Steric-hindrance-protected arylimidazole polymer, ionic polymer thereof, ion exchange membrane thereof, and use thereof

Abstract

Disclosed in the present invention are a polymer, an ionic polymer thereof, an ion exchange membrane thereof and the use thereof. Specifically disclosed are a steric-hindrance-protected arylimidazole polymer and an ionic polymer thereof. The polymer of the present invention has good alkaline stability and device stability, and can be applied to the technical fields of alkaline fuel cells, alkaline electrolysis water hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, salt lake lithium extraction, electrodialysis, water treatment, membrane humidification, etc.

Description

A sterically hindered arylimidazolium polymer, its ionic polymer, its ion exchange membrane, and its applications.

[0001] This application claims priority to Chinese Patent Application No. 202411593534X, filed on November 8, 2024. This application also claims priority to Chinese Patent Application No. 2025116117992, filed on November 5, 2025. The full text of the aforementioned Chinese patent applications is incorporated herein by reference. Technical Field

[0002] This invention relates to a sterically hindered aryl imidazole polymer, its ionic polymer, its ion exchange membrane, and its applications. Background Technology

[0003] Fuel cells, water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, acid separation, and lithium extraction from salt lakes all rely on functional polymer thin film materials. The essence of these films lies in their selective permeability to ions. However, such films are still very scarce, especially ion exchange membranes with high stability and high selectivity suitable for strong acid and alkali environments. Ion exchange membranes are composed of polymers containing ionic groups, and their stability is determined by the polymer chain backbone and the ionic groups on the backbone.

[0004] In recent years, researchers have proposed using ether-free carbon chains as the polymer backbone, thus solving the problem of backbone stability. Various quaternary ammonium salt ions have also been developed as anion exchange groups, but most of these quaternary ammonium salt ions exhibit low stability, making them unsuitable for practical applications.

[0005] Fan et al. disclosed a polymer containing an imidazole structure (Nature Communications, 2019, 10:2306; DOI:10.1038 / s41467-019-10292-z), in which the imidazole ring is placed in the main chain of the polymer, resulting in a decrease in device stability.

[0006] In existing technologies, the imidazole cationic functional groups are located in the main chain rather than the side chains. Therefore, once the polymer degrades, the ionic functional groups fail, and the main chain also breaks, leading to a significant decrease in mechanical strength and consequently, insufficient stability of the ion exchange membrane. Therefore, it is essential to explore a novel ion exchange membrane with excellent alkaline stability and device stability. Summary of the Invention

[0007] The technical problem this invention aims to solve is to overcome the shortcomings of existing ion exchange membranes in terms of alkali stability and device stability. To this end, this invention provides a sterically protected arylimidazolium polymer, its ionic polymer, its ion exchange membrane, and its applications. The functional groups in this type of sterically protected arylimidazolium polymer exhibit charge delocalization and large steric hindrance groups, significantly reducing the probability of these functional groups being attacked by hydroxides, thereby further improving the material's stability. The polymer film prepared based on this polymer has the following advantages: large size, thin thickness, high alkali stability, high ionic conductivity, and high device stability, making it suitable for many fields.

[0008] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0009] This invention provides an aryl imidazole polymer I with steric hindrance protection;

[0010] in,

[0011] n is an integer between 1 and 5000;

[0012] A and A' are each independently... 9,9'-spirobisfluorene, tetraphenylethylene, optionally with one or more R a1 Replacement C 6-10 Aryl, -(C 6-10 aryl)-(CR a4 R a5 ) m -(C 6-10 aryl)- or -(C 6-10 (Aryl)-(L) p -(C 6-10 (aryl)-;

[0013] m is an integer from 1 to 6; p is an integer from 1 to 3;

[0014] L is the arbitrary subject of R L Replacement C 6-10 Aryl, of which R L C 6-10 Aryl;

[0015] R a1 Independently for optional use by one or more R a1-1 Replacement C 6-10 Aryl;

[0016] R a2 and R a3 Each is independently H, and optionally by one or more R. a2-1 Replacement C 6-10aryl, optionally with one or more R a2- 2 The substituted 5-10 heteroaryl group, optionally replaced by one or more R a2-3 Replacement C 1-6 Alkyl, optionally with one or more R a2-4 The substituted 3-10 membered cycloalkyl group; wherein the number of heteroatoms in the 5-10 membered heteroaryl group is 1, 2 or 3, and the heteroatoms are selected from one or more of N, O and S;

[0017] R a4 and R a5 Each is independently H, arbitrarily controlled by one or more R a4-1 Replacement C 1-6 Alkyl groups or optionally one or more R a4-2 Replacement C 6-10 Aryl;

[0018] R a1-1 R a2-1 R a2-2 R a2-3 R a2-4 R a4-1 and R a4-2 Each is independently a halogen or C 1-6 alkyl;

[0019] One of B and B' is Another one is X is NR x , O or S, where R x For H or C 1-6 alkyl;

[0020] R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” and R b9” Each is independently N,N,N-trimethylpentanenyl, optionally surrounded by one or more R b1-1 Replacement C 6-10 aryl, optionally with one or more R b1-2The substituted 5-10 heteroaryl group, optionally replaced by one or more R b1-3 Replacement C 1-6 Alkyl, optionally with one or more R b1-4 The substituted 3-10 membered cycloalkyl group, wherein the number of heteroatoms in the 5-10 membered heteroaryl group is 1, 2 or 3, and the heteroatoms are selected from one or more of N, O and S;

[0021] R b10 and R b11 Each is independently H, and optionally by one or more R. b10-1 Replacement C 1-6 Alkyl, optionally with one or more R b10-2 Replacement C 6-10 aryl or optionally aryl by one or more R b10-3 Substituted 3-10 membered cycloalkyl groups;

[0022] Or, R b10 and R b11 Together with the carbon atom it is attached to, it is formed: optionally by one or more R b10-4 Substituted 5-10 membered cycloalkyl groups

[0023] R b1-1 R b1-2 R b1-3 R b1-4 R b10-1 R b10-2 R b10-3 and R b10-4 Each is independently carbonyl, halogen, or C. 1-6 alkyl;

[0024] A and A' are the same or different; B and B' are the same or different.

[0025] In some embodiments, in arylimidazolium polymer I, each individual structural unit They may be the same or different.

[0026] In some implementations, n is 1-2000, preferably 800-1200.

[0027] In some implementations, n is 40-300; preferably 50-200; for example 70-140, or 122.

[0028] In some implementations, X is NR x .

[0029] In some embodiments, the term C in this invention 6-10 The aryl group can be phenyl or naphthyl independently; for example, A, A', L, R.L R a1 R a2 R a3 R a4 R a5 R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” R b10 R b11 and R b10-2 C mentioned in 1-6 alkyl.

[0030] In some embodiments, the term C in this invention 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl; for example, R a2 R a3 R a4 R a5 R a1-1 R a2-1 R a2-2 R a2-3 R a2-4 R a4-1 R a4-2 R x R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” Rb10 R b11 R b1-1 R b1-2 R b1-3 R b1-4 R b10-1 R b10-2 R b10-3 and R b10-4 C mentioned in 1-6 alkyl.

[0031] In some embodiments, the term 5-10 heteroaryl in this invention independently refers to pyrroleyl, furanyl, thiopheneyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidine, pyrazinyl, benzopyrroleyl, benzofuranyl, benzothiopheneyl, benzooxazolyl, benzoisooxazolyl, benzothiazolyl, benzoisothiazolyl, benzopyrazolyl, benzoimidazolyl, benzopyridyl, benzopyrimidine, benzopyrazinyl, thiazothiazolyl, pyridopyridyl, pyridopyrazinyl, or pyridopyrimidineyl; for example, R a2 R a3’ R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” and R b9” The 5-10 aryl compounds mentioned in the text.

[0032] In some embodiments, the term 3-10 membered cycloalkyl in this invention is independently cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; for example, R a2 R a3’ R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 Rb6 R b6’ R b7’ R b7” R b8” and R b9” The 3-10 membered cycloalkyl groups mentioned in the text.

