Polynaphthylpiperidine cross-linked anion exchange membrane with hydrophilic and hydrophobic structure as well as preparation method and application of polynaphthylpiperidine cross-linked anion exchange membrane

Abstract

The invention provides a polynaphthylpiperidine cross-linked polymer. The polynaphthylpiperidine cross-linked polymer comprises a structural unit as shown in a formula (I) which is described in the specification. The invention also provides a polynaphthylpiperidine cross-linked anion exchange membrane with a hydrophilic and hydrophobic structure and a preparation method of the polynaphthylpiperidine cross-linked anion exchange membrane, monomers with relatively large molecular weight are introduced, and ion transmission is accelerated by forming a developed high ion conduction channel, so that the ion conductivity is improved; a cross-linked network structure is constructed by using a cross-linking agent, so that the dimensional stability and the mechanical property are improved; the method for green preparation of the anion exchange membrane by using solid acid and solid superacid catalysts is provided for the first time, the catalyst can be recycled, and the method is green, environment-friendly and low in cost; according to the invention, hydrophilic and hydrophobic chain segments are introduced to construct a microphase separation structure, so that a developed ion transmission channel can be formed, rapid transmission of ions is promoted, and the ionic conductivity and alkali stability are improved. The anion exchange membrane has ultrahigh conductivity, excellent mechanical stability and excellent alkali resistance. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of hydrogen production by electrolyzing water with an anion exchange membrane, and relates to a poly(naphthylpiperidine) cross-linked polymer and its preparation method, application, an anion exchange membrane and its application, and particularly relates to a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures and its preparation method and application. Background Art

[0002] Hydrogen is an ideal energy carrier for decarbonization and storing renewable electricity. Electrolyzing water using the electricity of renewable energy can produce high-purity hydrogen without carbon emissions, which is considered a sustainable method for energy conversion and storage. Anion exchange membrane water electrolysis for hydrogen production (AEMWE) combines the advantages of mature alkaline water electrolysis for hydrogen production (AWE) and proton exchange membrane water electrolysis for hydrogen production (PEMWE), and has significant advantages. Assembling an AEMWE cell with a zero-gap of a solid polymer electrolyte AEM can operate at a high current density and produce pressurized and high-purity hydrogen. At the same time, the alkaline working environment provides the possibility of using platinum-group metal-free catalysts and inexpensive metal hardware. However, as the core component of AEMWE, AEMs and anion exchange polyelectrolytes (AEPs) still cannot guarantee high current density and lifespan. Although researchers have developed several commercial AEMs and anion exchange ionomers (AEIs). However, to achieve the practical application of AEMWE, higher-performance AEMs are needed. Due to the strong nucleophilicity and alkalinity of hydroxides, ideal AEMs have high ionic conductivity, strong mechanical properties, and lasting chemical stability, which are necessary conditions to meet the harsh working environment. Therefore, it is very important to improve the chemical stability, mechanical stability, and ionic conductivity of anion exchange membranes.

[0003] In the past two decades, a great deal of work has been done in improving the chemical stability of AEMs. AEMs with ether bonds in the polymer backbone will undergo main-chain cleavage of C-O bonds and / or radical-initiated degradation in an alkaline environment. Therefore, AEMs with an all-carbon backbone are considered the best materials. For example, in the patent: a poly(biphenyl alkane) anion exchange membrane invented in 201510940136.5, the OH - ionic conductivity reaches 128 mS cm -1 , and 90% of the conductivity retention rate remains after soaking in 1 M NaOH solution for 60 days; in the patent: a poly(fluorene piperidine) anion exchange membrane invented in 202110306762.4, the OH - ionic conductivity is 60 mS cm -1, after being soaked in 2M NaOH solution for 480h, the conductivity loss of the membrane is 5.4%. However, all of the above research schemes use liquid acid (trifluoromethanesulfonic acid) as the catalyst, which requires a large amount of catalyst and the catalyst cannot be recycled, resulting in problems such as non-environmental protection of the production process and high costs.

[0004] Therefore, how to find a more suitable way to solve the above problems existing in the prior art has become one of the focuses widely concerned by many front-line researchers in the industry. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a poly(naphthylpiperidine) cross-linked polymer, its preparation method, application, an anion exchange membrane and its application, especially a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures. The anion exchange membrane provided by the present invention has high alkali resistance, good mechanical stability and high ionic conductivity. In the preparation process, for the first time, solid acid and solid superacid catalysts are proposed to prepare the anion exchange membrane greenly, which is environmentally friendly and low-cost; by introducing hydrophilic and hydrophobic chain segments to construct a microphase separation structure, it helps to form a developed ion transport channel, promotes the rapid transport of ions, thereby improving the ionic conductivity and alkali stability; using a cross-linking agent to construct a cross-linked network structure improves the dimensional stability and mechanical properties; by introducing monomers with larger molecular weights, a developed high-ion conduction channel can be formed, accelerating ion transport, thereby improving the ionic conductivity. Moreover, the preparation method is simple, the conditions are mild, it is environmentally friendly, and it is more suitable for the popularization and application of industrial production, and has good application prospects in the field of electrolytic water hydrogen production.

