Aryl ketone-based poly (aryl-alkylene) polymer electrolyte as well as preparation method and application thereof

Abstract

The invention relates to an aryl ketone-based poly (aryl-alkylene) polymer electrolyte as well as a preparation method and application thereof, and belongs to the technical field of compound synthesis. The compound is obtained by carrying out functionalization reaction on aryl ketone polymers, the functionalization reaction is selected from one or more of quaternization reaction, sulfonation reaction and phosphorylation reaction; wherein x is any integer greater than or equal to 1, and y is an integer greater than or equal to 0; a and C are aryl structural units; and B and D are alkylene structural units obtained by reaction of ketone monomers. The aryl ketone-based poly (aryl-alkylene) polymer electrolyte has the advantages of high ionic conductivity, long service life, good mechanical property and the like. The preparation is simple, the reaction condition is mild, the operation is easy, the cost is low, and large-scale industrial production can be realized.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of compound synthesis, and particularly relates to a kind of poly (aryl-alkylene) polymer electrolyte based on aryl ketone and a preparation method and application thereof. BACKGROUND

[0002] Electrolytic water hydrogen production, fuel cell, salt lake lithium extraction, flow battery, electrocatalytic carbon dioxide reduction, acid separation, supercapacitor and the like need to use the polymer film with selective permeability to ions. However, at present, the commercially available film of this kind is still very limited, especially the ion polymer electrolyte membrane with high stability and high selectivity in strong acid and strong base environment. Therefore, the development of the film with strong stability and high ion conductivity is of great significance to its large-scale commercial application. At present, many strategies have been applied to improve the above-mentioned performance of the film, for example, the preparation method of the film with polyphenyl ether as main chain and side chain with bulky rigid structure for anion exchange membrane fuel cell application is disclosed in the invention patent CN117766828A, but the introduction of ether bond will reduce the chemical stability of the film. The invention patent CN113659180A discloses a kind of anion exchange membrane containing twisted aryl and ketone monomer, adhesive and preparation and application, but the twisted aryl will affect the occurrence of polymerization reaction due to its large steric hindrance, thereby causing the film-forming property and mechanical stability of the polymer film to be relatively poor. The invention patent CN116606438A discloses a kind of main chain spirocyclic ammonium polybenzimidazole and a preparation method and application of anion exchange membrane and ionomer solution thereof, but such ion polymer faces problems such as poor stability and low ion conductivity. SUMMARY

[0003] To solve the above technical problems, the present application provides a kind of poly (aryl-alkylene) polymer electrolyte based on aryl ketone and a preparation method and application thereof, which can effectively realize the rapid conduction of ions while maintaining its strong mechanical stability and high chemical stability.

[0004] The first object of the present application is to provide a kind of poly (aryl-alkylene) polymer electrolyte based on aryl ketone, which is obtained by functionalization reaction of the following aryl ketone polymer;The functionalization reaction is selected from one or more of quaternization reaction, sulfonation reaction and phosphatization reaction;

[0005]

[0006] Wherein, x is any integer greater than or equal to 1, and y is an integer greater than or equal to 0;

[0007] A and C are aryl structural units;

[0008] B and D are alkylene structural units obtained by reaction of ketone monomers.

[0009] In one embodiment of the present application, A and C are independently selected from the following structures:

[0010]

[0011] In one embodiment of the present application, B is obtained from one or more of the following ketone monomers by a Friedel-Crafts alkylation reaction;

[0012]

[0013] wherein a, b are independently integers greater than or equal to 1;

[0014] X and Y are independently selected from one or more of F, Cl, Br and I.

[0015] In one embodiment of the present application, D is obtained from one or more of the following ketone monomers by a Friedel-Crafts alkylation reaction;

[0016]

[0017] wherein a, b, c, d, e, f, g, h, i, j, k, 1 are independently integers greater than or equal to 1;

[0018] m, n, o, p, q, r, s, t are independently integers greater than or equal to 0;

[0019] X and Y are independently selected from one or more of F, Cl, Br and I.

[0020] In one embodiment of the present application, the quaternization reaction specifically comprises the following steps: under the action of a base, the aryl ketone polymer and a quaternization functional reagent are reacted in an organic solvent, and then precipitated by a precipitant to obtain the quaternized polymer electrolyte.