[0033] In some embodiments, the term halogen in this invention refers to F, Cl, Br, or I.

[0034] In some implementations, A and A' are independently -(C 6-10 (Aryl)-(L) p -(C 6-10 Aryl)-.

[0035] In some embodiments, L is phenyl or naphthyl, preferably phenyl.

[0036] In some implementations, the R L It is phenyl or naphthyl; preferably phenyl.

[0037] In some implementations, p is 1 or 2, preferably 1.

[0038] In some implementations, A and A' are each independently...

[0039] In some implementations, A and A' are each independently...

[0040] In some implementations, A and A' are each independently...

[0041] In some implementations, A and A' are each independently...

[0042] In some implementations, A and A' are each independently...

[0043] In some embodiments, the polymer I comprises structural segments. One or more of them.

[0044] In some embodiments, the polymer I comprises structural segments.

[0045] In some implementation schemes, R b3 and R b4 It is a methyl group.

[0046] In some implementation schemes, Rb1 and R b2 It is a methyl group.

[0047] In some implementation schemes, R b5 and R b6 For H.

[0048] In some embodiments, the polymer I comprises structural segments.

[0049] In some implementations, B and B' are each independently...

[0050] In some implementations, B and B' are

[0051] In some embodiments, in arylimidazolium polymer I, structural fragments The molar ratio of the total amount of structural segments A and A' is (0.001-1):1.

[0052] In some embodiments, arylimidazolium polymer I, when containing structural segments At that time, structural fragments Structural fragments The molar ratio between the total amount of structural fragments A and A' is (0.001-1):(0-0.999):1.

[0053] In some embodiments, any structural segment in arylimidazolium polymer I Independently

[0054] In some embodiments, any structural segment in arylimidazolium polymer I The R b10 and R b11 Each of them independently consists of hydrogen, methyl, ethyl, trifluoromethyl, pyridyl, piperidinyl, phenyl, o-tolyl, m-tolyl, p-tolyl, or mesityleliyl.

[0055] In some implementations, A and A' are each independently... B and B' are

[0056] In some implementations, A and A' are each independently... B and B' are

[0057] In some embodiments, polymer I is any of the following compounds:

[0058] In some embodiments, polymer I can be prepared by polymerizing components 1 and 2 via a Friedel-Crafts reaction in the presence of an acid catalyst.

[0059] Component 1 is HAH and H-A'-H, wherein A and A' are as defined above.

[0060] The component 2 is in Each independently The substituents are defined as above, for example, R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” R b10 and R b11 .

[0061] In some implementations, when A and A' are the same, only HAH or only H-A'-H exists; when When they are the same, only one exists. Or only exist

[0062] In some embodiments, in component 1, the HAH and H-A'-H are each independently selected from... One or more of the following;

[0063] In component 2, the Each independently selected One or more of the following, wherein component 2 contains at least one of the following:

[0064] In some embodiments, in component 1, the HAH and H-A'-H are each independently selected from... One or more of them.

[0065] In some embodiments, in component 1, the HAH and H-A'-H are each independently selected from... One or more of them.

[0066] In some embodiments, component 1 is Or component 1 is

[0067] In some embodiments, component 1 is

[0068] In some embodiments, component 1 is

[0069] In some embodiments, component 1 is Among the compounds With compounds The molar ratio is 1:(0.01-10); preferably 1:(0.5-5); for example 1:3.

[0070] In some implementations, component 2 is

[0071] In some embodiments, the acid catalyst may be a Lewis acid, preferably one or more of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin, and more preferably trifluoromethanesulfonic acid.

[0072] In some embodiments, the polymer I can be prepared by the following steps: taking component 1 (e.g.) ) and component 2 (e.g. The polymer I is obtained by a Friedel-Crafts reaction in the presence of a trifluoromethanesulfonic acid catalyst.

[0073] In some embodiments, polymer I can be prepared by the following steps: The polymer I was obtained by a Friedel-Crafts reaction under the conditions of trifluoromethanesulfonic acid.

[0074] In some implementation schemes, The polymer I was obtained by a Friedel-Crafts reaction under the conditions of trifluoromethanesulfonic acid.

[0075] In some implementation schemes, The polymer I was obtained by a Friedel-Crafts reaction under the conditions of trifluoromethanesulfonic acid.

[0076] In some implementation schemes, The polymer I was obtained by a Friedel-Crafts reaction under the conditions of trifluoromethanesulfonic acid.

[0077] In some implementation schemes, The polymer I was obtained by a Friedel-Crafts reaction under the conditions of trifluoromethanesulfonic acid.

[0078] In some implementation schemes, The polymer I was obtained by a Friedel-Crafts reaction under the conditions of trifluoromethanesulfonic acid.

[0079] The Friedel-Crafts reaction conditions are those commonly used in the field.

[0080] In some embodiments, the Friedel-Crafts reaction can be carried out in a solvent, wherein the solvent can be a halocarbon solvent, such as 1,2-dichloroethane.

[0081] In some embodiments, the molar ratio of component 1 to component 2 is 1:(0.8-1.5); preferably 1:(1-1.3), for example 1:1.3.

[0082] In some embodiments, the molar ratio of component 1 to the acid catalyst is 1:(0.5-50); preferably 1:(8-20), more preferably 1:(12-15); for example, 1:13.

[0083] In some embodiments, the Friedel-Crafts reaction is carried out under conventional reaction conditions in the art, preferably at a reaction temperature of 0-40°C; more preferably 0-25°C.

[0084] In some embodiments, the Friedel-Crafts reaction is carried out under conventional reaction conditions in the art, preferably for a reaction time of 0.5-48 h, more preferably 2-8 h, for example 6 h.

[0085] This invention provides a method for preparing polymer I of sterically hindered aryl imidazole as described above, wherein component 1 and component 2 are polymerized by Friedel-Crafts reaction in the presence of an acid catalyst.

[0086] Component 1 is HAH and H-A'-H, wherein A and A' are as defined above.

[0087] The component 2 is in Each independently The substituents are defined as above, for example, R b1 R b1’ R b1” R b2 R b2’ Rb2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” R b10 and R b11 .

[0088] The preparation method and reaction conditions are as described in any of the previous schemes.

[0089] This invention provides an ionic polymer, wherein the N atoms in B and B' of the aforementioned polymer I are ionized to form a structure containing the segment NR. b12 An ionic polymer; wherein one of B and B' is The other is

[0090] The R b12 The methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, isopropyl, isobutyl, cyclopentyl, or cyclohexyl groups are preferred.

[0091] In some embodiments, the ionic polymer can be prepared by reacting the polymer I with a monohalogenated compound R under alkaline or alkaline-free conditions. b12 -X undergoes a substitution reaction to obtain the ionic polymer.

[0092] In some embodiments, the monohalogenated compound R b12 -X is one or more of the following: iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, 2-bromoethylamine, 2-bromoethanol, cyclopropyl iodine, isopropyl iodine, isobutyl iodine, cyclopentyl iodine, cyclohexyl iodine, and (5-bromopentyl)trimethylammonium bromide.

[0093] In some embodiments, the monohalogenated compound R b12 -X represents iodomethane.

[0094] In some embodiments, the ionic polymer contains at least ionized structural segments. One or more of the following; where X is NR x O or S, R x C 1-6 Alkyl; R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b8” R b9” R b5 R b6 R b6’ R b7’ R b7” and R b12 The definition is as described above.

[0095] In some implementations, X is NR x .

[0096] In some embodiments, the ionic polymer contains at least ionized structural segments.

[0097] In some implementation schemes, R b12 Independently, it is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, isopropyl, isobutyl, cyclopentyl, or cyclohexyl.

[0098] In some implementation schemes, R b12 It is a methyl group.

[0099] In some embodiments, the ionic polymer contains at least ionized structural segments.

