Cationic polymer based on polyaryl isatin as well as preparation method and application of cationic polymer

Abstract

The invention provides a cationic polymer based on polyaryl isatin as well as a preparation method and application of the cationic polymer. The cationic polymer is a novel polyaryl isatin skeleton synthesized through Friedel-Crafts condensation polymerization under the catalysis of superacid; the isatin structural unit in the cationic polymer has a huge molecular volume so as to improve the dimensional stability and mechanical property of the cationic polymer after film formation, and meanwhile, the N site of the grafted cation on the cationic polymer is positioned on the para-position of the isatin structural unit; the remote grafting strategy can further improve the cation alkali-resistant stability of the membrane, so that the cationic polymer disclosed by the invention shows very high ionic conductivity and mechanical and chemical stability; the polymer can be used as an anion exchange membrane or an anion exchange polymer binder for alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction and flow batteries.

Description

Technical Field

[0001] The present invention relates to the field of new energy electrochemical devices, and particularly to a cationic polymer based on polyaryl isatin, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, with the increasing demand for alternative energy worldwide, the application of anion exchange membranes and anion exchange polymer binders in new energy electrochemical devices has also attracted more and more attention from researchers. They can be applied in fields such as alkaline fuel cells, water electrolysis, carbon dioxide reduction, and flow batteries, and have good development prospects. They also play a crucial role in traditional industries such as the chlor-alkali industry, heavy metal recovery, water treatment, and hydrometallurgy, and have received extensive attention. In fields such as alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction, and flow batteries, the stability, conductivity, and mechanical properties of anion exchange membranes and anion exchange polymer binders are crucial. However, traditional anion exchange membranes and anion exchange polymer binders often exhibit low stability, insufficient conductivity, and mechanical properties in alkaline environments.

[0003] Regarding the cationic polymer materials for anion exchange membranes used in alkaline environments: Chinese Patent Application CN110903449A provides an isatin aromatic polycopolymer, a preparation method, and an application thereof. An isatin structural unit is introduced into the copolymer to facilitate cross-linking and functionalization of the polymer. However, in this scheme, the piperidinium salt is connected to an electron-withdrawing aromatic hydrocarbon structure at the γ position, which leads to easy Hofmann elimination at the β position of the piperidinium salt, reducing stability. Another example is Chinese Patent Application CN11644834A, which provides a side-chain type anion exchange membrane. By eliminating unstable ether bonds in the polymer main chain, the membrane has strong alkali resistance, and at the same time, a flexible side chain is introduced to form an ion channel. However, in this scheme, the alkane chain connected from isatin is directly connected to N in the ammonium salt. An additional β-position H is introduced in this type of molecular structure, making Hofmann elimination more likely to occur, thus affecting the chemical stability of the ammonium salt. It can be seen that the prior art already has the idea of using isatin structure monomers as the main chain of cationic polymers to improve dimensional stability, but there are still defects in insufficient chemical stability. Therefore, it is necessary to find a new type of cationic polymer material to improve the mechanical strength of anion exchange membranes while increasing their ionic conductivity and chemical stability. Summary of the Invention

[0004] The object of the present invention is a cationic polymer based on polyaryl isatin, its preparation method and application. The cationic polymer based on polyaryl isatin has excellent mechanical strength, high ionic conductivity and high chemical stability, and can be used as an anion exchange membrane or an anion exchange polymer binder in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction and flow batteries.

[0005] To achieve the above object, in the first aspect, the present technical solution provides a cationic polymer based on polyaryl isatin, and the structural general formula is shown as the following formula (1):

[0006]

[0007] Wherein Ar is any one or a combination of two or more of aromatic monomers;

[0008] In formula (1), R1-R4 are each independently selected from any one of hydrogen, hydroxyl group, C1-C10, and halogen, wherein the halogen is any one of F, Cl, Br, and I; R5 in formula (1) is H, a para-piperidine quaternary ammonium salt structural unit shown in formula (2), a para-piperidine tertiary amine spiro structural unit shown in formula (3), a meta-piperidine ammonium salt structural unit shown in formula (4), a meta-piperidine tertiary amine spiro structural unit shown in formula (5), a meta-quinuclidine structural unit shown in formula (6), and a para-quinuclidine structural unit shown in formula (7), and X in formula (2) to formula (7) is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3:

[0009]

[0010] Specifically, in formula (2), R1 and R2 are each independently selected from any one of hydrogen or a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms, hydrogen or a substituted or unsubstituted cycloalkyl group with 1 to 10 carbon atoms, hydrogen or a substituted or unsubstituted alkenyl group with 1 to 10 carbon atoms, and hydrogen or a substituted or unsubstituted aryl group with 1 to 10 carbon atoms, R3 is selected from hydrogen or an alkyl group of C1-C10, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0011] In formula (3), n is an integer from 0 to 10, R1 is selected from hydrogen or an alkyl group of C1-C10, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0012] In formula (4), R1 and R2 are each independently selected from any one of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and hydrogen, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0013] In formula (5), n is an integer from 0 to 10, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0014] In formula (6), R1 is selected from any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and hydrogen, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0015] In formula (7), R1 is selected from any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and hydrogen, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0016] It should be noted that the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, the substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, the substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and hydrogen, the substituted or unsubstituted aryl group having 1 to 10 carbon atoms mentioned in this solution refer to alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups with or without substituents. If there are substituents, the carbon chain length of the substituents is 1 to 10.

[0017] It should be noted that as can be seen from the structural general formula (1), the cation position in the cation corresponding to R5 is located at the para or meta position of the isatin structural monomer, which can effectively avoid the Hofmann elimination reaction. Specifically, the cations N+ corresponding to R5 are not directly connected to the NH site of the isatin structural monomer through an alkyl group, but are externally connected to the isatin structural monomer, which can effectively reduce the number of β-H, thereby reducing the Hofmann elimination reaction.

[0018] Preferably, the substituents of R1 and R2 in formula (2), R1 in formula (3), R1 and R2 in formula (4), and R1 in formula (6) and formula (7) are each independently selected from a hydroxyl group, a sulfonic acid group, or a halogen atom.

[0019] In a more preferred embodiment, R1 and R2 in formula (2), R1 in formula (3), R1 and R2 in formula (4), and R1 in formula (6) and formula (7) are each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, phenyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, bromomethyl, bromoethyl, bromopropyl, bromobutyl, bromopentyl, bromohexyl, bromoheptyl, bromooctyl, vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, propanesulfonyl, butanesulfonyl.

[0020] In addition, in some embodiments, Ar is at least one of phenyl structural monomers of the following formula (8) to formula (46):

[0021]

[0022]

[0023] Among them, R1 in formula (11) is any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I;

[0024] n in formula (12) is an integer from 0 to 20;

[0025] [[ID=CH=20]]R2 and R3 in formula (14) are each independently selected from any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I;

[0026] R4 in formula (15) is any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms, and a substituted or unsubstituted alkene having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I;

[0027] n in formula (16) is an integer from 1 to 10;

[0028] In formulas (21) to (23), n is an integer from 0 to 8.

[0029] In some embodiments, the number-average molecular weight of the polyaryl isatin-based cationic polymer of this solution is 0.1 - 1 million.

[0030] In some embodiments, the molar ratio of the structural unit shown in formula (1) to at least one of the structural units shown in formulas (2) to (6) and formula (42) is 0.005 - 100:1. When X in the structural units shown in formulas (2) to (7) - is OH - the ion exchange capacity of the isatin group-based cationic polymer is 0.1 mmol / g - 10 mmol / g.

