Polyaralkyl polymers and methods of making, polyaralkyl polymer flat sheet membranes and methods of making, anion exchange membranes and methods of making and applications

Abstract

The application relates to the technical field of high-molecular functional materials, and discloses a polyaralkyl polymer and a preparation method thereof, a polyaralkyl polymer flat film and a preparation method thereof, an anion exchange film and a preparation method and application thereof. The polyaralkyl polymer has a structural unit shown in formula (I-1) or formula (I-2). The polyaralkyl polymer flat film provided by the application has the advantages of thin thickness, high mechanical strength, good stability and excellent ion conduction performance; and the anion exchange film provided by the application has excellent mechanical strength, electric conductivity and alkali stability. Formula (I-1); formula (I-2).

Description

Technical Field

[0001] This invention relates to the field of polymer functional materials technology, specifically to a polyarylene polymer and its preparation method, a polyarylene polymer flat sheet film and its preparation method, and an anion exchange film and its preparation method and application. Background Technology

[0002] Advanced energy and chemical technologies, such as hydrogen fuel cells, water electrolysis hydrogen production systems, metal-air batteries, flow batteries, carbon dioxide electrochemical reduction devices, supercapacitors, and acid treatment separation and lithium extraction from salt lakes, all heavily rely on high-performance functional polymer membranes. The core mechanism of these membranes lies in achieving precise selective ion permeation. However, current research in this field still falls short of fully meeting rapidly growing industrial demands, particularly in the development of ion exchange membranes that combine high conductivity and high stability, where significant technological bottlenecks remain.

[0003] In recent years, all-carbon framework structures have been widely proposed in research to fundamentally improve framework stability. Currently, superacid polycondensation is the most ideal method for constructing all-carbon frameworks, and it allows for the convenient introduction of cationic groups. For example, Jannasch et al. (Adv. Funct. Mater. 2017, 1702758; DOI: 10.1002 / adfm.201702758) reported the synthesis of high-molecular-weight poly(arylN-methylpiperidine) electrolytes via terphenyl and N-methyl-4-piperidinone under superacid catalysis. Furthermore, Hu et al. (Angew. Chem. Int. Ed. 2022, 61,e202114892; DOI: 10.1002 / anie.202114892) studied the copolymerization of terphenyl and N-methyl-4-piperidinone by incorporating trifluoroacetophenone, which improved ion transport. CN112759778A discloses a high-strength alkaline anion exchange polymer crosslinked membrane and its preparation method. The alkaline anion exchange polymer crosslinked membrane obtained by this method exhibits high mechanical strength and excellent dimensional stability. This type of alkaline anion exchange polymer crosslinked membrane, with its excellent physicochemical properties, demonstrates good battery performance when applied in alkaline polymer membrane fuel cells. However, a drawback is that the basic monomers are all biphenyl and piperidinone, and the limited monomer diversity hinders the development of structural diversity. In summary, to further promote the development of high-performance anion exchange membranes, it is urgent to explore and develop novel polymeric monomers to synthesize novel polyaromatic anion exchange membranes.

[0004] Therefore, finding more diverse polymerizable monomers and developing simple and effective synthesis strategies to prepare low-cost, high-performance polyarylene anion exchange membrane materials is currently the focus and challenge of research. Summary of the Invention

[0005] The purpose of this invention is to overcome the problem that the synthesis system of polyarylene piperidine anion exchange membranes (AEMs) in the prior art is highly dependent on the single combination of "p-terphenyl + N-methyl-4-piperidinone", which leads to severe homogenization of the main chain structure and limited performance regulation space.

[0006] To achieve the above objectives, a first aspect of the present invention provides a polyarylene polymer having structural units shown in formula (I-1) or formula (I-2): Formula (I-1); Formula (I-2); Formula (II-1); Equation (II-2); Formula (II-3); In equations (I-1) and (I-2), A is free to choose C. 6-30 An aromatic compound that leaves at least one of the linking groups formed by any two H atoms that can leave; B is selected from at least one of the linking groups shown in formula (II-1), formula (II-2), and formula (II-3); wherein R3 and R4 are each independently selected from C. 1-10 Alkyl; or, R3 and R4 cyclize together to form C 3-6 The ring structure; X is selected from at least one of F, Cl, Br, I, and HCO3; R1 and R2 are each independently selected from H, unsubstituted or halogenated C. 1-10 Alkyl, unsubstituted or C 1-10 phenyl groups substituted with at least one group in the alkyl group, unsubstituted or C 1-10 At least one of the pyridyl groups substituted with at least one group of the alkyl group; or, R1 and R2 are cyclized together to form C 3-8 Circular structure; 0≤a≤1, 0≤b≤1, and a+b=1.

[0007] A second aspect of the present invention provides a method for preparing the polyarylene polymer described in the first aspect, the method comprising: In the presence of an acid catalyst, ketal monomer C and aromatic monomer D undergo a Friedel-Crafts reaction to obtain the polyarylene polymer; wherein the ketal monomer C has at least one of the structures shown in formula (III-1), formula (III-2), and formula (III-3); and the aromatic monomer D is C 6-30 Aromatic compounds; Equation (III-1); Equation (III-2); Formula (III-3); In Equations (III-1), (III-2), and (III-3), the definitions of R3, R4, and X are the same as those described in the first aspect.

