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). An ether bond group is introduced into the formula (1), the ether bond group is located between rigid structures, the molecular chain of the anion exchange resin is easier to bend and extend due to the rotatability of the ether bond, the flexibility of the anion exchange resin is improved, and the anion exchange resin has better mechanical strength and flexibility. On the other hand, oxygen atoms in ether bonds have high electronegativity and can interact with water molecules through hydrogen bonds, and the hydrophilic performance of the anion exchange resin is improved.

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 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 prior art, the anion exchange membrane cannot have good hydrophilic performance and flexibility, and 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, the anion exchange resin comprising 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 is selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, the heteroatom comprising at least one of halogen, O, N or S, and / or R2 is selected from at least one of a cyclic group, a substituted or unsubstituted alkyl chain of C1-C10, and a heteroatom-containing group, wherein the heteroatom comprises at least one of halogen, O, N or S, 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 shown in formula (2) and formula (3):

[0008]

[0009] In an embodiment, R3, R4 and R5 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.

[0010] In an embodiment, the n1 is a positive integer from 3 to 15, and / or, the n2 is a positive integer from 10 to 110; and / or

[0011] The X - comprises at least one of iodine ion, bicarbonate ion, triflate ion, bromine ion, p-toluene sulfonate ion; and / or

[0012] The R1 is selected from at least one of hydroxyl, C1-C2 substituted or unsubstituted chain alkyl, and / or, the R2 is selected from at least one of phenyl ring group, C1-C2 substituted or unsubstituted chain alkyl, carbonyl; and / or

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

[0014]

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

[0016]

[0017] wherein, the n1 is a positive integer from 3 to 15, and / or, the n2 is a positive integer from 80 to 90, and / or, n3 represents a degree of polymerization, the n3 is a positive integer from 10 to 20.

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

[0019]

[0020]

[0021] In a second aspect, the embodiments of the present application further provide a preparation method of an anion exchange resin, comprising the following steps:

[0022] providing a first monomer, a second monomer and a hydroxy ketone monomer, the first monomer being a monomer containing a nitrogen-containing heterocyclic ring, the second monomer being a monomer containing an aromatic ring;

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

[0024] subjecting the polymer to quaternization treatment 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, R1 is selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, the heteroatom including at least one of halogen, O, N, or S, and / or, R2 is selected from at least one of a cyclic group, a substituted or unsubstituted alkyl chain of C1-C10, and a heteroatom-containing group, the heteroatom including at least one of halogen, O, N, or S, 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.

[0028] In an embodiment, the first monomer includes 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]

[0031] In an embodiment, R3, R4, R5 are each independently selected from at least one of H, a substituted or unsubstituted hydrocarbon group, a substituted or unsubstituted alkenyl group, and a substituted or unsubstituted aromatic ring.

[0032] In an embodiment, the piperidone monomer includes one or more of the following structures:

[0033]

[0034] and / or

[0035] The quinuclidone monomer includes one or more of the following structures:

[0036]

[0037] In an embodiment, the second monomer includes one or more of the following structures:

[0038]

[0039] and / or;

[0040] The hydroxyketone monomer has a structure as shown in formula (7):

[0041]

[0042] R1is selected from at least one of H, a cyclic group, a C0-C10 substituted or unsubstituted alkyl chain, and a heteroatom-containing group, the heteroatom comprising at least one of halogen, O, N, or S, and / or R2is selected from at least one of a cyclic group, a C1-C10 substituted or unsubstituted alkyl chain, and a heteroatom-containing group, the heteroatom comprising at least one of halogen, O, N, or S.

[0043] In an embodiment, the hydroxy ketone monomer comprises one or more of the following structures:

[0044]

[0045]

[0046] In an embodiment, the mixing of the first monomer, the second monomer, and the hydroxy ketone monomer to allow the first monomer, the second monomer, and the hydroxy ketone monomer to undergo a polymerization reaction to generate a polymer comprises:

[0047] mixing the first monomer, the second monomer, and the hydroxy ketone monomer to obtain a first mixture;

[0048] adding an acid catalyst to the first mixture at a temperature of no more than 0°C to obtain a reaction solution;

[0049] allowing the reaction solution to undergo a polymerization reaction at a temperature of 0°C-20°C to obtain a first mixture;

[0050] filtering, washing, and drying the first mixture to obtain the polymer.

