Polyaryl isatin-based cationic polymer, preparation method therefor, and use thereof

Abstract

Provided in the present invention are a polyaryl isatin-based cationic polymer, a preparation method therefor, and the use thereof. The cationic polymer is a novel polyaryl isatin scaffold synthesized by a Friedel-Crafts polycondensation reaction under the catalysis of a superacid. An isatin structural unit in the cationic polymer possesses a very large molecular volume, which can improve the dimensional stability and mechanical properties of the cationic polymer after film formation; in addition, the N site of a cation grafted onto the cationic polymer is located on the para-position of the isatin structural unit, and such a remote grafting strategy can further improve the alkali resistance stability of the cation in the film. Therefore, the cationic polymer of the present invention exhibits extremely high ionic conductivity and mechanical and chemical stability, and can thus be used as an anion exchange membrane or an anion exchange polymer adhesive for alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction and flow batteries.

Description

Cationic polymer based on polyarylindigo and preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the field of new energy chemical devices, in particular to a cationic polymer based on polyarylindigo and a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the increasing demand for alternative energy worldwide, anion exchange membranes and anion exchange polymer binders have attracted more and more attention from researchers in the application of new energy electrochemical devices. They can be applied in the fields of 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 chlor-alkali industry, heavy metal recovery, water treatment, and hydrometallurgy, and have received very extensive attention. In the fields of alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction, and flow batteries, the stability, electrical 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 and insufficient electrical conductivity and mechanical properties in alkaline environments.

[0003] Cationic polymer materials for anion exchange membranes used in alkaline environments: Chinese patent application CN110903449A provides an indigo aromatic hydrocarbon copolymer, a preparation method and application, which introduces indigo structural units into the copolymer to facilitate crosslinking and functionalization of the polymer. However, the piperidine ammonium salt in this scheme is connected to an electron-withdrawing aromatic hydrocarbon structure at the γ position, which causes the β position of the piperidine ammonium salt to easily undergo Hofmann elimination, reducing stability. For example, Chinese patent application CN11644834A provides a side-chain type anion exchange membrane, which cancels the unstable ether bond in the polymer backbone to make the membrane strongly resistant to alkali, and introduces flexible side chains to form ion channels. However, in this scheme, the alkane chain connected to the indigo is directly connected to N in the ammonium salt, which introduces an additional β-position H in this type of molecular structure, making it more prone to Hofmann elimination, thereby affecting the chemical stability of the ammonium salt. It can be seen that existing technologies have already involved the concept of using indigo structural monomers as the main chain of cationic polymers to improve dimensional stability, but still have the defect of 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 improving their ionic conductivity and chemical stability. SUMMARY

[0004] The application aims to provide a polyarylindigo-based cationic polymer, a preparation method and application thereof, which has excellent mechanical strength, high ion conductivity and high chemical stability, and can be used as an anion exchange membrane or an anion exchange polymer adhesive in alkaline electrolytic water, alkaline fuel cells, carbon dioxide reduction and flow batteries.

[0005] To achieve the above object, in a first aspect, the technical scheme provides a polyarylindigo-based cationic polymer, a structure general formula is as shown in the following formula (1):

[0006] wherein Ar is any one or more than two combinations of aromatic monomers;

[0007] R1-R4 in formula (1) are each independently selected from hydrogen, hydroxyl, C1-C10, any one of halogen, wherein halogen is any one of F, Cl, Br and I; R5 in formula (1) is at least one of H, a piperidine tertiary ammonium salt structure unit as shown in formula (2), a piperidine tertiary amine spiro ring structure unit as shown in formula (3), a meta-piperidine ammonium salt structure unit as shown in formula (4), a meta-piperidine tertiary amine spiro ring structure unit as shown in formula (5), a meta-quinuclidine structure unit as shown in formula (6) and a para-quinuclidine structure unit as shown in formula (7), and X in formula (2)-(7) is selected from any one of F, Cl, Br, I, OH, BF4 and HCO3.

[0008] Specifically, in formula (2), R1 and R2 are each independently selected from any one of hydrogen, a substituted or unsubstituted alkyl with 1-10 carbon atoms, a substituted or unsubstituted cycloalkyl with 1-10 carbon atoms, a substituted or unsubstituted alkenyl with 1-10 carbon atoms, a substituted or unsubstituted aryl with 1-10 carbon atoms, R3 is selected from hydrogen or C1-C10 alkyl, and X is selected from any one of F, Cl, Br, I, OH, BF4 and HCO3.

[0009] In formula (3), n is an integer of 0-10, R1 is selected from hydrogen or C1-C10 alkyl, and X is selected from any one of F, Cl, Br, I, OH, BF4 and HCO3.

[0010] In formula (4), R1 and R2 are each independently selected from any one of hydrogen, a substituted or unsubstituted alkyl with 1-10 carbon atoms, a substituted or unsubstituted cycloalkyl with 1-10 carbon atoms, a substituted or unsubstituted alkenyl with 1-10 carbon atoms, a substituted or unsubstituted aryl with 1-10 carbon atoms, and X is selected from any one of F, Cl, Br, I, OH, BF4 and HCO3.

[0011] 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.

[0012] In formula (6), R1 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, and a substituted or unsubstituted aryl group with 1 to 10 carbon atoms, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0013] In formula (7), R1 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, and a substituted or unsubstituted aryl group with 1 to 10 carbon atoms, and X is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3.

[0014] It should be noted that the substituted or unsubstituted alkyl group with 1 to 10 carbon atoms, hydrogen, substituted or unsubstituted cycloalkyl group with 1 to 10 carbon atoms, hydrogen, substituted or unsubstituted alkenyl group with 1 to 10 carbon atoms, hydrogen, and substituted or unsubstituted aryl group with 1 to 10 carbon atoms mentioned in the present solution refer to the alkyl group, cycloalkyl group, alkenyl group, and aryl group with or without a substituent group, and if the substituent group is present, the carbon chain length of the substituent group is 1 to 10.

[0015] It should be noted that from the structural general formula (1), it can be seen that the cationic site in the cation corresponding to R5 is located at the para position or the meta position of the indigo 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 indigo structural monomer through an alkyl group, but are externally connected to the indigo structural monomer, which can effectively reduce the number of β-H, thereby reducing the Hofmann elimination reaction.

[0016] 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.

[0017] In more preferred embodiments, R1and R2in formula (2), R1in formula (3), R1and R2in formula (4), R1in 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, propanesulfonic acid, butanesulfonic acid.

[0018] Further, in some embodiments, Ar is at least one of the phenyl structural monomers of formulae (8) to (46) as follows:

[0019] wherein R1in 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, 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, I;

[0020] n in formula (12) is an integer of 0 to 20;

[0021] R2, R3in 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, 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, I;

[0022] R4in 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, 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, I;

[0023] n in formula (16) is an integer of 1 to 10;

[0024] n in formulae (21) to (23) is an integer of 0 to 8.

[0025] In some embodiments, the polyarylindo-based cationic polymer has a number average molecular weight of 0.1-100 million.

[0026] In some embodiments, the molar ratio of the structural unit represented by formula (1) to at least one of the structural units represented by formula (2) to formula (6) and formula (42) is 0.005-100:1, and when X - is OH - the ion exchange capacity of the indigo-based cationic polymer is 0.1 mmol / g-10 mmol / g.

[0027] In some embodiments, the molar ratio of the structural unit represented by formula (1) to at least one of the structural units represented by formula (8) to formula (45) is 1:0.001-0.67.

[0028] The second aspect, the technical scheme provides a kind of intermediate based on polyarylindo-based cationic polymer, structural formula is as follows formula (47) is shown:

[0029] Wherein R1-R4 in formula (47) is each independently selected from hydrogen, hydroxyl, C1-C10, any one of halogen, wherein halogen is any one of F, Cl, Br, I, R5 is the structural unit of piperidine tertiary amine salt class represented by formula (48), the structural unit of m-piperidine tertiary amine class represented by formula (49), the structural unit of piperidine tertiary amine spirocycle class represented by formula (50), the structural unit of m-piperidine tertiary amine spirocycle class represented by formula (51);

[0030] Wherein n in formula (50) is 0-10 integer, R1 is selected from hydrogen or C1-C10 substituted or unsubstituted alkyl;

[0031] n in formula (51) is 0-10 integer:

[0032] Wherein R1 and R2 in formula (48) are each independently selected from hydrogen or the substituted or unsubstituted alkyl of carbon atom number 1-10, hydrogen or the substituted or unsubstituted cycloalkyl of carbon atom number 1-10, hydrogen or the substituted or unsubstituted alkenyl of carbon atom number 1-10, hydrogen or the substituted or unsubstituted aryl of carbon atom number 1-10.