[0021] Further, the quaternization functional reagent is selected from one or more of trimethylamine, triethylamine, perfluorotriethylamine, tripropylamine, perfluorotripropylamine, tributylamine, perfluorotributylamine, tripentylamine, perfluorotripentylamine, trihexylamine, perfluorotrihexylamine, triheptylamine, perfluorotriheptylamine, N-methylpiperidine, quinuclidine, pyridine, imidazole and pyrrole.

[0022] Further, the base is selected from 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, Ν,Ν-dimethylethylenediamine and Ν,Ν-diisopropylethylamine.

[0023] Further, the organic solvent is selected from one or more of dimethyl sulfoxide, Ν,Ν-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0024] Further, the precipitant is selected from one or more of water, methanol, ethanol, diethyl ether, ethyl acetate, toluene, xylene, ethylbenzene, tetrahydrofuran, chloroform, and dichloromethane.

[0025] In one embodiment of the present application, the sulfonation reaction specifically includes the following steps: the aryl ketone-based polymer, thioacetate, and peroxobenzoic acid-based compound are reacted in an organic solvent, and then precipitated by an inorganic salt to obtain a sulfonated polymer electrolyte.

[0026] Further, the thioacetate is selected from one or more of lithium thioacetate, beryllium thioacetate, sodium thioacetate, magnesium thioacetate, aluminum thioacetate, potassium thioacetate, calcium thioacetate, titanium thioacetate, chromium thioacetate, manganese thioacetate, iron thioacetate, copper thioacetate, nickel thioacetate, cobalt thioacetate, and zinc thioacetate.

[0027] Further, the peroxobenzoic acid-based compound is selected from one or more of peroxobenzoic acid, meta-chloroperbenzoic acid, tert-butyl peroxobenzoate, tert-amyl peroxobenzoate, tert-hexyl peroxobenzoate, and 4-nitroperoxybenzoic acid.

[0028] Further, the inorganic salt is selected from one or more of sodium chloride, potassium chloride, sodium carbonate, potassium carbonate, sodium sulfate, potassium sulfate, sodium nitrate, potassium nitrate, sodium acetate, and potassium acetate.

[0029] Further, the organic solvent is selected from one or more of dimethyl sulfoxide, Ν,Ν-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0030] In one embodiment of the present application, the phosphonation reaction specifically includes the following steps: the aryl ketone-based polymer, phosphite-based compound, and alcohol-based compound are reacted in an organic solvent, and then precipitated by a precipitant to obtain a phosphonated polymer electrolyte.

[0031] Further, the phosphite-based compound is selected from one or more of diethyl phosphite, triethyl phosphite, dibenzyl phosphite, dibutyl phosphite, di-n-propyl phosphite, triisopropyl phosphite, tri-n-hexyl phosphite, tribenzyl phosphite, triethyl phosphite, triisooctyl phosphite, and didecyl phenyl phosphite.

[0032] Further, the alcohol compound is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, carbitol acetate, diethyl carbitol, and phenyl carbinol.

[0033] Further, the precipitant is selected from one or more of water, methanol, ethanol, diethyl ether, ethyl acetate, toluene, xylene, ethylbenzene, tetrahydrofuran, chloroform, and dichloromethane.

[0034] Further, the organic solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0035] A second object of the present application is to provide a preparation method of the aryl ketone-based poly(aryl-alkylene) polymer electrolyte.

[0036] S1, under the action of a catalyst, aryl monomer A, aryl monomer C, alkylene monomer B, and alkylene monomer D are subjected to a polycondensation reaction in a solvent to obtain an aryl ketone polymer;

[0037] S2, the aryl ketone polymer of S1 is subjected to a functionalization reaction to obtain the aryl ketone-based poly(aryl-alkylene) polymer electrolyte.

[0038] In an embodiment of the present application, in S1, the catalyst is selected from one or more of triflic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methylsulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin;

[0039] The solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0040] In an embodiment of the present application, in S1, the molar ratio of the catalyst to the total amount of monomers is 1:(0.1-10).

[0041] In an embodiment of the present application, in S2, during the functionalization reaction, the molar ratio of the aryl ketone polymer to the functional monomer is 1:(0.5-20).