[0051] In an embodiment, the acid catalyst comprises one or more of methylsulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid, and heptafluorobutyric acid; and / or

[0052] the molar ratio between the first monomer, the second monomer, and the hydroxy ketone monomer is (1-1.5):1:(0.05-0.15).

[0053] In an embodiment, the quaternization of the polymer comprises:

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

[0055] allowing the second mixture to undergo a quaternization reaction at a temperature of 10°C-100°C for 4h-36h to obtain a second mixture, and filtering, washing, and drying the second mixture 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, 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, cyclohexyl p-toluenesulfonate; and / or

[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 further 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 further 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 further 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 rigid 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, an ether bond group is introduced in formula (1), and the ether bond group is located between the rigid structures. The rotatability of the ether bond makes the molecular chain of the anion exchange resin more flexible and stretchy, thereby improving the flexibility of the anion exchange resin and enabling the anion exchange resin to have good mechanical strength and flexibility at the same time. On the other hand, the oxygen atom in the ether bond has high electronegativity and can interact with water molecules through hydrogen bonds, thereby improving the hydrophilic property of the anion exchange resin. In addition, the nitrogen-containing heterocyclic cations in formula (1) are connected through the structure unit containing the ether bond. The structure unit containing the ether bond enlarges the spacing between the nitrogen-containing heterocyclic cations, increases the free volume cavity and ion transmission channel in the anion exchange resin, further improves the water absorption property and ion transmission capacity of the anion exchange resin, and enables the anion exchange resin to have good hydrophilic property and flexibility at the same time. DETAILED DESCRIPTION

[0063] The technical solutions in the embodiments of the present application will be clearly and completely described 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 a person 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 anion exchange membrane cannot have good hydrophilic property and flexibility, and 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 formula (1), Ar represents an organic group containing an aromatic ring, and / or R1 is 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 at least one of a cyclic group, a C1-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 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.

[0068] In this embodiment, on the one hand, Ar contains an aromatic ring, and A contains a nitrogen-containing heterocyclic cation. After Ar and A are connected, they can form a rigid structure with a certain supporting effect, thereby improving the mechanical strength of the anion exchange resin and ensuring the structural stability of the anion exchange resin. In addition, an ether bond group is introduced into formula (1). The ether bond group is located between the rigid structures. The rotatability of the ether bond makes the molecular chain of the anion exchange resin easier to bend and stretch, thereby improving the flexibility of the anion exchange resin, and making the anion exchange resin have good mechanical strength and flexibility. On the other hand, the oxygen atom in the ether bond has a high electronegativity and can interact with water molecules through hydrogen bonds, thereby improving the hydrophilicity of the anion exchange resin. In addition, the nitrogen-containing heterocyclic cations in formula (1) are connected by a structural unit containing an ether bond. The structural unit containing an ether bond expands the distance between the nitrogen-containing heterocyclic cations, increases the free volume cavity and ion transmission channel in the anion exchange resin, further improves the water absorption performance and ion transmission capacity of the anion exchange resin, and makes the anion exchange resin have good hydrophilicity and flexibility.

[0069] In one embodiment, R1 is selected from at least one of a hydroxyl group, a C1-C2 substituted or unsubstituted chain alkyl group, and / or R2 is selected from at least one of a benzene ring group, a C1-C2 substituted or unsubstituted chain alkyl group, and a carbonyl group.

[0070] In one embodiment, X - It includes at least one of iodide ion, bicarbonate ion, trifluoromethanesulfonate ion, bromide ion and p-toluenesulfonate ion.