[0006] The present invention provides a poly(naphthylpiperidine) polymer, and the poly(naphthylpiperidine) polymer includes a structural unit shown in formula (I):

[0007]

[0008] wherein, n = 0.5 to 0.99;

[0009] The A1 is selected from one or more of the groups shown in formula (1) to formula (3):

[0010]

[0011] The A2 is selected from the group shown in formula (4):

[0012]

[0013] The R is selected from one or more of the groups shown in formula (5) to formula (6):

[0014]

[0015] R’ is selected from one or more of the groups represented by Formula (7) to Formula (8):

[0016]

[0017] The R 1 is selected from one or more of the groups represented by Formula (9) to Formula (14):

[0018]

[0019] The present invention provides a poly(naphthylpiperidine) cross-linked polymer, and the poly(naphthylpiperidine) cross-linked polymer includes a structural unit represented by Formula (I). Compared with the prior art, the present invention creatively designs a poly(naphthylpiperidine) cross-linked polymer with a specific structure. As an anion exchange membrane, the poly(naphthylpiperidine) cross-linked polymer has excellent technical effects, and is an anion exchange membrane with high alkali resistance, good mechanical stability and ultra-high ionic conductivity. By introducing hydrophilic and hydrophobic segments and constructing a microphase separation structure, the present invention helps to form a developed ion transport channel, promotes the rapid transport of ions, and thus improves the ionic conductivity; by introducing monomers with a relatively large molecular weight, a developed high-ion conduction channel can be formed to accelerate the ion transport; a cross-linking agent is used to construct a cross-linked network structure, improving the dimensional stability and mechanical properties; a new technical route for green preparation of anion exchange membranes using solid acids and solid superacids is adopted, which is of great significance for achieving the dual-carbon goal; and the preparation method is simple, and it has good application prospects in the field of electrolysis of water to produce hydrogen.

[0020] The present invention also provides a preparation method of the poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures, and it is applied to the field of electrolysis of water to produce hydrogen; (1) The present invention proposes to introduce monomers with a relatively large molecular weight, which can form a developed high-ion conduction channel to accelerate the ion transport, thereby improving the ionic conductivity. (2) The present invention proposes to use a cross-linking agent to construct a cross-linked network structure, improving the dimensional stability and mechanical properties. (3) The present invention first proposes a method for green preparation of anion exchange membranes using solid acids and solid superacid catalysts. The catalysts can be recycled, which is green, environmentally friendly and low in cost. (4) The present invention proposes to introduce hydrophilic and hydrophobic segments and construct a microphase separation structure, which helps to form a developed ion transport channel, promotes the rapid transport of ions, and thus improves the ionic conductivity and alkali stability.

[0021] The anion exchange membrane provided by the present invention has high alkali resistance, good mechanical stability and high ionic conductivity, and the preparation method is simple, the conditions are mild, it is green and environmentally friendly, and it is more suitable for the popularization and application of industrial production, and has good application prospects in the field of electrolysis of water to produce hydrogen.

[0022] The experimental results show that the anion exchange membrane prepared by the present invention has ultra-high OH- Conductivity (190.7 mS cm -1 @ 80 °C) and excellent mechanical stability; after being soaked in 1 M KOH at 80 °C for 1000 h, the conductivity loss is only 2.6%, showing excellent alkali resistance; the anion exchange membrane prepared by the present invention can stably operate for 1000 h in an alkaline electrolyzed water membrane electrode, and the voltage hardly decays. The anion exchange membrane prepared by the present invention can be applied to fields such as alkaline electrolyzed water hydrogen production, alkaline fuel cells, and carbon dioxide catalytic reduction. Detailed implementation manners

[0023] In order to further understand the present invention, the preferred implementation manners of the present invention will be described below in conjunction with embodiments. However, it should be understood that these descriptions are only for further explaining the features and advantages of the present invention rather than limiting the claims of the present invention.

[0024] There are no particular restrictions on the sources of all raw materials of the present invention, and they can be purchased on the market or prepared by conventional methods well-known to those skilled in the art.

[0025] There are no particular restrictions on the purity of the raw materials used in the present invention, and the purity requirements of the raw materials for preparing the AEMWE cathode electrode material well-known to those skilled in the art can be used.

[0026] The present invention provides a poly(naphthylpiperidine) cross-linked polymer, and the poly(naphthylpiperidine) cross-linked polymer includes a structural unit shown in formula (I):

[0027]

[0028] wherein, n = 0.5 to 0.99;

[0029] The A1 is selected from one or more of the groups shown in formula (1) to formula (3):

[0030]

[0031] The A2 is selected from the group shown in formula (4):

[0032]

[0033] The R is selected from one or more of the groups shown in formula (5) to formula (6):

[0034]

[0035] The R' is selected from one or more of the groups shown in formula (7) to formula (8):

[0036]

[0037] The R1 One or more selected from the groups represented by Formula (9) to Formula (14):

[0038]

[0039] In the present invention, n is 0.5 to 0.99, can be 0.6 to 0.9, or can be 0.7 to 0.8.

[0040] The present invention provides a method for preparing a polynaphthopiperidine polymer as described in the above technical solution, comprising the following steps:

[0041] 1) Mixing A1 monomer, A2 monomer, hydrophilic group monomer, hydrophobic group monomer containing R1, crosslinking agent R and an organic solvent to obtain a homogeneous solution;

[0042] 2) Reacting the homogeneous solution obtained in the above step under the action of an acid catalyst, pouring it into a precipitant for precipitation to obtain a solid polymer;

[0043] 3) Carrying out a light-shielded reaction on the solid polymer, solvent, crosslinking agent R' and quaternization reagent obtained in the above step, and then performing precipitation to obtain a crosslinked polynaphthopiperidine polymer.

[0044] In the present invention, first, A1 monomer, A2 monomer, hydrophilic group monomer, hydrophobic group monomer containing R1, crosslinking agent R and an organic solvent are mixed to obtain a homogeneous solution.

[0045] In the present invention, the A1 monomer preferably includes one or more of biphenyl, p-terphenyl and m-terphenyl, and more preferably biphenyl, p-terphenyl or m-terphenyl.

[0046] In the present invention, the A2 monomer preferably includes 1,1'-binaphthalene.

[0047] In the present invention, the hydrophilic group monomer preferably includes N-methyl-4-piperidone.

