Hydrophobic chain segment-containing multi-block dibenzofuran polyaryl piperidine anion exchange membrane and application thereof

Abstract

The invention provides a multi-block dibenzofuran polyaryl piperidine polymer. The multi-block dibenzofuran polyaryl piperidine polymer comprises a structural unit as shown in a formula (I) which is described in the specification. The anion exchange membrane polymeric material prepared from the multi-block dibenzofuran polyaryl piperidine polymer has excellent anion transmission capacity, good mechanical strength and excellent alkali-resistant stability under the alkaline condition, and can be used as an excellent membrane device of a water electrolysis hydrogen production reaction device; and the method has certain practical application potential. The preparation method disclosed by the invention is very simple and short in preparation process. The invention provides a preparation method and strategy for preparing the anion exchange membrane in a green way by adopting the solid acid and the solid superacid catalyst for the first time, the solid acid and the solid superacid catalyst used in the invention are easy to separate and recover and can be repeatedly used, and the technical route is green and environment-friendly. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of anion exchange membrane preparation for hydrogen production by electrolysis of water, and relates to a multi-block dibenzofuran polyarylpiperidine polymer and its preparation method and application, an anion exchange membrane and its application, and in particular to a multi-block dibenzofuran polyarylpiperidine anion exchange membrane containing hydrophobic segments and its application. Background Art

[0002] Hydrogen is an ideal environmentally friendly energy carrier for preventing climate change and meeting growing global energy demand due to its high calorific value (140 MJ / kg) and carbon-free nature when produced from renewable energy. Water electrolyzers can efficiently and carbon-free produce green hydrogen from renewable energy. Alkaline water electrolysis (AWE), proton exchange membrane water electrolysis (PEMWE), and anion exchange membrane water electrolysis (AEMWE) are the main water electrolysis hydrogen production technologies. Anion exchange membrane water electrolysis has garnered significant attention in recent years. First, AEM water electrolysis offers higher hydrogen yields and improved energy efficiency, enabling efficient conversion of renewable energy into hydrogen. Second, AEM water electrolysis systems are compact and easy to operate, reducing the complexity of equipment setup and operation. Third, AEM water electrolysis uses non-precious metal catalysts, reducing system costs. Therefore, AEM water electrolysis holds great potential and advantages for future large-scale hydrogen production.

[0003] Anion exchange membranes are one of the main components in the anion exchange membrane water electrolysis process. Chemical stability, mechanical stability, and ionic conductivity are the three most important parameters for evaluating anion exchange membranes. Anion exchange membranes need to maintain stable performance in alkaline environments and have excellent hydroxide ion transport capacity. Currently, polymer backbone materials mainly include polyaryls, polyolefins, poly(etherimides), polysulfones, and polystyrenes. For example, polyarylpiperidine anion exchange membranes (J. Mater. Chem. A, 2022, 10, 16478) have excellent alkaline stability and ionic conductivity. Another example is the polyarylpiperidine anion exchange membrane containing oxyfluorene and its preparation method disclosed in patent 202310682940.2. The polyarylpiperidine anion exchange membrane mentioned in the invention has good ionic conductivity after the introduction of oxygen-containing hydrophilic groups. At the same time, its high molecular weight, simple preparation process, and low cost make it one of the candidates for constructing new high-efficiency anion exchange membranes. However, this type of membrane has poor mechanical stability and is prone to membrane degradation, resulting in a decrease in mechanical strength and affecting the conductivity performance to a certain extent.

[0004] Therefore, how to develop a multi-block polyarylpiperidine anion exchange membrane with better performance and solve the above-mentioned problems of the existing polyarylpiperidine anion exchange membrane has become one of the focuses of widespread attention of 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 multi-block dibenzofuran polyarylpiperidine polymer and its preparation method, application, an anion exchange membrane and its application, in particular a multi-block dibenzofuran polyarylpiperidine anion exchange membrane containing a hydrophobic segment. The anion exchange membrane polymer material prepared by the present invention has excellent anion transport capacity, good mechanical strength, and excellent alkali resistance stability under alkaline conditions. It can be used as an excellent membrane device for water electrolysis hydrogen production reaction equipment and has certain practical application potential. In addition, the preparation method of the present invention is very simple, the conditions are mild, and the preparation process is short, which is more suitable for promotion and application of industrial production.

