on the one hand, and can accurately control the reaction progress and reduce the reaction out of control caused by too fast reaction on the other hand.

[0119] In an embodiment, the acid catalyst includes one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid and heptafluorobutyric acid.

[0120] In an embodiment, the molar ratio of the first monomer to the ketone monomer is (1-9):1. Alternatively, the molar ratio of the first monomer to the ketone monomer can be any one of 1:1, 3:1, 5:1, 7:1, 9:1 or a range between any two of them, which is not limited herein.

[0121] In an embodiment, the number of moles of the second monomer is N1, the sum of the number of moles of the first monomer and the ketone monomer is N2, and the ratio of N1 to N2 is 1:(1-5). Alternatively, the ratio of N1 to N2 can be any one of 1:1, 1:2, 1:3, 1:4, 1:5 or a range between any two of them, which is not limited herein.

[0122] In an embodiment, step S3 specifically includes:

[0123] S31, adding the polymer and the quaternization reagent into the solvent A to obtain a second mixed solution;

[0124] S32, performing quaternization reaction on the second mixed solution at a temperature of 10-100℃ for 4-36h to obtain a third mixed solution, and filtering, washing and drying the third mixed solution to obtain the anion exchange resin.

[0125] In the embodiment, the temperature of the quaternization reaction can be any one of 10℃, 30℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃ or a range between any two of them, which is not limited herein. The time of the quaternization reaction can be any one of 4h, 8h, 12h, 18h, 22h, 28h, 36h or a range between any two of them, which is not limited herein.

[0126] In an embodiment, 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 benzenesulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, and cyclohexyl p-toluenesulfonate.

[0127] In an embodiment, the solvent A comprises one or more of dichloromethane, chloroform, tetrahydrofuran, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, acetonitrile.

[0128] The present application also provides an anion exchange membrane comprising the anion exchange resin as described above or prepared by the method as described above.

[0129] The present application also provides a membrane electrode comprising the anion exchange resin as described above or prepared by the method as described above, or comprising the anion exchange membrane as described above.

[0130] The present application also provides a water electrolysis hydrogen production system comprising the anion exchange resin as described above or prepared by the method as described above, or comprising the anion exchange membrane as described above, or comprising the membrane electrode as described above.

[0131] The present application is further illustrated by the following specific examples.

[0132] Example 1

[0133] (1) 0.3 moL of p-terphenyl, 0.288 moL of N-methyl-4-piperidone were added into 100 mL of dichloromethane to obtain a mixed solution, then 22.8 mL of trifluoroacetic acid and 240 mL of trifluoromethanesulfonic acid were added dropwise into the mixed solution at 0°C, and after the dropwise addition was completed, an oligomerization reaction was carried out at 0°C to obtain a first mixture.

[0134] (2) 0.072 moL of methyl pyruvate was added into the first mixture, and a polymerization reaction was carried out at a temperature of 10°C for 4 h to obtain a second mixture.

[0135] (3) The second mixture was discharged from an extruder into pure water, filtered, washed with pure water, and dried to obtain a polymer.

[0136] (4) 0.1 mol of the polymer and 0.15 mol of methyl iodide were added to 200 mL of dimethyl sulfoxide and mixed well, and a quaternary ammonium reaction was performed at 80°C for 15 h. The product after the quaternary ammonium reaction was precipitated using 2 L of ethyl acetate, filtered, washed with ethyl acetate, and dried to obtain an anion exchange resin. The molecular weight of the anion exchange resin was 48559, the molecular weight distribution was 1.68, and the anion exchange resin included the following structure:

[0137]

[0138] Example 2

[0139] The main difference between Example 2 and Example 1 is that:

[0140] N-methyl-4-piperidone was replaced with quinuclidone, and the rest was the same as Example 1;

[0141] The molecular weight of the anion exchange resin obtained in Example 2 was 57346, the molecular weight distribution was 1.64, and the anion exchange resin included the following structure:

[0142]

[0143] Example 3

[0144] The main difference between Example 3 and Example 1 is that:

[0145] Methyl pyruvate was replaced with 4,4,4-trifluoro-1-(4-bromophenyl)-1,3-butanedione, and the rest was the same as Example 1;

[0146] The molecular weight of the anion exchange resin obtained in Example 3 was 49653, the molecular weight distribution was 1.66, and the anion exchange resin included the following structure:

[0147]

[0148] Example 4

[0149] The main difference between Example 4 and Example 1 is that:

[0150] Step (1) is: 0.3 moL of p-terphenyl, 0.288 moL of N-methyl-4-piperidone, and 0.06 mol of 9,9-dimethylfluorene were added to 100 mL of dichloromethane to obtain a mixed solution, and then 22.8 mL of trifluoroacetic acid and 240 mL of trifluoromethanesulfonic acid were added dropwise to the mixed solution at 0°C. After the dropwise addition was completed, a oligomerization reaction was performed at 0°C to obtain a first mixture;

[0151] The rest is the same as Example 1.