[0048] In the present invention, the hydrophobic group monomer containing R1 preferably includes one or more of trifluoroacetone, trifluoroacetophenone, 4-(trifluoroacetyl)toluene, 2,2,2,4'-tetrafluorobenzophenone, 2,2,2-trifluoro-1-(3,4,5-trifluorophenyl)ethanone and octafluoromethyl phenyl ketone, and more preferably trifluoroacetone, trifluoroacetophenone, 4-(trifluoroacetyl)toluene, 2,2,2,4'-tetrafluorobenzophenone, 2,2,2-trifluoro-1-(3,4,5-trifluorophenyl)ethanone or octafluoromethyl phenyl ketone.

[0049] In the present invention, the crosslinking agent R preferably includes triphenylbenzene, kekulene.

[0050] In the present invention, the organic solvent preferably includes one or more of dimethyl sulfoxide, N-methylpyrrolidone, dichloromethane and tetrahydrofuran, and more preferably dimethyl sulfoxide, N-methylpyrrolidone, dichloromethane or tetrahydrofuran.

[0051] In the present invention, the molar ratio of the A1 monomer to the A2 monomer is preferably (0.5-0.99):(0.5-0.01), more preferably (0.6-0.9):(0.4-0.1), and more preferably (0.7-0.8):(0.3-0.2).

[0052] In the present invention, the molar ratio of the A1 monomer to the hydrophilic group monomer is preferably (0.5-1):(0.55-0.99), more preferably (0.6-0.9):(0.6-0.9), and more preferably (0.7-0.8):(0.7-0.8).

[0053] In the present invention, the molar ratio of the A1 monomer to the hydrophobic group monomer containing R1 is preferably (0.5-1):(0.11-0.55), more preferably (0.6-0.9):(0.2-0.5), and more preferably (0.7-0.8):(0.3-0.4).

[0054] In the present invention, the molar ratio of the A1 monomer to the crosslinking agent R is preferably (0.5-1): (0.005-0.1), more preferably (0.6-0.9): (0.01-0.08), and more preferably (0.7-0.8): (0.03-0.05);

[0055] In the present invention, the homogeneous solution obtained in the above steps is reacted under the action of an acid catalyst, and then a precipitant is added for precipitation to obtain a solid polymer.

[0056] In the present invention, the acid catalyst preferably includes solid acid and organic liquid acid.

[0057] In the present invention, the solid acid includes one or more of ZSM-5, Y-type molecular sieve and β-type molecular sieve, and more preferably ZSM-5, Y-type molecular sieve or β-type molecular sieve.

[0058] In the present invention, the acid catalyst also preferably includes a solid superacid.

[0059] In the present invention, the solid superacid preferably comprises SO 4 2- / ZrO 2 , WO 3 / ZrO 2 、MoO 3 / ZrO 2 and B 2 O3 / ZrO 2 One or more of them, more preferably SO 4 2- / ZrO 2 、WO 3 / ZrO 2 、MoO 3 / ZrO 2 or B 2 O 3 / ZrO 2。

[0060] In the present invention, the organic liquid acid preferably includes trifluoroacetic acid and / or trifluoromethanesulfonic acid, more preferably trifluoroacetic acid or trifluoromethanesulfonic acid.

[0061] In the present invention, the mass ratio of the total mass of the A1 monomer and the A2 monomer to the mass of the solid acid is preferably 1:(50 - 100), more preferably 1:(60 - 90), and even more preferably 1:(70 - 80).

[0062] In the present invention, the mass ratio of the total mass of the A1 monomer and the A2 monomer to the mass of the solid superacid is preferably 1:(20 - 60), more preferably 1:(28 - 52), and even more preferably 1:(36 - 44).

[0063] In the present invention, the molar ratio of the total number of moles of the A1 monomer and the A2 monomer to the mole of the liquid acid is preferably 1:(5 - 13), more preferably 1:(6 - 12), even more preferably 1:(7 - 11), and even more preferably 1:(8 - 10).

[0064] In the present invention, the temperature of the reaction is preferably -4 to 150 °C, more preferably 0 to 150 °C, and even more preferably 0 to 100 °C.

[0065] In the present invention, the reaction time is preferably 4 to 72 h, more preferably 20 to 60 h, and even more preferably 35 to 45 h.

[0066] In the present invention, the precipitant preferably includes anhydrous methanol.

[0067] In the present invention, after the precipitation, it preferably further includes the steps of solution washing and water washing.

[0068] Finally, in the present invention, the solid polymer, solvent, crosslinking agent R', and quaternization reagent obtained in the above steps are subjected to a light-shielded reaction, and then a polynepivacaine cross-linked polymer is obtained after precipitation.

[0069] In the present invention, the quaternization reagent preferably includes methyl iodide.

[0070] In the present invention, R' preferably includes 4-chloromethylstyrene (VBC) and / or 4,4'-trimethylenebis(1-methylpiperidine), more preferably 4-chloromethylstyrene or 4,4'-trimethylenebis(1-methylpiperidine).

[0071] In the present invention, the molar ratio of the solid polymer to the quaternization reagent is preferably 1:(0.8 - 1.3), more preferably 1:(0.9 - 1.2), and even more preferably 1:(1.0 - 1.1).

[0072] In the present invention, the molar ratio of the solid polymer to the crosslinking agent R' is preferably 1:(0.001 - 0.1), more preferably 1:(0.01 - 0.08), and even more preferably 1:(0.03 - 0.05).

[0073] In the present invention, the solvent preferably includes dimethyl sulfoxide.

[0074] In the present invention, the temperature of the light-shielded reaction is preferably 40 - 90 °C, more preferably 50 - 80 °C, and even more preferably 60 - 70 °C.

[0075] In the present invention, the time of the light-shielded reaction is preferably 4 - 72 h, more preferably 20 - 60 h, and even more preferably 35 - 45 h.

[0076] In the present invention, the solvent used for the precipitation reaction solution in step 3) preferably includes ethyl acetate.

[0077] In the present invention, the poly(naphthylpiperidine) crosslinked polymer is specifically preferably a poly(naphthylpiperidine) crosslinked polymer containing hydrophilic and hydrophobic structures.