[0008] A third aspect of the present invention provides a method for preparing polyarylene polymer sheet films, the method comprising: (1) The polyaromatic polymer is first mixed with an organic solvent to obtain material I; (2) The material I is cast or cast onto a substrate to obtain the polyarylene polymer flat film; The polyaromatic polymer is the polyaromatic polymer described in the first aspect.

[0009] A fourth aspect of the present invention provides a polyarylene polymer sheet film prepared by the method described in the third aspect.

[0010] A fifth aspect of the present invention provides a method for preparing anion exchange films, the method comprising: The anion exchange membrane is obtained by immersing a polyarylene polymer sheet film in an alkaline solution and then washing it. The polyarylene polymer flat sheet film is the polyarylene polymer flat sheet film described in the fourth aspect.

[0011] A sixth aspect of the present invention provides an anion exchange membrane prepared by the method described in the fifth aspect.

[0012] The seventh aspect of the present invention provides the application of the anion exchange membrane described in the sixth aspect in advanced energy and chemical technologies.

[0013] Compared with the prior art, the present invention has at least the following beneficial effects: 1. The polyarylene polymer provided by this invention uses acetal spirocyclic monomers as polymerizing monomers. Through the high reactivity of acetal monomers, a new all-carbon skeleton system with a unique rigid-flexible structure is constructed, which significantly enriches the material library of polyarylene AEMs and opens up a new path for developing a new generation of membrane materials with high ionic conductivity, excellent dimensional stability and strong alkali resistance.

[0014] 2. The preparation method of polyaromatic polymers provided by the present invention is simple, mild, and easy to operate; its raw material monomers are inexpensive and readily available, the preparation cost is low, and it can be mass-produced industrially.

[0015] 3. The polyarylene polymer flat film provided by the present invention has the advantages of thin thickness, high mechanical strength, good stability and excellent ion conduction performance.

[0016] 4. The anion exchange membrane provided by the present invention has excellent mechanical strength, electrical conductivity and alkali stability. Attached Figure Description

[0017] Figure 1 This is the 1H NMR spectrum of the polyarylene polymer PBP-3 prepared in Example 3; Figure 2 These are the conductivity test data for the anion exchange membrane AEM-3 prepared in Example 3; Figure 3 This is a water electrolysis polarization curve of the anion exchange membrane AEM-3 prepared in Example 3. Detailed Implementation

[0018] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0019] In this invention, unless otherwise specified, groups of the same type have similar interpretations, and will not be described in detail here.

[0020] Halogens include: fluorine, chlorine, bromine, and iodine.

[0021] C 6-30 Aromatic compounds refer to aromatic compounds with a total number of carbon atoms of 6-30 (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30). Examples include benzene, naphthalene, anthracene, phenanthrene, biphenyl, etc.

[0022] C 1-10 Alkyl refers to a straight-chain or branched alkyl group with a total number of carbon atoms of 1-10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10). For example, it can be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, etc.

[0023] C 3-6 The ring structure indicates that the number of cyclic carbon atoms in the ring structure is 3, 4, 5 or 6.

[0024] 15-18 membered ring crown ether compounds refer to crown ether compounds with a total number of 15-18 ring skeleton atoms (e.g., 15, 16, 17, 18), including multiple oxygen atoms. Examples include 15-crown-5, 18-crown-6, etc.

[0025] C 1-5 Alkoxy refers to a straight-chain or branched alkoxy group with a total number of carbon atoms of 1-5 (e.g., 1, 2, 3, 4, 5). Examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, etc.

[0026] C 6-12 A phenoxy group represents a phenoxy structure with a total number of carbon atoms of 6-12 (e.g., 6, 7, 8, 9, 10, 11, or 12) that are attached to a benzene ring and may have alkyl substituents. Examples include phenoxy, methylphenoxy, ethylphenoxy, dimethylphenoxy, propylphenoxy, butylphenoxy, pentylphenoxy, hexylphenoxy, etc.

[0027] When the organic compounds of the present invention contain substituents, unless otherwise specified, there are no particular requirements for the specific substitution position of the substituents, and they can be any position that can be substituted.

[0028] In this invention, Indicates a connection key.

[0029] As previously stated, a first aspect of the present invention provides a polyarylene polymer having structural units shown in formula (I-1) or formula (I-2): Formula (I-1); Formula (I-2); Formula (II-1); Equation (II-2); Formula (II-3); In equations (I-1) and (I-2), A is free to choose C. 6-30 An aromatic compound that leaves at least one of the linking groups formed by any two H atoms that can leave; B is selected from at least one of the linking groups shown in formula (II-1), formula (II-2), and formula (II-3); wherein R3 and R4 are each independently selected from C. 1-10 Alkyl; or, R3 and R4 cyclize together to form C 3-6 The ring structure; X is selected from at least one of F, Cl, Br, I, and HCO3; R1 and R2 are each independently selected from H, unsubstituted or halogenated C. 1-10 Alkyl, unsubstituted or C 1-10 phenyl groups substituted with at least one group in the alkyl group, unsubstituted or C 1-10 At least one of the pyridyl groups substituted with at least one group of the alkyl group; or, R1 and R2 are cyclized together to form C 3-8 Circular structure; 0≤a≤1, 0≤b≤1, and a+b=1.