[0100] In some embodiments, the anion in the ionic polymer can be replaced by other anions; wherein the anion is a conventional anion in the art, preferably selected from F. - Cl - ,Br - I - CO3 2- HCO3 - OH - OTf - (trifluoromethanesulfonate), OTs - (p-Toluenesulfonate), BF4- NO3 - One or more of ClO4 and PF6-, preferably selected from I - Cl - and OH - One or more of the following; best is I - Cl - or OH - .

[0101] In some embodiments, the anion of the ionic polymer is I. - .

[0102] In some embodiments, the anion of the ionic polymer is Cl. - .

[0103] In some embodiments, the anion of the ionic polymer is OH. - .

[0104] In some embodiments, the base is one or more selected from sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

[0105] In some implementations, the alkali is potassium carbonate.

[0106] The reaction conditions for the substitution reaction are conventional reaction conditions in the art.

[0107] In some embodiments, the weight ratio of polymer I to the monohalogenated compound is 1:(1-2); preferably 1:(1-1.5), for example 1:1.368.

[0108] In some embodiments, the weight ratio of polymer I to the monohalogenated compound is 1:(1-1.7); preferably 1:1.55 or 1:1.6.

[0109] In some embodiments, in the substitution reaction, when a base is present, the weight ratio of the polymer I to the base is 1:(0.4-3), preferably 1:(0.6-1.2), for example 1:0.8.

[0110] In some embodiments, during the substitution reaction, when a base is present, the weight ratio of polymer I to the base is 1:0.91 or 1:0.93.

[0111] In some embodiments, the reaction temperature of the substitution reaction is 0-100°C, preferably 25-80°C, for example 70°C.

[0112] In some embodiments, the reaction time of the substitution reaction is 0.5-48 h, preferably 6-24 h, for example 12 h.

[0113] The present invention also provides an ionic polymer membrane, which can be prepared by the following method: dissolving the above-mentioned ionic polymer in a solvent to obtain a polymer solution, and then preparing the above-mentioned polymer solution into the ionic polymer membrane by an automatic film coating machine.

[0114] In some embodiments, the solvent is dimethyl sulfoxide.

[0115] The present invention also provides an application of the above-mentioned ion-modified polymer membrane in alkaline fuel cells, alkaline water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification; preferably, its application in alkaline fuel cells.

[0116] The present invention also provides a polymer intermediate, which is... The definitions of each substituent are as above.

[0117] In some implementations, the polymer intermediate is

[0118] This invention provides an ionized crosslinked polymer, which can be prepared by the following steps: under alkaline or alkaline-free conditions, the above polymer I and a polyhalogenated compound undergo an ionized crosslinking reaction, and then the remaining nitrogen sites of the intermediate polymer undergo a non-crosslinking ionization reaction with a monohalogenated compound to obtain the ionized crosslinked polymer.

[0119] Alternatively, under alkaline or alkaline-free conditions, the above polymer I and the monohalogenated compound undergo a non-crosslinking ionization reaction. After the reaction is complete, the remaining nitrogen sites of the intermediate polymer undergo an ionization crosslinking reaction with the polyhalogenated compound to obtain the ionized crosslinked polymer.

[0120] Alternatively, under alkaline or alkaline-free conditions, the above polymer I is reacted simultaneously with a polyhalogenated compound and a monohalogenated compound, and after the reaction is complete, the ionized crosslinked polymer is obtained.

[0121] In some embodiments, the polyhalogenated compound is selected from... One or more; Y is F, Cl, Br or I; p is an integer between 0 and 12;

[0122] In some embodiments, the monohalogenated compound is one or more selected from iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, cyclopropyl iodine, isopropyl iodine, isobutyl iodine, cyclopentyl iodine, cyclohexyl iodine, and (5-bromopentyl)trimethylammonium bromide.

[0123] In some implementation schemes, the polyhalogenated compound is Y is Cl, Br, or I; preferably Br.

[0124] In some implementations, the monohalogenated compound is iodomethane.

[0125] In some embodiments, when a base is present in the reaction, the base is one or more of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine, and N,N-diisopropylethylamine.

[0126] The present invention provides a polymer sheet film, wherein the polymer sheet film is prepared by the following steps: dissolving the above-mentioned polymer I, the above-mentioned ionic polymer or the above-mentioned ionized crosslinked polymer in an organic solvent to obtain a polymer solution, casting or casting the polymer solution on a substrate, and drying to obtain the polymer sheet film.

[0127] In some embodiments, the organic solvent is one or more selected from dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0128] In some embodiments, the substrate is a glass plate, copper sheet, iron sheet, ceramic plate, polytetrafluoroethylene plate, polyethylene terephthalate-based film, polyamide-based film, polytetrafluoroethylene film, polyethylene-based film, polypropylene-based film, carbon fiber-based film, or glass fiber-based film.

[0129] This invention provides a polymer hollow fiber membrane, which is prepared by the following steps:

[0130] (1) Dissolve the above polymer I, the above ionic polymer or the above ionized crosslinked polymer in an organic solvent to obtain a polymer solution;

[0131] (2) Immerse the hollow fiber base membrane in the polymer solution, and after immersion, remove and dry it to obtain the polymer hollow fiber membrane; or, prepare the polymer hollow fiber membrane by dry-wet spinning method using the polymer solution.

[0132] In some embodiments, the organic solvent is one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0133] In some embodiments, the hollow fiber membrane is a ceramic hollow fiber membrane, a polytetrafluoroethylene hollow fiber membrane, a polyvinylidene fluoride hollow fiber membrane, a polyethylene terephthalate-based hollow fiber membrane, a polyamide hollow fiber membrane, a polyethylene hollow fiber membrane, a polypropylene hollow fiber membrane, a carbon fiber hollow fiber membrane, or a glass hollow fiber membrane.

[0134] The present invention also provides an ion exchange membrane comprising one or more of the above-described polymer I, the above-described ionic polymer, or the above-described ionized crosslinked polymer.

[0135] In some embodiments, the ion exchange membrane is prepared by the following method: dissolving the above-mentioned polymer I, the above-mentioned ionic polymer, or the above-mentioned ionized crosslinked polymer in an organic solvent (e.g., dimethyl sulfoxide) to obtain a polymer solution, filtering to remove impurities and degassing for later use; pouring the polymer solution onto an automatic membrane scraper, scraping it out using a scraper at a height, and drying it to form the ion exchange membrane.

[0136] The present invention also provides a proton exchange thin film, which is prepared by the following steps:

[0137] The above-mentioned polymer flat film or polymer hollow fiber film is immersed in an aqueous solution of phosphoric acid, wherein the concentration of the aqueous solution of phosphoric acid is 0.1-20 mol / L and the immersion temperature is 0-90℃, to obtain the proton exchange membrane.

[0138] This invention also provides an anion exchange membrane, which is prepared by the following steps:

[0139] The above-mentioned polymer flat sheet film or polymer hollow fiber film is immersed in aqueous solutions of hydroxide, bromide, chloride, fluoride, nitrate, or bicarbonate. After immersion, it is washed with pure water to obtain the anion exchange membrane.

[0140] The hydroxide is one or more selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, and ammonium hydroxide;

[0141] The bromide is one or more of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide;

[0142] The chloride is one or more of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride;

[0143] The fluoride is one or more of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride;

[0144] The nitrate mentioned is one or more of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate;

[0145] The bicarbonate salt is one or more of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, ammonium bicarbonate, magnesium bicarbonate, and calcium bicarbonate;

[0146] Applications of a polymer flat sheet membrane, a polymer hollow fiber membrane, a proton exchange membrane, and an anion exchange membrane in alkaline fuel cells, alkaline water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification.

[0147] Definitions and Explanations

[0148] Unless otherwise stated, the following terms and phrases used herein are intended to have the following meanings. A particular term or phrase should not be considered uncertain or unclear unless specifically defined, but should be understood in its ordinary sense.

[0149] When a product name appears in this article, it is intended to refer to the corresponding product or its active ingredient.