[0078] The present invention provides an anion exchange membrane, and the anion exchange membrane is a poly(naphthylpiperidine) crosslinked polymer anion exchange membrane;

[0079] The anion exchange membrane includes the alkalized poly(naphthylpiperidine) crosslinked polymer;

[0080] The poly(naphthylpiperidine) crosslinked polymer is the poly(naphthylpiperidine) crosslinked polymer described in the above technical solution or the poly(naphthylpiperidine) crosslinked polymer prepared by the preparation method described in any one of the above technical solutions.

[0081] In the present invention, the poly(naphthylpiperidine) crosslinked polymer anion exchange membrane is preferably prepared by the following steps:

[0082] After mixing the poly(naphthylpiperidine) crosslinked polymer with a polar solution, an anion exchange resin homogeneous casting solution is obtained. Then, after forming the anion exchange resin homogeneous casting solution on a substrate, it is dried and then subjected to alkalization treatment to obtain a poly(naphthylpiperidine) crosslinked anion exchange membrane in the hydroxide form.

[0083] In the present invention, the concentration of the homogeneous solution of the anion exchange resin is preferably 5 wt% to 30 wt%, more preferably 10 wt% to 25 wt%, and even more preferably 15 wt% to 20 wt%.

[0084] In the present invention, the method of alkalization treatment preferably includes soaking in an alkali solution.

[0085] In the present invention, the time of alkalization treatment is preferably 12 to 72 h, more preferably 22 to 62 h, and even more preferably 32 to 52 h.

[0086] The present invention provides the application of the poly(naphthylpiperidine) cross-linked polymer described in the above technical solution, the poly(naphthylpiperidine) cross-linked polymer prepared by the preparation method described in any one of the above technical solutions, or the poly(naphthylpiperidine) cross-linked anion exchange membrane prepared by the preparation method described in any one of the above technical solutions in the field of hydrogen production by electrolyzing water.

[0087] In order to complete and refine the overall technical solution of the present invention, better ensure the structure of the poly(naphthylpiperidine) cross-linked polymer, and further improve the performance of the anion exchange membrane, the above-mentioned poly(naphthylpiperidine) cross-linked polymer and its preparation method, application, an anion exchange membrane and its application may specifically include the following contents:

[0088] A preparation method of a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures. The poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures is polymerized from A1, A2, R1, R / R', and N-methyl-4-piperidone. Among them, A1 is at least one of biphenyl, p-terphenyl, and m-terphenyl, A2 is 1,1'-binaphthalene, R1 is one of trifluoroacetone, trifluoroacetophenone, 4-(trifluoroacetyl)toluene, 2,2,4'-tetrafluoroacetophenone, 2,2,2-trifluoro-1-(3,4,5-trifluorophenyl)ethanone, octafluoromethyl phenyl ketone, R is one of triphenylbenzene and coronene, and R' is one of VBC and 4,4'-trimethylenebis(1-methylpiperidine);

[0089] The structural formula of the poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures is as follows:

[0090]

[0091] Among them, n = 0.5 to 0.99;

[0092]

[0093] Among them, N-methyl-4-piperidone is a hydrophilic group, and R1 is a hydrophobic group.

[0094] The present invention provides a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures, which is prepared by polymerizing A1, A2, R1, R / R', and N-methyl-4-piperidone. Among them, A1 is at least one of biphenyl, p-terphenyl, and m-terphenyl, A2 is 1,1'-binaphthalene, R1 is one of trifluoroacetone, trifluoroacetophenone, 4-(trifluoroacetyl)toluene, 2,2,2,4'-tetrafluorobenzophenone, 2,2,2-trifluoro-1-(3,4,5-trifluorophenyl)ethanone, and octafluoromethyl phenyl ketone, R is one of triphenylbenzene and kekulene, and R' is one of VBC and 4,4'-trimethylenebis(1-methylpiperidine).

[0095] The present invention provides a method for preparing a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures, including a poly(naphthylpiperidine) cross-linked anion exchange membrane described in the above technical solution, specifically including the following steps:

[0096] (1) Dissolve A1, A2, N-methyl-4-piperidone, R1, and cross-linking agent R in the above technical solution in a solvent to obtain a homogeneous solution, add one or two or more of organic liquid acid, solid acid, and solid superacid, react at -4 - 150 °C for 4 - 72 h, after the reaction is completed, precipitate with anhydrous methanol (if solid acid or solid superacid is used, filtration is required first and then precipitation), wash with an aqueous solution of K 2 CO 3 and wash with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer;

[0097] (2) Dissolve the yellow fibrous solid poly(naphthylpiperidine) cross-linked polymer obtained in step (1), cross-linking agent R', and iodomethane in dimethyl sulfoxide, wrap it with tin foil and heat and stir for 12 - 72 h, then pour the reaction solution into ethyl acetate for precipitation, and wash with deionized water to obtain a quaternized poly(naphthylpiperidine) cross-linked polymer;

[0098] (3) Dissolve the quaternized poly(naphthylpiperidine) cross-linked polymer obtained in step (2) in dimethyl sulfoxide to form a homogeneous solution with a certain concentration, dry it in a vacuum oven at 30 - 100 °C for 6 - 36 h, then perform alkalization treatment on the dried membrane, completely replace I - on the membrane with OH - , and then wash the surface of the membrane with deionized water to obtain a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures.

[0099] Specifically, the solvent used in step (1) is one or two or more of dimethyl sulfoxide, N-methylpyrrolidone, dichloromethane, and tetrahydrofuran.

[0100] Specifically, in the step (1), the molar ratio of A1, A2, R / R', N-methyl-4-piperidone, and R1 is (0.5-0.99):(0.5-0.01):(0.005-0.1):(0.55-0.99):(0.11-0.55).