[0033] R1 in formula (49) is selected from hydrogen or the substituted or unsubstituted alkyl of carbon atom number 1-10, hydrogen or the substituted or unsubstituted cycloalkyl of carbon atom number 1-10, hydrogen or the substituted or unsubstituted alkenyl of carbon atom number 1-10, hydrogen or the substituted or unsubstituted aryl of carbon atom number 1-10.

[0034] It should be noted that when R5in formula (46) is a piperidine tertiary amine spiro ring structure unit shown in formula (49), 2-(piperidin-4-yl)ethanol is subjected to a ring-forming reaction to obtain a piperidine tertiary amine spiro ring precursor, and the piperidine tertiary amine spiro ring precursor is reacted with a basic indigo monomer. When R5in formula (46) is a m-piperidine tertiary amine spiro ring structure unit shown in formula (50), 2-(piperidin-3-yl)ethanol is subjected to a ring-forming reaction to obtain a m-piperidine tertiary amine spiro ring precursor, and the m-piperidine tertiary amine spiro ring precursor is reacted with a basic indigo monomer. The number of n in the piperidine tertiary amine spiro ring structure unit shown in formula (49) and the m-piperidine tertiary amine spiro ring structure unit shown in formula (50) is related to the carbon chain length of the dibromo or diiodo alkane added in the ring-forming reaction.

[0035] Similarly, when R5in formula (47) is a piperidine tertiary amine salt structure unit shown in formula (48), the basic indigo monomer is reacted with a Boc-protected bromo-piperidine tertiary amine salt to obtain a Boc-protected piperidine tertiary amine salt precursor, and the Boc-protected piperidine tertiary amine salt precursor is subjected to a de-Boc protection reaction.

[0036] The structure of the Boc-protected bromo-piperidine tertiary amine salt is shown in the following formula (52):

[0037] When R5in formula (47) is a m-piperidine tertiary amine structure unit shown in formula (49), the basic indigo monomer is reacted with a Boc-protected bromo-m-piperidine tertiary amine salt to obtain a Boc-protected m-piperidine tertiary amine salt precursor, and the Boc-protected m-piperidine tertiary amine salt precursor is subjected to a de-Boc protection reaction.

[0038] The structure of the Boc-protected bromo-m-piperidine tertiary amine salt is shown in the following formula (53):

[0039] In some embodiments, n in formula (52) and (53) is an integer greater than 1.

[0040] In some specific embodiments, the specific reaction is as follows:

[0041] In a third aspect, the present application provides a preparation method of a polyarylindigo-based cationic polymer, characterized in that an intermediate of a polyarylindigo-based cationic polymer shown in formula (47) is subjected to a polymerization reaction with an aromatic structure monomer to obtain.

[0042] In some embodiments, the structure of the aromatic structure monomer is shown in the following formula (59)-(95):

[0043] wherein in formula (62), R1 is any one of substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aryl 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 of 0 to 20; in formula (65), R2 and R3 are each independently selected from any one of substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aryl 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 substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aryl, and 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; in formula (67), n is an integer of 1 to 10; and in formulas (72) to (74), n is an integer of 0 to 8, and R1 and R2 are each independently selected from any one of substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aryl 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.

[0044] It should be noted that the present scheme synthesizes a series of novel cationic polymers of polyarylene-indigo skeleton through a Friedel-Crafts polycondensation reaction catalyzed by a super acid, and the polycondensation reaction is performed in the presence of a solvent and a catalyst, the catalyst includes any one or a combination of at least two of trifluoroacetic acid, methylsulfonic acid, triflic acid, pentafluoropropionic acid, and heptafluorobutyric acid, and the solvent includes any one or a combination of at least two of dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran.

[0045] In some embodiments, the temperature of the polycondensation reaction is -20°C to 80°C, and the time of the polycondensation reaction is 0.1 h to 120 h.

[0046] In addition, it should be noted that the present scheme performs an alkylation reaction on a polymerization product obtained by performing a polymerization reaction on an indigo monomer represented by formula (20) and an aromatic structure monomer, and the alkylation reagent includes any one or a combination of at least two of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, vinyl iodide, propenyl iodide, butenyl iodide, methyl iodide, ethyl iodide, propyl iodide, 1,3-propane sulfonic acid lactone, 1,4-butane sulfonic acid lactone, and 2,4-butane sulfonic acid lactone, and the alkylation reagent is dissolved in any one or a combination of at least two of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N-methyl pyrrolidone, dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran.

[0047] In some embodiments, the temperature of the alkylation reaction is 0°C to 60°C, and the time of the alkylation reaction is 0.5h to 120h.

[0048] In a fourth aspect, the present application provides a method for preparing a cationic polymer based on polyarylide, which comprises subjecting a structure shown in formula (54) to a nucleophilic substitution reaction with a structure shown in formula (55) or a structure shown in formula (56), wherein formula (54) is as follows:

[0049] Formula (55) is as follows:

[0050] Formula (56) is as follows:

[0051] In formula (54), R1-R4 are each independently selected from hydrogen, hydroxyl, C1-C10, any one of halogen, wherein halogen is any one of F, Cl, Br, I;

[0052] In formula (55), R1 is selected from any one of substituted or unsubstituted alkyl with carbon atom number 1-10, hydrogen, or substituted or unsubstituted cycloalkyl with carbon atom number 1-10, hydrogen, or substituted or unsubstituted alkenyl with carbon atom number 1-10, hydrogen, or substituted or unsubstituted aryl with carbon atom number 1-10, and X is halogen, any one of F, Cl, Br, I;

[0053] In formula (56), R1 is selected from any one of substituted or unsubstituted alkyl with carbon atom number 1-10, hydrogen, or substituted or unsubstituted cycloalkyl with carbon atom number 1-10, hydrogen, or substituted or unsubstituted alkenyl with carbon atom number 1-10, hydrogen, or substituted or unsubstituted aryl with carbon atom number 1-10, and X is halogen, any one of F, Cl, Br, I.

[0054] In some embodiments, the structure shown in formula (57) is reacted with methyl iodide to obtain an intermediate, and the intermediate is reacted with hydrogen halide at high temperature to obtain the structure shown in formula (55); or the structure shown in formula (58) is reacted with methyl iodide to obtain an intermediate, and the intermediate is reacted with hydrogen halide at high temperature to obtain the structure shown in formula (56);

[0055] Formula (57) is as follows:

[0056] Formula (58) is as follows:

[0057] R1in formula (57) is selected from any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms;

[0058] R1in formula (58) is selected from any one of a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, hydrogen, or a substituted or unsubstituted aryl group having 1 to 10 carbon atoms.

[0059] In some embodiments, the reaction is as follows:

[0060] In some embodiments, Ar is at least one of the phenyl monomers of formulae (8) to (46) as follows:

[0061] In a fifth aspect, the present application provides an anion exchange membrane, which is prepared by dissolving the polyarylidene-based cationic polymer of the first aspect of the present application in a solution and solidifying or casting a film, or by blending the polyarylidene-based cationic polymer of the first aspect of the present application with other high molecular materials, and then dissolving the blend in a solution and solidifying or casting a film.

[0062] In an alternative embodiment, the high molecular material includes, but is not limited to, other anion exchange polymers, such as polyimidazolium anion exchange polymers, poly-piperidine tertiary amine cationic polymers, and the like, and specific examples can be polyphenyl ether, polytetrafluoroethylene, polyvinyl alcohol, polysulfone, pectin, and the like.

[0063] In an alternative embodiment, the solution used to dissolve the cationic polymer includes any one or a combination of at least two of dimethyl sulfoxide, 1-methyl-2-pyrrolidone, dimethyl formamide, dimethyl acetamide, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, glycerol, or water.

[0064] In an alternative embodiment, the cationic polymer solution is cast or cast onto a substrate and subjected to a drying process.

[0065] In an alternative embodiment, the substrate includes any one or a combination of at least two of a glass plate, a polytetrafluoroethylene plate, a ceramic plate, a steel strip, 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.

[0066] In an alternative embodiment, the drying temperature is one temperature or a plurality of temperature stages ranging from 80 to 280°C.

[0067] In an alternative embodiment, the drying time is from 0.1 to 120 hours.