[0150] In this document, the term "substitution" or "substituent" refers to the replacement of a hydrogen atom in a group by a specified group, wherein the number of hydrogen atoms replaced can be one or more. When the substitution position is not specified, substitution can occur at any position, but only if a stable or chemically viable chemical is formed is it permitted. For example, 1, 2, 3, or 4. For instance, 9,9'-spirobisfluoreneyl indicates that one or more hydrogen atoms in 9,9'-spirobisfluorene are substituted; specifically, it can be... For example, tetraphenylethylene indicates that one or more hydrogen atoms in tetraphenylethylene are substituted; specifically, it can be... wait.

[0151] In this article, chemical structural formulas The symbol indicates a connection point, but it is only permitted if a stable or chemically viable chemical is formed.

[0152] In this document, “------” in a chemical structural formula indicates a connection position. When contained in a cyclic group (e.g., cycloalkyl, aryl, or heteroaryl) and the connected ring atom is not specified, “------” can be connected to any ring atom in the cyclic group, but this is only permitted if a stable or chemically viable chemical is formed.

[0153] Without violating common sense in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0154] The reagents and raw materials used in this invention are all commercially available.

[0155] Compared with the prior art, the advantages and beneficial effects of the present invention are as follows:

[0156] This invention is the first to use sterically hindered aryl imidazole structures as side chains to synthesize sterically hindered aryl imidazole monomers, and then prepares ion exchange membranes from these monomers via superacid-catalyzed Friedel-Crafts reactions.

[0157] Compared to various anion exchange resins with quaternary ammonium cationic functional groups, the nitrogen atom on the imidazole ring is in a sp... 2 Hybrid configuration. Using this as the ionization site, the resulting cationic species have a larger charge delocalization space, which helps reduce the probability of them being attacked by hydroxide ions and provides better base stability.

[0158] Compared to other structures with imidazole as the cationic functional group, the imidazole structure prepared in this invention is ingeniously designed to protect the cationic center from steric hindrance, thereby further improving the basic stability of the cationic functional group.

[0159] The sterically hindered aryl imidazole polymer of the present invention has a simple preparation method with mild conditions, is easy to operate, has low preparation cost, and can be mass-produced industrially.

[0160] The steric hindrance-protected aryl imidazole polymer of the present invention can be formed into a film using common industrial methods such as coating. The polymer film prepared has advantages such as large size, thin thickness, high mechanical strength, good stability and excellent ion conductivity. It can be used in fuel cells, water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, electrodialysis, water treatment, membrane humidification, nickel-hydrogen batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes and other fields. Attached Figure Description

[0161] Figure 1 shows the 1H NMR spectrum of the product from step 1 (precursor compound A1).

[0162] Figure 2 shows the 1H NMR spectrum of the product (compound 1) from step 2.

[0163] Figure 3 shows the hydrogen NMR spectrum of polymer 1.

[0164] Figure 4 shows the hydrogen NMR spectrum of polymer 2.

[0165] Figure 5 shows the hydrogen NMR spectrum of polymer 7.

[0166] Figure 6 shows the 1H NMR spectrum of ionic polymer 1.

[0167] Figure 7 shows the 1H NMR spectrum of ionic polymer 2.

[0168] Figure 8 shows the 1H NMR spectrum of ionic polymer 7.

[0169] Figure 9 shows a photograph of ionomer membrane 1.

[0170] Figure 10a is the gel permeation chromatogram of polymer 1; Figure 10b is the gel permeation chromatogram of polymer 2; Figure 10c is the gel permeation chromatogram of polymer 7.

[0171] Figure 11 shows the tensile properties of ionomer film 1.

[0172] Figure 12 shows the electrical conductivity of ionomer film 1.

[0173] Figure 13 shows the alkali stability of the commercial membrane PiperIon A60.

[0174] Figure 14 shows the alkali stability of ionomer membrane 1.

[0175] Figure 15 shows the conductivity of ionomer membrane 1 and commercial membrane PiperIon A60 after approximately 500 hours in caustic soda (10M NaOH).

[0176] Figure 16 shows the water electrolysis performance of ion-modified polymer membrane 1.

[0177] Figure 17 shows the device stability of ionomer membrane 1 and commercial membrane PiperIon A60.

[0178] Figure 18 shows the water absorption rate data (mass change after water absorption) of ionomer membranes 1, 2, and 7.

[0179] Figure 19 shows the swelling data (size change after water absorption) of ionomer membranes 1, 2, and 7.

[0180] Figure 20 shows the mechanical properties of ionomer membranes 1, 2, and 7 (dry state test, samples not soaked in water).

[0181] Figure 21 shows the polarization curve data of ionomer membranes 1, 2 and 7.

[0182] Figure 22 shows the ionomer membrane 1 and the commercial membrane PiperIon A60 in 1M KOH solution at 1A / cm. 2 Stability data after 2500 hours of operation in the environment.

[0183] Figure 23 shows the results of ionomer membrane 1 and commercial membrane PiperIon A60 in 5M KOH solution at 0.5 A / cm. 2 Stability data after 2000 hours of operation in the environment.

[0184] Figure 24 shows the results of ionomer membrane 1 and commercial membrane PiperIon A60 in 10M KOH solution at 0.5 A / cm. 2 Stability data after 700 hours of operation in the environment.

[0185] Figure 25 shows the ionomer membrane 7 (left side: current density 1A / cm). 2 Right side: Current density 2A / cm 2 Stability data after 500 h of operation in 1 M KOH solution. Detailed Implementation

[0186] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0187] Synthesis of sterically hindered aryl imidazolium monomers (compound 1)

[0188] Step 1

[0189] In a nitrogen-filled reactor, diethyl ether (450 mL), tetrahydrofuran (450 mL), and 2,5-dibromo-1,3-benzene (53.69 g) were added and mixed thoroughly. Butyllithium (2.5 M / L, 85.5 mL) and methyl trifluoroacetate (24.56 mL) were added at -78 °C. After 1 h, butyllithium (2.5 M / L, 105.8 mL) and dimethylformamide (23.63 mL) were added. After another 1 h, sufficient hydrochloric acid was added, and the mixture was stirred for 10 min. Extraction was performed with ethyl acetate, and finally recrystallized from petroleum ether to obtain the monomer precursor compound A1 (20 g, yield 43.2%). NMR spectroscopy was used. 1 ¹H NMR (400MHz, Methanol-d⁴) δ 10.64 (s, 1H), 7.40 (s, 2H), 2.65 (s, 6H). The NMR data are shown in Figure 1.

[0190] Step 2

[0191] Precursor compound A1 (20 g) was mixed with butanedione (40 mL), ammonium acetate (70 g), acetic acid (20 mL), and ethanol (100 mL), and stirred at 85 °C for 12 h. The solution was then recrystallized in acetonitrile to obtain a pure, sterically hindered aryl imidazole monomer compound 1 (20.6 g, 80% yield). NMR spectroscopy was performed. 1 ¹H NMR (400MHz, Methanol-d⁴) δ 7.36 (s, 2H), 2.21 (s, 6H), 2.17 (s, 6H). The NMR data are shown in Figure 2.

[0192] Example 1

[0193] Preparation of Polymer 1

[0194] aromatic monomers After mixing compound 1 (0.6 g) and compound 2 (1 g) with 1,2-dichloroethane (3 mL), trifluoromethanesulfonic acid (3 mL) was added dropwise to the solution at 0 °C (at a rate of 2 mL / min). After the addition was complete, the reaction was allowed to proceed for 15 min. Then, the temperature was raised to 25 °C and the reaction was allowed to proceed for 6 h to obtain the precursor. The precursor was then mixed with N-methylpyrrolidone to obtain a precursor solution. After filtration, a precipitant consisting of diethyl ether and isopropanol was added to the filtrate. After precipitation, the precipitate was washed and dried to obtain polymer 1 (1.2 g). 1 ¹H NMR (400MHz, DMSO-d⁶) δ 14.12 (s, 2H), 7.89 (s, 8H), 7.26 (s, 4H), 7.10 (s, 2H), 2.29 (s, 6H), 2.15 (s, 6H). The NMR data are shown in Figure 3.