[0006] The present invention provides a multi-block dibenzofuran polyarylpiperidine polymer, wherein the multi-block dibenzofuran polyarylpiperidine polymer comprises a structural unit represented by formula (I):

[0007]

[0008] Wherein, x=0.1-0.3, y=0.9-0.7;

[0009] The Ar is selected from one or more groups represented by formula (1) to formula (9):

[0010]

[0011]

[0012] The R1 is selected from one or more groups represented by formula (10) to formula (14):

[0013]

[0014] The R2 is selected from one or more groups represented by formula (15) to formula (17):

[0015]

[0016] The present invention provides a method for preparing a multi-block dibenzofuran-based polyarylpiperidine polymer as described in the above technical solution, comprising the following steps:

[0017] 1) mixing the Ar monomer, the hydrophilic group monomer and the organic solvent to obtain a solution, and then adding the cationic group monomer and the hydrophobic segment monomer containing the R1 group to obtain a mixed solution;

[0018] 2) reacting the mixed solution obtained in the above step under the action of an acid catalyst, and then adding a precipitant to precipitate the mixed solution to obtain a multi-block polymer;

[0019] 3) reacting the multi-block polymer obtained in the above step, the solvent and the quaternary ammonium agent in the dark, and then precipitating the resultant to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer.

[0020] Preferably, the Ar monomer includes one or more of biphenyl, p-terphenyl, m-terphenyl, triphenylmethane, 4-benzylbiphenyl, binaphthyl, erene, 4,4′-trimethylenebis(1-methylpiperidine) and 1,3,5-triphenylbenzene;

[0021] The hydrophilic group monomer includes dibenzofuran;

[0022] The organic solvent includes one or more of dichloromethane, n-hexane, tetrahydrofuran and N,N-dimethylformamide;

[0023] The molar ratio of the Ar monomer to the hydrophilic group monomer is 1:(1-100);

[0024] The cationic group monomer includes N-methyl-4-piperidone;

[0025] The hydrophobic segment monomer containing the R1 group includes one or more of 1,1,1-trifluoroacetone, 2,2,2-trifluoroacetophenone, benzoyltrifluoroacetone, 7-bromo-1,1,1-trifluoro-2-heptanone and ethyl 3,3,3-trifluoropyruvate;

[0026] The molar ratio of the cationic group monomer to the hydrophobic segment monomer containing the R1 group is 1:(1-15).

[0027] Preferably, the ratio of the total molar number of the Ar monomer and the hydrophilic group monomer to the total molar number of the cationic group monomer and the hydrophobic segment monomer containing the R1 group is 1:(1-10);

[0028] In the mixed solution, the mass concentration of the sum of all monomers is 5% to 50%;

[0029] The acid catalyst includes solid acid and liquid acid;

[0030] The solid acid includes Al2O3 / B2O3, BPO4, H4SiW 12 O 40 , one or more of β-type molecular sieve, ZSM-5 and Y-type molecular sieve;

[0031] The acid catalyst also includes a solid superacid;

[0032] The solid superacid includes S2O82- / CeO2-RF、Pt-SO4 2- / ZrO2-Al2O3、SO4 2- / ZrO2-NiO / Al2O3 and SO4 2- / Fe2O3 one or more;

[0033] The liquid acid includes one or more of trifluoroacetic acid, carborane acid and trifluoromethanesulfonic acid.

[0034] Preferably, the mass ratio of the total mass of the Ar monomer and the hydrophilic group monomer to the solid acid is 100:(50-100);

[0035] The mass ratio of the total mass of the Ar monomer and the hydrophilic group monomer to the solid superacid is 100:(20-60);

[0036] The molar ratio of the total molar number of the Ar monomer and the hydrophilic group monomer to the liquid acid is 1:(5-13);

[0037] The reaction temperature is -4 to 150 ° C. If only organic liquid acid is used, the reaction temperature is

[0038] -4~100℃; the reaction temperature when using only solid acid is 60~150℃, and the reaction temperature when using solid acid and organic liquid acid in combination is 10~60℃;

[0039] The reaction time is 4 to 72 hours;

[0040] The precipitant includes one or more of methanol, ethanol, acetonitrile and n-hexane;

[0041] The method further comprises the steps of solution washing and water washing after the precipitation.