[0068] In an alternative embodiment, the cationic polymer is placed in a cast film machine to produce a flat film. In some embodiments, the film has a thickness of from 1 to 500 microns.

[0069] In a sixth aspect, the present application provides an anion exchange polymer binder prepared by dissolving the poly-para-phenylenediamine-based cationic polymer of the first aspect of the present application in a solvent.

[0070] In a seventh aspect, the present application provides a method of preparing the anion exchange polymer binder of the fourth aspect of the present application by spraying or dropping the anion exchange polymer solution described above onto a metal-based catalyst or onto a metal-based or carbon-based conductive substrate after blending with a powder catalyst.

[0071] In an alternative embodiment, the substrate comprises a nickel mesh, a nickel fiber felt, a nickel foam, a stainless steel mesh, a stainless steel felt, a stainless steel foam, a titanium mesh, a titanium fiber felt, a titanium foam, a copper mesh, a PTFE-based magnetron sputtered copper, a copper sheet, a carbon paper, a carbon cloth, and the like.

[0072] In an eighth aspect, the present application provides the use of the poly-para-phenylenediamine-based cationic polymer, which can be used in alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

[0073] In a ninth aspect, the present application provides the use of the anion exchange membrane, which can be used in alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

[0074] In a tenth aspect, the present application provides the use of the anion exchange polymer binder, which can be used in alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

[0075] Compared with the prior art, the technical solution has the following characteristics and beneficial effects:

[0076] The cationic polymer based on polyaryl indigo provided in this scheme is a novel polyaryl indigo framework synthesized through Friedel-Crafts polymerization catalyzed by a superacid. It comprises indigo structural units with characteristics such as large volume, torsional resistance, and rigidity. These indigo structural units give the cationic polymer a higher molecular density and a more compact structure, which not only increases the glass transition temperature of the subsequently prepared anion exchange membrane but also enhances the mechanical strength and stability of the cationic polymer, thereby improving its internal dimensional stability and enhancing its mechanical properties. Furthermore, the rigidity and torsional resistance of the indigo structural units enable the cationic polymer to maintain good morphological stability during anion exchange membrane preparation, which helps prevent deformation or distortion of the membrane during use, thus maintaining stable membrane performance.

[0077] Furthermore, the hydrogen bonding between the carbonyl group on the indigo structural unit of the cationic polymer and water molecules, as well as the electrostatic interaction (hydrogen bonding (tertiary amines still have lone pairs of electrons)) between the tertiary N group on the indigo group and water molecules, can regulate the dispersion of water inside the cationic polymer, which helps to construct Grotthuss transport channels and improve ionic conductivity. The N site of the grafted cation on the cationic polymer is located at the para position of the indigo structural unit. This bonding method reduces β hydrogen, thereby avoiding Hoffmann elimination reaction. This long-range grafting strategy can further improve the cationic alkali resistance stability of the membrane.

[0078] Therefore, the cationic polymer of the present invention has extremely excellent mechanical strength and elongation, and exhibits high ionic conductivity and mechanical and chemical stability, and can be used as anion exchange membrane or anion exchange polymer binder in alkaline water electrolysis, alkaline fuel cells, carbon dioxide reduction and flow batteries. Attached Figure Description

[0079] Figure 1 shows the NMR spectrometry of the anion exchange polymer obtained in Example 1 of this invention. 1 H spectrum.

[0080] Figure 2 is a schematic diagram of the mechanical tensile strength of Embodiments 1-11 of the present invention.

[0081] Figure 3 is a schematic diagram of the mechanical tensile strength of comparative examples 1-4.

[0082] Figure 4 is a schematic diagram of the ionic conductivity at 80°C in Examples 1-11 of the present invention.

[0083] Figure 5 is a schematic diagram of the ionic conductivity at 80℃ for Comparative Examples 1-4.

[0084] Figure 6 is a schematic diagram of the residual ionic conductivity of Examples 1-11 of the present invention after treatment at 1M KOH and 80℃ for 2000h.

[0085] Figure 7 is a schematic diagram of the ion conductivity residual rate of Comparative Examples 1-4 after 2000 h of treatment at 1 M KOH, 80°C.

[0086] Figure 8 is a schematic diagram of the specific structure of an MEA electrolytic cell.

[0087] Figure 9 is the test result of the alkaline electrolysis water of Examples 1-11 of the present application (1 M KOH, 80°C, the highest current density corresponding to a 2V cell voltage).

[0088] Figure 10 is the test result of the alkaline electrolysis water of Comparative Examples 1-4 of the present application (1 M KOH, 80°C, the highest current density corresponding to a 2V cell voltage).

[0089] Figure 11 is a schematic diagram of the specific structure of a Flow cell electrolytic cell.

[0090] Figure 12 is the experimental result of Examples 1 to 4 of the present application as anion exchange membranes for carbon dioxide reduction Flow cell electrolytic cells (500 mA cm -2 current density, cell voltage comparison).

[0091] Figure 13 is the experimental result of Comparative Examples 1 to 4 of the present application as anion exchange membranes for carbon dioxide reduction Flow cell electrolytic cells (500 mA cm -2 current density, cell voltage comparison).

[0092] Figure 14 is the nuclear magnetic resonance diagram of the quinuclidinyl quaternary ammonium salt intermediate obtained in Example 13. DETAILED DESCRIPTION

[0093] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments in the present application belong to the scope of protection of the present application.

[0094] Those skilled in the art should understand that in the disclosure of the present application, the terms "longitudinal", "transverse", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, which are only for the convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, therefore the above terms cannot be understood as a limitation of the present application.

[0095] It is to be understood that the terms "one", "said", "the" and "s" used herein are open terms that are used not to limit the number of items, but to mean one or more. It is also to be understood that the term "a" or "an" as used herein when used to modify a singular noun does not exclude the plural noun "the term "at least one" as used herein when used to modify a singular noun does not exclude the plural noun, but rather, means "one or more".

[0096] When specific experimental procedures or conditions are not mentioned in the examples, the procedures or conditions are performed according to the conventional experimental procedures described in the literature in the art. When the manufacturer of a reagent or instrument is not mentioned, the reagent or instrument is a conventional reagent product that can be commercially available.

[0097] To verify the feasibility and performance of the polyarylindigo-based cationic polymer of the present scheme, the present inventors designed the following experiments:

[0098] I. Example design:

[0099] 1.1 Preparation of indigo monomer substituted with piperidine tertiary ammonium salt structural unit:

[0100] After weighing 13.59 mmol of indigo, 5 mL of DMF was added to dissolve and disperse the reactants, followed by the addition of 13.59 mmol of NaH at 0°C for 30 minutes, and finally the addition of 13.59 mmol of 4-(bromomethyl)piperidine-1-carboxylic acid tert-butyl ester for continuous stirring for 6 hours, during which the temperature was allowed to rise to room temperature. After monitoring by TLC, the reaction was completed, the reaction solution was diluted with dichloromethane, extracted with distilled water, filtered, and the filtrate was dried with anhydrous sodium sulfate. The crude product was obtained after concentration, and the crude product was quickly passed through a short silica gel column, recrystallized with dichloromethane to obtain the pure product. The piperidine tertiary ammonium salt structural unit substituted indigo monomer was obtained after drying the intermediate, with a yield of 90%. The addition of an appropriate amount of trifluoroacetic acid, 3 mL of dichloromethane, and stirring at room temperature can obtain the piperidine tertiary ammonium salt structural unit with a Boc protecting group removed, which can be directly used for the next step of superacid catalyzed polymerization.

[0101] The specific reaction equation is shown below:

[0102] Preparation of cationic polymer:

[0103] Example 1:

[0104] 1) Take 7.26 mmol of biphenyl, add 8.71 mmol of the above-mentioned indigo monomer substituted with a piperidinyl tertiary ammonium salt structural unit at the para position, 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 at 0°C, and after 10 hours of reaction, pour the viscous product into a 1M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, and then filter to obtain a white solid product, which is washed with deionized water and dried to obtain an intermediate polymer with a yield of 90%.

[0105] 2) Quaternization reaction: take 1.0 g of the above-mentioned intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of iodomethane, and react at room temperature for 12 hours, then increase the temperature to 60°C and react for 12 hours, pour the reaction product into a solvent containing ethyl ether (volume ratio of ethyl ether to ethanol is 6:1) and ethanol, obtain a white precipitate, then wash with ethyl acetate three times, wash with water, and dry to obtain an anion exchange polymer with an anion of I - , with a yield of 92%.