[0152] The molecular weight of the anion exchange resin obtained in Example 4 is 59853, the molecular weight distribution is 1.66, and the anion exchange resin comprises the following structure:

[0153]

[0154] Example 5

[0155] The main difference between Example 5 and Example 1 is that:

[0156] Methyl pyruvate is replaced by butanedione, and the rest is the same as Example 1;

[0157] The molecular weight of the anion exchange resin obtained in Example 5 is 46730, the molecular weight distribution is 1.68, and the anion exchange resin comprises the following structure:

[0158]

[0159] Example 6

[0160] The main difference between Example 6 and Example 1 is that:

[0161] Methyl pyruvate is replaced by heptane-3,4-dione, and the rest is the same as Example 1;

[0162] The molecular weight of the anion exchange resin obtained in Example 6 is 47210, the molecular weight distribution is 1.68, and the anion exchange resin comprises the following structure:

[0163]

[0164] Comparative Example 1

[0165] (1) 0.3 moL of p-terphenyl and 0.324 moL of N-methyl-4-piperidone were added to 100 mL of dichloromethane to obtain a mixture, then 22.8 mL of trifluoroacetic acid and 240 mL of trifluoromethanesulfonic acid were added dropwise to the mixture at 0°C, after the dropwise addition was completed, the oligomerization reaction was carried out at 0°C, and after the oligomerization reaction was completed, the polymerization reaction was carried out at 10°C for 4 h to obtain a first mixture containing a polymer;

[0166] (2) The first mixture was discharged from the extruder into pure water, filtered, washed with pure water, and dried to obtain a polymer;

[0167] (3) 0.1 mol of the polymer and 0.15 mol of methyl iodide were added to 200 mL of dimethyl sulfoxide and mixed uniformly, and a quaternary ammonium reaction was carried out at 80°C for 15 h. The product after the quaternary ammonium reaction was precipitated using 2 L of ethyl acetate, filtered, washed with ethyl acetate, and dried to obtain an anion exchange resin. The molecular weight of the anion exchange resin was 45790, the molecular weight distribution was 1.68, and the structure of the anion exchange resin was as follows:

[0168]

[0169] Comparative Example 2

[0170] (1) 0.3 mol of p-terphenyl and 0.324 mol of quinuclidone were added to 100 mL of dichloromethane to obtain a mixed solution, and then 22.8 mL of trifluoroacetic acid and 240 mL of trifluoromethanesulfonic acid were added dropwise to the mixed solution at 0°C. After the dropwise addition was completed, an oligomerization reaction was carried out at 0°C, and a polymerization reaction was carried out at 10°C for 4 h to obtain a first mixture containing a polymer;

[0171] (2) The first mixture was discharged from an extruder into pure water, filtered, washed with pure water, and dried to obtain a polymer;

[0172] (3) 0.1 mol of the polymer and 0.15 mol of methyl iodide were added to 200 mL of dimethyl sulfoxide and mixed uniformly, and a quaternary ammonium reaction was carried out at 80°C for 15 h. The product after the quaternary ammonium reaction was precipitated using 2 L of ethyl acetate, filtered, washed with ethyl acetate, and dried to obtain an anion exchange resin. The molecular weight of the anion exchange resin was 45790, the molecular weight distribution was 1.68, and the structure of the anion exchange resin was as follows:

[0173]

[0174] Test method:

[0175] 1. Mechanical property test

[0176] The test method referred to GB T 20042.3, the tensile strength and elongation at break of the anion exchange resins prepared in Example 1-Example 6 and Comparative Example 1-Comparative Example 2 were tested. The sample thickness and width were measured under the condition of constant temperature and humidity, in which the temperature was 23°C±2°C and the relative humidity was 50%±10%. The sample was placed in a test fixture, and different tensile speeds could be selected in the range of 50 mm / min-200 mm / min when the tensile strength and elongation at break were measured. For each tensile speed, a separate sample should be applied. After the sample was broken, the corresponding load value was read, and the test results are shown in Table 1.