[0101] Specifically, in the step (1), the organic liquid acid is one or both of trifluoroacetic acid and trifluoromethanesulfonic acid, the solid acid is one or two or more of ZSM-5 (silica-alumina ratio of 5-40), Y-type molecular sieve (silica-alumina ratio of 3-6), and β-type molecular sieve (silica-alumina ratio of 6-40), and the solid superacid is SO 4 2- / ZrO 2 ,WO 3 / ZrO 2 ,MoO 3 / ZrO 2 ,B 2 O 3 / ZrO 2 one or two or more of them.

[0102] Specifically, in the step (1), the molar ratio of (A1+A2) to the organic liquid acid is 1:(5-13); the mass ratio of (A1+A2) to the solid acid is 1:(50-100) wt%, and the mass ratio of (A1+A2) to the solid superacid is 1:(20-60) wt%.

[0103] Specifically, in the step (2), the dosage of dimethyl sulfoxide is 10-50 mL.

[0104] Specifically, in the step (2), the molar ratio of polynaphthapiperidine to methyl iodide is 1:(0.8-1.3).

[0105] Specifically, in the step (3), the concentration of the homogeneous solution is 5-30 wt%.

[0106] Specifically, in the step (3), the alkaline solution used for alkalization treatment is sodium hydroxide or potassium hydroxide, with a concentration of 0.5-3 mol / L and an alkalization time of 12-72 h.

[0107] The above technical solution of the present invention provides a poly(naphthylpiperidine) cross-linked polymer, its preparation method, application, a poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures, and its preparation method and application. The poly(naphthylpiperidine) cross-linked polymer designed by the present invention has a specific structure. As an anion exchange membrane, this poly(naphthylpiperidine) cross-linked polymer has excellent technical effects and is an anion exchange membrane with high alkali resistance, good mechanical stability, and ultra-high ionic conductivity. By introducing hydrophilic and hydrophobic chain segments and constructing a microphase separation structure, the present invention helps to form a well-developed ion transport channel, promotes the rapid transport of ions, and thus improves the ionic conductivity. By introducing monomers with larger molecular weights, a well-developed high-ion conduction channel can be formed to accelerate ion transport. Using a cross-linking agent to construct a cross-linked network structure improves the dimensional stability and mechanical properties. Adopting a new technical route for green preparation of anion exchange membranes using solid acids and solid superacids is of great significance for achieving the dual-carbon goal. Moreover, the preparation method is simple and has good application prospects in the field of electrolytic water hydrogen production.

[0108] The present invention also provides a preparation method for the poly(naphthylpiperidine) cross-linked anion exchange membrane with hydrophilic and hydrophobic structures and applies it to the field of electrolytic water hydrogen production; (1) The present invention proposes to introduce monomers with larger molecular weights, which can form a well-developed high-ion conduction channel to accelerate ion transport, thereby improving the ionic conductivity. (2) The present invention proposes to use a cross-linking agent to construct a cross-linked network structure, which improves the dimensional stability and mechanical properties. (3) The present invention first proposes a method for green preparation of anion exchange membranes using solid acids and solid superacid catalysts. The catalysts can be recycled, are green and environmentally friendly, and have low costs. (4) The present invention proposes to introduce hydrophilic and hydrophobic chain segments and construct a microphase separation structure, which helps to form a well-developed ion transport channel, promotes the rapid transport of ions, and thus improves the ionic conductivity and alkali stability.

[0109] The anion exchange membrane provided by the present invention has high alkali resistance, good mechanical stability, and high ionic conductivity. Moreover, the preparation method is simple, the conditions are mild, it is green and environmentally friendly, and it is more suitable for the popularization and application of industrial production and has good application prospects in the field of electrolytic water hydrogen production.

[0110] Experimental results show that the anion exchange membrane prepared by the present invention has ultra-high OH - conductivity (190.7 mS cm -1 @ 80 °C) and excellent mechanical stability; after soaking in 1 M KOH at 80 °C for 1000 h, the conductivity loss is only 2.6%, showing excellent alkali resistance; the anion exchange membrane prepared by the present invention can stably operate for 1000 h in an alkaline electrolytic water membrane electrode, and the voltage hardly decays. The anion exchange membrane prepared by the present invention can be applied to fields such as alkaline electrolytic water hydrogen production, alkaline fuel cells, and carbon dioxide catalytic reduction.

[0111] To further illustrate the present invention, the following provides a detailed description of a poly(naphthylpiperidine) polymer provided by the present invention, its preparation method, application, an anion exchange membrane and its application in conjunction with embodiments. However, it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation manners and specific operation processes are given. It is only to further illustrate the features and advantages of the present invention, rather than a limitation on the claims of the present invention. The protection scope of the present invention is not limited to the following embodiments either.

[0112] Comparative Example 1

[0113] (1) Dissolve 2.303 g of p-terphenyl, 0.871 g of N-methyl-4-piperidone, and 0.370 g of trifluoroacetone in 3 ml of dichloromethane to obtain a homogeneous solution. Add 0.75 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid, react at 0 °C for 16 h, precipitate with anhydrous methanol, wash with an aqueous solution of K 2 CO 3 and then wash with deionized water to obtain a white fibrous solid;

[0114] (2) Weigh 1 g of the product obtained in step (1) and dissolve it in 1 ml of iodomethane in dimethyl sulfoxide. Wrap it with tin foil and heat with stirring for 24 h. Then pour the reaction solution into ethyl acetate for precipitation, and wash with deionized water to obtain a quaternized polymer;

[0115] (3) Weigh 0.5 g of the product obtained in step (2) and dissolve it in 10 ml of dimethyl sulfoxide. Pour it into a petri dish and dry it in a vacuum oven at 80 °C for 36 h. Then soak the dried membrane in 1 mol / L potassium hydroxide for 24 h to completely replace the I - on the membrane with OH - . Then wash the surface of the membrane with deionized water to obtain AEM-1. The relevant properties of the membrane are shown in Table 1.