[0106] 3) Membrane formation and ion exchange: take 120 mg of the above-mentioned anion exchange polymer, add 5 mL of dimethyl sulfoxide, dissolve thoroughly, pour into a glass petri dish with a diameter of 6 cm, dry to form a membrane at 120°C, peel the membrane from the glass, and soak the anion exchange membrane in a 1M KOH solution, ion exchange at 80°C for 12 hours to obtain a basic membrane with an anion of OH - . The final anion exchange polymer is characterized by a nuclear magnetic resonance spectrometer of the Bruker AVANCE NEO (500 MHz) type, and the hydrogen spectrum nuclear magnetic chart is shown in Figure 1.

[0107] Example 2

[0108] 1) Take 8.68 mmol of biphenyl in a 100 mL flask, add 0.044 mmol of triptycene and 0.044 mmol of 9,9'-spirobifluorene, add 8.68 mmol of the above-mentioned indigo monomer substituted with a piperidinyl tertiary ammonium salt structural unit at the para position, then 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 a 1M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain a white solid product, wash with deionized water, and dry to obtain an intermediate polymer with a yield of 86%.

[0109] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was taken in 20 mL of dimethylsulfoxide, followed by the addition of 1.0 mL of iodomethane. The reaction was carried out at room temperature for 12 hours, followed by an increase in temperature to 60 °C for 12 hours. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol is 6:1) to obtain a precipitate, which was then washed with ethyl acetate three times, followed by washing with water and drying to obtain an anion exchange polymer with an anion of I", with a yield of 97%.

[0110] 3) Membrane formation and ion exchange: 120 mg of the above anion exchange polymer was taken in 5 mL of dimethylsulfoxide, which was dissolved thoroughly and poured into a glass petri dish of 6 cm diameter, which was dried to form a membrane at 120 °C. The membrane was peeled off from the glass. The anion exchange membrane was soaked in a 1 M KOH solution and ion exchanged at 80 °C for 12 hours to obtain an anion exchange membrane with an anion of OH - .

[0111] Example 3:

[0112] 1) 8.68 mmol of biphenyl was taken, followed by the addition of 0.12 mmol of o-terphenyl, 8.68 mmol of the above indigoid monomer substituted with a piperidinyl tertiary ammonium salt structural unit at the para position, followed by the addition of 8.8 mL of dichloromethane to dissolve and disperse the reactants. 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid were added at 0 °C and the reaction was carried out for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, which was soaked at room temperature for 24 hours and filtered to obtain a white solid product, which was washed thoroughly with deionized water and dried to obtain an intermediate polymer with a yield of 91%.

[0113] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was taken in 20 mL of dimethylsulfoxide, followed by the addition of 1.0 mL of iodomethane. The reaction was carried out at room temperature for 12 hours, followed by an increase in temperature to 60 °C for 12 hours. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol is 6:1) to obtain a precipitate, which was then washed with ethyl acetate three times, followed by washing with water and drying to obtain an anion exchange polymer with an anion of I", with a yield of 95%.

[0114] 3) Membrane formation and ion exchange: 120 mg of the above anion exchange polymer was taken in 5 mL of dimethylsulfoxide, which was dissolved thoroughly and poured into a glass petri dish of 6 cm diameter, which was dried to form a membrane at 120 °C. The membrane was peeled off from the glass. The anion exchange membrane was soaked in a 1 M KOH solution and ion exchanged at 80 °C for 12 hours to obtain an anion exchange membrane with an anion of OH - .

[0115] Example 4:

[0116] 1) 7.00 mmol of biphenyl, 1.86 mmol of N-vinylcarbazole, 9.00 mmol of p- piperidinium tertiary ammonium salt- substituted indigoid monomer, and 8.8 mL of dichloromethane were weighed and mixed. 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid were added at 0°C and reacted for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, soaked at room temperature for 24 hours, filtered to obtain a white solid product, washed with deionized water, and dried to obtain an intermediate polymer at a yield of 91%.

[0117] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was weighed, 20 mL of dimethyl sulfoxide was added, followed by 1.0 mL of iodomethane, and reacted at room temperature for 12 hours, and then the temperature was increased to 60°C and reacted for 12 hours. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol: 6:1) to immediately obtain a precipitate, which was washed with ethyl acetate three times, washed with water, and dried to obtain an anion-exchange polymer having an anion of I- at a yield of 97%.

[0118] 3) Membrane formation and ion exchange: 120 mg of the above anion-exchange polymer was weighed, 5 mL of dimethyl sulfoxide was added, and dissolved, and then poured into a 6 cm diameter glass petri dish, and dried at 120°C to form a membrane, and the membrane was peeled off from the glass. The anion-exchange membrane was immersed in a 1 M KOH solution, and ion-exchanged at 80°C for 12 hours to obtain an anion-exchange membrane having an anion of OH - .

[0119] Example 5:

[0120] 1) 7.00 mmol of biphenyl, 1.86 mmol of N-vinylcarbazole, 9.00 mmol of p- piperidinium tertiary ammonium salt- substituted indigoid monomer, and 8.8 mL of dichloromethane were weighed and mixed. 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid were added at 0°C and reacted for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, soaked at room temperature for 24 hours, filtered to obtain a white solid product, washed with deionized water, and dried to obtain an intermediate polymer at a yield of 91%.

[0121] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was weighed, 20 mL of dimethyl sulfoxide was added, followed by 1.0 mL of iodomethane, and reacted at room temperature for 12 hours, and then the temperature was increased to 60°C and reacted for 12 hours. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol: 6:1) to immediately obtain a precipitate, which was washed with ethyl acetate three times, washed with water, and dried to obtain an anion-exchange polymer having an anion of I- anion exchange polymer with a yield of 95%.

[0122] 3) Membrane formation and ion exchange: 120 mg of the above anion exchange polymer was weighed, 5 mL of dimethyl sulfoxide was added, and the mixture was thoroughly dissolved and poured into a glass petri dish with a diameter of 6 cm. The mixture was dried at 120°C to form a membrane, and the membrane was peeled off from the glass. The anion exchange membrane was immersed in a 1 M KOH solution, and ion exchanged at 80°C for 12 hours to obtain an anion exchange membrane with OH - anions.

[0123] Example 6:

[0124] 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 8.68 mmol of an indigo intermediate substituted with an amine at the N-H position (for the preparation of the intermediate, refer to the p- piperidinium tertiary ammonium salt- substituted indigo monomer) was added, followed by 6 mL of dichloromethane to dissolve and disperse the reactants. 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid were added at 0°C, and the reaction was performed for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, immersed at room temperature for 24 hours, and filtered to obtain a white solid product, which was washed with deionized water and dried to obtain an intermediate polymer with a yield of 89%.

[0125] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was weighed, 20 mL of dimethyl sulfoxide was added, followed by 1.0 mL of iodomethane, and the reaction was performed at room temperature for 12 hours, followed by increasing the temperature to 60°C for 12 hours. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol was 6:1), and a yellow precipitate was obtained by precipitation, followed by washing with ethyl acetate three times, washing with water, and drying to obtain an anion exchange polymer with I- anions with a yield of 98%.

[0126] 3) Membrane formation and ion exchange: 120 mg of the above anion exchange polymer was weighed, 5 mL of dimethyl sulfoxide was added, and the mixture was thoroughly dissolved and poured into a glass petri dish with a diameter of 6 cm. The mixture was dried at 120°C to form a membrane, and the membrane was peeled off from the glass. The anion exchange membrane was immersed in a 1 M KOH solution, and ion exchanged at 80°C for 12 hours to obtain an anion exchange membrane with OH - anions.

[0127] Example 7:

[0128] 1) Take 8.68 mmol of biphenyl in a 100 mL flask, add triptycene 0.044 mmol and 9,9'-spirobifluorene 0.044 mmol, then add 8.68 mmol of N-H corresponding amine substituted indigo intermediate (for the preparation of this intermediate, refer to the piperidinium salt substituted indigo monomer), then 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 a 1M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, and filter to obtain a white solid product. After washing with deionized water, dry the product to obtain an intermediate polymer with a yield of 86%.

[0129] 2) Quaternization reaction: take 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of iodomethane, and react at room temperature for 12 hours, then increase the temperature to 60°C and react for 12 hours. Pour the reaction product into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol is 6:1), precipitate to obtain a yellow precipitate, then wash with ethyl acetate three times, wash with water and dry to obtain an anion exchange polymer with I- as the anion, with a yield of 95%.