[0042] A third object of the present application is to provide a polymer electrolyte membrane prepared from the aryl ketone-based poly(aryl-alkylene) polymer electrolyte.

[0043] In an embodiment of the present application, the thickness of the polymer electrolyte membrane is 5 μm-500 μm.

[0044] In one embodiment of the present application, the polymer electrolyte membrane is selected from a flat sheet membrane, a hollow fiber membrane, a proton exchange membrane, or an anion exchange membrane.

[0045] In one embodiment of the present application, the flat sheet membrane is prepared by dissolving an aryl ketone-based poly(aryl-alkylene) polymer electrolyte in an organic solvent to obtain a polymer solution, and then casting or flow-casting the polymer solution on a substrate, and drying to obtain the flat sheet membrane.

[0046] Further, the concentration of the polymer solution is 0.1 wt% to 20 wt%.

[0047] Further, the organic solvent is selected from one or more of dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

[0048] Further, the substrate is selected from a glass plate, a copper sheet, an iron sheet, a stainless steel sheet, a ceramic plate, a polytetrafluoroethylene plate, a polyethylene terephthalate-based membrane, a polyamide-based membrane, a polytetrafluoroethylene-based membrane, a polyethylene-based membrane, a polypropylene-based membrane, a cellulose derivative-based membrane, a polysulfone-based membrane, a polyamide-based membrane, a polyimide-based membrane, a polyester-based membrane, a polyolefin-based membrane, a vinyl-based polymer membrane, a silicon-containing polymer membrane, a fluorine-containing polymer membrane, a chitin-based polymer membrane, a polyaromatic hydrocarbon-based membrane, a carbon fiber-based membrane, or a glass fiber-based membrane.

[0049] In one embodiment of the present application, the hollow fiber membrane is prepared by immersing a hollow fiber membrane in the polymer solution, and drying to obtain the flat sheet membrane, or by using a dry-wet spinning technique to prepare the hollow fiber membrane from the polymer solution.

[0050] Further, the hollow fiber membrane is selected from 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.

[0051] In one embodiment of the present application, the preparation of the proton exchange membrane specifically comprises the following steps: soaking the aryl ketone-based poly(aryl-alkylene) polymer electrolyte in an acidic solution with a concentration of 0.1-20 mol / L to obtain an acidified polymer; then dissolving the acidified polymer in an organic solvent to obtain a polymer solution; and finally, casting or flow-casting the polymer solution on a substrate, or soaking a hollow fiber membrane in the polymer solution, or preparing a hollow fiber membrane from the polymer solution by dry-wet spinning technology, and drying to obtain the proton exchange membrane.

[0052] Alternatively, the flat sheet membrane or the hollow fiber membrane is soaked in an acidic solution with a concentration of 0.1-20 mol / L, and dried to obtain the proton exchange membrane.

[0053] Further, the acidic solution is selected from one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, methanesulfonic acid, and trifluoromethanesulfonic acid.

[0054] In one embodiment of the present application, the preparation of the anion exchange membrane specifically comprises the following steps: soaking the flat sheet membrane or the hollow fiber membrane in an aqueous hydroxide solution, an aqueous bromide solution, an aqueous chloride solution, an aqueous fluoride solution, an aqueous nitrate solution, or an aqueous bicarbonate solution, and then washing with pure water to obtain the anion exchange membrane.

[0055] Further, the hydroxide is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonium hydroxide.

[0056] Further, the bromide is selected from one or more of sodium bromide, potassium bromide, cesium bromide, ammonium bromide, magnesium bromide, and calcium bromide.

[0057] Further, the chloride is selected from one or more of sodium chloride, potassium chloride, cesium chloride, ammonium chloride, magnesium chloride, and calcium chloride.

[0058] Further, the fluoride is selected from one or more of sodium fluoride, potassium fluoride, cesium fluoride, ammonium fluoride, magnesium fluoride, and calcium fluoride.

[0059] Further, the nitrate is selected from one or more of sodium nitrate, potassium nitrate, cesium nitrate, ammonium nitrate, magnesium nitrate, and calcium nitrate.

[0060] Further, the bicarbonate is selected from one or more of sodium bicarbonate, potassium bicarbonate, magnesium bicarbonate, cesium bicarbonate, ammonium bicarbonate, and calcium bicarbonate.