[0031] In some embodiments, the molar ratio of the structural unit shown in formula (1) to at least one of the structural units shown in formulas (8) to (45) is 1:0.001 - 0.67.

[0032] Second solution, this technical solution provides an intermediate of a polyaryl isatin-based cationic polymer, and the structural formula is as shown in the following formula (47):

[0033]

[0034] Among them, R1 - R4 in formula (47) are each independently selected from any one of hydrogen, hydroxyl group, C1 - C10, and halogen, where the halogen is any one of F, Cl, Br, and I, and R5 is a para-piperidine tertiary ammonium salt structural unit shown in formula (48), a meta-piperidine tertiary amine structural unit shown in formula (49), a para-piperidine tertiary amine spirocyclic structural unit shown in formula (50), and a meta-piperidine tertiary amine spirocyclic structural unit shown in formula (51);

[0035]

[0036] Among them, n in formula (50) is an integer from 0 to 10, and R1 is selected from hydrogen or a substituted or unsubstituted alkyl group with C1 - C10;

[0037] n in formula (51) is an integer from 0 to 10:

[0038] Among them, R1 and R2 in formula (48) are each independently selected from any one of hydrogen or a substituted or unsubstituted alkyl group with 1 - 10 carbon atoms, hydrogen or a substituted or unsubstituted cycloalkyl group with 1 - 10 carbon atoms, hydrogen or a substituted or unsubstituted alkenyl group with 1 - 10 carbon atoms, and hydrogen or a substituted or unsubstituted aryl group with 1 - 10 carbon atoms;

[0039] In formula (49), R1 is selected from any one of hydrogen, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, and hydrogen, a substituted or unsubstituted aryl group having 1 to 10 carbon atoms.

[0040] It should be noted that when R5 in formula (46) is the para-piperidine tertiary amine spiro ring structural unit shown in formula (49), 2-(piperidin-4-yl)ethanol is subjected to a cyclization reaction to obtain a para-piperidine tertiary amine spiro ring precursor, and the para-piperidine tertiary amine spiro ring precursor is reacted with the basic isatin monomer. When R5 in formula (46) is the meta-piperidine tertiary amine spiro ring structural unit shown in formula (50), 2-(piperidin-3-yl)ethanol is subjected to a cyclization reaction to obtain a meta-piperidine tertiary amine spiro ring precursor, and the meta-piperidine tertiary amine spiro ring precursor is reacted with the basic isatin monomer. The number of n in the para-piperidine tertiary amine spiro ring structural unit shown in formula (49) and the meta-piperidine tertiary amine spiro ring structural unit shown in formula (50) is related to the carbon chain length of the dibromo or diiodoalkane added in the cyclization reaction.

[0041] Similarly, when R5 in formula (47) is the para-piperidine quaternary ammonium salt structural unit shown in formula (48), the basic isatin monomer is reacted with the bromo para-piperidine quaternary ammonium salt with a Boc protecting group to obtain a para-piperidine quaternary ammonium salt precursor with a boc protecting group, and the Boc protecting group of the para-piperidine quaternary ammonium salt precursor with a boc protecting group is removed.

[0042] The structural formula of the bromo para-piperidine quaternary ammonium salt with a Boc protecting group is shown in the following formula (52):

[0043]

[0044] When R5 in formula (47) is the meta-piperidine tertiary amine structural unit shown in formula (49), the basic isatin monomer is reacted with the bromo meta-piperidine quaternary ammonium salt with a Boc protecting group to obtain a meta-piperidine quaternary ammonium salt precursor with a boc protecting group, and the Boc protecting group of the meta-piperidine quaternary ammonium salt precursor with a boc protecting group is removed;

[0045] The structural formula of the bromo meta-piperidine quaternary ammonium salt with a Boc protecting group is shown in the following formula (53):

[0046]

[0047] In some embodiments, n in formulas (52) and (53) is an integer greater than 1.

[0048] In some specific embodiments, the specific reaction formula is as follows:

[0049]

[0050] Thirdly, the present solution provides a method for preparing a cationic polymer based on polyaryl isatin, which is characterized in that a polymerization reaction is carried out between an intermediate of the cationic polymer based on polyaryl isatin shown in formula (47) and an aromatic structure monomer.

[0051] In some embodiments, the structure of the aromatic structure monomer is as shown in the following formulas (59)-(95):

[0052]

[0053]

[0055] In formula (62), R1 is any one of a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, and aryl group having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I; in formula (63), n is an integer from 0 to 20; in formula (65), R2 and R3 are each independently selected from any one of a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, and aryl group having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I; in formula (66), R4 is any one of a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group, and olefin having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I; in formula (67), n is an integer from 1 to 10; in formulas (72)-(74), n is an integer from 0 to 8, and R1 and R2 are each independently selected from any one of a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, and aryl group having 1 to 10 carbon atoms, wherein the substituent is a hydroxyl group or a halogen atom, and the halogen atom is any one of F, Cl, Br, and I.

[0056] It should be noted that in the present solution, a series of novel cationic polymers with a polyarylene-isatin backbone are synthesized through a Friedel-Crafts polycondensation reaction under the catalysis of a superacid. Correspondingly, the polymerization reaction is carried out in the presence of a solvent and a catalyst, and the catalyst includes any one or at least two combinations of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid, and the solvent includes any one or at least two combinations of dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran.

[0057] In some embodiments, the temperature of the polymerization reaction is -20°C to 80°C, and the time of the polymerization reaction is 0.1 h to 120 h.

[0058] In addition, it should be noted that in this solution, the polymerization product obtained by polymerizing the isatin monomer shown in formula (20) with the aromatic structure monomer is subjected to an alkylation reaction with an alkylating agent, and the alkylating agent includes any one or at least two combinations of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, vinyl iodide, allyl iodide, butenyl iodide, iodomethanol, iodoethanol, iodopropanol, 1,3 - propane sultone, 1,4 - butane sultone, 2,4 - butane sultone. The alkylating agent is dissolved in any one or at least two combinations of solvents such as dimethyl sulfoxide, N,N - dimethylformamide, acetonitrile, N - methylpyrrolidone, dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran.

[0059] In some embodiments, the temperature of the alkylation reaction is 0°C to 60°C, and the time of the alkylation reaction is 0.5 h to 120 h.

[0060] Fourthly, this solution provides a preparation method of a cationic polymer based on polyaryl isatin, which is obtained by subjecting the structure shown in formula (54) to a nucleophilic substitution reaction with the structure of formula (55) or the structure of formula (56), where formula (54) is as follows:

[0061]

[0062] Formula (55) is as follows:

[0063]

[0064] Formula (56) is as follows:

[0065]

[0066] Among them, R1 - R4 in formula (54) are each independently selected from any one of hydrogen, hydroxyl group, C1 - C10, and halogen, where the halogen is any one of F, Cl, Br, and I;

[0067] R1 in formula (55) is selected from any one of a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted cycloalkyl group with 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted alkenyl group with 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted aryl group with 1 to 10 carbon atoms: X is a halogen which is any one of F, Cl, Br, and I;

[0068] R1 in formula (56) is selected from any one of a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted cycloalkyl group with 1 to 10 carbon atoms, hydrogen, a substituted or unsubstituted alkenyl group with 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted aryl group with 1 to 10 carbon atoms, and X is a halogen which is any one of F, Cl, Br, and I.

[0069] In some embodiments, the structure of formula (57) is reacted with methyl iodide to obtain an intermediate, and then the intermediate is reacted with hydrogen halide at high temperature to obtain the structure of formula (55); alternatively, the structure of formula (58) is reacted with methyl iodide to obtain an intermediate, and then the intermediate is reacted with hydrogen halide at high temperature to obtain the structure of formula (56).