[0130] 3) Film formation and ion exchange: take 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, dissolve thoroughly, then pour into a glass culture dish with a diameter of 6 cm, dry to form a film at 120°C, and peel the film off the glass. Soak the anion exchange film in a 1M KOH solution, ion exchange at 80°C for 12 hours to obtain an anion exchange film with OH - as the anion.

[0131] 1.2 Preparation of meta-piperidinium salt structural unit substituted indigo monomer:

[0132] Take 13.59 mmol of indigo, add 5 mL of DMF to dissolve and disperse the reactants, then add 13.59 mmol of NaH at 0°C and stir for 30 minutes, finally add 13.59 mmol of 3-(bromomethyl)piperidine-1-carboxylic acid tert-butyl ester and continue to stir for 6 hours, allowing the temperature to rise to room temperature during the reaction. Monitor by TLC, after the reaction is complete, dilute the reaction liquid with dichloromethane, extract with distilled water, dry the filtrate with anhydrous sodium sulfate, concentrate to obtain the crude product, pass the crude product quickly through a short silica gel column, recrystallize with dichloromethane to obtain the pure product, and dry the intermediate to obtain the meta-piperidinium salt structural unit substituted indigo monomer with a yield of 93%. Add appropriate amount of trifluoroacetic acid, 3 mL of dichloromethane, and stir at room temperature to obtain the piperidinium salt structural unit with Boc protection group removed, which can be directly used for the next step of superacid catalyzed polymerization.

[0133] The specific reaction equation is shown below:

[0134] 1) Take 8.68mmol of biphenyl in a 100ml flask, add 0.044mmol of triptycene and 0.044mmol of 9,9'-spirobifluorene, then add 8.68mmol of the above-mentioned meta-piperidine ammonium salt structure unit, then add 6ml of dichloromethane to dissolve and disperse the reactants. Add 1.5ml of trifluoroacetic acid and 8.8ml of trifluoromethanesulfonic acid at 0°C, and react for 6 hours. Pour the viscous product into a 1M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, filter to obtain white solid product, wash with deionized water and dry to obtain the intermediate polymer with a yield of 88%.

[0135] 2) Quaternary ammonium reaction: take 1.0g of the above-mentioned intermediate polymer, add 20ml of dimethyl sulfoxide, then add 1.0ml of iodomethane, react at room temperature for 12 hours, then increase the temperature to 60°C and react for 12 hours. Pour the reaction product into a solvent containing ethyl ether (volume ratio of ethyl ether to ethanol is 6:1), precipitate to obtain yellow precipitate, then wash with ethyl acetate three times, wash with water and dry to obtain anion exchange polymer with I- as anion, with a yield of 96%.

[0136] 3) Film formation and ion exchange: take 120mg of the above-mentioned anion exchange polymer, add 5ml of dimethyl sulfoxide, dissolve thoroughly, pour into a glass culture dish with a diameter of 6cm, dry into a film at 120°C, and peel the film from the glass. Soak the anion exchange film in a 1M KOH solution, ion exchange at 80°C for 12 hours to obtain an anion exchange film with OH - as anion.

[0137] 1.3 Preparation of indigo monomer substituted with piperidine tertiary amine spiro structure unit:

[0138] Add 8.1ml of 1,5-dibromopentane to a 100ml acetonitrile solution of 7.74g of 4-piperidinol and 9g of potassium carbonate. The mixture is refluxed for 24h, and then the acetonitrile is removed under vacuum using a rotary evaporator. The remaining solid mixture is washed with cold acetonitrile and dried, then transferred to a round-bottom flask containing 42ml of hydrogen bromide solution (48wt%). After stirring at 110°C for 33h, the volatile part of the solution is evaporated under reduced pressure to obtain a semi-dry product. Wash with cold acetone and dry to remove residual acetonitrile, then dissolve the resulting product in dichloromethane and remove the inorganic salts by filtration. Then spin dry using a rotary evaporator to obtain a crude solid product, and finally wash the resulting solid residue with ether and dry to obtain light brown 3-(2-bromoethyl)-6-azaspiro[5.5]undecane-6-bromide.

[0139] Take 13.59 mmol of indigo, dissolve and disperse the reactants in 5 mL of DMF, then add 13.59 mmol of NaH at 0°C and stir for 30 minutes, and finally add 13.59 mmol of 3-(2-bromoethyl)-6-azaspiro[5.5]undecane-6- ammonium bromide and continue stirring for 6 hours, allowing the temperature to rise to room temperature during this time. Monitor the reaction by TLC, and after the reaction is complete, dilute the reaction solution with dichloromethane, extract with distilled water, filter, dry the filtrate with anhydrous sodium sulfate, concentrate, recrystallize with dichloromethane, and dry the intermediate to obtain the indigo monomer substituted with a meta-piperidine tertiary amine spiro ring structure unit, with a yield of 92%.

[0140] The specific reaction equation is shown below:

[0141] Example 9:

[0142] 1) Take 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 an indigo intermediate substituted with a spiro ring amine at the N-H position, and then 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 a 1M (mol / L) K2CO3 solution, soak at room temperature for 24 hours, and filter to obtain a white solid product, which is washed thoroughly with deionized water and dried to obtain an intermediate polymer, with a yield of 92%.

[0143] 2) Quaternary ammonium reaction: take 1.0 g of the above intermediate polymer, add 20 mL of dimethyl sulfoxide, then add 1.0 mL of iodomethane, and 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 containing ethyl ether and ethanol (volume ratio of ethyl ether to ethanol is 6:1), and immediately obtain a precipitate, then wash three times with ethyl acetate, wash with water, and dry to obtain an anion exchange polymer with an I- anion, with a yield of 93%.

[0144] 3) Film formation and ion exchange: take 120 mg of the above anion exchange polymer, add 5 mL of dimethyl sulfoxide, dissolve thoroughly, pour into a glass petri dish with a diameter of 6 cm, dry to form a film at 120°C, and peel the film from the glass. Soak the anion exchange film in a 1M KOH solution, ion exchange at 80°C for 12 hours, and obtain an anion exchange film with an OH - anion.

[0145] IV. Preparation of an indigo monomer substituted with a meta-piperidine tertiary amine spiro ring structure unit:

[0146] To a solution of 7.74 g of 3-piperidinethanol and 9 g of potassium carbonate in 100 mL of acetonitrile was added 8.1 mL of 1,5-dibromopentane. The mixture was refluxed for 24 h, and then acetonitrile was removed under vacuum using a rotary evaporator. The remaining solid mixture was washed with cold acetonitrile and dried, and then transferred to a round bottom flask containing 42 mL of a hydrogen bromide 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. Washing with cold acetone and drying to remove residual acetonitrile, and then dissolving the resulting product in dichloromethane and removing inorganic salts by filtration. The crude solid product was then spin-dried using a rotary evaporator, and finally the resulting solid residue was washed with diethyl ether and dried to obtain the meta-piperidinyl tertiary amine spirocyclic side chain cationic intermediate.

[0147] To a solution of 7.74 g of 3-piperidinethanol and 9 g of potassium carbonate in 100 mL of acetonitrile was added 8.1 mL of 1,5-dibromopentane. The mixture was refluxed for 24 h, and then acetonitrile was removed under vacuum using a rotary evaporator. The remaining solid mixture was washed with cold acetonitrile and dried, and then transferred to a round bottom flask containing 42 mL of a hydrogen bromide 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. Washing with cold acetone and drying to remove residual acetonitrile, and then dissolving the resulting product in dichloromethane and removing inorganic salts by filtration. The crude solid product was then spin-dried using a rotary evaporator, and finally the resulting solid residue was washed with diethyl ether and dried to obtain the meta-piperidinyl tertiary amine spirocyclic side chain cationic intermediate.

[0148] The specific reaction equation is shown below:

[0149] Example 10

[0150] 1) To a 100 mL flask was added 8.68 mmol of biphenyl, 0.044 mmol of triptycene, 0.044 mmol of 9,9'-spirobifluorene, and 8.68 mmol of the indigo intermediate with the N-H position substituted with a meta-spirocyclic amine, followed by the addition of 6 mL of dichloromethane to dissolve and disperse the reactants. At 0 °C, 1.5 mL of trifluoroacetic acid and 8.8 mL of triflic acid were added, and the reaction was allowed to proceed for 6 h. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, soaked at room temperature for 24 h, and filtered to obtain a white solid product, which was washed with deionized water and dried to obtain the intermediate polymer with a yield of 90%.