[0061] A fourth object of the present application is to provide an application of the polymer electrolyte membrane in electrolytic water hydrogen production, carbon dioxide reduction, and fuel cells.

[0062] The technical scheme of the present application has the following advantages compared with the prior art:

[0063] (1) The aryl ketone-based poly(aryl-alkylene) polymer electrolyte has rigid-flexible aryl ketone side chains, which improves the spacing between chains, reduces the force between molecular chains, makes the self-assembly of polymer chain segments easier to proceed, and thus forms an excellent microphase separation structure to accelerate ion transmission. At the same time, the rigid-flexible side chains can effectively improve the dimensional stability and mechanical properties of the film.

[0064] (2) The functional groups on the aryl ketone-based poly(aryl-alkylene) polymer electrolyte have a long spacing with the main chain, and due to the presence of aromatic rings on the side chain, the attack of free radicals and ions on the main chain can be effectively reduced, thereby effectively improving the chemical stability of the polymer electrolyte.

[0065] (3) The aryl ketone-based poly(aryl-alkylene) polymer electrolyte has high ionic conductivity, long service life, good mechanical properties and other advantages. It is simple to prepare, has mild reaction conditions, is easy to operate, has low cost, and can be mass industrialized. BRIEF DESCRIPTION OF DRAWINGS

[0066] In order to make the content of the present application more easily understood, the present application will be further described in detail below according to specific embodiments of the present application and in conjunction with the drawings, in which:

[0067] Figure 1 The H nuclear magnetic resonance spectrum of PmTP of Test Example 1 of the present application is as follows: 1

[0068] Figure 2 The H nuclear magnetic resonance spectrum of QPmTP of Test Example 1 of the present application is as follows: 1

[0069] Figure 3 The H nuclear magnetic resonance spectrum of PFPC4 of Test Example 1 of the present application is as follows: 1

[0070] Figure 4 The H nuclear magnetic resonance spectrum of QPFPC4 of Test Example 1 of the present application is as follows: 1

[0071] Figure 5 The physical map of QPmTP-OH film of Test Example 2 of the present application is as follows:

[0072] Figure 6 The physical map of QPFPC4-OH film of Test Example 2 of the present application is as follows:

[0073] Figure 7 ​​​​Figure for testing the water electrolysis performance of QPmTP-OH membrane and PiperION membrane in Example 3 of the present application at 60℃;

[0074] Figure 8 Figure for testing the water electrolysis performance of QPmTP-OH membrane in Example 3 of the present application at 60℃ and 80℃;

[0075] Figure 9 Figure for testing the solid content of QPFPC4-OH membrane and PiperION membrane in Example 4 of the present application after 50h testing at 80℃;

[0076] Figure 10 Figure for testing the mechanical properties of QP(FP-co-mTP)-OH membrane and PiperION membrane in Example 5 of the present application;

[0077] Figure 11 Figure for testing the swelling properties of SP(FP-co-mTP)-H membrane and PiperION membrane in Example 6 of the present application at 80℃;

[0078] Figure 12 Figure for the surface morphology of PP(FP-co-mTP)-H membrane in Example 7 of the present application by scanning electron microscope. DETAILED DESCRIPTION

[0079] The present application will be further described in conjunction with the accompanying drawings and specific examples, so that those skilled in the art can better understand the present application and implement it, but the examples are not intended to limit the present application.

[0080] In the present application, unless otherwise specified, m and n in the structural formula in the examples of the present application are the percentage of the two structures in the box, both are 50%, and the structural formula of the polymer only shows one possible molecular structure, and does not represent all molecular chains are this structure, because it is a copolymer, the connection mode inside the molecular chain is various.