[0070] Among them, the structural formula (57) is as follows:

[0071]

[0072] Among them, the structural formula (58) is as follows:

[0073]

[0074] Among them, R1 in formula (57) is selected from any one of substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms, hydrogen, substituted or unsubstituted cycloalkyl groups with 1 to 10 carbon atoms, hydrogen, substituted or unsubstituted alkenyl groups with 1 to 10 carbon atoms, hydrogen, or substituted or unsubstituted aryl groups with 1 to 10 carbon atoms;

[0075] R1 in formula (58) is selected from any one of substituted or unsubstituted alkyl groups with 1 to 10 carbon atoms, hydrogen, substituted or unsubstituted cycloalkyl groups with 1 to 10 carbon atoms, hydrogen, substituted or unsubstituted alkenyl groups with 1 to 10 carbon atoms, hydrogen, or substituted or unsubstituted aryl groups with 1 to 10 carbon atoms.

[0076] In some specific embodiments, the reaction formula is as follows:

[0077]

[0078] In some embodiments, Ar is at least one of the phenyl structural monomers of the following formulas (8) to (46):

[0079]

[0080]

[0081] Fifth aspect, the present invention provides an anion exchange membrane, which is prepared by dissolving the cationic polymer based on polyarylisatin of the first aspect of the present invention in a solution for curing or by processing with a casting film machine, or by blending the cationic polymer based on polyarylisatin of the first aspect of the present invention with other polymer materials and then dissolving in a solution for curing or by processing with a casting film machine.

[0082] In an alternative embodiment, the polymer material includes, but is not limited to, other anion exchange polymers, such as polyimidazolium salt anion exchange polymers, poly(piperidine tertiary amine) cationic polymers, etc. Specific examples may be polyphenylene ether, polytetrafluoroethylene, polyvinyl alcohol, polysulfone, pectin, etc.

[0083] In an alternative embodiment, the solution for dissolving the cationic polymer includes any one or at least two combinations of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol, or water.

[0084] In an alternative embodiment, the cationic polymer solution is cast or cast onto a substrate and dried.

[0085] In an alternative embodiment, the substrate includes any one or at least two combinations of a glass plate, a polytetrafluoroethylene plate, a ceramic plate, a steel belt, a polyethylene terephthalate-based film, a polyamide-based film, a polytetrafluoroethylene porous film, a polyethylene porous film, a polypropylene porous film, glass fiber, or carbon fiber.

[0086] In an alternative embodiment, the drying temperature is one temperature in the range of 80 to 280 °C or drying in multiple temperature stages.

[0087] In an alternative embodiment, the drying time is 0.1 to 120 h.

[0088] In an alternative embodiment, the cationic polymer is placed in a casting film machine to prepare a flat film. In some embodiments, the specific thickness of the film is 1 to 500 μm.

[0089] In a sixth aspect, the present invention provides an anion exchange polymer adhesive, which is prepared by dissolving the poly(aryliminoisoindoline)-based cationic polymer described in the first aspect of the present invention in a solvent.

[0090] In a seventh aspect, the present invention further provides a method for preparing the anion exchange polymer adhesive described in the fourth aspect of the present invention. This method is to spray or drop the above-mentioned anion exchange polymer solution on a certain metal substrate catalyst, or spray or drop it on a certain metal substrate or carbon-based conductive substrate after blending with a powder catalyst.

[0091] In an alternative embodiment, the substrate includes a nickel mesh, a nickel fiber felt, nickel foam, a stainless steel mesh, a stainless steel felt, stainless steel foam, a titanium mesh, a titanium fiber felt, titanium foam, a copper mesh, PTFE-based magnetron sputtered copper, a copper sheet, carbon paper, carbon cloth, etc.

[0092] In the eighth aspect, the present invention provides the application of a cationic polymer based on polyarylisatin, which can be used in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

[0093] In the ninth aspect, the present invention provides the application of an anion exchange membrane, which can be used in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

[0094] In the tenth aspect, the present invention provides the application of an anion exchange polymer binder, which can be used in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

[0095] Compared with the prior art, the present technical solution has the following characteristics and beneficial effects:

[0096] The cationic polymer based on polyaryl isatin provided by this solution is a novel polyaryl isatin skeleton synthesized by Friedel-Crafts polycondensation reaction under the catalysis of superacid, including isatin structural units with structural characteristics such as large volume, anti-torsion, and rigidity. This isatin structural unit makes the cationic polymer have a higher molecular density and a more compact structure, not only increasing the glass transition temperature of the subsequently prepared anion exchange membrane, but also enhancing the mechanical strength and stability of the cationic polymer to improve the dimensional stability inside the cationic polymer, thereby enhancing the mechanical properties of the cationic polymer; and the rigidity and anti-torsion of the isatin structural unit enable the cationic polymer to maintain good morphological stability when preparing the anion exchange membrane, which helps to prevent the membrane from deforming or distorting during use, thus maintaining the stable performance of the membrane.

[0097] In addition, the hydrogen bond interaction between the carbonyl group on the isatin structural unit of the cationic polymer and water molecules, as well as the electrostatic interaction (hydrogen bond (tertiary amines still have lone pairs of electrons)) between the tertiary N on the isatin group and water molecules, can regulate the dispersion of water inside the cationic polymer, helping to construct a Grotthuss transport channel and improve the ionic conductivity; the N site of the grafted cation on the cationic polymer is located at the para position of the isatin structural unit. This kind of bonding method reduces β-hydrogen, thus avoiding Hofmann elimination reaction. This remote grafting strategy can further improve the alkali resistance stability of the cations in the membrane.

[0098] Therefore, the cationic polymer of the present invention has extremely excellent mechanical strength and elongation rate, and exhibits high ionic conductivity, mechanical and chemical stability, and can be used as an anion exchange membrane or an anion exchange polymer binder in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries. Description of the Drawings

[0099] Figure 1 is the nuclear magnetic resonance of the anion exchange polymer obtained in Example 1 of the present invention1 1H NMR spectrum.

[0100] Figure 2 Schematic diagram of the mechanical tensile strength of Examples 1-11 of the present invention.

[0101] Figure 3 Schematic diagram of the mechanical tensile strength of Comparative Examples 1-4.

[0102] Figure 4 Schematic diagram of the ionic conductivity of Examples 1-11 of the present invention at 80 °C

[0103] Figure 5 Schematic diagram of the ionic conductivity of Comparative Examples 1-4 at 80 °C.

[0104] Figure 6 Schematic diagram of the remaining rate of ionic conductivity of Examples 1-11 of the present invention after treatment in 1M KOH at 80 °C for 2000 h.

[0105] Figure 7 Schematic diagram of the remaining rate of ionic conductivity of Comparative Examples 1-4 after treatment in 1M KOH at 80 °C for 2000 h.

[0106] Figure 8 Schematic diagram of the specific structure of the MEA electrolytic cell.

[0107] Figure 9 Test results of alkaline electrolyzed water of Examples 1-11 of the present invention (the highest current density corresponding to a cell voltage of 2 V at 1M KOH and 80 °C).

[0108] Figure 10 Test results of alkaline electrolyzed water of Comparative Examples 1-4 of the present invention (the highest current density corresponding to a cell voltage of 2 V at 1M KOH and 80 °C).

[0109] Figure 11 Schematic diagram of the specific structure of the Flow cell electrolytic cell.

[0110] Figure 12 Experimental results of Examples 1 to 4 of the present invention as the anion exchange membrane of the carbon dioxide reduction Flow cell electrolytic cell (cell voltage comparison at a current density of 500 mA cm -2 ).