[0151] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was added to 20 mL of dimethyl sulfoxide, followed by the addition of 1.0 mL of iodomethane, and the reaction was allowed to proceed at room temperature for 12 h, and then at 60 °C for 12 h. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol was 6:1), and a precipitate was immediately obtained, which was then washed with ethyl acetate three times, washed with water, and dried to obtain the anion I- anion exchange polymer with a yield of 91%.

[0152] 3) Film formation and ion exchange: 120 mg of the above anion exchange polymer was weighed, 5 mL of dimethyl sulfoxide was added, and the reaction was dissolved and poured into a glass petri dish with a diameter of 6 cm. The film was dried at 120°C, and the film was peeled off from the glass. The anion exchange film was immersed in a 1 M KOH solution, and ion exchange was performed at 80°C for 12 hours to obtain an anion exchange membrane with OH - anions.

[0153] V. Preparation of an indigo monomer substituted with a meta-quinuclidine structural unit

[0154] After 13.59 mmol of indigo was weighed, 5 mL of DMF was added to dissolve and disperse the reactants, 13.59 mmol of NaH was then added at 0°C for 30 minutes, and finally 13.59 mmol of 3-(bromomethyl)quinolone was added for continuous stirring for 6 hours, during which the temperature was allowed to rise to room temperature. After the reaction was completed, the reaction solution was diluted with dichloromethane and extracted with distilled water, and the filtrate was dried with anhydrous sodium sulfate after filtration. The crude product was obtained after concentration, and the pure product was obtained by recrystallization with dichloromethane. The meta-quinuclidine camphor salt structural unit-substituted indigo monomer was obtained by drying the intermediate, with a yield of 89%.

[0155] The specific reaction equation is shown below:

[0156] Example 11:

[0157] 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 the indigo intermediate substituted with a quinuclidine 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 at 0°C, and the reaction was performed for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, and the white solid product was obtained by filtration after immersion at room temperature for 24 hours, followed by washing with deionized water and drying, with a yield of 93%.

[0158] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was weighed into a 20 mL dimethyl sulfoxide solution, followed by the addition of 1.0 mL of iodomethane. The reaction was allowed to proceed at room temperature for 12 hours, followed by an increase in temperature to 60 °C for 12 hours. The reaction product was poured into an ethyl ether solution containing ethanol (volume ratio of ethyl ether to ethanol = 6:1) to precipitate a yellow precipitate, which was washed three times with ethyl acetate, followed by washing with water and drying to obtain an anion exchange polymer having an anion of I"with a yield of 95%.

[0159] 3) Film formation and ion exchange: 120 mg of the above anion exchange polymer was weighed into 5 mL of dimethyl sulfoxide, which was thoroughly dissolved and poured into a glass petri dish having a diameter of 6 cm. The film was dried at 120 °C to form a film, which was peeled off from the glass. The anion exchange film was immersed in a 1 M KOH solution and ion exchanged at 80 °C for 12 hours to obtain an anion exchange film having an anion of OH - .

[0160] VI. Preparation of an indigo monomer substituted with a para-quinuclidine structural unit

[0161] Example 12:

[0162] 1) 8.68 mmol of biphenyl was weighed into a 100 mL flask, followed by the addition of triptycene 0.044 mmol and 9,9'-spirobifluorene 0.044 mmol, and 8.68 mmol of an indigo intermediate modified at the N-H site with a para-quinuclidine group, followed by the addition of 6 mL of dichloromethane to dissolve and disperse the reactants. 1.5 mL of trifluoroacetic acid and 8.8 mL of trifluoromethanesulfonic acid were added at 0 °C, and the reaction was allowed to proceed for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, which was immersed at room temperature for 24 hours, and a white solid product was obtained by filtration, which was washed with deionized water and dried to obtain an intermediate polymer with a yield of 90%.

[0163] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was weighed into a 20 mL dimethyl sulfoxide solution, followed by the addition of 1.0 mL of iodomethane. The reaction was allowed to proceed at room temperature for 12 hours, followed by an increase in temperature to 60 °C for 12 hours. The reaction product was poured into an ethyl ether solution containing ethanol (volume ratio of ethyl ether to ethanol = 6:1) to precipitate a yellow precipitate, which was washed three times with ethyl acetate, followed by washing with water and drying to obtain an anion exchange polymer having an anion of I"with a yield of 91%.

[0164] 3) Film formation and ion exchange: 120 mg of the above anion exchange polymer was weighed into 5 mL of dimethyl sulfoxide, which was thoroughly dissolved and poured into a glass petri dish having a diameter of 6 cm. The film was dried at 120 °C to form a film, which was peeled off from the glass. The anion exchange film was immersed in a 1 M KOH solution and ion exchanged at 80 °C for 12 hours to obtain an anion exchange film having an anion of OH- anion exchange membrane.

[0165] VII. Preparation of polyarylide cationic polymer modified with quinuclidinium quaternary salt:

[0166] Example 13:

[0167] 1) Preparation of quinuclidinium quaternary salt intermediate

[0168] Quinuclidine-4-methanol (1.41 g, 10 mmol, 1 eq) was dissolved in anhydrous ethanol (30 mL) in a round bottom flask. The solution was cooled to 0 °C using an ice bath, then iodomethane (1.25 mL, 20 mmol, 2 eq) was added dropwise. After removing the ice bath, the reaction mixture was stirred at room temperature overnight. Next, the mixture was cooled to 0 °C for about 10 min, and the white intermediate was collected by filtration. The white intermediate was washed with cold ethanol and dried under vacuum. Subsequently, the intermediate (2.83 g, 10 mmol) and aq HBr (48 wt%, 25 mL) were added to a round bottom flask, and the solution was stirred at 110 °C for 2 days. After that, the partial solvent was removed by distillation under reduced pressure, and the final product was washed with cold acetone and dried under vacuum to obtain the quinuclidinium quaternary salt intermediate. The NMR chart of the quinuclidinium quaternary salt intermediate is shown in FIG. 14.

[0169] 2) Preparation of polyarylide cationic polymer modified with quinuclidinium quaternary salt

[0170] Dissolve 11 mmol of indigo and 10 mmol of biphenyl in 10 mL of dichloromethane, and add a mixed solution of 17 mL of trifluoroacetic acid and trifluoromethanesulfonic acid (molar ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:5) dropwise to the reaction system. After the dropwise addition is completed, stir the reaction for 5 h. After the reaction is completed, precipitate the viscous reaction liquid in methanol, wash with K2CO3 solution multiple times, wash with water until neutral, filter, and dry under vacuum (temperature is 60 °C, time is 24 h) to obtain a polyindigo biphenyl polymer. The obtained polymer is vacuum dried at 60 °C for 24 h. Then, grafting of quinuclidinium quaternary salt is performed. Dissolve 1 mmol of the polyindigo biphenyl polymer in DMF at 60 °C, then cool to 0 °C in an ice bath, slowly add 1.5 mmol of NaH, then move to room temperature conditions, stir for 1 h, then add 1.5 mmol of the quinuclidinium quaternary salt intermediate prepared in 1) above, then warm to 60 °C, and stir for 12 h of reaction. After cooling, pour the reaction product into a solvent containing ethyl ether (volume ratio of ethyl ether to ethanol is 6:1), precipitate to obtain a yellow precipitate, then wash with ethyl acetate three times, wash with water, and dry to obtain an anion exchange polymer with an anion of I - ​

[0171] 3) Membrane formation and ion exchange: 120 mg of the above anion exchange polymer was weighed, 5 mL of dimethylsulfoxide was added, and the mixture was thoroughly dissolved. The solution was poured into a glass petri dish with a diameter of 6 cm, and the solvent was evaporated at 120°C to form a film. The film was peeled off the glass. The anion exchange membrane was immersed in 1 M KOH solution, and ion exchange was performed at 80°C for 12 hours to obtain an anion exchange membrane having OH - as an anion.

[0172] II. Design of Comparative Examples

[0173] Comparative Example 1

[0174] An anion exchange membrane based on a biphenyl group was provided, and the membrane was prepared as follows:

[0175] 1) 19.06 mmol of biphenyl was weighed, and 19.06 mmol of N-methyl-4-piperidone was added. Then, 5 mL of dichloromethane was added to dissolve and disperse the reactants. At 0°C, 0.8 mL of trifluoroacetic acid and 5 mL of trifluoromethanesulfonic acid were added, and the mixture was reacted for 6 hours. The viscous product was poured into a 1 M (mol / L) K2CO3 solution, and the mixture was soaked at room temperature for 24 hours. The white solid product was filtered, washed with deionized water, and dried to obtain an intermediate polymer, with a yield of 93%.