[0042] Preferably, the quaternizing agent includes one or more of 1,5-dibromopentane, 1,4-dibromobutane and iodomethane;

[0043] The solvent includes one or more of ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform and N,N-dimethylformamide;

[0044] The temperature of the light-proof reaction is 20 to 120°C;

[0045] The light-avoidance reaction time is 12 to 72 hours;

[0046] The solvent used in the precipitation reaction solution in step 3) includes one or more of methanol, acetonitrile, diethyl ether and ethyl acetate;

[0047] The multi-block dibenzofuran polyarylpiperidine polymer is specifically a multi-block dibenzofuran polyarylpiperidine polymer containing a hydrophobic segment.

[0048] The present invention provides the use of the multi-block dibenzofuran polyarylpiperidine polymer described in the above technical solution or the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method described in any one of the above technical solutions in anion exchange membrane.

[0049] The present invention provides an anion exchange membrane, which is a multi-block dibenzofuran polyarylpiperidine anion exchange membrane;

[0050] The anion exchange membrane includes an alkalized multi-block dibenzofuran polyarylpiperidine polymer;

[0051] The multi-block dibenzofuran polyarylpiperidine polymer is the multi-block dibenzofuran polyarylpiperidine polymer described in the above technical solution or the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method described in any one of the above technical solutions.

[0052] Preferably, the multi-block dibenzofuran polyarylpiperidine anion exchange membrane is prepared by the following steps:

[0053] A multi-block dibenzofuran polyarylpiperidine 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 immersed in a potassium hydroxide solution and dried to obtain a multi-block dibenzofuran polyarylpiperidine anion exchange membrane in the hydroxide form;

[0054] The concentration of the anion exchange resin homogeneous solution is 5wt% to 30wt%;

[0055] The soaking time is 12 to 36 hours;

[0056] The soaking temperature is 25-80°C.

[0057] The present invention provides the use of the multi-block dibenzofuran polyarylpiperidine polymer described in the above technical solution, the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method described in any one of the above technical solutions, or the multi-block dibenzofuran polyarylpiperidine anion exchange membrane described in any one of the above technical solutions in the field of hydrogen production by electrolysis of water.

[0058] The present invention provides a multi-block dibenzofuran polyarylpiperidine polymer, comprising a structural unit represented by formula (I). Compared with the prior art, the present invention believes that by adding hydrophobic groups to the multi-block dibenzofuran polyarylpiperidine membrane, strong hydrophobic interactions can promote the centralized distribution of the hydrophobic domains, thereby allowing the hydrophilic ionic groups to frequently self-aggregate, forming a distinct microphase separation structure and constructing a well-developed ion channel, thereby enabling modification thereof, thereby developing a multi-block dibenzofuran polyarylpiperidine anion exchange membrane with improved electrical conductivity and mechanical properties.

[0059] Based on this, the present invention creatively designed a multi-block dibenzofuran-type polyarylpiperidine polymer with a specific structure. The presence of dibenzofuran in the structure gives the polymer a larger ion group and tends to connect with the aromatic main chain to form ion channels, accelerating the transmission of anions; it also promotes a more obvious phase separation morphology, thereby more effectively delaying the degradation of AEMs by hydroxide ions; because dibenzofuran is a planar molecule, the ion-dipole interaction between the oxygen atoms and the cationic groups also contributes to the filling efficiency. Therefore, the membrane with a high dibenzofuran content has a higher density, and its hydrophilicity increases the flexibility or elongation of the membrane. Moreover, the presence of 2,2,2-trifluoroacetophenone as a hydrophobic group makes the strong hydrophobic interaction promote the concentrated distribution of the hydrophobic domain, so that the hydrophilic ionic groups can frequently self-aggregate, forming a clear microphase separation structure and building a developed ion channel. The present invention also provides a method for preparing a multi-block dibenzofuran polyaryl piperidine polymer. The technical route of green preparation of anion exchange membrane using solid acid and solid superacid catalyst has good catalytic effect, mild catalytic environment, easy separation and recovery, can be reused multiple times, and is environmentally friendly.

[0060] The presence of dibenzofuran in the hydrophobic segment-containing multi-block dibenzofuran polyarylpiperidine anion exchange membrane provided by the present invention is conducive to the formation of ion channels and phase separation morphology, thereby accelerating the transmission of anions and improving electrical conductivity; at the same time, it effectively delays the degradation of AEMs by hydroxide ions and enhances the service life of the membrane. The presence of hydrophobic groups enables strong hydrophobic interactions to promote the centralized distribution of hydrophobic domains, so that hydrophilic ionic groups can frequently self-aggregate to form a distinct microphase separation structure and build a developed ion channel. Moreover, the preparation process adopts a technical route for the green preparation of anion exchange membranes using solid acid and solid superacid catalysts, which has good catalytic effect and is easy to separate and recover. Under the premise of appropriately increasing the reaction temperature and reaction time and selecting a high-boiling point solvent, complete replacement of liquid superacids can be achieved.