[0195] Preparation of polymer 2-7

[0196] Preparation of Polymer 2

[0197] aromatic monomers After mixing compound 1 (0.4 g) and compound 2 (1 g) with 1,2-dichloroethane (3 mL), trifluoromethanesulfonic acid (3 mL) was added dropwise to the solution at 0 °C (dropping rate 2 mL / min). After the addition was complete, the reaction was allowed to proceed for 15 min. Then, the temperature was raised to 25 °C and the reaction was allowed to proceed for 6 h to obtain the precursor. The precursor was then mixed with N-methylpyrrolidone to obtain a precursor solution. After filtration, a precipitant consisting of diethyl ether and isopropanol was added to the filtrate. After precipitation, the precipitate was washed and dried to obtain polymer 1 (1 g). 1¹H NMR (400MHz, DMSO-d⁶) δ 14.10 (s, 2H), 7.83 (s, 4H), 7.23 (s, 4H), 7.05 (s, 2H), 2.27 (s, 6H), 2.13 (s, 6H). The NMR data are shown in Figure 4.

[0198] Preparation of Polymer 7

[0199] aromatic monomers (0.3g) and After mixing compound 1 (0.15 g) and compound 2 (1 g) with 1,2-dichloroethane (3 mL), trifluoromethanesulfonic acid (3 mL) was added dropwise to the solution at 0 °C (at a rate of 2 mL / min). After the addition was complete, the reaction was allowed to proceed for 15 min. Then, the temperature was raised to 25 °C and the reaction was allowed to proceed for 6 h to obtain the precursor. The precursor was then mixed with N-methylpyrrolidone to obtain a precursor solution. After filtration, a precipitant consisting of diethyl ether and isopropanol was added to the filtrate. After precipitation, the precipitate was washed and dried to obtain polymer 7 (1.1 g). 1 ¹H NMR (400MHz, DMSO-d⁶) δ 14.13 (s, 2H), 7.86 (s, 5H), 7.25 (s, 4H), 7.05 (s, 2H), 2.28 (s, 6H), 2.13 (s, 6H). The NMR data are shown in Figure 5.

[0200] The preparation method is the same as in Example 1, except that the only difference lies in the aromatic monomers. The aromatic monomers and the resulting polymers are shown in the table below:

[0201] Example 8

[0202] Preparation of ionic polymer 1

[0203] Polymer 1 (5g) was dissolved in DMSO, and K2CO3 (4g) and iodomethane (3mL, 6.84g) were added. The mixture was reacted at 70℃ for 12h. After the reaction was completed, the solution was added dropwise to ethyl acetate to obtain a white precipitate. The precipitate was filtered, dried, washed with water, filtered again, and dried to obtain ionic polymer 1 (6.5g). 1 ¹H NMR (400MHz, DMSO-d6) δ 8.21–7.66 (s, 8H), 7.31 (s, 4H), 7.13 (s, 2H), 3.51 (s, 6H), 2.37 (s, 6H), 2.04 (s, 6H). The NMR data are shown in Figure 6.

[0204] Preparation of ionic polymers 2-7

[0205] Ionic polymers 2-7 were prepared according to the preparation method of ionic polymer 1 in Example 8, except that the polymers were different. The ionic polymers 2-7 were prepared by using the above-mentioned polymers 2-7.

[0206] Preparation of ionic polymer 2

[0207] Polymer 2 (4.3 g) was dissolved in DMSO, and K2CO3 (4 g) and iodomethane (3 mL, 6.84 g) were added. The mixture was reacted at 70 °C for 12 h. After the reaction was complete, the solution was added dropwise to ethyl acetate to obtain a white precipitate. The precipitate was filtered, dried, washed with water, filtered again, and dried to obtain ionic polymer 2 (5.6 g). 1 ¹H NMR (400MHz, DMSO-d⁶) δ 7.87 (s, 4H), 7.28 (s, 4H), 7.08 (s, 2H), 3.50 (s, 6H), 2.36 (s, 6H), 2.02 (s, 6H). The NMR data are shown in Figure 7.

[0208] Preparation of ionic polymer 7

[0209] Polymer 7 (4.4 g) was dissolved in DMSO, and K2CO3 (4 g) and iodomethane (3 mL, 6.84 g) were added. The mixture was reacted at 70 °C for 12 h. After the reaction was complete, the solution was added dropwise to ethyl acetate to obtain a white precipitate. The precipitate was filtered, dried, washed with water, filtered again, and dried to obtain ionic polymer 7 (5.7 g). 1 ¹H NMR (400MHz, DMSO-d⁶) δ 7.89 (s, 5H), 7.28 (s, 4H), 7.08 (s, 2H), 3.50 (s, 6H), 2.36 (s, 6H), 2.02 (s, 6H). The NMR data are shown in Figure 8.

[0210] Application Example 1

[0211] Ion-polymer membrane 1

[0212] Ionic polymer 1 was dissolved in dimethyl sulfoxide. After complete dissolution, the solution was filtered to remove impurities and degassing. The polymer solution was poured onto an automatic film-forming machine, and the doctor blade height was adjusted according to actual needs to form a film with a thickness of 60 μm. The film was dried at high temperature, and after forming, it was immersed in 1M NaCl solution at 80℃ for 24 h to obtain ionic polymer membrane 1. The obtained ionic polymer membrane was uniform, transparent, pore-free, bubble-free, and had good film-forming properties. A photograph of the ionic polymer membrane is shown in Figure 9.

[0213] Application Example 2-7

[0214] Ion-polymer membrane 2-7

[0215] According to the method for preparing ionic polymer membrane 1, ionic polymers 2-7 are respectively prepared into membranes, and ionic polymer membranes 2-7 are obtained accordingly.

[0216] Effect Example

[0217] Gel permeation chromatography

[0218] A polymer solution with a concentration of approximately 0.1% was prepared using chromatographic grade DMSO. This solution was then placed in a 2 mL sample vial and inserted into the autosampler of a gel permeation chromatograph. The test flow rate was set to 1 mL / min to determine the weight-average molecular weight and polymer dispersibility index of the polymer.

[0219] Water absorption rate and swelling degree

[0220] Cut Cl-type AEM into several 3cm*3cm pieces, place them in deionized water and heat to 30℃, maintain for 12 hours, then remove them and quickly wipe off the deionized water on the membrane surface with lint-free paper. Quickly measure the membrane's edge length and weight. Subsequently, place the membranes in deionized water at 60℃ and 80℃ sequentially, repeating the above measurement operation. After completion, flatten the membranes and place them in an 80℃ oven to dry for 12 hours. Then quickly remove and measure the edge length and weight of the dried membrane samples.

[0221] Ionic conductivity

[0222] First, the ion exchange membrane was cut to a size of 0.5cm*1.2cm and placed into a polysulfone mold with Pt sheets. The spacing between the Pt sheets, the width of the membrane, and the thickness were measured and recorded. Tests were conducted in deionized water at 30℃, 40℃, 50℃, 60℃, 70℃, and 80℃. Before testing, the assembled simple electrolytic cell was placed in the test environment for 10 minutes to ensure that the membrane and the measurement system were at the same and stable temperature. The test was conducted in constant voltage mode with an amplitude of 10mV and a test frequency range of 0.1Hz-100kHz.

[0223] Wet mechanical property testing

[0224] Immerse the ion exchange membrane in pure water at room temperature for 12 hours. After removing it and drying the surface moisture, cut it into dumbbell shape according to ASTM D638-14 standard. Measure and record the membrane thickness and the width at the narrowest point in the middle. Place it parallel to the tensile direction of the testing machine and perform a tensile test under environmental conditions. Set the tensile speed to 10 mm / min. Record the initial length, breaking length, and tensile force at break. Take the average value of three measurements.