[0030] Preferably, in equations (I) and (I-2), A is selected from C. 6-20 The aromatic compound is formed by removing at least one of two linking groups that can be removed by any two H atoms; the aromatic compound is selected from C atoms substituted with phenyl groups. 1-5 Alkanes, 15-18 membered ring crown ethers substituted with phenyl groups, unsubstituted or C-shaped rings 1-5 Alkyl, C 1-5 Alkoxy, C 6-12 Benzene substituted with at least one group in the phenoxy group, unsubstituted or C 1-5 Biphenyls substituted with at least one group in an alkyl group, unsubstituted or C 1-5 Fluorene substituted with at least one group in an alkyl group, unsubstituted or C 1-5 Carbazole substituted with at least one group in the alkyl group, unsubstituted or C 1-5 terphenyls substituted with at least one group in an alkyl group, unsubstituted or C 1-5 At least one of the diphenyl ethers substituted with at least one of the alkyl groups.

[0031] Preferably, in formulas (I) and (I-2), B is selected from at least one of the linking groups shown in formulas (II-1), (II-2), and (II-3); wherein R3 and R4 are each independently selected from C. 1-5 Alkyl; or, R3 and R4 cyclize together to form C 4-5 The ring structure; X is selected from at least one of F, Cl, Br, I, and HCO3.

[0032] Preferably, in formulas (I) and (I-2), R1 and R2 are each independently selected from H, unsubstituted or halogenated C. 1-5 Alkyl, unsubstituted or C 1-5 phenyl groups substituted with at least one group in the alkyl group, unsubstituted or C 1-5 At least one of the pyridyl groups substituted with at least one group of the alkyl group; or, R1 and R2 are cyclized together to form C 3-6 Its ring-shaped structure.

[0033] More preferably, in equations (I) and (I-2), A is selected from C.6-20 The aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave the compound; the aromatic compound is selected from at least one of the following compounds: , , , , , , , , , , , , , , .

[0034] More preferably, in formula (I) and formula (I-2), B is selected from at least one of the linking groups shown in formula (II-4), formula (II-5), formula (II-6), formula (II-7), and formula (II-8); Equation (II-4); Equation (II-5); Equation (II-6); Equation (II-7); Equation (II-8); In formulas (II-4), (II-5), (II-6), (II-7), and (II-8), X is selected from at least one of F, Cl, Br, I, and HCO3; More preferably, in formulas (I) and (I-2), R1 and R2 are each independently selected from at least one of H, methyl, ethyl, trifluoromethyl, pyridyl, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, and mesitylene; or, R1 and R2 together cyclize to form C 5-6 Its ring-shaped structure.

[0035] Preferably, the polyarylene polymer is selected from any one of the following: , , , .

[0036] More preferably, the molecular weight of the polyaromatic polymer is ≤10 million g / mol.

[0037] As previously described, a second aspect of the present invention provides a method for preparing the polyarylene polymer described in the first aspect, the method comprising: In the presence of an acid catalyst, ketal monomer C and aromatic monomer D undergo a Friedel-Crafts reaction to obtain the polyarylene polymer; wherein the ketal monomer C has at least one of the structures shown in formula (III-1), formula (III-2), and formula (III-3); and the aromatic monomer D is C 6-30 Aromatic compounds; Equation (III-1); Equation (III-2); Formula (III-3); In Equations (III-1), (III-2), and (III-3), the definitions of R3, R4, and X are the same as those described in the first aspect.

[0038] Preferably, the molar ratio of the ketal monomer C to the aromatic monomer D is 0.2-1.5:1.

[0039] Preferably, the acid catalyst is selected from at least one of trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methanesulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin.

[0040] More preferably, the amount of acid catalyst used is 0.2-1 mL relative to 1 mmol of the ketal monomer C.

[0041] More preferably, the ketal monomer C is selected from at least one of the following compounds: , , , , ; Wherein, X is selected from at least one of F, Cl, Br, I, and HCO3.

[0042] More preferably, the aromatic monomer D is selected from C substituted with phenyl groups. 1-5 Alkanes, 15-18 membered ring crown ethers substituted with phenyl groups, unsubstituted or C-shaped rings 1-5 Alkyl, C 1-5 Alkoxy, C 6-12 Benzene substituted with at least one group in the phenoxy group, unsubstituted or C 1-5 Biphenyls substituted with at least one group in an alkyl group, unsubstituted or C 1-5 Fluorene substituted with at least one group in an alkyl group, unsubstituted or C 1-5 Carbazole substituted with at least one group in the alkyl group, unsubstituted or C 1-5 terphenyls substituted with at least one group in an alkyl group, unsubstituted or C 1-5At least one of the diphenyl ethers substituted with at least one of the alkyl groups.

[0043] More preferably, the aromatic monomer D is selected from at least one of benzene, biphenyl, 4,4-dimethylbiphenyl, fluorene, 9,9-dimethylfluorene, p-terphenyl, m-terphenyl, o-terphenyl, diphenylmethane, 1,2-diphenylethane, 1,3-diphenylpropane, p-xylene dimer, 2,2-bis(3,4-dimethylphenyl)hexafluoropropane, 2,3-dimethyl-2,3-diphenylbutane, and 1,2-bis(1-naphthyl)ethane.