[0177] a. Tensile strength: the maximum load that can be borne by the anion exchange resin under the action of pure tensile force before breaking, and the ratio of the width of the tensile film material, divided into transverse and longitudinal tensile strength, used to evaluate the mechanical strength of the film;

[0178] b. Elongation at break: the ratio of the distance between two points at the maximum load before breaking to the original length, indicating the maximum deformation that the alkaline film can bear before breaking, used to represent the flexibility of the film.

[0179] 2. Water absorption swelling performance test

[0180] Swelling performance test: the anion exchange resins prepared from Examples 1-4 and Comparative Examples 1-2 were prepared into films, the films were cut into 1cm*4cm size, and were placed in 1mol / L potassium hydroxide solution for three times of base exchange, and were tested for swelling performance in deionized water at 80℃, and the test results are shown in Table 1;

[0181] Water absorption performance test: the anion exchange resins prepared from Examples 1-4 and Comparative Examples 1-2 were prepared into films, the films were cut into 5cm*5cm size, and were placed in 1mol / L potassium hydroxide solution for three times of base exchange, and were tested for water absorption performance in deionized water at 80℃, and the test results are shown in Table 1.

[0182] 3. OH - Ion conductivity performance test

[0183] The anion exchange resins prepared from Examples 1-4 and Comparative Examples 1-2 were prepared into films, and the films were cut into 10mm*45mm as samples. The samples were placed in 1mol / L potassium hydroxide aqueous solution, and were ion exchanged at 80℃ for 24h. After ion exchange was completed, the samples were washed with deionized water until neutral, and were stored in deionized water. Before testing, the thickness and width of the film were measured with a thickness gauge and a ruler respectively, and the average values of three tests were taken as the width a and the thickness b. At least three points were taken for each group of samples.

[0184] The ion conductivity test was tested by four-electrode probe method. First, the sample was laid flat on the platinum wire electrode without wrinkles, ensuring good contact between the sample and the platinum wire electrode, then the cover was placed lightly, and the screw was tightened with a wrench. After tightening, the sample should have no protrusions, and the assembly of the test module was completed. The test fixture was connected to the temperature and humidity control system. After connection, nitrogen was purged, and the flow rate on both sides was set to 500sccm. The humidification condition was set to 100% RH, and the temperature of the pipeline was set to be 5℃ higher than the temperature of the test device; then the temperature and humidity device was started, and after reaching the set condition, the electrolysis process was started, and nitrogen was purged throughout the process, and the gas flow rate was constant.

[0185] In the electrolysis process, the electrode undergoes an electrochemical reaction, and the carbonate (hydrogen) ions in the anion exchange membrane are exchanged in situ to CO32-. 2 is discharged in the form of gas until all the anions in the membrane are exchanged in situ to OH - When the potential fluctuation value is less than 1%, it is determined that the electrolysis process is complete, and the system reaches an equilibrium state.

[0186] After the electrolysis reaches an equilibrium state, EIS testing 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 membrane 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:

[0187] σ = l / (a x b x R)

[0188] In the formula:

[0189] σ is the in-plane ion conductivity of the sample, in units of millisiemens per centimeter (mS / cm);

[0190] l is the distance between the electrodes, in units of centimeters (cm);

[0191] a is the width of the membrane sample, in units of centimeters (cm);

[0192] b is the thickness of the membrane sample, in units of centimeters (cm);

[0193] R is the measured impedance of the membrane sample, in units of ohms (Ω);

[0194] The test results are shown in Table 1.

[0195] 4. Polarization performance test

[0196] The polarization performance of the anion exchange membrane electrolysis cell was tested under the conditions of an anode bare membrane-cathode platinum carbon catalytic system at 70°C and 2M KOH, and the test results are shown in Table 2.

[0197] Table 1

[0198]

[0199] Table 2

[0200]

[0201]

[0202] According to the test results in Table 1 and Table 2, the anion exchange resins prepared in Examples 1 to 6 have high conductivity and low impedance, and when the polarization performance test is performed, the anion exchange resins have relatively low cell voltage at a current density of 0.5 A / cm 2 and a current density of 1 A / cm 2 . The anion exchange resins of the present application have good ion transport performance. The reason is that Ar contains an aromatic ring, A contains a nitrogen-containing heterocyclic cation, and Ar and A can form a skeleton structure with certain support effect after being connected, thereby improving the mechanical strength of the anion exchange resin and ensuring the structural stability of the anion exchange resin. In addition, the carbonyl group is introduced in formula (1), the carbonyl group has strong electronegativity and conjugation ability, the carbonyl group can disperse the positive charge of the nitrogen-containing heterocyclic cation, weaken the electron-withdrawing effect of the nitrogen-containing heterocyclic cation on the skeleton structure, reduce the polarization degree of the chemical bond of the skeleton structure, and further improve the stability of the skeleton structure, so that the skeleton structure is not easy to break, and the structural stability of the anion exchange resin and the continuity of the ion transport channel are ensured. In addition, the carbonyl group is a strong polar group, and the carbonyl group and the skeleton structure form a significant polarity difference, which can induce the polymer molecules to realize nanoscale phase separation, promote the formation of high-speed ion transport channels, reduce the ion transport resistance, and improve the ion transport performance of the anion exchange membrane.