[0061] This invention proposes, for the first time, a green method and strategy for preparing anion exchange membranes using solid acids and solid superacid catalysts. The solid acids and solid superacid catalysts used in this invention are easily separated and recovered, allowing for repeated reuse. This technology is both green and environmentally friendly. Notably, at low temperatures, the addition of solid acids can reduce the amount of liquid superacid required by 30%, and the addition of solid superacids can reduce the amount of liquid superacid required by 50%.

[0062] Experimental results show that the multi-block dibenzofuran-containing polyarylpiperidine anion exchange membrane containing hydrophobic segments prepared by the present invention has excellent electrical conductivity (168mS / cm@80℃) and alkali stability (in 80℃, 1M KOH solution, the conductivity retention rate is as high as 93% after 2000h); the alkaline electrolysis membrane electrode assembly (AEMWE) composed of the multi-block dibenzofuran-containing polyarylpiperidine anion exchange membrane containing hydrophobic segments requires only 2.31V for stable operation for 1500h; at the same time, the polyarylpiperidine anion exchange membrane containing hydrophobic segments has high mechanical strength, good flexibility, and is not easy to break, making it suitable for industrial cast film formation and realizing industrial application. DETAILED DESCRIPTION

[0063] In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention rather than limiting the patent claims of the present invention.

[0064] All raw materials of the present invention are not particularly limited in their sources and can be purchased from the market or prepared according to conventional methods well known to those skilled in the art.

[0065] The raw materials used in the present invention are not particularly limited in purity, and analytically pure materials or materials with a purity level known to those skilled in the art for preparing anion exchange membranes may be used.

[0066] The present invention provides a multi-block dibenzofuran polyarylpiperidine polymer, wherein the multi-block dibenzofuran polyarylpiperidine polymer comprises a structural unit represented by formula (I):

[0067]

[0068] Wherein, x=0.1-0.3, y=0.9-0.7;

[0069] The Ar is selected from one or more groups represented by formula (1) to formula (9):

[0070]

[0071]

[0072] The R1 is selected from one or more groups represented by formula (10) to formula (14):

[0073]

[0074] The R2 is selected from one or more groups represented by formula (15) to formula (17):

[0075]

[0076] In the present invention, x=0.1-0.3, y=0.9-0.7, may be x=0.14-0.26, y=0.86-0.74, may be x=0.18-0.22, y=0.82-0.78.

[0077] The present invention provides a method for preparing a multi-block dibenzofuran-based polyarylpiperidine polymer as described in the above technical solution, comprising the following steps:

[0078] 1) mixing the Ar monomer, the hydrophilic group monomer and the organic solvent to obtain a solution, and then adding the cationic group monomer and the hydrophobic segment monomer containing the R1 group to obtain a mixed solution;

[0079] 2) reacting the mixed solution obtained in the above step under the action of an acid catalyst, and then adding a precipitant to precipitate the mixed solution to obtain a multi-block polymer;

[0080] 3) reacting the multi-block polymer obtained in the above step, the solvent and the quaternary ammonium agent in the dark, and then precipitating the reaction to obtain a dibenzofuran-based polyarylpiperidine polymer.

[0081] The present invention first mixes Ar monomer, hydrophilic group monomer and organic solvent to obtain a solution, and then adds cationic group monomer and hydrophobic segment monomer containing R1 group to obtain a mixed solution.

[0082] In the present invention, the Ar monomer preferably includes one or more of biphenyl, p-terphenyl, m-terphenyl, triphenylmethane, 4-benzylbiphenyl, binaphthyl, erene, 4,4′-trimethylenebis(1-methylpiperidine) and 1,3,5-triphenylbenzene, more preferably biphenyl, p-terphenyl, m-terphenyl, triphenylmethane, 4-benzylbiphenyl, binaphthyl, erene, 4,4′-trimethylenebis(1-methylpiperidine) or 1,3,5-triphenylbenzene.

[0083] In the present invention, the hydrophilic group monomer preferably includes dibenzofuran.