[0225] Alkali stability test

[0226] First, the ion exchange membrane sample from Application Example 1 was immersed in 1M NaOH solution for 48 hours to allow for complete ion exchange to the form OH-.- The sample was soaked in deionized water for 24 hours to remove residual NaOH solution from the surface. Then, it was placed in a polytetrafluoroethylene bottle containing 10M NaOH solution and transferred as a whole to an oven set at 80°C. A portion of the sample was taken out at intervals for NMR structural characterization.

[0227] Electrolysis water performance test

[0228] The commercial PiperIon A60 membrane and the ion exchange membrane from Application Example 1 were soaked in deionized water for 12 hours and then cut into 3*3cm pieces. 2 Membrane electrodes, of different sizes, were fabricated by spraying cathodes (NiCo) and anodes (Pt / C), and then installed in an electrolytic cell for water electrolysis testing. The test employed a self-circulating liquid flow system, supplying the anode and cathode with the same type and concentration of electrolyte (1M KOH aqueous solution). The heating element and test circuit were connected, and after heating to the predetermined temperature, the electrolyzer was initially set to 200 mA / cm² before the formal test. 2 Activation was performed at a current density of 50 mA / cm² for 30 min. The polarization curves were obtained by constant current charging with a current source and measuring the corresponding voltage. 2 , at 50mA / cm 2 The gradient is increased until the cell voltage reaches the safe protection voltage of 2.3V. Each current density is maintained for 5 minutes to allow the electrolytic cell voltage to stabilize.

[0229] Device stability performance testing

[0230] The commercial PiperIon A60 membrane and the ion exchange membrane from Application Example 1 were soaked in deionized water for 12 hours and then cut into 2*2cm pieces. 2 Membrane electrodes, of varying sizes, were fabricated by spraying cathodes (NiCo) and anodes (Pt / C) and then mounted in an electrolytic cell for water electrolysis stability testing. The test employed a self-circulating liquid flow system, supplying the anode and cathode with the same type and concentration of electrolyte (1M KOH aqueous solution). The heating element and test circuit were connected, and the stability test was conducted after reaching the predetermined temperature. During long-term testing, a storage tank was used to replenish the electrolyte to ensure a constant electrolyte concentration.

[0231] Cut the purchased platinum-plated nickel foam into 2*2cm pieces. 2 The size is used as the anode and cathode of the electrolyzer. The stability of the exchange membrane in 5M and 10M KOH solutions is tested using the same method as above.

[0232] Dry mechanical property testing

[0233] The ion exchange membrane was dried in an 80℃ oven at room temperature for 12 hours. After being removed, it was cut into dumbbell shape according to ASTM D638-14. The thickness and width of the thinnest part of the membrane were measured and recorded. The membrane was placed parallel to the tensile direction of the testing machine and subjected to tensile testing under environmental conditions. The tensile speed was set to 10 mm / min. The initial length, breaking length and tensile force at break were recorded. The average value was taken for three measurements.

[0234] Example 1 (Gel Permeation Chromatography)

[0235] Polymers 1, 2, and 7 were subjected to gel permeation chromatography as described above, and the results are shown in Figures 10a, 10b, and 10c. As shown in Figures 10a-10c, the weight-average molecular weights of polymers 1, 2, and 7 are 145kJ, 45kJ, and 216kJ, respectively, and their number-average molecular weights are 71kJ, 31kJ, and 55kJ, respectively. Polymer 2 has a lower molecular weight due to the lower reactivity of biphenyl, while polymers 1 and 7 achieve higher molecular weights. This demonstrates that the aryl imidazole monomer (compound 1) synthesized in this invention has high reactivity, is well-suited to the superacid-catalyzed Friedel-Crafts reaction, and the prepared polymers can achieve high molecular weights, fully meeting the requirements of practical applications.

[0236] According to the experimental results in Figures 10a-c, the degree of polymerization n of polymer 1 is 140, the degree of polymerization n of polymer 2 is 70, and the degree of polymerization n of polymer 7 is 122; where n = (number average molecular weight / repeating unit molecular weight).

[0237] Example 2

[0238] The ionomer membrane 1 from Application Example 1 and the commercial membrane PiperIon A60 were subjected to the above wet mechanical property tests, and the test results are shown in Figure 11. As can be seen from Figure 11, the ionomer membrane 1 has a tensile strength of 45 MPa and an elongation at break of 63% at room temperature, exhibiting excellent tensile strength and elongation at break, indicating that it possesses good mechanical properties.

[0239] Example 3

[0240] Will use Cl - The ion-modified polymer membrane 1, designed to counteract ions, was directly used in the above ionic conductivity test, and the test results are shown in Figure 12. As can be seen from Figure 12, the ion-modified polymer membrane 1 exhibits an ionic conductivity of 27 mS / cm at 80℃, demonstrating excellent ionic conductivity that meets the requirements for practical applications in devices.

[0241] Example 4

[0242] The commercial PiperIon A60 membrane was immersed in a 10M NaOH solution at 80℃ for a period of time (1 day), and then subjected to NMR testing. The test results are shown in Figure 13. As can be seen from Figure 13, after immersion in the 10M NaOH solution at 80℃ for a period of time, obvious new peaks appeared in the NMR results of the commercial PiperIon A60 membrane. Moreover, with the increase of alkaline treatment time, the peak area of ​​the newly appearing peaks gradually increased. This means that the commercial PiperIon A60 membrane underwent significant degradation in 10M NaOH, and the degradation became more and more serious with the increase of time.

[0243] After immersing the ionomer membrane 1 in a 10M NaOH solution at 80℃ for a period of time (1 day), NMR testing was performed, and the results are shown in Figure 14. As can be seen from Figure 14, the NMR results of the ionomer membrane 1 remained essentially unchanged, indicating that the ionomer membrane 1 remained basically stable during this process and exhibited excellent alkali stability.

[0244] Example 5

[0245] The ionic conductivity of ionomer membrane 1 and commercial membrane PiperIon A60 was tested as described above after being treated with caustic soda (10M NaOH) for about 500 hours. The test results are shown in Figure 15.

[0246] As shown in Figure 15, the conductivity of the commercial membrane PiperIon A60 decreased to about 10% of its original value, while the conductivity of the ionomer membrane 1 also decreased. However, after being immersed in alkali for nearly 1000 hours, it still retained about 50% of its initial ionic conductivity. Therefore, the ionomer membrane 1 exhibits significantly better alkaline stability than the commercial membrane PiperIon A60.

[0247] Example 6

[0248] The electrolysis performance of ion-polymer membrane 1 and commercial membrane PiperIon A60 was tested as described above, and the test results are shown in Figure 16.

[0249] As shown in Figure 16, in terms of water electrolysis performance, the ion-modified polymer membrane 1 performs best at 1 A / cm². 2 At a given current density, the voltage is only 1.78V, essentially on par with the commercial PiperIon A60 membrane, demonstrating excellent performance. This invention, through structural design, introduces molecular building blocks containing sterically hindered aryl imidazoles into the side chains of a polymer, resulting in a novel ion-exchange polymer. This polymer can be used to prepare anion exchange membranes. These membranes have achieved excellent results in applications such as anion exchange membrane water electrolysis and anion exchange membrane fuel cells.

[0250] Example 7

[0251] The ion-modified polymer membrane 1 and the commercial membrane PiperIon A60 were subjected to the device stability test as described above, and the test results are shown in Figure 17.

[0252] As shown in Figure 17, after 20 hours of operation, the voltage of the commercial membrane PiperIon A60 began to exceed that of the ionomer membrane 1, indicating that the commercial membrane had already experienced a certain degree of failure. The voltage rise of the ionomer membrane 1 was significantly less than that of the commercial membrane PiperIon A60. Therefore, the ionomer membrane 1 has longer device stability compared to the commercial membrane PiperIon A60.

[0253] Example 8

[0254] The water absorption rate and swelling degree of ionomer membranes 1, 2 and 7 were tested as described above, and the test results are shown in Figures 18 and 19.