[0203] According to the test results in Table 1, the anion exchange resins prepared in Examples 1 to 6 have low swelling rate and high water absorption rate. The reason is that the aromatic ring and the nitrogen-containing heterocyclic cation in formula (1) have large volume, which can enhance the mechanical strength and stability of the anion exchange resin, and reduce the excessive swelling of the anion exchange resin. In addition, the carbonyl group has high electronegativity, can interact with water molecules through hydrogen bonds, and can improve the hydrophilicity of the anion exchange resin, so that the anion exchange resin has good water absorption rate and low swelling rate.

[0204] According to the comparison of Examples 1 to 4 and Examples 5 and 6, when R3 in formula (1) is selected from alkoxy and / or halophenyl, the mechanical properties, anti-swelling properties, water absorption properties and electrochemical properties of the anion exchange resin can be further improved.

[0205] The above describes the embodiments of the present application in detail, and the specific examples are applied to explain the principles and implementation modes of the present application; the above examples are only used to help understand the method and core idea of the present application; meanwhile, according to the idea of the present application, the specific implementation mode and application range can be changed by those skilled in the art; and according to the above, the content of the specification should not be understood as a limitation of the present application.

Claims

1. An anion exchange resin, characterized in that The anion exchange resin comprises a structure as shown in formula (1): In the formula (1), Ar represents an organic group containing an aromatic ring, and / or R1 and R3 are independently selected from at least one of H, a cyclic group, a C0-C10 substituted or unsubstituted alkyl chain and a heteroatom-containing group, wherein the heteroatom includes at least one of halogen, O, N or S, and / or R2 is selected from a cyclic group or a C0-C10 substituted or unsubstituted alkyl chain, and / or A represents a substituted or unsubstituted nitrogen-containing heterocyclic cation, and / or X - represents an anion, and / or, n1 and n2 represent the degree of polymerization.

2. The anion exchange resin according to claim 1, characterized in that The A comprises at least one of the structures shown in formula (2) and formula (3):

3. The anion exchange resin according to claim 2, characterized in that R4, R5, and R6 are each independently selected from at least one of H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aromatic ring.

4. The anion exchange resin according to any one of claims 1 to 3, characterized in that Said n1 is a positive integer of 10-50, and / or said n2 is a positive integer of 50-90; and / or The X - including at least one of iodide ion, trifluoroacetate ion, bromide ion, p-toluenesulfonate ion, chloride ion, hydroxide ion, bicarbonate ion, and carbonate ion; and / or The R1 is selected from at least one of a halogenated alkyl group and a C1-C2 unsubstituted chain alkyl group, and / or the R2 is selected from a C0 alkyl group, and / or the R3 is selected from at least one of a C1-C3 substituted or unsubstituted chain alkyl group, an alkoxy group, and a halogenated phenyl group; and / or The Ar comprises one or more of the following structures:

5. The anion exchange resin according to claim 4, characterized in that The anion exchange resin has a structure as shown in formula (4): Wherein, n1 is a positive integer of 10-50, and / or n2 and n3 are both positive integers, and the sum of n2 and n3 is 50-90.

6. The anion exchange resin according to claim 4, characterized in that The structure of formula (1) is one or more of the following:

7. A method for preparing an anion exchange resin, characterized in that: The following steps are involved: Providing a first monomer, a second monomer and a ketone monomer, wherein the first monomer is a monomer containing a nitrogen-containing heterocyclic ring, and the second monomer is a monomer containing an aromatic ring; causing the first monomer, the second monomer, and the ketone monomer to undergo a polymerization reaction to generate a polymer; quaternizing the polymer to obtain the anion exchange resin; Wherein, the anion exchange resin comprises a structure as shown in formula (1): In the formula (1), Ar represents an organic group containing an aromatic ring, and / or R1 and R3 are independently selected from at least one of H, a cyclic group, a C0-C10 substituted or unsubstituted alkyl chain and a heteroatom-containing group, wherein the heteroatom includes at least one of halogen, O, N or S, and / or R2 is selected from a cyclic group or a C0-C10 substituted or unsubstituted alkyl chain, and / or A represents a substituted or unsubstituted nitrogen-containing heterocyclic cation, and / or X - represents an anion, and / or, n1 and n2 represent the degree of polymerization.