[0176] 2) Quaternization reaction: 1.0 g of the above intermediate polymer was weighed, and 20 mL of dimethylsulfoxide was added. Then, 1.0 mL of iodomethane was added, and the mixture was reacted at room temperature for 12 hours. The temperature was then increased to 60°C, and the mixture was reacted for another 12 hours. The reaction product was poured into a solvent containing ethanol in diethyl ether (volume ratio of diethyl ether to ethanol was 6:1), and a yellow precipitate was obtained. The precipitate was washed with ethyl acetate three times, washed with water, and dried to obtain an anion exchange polymer having I - as an anion, with a yield of 96%.

[0177] 3) Membrane formation and ion exchange: 120 mg of the above anion exchange polymer was weighed, 5 mL of dimethylsulfoxide was added, and the mixture was thoroughly dissolved. The solution was poured into a glass petri dish with a diameter of 6 cm, and the solvent was evaporated at 120°C to form a film. The film was peeled off the glass. The anion exchange membrane was immersed in 1 M KOH solution, and ion exchange was performed at 80°C for 12 hours to obtain an anion exchange membrane having OH - as an anion.

[0178] Comparative Example 2

[0179] An anion exchange polymer 37-50-grade T, produced by Dioxide materials company.

[0180] Comparative Example 3

[0181] Provided is an anion exchange membrane polymer FAB-PK-130, produced by FuMA-Tech, Germany.

[0182] Comparative Example 4

[0183] Provided is an anion exchange polymer Piperion, produced by Ionomer, USA.

[0184] III. Performance Test

[0185] 3.1 Tensile strength test

[0186] The tensile strength of the anion exchange membrane at room temperature was measured using a tensile testing machine (manufacturer: Shimadzu, model: AGS-X10KN).

[0187] 3.2 Ion conductivity test

[0188] The OH ion conductivity of the fully wet anion exchange membrane in pure water was measured using the four-electrode alternating current impedance method. - The ion conductivity was measured by taking a film material with an area of 2*2 cm and a thickness of 25 μm, using an Autolab 302N electrochemical workstation, performing an alternating current impedance test at a frequency of 0.1 Hz to 1000 KHz, and fitting the curve to calculate the ion conductivity. 2

[0189] 3.3 Stability test

[0190] The remaining rate of anions in the anion exchange membrane was measured by observing the change in the hydrogen spectrum nuclear magnetic spectrum after 2000 h of immersion of the anion exchange membrane in a 1M NaOH solution at 80°C.

[0191] As can be seen from FIGS. 2-3, the tensile strength of Examples 1-11 is higher than that of Comparative Examples 1-4, indicating that the mechanical strength of the anion exchange membrane provided by the present application is significantly improved; as can be seen from FIGS. 4-7, the ion conductivity of Examples 1-11 is higher than that of Comparative Examples 1-4, and the ion conductivity remaining rate of Examples 1-11 is also higher than that of Comparative Examples 1-4, indicating that the stability of Examples 1-11 is not significantly affected.

[0192] The performance test data of the anion exchange membranes finally obtained in Example 12 and Example 13 are shown in Table 1 below:

[0193] Table 1 Performance test table of Example 12 and Example 13

[0194] ​Notes: 1) represents the highest current density of anion exchange membrane in 1M KOH, 80℃, 2V cell voltage. 2) the ion conductivity residual rate of examples 12-13 of the present application after 2000h treatment in 1M KOH, 80℃. The highest current density of anion exchange membrane shown in examples 12, 13 in 1M KOH, 80℃, 2V cell voltage is superior to that of comparative examples 1-4, showing excellent performance. And the anion exchange membrane shown in examples 12-13 also has higher ion conductivity than comparative examples 1-4. Moreover, after 2000h treatment in 1M KOH, 80℃, examples 12-13 of the present application still have much higher ion conductivity residual rate than comparative examples. When these two membranes are used in CO2 reduction flow cell, at 500mAcm -2 , the cell voltage is lower than that of comparative examples 1-4.

[0195] Four, application:

[0196] 4.1 Application Example 1: Application of anion exchange membrane in alkaline electrolytic water

[0197] The specific structure of MEA electrolytic cell is shown in Figure 8: component ① stainless steel pad; component ② copper electrode; component ③ graphite electrolyte flow chamber; component ④ cathode catalyst; component ⑤ ion transfer membrane; component ⑥ anode catalyst.

[0198] This test uses NiFeOOH / nickel mesh as anode gas diffusion electrode (1.0cm 2 ), platinum carbon / carbon cloth as cathode gas diffusion electrode (1.0cm 2 ), and anion exchange membrane as membrane material. The above-mentioned membrane electrode assembly (MEA) is assembled into the device, and 100mL·min -1 of 1M KOH is continuously supplied to the anode and cathode, the electrolytic cell operating temperature is room temperature, 40℃, 60℃, 80℃ respectively, and Autolab with 10A current amplifier is used to test the performance. Before polarization curve test, cyclic voltammetry (CV) is used for activation for 1h, voltage range is 1.0-2.6V, scan rate: 200mV·s -1 . The voltage range used in polarization curve test is 1.0-2.6V, scan rate: 10mV·s -1 .

[0199] The catalyst preparation process is as follows:

[0200] First, the nickel mesh is pretreated. The specific operation is as follows: first, the nickel mesh is placed in 3mol / L oxalic acid aqueous solution at 100℃ for 1h, and then washed with deionized water and anhydrous ethanol several times, and dried for standby use.

[0201] Preparation of FeNiOOH catalyst: 360 mg Fe(NO)3 was dissolved in 12 mL water solution, then the etched nickel mesh was put into the solution, followed by the addition of 70 mg Na2S2O3, after 10 minutes of reaction, the product was washed with deionized water and anhydrous ethanol for several times, and dried for use. Preparation of platinum / carbon cloth catalyst: 60% platinum / carbon powder was dispersed in an ethanol solution, and an appropriate amount of Nafion solution was added to dissolve it completely, then it was sprayed onto the carbon cloth, and the loading amount was about 1.5-2 mg / cm 2 .

[0202] The test results of alkaline electrolysis water MEA are shown in Figures 9-10. The results show that the anion exchange membranes shown in Examples 1-11 exhibit excellent performance at a current density of 2 A·cm -2 at a water temperature of 60°C, using 1M KOH electrolyte, and the cell voltage of Examples 1-11 is less than that of Comparative Examples 1-4. In addition, the anion exchange membrane of Example 3 exhibits excellent current density at a cell voltage of 2.0V at room temperature, 40°C, 60°C, and 80°C, respectively, and is among the best in the reported performance of anion exchange membrane alkaline electrolysis water.

[0203] 4.2 Application Example 2: Application of Anion Exchange Membrane in Carbon Dioxide Electrochemical Reduction

[0204] Based on Example 1, the anion exchange membrane prepared in this case was used for CO2RR, i.e. CO2 reduction.

[0205] Flow cell electrolysis cell equipment was used: The specific structure of the Flow cell electrolysis cell is shown in 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.

[0206] Anion exchange membranes prepared using Examples 1-11 and Comparative Examples 1-4; 2) KOH solution as electrolyte; 3) S(Ni,Fe)OOH and cobalt phthalocyanine (CoPc) as anode and cathode catalysts for water oxidation and CO2 reduction, respectively; 4) CO2 flow rate of 20 sccm; 5) flow rates of anode electrolyte and cathode electrolyte are 35 ml / min and 10 ml / min, respectively; 6) reduction of CO2 introduced into the electrolysis cell within a certain voltage range. This voltage is set according to actual operation.

[0207] The final measured results are shown in FIG. 12 and FIG. 13. Comparing the experimental results of Examples 1-4 used as an anion exchange membrane and the experimental results of Comparative Example 4 used as an anion transport membrane, it can be seen that the Cell Voltage corresponding to the reduction of CO2 at different current densities is the smallest for Example 3, and the performance is superior to Comparative Examples 1-4.

[0208] The present application is not limited to the above-mentioned best mode, and anyone can derive other various forms of products under the inspiration of the present application, but regardless of any changes in shape or structure, any technical solution having the same or similar technical solutions as the present application falls within the scope of the present application.