[0044] Preferably, the Friedel-Crafts reaction is carried out in the presence of a solvent selected from at least one of dichloromethane, chloroform, and carbon tetrachloride.

[0045] More preferably, the amount of solvent used is 5-15 mL relative to 1 mmol of the ketal monomer C.

[0046] More preferably, the conditions for the Friedel-Crafts reaction include: a temperature of -10°C to 0°C, a time of 20-80 h, and a rotation speed of 100-800 rpm.

[0047] According to a particularly preferred embodiment, the Friedel-Crafts reaction is carried out with the participation of ketone monomer E to obtain the polyarylene polymer.

[0048] Preferably, the ketone monomer E is selected from at least one of the compounds shown in formula (IV-1), formula (IV-2), formula (IV-3), and formula (IV-4); Formula (IV-1); Formula (IV-2); Formula (IV-3); Formula (IV-4); In Equation (IV-1), the definitions of R1 and R2 are the same as those described in the first aspect.

[0049] More preferably, the molar ratio of the ketal monomer C, the aromatic monomer D, and the ketone monomer E is 0.2-1:1:0.001-0.8.

[0050] According to a particularly preferred embodiment, the Friedel-Crafts reaction is carried out with the participation of aromatic crosslinking agent monomer F to obtain the polyarylene polymer.

[0051] Preferably, the aromatic crosslinking agent monomer F is selected from at least one of triphenylmethane, 1,3,5-triphenylbenzene, 9,9'-spirobisfluorene, tetraphenylethylene, tetraphenylmethane, and hexaphenylbenzene.

[0052] More preferably, the molar ratio of the ketal monomer C, the aromatic monomer D, and the aromatic crosslinking agent monomer F is 1:0.8-1.2:0.001-0.3.

[0053] According to a particularly preferred embodiment, the preparation method further includes: sequentially washing and drying the intermediate product obtained from the Friedel-Crafts reaction to obtain the polyaromatic polymer. Exemplarily, the polyaromatic polymer is a pale yellow powder.

[0054] Preferably, the drying conditions I include: a temperature of 80-100℃ and a time of 25-35 h.

[0055] The present invention does not have any special requirements for the specific operation of the washing process. Those skilled in the art can perform the washing process according to known technical means in the field. The present invention will not elaborate further here, and those skilled in the art should not understand it as a limitation of the present invention.

[0056] As previously described, a third aspect of the present invention provides a method for preparing polyarylene polymer sheet films, the method comprising: (1) The polyaromatic polymer is first mixed with an organic solvent to obtain material I; (2) The material I is cast or cast onto a substrate to obtain the polyarylene polymer flat film; The polyaromatic polymer is the polyaromatic polymer described in the first aspect.

[0057] Preferably, in step (1) of the method, the organic solvent is selected from at least one of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene and ethyl acetate.

[0058] Preferably, the amount of organic solvent used is 30-50 mL relative to 1 g of the polyaromatic polymer.

[0059] More preferably, in step (2) of the method, the substrate is selected from at least one of glass plate, copper sheet, iron sheet, ceramic plate, polytetrafluoroethylene plate, polyethylene terephthalate film, polyamide film, polytetrafluoroethylene film, polyethylene film, polypropylene film, carbon fiber film, and glass fiber film.

[0060] More preferably, the method further includes: drying the material II obtained by casting or casting to obtain the polyarylene polymer flat film.

[0061] More preferably, the drying conditions II include a temperature of 80-120°C and a time of 2-20 h.

[0062] As previously described, a fourth aspect of the present invention provides a polyarylene polymer sheet film prepared by the method described in the third aspect.

[0063] As previously described, a fifth aspect of the present invention provides a method for preparing anion exchange films, the method comprising: The anion exchange membrane is obtained by immersing a polyarylene polymer sheet film in an alkaline solution and then washing it. The polyarylene polymer flat sheet film is the polyarylene polymer flat sheet film described in the fourth aspect.

[0064] Preferably, the alkaline solution is selected from at least one of sodium hydroxide solution, potassium hydroxide solution, and lithium hydroxide solution.

[0065] More preferably, the concentration of the alkaline solution is 0.5-1.5 M.

[0066] More preferably, the soaking time is 8-48 hours.

[0067] The present invention does not have any special requirements for the specific operation of the washing process. Those skilled in the art can perform the washing process according to known technical means in the field. The present invention will not elaborate further here, and those skilled in the art should not understand it as a limitation of the present invention.

[0068] As previously stated, a sixth aspect of the present invention provides an anion exchange membrane prepared by the method described in the fifth aspect.

[0069] As previously stated, the seventh aspect of the present invention provides the application of the anion exchange membrane described in the sixth aspect in advanced energy and chemical technologies.

[0070] Preferably, the advanced energy and chemical technology is selected from at least one of anion membrane fuel cells, anion membrane 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.

[0071] The present invention will be described in detail below through examples. Unless otherwise specified, the reagents and materials used in the following examples and comparative examples are commercially available.