[0255] As shown in Figure 18, the ionomer membrane 1 has a low water absorption rate and relatively low water absorption capacity, which is beneficial for reducing mechanical properties. In contrast, the ionomer membrane 2 has a relatively high water absorption rate, exceeding 100% at 80°C, which is beneficial for improving ionic conductivity. In comparison, the ionomer membrane 7 exhibits a moderate water absorption rate, achieving a good balance between improving ionic conductivity and reducing mechanical properties.

[0256] As shown in Figure 19, the swelling degree of ionomer membranes 1, 2 and 7 corresponds well with their water absorption rate data. Among them, ionomer membrane 1 has a lower water absorption rate, so the dimensional change is small and the dimensional stability is the best. Ionomer membrane 2 has a higher water absorption rate, which also leads to a greater swelling degree and relatively poor dimensional stability. In contrast, ionomer membrane 7 has a moderate water absorption rate, but the dimensional change is still within an acceptable range, and it is only 16% at 80°C, which shows good dimensional stability.

[0257] Example 9

[0258] The ionomer membranes 1, 2 and 7 were subjected to the above dry mechanical property tests, and the test results are shown in Figure 20.

[0259] As shown in Figure 20, the mechanical properties of ionomer films 1, 2 and 7 are quite similar in the dry state. The tensile strength is above 40 MPa and the elongation at break is above 29%, indicating good mechanical properties that meet the requirements of practical use.

[0260] Example 10

[0261] The electrolysis performance of ion-polymer membranes 1, 2 and 7 was tested as described above, and the test results are shown in Figure 21.

[0262] As shown in Figure 21, at 3A / cm 2 At current density, the voltages of ionomer membranes 1, 2, and 7 and the commercial membrane PiperION A60 are 2.00V, 1.87V, 1.88V, and 1.93V, respectively. Among them, ionomer membrane 1 has relatively low ionic conductivity and poor performance, while the performance of ionomer membranes 2 and 7 is similar, both showing superior performance compared to the commercial membrane PiperION A60.

[0263] Example 11

[0264] The ion-modified polymer membranes 1 and 7 and the commercial membrane PiperIon A60 were subjected to the device stability tests described above, and the test results are shown in Figures 22-25.

[0265] Figure 22 shows the ionomer membrane 1 and the commercial membrane PiperIon A60 at 1M KOH and 1A / cm. 2 Stability data were obtained after 2500 hours of operation in the environment. Both membranes operated stably. The voltage decay rate of the commercial membrane PiperIon A60 was 43 μV / h, while that of the ionomer membrane 1 was 25 μV / h, showing slightly better stability than the commercial membrane PiperIon A60.

[0266] Figure 23 shows the results of ionomer membrane 1 and commercial membrane PiperIon A60 at 5M KOH and 0.5A / cm. 2 Stability data from 2000 hours of operation in the environment shows that the voltage of the commercial membrane PiperIon A60 has increased significantly, with a voltage decay rate of 160 μV / h, while the ionomer membrane 1 remains stable with a voltage decay rate of only 16 μV / h, demonstrating significantly better stability than the commercial membrane PiperIon A60.

[0267] Figure 24 shows the ionomer membrane 1 and the commercial membrane PiperIon A60 at 10M KOH and 0.5A / cm. 2 Stability data were collected after 700 hours of operation in the environment. The commercial membrane PiperIon A60 showed a significant voltage increase with a voltage decay rate of 3.3 mV / h, and the voltage exceeded 3 V after 250 hours of operation, indicating significant structural degradation. In contrast, the ionomer membrane 1 operated relatively stably for 700 hours with only a slight voltage increase and a voltage decay rate of only 0.18 mV / h, further verifying its superior stability compared to the commercial membrane PiperIon A60.

[0268] Figure 25 (left side) shows the ionomer membrane 7 in 1M KOH solution at a flow rate of 1 A / cm.2 The stability of the current density after 500 hours of operation was measured, with a voltage decay rate of 11 μV / h. Figure 25 (right side) shows the ionomer membrane 7 operating at 2 A / cm² in 1 M KOH solution. 2 The stability of the current density operation for 500 hours and the voltage decay rate of 30 μV / h demonstrate that after adjusting the main chain structure of the polymer, the exchange membrane in this invention still has excellent device stability and can achieve stable operation at high current densities, showing great potential for industrial applications.

Claims

1. A polymer I containing sterically hindered aryl imidazole, characterized in that, n is an integer between 1 and 5000; A and A' are each independent of each other. 9,9'-spirobisfluorene, tetraphenylethylene, optionally with one or more R a1 Replacement C 6-10 Aryl, -(C 6-10 aryl)-(CR a4 R a5 ) m -(C 6-10 aryl)-, or, -(C 6-10 (Aryl)-(L) p -(C 6- 10 (aryl)-; m is an integer from 1 to 6; p is an integer between 1 and 3; L is the arbitrary subject of R L Replacement C 6-10 Aryl, of which R L C 6-10 Aryl; R a1 Independently for optional use by one or more R a1-1 Replacement C 6-10 Aryl; R a2 and R a3 Each is independently H, and optionally by one or more R. a2-1 Replacement C 6-10 aryl, optionally with one or more R a2- 2 The substituted 5-10 heteroaryl group, optionally replaced by one or more R a2-3 Replacement C 1-6 Alkyl, optionally with one or more R a2-4 The substituted 3-10 membered cycloalkyl group; wherein the number of heteroatoms in the 5-10 membered heteroaryl group is 1, 2 or 3, and the heteroatoms are selected from one or more of N, O and S; R a4 and R a5 Each is independently H, arbitrarily controlled by one or more R a4-1 Replacement C 1-6 Alkyl groups or optionally one or more R a4-2 Replacement C 6-10 Aryl; R a1-1 R a2-1 R a2-2 R a2-3 R a2-4 R a4-1 and R a4-2 Each is independently halogen or C 1-6 alkyl; One of B and B' is The other is X is NR x , O or S, where R x For H or C 1-6 alkyl; R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” and R b9” Each is independently N,N,N-trimethylpentanenyl, optionally surrounded by one or more R b1-1 Replacement C 6-10 aryl, optionally with one or more R b1-2 The substituted 5-10 heteroaryl group, optionally replaced by one or more R b1-3 Replacement C 1-6 Alkyl, optionally with one or more R b1-4 The substituted 3-10 membered cycloalkyl group, wherein the number of heteroatoms in the 5-10 membered heteroaryl group is 1, 2 or 3, and the heteroatoms are selected from one or more of N, O and S; R b10 and R b11 Each is independently H, and optionally by one or more R. b10-1 Replacement C 1-6 Alkyl, optionally with one or more R b10-2 Replacement C 6-10 aryl or optionally aryl by one or more R b10-3 Substituted 3-10 membered cycloalkyl groups; Or, R b10 and R b11 Together with the carbon atom it is attached to, it is formed: optionally by one or more R b10-4 Substituted 5-10 membered cycloalkyl groups R b1-1 R b1-2 R b1-3 R b1-4 R b10-1 R b10-2 R b10-3 and R b10-4 Each is independently carbonyl, halogen, or C. 1-6 alkyl; A and A' are the same or different; B and B' are the same or different; each independent structural unit They may be the same or different.