[0081] Example 1

[0082] The aryl ketone-based poly(aryl-alkylene) polymer electrolyte and the preparation method thereof of the present embodiment specifically comprises the following steps:

[0083]

[0084] S1, Preparation of polymer: 4.61 g (20 mmol) of m-terphenyl (CAS No.: 92-06-8), 7.08 g (24 mmol) of 1-bromo-3-trifluoroacetylphenylpropane (CAS No.: 2638568-95-1) were dissolved in 12 mL of dichloromethane, stirred at room temperature for 10 min, while slowly adding 4 mL of trifluoromethanesulfonic acid, the dropwise time was controlled at about 1 h; then continue to stir for 6 h until the solution becomes viscous; 20 mL of dichloromethane was added to the viscous solution, after stirring uniformly, the reaction liquid was precipitated in methanol, and after vacuum drying, the polymer powder, namely PmTP, was obtained;

[0085] S2, Preparation of aryl ketone-based poly(aryl-alkylene) polymer electrolyte: 5 g (10.82 mmol) of polymer powder PmTP was dissolved in 20 mL of tetrahydrofuran, 25 mL of trimethylamine solution (50 mmol) was added, and stirred at room temperature for 72 h; then the product was poured into a beaker, heated to 60°C to remove excess trimethylamine and part of the solvent, and when the reaction liquid became very viscous, methanol was added for dilution; the diluted reaction liquid was precipitated in anhydrous ether, and after vacuum drying, the aryl ketone-based poly(aryl-alkylene) polymer electrolyte powder, namely QPmTP, was obtained.

[0086] Example 2

[0087] The aryl ketone-based poly(aryl-alkylene) polymer electrolyte and the preparation method thereof of the present embodiment specifically comprises the following steps:

[0088]

[0089] S1, Preparation of polymer: 4.61 g (20 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3), 7.08 g (24 mmol) of 1-bromo-4-trifluoroacetylphenylbutane were dissolved in 16 mL of dichloromethane, stirred at room temperature for 10 min, while slowly adding 4 mL of trifluoromethanesulfonic acid, the dropwise time was controlled at about 1 h; then continue to stir for 6 h until the solution becomes viscous; 20 mL of dichloromethane was added to the viscous solution, after stirring uniformly, the reaction liquid was precipitated in methanol, and after vacuum drying, the polymer powder, namely PFPC4, was obtained;

[0090] S2, Preparation of aryl ketone-based poly(aryl-alkylene) polymer electrolyte: 5 g (10.22 mmol) of polymer powder P(FP-co-mTP) was dissolved in 20 mL of tetrahydrofuran, 25 mL of trimethylamine solution (50 mmol) was added, and stirred at room temperature for 72 h; then the product was poured into a beaker, and the excess trimethylamine and part of the solvent were removed by heating the heating plate at 60°C, when the reaction liquid became very viscous, methanol was added for dilution; the diluted reaction liquid was precipitated in anhydrous ether, and after vacuum drying, aryl ketone-based poly(aryl-alkylene) polymer electrolyte powder, namely QP(FP-co-mTP), was obtained.

[0091] Example 3

[0092] The aryl ketone-based poly(aryl-alkylene) polymer electrolyte and the preparation method thereof of the present embodiment specifically include the following steps:

[0093]

[0094] S1, Preparation of polymer: 2.303 g (10 mmol) of m-terphenyl (CAS No.: 92-06-8), 1.943 g (10 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3), and 7.08 g (24 mmol) of 1-bromo-3-trifluoroacetylphenyl propane (CAS No.: 2638568-95-1) were dissolved in 16 mL of dichloromethane, stirred at room temperature for 10 min, and 4 mL of triflic acid was slowly added dropwise, with the dropwise time controlled at about 1 h; then stirring was continued for 6 h until the solution became viscous; 20 mL of dichloromethane was added to the viscous solution, and after stirring uniformly, the reaction liquid was precipitated in methanol, and after vacuum drying, polymer powder, namely P(FP-co-mTP), was obtained.

[0095] S2, Preparation of aryl ketone-based poly(aryl-alkylene) polymer electrolyte: 5 g (10.22 mmol) of polymer powder P(FP-co-mTP) was dissolved in 20 mL of tetrahydrofuran, 25 mL of trimethylamine solution (50 mmol) was added, and stirred at room temperature for 72 h; then the product was poured into a beaker, and the excess trimethylamine and part of the solvent were removed by heating the heating plate at 60°C, when the reaction liquid became very viscous, methanol was added for dilution; the diluted reaction liquid was precipitated in anhydrous ether, and after vacuum drying, aryl ketone-based poly(aryl-alkylene) polymer electrolyte powder, namely QP(FP-co-mTP), was obtained.