[0072] 1,4-Dioxa-7-azaspiro[4,4]nonane: raw material monomer, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 176-33-0; 8-Methyl-1,4-dioxa-8-azaspiro[4.5]decane: raw material monomer, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 28286-05-7; 1,4-Dioxa-7-azaspiro[4,5]decane: raw material monomer, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 40369-91-3; Fluorene: Aromatic monomer D, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 86-73-7; Dibenzo-18-crown ether-6: Aromatic monomer D, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 14187-32-7; Terphenyl: Aromatic monomer D, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 92-94-4; Carbazole: Aromatic monomer D, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 86-74-8; Acetone: Ketone monomer E, purchased from Sinopharm Chemical Reagent Co., Ltd., brand name 67-64-1; Cyclohexanone: Ketone monomer E, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., brand name 108-94-1; 1,3,5-Triphenylbenzene: Aromatic crosslinking agent monomer F, purchased from Shanghai Maclean Biochemical Technology Co., Ltd., grade 612-71-5; Trifluoromethanesulfonic acid: purchased from Shanghai Titan Technology Co., Ltd., grade 1493-13-6; Trifluoroacetic acid: purchased from Shanghai Titan Technology Co., Ltd., grade 76-05-1; Dichloromethane: Purchased from Shanghai Titan Technology Co., Ltd., grade 75-09-2; Dimethyl sulfoxide: purchased from Shanghai Titan Technology Co., Ltd., grade 67-68-5.

[0073] Unless otherwise specified, room temperature / normal temperature refers to 25±1℃ in the following examples and comparative examples.

[0074] Preparation Example 1 The preparation method of ketal monomer C is as follows, and the specific components and their amounts are shown in Table 1.

[0075] (1) Add 10 mmol of raw material monomer, 15 mmol of anhydrous potassium carbonate and 30 mL of anhydrous acetonitrile to a dry 100 mL two-necked round-bottom flask in sequence, and stir magnetically to disperse the solid evenly to obtain a mixed solution. (2) Iodoalkane was slowly added dropwise to the above mixed solution using a syringe. After the addition was complete, a reflux condenser was installed, cooling water was introduced, and the mixture was heated to 75°C in an oil bath and stirred under reflux for 24 h to obtain the reaction solution. During the reaction, the reaction progress was tracked by thin-layer chromatography (TLC, developing solvent: dichloromethane / methanol = 9:1, v / v), and the disappearance of the raw material amine was detected by ninhydrin colorimetric reagent. (3) Cool the above reaction solution to room temperature, filter under reduced pressure to remove insoluble potassium carbonate solid, wash the filter cake twice with anhydrous acetonitrile, combine the filtrate and washing liquid, and remove the solvent by rotary evaporation under reduced pressure at 40°C to obtain a pale yellow viscous crude product. (4) Dissolve the above crude product in 20 mL of dichloromethane, exchange it twice with 15 mL of saturated sodium chloride solution, dry it with anhydrous magnesium sulfate for 30 min, filter to remove the desiccant, and remove dichloromethane by rotary evaporation under reduced pressure to obtain a white solid ketal monomer C.

[0076] Preparation Examples 2 to 4 The same process as in Preparation Example 1 was used, except that the types of raw material monomers were different, as listed in Table 1, to prepare ketal monomer C.

[0077] Table 1

[0078] Example 1 1. The preparation method of polyaromatic polymers is as follows, and the specific types and amounts of components are shown in Table 2.

[0079] (1) Dissolve 10 mmol of ketal monomer C, 10 mmol of aromatic monomer D, and 0.2 mmol of ketone monomer E (or 0.2 mmol of aromatic crosslinking agent monomer F) in 100 mL of dichloromethane, stir at 500 rpm at -5℃, and slowly add acid catalyst dropwise. After the addition is complete, continue stirring at 0℃ for 72 h to obtain intermediate product; (2) The above intermediate product was washed with 60 mL of deionized water and dried at 90 °C for 30 h to obtain polyarylene polymer PBP-1 (pale yellow powder, the structure of which is shown below).

[0080] ; The 1H NMR spectrum of the polyarylene polymer PBP-1 is as follows: 1H NMR (400 MHz, Chloroform-d) δ8.05 (s, 2H), 7.92 (s, 2H), 7.86 (s, 2H), 2.74 (s, 2H), 2.65 (s, 2H), 2.43(s, 4H), 1.9 (s, 6H), 1.32 (s, 6H). 2. The preparation method of polymer flat film is as follows: Take 500 mg of the polyarylene polymer from step 1, dissolve it in 20 mL of dimethyl sulfoxide to obtain a polymer solution, then coat the polymer solution onto a glass plate, and bake the glass plate at 100 °C for 6 h to obtain a polymer flat film PFF-1.

[0081] 3. The preparation method of anion exchange membrane is as follows: The polymer sheet film from step 2 was immersed in a 1 M sodium hydroxide aqueous solution at room temperature for 24 h. After immersion, the film was washed three times with deionized water to obtain the anion exchange membrane AEM-1.

[0082] Example 2 The process was similar to that in Example 1, except that the types of components were different, as listed in Table 2. Polyarylene polymer PBP-2 (pale yellow powder, the structure of which is shown below), polymer flat film PFF-2, and anion exchange film AEM-2 were prepared.