2. The polymer I according to claim 1, characterized in that, One or more of the following conditions must be met: (1) n is 1-2000, preferably 800-1200 or 40-300, and more preferably 50-200; for example 70-140, or for example 122; (2) A, A', L, R L R a1 R a2 R a3 R a4 R a5 R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” R b10 and R b11 In, the C 6-10 The aryl group can be phenyl or naphthyl independently; (3)R a2 R a3 R a4 R a5 R a1-1 R a2-1 R a2-2 R a2-3 R a2-4 R a4-1 R a4-2 R x R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” R b10 R b11 R b1-1 R b1-2 R b1-3 R b1-4 R b10-1 R b10-2 R b10-3 and R b10-4 In the middle; the C mentioned 1-6 The alkyl group is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl; (4)R a2 R a3’ R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” and R b9” The 5-10 member heteroaryl group is pyrrole, furanyl, thiophene, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidine, pyrazinyl, benzopyrrole, benzofuranyl, benzothiophene, benzooxazolyl, benzoisooxazolyl, benzothiazolyl, benzoisothiazolyl, benzopyrazolyl, benzoimidazolyl, benzopyridyl, benzopyrimidine, benzopyrazinyl, thiazothiazolyl, pyridopyridyl, pyridopyrazinyl, or pyridopyrimidineyl. (5)R a2 R a3’ R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” and R b9” In this context, the 3-10 membered cycloalkyl group is independently cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl; (6) The halogen is F, Cl, Br or I.

3. The polymer I according to claim 1, characterized in that, One or more of the following conditions must be met: (1) The A and A' are independently -(C 6-10 (Aryl)-(L) p -(C 6-10 (aryl)-; (2) The L is phenyl or naphthyl, preferably phenyl; (3) The R L It is phenyl or naphthyl; preferably phenyl. (4) p is 1 or 2, preferably 1; (5) The polymer I contains structural segments. One or more of the following; preferably, the polymer I comprises structural segments. More preferably, the polymer I comprises structural segments. (6)R b3 and R b4 It is methyl; (7)R b1 and R b2 It is methyl; (8)R b5 and R b6 For H; (9) In the polymer I, structural segments The molar ratio of the total amount of structural fragments A and A' is (0.001-1):1; (10) In the polymer I, when it contains structural segments At that time, structural fragments Structural fragments The molar ratio between the total amount of structural fragments A and A' is (0.001-1):(0-0.999):1; (11) Any structural segment in polymer I Independently (12) Any structural segment in polymer I The R b10 and R b11 Each of them independently consists of hydrogen, methyl, ethyl, trifluoromethyl, pyridyl, piperidinyl, phenyl, o-tolyl, m-tolyl, p-tolyl, or mesityleliyl.

4. The polymer I according to claim 1, characterized in that, One or more of the following conditions must be met: (1) A and A' are each independent of each other. The better location is Better for (2) B and B' are each independent of each other. The better location is Preferably, polymer I is any of the following compounds:

5. The polymer I according to claim 1, characterized in that, The polymer I can be prepared by the following steps: polymerizing component 1 and component 2 by Friedel-Crafts reaction in the presence of an acid catalyst; Wherein, component 1 is HAH and H-A'-H, wherein A and A' are defined as in any one of claims 1-4; The component 2 is The above Each independently Among them, R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b5 R b6 R b6’ R b7’ R b7” R b8” R b9” R b10 and R b11 As defined in any one of claims 1-4; When A and A' are the same, only HAH or only H-A'-H exists; when When they are the same, only one exists. Or only exist 6. The polymer I as described in claim 5, characterized in that, It meets one or more of the following conditions: (1) In component 1, HAH and H-A'-H are each independently... Preferably, in component 1, HAH and H-A'-H are each independently... More preferably, in component 1, HAH and H-A'-H are each independently... Ideally; component 1 is (2) Component 1 is Preferably, wherein the compound With compounds The molar ratio is 1:(0.01-10); preferably 1:(0.5-5); for example 1:3; or, component 1 is... (3) In component 2, the Each independently Component 2 contains at least Preferably, component 2 is (4) The acid catalyst is a Lewis acid, preferably one or more of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid and perfluorosulfonic acid resin, and more preferably trifluoromethanesulfonic acid; (5) A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (6) A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (7) A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (8) A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (9) A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (10) A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (11) will A Friedel-Crafts reaction was carried out under the conditions of trifluoromethanesulfonic acid to obtain polymer I; (12) The Friedel-Crafts reaction is carried out in a solvent, wherein the solvent is a halocarbon solvent, such as 1,2-dichloroethane; (13) The molar ratio of component 1 to component 2 is 1:(0.8-1.5); preferably 1:(1-1.3), for example 1:1.3; (14) The molar ratio of component 1 to the acid catalyst is 1:(0.5-50); preferably 1:(8-20), more preferably 1:(12-15); for example 1:13; (15) The reaction temperature of the Friedel-Crafts reaction is 0-40℃; preferably 0-25℃; (16) The reaction time of the Friedel-Crafts reaction is 0.5-48h, preferably 2-8h, for example 6h.

7. An ionic polymer, characterized in that, The ionic polymer is polymer I according to any one of claims 1-6, in which the N atoms in B and B' are ionized to form a structure containing the NR segment. b12 An ionic polymer; wherein one of B and B' is The other is The R b12 The molecule is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, isopropyl, isobutyl, cyclopentyl, or cyclohexyl, preferably methyl; Alternatively, the ionic polymer is prepared by the following steps: under alkaline or alkaline-free conditions, polymer I as described in any one of claims 1-6 is reacted with a monohalogenated compound Rb. 12 -X undergoes a substitution reaction to obtain the ionic polymer; Among them, the monohalogenated compound R b12 -X is one or more of iodomethane, iodoethane, iodopropane, iodobutane, iodopentane, iodohexane, iodoheptane, iodooctane, iodononane, iododecane, bromomethane, bromoethane, bromopropane, bromobutane, bromopentane, bromohexane, bromoheptane, bromooctane, bromononane, bromodecane, 2-bromoethylamine, 2-bromoethanol, cyclopropyliodine, isopropyliodine, isobutyliodine, cyclopentyliodine, cyclohexyliodine, and (5-bromopentyl)trimethylammonium bromide; preferably iodomethane.

8. The ionic polymer as described in claim 7, characterized in that, The ionic polymer contains at least ionized structural segments. One or more of the following; where X is NR x O or S, R x C 1-6 Alkyl; R b1 R b1’ R b1” R b2 R b2’ R b2” R b3 R b3’ R b3” R b4 R b4’ R b4” R b8” R b9” R b5 R b6 R b6’ R b7’ and R b7” As defined in any one of claims 1-4; preferably, the ionic polymer at least comprises ionized structural segments. (2) The base is one or more of sodium bicarbonate, potassium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, trimethylamine, triethylamine, N,N-dimethylethylenediamine and N,N-diisopropylethylamine; preferably potassium carbonate; (3) The weight ratio of polymer I to monohalogenated compound is 1:(1-2); preferably 1:(1-1.7); more preferably 1:(1-1.5), and for example 1:1.368, 1:1.55 or 1:1.6; (4) In the substitution reaction, when a base is present, the weight ratio of the polymer I to the base is 1:(0.4-3), preferably 1:(0.6-1.2), for example 1:0.8, 1:0.91 or 1:0.93; (5) The reaction temperature of the substitution reaction is 0-100℃, preferably 25-80℃, for example 70℃; (6) The reaction time of the substitution reaction is 0.5-48h, preferably 6-24h, for example 12h; (7) The anions in the ionic polymer are selected from F - Cl - ,Br - I - CO3 2- HCO3 - OH - OTf - OTs - BF4 - NO3 - One or more of ClO4 and PF6-, preferably selected from I - Cl - and OH - One or more of the following; best is I - Cl - or OH - .

9. An ionomer membrane, characterized in that, The ionic polymer membrane is prepared by the following method: dissolving the ionic polymer as described in claim 7 or 8 in a solvent to obtain a polymer solution, and then preparing the ionic polymer membrane by an automatic film coating machine. Preferably, the solvent is dimethyl sulfoxide.

10. The application of the ionic polymer as described in claim 7 or 8 in alkaline fuel cells, alkaline water electrolysis for hydrogen production, metal-air batteries, flow batteries, carbon dioxide reduction, supercapacitors, nickel-metal hydride batteries, zinc-manganese batteries, acid separation, lithium extraction from salt lakes, electrodialysis, water treatment, and membrane humidification, preferably in alkaline fuel cells.

11. A compound with the following structural formula:

Images