[0096] Example 4

[0097] The aryl ketone-based poly(aryl-alkylene) polymer electrolyte and the preparation method thereof of the present embodiment specifically include the following steps:

[0098]

[0099] S1, Preparation of the polymer: 2.303 g (10 mmol) of m-terphenyl (CAS No.: 92-06-8), 1.943 g (10 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3), 7.08 g (24 mmol) of 1-bromo-3-trifluoroacetylphenylpropane (CAS No.: 2638568-95-1) were dissolved in 16 mL of dichloromethane, stirred at room temperature for 10 min, and 4 mL of trifluoromethanesulfonic acid was slowly added dropwise, with the dropwise time controlled at about 1 h; then continue to stir for 6 h until the solution becomes viscous; 20 mL of dichloromethane was added to the viscous solution, stirred uniformly, and then precipitated in methanol, and vacuum dried to obtain the polymer powder, namely P(FP-co-mTP).

[0100] S2, Preparation of the aryl ketone-based poly(aryl-alkylene) polymer electrolyte: 5 g (10.22 mmol) of the polymer powder P(FP-co-mTP) was dissolved in 25 mL of dimethylacetamide, 1.4 g (12.264 mmol) of potassium thioacetate was added, and stirred at 50°C for 5 h, then the product was precipitated in methanol, and vacuum dried to obtain the intermediate powder P(FP-co-mTP)-SO; 5 g (10.33 mmol) of the intermediate powder P(FP-co-mTP)-SO was dissolved in 25 mL of dimethylacetamide, and 7.14 g (30.99 mmol) of m-chloroperbenzoic acid was slowly added at 0°C; the reaction solution was heated to 25°C, and then stirred for 5 h; the polymer solution after reaction was precipitated in 1 mol / L sodium chloride solution, and vacuum dried to obtain the aryl ketone-based poly(aryl-alkylene) polymer electrolyte powder, namely SP(FP-co-mTP).

[0101] Example 5

[0102] The aryl ketone-based poly(aryl-alkylene) polymer electrolyte and the preparation method thereof of the present embodiment specifically comprises the following steps:

[0103]

[0104] S1, Preparation of the polymer: 2.303 g (10 mmol) of m-terphenyl (CAS No.: 92-06-8), 1.943 g (10 mmol) of 9,9-dimethylfluorene (CAS No.: 4569-45-3), 7.08 g (24 mmol) of 1-bromo-3-trifluoroacetylphenylpropane (CAS No.: 2638568-95-1) were dissolved in 16 mL of dichloromethane, stirred at room temperature for 10 min, and 4 mL of trifluoromethanesulfonic acid was slowly added dropwise, with the dropwise time controlled at about 1 h; then continue to stir for 6 h until the solution becomes viscous; 20 mL of dichloromethane was added to the viscous solution, and after stirring uniformly, the reaction liquid was precipitated in methanol, and after vacuum drying, the polymer powder, P(FP-co-mTP), was obtained.

[0105] S2, Preparation of the aryl ketone-based poly(aryl-alkylene) polymer electrolyte: 5 g (10.22 mmol) of the polymer powder P(FP-co-mTP) was dissolved in 30 mL (167.5 mmol) of diethylcarbinol, 15 mL of triethyl phosphite (87.5 mmol) was added, and stirred at 140°C for 2 h; then the product was precipitated in methanol, and vacuum dried to obtain the aryl ketone-based poly(aryl-alkylene) polymer electrolyte powder, P(FP-co-mTP)-OCH2CH3.

[0106] Test Example 1

[0107] PmTP, QPmTP, PFPC4 and QPFPC4 1 The H nuclear magnetic resonance spectrum is shown in Figures 1-4 It can be seen from Figures 1-4 that PmTP, QPmTP, PFPC4 and QPFPC4 are successfully synthesized.

[0108] Test Example 2

[0109] Based on Example 1 and Example 2, 0.15 g of QPmTP and QPFPC4 were respectively dissolved in 10 mL of dimethyl sulfoxide to prepare a casting solution, and then the casting solution was uniformly coated on a glass flat plate, and baked at 80°C for 48 h, and then soaked in 1 mol / L aqueous sodium hydroxide solution for 24 h, and after taking out, repeatedly washed with pure water to obtain the OH-form ion exchange membrane, namely QPmTP-OH membrane and QPFPC4-OH membrane, and the actual figure is shown in Figures 5-6 It can be seen from Figures 5-6 that the film-forming properties of QPmTP-OH membrane and QPFPC4-OH membrane are excellent.