[0071] In one embodiment, n1 is a positive integer between 3 and 15. Alternatively, n1 can be any one of 3, 5, 7, 10, 13, 15, or a range between any two thereof, and is not limited thereto. In this embodiment, when n1 is less than 3, the structure of formula (1) is not ideal in improving the hydrophilicity and flexibility of the anion exchange resin. When n1 is greater than 15, the anion exchange resin is likely to be too soft, which is not conducive to improving the overall mechanical strength of the anion exchange resin and also reduces the conductivity of the anion exchange resin.

[0072] In one embodiment, n2 is a positive integer between 10 and 110. Alternatively, n2 can be any one of 10, 30, 50, 80, 90, 110, or any range between two thereof, without limitation. In this embodiment, when n2 is less than 10, the mechanical strength and exchange capacity of the anion exchange resin are likely to be reduced; when n2 is greater than 110, the ion exchange sites are likely to be crowded, the diffusion rate of anions within the anion exchange resin is reduced, and mass transfer resistance is increased.

[0073] In one embodiment, A comprises at least one of the structures shown in formula (2) and formula (3):

[0074]

[0075] In one embodiment, R3, R4, and R5 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.

[0076] In this embodiment, both formula (2) and formula (3) are cations with relatively large volume, which can naturally limit the water absorption rate 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.

[0077] In one embodiment, Ar comprises one or more of the following structures:

[0078]

[0079] In one embodiment, the anion exchange resin has a structure as shown in formula (4):

[0080]

[0081] Wherein, n1 is a positive integer of 3-15, and / or n2 is a positive integer of 80-90, and / or n3 represents the degree of polymerization, and n3 is a positive integer of 10-20.

[0082] In this embodiment, the structure shown in formula (4) can further improve the mechanical strength and stability of the anion exchange resin and reduce water absorption and expansion.

[0083] In one embodiment, the structure of formula (1) is one or more of the following:

[0084]

[0085]

[0086] The present application also provides a method for preparing an anion exchange resin, comprising the following steps:

[0087] S1, providing a first monomer, a second monomer and a hydroxy ketone monomer, the first monomer being a monomer containing a nitrogen-containing heterocyclic ring, the second monomer being a monomer containing an aromatic ring;

[0088] S2, mixing the first monomer, the second monomer and the hydroxy ketone monomer to make the first monomer, the second monomer and the hydroxy ketone monomer undergo a polymerization reaction to generate a polymer;

[0089] S3, subjecting the polymer to quaternization treatment to obtain an anion exchange resin;

[0090] The anion exchange resin comprises a structure as shown in formula (1):

[0091]

[0092] In formula (1), Ar represents an organic group containing an aromatic ring, and / or R1 is selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10 and a heteroatom-containing group, the heteroatom including at least one of halogen, O, N or S, and / or R2 is selected from at least one of a cyclic group, a substituted or unsubstituted alkyl chain of C1-C10 and a heteroatom-containing group, wherein the heteroatom includes at least one of halogen, O, N or S, and / or A represents a substituted or unsubstituted nitrogen-containing heterocyclic ring cation, and / or X - represents an anion, and / or n1 and n2 represent the degree of polymerization.

[0093] In this embodiment, on the one hand, Ar contains an aromatic ring, A has a nitrogen-containing heterocyclic ring cation, and Ar and A can form a rigid structure with certain support after being connected, which improves the mechanical strength of the anion exchange resin and ensures the structural stability of the anion exchange resin; in addition, an ether bond group is introduced in formula (1), and the ether bond group is located between the rigid structures, and the rotatability of the ether bond makes the molecular chain of the anion exchange resin more flexible and stretchy, thereby improving the flexibility of the anion exchange resin and making the anion exchange resin have good mechanical strength and flexibility at the same time. On the other hand, the oxygen atom in the ether bond has high electronegativity and can interact with water molecules through hydrogen bonds, thereby improving the hydrophilic property of the anion exchange resin; in addition, the nitrogen-containing heterocyclic ring cations in formula (1) are connected through structure units containing ether bonds, the structure units containing ether bonds expand the spacing between the nitrogen-containing heterocyclic ring cations, increase the free volume cavities and ion transmission channels in the anion exchange resin, and further improve the water absorption property and ion transmission capacity of the anion exchange resin, so that the anion exchange resin can have good hydrophilicity and flexibility at the same time.