[0111] Figure 13 Experimental results of Comparative Examples 1 to 4 of the present invention as the anion exchange membrane of the carbon dioxide reduction Flow cell electrolytic cell (cell voltage comparison at a current density of 500 mA cm -2 ).

[0112] Figure 14It is the NMR chart of the quinine-based quaternary ammonium salt intermediate obtained in Example 13. Detailed implementation manners

[0113] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention belong to the scope of protection of the present invention.

[0114] Those skilled in the art should understand that in the disclosure of the present invention, the orientation or positional relationships indicated by the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc. are based on the orientation or positional relationships shown in the drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation. Therefore, the above terms should not be construed as limiting the present invention.

[0115] It can be understood that the term "one" should be understood as "at least one" or "one or more". That is, in one embodiment, the number of an element can be one, and in other embodiments, the number of the element can be multiple. The term "one" should not be construed as limiting the quantity.

[0116] For those embodiments where specific experimental steps or conditions are not indicated, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments whose manufacturers are not indicated, they are all conventional reagent products that can be obtained through commercial purchase.

[0117] In order to verify the feasibility and performance of the cationic polymer based on polyaryl isatin in this solution, the present inventor first designed the following experiments:

[0118] I. Embodiment design:

[0119] 1.1 Preparation of isatin monomers substituted with para-piperidine tertiary ammonium salt structural units:

[0120] After weighing 13.59 mmol of isatin, 5 mL of DMF was added to dissolve and disperse the reactants. Subsequently, 13.59 mmol of NaH was added under the condition of 0 °C and stirred for 30 minutes. Finally, 13.59 mmol of tert-butyl 4-(bromomethyl)piperidine-1-carboxylate was added and the reaction was continued with stirring for 6 h, during which the temperature was allowed to rise to room temperature. Monitored by TLC, after the reaction was completed, the reaction solution was diluted with dichloromethane, extracted with distilled water, the filtrate was dried over anhydrous sodium sulfate after filtration, and the crude product was obtained after concentration. The crude product was quickly passed through a short silica gel column and recrystallized from dichloromethane to obtain the pure product. The intermediate was dried to obtain the isatin monomer substituted with the para-piperidine quaternary ammonium salt structural unit, and the yield was 90%. Adding an appropriate amount of trifluoroacetic acid and 3 mL of dichloromethane, stirring at room temperature can obtain the para-piperidine quaternary ammonium salt structural unit with the Boc protecting group removed, which can be directly used for the next superacid-catalyzed polymerization.

[0121] The specific reaction equation is as follows:

[0122]

[0123] Preparation of cationic polymer:

[0124] Example 1:

[0125]

[0126] 1) Weigh 7.26 mmol of biphenyl, then add 8.71 mmol of the above-mentioned isatin monomer substituted with the para-piperidine quaternary ammonium salt structural unit. Subsequently, 5 mL of dichloromethane was added to dissolve and disperse the reactants. 0.8 mL of trifluoroacetic acid and 5 mL of trifluoromethanesulfonic acid were added under the condition of 0 °C. After reacting for 10 hours, the viscous product was poured into 1 M (mol / L) K2CO3 solution, soaked at room temperature for 24 hours, and then filtered to obtain a white solid product. After washing thoroughly with deionized water and drying, the intermediate polymer was obtained, and the yield was 90%;

[0127] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide and react at room temperature for 12 hours. Subsequently, the temperature was raised to 60 °C and reacted for 12 hours. The reaction product was poured into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to obtain a white precipitate. Subsequently, it was washed three times with ethyl acetate, washed with water and dried to obtain the anion exchange polymer with the anion of I - The yield was 92%.

[0128] 3) Film formation and ion exchange: Weigh 120 mg of the above anion-exchange polymer, add 5 mL of dimethyl sulfoxide, and after complete dissolution, pour it into a glass petri dish with a diameter of 6 cm. Dry it to form a film at 120 °C, peel the film from the glass, and soak the anion-exchange membrane in 1 M KOH solution for ion exchange at 80 °C for 12 hours to obtain an alkaline membrane with OH - as the anion. Use a nuclear magnetic resonance spectrometer of model Bruker AVANCE NEO (500 MHz) to characterize and analyze the finally obtained anion-exchange polymer. The 1H NMR spectrum is as shown in Figure 1 .

[0129] Example 2

[0130]

[0131] 1) Weigh 8.68 mmol of biphenyl into a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of the above indigo monomer substituted with a para-piperidinium quaternary ammonium salt structural unit. Subsequently, add 6 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak it at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 86%.

[0132] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion-exchange polymer with I- as the anion, and the yield is 97%.

[0133] 3) Film formation and ion exchange: Weigh 120 mg of the above anion-exchange polymer, add 5 mL of dimethyl sulfoxide, and after complete dissolution, pour it into a glass petri dish with a diameter of 6 cm. Dry it to form a film at 120 °C, peel the film from the glass. Soak the anion-exchange membrane in 1 M KOH solution for ion exchange at 80 °C for 12 hours to obtain an anion-exchange membrane with OH - as the anion.

[0134] Example 3:

[0135]

[0136] 1) Weigh 8.68 mmol of biphenyl, add 0.12 mmol of o - terphenyl, then add 8.68 mmol of the above - mentioned isatin monomer substituted with a para - piperidine quaternary ammonium salt structural unit. Subsequently, add 8.8 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K₂CO₃ solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 91%.

[0137] 2) Quaternization reaction: Weigh 1.0 g of the above - mentioned intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to obtain a precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion - exchange polymer with an anion of I⁻, and the yield is 95%.

[0138] 3) Film - forming and ion - exchange: Weigh 120 mg of the above - mentioned anion - exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion - exchange membrane in 1 M KOH solution and perform ion - exchange at 80 °C for 12 hours to obtain an anion - exchange membrane with an anion of OH - ⁻.

[0139] Example 4:

[0140]

[0141] 1) Weigh 7.00 mmol of biphenyl, add 1.86 mmol of N - vinylcarbazole, then add 9.00 mmol of the isatin monomer substituted with a para - piperidine quaternary ammonium salt structural unit. Subsequently, add 8.8 mL of dichloromethane to dissolve and disperse the reactants. At 0 °C

[0142] add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid and react for 6 hours. Pour the viscous product into 1 M (mol / L)

[0143] K₂CO₃ solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 91%.

[0144] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1), immediately obtain a precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion-exchange polymer with an anion of I-, and the yield is 97%.

[0145] 3) Film formation and ion exchange: Weigh 120 mg of the above anion-exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion-exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion-exchange membrane with an anion of OH - -.

[0146] Example 5:

[0147]

[0148] 1) Weigh 7.00 mmol of biphenyl, add 1.86 mmol of N-vinylcarbazole, then add 9.00 mmol of isatin monomer substituted with a para-piperidine quaternary ammonium salt structural unit, and then add 8.8 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L)

[0149] K2CO3 solution, soak it at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and dry it to obtain an intermediate polymer, and the yield is 92%.

[0150] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 0.4 mL of methyl iodide and 430 mg of 1,3-propanesultone, and react at 60 °C for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to obtain a precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion-exchange polymer with an anion of I - -, and the yield is 95%.

[0151] 3) Film formation and ion exchange: Weigh 120 mg of the above anion-exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion-exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion-exchange membrane with an anion of OH -Anion exchange membrane.