[0116] Comparative Example 2

[0117] (1) Dissolve 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, and 1.245 g of N-methyl-4-piperidone in 3 ml of dichloromethane to obtain a homogeneous solution. Add 0.75 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid, react at 0 °C for 12 h, precipitate with anhydrous methanol, wash with an aqueous solution of K 2 CO 3 and then wash with deionized water to obtain a white fibrous solid; The subsequent steps are the same as those in steps (2) and (3) of Comparative Example 1 to obtain AEM-2. The relevant properties of the membrane are shown in Table 1.

[0118] Comparative Example 3

[0119] (1) 2.303 g of p - terphenyl and 1.245 g of N - methyl - 4 - piperidone were dissolved in 3 ml of dichloromethane to obtain a homogeneous solution. 0.75 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 16 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2 CO 3 , and then washed with deionized water to obtain a white fibrous solid; the subsequent steps were the same as those in step (2) and step (3) of Comparative Example 1, and AEM - 3 could be obtained. The relevant properties of the membrane are shown in Table 1.

[0120] Example 1

[0121] (1) 2.073 g of p - terphenyl, 0.254 g of 1,1’ - binaphthalene, 0.871 g of N - methyl - 4 - piperidone and 0.370 g of trifluoroacetone were dissolved in 4 ml of dichloromethane to obtain a homogeneous solution. 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 24 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2 CO 3 , and then washed with deionized water to obtain a yellow fibrous solid, poly(naphthylpiperidine) polymer;

[0122] (2) 1 g of the product obtained in step (1) and 1 ml of iodomethane were dissolved in dimethyl sulfoxide, and then 0.1 ml of VBC was quickly added. It was wrapped with tin foil and stirred with heating for 24 h. Then the reaction solution was poured into ethyl acetate for precipitation and washed with deionized water to obtain a quaternized polymer; the subsequent steps were the same as those in step (3) of Comparative Example 1, and AEM - 4 could be obtained. The relevant properties of the membrane are shown in Table 1.

[0123] Example 2

[0124] (1) 1.388 g of biphenyl, 0.254 g of 1,1’ - binaphthalene, 0.03 g of triphenylbenzene, 0.871 g of N - methyl - 4 - piperidone and 0.370 g of trifluoroacetone were dissolved in 3.5 ml of dichloromethane to obtain a homogeneous solution. 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 24 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2 CO 3 , and then washed with deionized water to obtain a yellow fibrous solid, poly(naphthylpiperidine) polymer; the subsequent steps were the same as those in step (2) and step (3) of Comparative Example 1, and AEM - 5 could be obtained. The relevant properties of the membrane are shown in Table 1.

[0125] Example 3

[0126] (1) 2.073 g of m-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone and 0.370 g of trifluoroacetone were dissolved in 4 ml of dichloromethane to obtain a homogeneous solution. 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 24 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2 CO 3 , and then washed with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps were the same as steps (2) and (3) in Comparative Example 1, and AEM-6 could be obtained. The relevant properties of the membrane are shown in Table 1.

[0127] Example 4

[0128] (1) 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone and 0.575 g of trifluorophenylethone were dissolved in 4.5 ml of dichloromethane to obtain a homogeneous solution. 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 24 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2 CO 3 , and then washed with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps were the same as steps (2) and (3) in Comparative Example 1, and AEM-7 could be obtained. The relevant properties of the membrane are shown in Table 1.

[0129] Example 5

[0130] (1) 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone and 0.621 g of 4-(trifluoroacetyl)toluene were dissolved in 4.5 ml of dichloromethane to obtain a homogeneous solution. 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 24 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2 CO 3 , and then washed with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps were the same as steps (2) and (3) in Comparative Example 1, and AEM-8 could be obtained. The relevant properties of the membrane are shown in Table 1.

[0131] Example 6

[0132] (1) 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone and 0.634 g of 2,2,2,4'-tetrafluorophenylethone were dissolved in 4.5 ml of dichloromethane to obtain a homogeneous solution. 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid were added, and the reaction was carried out at 0 °C for 24 h. It was precipitated with anhydrous methanol and washed with an aqueous solution of K 2CO 3 Wash with an aqueous solution of CO , and then wash with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps are the same as those in step (2) and step (3) of Comparative Example 1, and then AEM-9 can be obtained. The relevant properties of the membrane are shown in Table 1.

[0133] Example 7

[0134] (1) Dissolve 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone, and 0.753 g of 2,2,2-trifluoro-1-(3,4,5-trifluorophenyl)ethanone in 4.5 ml of dichloromethane to obtain a homogeneous solution. Add 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid, react at 0 °C for 24 h, precipitate with anhydrous methanol, and wash with an aqueous solution of K 2 CO 3 Wash with an aqueous solution of CO , and then wash with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps are the same as those in step (2) and step (3) of Comparative Example 1, and then AEM-10 can be obtained. The relevant properties of the membrane are shown in Table 1.

[0135] Example 8

[0136] (1) Dissolve 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone, and 0.871 g of octafluoromethylphenyl ketone in 4.5 ml of dichloromethane to obtain a homogeneous solution. Add 0.750 ml of trifluoroacetic acid and 7.5 ml of trifluoromethanesulfonic acid, react at 0 °C for 24 h, precipitate with anhydrous methanol, and wash with an aqueous solution of K 2 CO 3 Wash with an aqueous solution of CO , and then wash with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps are the same as those in step (2) and step (3) of Comparative Example 1, and then AEM-11 can be obtained. The relevant properties of the membrane are shown in Table 1.

[0137] Example 9

[0138] (1) Dissolve 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone, and 0.575 g of trifluoroacetophenone in 4 ml of dimethyl sulfoxide to obtain a homogeneous solution. Add 2.2 g of ZSM-5 (the silicon-aluminum ratio is 30), react at 125 °C for 60 h, filter ZSM-5 (the silicon-aluminum ratio is 30), recover the filtered ZSM-5 (the silicon-aluminum ratio is 30), precipitate the remaining homogeneous solution with anhydrous methanol, and wash with an aqueous solution of K 2 CO 3Wash with an aqueous solution and then with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps are the same as those in steps (2) and (3) of Comparative Example 1, and AEM-12 can be obtained. The relevant properties of the membrane are shown in Table 1.