[0083] ; The 1H NMR spectrum of the polyarylene polymer PBP-2 is as follows: 1 H NMR (400 MHz, Chloroform-d) δ8.15 (s, 4H), 8.05 (s, 4H), 7.86 (s, 4H), 2.59 (s, 6H), 2.40 (s, 2H), 1.28(s, 6H). Example 3 The process was similar to that in Example 1, except that the types of components were different, as listed in Table 2. Polyarylene polymer PBP-3 (pale yellow powder, the structure of which is shown below), polymer flat film PFF-3, and anion exchange film AEM-3 were prepared.

[0084] ; Figure 1 This is the 1H NMR spectrum of the polyarylene polymer PBP-3 prepared in Example 3. The 1H NMR spectrum of PBP-3 is as follows: 1H NMR (400 MHz, Chloroform-d) δ 8.12 (s, 4H), 8.06 (s, 4H), 7.88 (s,4H), 2.62 (s, 6H), 2.42 (s, 2H), 1.32 (s, 6H). Figure 2 These are the conductivity test data for the anion exchange membrane AEM-3 prepared in Example 3. From... Figure 2 As can be seen from the data, the ionic conductivity of AEM-3 at 30℃ is ≥70 mS / cm, and it increases continuously with increasing temperature, reaching 150 mS / cm at 80℃.

[0085] Figure 3 This is a water electrolysis polarization curve of the anion exchange membrane AEM-3 prepared in Example 3. From... Figure 3 As can be seen from this, when AEM-3 is used as an anion exchange membrane for water electrolysis, the current density at 60℃ and 1.8 V is ≥1.5 A / cm². 2 .

[0086] Example 4 The process was similar to that in Example 1, except that the types of components were different, as listed in Table 2. Polyarylene polymer PBP-4 (pale yellow powder, the structure of which is shown below), polymer flat film PFF-4, and anion exchange film AEM-4 were prepared.

[0087] ; The 1H NMR spectrum of the polyarylene polymer PBP-4 is as follows: 1 H NMR (400 MHz, Chloroform-d) δ9.25 (s, 1H), 8.16 (s, 2H), 8.04 (s, 2H), 7.88 (s, 2H), 2.49 (s, 4H), 2.40 (s, 4H), 1.28 (s, 6H). Example 5 The same process as in Example 1 was used, except that the types of components were different, as listed in Table 2, to prepare polyaromatic polymer PBP-5 (the structure of which is shown below), polymer flat film PFF-5, and anion exchange film AEM-5.

[0088] ; The 1H NMR spectrum of the polyarylene polymer PBP-5 is as follows: 1H NMR (400 MHz, Chloroform-d) δ8.13 (s, 2H), 8.02 (s, 2H), 2.49 (s, 2H), 2.40 (s, 4H), 1.28 (s, 6H). Example 6 The same process as in Example 1 was used, except that the types of components were different, as listed in Table 2, to prepare polyarylene polymer PBP-6 (the structure of which is shown below), polymer flat film PFF-6, and anion exchange film AEM-6.

[0089] ; The 1H NMR spectrum of the polyarylene polymer PBP-6 is as follows: 1 H NMR (400 MHz, Chloroform-d) δ8.14 (s, 4H), 8.08 (s, 4H), 7.86 (s, 4H), 2.62 (s, 6H), 2.55 (s, 2H) 2.42 (s,2H), 1.46 (s, 6H),1.32 (s, 6H). Comparative Example 1 The process was similar to that of Example 1, except that the types of components were different, as listed in Table 2. Comparative Example 1 could not prepare polyaromatic polymers.

[0090] Comparative Example 2 The process was similar to that of Example 1, except that the types of components were different, as listed in Table 2. Comparative Example 2 could not prepare polyaromatic polymers.

[0091] Table 2

[0092] The names and yields of the polyarylene polymers prepared in each embodiment, the types of groups corresponding to A, R1, R2, R3, and R4 in formulas (I) and (II), and the names of the polymer flat film and the anion exchange film are shown in Table 3.

[0093] Table 3

[0094] Test Example 1 1. Thickness: The thickness of the polymer flat film was tested using a mechanical contact thickness gauge, Langguang CHY-C2A. 2. Tensile strength: The tensile strength of the polymer flat film was tested using a Shimadzu AGS-X universal testing machine; 3. Young's modulus: The Young's modulus of the polymer flat film was tested using a Shimadzu AGS-X universal testing machine; 4. Nanofiltration separation test: The polymer flat sheet membrane was used for nanofiltration separation of waste acid from aluminum oxidation. The waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L was used as the mother liquor. The solution was filtered at 3 atmospheres and room temperature. The sulfuric acid concentration of the filtrate was tested using an acid-base concentration meter, and the aluminum ion concentration of the filtrate was tested using a spectrophotometer. 5. Diffusion Dialysis Test: The polymer flat film was used for diffusion dialysis of waste acid from aluminum oxidation. The mother liquor was a waste liquid with a sulfuric acid concentration of 150 g / L and an aluminum ion concentration of 20 g / L. Dialysis was performed at room temperature. The sulfuric acid concentration of the dialysis solution was tested using an acid-base concentration meter, and the aluminum ion concentration of the dialysis solution was tested using a spectrophotometer.