[0110] Test Example 3

[0111] (1) Based on Test Example 2, the water electrolysis performance of the QPmTP-OH membrane and the PiperION membrane (Versogen Company) was tested, the self-made NiFe catalyst, PiperIon ionomer and isopropyl alcohol were prepared into a catalyst ink, and the catalyst ink was uniformly sprayed onto the membrane by ultrasonic spraying to prepare a membrane electrode; two kinds of membrane electrodes were assembled into an electrolysis tank, and the effective test area of the membrane electrode was 2*2 cm 2 The water electrolysis performance test was carried out at 60°C, and the results are shown in Figure 7 From Figure 7 it can be seen that the current density of the QPmTP-OH membrane of Example 1 and the PiperION membrane of Comparative Example 1 is 9.6 A cm -2 and 6.16 A cm -2 respectively under a voltage of 2.2V; it can be seen that the water electrolysis performance of the QPmTP-OH membrane is much higher than that of the PiperION membrane, which shows that the QPmTP-OH membrane has excellent water electrolysis performance. In addition, the QPmTP-OH membrane also shows a lower overpotential in the ohmic interval of the polarization curve, which shows that it has excellent ionic conductivity.

[0112] (2) Based on the above experiment, the water electrolysis performance test results of the QPmTP-OH membrane at 60°C and 80°C are shown in Figure 8 From Figure 8 it can be seen that the current density of the QPmTP-OH membrane at 60°C and 80°C is 9.6 A cm -2 and 11.2 A cm -2 respectively under a voltage of 2.2V; it shows that the QPmTP-OH membrane has excellent water electrolysis performance at different temperatures.

[0113] Test Example 4

[0114] Based on Test Example 2, the chemical stability of the QPFPC4-OH membrane and the PiperION membrane (Versogen Company) was tested, and the membranes were immersed in a 5 mol / L KOH solution at 80°C. The solid content test results of the membranes after 50h immersion are shown in Figure 9 From Figure 9 it can be seen that the solid content of the QPFPC4-OH membrane and the PiperION membrane is 98.9% and 96.3% respectively; it can be seen that the solid content of the QPFPC4-OH membrane is higher than that of the PiperION membrane, which shows that the QPFPC4-OH membrane has excellent chemical stability.

[0115] Test Example 5

[0116] Referring to Test Example 2, a QP(FP-co-mTP)-OH membrane was prepared. The mechanical properties of the QP(FP-co-mTP)-OH membrane and the PiperION membrane (Versogen) were tested. The membrane sample used in the test was 4cm*1cm in size, with an effective tensile length of 2cm and a tensile rate of 5mm / min. The results are as follows: Figure 10 As shown. From Figure 10 It can be seen that the tensile strengths of the QP(FP-co-mTP)-OH membrane in Example 3 and the PiperION membrane in Comparative Example 1 are 43.7 MPa and 31.9 MPa, respectively. It is evident that the tensile strength of the QP(FP-co-mTP)-OH membrane is significantly higher than that of the PiperION membrane. In addition, the elongation at break of the QP(FP-co-mTP)-OH membrane (5.1%) is also better than that of the PiperION membrane (3.3%), indicating that the QP(FP-co-mTP)-OH membrane has excellent mechanical properties.

[0117] Test Example 6

[0118] Based on Example 4, 0.15 g of SP (FP-co-mTP) was dissolved in 10 mL of dimethyl sulfoxide to prepare a casting solution. The casting solution was then uniformly coated onto a glass plate and dried at 80 °C for 48 h. Afterward, it was immersed in a 1 mol / L dilute sulfuric acid solution for 24 h. The solution was then repeatedly washed with pure water to obtain H. + The form of ion exchange membrane, namely SP(FP-co-mTP)-H membrane.

[0119] The dimensional stability of SP (FP-co-mTP)-H membranes and PiperION membranes (Versogen) was tested. Membrane samples measuring 1 cm x 4 cm were used. The membranes were immersed in pure water at 80°C for 24 hours, and their length changes were measured. The results are as follows: Figure 11 As shown. From Figure 11 It can be seen that the swelling ratios of SP(FP-co-mTP)-H membrane and PiperION membrane are 7.8% and 5.5%, respectively; it is evident that the swelling ratio of SP(FP-co-mTP)-H membrane is significantly lower than that of PiperION membrane, indicating that SP(FP-co-mTP)-H membrane has excellent dimensional stability.