[0139] Example 10

[0140] (1) Dissolve 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone, and 0.575 g of trifluoroacetophenone in 4.5 ml of dimethyl sulfoxide to obtain a homogeneous solution. Add 1 g of the recovered ZSM-5 (silica-alumina ratio of 30) from Example 9 and 1 g of SO 4 2- / ZrO 2 , react at 100 °C for 72 h, filter ZSM-5 (silica-alumina ratio of 30) and SO 4 2- / ZrO 2 , and recycle the filtered ZSM-5 (silica-alumina ratio of 30) and SO 4 2- / ZrO 2 . Precipitate the remaining homogeneous solution with anhydrous methanol, wash with an aqueous solution of K 2 CO 3 , and then with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps are the same as those in steps (2) and (3) of Comparative Example 1, and AEM-13 can be obtained. The relevant properties of the membrane are shown in Table 1.

[0141] Example 11

[0142] (1) Dissolve 2.073 g of p-terphenyl, 0.254 g of 1,1'-binaphthalene, 0.871 g of N-methyl-4-piperidone, and 0.575 g of trifluoroacetophenone in 4.5 ml of dimethyl sulfoxide to obtain a homogeneous solution. Add 1 g of SO 4 2- / ZrO 2 and 3.5 ml of trifluoromethanesulfonic acid, react at 30 °C for 48 h, filter SO 4 2- / ZrO 2 , and recycle the filtered SO 4 2- / ZrO 2 . Precipitate the remaining homogeneous solution with anhydrous methanol, wash with an aqueous solution of K 2 CO 3 , and then with deionized water to obtain a yellow fibrous solid poly(naphthylpiperidine) polymer; the subsequent steps are the same as those in steps (2) and (3) of Comparative Example 1, and AEM-14 can be obtained. The relevant properties of the membrane are shown in Table 1.

[0143] Referring to Table 1, Table 1 shows the performance of the anion exchange membranes prepared in the examples and comparative examples of the present invention.

[0144] Table 1

[0145]

[0146]

[0147] In Table 1, a was measured at 80 °C; b was measured after soaking at 25 °C for 24 h; c was measured after soaking at 30 °C for 24 h; d was measured after soaking in 1 M KOH at 80 °C for 1000 h; e was measured on an alkaline electrolyzed water membrane electrode; f was measured after operating on an alkaline electrolyzed water membrane electrode for 1000 h.

[0148] From the above specific introductions and performance tables of the comparative examples and examples, it can be seen that: (1) After adding 1,1'-binaphthalene monomer, by introducing monomers with larger molecular weights, developed high-ion conduction channels can be formed to accelerate ion transport, so that the conductivity, ion exchange capacity and tensile strength of the membrane are improved, and the swelling rate and water absorption rate are reduced, indicating that the mechanical strength is improved and the membrane stability is significantly improved; (2) After using the cross-linking agent, by constructing a cross-linked network structure, the dimensional stability and mechanical properties are improved, proving that adding the cross-linking agent can improve the mechanical properties; (3) After introducing the hydrophobic chain segment, due to the combination of hydrophilic and hydrophobic chain segments to construct a microphase separation structure, it helps to form developed ion transport channels and promote the rapid transport of ions, thereby increasing the ionic conductivity. It is proved that adding the binaphthalene structure and hydrophilic and hydrophobic structures can not only improve the conductivity of the membrane, but also enhance the alkali stability and mechanical strength of the membrane. (4) Using solid acids and solid superacid catalysts is a new type of anion exchange membrane technology route that is efficient, easy to separate and easy to recycle. As long as the reaction temperature and time are appropriately increased and high-boiling solvents are selected, liquid superacids can be replaced. It can be seen from the examples that at a lower temperature, the usage amount of liquid superacid can be reduced by 50% by adding solid superacid. Therefore, the use of solid acids and solid superacid catalysts is of great significance for achieving the goals of "green chemistry" and "dual carbon".

[0149] The present invention has successfully prepared an anion exchange membrane with high alkali resistance, good mechanical stability and ultra-high ionic conductivity; especially by introducing hydrophilic and hydrophobic chain segments to construct a microphase separation structure, it helps to form developed ion transport channels and promote the rapid transport of ions, thereby increasing the ionic conductivity. The ionic conductivity of the anion exchange membrane of the present invention is as high as 190.7 mS cm at 80 °C -1; By introducing monomers with relatively large molecular weights, the present invention can accelerate ion transport by forming well-developed high-ion conduction channels. The present invention uses crosslinking agents to construct a crosslinked network structure, improving dimensional stability and mechanical properties. The present invention adopts a new technical route for green preparation of anion exchange membranes using solid acids and solid superacids, which is of great significance for achieving the dual-carbon goal. Moreover, the preparation method is simple and has good application prospects in the field of electrolytic water hydrogen production.