[0084] In the present invention, the organic solvent preferably includes one or more of dichloromethane, n-hexane, tetrahydrofuran and N,N-dimethylformamide, more preferably dichloromethane, n-hexane, tetrahydrofuran or N,N-dimethylformamide.

[0085] In the present invention, the molar ratio of the Ar monomer to the hydrophilic group monomer is preferably 1:(1-100), more preferably 1:(20-80), and even more preferably 1:(40-60).

[0086] In the present invention, the cationic group monomer preferably includes N-methyl-4-piperidone.

[0087] In the present invention, the hydrophobic segment monomer containing the R1 group preferably includes one or more of 1,1,1-trifluoroacetone, 2,2,2-trifluoroacetophenone, benzoyltrifluoroacetone, 7-bromo-1,1,1-trifluoro-2-heptanone and 3,3,3-trifluoropyruvate, more preferably 1,1,1-trifluoroacetone, 2,2,2-trifluoroacetophenone, benzoyltrifluoroacetone, 7-bromo-1,1,1-trifluoro-2-heptanone or 3,3,3-trifluoropyruvate.

[0088] In the present invention, the molar ratio of the cationic group monomer to the hydrophobic segment monomer containing the R1 group is preferably 1:(1-15), more preferably 1:(4-12), and even more preferably 1:(7-9).

[0089] In the present invention, the ratio of the total molar number of the Ar monomer and the hydrophilic group monomer to the total molar number of the cationic group monomer and the hydrophobic segment monomer containing the R1 group is preferably 1: (1 to 10), more preferably 1: (3 to 8), and more preferably 1: (5 to 6).

[0090] In the present invention, the mixed solution obtained in the above steps is reacted under the action of an acid catalyst, and then poured into a precipitant for precipitation to obtain a four-monomer polymer.

[0091] In the present invention, the acid catalyst includes solid acid and liquid acid.

[0092] In the present invention, the solid acid preferably includes Al2O3 / B2O3, BPO4, H4SiW 12 O 40 , β-type molecular sieve, ZSM-5 and Y-type molecular sieve, more preferably Al2O3 / B2O3, BPO4, H4SiW 12 O 40 , β-type molecular sieve, ZSM-5 or Y-type molecular sieve.

[0093] In the present invention, the acid catalyst preferably further comprises a solid superacid.

[0094] In the present invention, the solid superacid preferably comprises S2O8 2- / CeO2-RF、Pt-SO4 2- / ZrO2-Al2O3、SO4 2- / ZrO2-NiO / Al2O3 and SO4 2- / Fe2O3, more preferably S2O8 2- / CeO2-RF、Pt-SO4 2- / ZrO2-Al2O3、SO4 2- / ZrO2-NiO / Al2O3 or SO4 2- / Fe2O3.

[0095] In the present invention, the liquid acid preferably includes one or more of trifluoroacetic acid, carborane acid and trifluoromethanesulfonic acid, more preferably trifluoroacetic acid, carborane acid or trifluoromethanesulfonic acid.

[0096] In the present invention, the mass ratio of the total mass of the Ar monomer and the hydrophilic group monomer to the solid acid is preferably 100:(50-100), more preferably 100:(60-90), and even more preferably 100:(70-80).

[0097] In the present invention, the mass ratio of the total mass of the Ar monomer and the hydrophilic group monomer to the solid superacid is preferably 100:(20-60), more preferably 100:(25-55), more preferably 100:(30-50), and more preferably 100:(35-45).

[0098] In the present invention, the molar ratio of the total molar number of the Ar monomer and the hydrophilic group monomer to the liquid acid is preferably 1:(5-13), more preferably 1:(6-13), more preferably 1:(7-11), and more preferably 1:(8-10).

[0099] In the present invention, the reaction temperature is preferably -4 to 150°C, more preferably 0 to 150°C, and even more preferably 0 to 100°C.

[0100] In the present invention, the reaction time is preferably 4 to 72 hours, more preferably 20 to 60 hours, and even more preferably 35 to 45 hours.

[0101] In the present invention, the precipitant preferably includes one or more of methanol, ethanol, acetonitrile and n-hexane, more preferably methanol, ethanol, acetonitrile or n-hexane.

[0102] In the present invention, the precipitation is preferably followed by steps of solution washing and water washing.

[0103] Finally, the present invention conducts a light-proof reaction on the multi-block polymer obtained in the above steps, the solvent and the quaternary ammonium agent, and then precipitates the multi-block dibenzofuran polyarylpiperidine polymer.