[0094] In an embodiment, the first monomer includes at least one of a piperidone monomer and a quinuclidone monomer, the structure of the piperidone monomer is shown in formula (5), and the structure of the quinuclidone monomer is shown in formula (6):

[0095]

[0096]

[0097] In an embodiment, R3, R4, and R5 are independently selected from at least one of H, 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 includes one or more of the following structures:

[0099]

[0100] In an embodiment, the quinuclidone monomer includes one or more of the following structures:

[0101]

[0102] In an embodiment, the second monomer includes one or more of the following structures:

[0103]

[0104] In an embodiment, the structure of the hydroxy ketone monomer is shown in formula (7):

[0105]

[0106] wherein R1 is selected from at least one of H, a cyclic group, a substituted or unsubstituted alkyl chain of C0-C10, and a heteroatom-containing group, the heteroatom including at least one of halogen, O, N, or S, and / or R2 is selected from at least one of a cyclic group, a substituted or unsubstituted alkyl chain of C1-C10, and a heteroatom-containing group, the heteroatom including at least one of halogen, O, N, or S.

[0107] In an embodiment, the hydroxy ketone monomer includes one or more of the following structures:

[0108]

[0109] Step S2 specifically includes:

[0110] S21, mixing the first monomer, the second monomer, and the hydroxy ketone monomer to obtain a first mixed solution;

[0111] S22, adding an acid catalyst to the first mixed solution at a temperature of not greater than 0°C to obtain a reaction solution.

[0112] S23, polymerizing the reaction solution under a temperature condition of 0-20°C to obtain a first mixture;

[0113] S24, filtering, washing and drying the first mixture to obtain a polymer.

[0114] 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°C, which can reduce the decomposition or deactivation of the acid catalyst at high temperature on the one hand, and accurately control the reaction progress and reduce the reaction out of control caused by too fast reaction on the other hand.

[0115] In an embodiment, the acid catalyst includes one or more of methyl sulfonic acid, pentafluoropropionic acid, trifluoroacetic acid, triflic acid and heptafluorobutyric acid.

[0116] The molar ratio between the first monomer, the second monomer and the hydroxy ketone monomer is (1-1.5):1:(0.05-0.15). Alternatively, the molar ratio between the first monomer, the second monomer and the hydroxy ketone monomer can be any one of 1:1:0.15, 1:1:0.12, 1:1:0.1, 1:1:0.05, 1.5:1:0.05, or a range between any two of them, which is not limited herein. In the embodiment, the molar ratio between the first monomer, the second monomer and the hydroxy ketone monomer is controlled within the above range, which can further accurately control the size of the hydrophilic microzone and the hydrophobic microzone, optimize the continuity of the ion channel and the water-swellable property, so that the anion exchange resin has better ion transfer capacity, hydrophilic performance and flexibility.

[0117] In an embodiment, step S3 specifically includes:

[0118] S31, adding the polymer and the quaternary ammonium reagent into the solvent A to obtain a second mixed solution;

[0119] S32, performing quaternary ammonium reaction on the second mixed solution under a temperature condition of 10-100°C for 4-36h to obtain a second mixture, and filtering, washing and drying the second mixture to obtain an anion exchange resin.

[0120] In the embodiment, the temperature of the quaternary ammonium reaction can be any one of 10°C, 30°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, or a range between any two of them, which is not limited herein. The time of the quaternary ammonium 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.

[0121] 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, ethyl propylsulfonate, ethyl ethanesulfonate, but-3-yn-1-yl methanesulfonate, allyl allyl sulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, methyl nitrobenzenesulfonate, methyl triflate, ethyl triflate, methyl trifluoroacetate, ethyl tosylate, cyclobutyl toluene-4-sulfonate, butyl tosylate, neopentyl benzene sulfonate, tetrahydro-2H-pyran-4-yl methanesulfonate, cyclohexyl p-toluenesulfonate.

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] The present application is further described below by specific examples.