[0095] The thickness, tensile strength, and Young's modulus of the polymer flat film obtained in the aforementioned examples and preparation examples were tested using the methods described above. Nanofiltration separation and diffusion dialysis tests were also performed on the films, and the results are shown in Table 4.

[0096] Table 4

[0097] Test Example 2 1. Tensile strength: The tensile strength of the anion exchange membrane was tested using a Shimadzu AGS-X universal testing machine; 2. Young's modulus: The Young's modulus of the anion exchange membrane was tested using a Shimadzu AGS-X universal testing machine; 3. Ionic conductivity (30℃): The ionic conductivity of the anion exchange membrane at 30℃ was tested using the four-electrode method. 4. Ionic conductivity (80℃): The ionic conductivity of the anion exchange membrane at 80℃ was tested using the four-electrode method. 5. Using anion exchange membranes as the diaphragm in anion exchange membrane fuel cells: The swelling rate was tested using a micrometer (micrometer) and an electronic balance (in conjunction with the immersion weighing method); the H2 / O2 power density was tested using a DC 980Pro fuel cell testing system at 80℃ and 1.3 bar. 6. Application of anion exchange membrane in vanadium redox flow battery separator: Vanadium ion permeability was tested using a UV-Vis spectrophotometer; it was immersed in VOCs at 80°C. 2+ / H2SO4 (VO 2+ The conductivity was measured by placing the solution (1.5M concentration of vanadium redox flow battery and 3M concentration of H2SO4) in the solution for 30 days using the four-electrode method of an electrochemical workstation. The solution was then assembled into a vanadium redox flow battery, and the coulombic efficiency was measured using a Xinwei battery charge-discharge tester.

[0098] 7. Using anion exchange membranes as diaphragms in anion exchange membrane water electrolysis: The swelling rate was tested using a micrometer (micrometer) and an electronic balance (in conjunction with the immersion weighing method); the current density was tested using an electrochemical workstation at 60℃ and 1.8 V.

[0099] The tensile strength, Young's modulus, and ionic conductivity of the anion exchange membranes obtained in the aforementioned examples and preparation examples were tested using the methods described above. These membranes were then used as separators for anion exchange membrane fuel cells, vanadium redox flow batteries, and anion exchange membrane water electrolysis, and their performance parameters were measured. The results are shown in Table 5.

[0100] Table 5

[0101] Note: AEM-DP was prepared according to the method disclosed in Adv. Funct. Mater. 2018, 28, 1702758.

[0102] The results above show that the polymer flat film prepared using the polyarylene polymer provided by the present invention has the advantages of thin thickness, high mechanical strength, good stability and excellent ion conductivity; the prepared anion exchange film has excellent mechanical strength, electrical conductivity and alkali stability.

[0103] Specifically, the polymer flat sheet films provided by this invention have a thickness of ≤60 μm and can selectively allow sulfuric acid to pass through while partially retaining aluminum ions, achieving partial purification and reuse of waste acid. The anion exchange films provided by this invention have a tensile strength ≥30 MPa, a Young's modulus ≥280 MPa, an ionic conductivity ≥60 mS / cm at 30℃, and an ionic conductivity ≥105 mS / cm at 80℃. When used as membranes in anion exchange membrane fuel cells, their swelling ratio is ≤25%, exhibiting good dimensional stability, and an H2 / O2 power density ≥0.55 W / cm² at 80℃ and 1.3 bar. 2 When used as a separator in vanadium redox flow batteries, the vanadium ion permeability is ≤7.5×10⁻⁶. -7 cm 2 / s, at 80℃, it is immersed in VO 2+ / H2SO4 (VO 2+ After 30 days in solutions with a concentration of 1.5M for sodium hydroxide and 3M for H₂SO₄, the conductivity decreased by ≤0.32%. When assembled into an all-vanadium redox flow battery, the coulombic efficiency was ≥83%. When used as a membrane in anion exchange membrane water electrolysis, its swelling ratio was ≤25%, exhibiting good dimensional stability, and the current density at 60℃ and 1.8 V was ≥0.85 A / cm². 2 .

[0104] In summary, this invention provides a polymer sheet film and anion exchange film with overall performance comparable to existing technologies. These polymer sheet films and anion exchange films use polyarylene polymers as raw materials, significantly enriching the material library of polyarylene AEMs and opening up a new path for developing next-generation membrane materials with high ionic conductivity, excellent dimensional stability, and strong alkali resistance.

[0105] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polyaromatic polymer, characterized in that, The polyarylene polymer has the structural unit shown in formula (I-1) or formula (I-2): Equation (I-1); Equation (I-2); Formula (II-1); Equation (II-2); Formula (II-3); In equations (I-1) and (I-2), A is free to choose C. 6-30 An aromatic compound that leaves at least one of the linking groups formed by any two H atoms that can leave; B is selected from at least one of the linking groups shown in formula (II-1), formula (II-2), and formula (II-3); wherein R3 and R4 are each independently selected from C. 1-10 Alkyl; or, R3 and R4 together cyclize to form C 3-6 The ring structure; X is selected from at least one of F, Cl, Br, I, and HCO3; R1 and R2 are each independently selected from H, unsubstituted or halogenated C. 1-10 Alkyl, unsubstituted or C 1-10 phenyl groups substituted with at least one group in the alkyl group, unsubstituted or C 1-10 At least one of the pyridyl groups substituted with at least one group of the alkyl group; or, R1 and R2 are cyclized together to form C 3-8 Circular structure; 0≤a≤1, 0≤b≤1, and a+b=1.