[0104] In the present invention, the quaternizing agent preferably includes one or more of 1,5-dibromopentane, 1,4-dibromobutane and iodomethane, and more preferably 1,5-dibromopentane, 1,4-dibromobutane or iodomethane.

[0105] In the present invention, the solvent preferably includes one or more of ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform and N,N-dimethylformamide, more preferably ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform or N,N-dimethylformamide.

[0106] In the present invention, the temperature of the light-shielding reaction is preferably 20 to 120°C, more preferably 40 to 100°C, and even more preferably 60 to 80°C.

[0107] In the present invention, the light-shielding reaction time is preferably 12 to 72 hours, more preferably 22 to 62 hours, and even more preferably 32 to 52 hours.

[0108] In the present invention, the solvent used for the precipitation reaction solution in step 3) preferably includes one or more of methanol, acetonitrile, diethyl ether and ethyl acetate, more preferably methanol, acetonitrile, diethyl ether or ethyl acetate.

[0109] In the present invention, the multi-block dibenzofuran-based polyarylpiperidine polymer is preferably a multi-block dibenzofuran-based polyarylpiperidine polymer containing a hydrophobic segment.

[0110] The present invention provides the use of the multi-block dibenzofuran polyarylpiperidine polymer described in the above technical solution or the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method described in any one of the above technical solutions in anion exchange membrane.

[0111] The present invention provides an anion exchange membrane, which is a multi-block dibenzofuran polyarylpiperidine anion exchange membrane;

[0112] The anion exchange membrane includes an alkalized multi-block dibenzofuran polyarylpiperidine polymer;

[0113] The multi-block dibenzofuran polyarylpiperidine polymer is the multi-block dibenzofuran polyarylpiperidine polymer described in the above technical solution or the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method described in any one of the above technical solutions.

[0114] In the present invention, the multi-block dibenzofuran-based polyarylpiperidine anion exchange membrane is preferably prepared by the following steps:

[0115] A multi-block dibenzofuran polyarylpiperidine polymer is mixed with a polar solution to obtain an anion exchange resin homogeneous casting solution, which is then formed into a film on a substrate, which is then immersed in a potassium hydroxide solution and dried to obtain a multi-block dibenzofuran polyarylpiperidine anion exchange membrane in the hydroxide form.

[0116] In the present invention, the concentration of the anion exchange resin homogeneous solution is preferably 5 wt% to 30 wt%, more preferably 10 wt% to 25 wt%, and even more preferably 15 wt% to 20 wt%.

[0117] In the present invention, the soaking time is preferably 12 to 36 hours, more preferably 17 to 30 hours, and even more preferably 22 to 25 hours.

[0118] In the present invention, the soaking temperature is preferably 25 to 80°C, more preferably 35 to 70°C, and even more preferably 45 to 60°C.

[0119] The present invention provides the use of the multi-block dibenzofuran polyarylpiperidine polymer described in the above technical solution, the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method described in any one of the above technical solutions, or the multi-block dibenzofuran polyarylpiperidine anion exchange membrane described in any one of the above technical solutions in the field of hydrogen production by electrolysis of water.

[0120] The preparation method provided by the present invention comprises: (1) subjecting an aromatic compound, dibenzofuran, a hydrophobic chain and N-methyl-4-piperidone to a one-pot Friedel-Crafts hydroxyalkylation reaction to obtain a polyarylpiperidine copolymer; (2) dissolving the multi-block polyarylpiperidine copolymer obtained in (1) and reacting it with iodomethane to obtain a corresponding polymer; (3) configuring the polymer obtained in (2) into a casting solution, filtering it, and then using a roll-to-roll automatic casting machine to obtain a quaternary ammonium-type multi-block dibenzofuran-containing polyarylpiperidine anion exchange membrane. The anion exchange membrane polymer material has excellent anion transport capacity (168mS.cm) under alkaline conditions. -1 @80℃), good mechanical strength (44.5Mpa), and excellent alkali stability (immersion in 80℃, 1M KOH solution for 2000h. Conductivity loss <5%). It can be used as an excellent membrane device for water electrolysis hydrogen production reaction device and has certain practical application potential. In addition, the preparation method of the present invention is very simple and the preparation process is short. The present invention proposes for the first time a preparation method and strategy for the green preparation of anion exchange membranes using solid acids and solid superacid catalysts. The solid acid and solid superacid catalyst used in the present invention are easy to separate and recover and can be reused many times. Its technical route is green and environmentally friendly.