[0152] Example 6:

[0153]

[0154] 1) Weigh 8.68 mmol of biphenyl in a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of the N-H position corresponding amine-substituted isatin intermediate (for the preparation of this intermediate, refer to the isatin monomer substituted with the para-piperidine quaternary ammonium salt structural unit), and then add 6 mL of dichloromethane to dissolve and disperse the reactants.

[0155] Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 89%.

[0156] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with an anion of I-, and the yield is 98%.

[0157] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it to form a film at 120 °C, and peel the film off the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain a basic membrane with an anion of OH -

[0158] Example 7:

[0159]

[0160] ​1) Weigh 8.68 mmol of biphenyl into a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of the N-H position corresponding amine-substituted isatin intermediate (for the preparation of this intermediate, refer to the isatin monomer substituted with a para-piperidine quaternary ammonium salt structural unit). Subsequently, add 6 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 86%.

[0161] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with an anion of I-, and the yield is 95%.

[0162] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion exchange membrane with an anion of OH - -.

[0163] 1.2 Preparation of isatin monomer substituted with a meta-piperidine ammonium salt structural unit:

[0164] Weigh 13.59 mmol of isatin and add 5 mL of DMF to dissolve and disperse the reactants. Then add 13.59 mmol of NaH and stir at 0 °C for 30 minutes. Finally, add 13.59 mmol of tert-butyl 3-(bromomethyl)piperidine-1-carboxylate and continue to stir and react for 6 h, allowing the temperature to rise back to room temperature during this period. After monitoring by TLC, when the reaction is completed, dilute the reaction solution with dichloromethane, extract it with distilled water, filter, dry the filtrate with anhydrous sodium sulfate, concentrate to obtain a crude product, quickly pass the crude product through a short silica gel column once, and recrystallize it with dichloromethane to obtain a pure product. Dry the intermediate to obtain an isatin monomer substituted with a meta-piperidine quaternary ammonium salt structural unit with a yield of 93%. Add an appropriate amount of trifluoroacetic acid and 3 mL of dichloromethane, stir at room temperature to obtain the para-piperidine quaternary ammonium salt structural unit with the Boc protecting group removed, which can be directly used for the next superacid-catalyzed polymerization.

[0165] The specific reaction equations are as follows:

[0166]

[0167] Example 8

[0168]

[0169] 1) Weigh 8.68 mmol of biphenyl into a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of the above-mentioned meta-piperidinium ammonium salt structural unit. Subsequently, add 6 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 88%.

[0170] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with an anion of I− with a yield of 96%.

[0171] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion exchange membrane with an anion of OH - −

[0172] 1.3 Preparation of isatin monomers substituted with para-piperidine tertiary amine spirocyclic structural units:

[0173] 8.1 mL of 1,5-dibromopentane was added to a 100 mL acetonitrile solution of 7.74 g of 4-piperidinoethanol and 9 g of potassium carbonate. The mixture was refluxed for 24 h, and then acetonitrile was removed using a rotary evaporator under vacuum. The remaining solid mixture was washed with cold acetonitrile and dried, and then transferred to a round-bottom flask containing 42 mL of hydrobromic acid solution (48 wt%). After stirring at 110 °C for 33 h, the volatile portion of the solution was evaporated under reduced pressure to obtain a semi-dry product. It was washed with cold acetone and dried to remove residual acetonitrile, then the resulting product was dissolved in dichloromethane, and inorganic salts were removed by filtration. Subsequently, it was dried by rotary evaporation to obtain a crude solid product, and finally the obtained solid residue was washed with ether and dried to obtain light brown 3-(2-bromoethyl)-6-azaspiro[5.5]undecane-6-ammonium bromide.

[0174] After weighing 13.59 mmol of isatin, 5 mL of DMF was added to dissolve and disperse the reactants. Subsequently, 13.59 mmol of NaH was added under the condition of 0 °C and stirred for 30 minutes. Finally, 13.59 mmol of 3-(2-bromoethyl)-6-azaspiro[5.5]undecane-6-ammonium bromide was added and the reaction was continued with stirring for 6 h, during which the temperature was allowed to rise to room temperature. Monitored by TLC, after the reaction was completed, the reaction solution was diluted with dichloromethane, extracted with distilled water, the filtrate was dried over anhydrous sodium sulfate after filtration, concentrated to obtain a crude product, recrystallized from dichloromethane to obtain a pure product, and the intermediate was dried to obtain an isatin monomer substituted with a meta-piperidinium quaternary ammonium salt structural unit, with a yield of 92%.

[0175] The specific reaction equation is as follows:

[0176]

[0177] Example 9:

[0178]

[0179] 1) 8.68 mmol of biphenyl was weighed into a 100 mL flask, 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene were added, and then 8.68 mmol of isatin intermediate substituted with spirocyclic amine at the N-H position was added. Subsequently, 6 mL of dichloromethane was added to dissolve and disperse the reactants. 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid were added under the condition of 0 °C, and the reaction was carried out for 6 h. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, soaked at room temperature for 24 h, and the white solid product was obtained by filtration. After being washed thoroughly with deionized water and dried, an intermediate polymer was obtained with a yield of 92%.

[0180] 2) Quaternization Reaction: 1.0 g of the intermediate polymer was weighed, and 20 mL of dimethyl sulfoxide was added, followed by 1.0 mL of iodomethane. The reaction was allowed to proceed at room temperature for 12 hours, and then the temperature was raised to 60°C and allowed to react for 12 hours. The reaction product was poured into an ether solvent containing ethanol (the volume ratio of ether to ethanol was 6:1), resulting in a precipitate. The precipitate was then washed three times with ethyl acetate, then washed with water, and dried to obtain an anion exchange polymer with an I- anion in a yield of 93%.

[0181] 3) Membrane formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, dissolve it completely, pour it into a glass petri dish with a diameter of 6 cm, dry it at 120°C to form a membrane, and peel the membrane from the glass.

[0182] The membrane was immersed in 1M KOH solution and ion exchange was carried out at 80℃ for 12 hours to obtain anion OH - 4. Preparation of indigo monomer substituted with meta-piperidine tertiary amine spirocyclic structural unit:

[0183] 8.1 mL of 1,5-dibromopentane was added to a solution of 7.74 g of 3-piperidineethanol and 9 g of potassium carbonate in 100 mL of acetonitrile.

[0184] The mixture was refluxed for 24 h and then acetonitrile was removed using a rotary evaporator under vacuum. The remaining solid mixture was washed with cold acetonitrile and dried, and then transferred to a round-bottom flask containing 42 mL of hydrogen bromide solution (48 wt %). After stirring at 110 ° C for 33 h, the volatile portion in the solution was evaporated under reduced pressure to obtain a semi-dried product. The product was washed with cold acetone and dried to remove residual acetonitrile, and then dissolved in dichloromethane and filtered to remove inorganic salts. A rotary evaporator was then used to dry the crude solid product, and the solid residue was finally washed with ether and dried to obtain a meta-piperidine tertiary amine spirocyclic side chain cationic intermediate.

[0185] 13.59 mmol of isatin was weighed and 5 mL of DMF was added to dissolve the reactants. Subsequently, 13.59 mmol of NaH was added and stirred at 0°C for 30 minutes. Finally, 13.59 mmol of a meta-piperidinyl tertiary amine spirocyclic side chain cationic intermediate was added and the reaction was stirred for 6 hours, during which time the temperature was allowed to return to room temperature. After completion of the reaction, as monitored by TLC, the reaction solution was diluted with dichloromethane and extracted with distilled water. The filtrate was filtered and dried over anhydrous sodium sulfate. The crude product was concentrated and recrystallized from dichloromethane to obtain the pure product. The intermediate was dried to obtain the isatin monomer substituted with a meta-piperidinyl tertiary ammonium salt structural unit in a yield of 91%.