[0150] The above has introduced in detail a poly(naphthylpiperidine) crosslinked anion exchange membrane with hydrophilic and hydrophobic structures, its preparation method, and its application. Specific examples are used in this article to elaborate on the principle and implementation mode of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention, including the best mode, and also enables any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that for those of ordinary skill in the art in this technical field, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. The protection scope of the present invention patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements that are not different from the literal description of the claims, or if they include equivalent structural elements that have no substantial difference from the literal description of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A polynaphthylpiperidine cross-linked polymer, characterized in that: The polynaphthyl piperidine cross-linked polymer comprises a structural unit shown in formula (I): Wherein, n = 0.5 to 0.99; The A1 is selected from one or more of the groups represented by formula (1) to formula (3): The A2 is selected from the group shown in formula (4): The R is selected from one or more of the groups represented by formula (5) to formula (6): The R' is selected from one or more of the groups represented by formula (7) to formula (8): The R1 is selected from one or more of the groups represented by formula (9) to formula (14):

2. A method for preparing the polynaphthylpiperidine cross-linked polymer as claimed in claim 1, characterized in that: The following steps are involved: 1) mixing A1 monomer, A2 monomer, hydrophilic group monomer, hydrophobic group monomer containing R1, crosslinking agent R and organic solvent to obtain a homogeneous solution; 2) reacting the homogeneous solution obtained in the above step under the action of an acid catalyst, and then pouring a precipitant into the solution for precipitation to obtain a solid polymer; 3) The solid polymer obtained in the above steps, the solvent, the crosslinking agent R' and the quaternary ammonium agent are reacted in the dark, and then precipitated to obtain a polynaphthylpiperidine crosslinked polymer.

3. The preparation method according to claim 2, characterized in that: The A1 monomer includes one or more of biphenyl, p-terphenyl and m-terphenyl; The A2 monomer includes 1,1'-binaphthyl; The hydrophilic group monomer includes N-methyl-4-piperidone; The cross-linking agent R comprises triphenylbenzene and / or erene; The crosslinking agent R' includes 4-chloromethylstyrene and / or 4,4'-trimethylenebis(1-methylpiperidine); The hydrophobic group monomer containing R1 includes one or more of trifluoroacetone, trifluoroacetophenone, 4-(trifluoroacetyl)toluene, 2,2,2,4'-tetrafluoroacetophenone, 2,2,2-trifluoro-1-(3,4,5-trifluorophenyl)ethanone and octafluoromethylphenyl ketone; The organic solvent includes one or more of dimethyl sulfoxide, N-methylpyrrolidone, dichloromethane and tetrahydrofuran; The molar ratio of the A1 monomer to the A2 monomer is (0.5-0.99): (0.5-0.01); The molar ratio of the A1 monomer to the hydrophilic group monomer is (0.5-1): (0.55-0.99); The molar ratio of the A1 monomer to the crosslinking agent R / R' is (0.5-1): (0.005-0.1); The molar ratio of the A1 monomer to the hydrophobic group monomer containing R1 is (0.5-1): (0.11-0.55).

4. The preparation method according to claim 2, characterized in that: The acid catalyst includes solid acid and organic liquid acid; The solid acid comprises one or more of ZSM-5, Y-type molecular sieve and β-type molecular sieve; The acid catalyst also includes a solid superacid; The solid superacid includes SO4 2- / ZrO2, WO3 / ZrO2, MoO3 / ZrO2 and B2O3 / ZrO2; The organic liquid acid includes trifluoroacetic acid and / or trifluoromethanesulfonic acid.

5. The preparation method according to claim 2, characterized in that: The mass ratio of the total mass of the A1 monomer and the A2 monomer to the solid acid is 1:(50-100); The mass ratio of the total mass of the A1 monomer and the A2 monomer to the solid superacid is 1:(20-60); The molar ratio of the total molar number of the A1 monomer and the A2 monomer to the organic liquid acid is 1:(5-13); The reaction temperature is -4 to 150°C; the reaction temperature using only organic liquid acid is -4 to 100°C; the reaction temperature using only solid acid is 60 to 150°C, and the reaction temperature using a solid acid and an organic liquid acid in combination is 10 to 60°C; The reaction time is 4 to 72 hours; The precipitant includes anhydrous methanol; The precipitation is followed by solution washing and water washing steps.

6. The preparation method according to claim 2, characterized in that: The quaternizing agent includes methyl iodide; The molar ratio of the solid polymer to the quaternary ammonium agent is 1:(0.8-1.3). The solvent includes dimethyl sulfoxide; The temperature of the light-proof reaction is 40 to 90°C; The light-proof reaction time is 4 to 72 hours; The solvent used in the precipitation reaction solution in step 3) includes ethyl acetate; The polynaphthyl piperidine cross-linked polymer is specifically a polynaphthyl piperidine cross-linked polymer containing a hydrophilic structure, a hydrophobic structure and a cross-linked network structure.

7. Use of the cross-linked polynaphthylpiperidine polymer according to claim 1 or the cross-linked polynaphthylpiperidine polymer prepared by the preparation method according to any one of claims 2 to 6 in anion exchange membrane.

8. An anion exchange membrane, characterized in that: The anion exchange membrane is a polynaphthylpiperidine cross-linked polymer anion exchange membrane; The anion exchange membrane includes an alkalized polynaphthylpiperidine cross-linked polymer; The polynaphthyl piperidine cross-linked polymer is the polynaphthyl piperidine cross-linked polymer according to claim 1 or the polynaphthyl piperidine cross-linked polymer prepared by the preparation method according to any one of claims 2 to 6.

9. The anion exchange membrane according to claim 8, characterized in that The polynaphthyl piperidine cross-linked polymer anion exchange membrane is prepared by the following steps: The cross-linked polynaphthyl piperidine polymer is mixed with a polar solution to obtain an anion exchange resin homogeneous casting solution, and the anion exchange resin homogeneous casting solution is formed into a film on a substrate, and then dried and alkalized to obtain a cross-linked polynaphthyl piperidine anion exchange membrane in the form of hydroxide; The concentration of the anion exchange resin homogeneous solution is 5wt% to 30wt%; The alkalization treatment method includes soaking in an alkali solution; The alkalization treatment time is 12 to 72 hours.

10. Use of the cross-linked polynaphthylpiperidine polymer according to claim 1, the cross-linked polynaphthylpiperidine polymer prepared by the preparation method according to any one of claims 2 to 6, or the cross-linked polynaphthylpiperidine anion exchange membrane prepared by the preparation method according to any one of claims 8 to 9 in the field of hydrogen production by water electrolysis.

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