[0121] The present invention is a complete and detailed overall technical solution that better ensures the structure of a multi-block dibenzofuran polyarylpiperidine polymer and further improves the performance of anion exchange membranes. The multi-block dibenzofuran polyarylpiperidine polymer, its preparation method, and application, an anion exchange membrane, and its application may specifically include the following:

[0122] A multi-block dibenzofuran polyarylpiperidine anion exchange membrane containing a hydrophobic segment, the structure of the multi-block dibenzofuran polyarylpiperidine anion exchange membrane containing a hydrophobic segment is as follows:

[0123]

[0124] The structure of Ar is:

[0125]

[0126] x=0.1~0.3.

[0127] Among them, the structure of R1 is:

[0128]

[0129] y=0.9~0.7;

[0130] The structure of R2:

[0131]

[0132] A method for preparing a hydrophobic segment-containing multi-block dibenzofuran polyarylpiperidine anion exchange membrane comprises the following steps:

[0133] (1) Preparation of a multi-block dibenzofuran-based polyarylpiperidine multi-block polymer containing a hydrophobic segment: dissolve an aromatic monomer and a hydrophilic group in a solvent at a molar ratio of 1:1 to 1:100, and add a cationic group and a hydrophobic segment after thorough stirring. The molar ratio of the sum of the aromatic monomer and the hydrophilic group to the sum of the cationic group and the hydrophobic segment is 1:1 to 1:10, and the molar ratio of the cationic group to the hydrophobic segment is 1:1 to 1:15. The concentration of the sum of all monomers in the solution is 5% to 50%. One or more of a solid acid, a solid superacid, or a liquid acid is added to the mixed solution as a catalyst.

[0134] Specifically, the mass ratio of the sum of the aromatic monomer and the hydrophilic group to the solid acid is 1:(50-100) wt%, the mass ratio of the sum of the aromatic monomer and the hydrophilic group to the solid superacid is 1:(20-60) wt%, and the molar ratio of the sum of the aromatic monomer and the hydrophilic group to the liquid acid is 1:(5-13). After reacting at -4-150° C. for 4-72 hours, a dark brown viscous solution is obtained. The reaction solution is then poured into a solvent for precipitation (if a solid acid or solid superacid is used, it must be filtered first, and the solid acid or solid superacid can be recovered and reused). Finally, it is washed with a solution and deionized water until neutral, and dried to obtain a multi-block polymer.

[0135] (2) Preparation of quaternized polymer: The multi-block polymer obtained in step (1) is dissolved in a solvent, fully dissolved, stirred evenly, and then a quaternized reagent is added to carry out a light-proof reaction; after the reaction is completed, the reaction solution is dropped into a solvent to precipitate a yellow precipitate, which is fully washed, filtered, and dried to obtain a quaternized polymer.

[0136] (3) Preparation of a multi-block dibenzofuran-based polyarylpiperidine anion exchange membrane containing hydrophobic segments: dissolving the quaternized polymer obtained in step (2) in a polar solvent, filtering out impurities after sufficient dissolution to obtain a 5-30 wt% homogeneous anion exchange resin casting solution; pouring the casting solution into a roll-to-roll automatic casting machine to form a membrane; soaking the membrane in 1M KOH at 25-80°C for 12-36 hours, drying under vacuum, and then storing the membrane in a vacuum environment for later use to obtain a multi-block dibenzofuran-based polyarylpiperidine anion exchange membrane containing hydrophobic segments in the form of hydroxide.

[0137] Specifically, the hydrophilic group is dibenzofuran; the aromatic monomer is selected from one or more of the following: biphenyl, p-terphenyl, m-terphenyl, triphenylmethane, 4-benzylbiphenyl, binaphthyl, erene, 4,4′-trimethylenebis(1-methylpiperidine), and 1,3,5-triphenylbenzene, with p-terphenyl being preferred. The cationic group is N-methyl-4-piperidone; the hydrophobic segment is selected from one or more of the following: 1,1,1-trifluoroacetone, 2,2,2-trifluoroacetophenone, benzoyltrifluoroacetone, 7-bromo-1,1,1-trifluoro-2-heptanone, and ethyl 3,3,3-trifluoropyruvate, with 2,2,2-trifluoroacetophenone being preferred.