[0120] Test Example 7

[0121] Based on Example 5, 0.15 g of P(FP-co-mTP)-OCH2CH3 was dissolved in 10 mL of dimethyl sulfoxide to prepare a casting solution. The casting solution was then uniformly coated onto a glass plate and dried at 80 °C for 48 h. Afterward, it was immersed in a 1 mol / L hydrochloric acid solution for 24 h. The solution was then repeatedly washed with pure water to obtain H... +Formal ion exchange membrane, i.e. PP(FP-co-mTP)-H membrane.

[0122] The surface morphology of the PP(FP-co-mTP)-H membrane was analyzed by electron scanning electron microscope, and the results are shown in Figure 12 It can be seen from Figure 12 that the surface of the PP(FP-co-mTP)-H membrane is smooth and flat, without defects such as cracks.

[0123] Obviously, the above examples are only examples for clearly illustrating the present application, and are not intended to limit the embodiments. Based on the above description, other different forms of changes or variations can be made by those skilled in the art. Here, it is not necessary and impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. An aryl ketone-based poly(aryl-alkylene) polymer electrolyte, characterized by, obtained from functionalization of an aryl ketone-based polymer; the functionalization is selected from one or more of a quaternization reaction, a sulfonation reaction, and a phosphonation reaction; wherein x is any integer greater than or equal to 1, and y is an integer greater than or equal to 0; A and C are aryl structural units; B and D are alkylene structural units obtained from reaction of ketone monomers.

2. The aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to claim 1, characterized by, A and C are independently selected from the following structures:

3. The aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to claim 1, characterized by, B is obtained from one or more of the following ketone monomers via a Friedel-Crafts alkylation reaction; wherein a, b are independently integers greater than or equal to 1; X and Y are independently selected from one or more of F, Cl, Br, and I.

4. The aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to claim 1, characterized by, D is obtained from one or more of the following ketone monomers via a Friedel-Crafts alkylation reaction; wherein a, b, c, d, e, f, g, h, i, j, k, 1 are independently integers greater than or equal to 1; m, n, o, p, q, r, s, t are independently integers greater than or equal to 0; X and Y are independently selected from one or more of F, Cl, Br, and I.

5. The method for preparing an aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to any one of claims 1 to 4, characterized in that, comprising the following steps: S1, aryl monomer A, aryl monomer C, alkylene monomer B, and alkylene monomer D are subjected to a polycondensation reaction in the presence of a catalyst to obtain an aryl ketone-based polymer; S2, the aryl ketone-based polymer obtained in S1 is subjected to a functionalization reaction to obtain the aryl ketone-based poly(aryl-alkylene) polymer electrolyte.

6. The method for preparing an aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to claim 5, characterized by, In S1, the catalyst is selected from one or more of triflic acid, trifluoroacetic acid, acetic acid, trichloroacetic acid, methylsulfonic acid, pentafluoropropionic acid, heptafluorobutyric acid, and perfluorosulfonic acid resin; the solvent is selected from one or more of dimethyl sulfoxide, Ν,Ν-dimethylformamide, Ν,Ν-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, chloroform, dichloromethane, toluene, ethylbenzene, xylene, and ethyl acetate.

7. The method for preparing an aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to claim 5, characterized by, In S1, the molar ratio of the catalyst to the total amount of monomers is 1:(0.1-10).

8. The method for preparing an aryl ketone-based poly(aryl-alkylene) polymer electrolyte according to claim 5, characterized by, In S2, the molar ratio of the aryl ketone-based polymer to the functional monomer during the functionalization reaction is 1:(0.5-20).

9. A polymer electrolyte membrane, characterized by, The polymer electrolyte membrane is prepared from the aryl ketone-based poly(aryl-alkylene) polymer electrolyte of any one of claims 1-4.

10. Use of the polymer electrolyte membrane of claim 9 in electrolysis of water for hydrogen production, carbon dioxide reduction, and fuel cells.

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