[0127] Example 1

[0128] (1) 0.3 moL of p-terphenyl, 0.324 moL of N-methyl-4-piperidone and 0.036 moL of hydroxyacetone were added to 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 to the mixed solution at 0°C, after the dropwise addition was completed, an oligomerization reaction was carried out at 0°C, and after the oligomerization reaction was completed, a polymerization reaction was carried out at 10°C for 4 h to obtain a first mixture containing a polymer;

[0129] (2) The first mixture was discharged from an extruder into pure water, filtered, washed with pure water and dried to obtain a polymer;

[0130] (3) 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 the quaternary ammonium reaction was carried out at 80°C for 15 hours. 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 48456, the molecular weight distribution was 1.68, and the anion exchange resin included the following structure:

[0131]

[0132] Example 2

[0133] The main difference between Example 2 and Example 1 is that:

[0134] N-methyl-4-piperidone was replaced with quinuclidone, and the rest was the same as Example 1.

[0135] The anion exchange resin obtained in Example 2 included the following structure, and the molecular weight of the anion exchange resin was 67346, and the molecular weight distribution was 1.70.

[0136]

[0137] Example 3

[0138] The main difference between Example 3 and Example 1 is that:

[0139] Hydroxypropanone was replaced with 3'-chloro-4-hydroxyphenylpropanone, and the rest was the same as Example 1.

[0140] The anion exchange resin obtained in Example 3 included the following structure, and the molecular weight of the anion exchange resin was 59653, and the molecular weight distribution was 1.68.

[0141]

[0142] Example 4

[0143] The main difference between Example 4 and Example 1 is that:

[0144] Hydroxypropanone was replaced with β-hydroxypropanoic acid, and the rest was the same as Example 1.

[0145] The anion exchange resin obtained in Example 4 included the following structure, and the molecular weight of the anion exchange resin was 62940, and the molecular weight distribution was 1.69.

[0146]

[0147] Comparative Example 1

[0148] (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 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, oligomerization was performed at 0°C, and after the oligomerization was completed, polymerization was performed at 10°C for 4 h to obtain a first mixture containing a polymer;

[0149] (2) The first mixture was discharged into pure water through an extruder, filtered, washed with pure water, and dried to obtain a polymer;

[0150] (3) 0.1 mol of the polymer and 0.15 mol of iodomethane were added to 200 mL of dimethyl sulfoxide and mixed uniformly, and quaternization was performed at 80°C for 15 h. The product after the quaternization 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:

[0151]

[0152] Comparative Example 2

[0153] (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, oligomerization was performed at 0°C, and after the oligomerization was completed, polymerization was performed at 10°C for 4 h to obtain a first mixture containing a polymer;

[0154] (2) The first mixture was discharged into pure water through an extruder, filtered, washed with pure water, and dried to obtain a polymer;

[0155] (3) 0.1 mol of the polymer and 0.15 mol of iodomethane were added to 200 mL of dimethyl sulfoxide and mixed uniformly, and quaternization was performed at 80°C for 15 h. The product after the quaternization 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:

[0156]

[0157] Test method:

[0158] 1. Mechanical property test

[0159] The test method refers to GB T 20042.3. The tensile strength and elongation at break of the anion exchange resins prepared in Example 1-Example 4 and Comparative Example 1-Comparative Example 2 were tested. The sample thickness and width were measured under constant temperature and humidity conditions at 23℃±2℃ and 50%±10% relative humidity. The sample was placed in the test fixture, and different tensile speeds can be used when measuring the tensile strength and elongation at break, selected from the range of 50mm / min-200mm / min. For each tensile speed, a separate sample should be used. After the sample breaks, the corresponding load value is read, and the test results are shown in Table 1.

[0160] a. Tensile strength: the maximum load that the anion exchange resin can withstand under the action of pure tensile force when it breaks, divided by the width of the tensile film material, divided into transverse and longitudinal tensile strength, used to evaluate the mechanical strength of the film;

[0161] b. Elongation at break: the ratio of the distance between two points to the original length when the anion exchange resin breaks under the maximum load, indicating the maximum deformation that the alkaline film can withstand before breaking, used to represent the flexibility of the film.