8. The method for preparing an anion exchange resin according to claim 7, wherein The first monomer includes at least one of a piperidone monomer and a quinuclidine monomer. The structure of the piperidone monomer is shown in formula (5), and the structure of the quinuclidine monomer is shown in formula (6):

9. The method for preparing an anion exchange resin according to claim 8, wherein R4, R5, and R6 are each independently selected from at least one of H, a substituted or unsubstituted alkyl group, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aromatic ring.

10. The method for preparing anion exchange resin according to claim 9, characterized in that: The piperidone monomer includes one or more of the following structures: The quinuclidine monomer includes one or more of the following structures:

11. The method for preparing an anion exchange resin according to claim 7, wherein The second monomer includes one or more of the following structures: The structure of the ketone monomer is shown in formula (7): wherein R1 and R3 are independently selected from at least one of H, a cyclic group, a C0-C10 substituted or unsubstituted alkyl chain, and a heteroatom-containing group, wherein the heteroatom comprises at least one of halogen, O, N, or S, and / or R2 is selected from a cyclic group or a C0-C10 substituted or unsubstituted alkyl chain.

12. The method for preparing an anion exchange resin according to claim 11, wherein The ketone monomer includes one or more of the following structures:

13. The method for preparing an anion exchange resin according to any one of claims 7 to 12, characterized in that: The step of causing the first monomer, the second monomer, and the ketone monomer to undergo a polymerization reaction to generate a polymer specifically includes: mixing the first monomer and the second monomer to obtain a first mixed solution; adding an acid catalyst to the first mixed solution at a temperature of -5°C to 5°C to obtain a reaction solution; The reaction solution is subjected to polymerization reaction at a temperature of 0° C. to 10° C. for 2 h to 6 h to obtain a first mixture; The ketone monomer is added to the first mixture, and the polymerization reaction is carried out at a temperature of 5°C-20°C for 2h-10h to obtain a second mixture. The second mixture is filtered, washed, and dried to obtain the polymer.

14. The method for preparing an anion exchange resin according to claim 13, wherein: The acid catalyst comprises one or more of methanesulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, trifluoromethanesulfonic acid and heptafluorobutyric acid; and / or The molar ratio of the first monomer to the ketone monomer is (1-9):1; and / or The molar number of the second monomer is N1, the sum of the molar numbers of the first monomer and the ketone monomer is N2, and the ratio of N1 to N2 is 1:(1-5).

15. The preparation method according to any one of claims 7 to 12, characterized in that: The step of quaternizing the polymer specifically comprises: adding the polymer and the quaternizing agent into solvent A to obtain a second mixed solution; The second mixed solution is subjected to a quaternization reaction at a temperature of 10° C. to 100° C. for 4 h to 36 h to obtain a third mixture, which is then filtered, washed, and dried to obtain the anion exchange resin.

16. The method for preparing an anion exchange resin according to claim 15, characterized in that: The quaternizing agent comprises one or more of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentane iodide, hexane iodide, ethyl bromide, propyl bromide, butyl bromide, pentane iodide, hexane bromide, cyclohexyl bromide, cyclopentane bromide, cyclohexyl bromide, methyl methanesulfonate, ethyl methanesulfonate, propyl methanesulfonate, butyl methanesulfonate, propyl ethanesulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allylsulfonate, 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 A includes one or more of dichloromethane, chloroform, chloroform, tetrahydrofuran, dimethyl sulfoxide, tetrahydrofuran, N-methyl-2-pyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide, and acetonitrile.

17. An anion exchange membrane, characterized in that The invention comprises the anion exchange resin according to any one of claims 1 to 6 or the anion exchange resin prepared by the method according to any one of claims 7 to 16.

18. A membrane electrode, characterized in that The invention comprises the anion exchange resin according to any one of claims 1 to 6 or the anion exchange resin prepared by the method according to any one of claims 7 to 16, or comprises the anion exchange membrane according to claim 17.

19. A water electrolysis hydrogen production system, characterized in that: The invention comprises the anion exchange resin according to any one of claims 1 to 6 or the anion exchange resin prepared by the method according to any one of claims 7 to 16, or the anion exchange membrane according to claim 17, or the membrane electrode according to claim 18.

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