[0186] The specific reaction equation is as follows:

[0187]

[0188] Example 10

[0189] 1) Weigh 8.68 mmol of biphenyl into a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of indigo intermediate with meta-spirocyclic amine substituted at the N-H position. Subsequently, add 6 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 90%.

[0190] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1), immediately obtain a precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with an anion of I - with a yield of 91%.

[0191] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion exchange membrane with an anion of OH -

[0192]

[0193] V. Preparation of indigo monomer substituted with meta-quinuclidine structural unit:

[0194] Weigh 13.59 mmol of indigo and add 5 mL of DMF to dissolve and disperse the reactants. Then add 13.59 mmol of NaH and stir at 0 °C for 30 minutes. Finally, add 13.59 mmol of 3-(bromomethyl)quinoline and continue to stir and react for 6 h, allowing the temperature to rise back to room temperature during this period. After monitoring by TLC, after the reaction is completed, dilute the reaction solution with dichloromethane, extract it with distilled water, filter, dry the filtrate with anhydrous sodium sulfate, concentrate to obtain a crude product, recrystallize with dichloromethane to obtain a pure product, and dry the intermediate to obtain an indigo monomer substituted with meta-quinuclidinium salt structural unit with a yield of 89%.

[0195] ​The specific reaction equations are as follows:

[0196]

[0197] Example 11:

[0198]

[0199] 1) Weigh 8.68 mmol of biphenyl into a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of indigo intermediate with quinuclidine substituted at the N-H position. Subsequently, add 6 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 93%.

[0200] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with I- as the anion, with a yield of 95%.

[0201] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion exchange membrane with OH - as the anion.

[0202] VI. Preparation of indigo monomers substituted with para-quinuclidine structural units:

[0203] Example 12:

[0204]

[0205] 1) Weigh 8.68 mmol of biphenyl into a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, then add 8.68 mmol of the isatin intermediate modified with p-quinuclidinyl at the N-H position. Subsequently, add 6 mL of dichloromethane to dissolve and disperse the reactants. Add 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid at 0 °C and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain the intermediate polymer with a yield of 90%.

[0206] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with I- as the anion, and the yield is 91%.

[0207] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain an anion exchange membrane with OH - as the anion.

[0208] VII. Preparation of a polyaryl isatin cationic polymer modified with quinine quaternary ammonium salt:

[0209] Example 13:

[0210] 1) Preparation of the quinine-based quaternary ammonium salt intermediate

[0211]

[0212] Dissolve quinuclidin-4-ylmethanol (1.41 g, 10 mmol, 1 equiv) in absolute ethanol (30 mL) and place it in a round-bottom flask. Cool the solution to 0 °C using an ice bath, and then add methyl iodide (1.25 mL, 20 mmol, 2 equiv) dropwise. After removing the ice bath, stir the reaction mixture at room temperature overnight. Next, cool the mixture to 0 °C for about 10 min, and filter to collect the white intermediate. Wash the white intermediate with cold ethanol and dry it under vacuum. Subsequently, add the intermediate (2.83 g, 10 mmol) and aqHBr (48 wt%, 25 mL) to a round-bottom flask, and stir the solution at 110 °C for 2 days. After that, remove some of the solvent by distillation under reduced pressure, wash the final product with cold acetone and dry it under vacuum to obtain the quinuclidinium salt intermediate. The NMR spectrum of the quinuclidinium salt intermediate is as shown in Figure 14 shown.

[0213] 2) Preparation of polyaryl isatin cationic polymer modified with quinuclidinium salt

[0214]

[0215] Dissolve 11 mmol of isatin and 10 mmol of biphenyl in 10 mL of dichloromethane. Add a mixed solution of 17 mL of trifluoroacetic acid and trifluoromethanesulfonic acid (the molar ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:5) dropwise to the reaction system. After the addition is complete, stir the reaction for 5 h. After the reaction is completed, precipitate the viscous reaction solution in methanol, wash it several times with K2CO3 solution, wash it with water until neutral, filter, and dry it under vacuum (temperature is 60 °C, time is 24 h) to obtain polyisatin biphenyl polymer; dry the obtained polymer under vacuum at 60 °C for 24 h. Then carry out the grafting of quinuclidinium salt. Dissolve 1 mmol of polyisatin biphenyl polymer in DMF at 60 °C, then cool it to 0 °C in an ice bath, slowly add 1.5 mmol of NaH, then transfer it to room temperature, stir for 1 h, then add 1.5 mmol of the quinuclidinium salt intermediate prepared in 1) above, then heat up to 60 °C, stir the reaction for 12 h, after cooling, pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, and then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with an anion of I - and a yield of 92%.

[0216] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it to form a film at 120 °C, and peel the film off the glass. Immerse the anion exchange membrane in 1 M KOH solution and carry out ion exchange at 80 °C for 12 hours to obtain an anion exchange membrane with an anion of OH - ​

[0217] II. Design Comparative Examples:

[0218] Comparative Example 1:

[0219] An anion exchange membrane based on a cationic polymer with a biphenyl group is provided, and the preparation method is as follows:

[0220]

[0221] 1) Weigh 19.06 mmol of biphenyl, then add 19.06 mmol of N-methyl-4-piperidone, and then add 5 mL of dichloromethane to dissolve and disperse the reactants. Add 0.8 mL of trifluoroacetic acid and 5 mL of trifluoromethanesulfonic acid under the condition of 0 °C, and react for 6 hours. Pour the viscous product into 1 M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash it thoroughly with deionized water and then dry it to obtain an intermediate polymer with a yield of 93%.

[0222] 2) Quaternization reaction: Weigh 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of methyl iodide, react at room temperature for 12 hours, and then raise the temperature to 60 °C and react for 12 hours. Pour the reaction product into a solvent of ether containing ethanol (the volume ratio of ether to ethanol is 6:1) to precipitate a yellow precipitate, then wash it three times with ethyl acetate, wash it with water and dry it to obtain an anion exchange polymer with an anion of I - with a yield of 96%.

[0223] 3) Film formation and ion exchange: Weigh 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, fully dissolve it and pour it into a glass petri dish with a diameter of 6 cm, dry it at 120 °C to form a film, and peel the film from the glass. Immerse the anion exchange membrane in 1 M KOH solution and perform ion exchange at 80 °C for 12 hours to obtain a basic membrane with an anion of OH - .

[0224] Comparative Example 2

[0225] Provide an anion exchange polymer 37-50-grade T, produced by Dioxide materials

[0226] Comparative Example 3

[0227] Provide an anion exchange membrane polymer FAB-PK-130, produced by FuMA-Tech GmbH, Germany

[0228] Comparative Example 4

[0229] Provide an anion exchange polymer Piperion, produced by Ionomer Company in the United States.

[0230] III. Performance Testing

[0231] 3.1 Tensile Strength Test

[0232] Use a tensile testing machine (manufacturer: Shimadzu Corporation, model: AGS-X10KN) to measure the tensile strength of the anion exchange membrane at room temperature.

[0233] 3.2 Ion Conductivity Test

[0234] Use the four-electrode alternating current impedance method to measure the OH - ion conductivity of the fully wet anion exchange membrane in pure water. The specific test parameters are as follows: Take a membrane material with an area of 2*2 cm 2 and a thickness of 25 μm. Use an Autolab 302N electrochemical workstation to conduct an alternating current impedance test within a frequency range of 0.1 Hz to 1000 KHz, and fit the curve to calculate the ion conductivity.