[0162] 2. Water absorption and swelling performance test

[0163] Swelling performance test: The anion exchange resins prepared in Example 1-Example 4 and Comparative Example 1-Comparative Example 2 were prepared into films, which were cut into 1cm*4cm size, placed in 1mol / L potassium hydroxide solution for three times, and the swelling performance test was carried out in 80℃ deionized water, and the test results are shown in Table 1.

[0164] Water absorption performance test: The anion exchange resins prepared in Example 1-Example 4 and Comparative Example 1-Comparative Example 2 were prepared into films, which were cut into 5cm*5cm size, placed in 1mol / L potassium hydroxide solution for three times, and the water absorption performance test was carried out in 80℃ deionized water, and the test results are shown in Table 1.

[0165] 3. OH - Ion conductivity performance test

[0166] The anion exchange resins prepared in Example 1-Example 4 and Comparative Example 1-Comparative Example 2 were prepared into films, and the films of 10mm×45mm were cut as samples. The samples were placed in 1mol / L potassium hydroxide aqueous solution, and ion exchange was carried out at 80℃ for 24h. After ion exchange was completed, the film was washed to neutral with deionized water and stored in deionized water. Before testing, the thickness and width of the film were measured with a thickness gauge and a ruler, 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.

[0167] The ion conductivity test adopts a four-electrode probe method for testing. First, the sample is laid flat on the platinum wire electrode without wrinkles, ensuring good contact between the sample and the platinum wire electrode, then the cover is placed lightly, and the screw is tightened with a wrench. After tightening, the sample should have no protrusions, and the assembly of the test module is complete. The test fixture is connected to the temperature and humidity control system. After connection, nitrogen is purged, and the flow rate on both sides is set to 500 sccm. The humidification condition is set to 100% RH, and the temperature of the pipeline is higher than the temperature of the test device by 5°C. Then start the temperature and humidity device, and after reaching the set conditions, start the electrolysis process, and maintain nitrogen purging throughout the process with constant gas flow.

[0168] The electrolysis process is as follows: a constant current method is used to electrolyze the membrane material to be tested, and the electrolysis current value can be adjusted within 2V to meet the actual test requirements. During the electrolysis process, the electrode undergoes an electrochemical reaction, and the carbonate (hydrogen) ions in the anion exchange membrane are exchanged in situ to CO 2 in the form of gas until all anions in the membrane are exchanged to OH - - in situ. When the potential fluctuation value is less than 1%, the electrolysis process is determined to be complete, and the system reaches an equilibrium state.

[0169] 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 and the real axis, and the in-plane ion conductivity of the sample is calculated according to the following formula:

[0170] σ = l / (a x b x R)

[0171] In the formula:

[0172] σ - the in-plane ion conductivity of the sample, in units of millisiemens per centimeter (mS / cm);

[0173] l - the distance between the electrodes, in units of centimeters (cm);

[0174] a - the width of the membrane sample, in units of centimeters (cm);

[0175] b - the thickness of the membrane sample, in units of centimeters (cm);

[0176] R - the measured impedance of the membrane sample, in units of ohms (Ω);

[0177] The test results are shown in Table 1.

[0178] 4. Polarization performance test

[0179] The polarization performance of the anion exchange membrane electrolytic cell was tested under the anode bare membrane-cathode platinum carbon catalytic system 70℃@2M KOH, and the test results are shown in Table 2.

[0180] Table 1

[0181]

[0182] Table 2

[0183]