2. The polyaromatic polymer according to claim 1, characterized in that, In equations (I-1) and (I-2), A is free to choose C. 6-20 The aromatic compound is formed by removing at least one of two linking groups that can be removed by any two H atoms; the aromatic compound is selected from C atoms substituted with phenyl groups. 1-5 Alkanes, 15-18 membered ring crown ethers substituted with phenyl groups, unsubstituted or C-shaped rings 1-5 Alkyl, C 1-5 Alkoxy, C 6-12 Benzene substituted with at least one group in the phenoxy group, unsubstituted or C 1-5 Biphenyls substituted with at least one group in an alkyl group, unsubstituted or C 1-5 Fluorene substituted with at least one group in an alkyl group, unsubstituted or C 1-5 Carbazole substituted with at least one group in the alkyl group, unsubstituted or C 1-5 terphenyls substituted with at least one group in an alkyl group, unsubstituted or C 1-5 At least one of the diphenyl ethers substituted with at least one group of an alkyl group; B is selected from at least one of the linking groups shown in formula (II-1), formula (II-2), and formula (II-3); wherein R3 and R4 are each independently selected from C. 1-5 Alkyl; or, R3 and R4 together cyclize to form C 4-5 The ring structure; X is selected from at least one of F, Cl, Br, I, and HCO3; R1 and R2 are each independently selected from H, unsubstituted or halogenated C. 1-5 Alkyl, unsubstituted or C 1-5 phenyl groups substituted with at least one group in the alkyl group, unsubstituted or C 1-5 At least one of the pyridyl groups substituted with at least one group of the alkyl group; or, R1 and R2 are cyclized together to form C 3-6 Its ring-shaped structure.

3. The polyaromatic polymer according to claim 2, characterized in that, In equations (I-1) and (I-2), A is free to choose C. 6-20 The aromatic compound is formed by removing at least one of the linking groups formed by any two H atoms that can leave; the aromatic compound is selected from at least one of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； B is selected from at least one of the linking groups shown in formula (II-4), formula (II-5), formula (II-6), formula (II-7), and formula (II-8); Equation (II-4); Equation (II-5); Equation (II-6); Equation (II-7); Equation (II-8); In formulas (II-4), (II-5), (II-6), (II-7), and (II-8), X is selected from at least one of F, Cl, Br, I, and HCO3; R1 and R2 are each independently selected from at least one of H, methyl, ethyl, trifluoromethyl, pyridyl, phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, and mesitylene; or, R1 and R2 together cyclize to form C 5-6 Circular structure; Preferably, the polyarylene polymer is selected from any one of the following: 、 、 、 。 4. A method for preparing the polyarylene polymer according to any one of claims 1-3, characterized in that, The method includes: In the presence of an acid catalyst, ketal monomer C and aromatic monomer D undergo a Friedel-Crafts reaction to obtain the polyarylene polymer; wherein the ketal monomer C has at least one of the structures shown in formula (III-1), formula (III-2), and formula (III-3); and the aromatic monomer D is C 6-30 Aromatic compounds; Equation (III-1); Equation (III-2); Formula (III-3); In Equations (III-1), (III-2), and (III-3), the definitions of R3, R4, and X correspond to the definitions in any one of claims 1-3.

5. The method according to claim 4, characterized in that, The Friedel-Crafts reaction is carried out with the participation of ketone monomer E to obtain the polyarylene polymer; the ketone monomer E is selected from at least one of the compounds shown in formula (IV-1), formula (IV-2), formula (IV-3), and formula (IV-4). Formula (IV-1); Formula (IV-2); Formula (IV-3); Formula (IV-4); In formula (IV-1), the definitions of R1 and R2 correspond to the definitions in any one of claims 1-3; And / or, the Friedel-Crafts reaction is carried out with the participation of aromatic crosslinking agent monomer F to obtain the polyarylene polymer; wherein the aromatic crosslinking agent monomer F is selected from at least one of triphenylmethane, 1,3,5-triphenylbenzene, 9,9'-spirobisfluorene, tetraphenylethylene, tetraphenylmethane, and hexaphenylbenzene.

6. A method for preparing polyarylene polymer sheet films, characterized in that, The method includes: (1) The polyaromatic polymer is mixed with an organic solvent to obtain material I; (2) The material I is cast or cast onto a substrate to obtain the polyarylene polymer flat film; The polyaromatic polymer is the polyaromatic polymer described in any one of claims 1-3.

7. The polyarylene polymer flat film prepared by the method of claim 6.

8. A method for preparing anion exchange membranes, characterized in that, The method includes: The anion exchange membrane is obtained by immersing a polyarylene polymer sheet film in an alkaline solution and then washing it. The polyarylene polymer flat sheet film is the polyarylene polymer flat sheet film according to claim 7.

9. The anion exchange membrane prepared by the method of claim 8.

10. The application of the anion exchange membrane according to claim 9 in advanced energy and chemical technologies.

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