[0235] 3.3 Stability Test

[0236] By immersing the anion exchange membrane in a 1M NaOH solution at 80°C and observing the changes in the hydrogen nuclear magnetic resonance spectrum after 2000 h, measure the remaining rate of anions in the anion exchange membrane.

[0237] From Figure 2-3 it can be seen that the tensile strengths of Examples 1-11 are all higher than those of Comparative Examples 1-4, indicating that the mechanical strength of the anion exchange membrane provided by the present invention has been significantly improved; from Figure 4-7 it can be seen that the ion conductivities of Examples 1-11 are all higher than those of Comparative Examples 1-4, and the remaining rate of ion conductivity of Examples 1-11 is also higher than that of Comparative Examples 1-4. It can be seen that the stability of Examples 1-11 has not been significantly affected.

[0238] The performance test data sheets of the anion exchange membranes finally obtained in Additional Example 12 and Example 13 are shown in Table 1 below:

[0239] Table 1 Performance Test Table of Example 12 and Example 13

[0240]

[0241] Notes: 1) It represents the highest current density corresponding to a cell voltage of 2 V for the anion exchange membrane in 1 M KOH at 80 °C. 2) The remaining rate of ionic conductivity of Examples 12 - 13 of the present invention after treatment in 1 M KOH at 80 °C for 2000 h. Using the anion exchange membranes shown in Examples 12 and 13, the highest current density corresponding to a cell voltage of 2 V in 1 M KOH at 80 °C is superior to that of Comparative Examples 1 - 4, showing excellent performance. Moreover, the anion exchange membranes shown in Examples 12 - 13 also have higher ionic conductivity than Comparative Examples 1 - 4. Not only that, after treatment in 1 M KOH at 80 °C for 2000 h, Examples 12 - 13 of the present invention still have a much higher remaining rate of ionic conductivity than the comparative examples. When these two membranes are used in a CO2 reduction flow cell, at a current density of 500 mA cm -2 the cell voltage is lower than that of Comparative Examples 1 - 4.

[0242] IV. Applications:

[0243] 4.1 Application Example 1: Application of Anion Exchange Membrane in Alkaline Water Electrolysis

[0244] The specific structure of the MEA electrolytic cell is as shown in the appendix Figure 8 as follows: Component ① stainless steel backing plate; Component ② copper electrode; Component ③ graphite electrolyte flow chamber; Component ④ cathode catalyst; Component ⑤ ion transport membrane; Component ⑥ anode catalyst.

[0245] In this test, NiFeOOH / nickel mesh was used as the anode gas diffusion electrode (1.0 cm 2 ), platinum carbon / carbon cloth was used as the cathode gas diffusion electrode (1.0 cm 2 ), and the anion exchange membrane was used as the membrane material. The above membrane electrode assembly (MEA) was assembled into the device, and 100 mL·min -1 of 1 M KOH was continuously introduced into the anode and cathode. The operating temperature of the electrolytic cell was room temperature, 40 °C, 60 °C, and 80 °C respectively, and an Autolab equipped with a 10 A current amplifier was used to test the performance. Before the polarization curve test, it was activated by cyclic voltammetry (CV) for 1 h, the voltage range was 1.0 - 2.6 V, and the scan rate was 200 mV·s -1 . The voltage range used for the polarization curve test was 1.0 - 2.6 V, and the scan rate was 10 mV·s -1 .

[0246] The preparation process of the catalyst is as follows:

[0247] First, the nickel mesh was pretreated. The specific operation was as follows: First, the nickel mesh was etched in a 3 mol / L oxalic acid aqueous solution at 100 °C for 1 hour, rinsed several times with deionized water and absolute ethanol respectively, and dried for standby.

[0248] Preparation of FeNiOOH catalyst: Dissolve 360 mg of Fe(NO)3 in 12 mL of aqueous solution, then place the etched nickel mesh in this solution, and then add 70 mg of Na2S2O3. After reacting for 10 minutes, rinse several times with deionized water and absolute ethanol, and dry for later use. Preparation of platinum-carbon / carbon cloth catalyst: Disperse 60% platinum-carbon powder in ethanol solution, add an appropriate amount of Nafion solution and dissolve it fully, then spray it onto the carbon cloth, and the loading amount is about 1.5 - 2 mg / cm 2 。

[0249] The test results of alkaline electrolyzed water MEA are as Figure 9-10 shown. The results show that using the anion exchange membranes shown in Examples 1 - 11, at a current density of 2 A·cm -2 and a water temperature of 60 °C, using 1 M KOH electrolyte, excellent performance is exhibited, and the cell voltages of Examples 1 - 11 are all less than those of Comparative Examples 1 - 4. In addition, the anion exchange membrane of Example 3 exhibits excellent current density at room temperature, 40 °C, 60 °C, and 80 °C respectively under a cell voltage of 2.0 V, and ranks among the top in the reported alkaline electrolyzed water performance of anion exchange membranes.

[0250] 4.2 Application Example 2: Application of anion exchange membrane in electrochemical reduction of carbon dioxide

[0251] Based on Example 1, the anion exchange membrane prepared in this case is used for CO2RR, that is, CO2 reduction.

[0252] Use Flow cell electrolyzer equipment: The specific structure of the Flow cell electrolyzer is as shown in the appendix Figure 11 : Component ① CO2 gas flow chamber; Component ② Silicone gasket; Component ③ Cathode (CO2RR) catalyst; Component ④ Cathode electrolyte flow chamber; Component ⑤ Ion transport membrane; Component ⑥ Anode catalyst; Component ⑦ Anode electrolyte flow chamber; Component ⑧ Backing plate.

[0253] Use the anion exchange membranes prepared in Examples 1 - 11 and Comparative Examples 1 - 4; 2) Use KOH solution as the electrolyte; 3) The anode and cathode catalysts for water oxidation and CO2 reduction are S(Ni,Fe)OOH and cobalt phthalocyanine (CoPc) respectively; 4) The CO2 flow rate is 20 sccm; 5) The flow rates of the anode electrolyte and the cathode electrolyte are 35 ml / min and 10 ml / min respectively; 6) Reduce the CO2 introduced into the electrolyzer within a certain voltage range. This voltage is set according to actual operation.

[0254] The final measured results are as Figure 12 、 Figure 13As shown, the experimental results of using Examples 1-4 as anion exchange membranes were compared with the experimental results of using Comparative Example-4 as an anion transport membrane. It can be seen that for the cell voltage corresponding to the reduction of CO2 at different current densities, the cell voltage used in Example 3 was the lowest, and its performance was superior to that of Comparative Examples 1-4.

[0255] The present invention is not limited to the above-mentioned optimal implementation manner. Any person can obtain other various forms of products under the inspiration of the present invention. However, no matter what changes are made in its shape or structure, as long as it has the same or similar technical solutions as this application, they all fall within the protection scope of the present invention.

Claims

1. A cationic polymer based on polyaryl isatin, characterized in that, The general structural formula is shown in the following formula (1): Wherein Ar is any one or a combination of two or more of aromatic monomers; R1-R4 in formula (1) are each independently selected from any one of hydrogen, hydroxyl, C1-C10, and halogen, wherein the halogen is any one of F, Cl, Br, and I, and n in formula (1) is an integer from 0 to 20; R5 in formula (1) is at least one of H, the para-piperidine quaternary ammonium salt structural unit shown in formula (2), the para-piperidine tertiary amine spiro ring structural unit shown in formula (3), the meta-piperidine ammonium salt structural unit shown in formula (4), the meta-piperidine tertiary amine spiro ring structural unit shown in formula (5), the meta-quinuclidine structural unit shown in formula (6), and the para-quinuclidine structural unit shown in formula (7), and X in formula (2) to formula (7) is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3:

2. The cationic polymer based on polyaryl isatin according to claim 1, wherein Ar is at least one of the phenyl structure monomers of the following formula (8) to formula (46):

3. The cationic polymer based on polyaryl isatin according to claim 1, characterized in that, The number-average molecular weight of the cationic polymer is 0.1×10⁴ to 1×10⁶, and the molar ratio of the structural unit represented by the formula (1) to at least one of the structural units represented by the formulas (2) to (7) is 0.005 to 100:

1. When X in the structural units represented by the formulas (2) to (7) - is OH - the ion exchange capacity of the cationic polymer is 0.1 mmol / g to 10 mmol / g.