[0184] According to the test results in Table 1, the anion exchange resins prepared in Examples 1 to 4 all have high tensile strength, elongation at break and water absorption. The anion exchange resins of the present application have good flexibility, mechanical strength and hydrophilicity. The reason is that Ar contains an aromatic ring and A contains a nitrogen-containing heterocyclic cation. After Ar is connected to A, a rigid structure with certain support function is formed, which improves the mechanical strength of the anion exchange resin and ensures the structural stability of the anion exchange resin. In addition, the ether bond group is introduced in formula (1), and the ether bond group is located between the rigid structures. The rotatability of the ether bond makes the molecular chain of the anion exchange resin more flexible and stretchable, thereby improving the flexibility of the anion exchange resin and making the anion exchange resin have good mechanical strength and flexibility at the same time. In addition, the oxygen atom in the ether bond has high electronegativity and can interact with water molecules through hydrogen bonds, thereby improving the hydrophilicity of the anion exchange resin. In addition, the nitrogen-containing heterocyclic cations in formula (1) are connected by structure units containing ether bonds, which expands the distance between the nitrogen-containing heterocyclic cations, increases the free volume cavity and ion transmission channel in the anion exchange resin, and further improves the water absorption and ion transmission capacity of the anion exchange resin, so that the anion exchange resin can have good hydrophilicity and flexibility at the same time.

[0185] In addition, according to the test results in Table 1, the anion exchange resins prepared in Examples 1 to 4 all have low swelling rate. The reason is that the aromatic ring and nitrogen-containing heterocyclic cation in formula (1) have large volume, which can enhance the mechanical strength and stability of the anion exchange resin, reduce the excessive swelling of the anion exchange resin, and make the anion exchange resin have good water absorption rate while having low swelling rate.

[0186] In addition, according to the test results in Table 1 and Table 2, the anion exchange resins prepared in Examples 1 to 4 all have high conductivity and low impedance. In addition, when the polarization performance test is carried out, the anion exchange resins have relatively low cell voltage under the current density of 0.5A / cm 2 and the current density of 1A / cm 2 , and have good electrochemical performance.

[0187] The above has introduced the embodiments of the present application in detail, and the principles and implementation manners of the present application are described by applying specific examples; the above embodiment description is only used for helping to understand the method of the present application and its core idea; meanwhile, for the person skilled in the art, according to the idea of the present application, the specific implementation manner and application range will have changes; and in conclusion, the content of the specification should not be understood as the 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 is 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 at least one of a cyclic group, a C1-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 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 R3, R4, and R5 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 3-15, and / or said n2 is a positive integer of 10-110; and / or The X - including at least one of iodide ion, bicarbonate ion, trifluoromethanesulfonate ion, bromide ion, and p-toluenesulfonate ion; and / or The R1 is selected from at least one of a hydroxyl group, a C1-C2 substituted or unsubstituted chain alkyl group, and / or the R2 is selected from at least one of a benzene ring group, a C1-C2 substituted or unsubstituted chain alkyl group, and a carbonyl 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 3-15, and / or n2 is a positive integer of 80-90, and / or n3 represents the degree of polymerization, and n3 is a positive integer of 10-20.

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 hydroxyketone monomer, wherein the first monomer is a monomer containing a nitrogen-containing heterocycle, and the second monomer is a monomer containing an aromatic ring; mixing the first monomer, the second monomer, and the hydroxyketone monomer so that the first monomer, the second monomer, and the hydroxyketone monomer 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 is 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 at least one of a cyclic group, a C1-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 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 R3, R4, and R5 are each independently selected from at least one of H, 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 hydroxyketone monomer is shown in formula (7): wherein R1 is 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 at least one of a cyclic group, a C1-C10 substituted or unsubstituted alkyl chain, and a heteroatom-containing group, wherein the heteroatom comprises at least one of halogen, O, N, or S.

12. The method for preparing an anion exchange resin according to claim 11, wherein The hydroxyketone 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 mixing the first monomer, the second monomer, and the hydroxyketone monomer so as to polymerize the first monomer, the second monomer, and the hydroxyketone monomer to generate a polymer specifically includes: mixing the first monomer, the second monomer, and the hydroxyketone monomer to obtain a first mixed solution; adding an acid catalyst to the first mixed solution at a temperature not greater than 0° C. to obtain a reaction solution; The reaction solution is subjected to a polymerization reaction at a temperature of 0° C. to 20° C. to obtain a first mixture; The first 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, the second monomer and the hydroxyketone monomer is (1-1.5):1:(0.05-0.15).

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 second mixture, which is then filtered, washed, and dried to obtain the anion exchange resin.

16. The method for preparing 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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