Claims

1. A cationic polymer based on polyarylindoamines, characterized in that, The structural general formula is shown in the following formula (1): wherein Ar is any one or more than two combinations of the aromatic monomers; R1-R4 in formula (1) are each independently selected from hydrogen, hydroxyl, C1-C10, any one of halogen, wherein halogen is any one of F, Cl, Br, I, and n in formula (1) is an integer from 0 to 20. R5in formula (1) is at least one of H, a para-piperidinium tertiary amine salt structural unit represented by formula (2), a para-piperidinium tertiary amine spiro ring structural unit represented by formula (3), a meta-piperidinium tertiary amine salt structural unit represented by formula (4), a meta-piperidinium tertiary amine spiro ring structural unit represented by formula (5), a meta-quinuclidine structural unit represented by formula (6), and a para-quinuclidine structural unit represented by formula (7), and X in formulas (2) to (7) is selected from any one of F, Cl, Br, I, OH, BF4, and HCO3:

2. The polyarylatine blue-based cationic polymer according to claim 1, characterized in that, Ar is at least one of the phenyl structural monomers of the following formulae (8) to (46):

3. The polyarylatine blue-based cationic polymer according to claim 1, characterized in that, The number average molecular weight of the cationic polymer is 0.1 to 10 million, and the molar ratio of the structural unit represented by formula (1) to at least one of the structural units represented by formulae (2) to (7) is 0.005 to 100: 1, and when X - is OH - , the ion exchange capacity of the cationic polymer is 0.1 to 10 mmol / g.

4. The polyarylatine blue-based cationic polymer 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 structural monomers of formula (8) to formula (46) is 1:0.001 to 0.

67.

5. An intermediate based on a cationic polymer of polyaryl indigo, characterized in that, The structural formula is shown in the following formula (47): wherein R1-R4 in formula (47) are each independently selected from hydrogen, hydroxyl, C1-C10, any one of halogen, wherein halogen is any one of F, Cl, Br, I, and R5 is a para-piperidine tertiary amine salt structural unit represented by formula (48), a meta-piperidine tertiary amine structural unit represented by formula (49), a para-piperidine tertiary amine spiro ring structural unit represented by formula (50), a meta-piperidine tertiary amine spiro ring structural unit represented by formula (51); 6. A process for the preparation of an intermediate of a cationic polymer based on polyarylated indigo, characterized in that, When R5 in formula (47) is a para-piperidine tertiary amine spiro ring structural unit shown in formula (50), the para-piperidine tertiary amine spiro ring precursor is obtained after the ring-forming reaction of 2-(piperidin-4-yl)ethanol, and the para-piperidine tertiary amine spiro ring precursor is reacted with the basic indigo monomer; when R5 in formula (47) is a meta-piperidine tertiary amine spiro ring structural unit shown in formula (51), the meta-piperidine tertiary amine spiro ring precursor is obtained after the ring-forming reaction of 2-(piperidin-3-yl)ethanol, and the meta-piperidine tertiary amine spiro ring precursor is reacted with the basic indigo 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 diiodo alkane added in the ring-forming reaction.

7. A process for the preparation of a cationic polymeric polyarylated indigo derivative according to claim 6, characterized in that When R5 in formula (47) is a para-piperidine tertiary amine salt structural unit shown in formula (48), the para-piperidine tertiary amine salt precursor with a boc protecting group is obtained by reacting the basic indigo monomer with a bromo para-piperidine tertiary amine salt with a Boc protecting group, and the para-piperidine tertiary amine salt precursor with a boc protecting group is subjected to a de-Boc protecting group reaction; when R5 in formula (47) is a meta-piperidine tertiary amine structural unit shown in formula (49), the meta-piperidine tertiary amine salt precursor with a boc protecting group is obtained by reacting the basic indigo monomer with a bromo meta-piperidine tertiary amine salt with a Boc protecting group, and the meta-piperidine tertiary amine salt precursor with a boc protecting group is subjected to a de-Boc protecting group reaction; The structure of the bromo-p-phenylpiperidinium tertiary ammonium salt with a Boc protecting group is shown below as formula (52): The structure of the bromo-m-piperidinium tertiary ammonium salt with a Boc protecting group is shown below as formula (53): wherein n in formula (52) and (53) is an integer greater than 1.

8. The preparation method of the polyarylide cationic polymer according to claim 7, characterized in that, The reaction is as follows:

9. A process for the preparation of a cationic polymer based on polyarylindigo, characterized in that, The intermediate of the polyarylide cationic polymer shown in formula (47) is subjected to a polymerization reaction with the aromatic structural monomer to obtain the polyarylide cationic polymer.

10. The process for the preparation of polyarylatine blue-based cationic polymers according to claim 9, characterized in that, The intermediate of the polyarylide cationic polymer shown in formula (47) is dissolved in a solvent and a catalyst is added for the polymerization reaction, the catalyst is any one or at least two combinations of trifluoroacetic acid, methylsulfonic acid, triflic acid, pentafluoropropionic acid, heptafluorobutyric acid, the solvent is any one or at least two combinations of dichloromethane, chloroform, tetrachloroethane, toluene, tetrahydrofuran, wherein the temperature of the polymerization reaction is -20°C to 80°C, and the time of the polymerization reaction is 0.1h to 120h.

11. The process for the preparation of polyarylatine blue-based cationic polymers according to claim 9, characterized in that, The polymerization product obtained after the polymerization reaction of the intermediate of the cationic polymer based on polyarylindigo represented by formula (47) and an aromatic monomer is subjected to an alkylation reaction with an alkylating agent, including any one or a combination of at least two of methyl iodide, ethyl iodide, propyl iodide, butyl iodide, ethylene iodide, propylene iodide, butylene iodide, methyl iodide, ethyl iodide, propyl iodide, 1,3-propane sulfonic acid lactone, 1,4-butane sulfonic acid lactone, 2,4-butane sulfonic acid lactone, and the alkylating agent is dissolved in any one or a combination of at least two of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, N-methyl pyrrolidone, dichloromethane, chloroform, tetrachloroethane, toluene, and tetrahydrofuran, the alkylation reaction is carried out at a temperature of 0-60°C for 0.5-120 hours.

12. A process for the preparation of a cationic polymer based on polyarylindigo, characterized in that, The structure shown in formula (54) is subjected to a nucleophilic substitution reaction with a structure shown in formula (55) or a structure shown in formula (56) to obtain a structure shown in formula (57), wherein formula (54) is as follows: Formula (55) is as follows: Formula (56) is shown below:

13. The process for the preparation of polyarylatine blue-based cationic polymers according to claim 12, characterized in that, The structure of formula (57) is reacted with methyl iodide to obtain an intermediate, and the intermediate is reacted with hydrogen halide at high temperature to obtain the structure of formula (55); or the structure of formula (58) is reacted with methyl iodide to obtain an intermediate, and the intermediate is reacted with hydrogen halide at high temperature to obtain the structure of formula (56); wherein the structural formula (57) is as follows: wherein the structural formula (58) is as follows:

14. [Amended according to Rule 26 20.05.2025] The process for the preparation of a polyarylated indigo-based cationic polymer according to claim 12, characterized in that, The reaction is as follows:

15. The process for the preparation of polyarylatine blue-based cationic polymers according to claim 12, characterized in that, Ar is at least one of the phenyl structural monomers of the following formulae (8) to (46):

16. An anion exchange membrane, characterized by, The cationic polymer based on polyarylindigo according to any one of claims 1 to 4 is dissolved in a solvent to obtain a solidified or cast film; or the cationic polymer based on polyarylindigo according to any one of claims 1 to 4 is blended with other polymer materials and then dissolved in a solvent to obtain a solidified or cast film.

17. An anion exchange polymeric binder characterized by, An anion exchange polymer adhesive solution is prepared by dissolving the cationic polymer based on polyarylindigo according to any one of claims 1 to 4 in a solvent.

18. Use of a cationic polymer based on polyarylindoamines, characterized in that, The cationic polymer based on polyarylindigo according to any one of claims 1 to 4 is used in alkaline electrolytic water, alkaline fuel cells, carbon dioxide reduction, and flow batteries; or the anion exchange membrane according to claim 16 is used in alkaline electrolytic water, alkaline fuel cells, carbon dioxide reduction, and flow batteries; or the anion exchange polymer adhesive according to claim 16 is used in alkaline electrolytic water, alkaline fuel cells, carbon dioxide reduction, and flow batteries.

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