4. The cationic polymer based on polyaryl isatin according to claim 1, characterized in that, The molar ratio of the structural unit shown in formula (1) to at least one of the aromatic structure monomers of formula (8) to formula (46) is 1:0.001 to 0.

67.

5. An intermediate of a cationic polymer based on polyaryl isatin, characterized in that, The structural formula is shown in the following formula (47): Wherein R1-R4 in formula (47) are each independently selected from any one of hydrogen, hydroxyl, C1-C10, and halogen, wherein the halogen is any one of F, Cl, Br, and I, and R5 is the para-piperidine quaternary ammonium salt structural unit shown in formula (48), the meta-piperidine tertiary amine structural unit shown in formula (49), the para-piperidine tertiary amine spiro ring structural unit shown in formula (50), and the meta-piperidine tertiary amine spiro ring structural unit shown in formula (51); 6. A preparation method of an intermediate of a cationic polymer based on polyaryl isatin, characterized in that, An intermediate for preparing the cationic polymer based on polyaryl isatin as claimed in claim 5. When R5 in formula (47) is the para-piperidine tertiary amine spiro ring structural unit shown in formula (50), the 2-(piperidin-4-yl)ethanol is subjected to a ring-forming reaction to obtain a para-piperidine tertiary amine spiro ring precursor, and the para-piperidine tertiary amine spiro ring precursor is reacted with the basic isatin monomer; when R5 in formula (47) is the meta-piperidine tertiary amine spiro ring structural unit shown in formula (51), the 2-(piperidin-3-yl)ethanol is subjected to a ring-forming reaction to obtain a meta-piperidine tertiary amine spiro ring precursor, and the meta-piperidine tertiary amine spiro ring precursor is reacted with the basic isatin monomer, wherein the number of n in the para-piperidine tertiary amine spiro ring structural unit shown in formula (50) and the meta-piperidine tertiary amine spiro ring structural unit shown in formula (51) is related to the carbon chain length of the dibromo- or diiodoalkane added in the ring-forming reaction.

7. The preparation method of a cationic polymer based on polyaryl isatin according to claim 6, characterized in that, When R5 in formula (47) is a para - piperidine quaternary ammonium salt structural unit shown in formula (48), the basic isatin monomer is reacted with bromo - para - piperidine quaternary ammonium salt with a Boc protecting group to obtain a para - piperidine quaternary ammonium salt precursor with a Boc protecting group, and then the Boc protecting group of the para - piperidine quaternary ammonium salt precursor with a Boc protecting group is removed; when R5 in formula (47) is a meta - piperidine tertiary amine structural unit shown in formula (49), the basic isatin monomer is reacted with bromo - meta - piperidine quaternary ammonium salt with a Boc protecting group to obtain a meta - piperidine quaternary ammonium salt precursor with a Boc protecting group, and then the Boc protecting group of the meta - piperidine quaternary ammonium salt precursor with a Boc protecting group is removed; The structural formula of the bromo - para - piperidine quaternary ammonium salt with a Boc protecting group is shown as the following formula (52): The structural formula of the bromo - meta - piperidine quaternary ammonium salt with a Boc protecting group is shown as the following formula (53): In formulas (52) and (53), n is an integer greater than 1.

8. A method for preparing a cationic polymer based on polyaryl isatin according to claim 7, characterized in that, The reaction formula is as follows:

9. A preparation method of a cationic polymer based on polyaryl isatin, characterized in that, It is obtained by carrying out a polymerization reaction between the intermediate of the cationic polymer based on polyaryl isatin shown in formula (47) as claimed in claim 6 and an aromatic structure monomer.

10. The preparation method of the cationic polymer based on polyaryl isatin according to claim 9, characterized in that, The intermediate of the cationic polymer based on polyaryl isatin with the structural formula shown in formula (47) and an aromatic structure monomer are dissolved in a solvent and a catalyst is added for polymerization reaction. The catalyst is any one or at least two combinations of trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, pentafluoropropionic acid, and heptafluorobutyric acid. The solvent is any one or at least two combinations of dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran. The temperature of the polymerization reaction is - 20°C to 80°C, and the time of the polymerization reaction is 0.1 h to 120 h.

11. The preparation method of the cationic polymer based on polyaryl isatin according to claim 9, characterized in that, The polymerization product obtained by carrying out a polymerization reaction between the intermediate of the cationic polymer based on polyaryl isatin shown in formula (47) and an aromatic structure monomer is subjected to an alkylation reaction with an alkylating agent. The alkylating agent includes any one or at least two combinations of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, vinyl iodide, allyl iodide, butenyl iodide, iodomethanol, iodoethanol, iodopropanol, 1,3 - propane sultone, 1,4 - butane sultone, and 2,4 - butane sultone. And the alkylating agent is dissolved in a solvent which is any one or at least two combinations of dimethyl sulfoxide, N,N - dimethylformamide, acetonitrile, N - methylpyrrolidone, dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran. The temperature of the alkylation reaction is 0°C to 60°C, and the time of the alkylation reaction is 0.5 h to 120 h.

12. A preparation method of a cationic polymer based on polyaryl isatin, characterized in that, It is obtained by carrying out a nucleophilic substitution reaction between the structure shown in formula (54) and the structure of formula (55) or the structure of formula (56), where formula (54) is as follows: Formula (55) is as follows: Formula (56) is shown as follows:

13. The preparation method of the cationic polymer based on polyaryl isatin according to claim 12, wherein, React the structure of formula (57) with methyl iodide to obtain an intermediate, and then react the intermediate with hydrogen halide at high temperature to obtain the structure of formula (55); or react the structure of formula (58) with methyl iodide to obtain an intermediate, and then react the intermediate with hydrogen halide at high temperature to obtain the structure of formula (56). The structural formula (57) is as follows: The structural formula (58) is as follows:

14. The preparation method of the cationic polymer based on polyaryl isatin according to claim 12, characterized in that, The reaction formula is as follows:

15. The preparation method of the cationic polymer based on polyaryl isatin according to claim 12, characterized in that, Ar is at least one of the phenyl structural monomers of the following formula (8) to formula (46):

16. An anion exchange membrane, characterized in that, Prepared by dissolving the polyaryl isatin-based cationic polymer according to any one of claims 1 to 4 in a solvent for curing or by processing with a casting film machine; or prepared by dissolving the polyaryl isatin-based cationic polymer according to any one of claims 1 to 4 after blending with other polymer materials in a solution for curing or by processing with a casting film machine.

17. An anion exchange polymer binder, characterized in that, An anion exchange polymer binder solution is prepared by dissolving the polyaryl isatin-based cationic polymer according to any one of claims 1 to 4 in a solvent.

18. Application of a cationic polymer based on polyaryl isatin, characterized in that, The polyaryl isatin-based cationic polymer according to any one of claims 1 to 4 is used in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries; or the anion exchange membrane according to claim 16 is used in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries; or the anion exchange polymer binder according to claim 16 is used in alkaline electrolyzed water, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

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