[0138] Specifically, the reaction solvent includes dichloromethane, n-hexane, tetrahydrofuran, and N,N-dimethylformamide; dichloromethane is preferably used in an amount of 3-20 mL.

[0139] Specifically, the solid acid catalyst includes Al2O3 / B2O3, BPO4, H4SiW 12 O 40, β-type molecular sieve (silicon-aluminum ratio: 6-40), ZSM-5 (silicon-aluminum ratio: 5-40), Y-type molecular sieve (silicon-aluminum ratio: 3-6); ZSM-5 (silicon-aluminum ratio preferably: 10-30) and Al2O3 / B2O3 are preferred.

[0140] Specifically, the solid superacid catalyst includes S2O8 2- / CeO2-RF、Pt-SO4 2- / ZrO2-Al2O3、SO4 2- / ZrO2-NiO / Al2O3、SO4 2- / Fe2O3; SO4 is preferred 2- / ZrO2-NiO / Al2O3. Liquid superacids include trifluoroacetic acid, carborane acid, and trifluoromethanesulfonic acid; trifluoroacetic acid and trifluoromethanesulfonic acid are preferably used.

[0141] Specifically, the precipitation solvent is one or more of methanol, ethanol, n-hexane, and acetonitrile; n-hexane is preferred, and the amount used is 150-500 mL.

[0142] Specifically, the washing solution carrier is a 0.5-3 M potassium carbonate or sodium carbonate solution; preferably potassium carbonate solution, and the amount used is 100-500 mL.

[0143] Specifically, based on the molar ratio, the optimal molar ratio of the aromatic monomer and the hydrophilic group is 10:90 to 40:70. The optimal molar ratio of the sum of the aromatic monomer and the hydrophilic group to the sum of the cationic group and the hydrophobic segment is 1:1 to 1:7. The optimal molar ratio of the cationic group to the hydrophobic segment is 1:1 to 1:10, and the optimal concentration of the sum of all monomers in the solution is 17% to 35%. The optimal mass ratio of the sum of the aromatic monomer and the hydrophilic group to the solid acid is 1:(70-100) wt%, the optimal mass ratio of the sum of the aromatic monomer and the hydrophilic group to the solid superacid is 1:(30-60) wt%, and the optimal molar ratio of the sum of the aromatic monomer and the hydrophilic group to the liquid acid is 1:(7-13). The optimal reaction temperature is 0-100°C, and the optimal reaction time is 12-60h.

[0144] Specifically, the solvent used to dissolve the monomer polymer is one or more of ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform, and N,N-dimethylformamide; preferably dimethyl sulfoxide, and the amount used is 10 to 100 mL.

[0145] Specifically, the quaternizing agent includes 1,5-dibromopentane, 1,4-dibromobutane, and methyl iodide, with methyl iodide being preferred. The amount of methyl iodide used is 0.5 to 10 mL by volume.

[0146] Specifically, the temperature of the quaternization reaction is 20 to 120° C., and the time is 12 to 72 hours.

[0147] Specifically, the solvent used in the precipitation reaction solution is one or more of methanol, acetonitrile, ether, and ethyl acetate; ethyl acetate is preferred, and the optimal amount is 100 to 500 mL.

[0148] Specifically, the polar solvent used to dissolve the quaternized polymer includes one or more of chloroform, dichloromethane, N,N-dimethylformamide, and dimethyl sulfoxide, with dimethyl sulfoxide being preferred; the optimal dosage is 15 to 100 mL; and the optimal solid content of the anion exchange resin homogeneous casting solution is 9 to 23 wt%.

[0149] Furthermore, a method for preparing a multi-block dibenzofuran polyarylpiperidine anion exchange membrane comprises the following steps:

[0150] (1) Preparation of multi-block dibenzofuran-based polyarylpiperidine multi-block polymers containing hydrophobic segments: aromatic monomers and hydrophilic groups are dissolved in a solvent at a molar ratio of 1:1 to 1:100, and cationic groups and hydrophobic segments are added after sufficient stirring. The molar ratio of the sum of the aromatic monomers and hydrophilic groups to the sum of the cationic groups and hydrophobic segments is 1:1 to 1:10, and the molar ratio of the cationic groups to the hydrophobic segments is 1:1 to 1:15. The concentration of the sum of all monomers in the solution is 5% to 50%. One or more of solid acid, solid superacid or liquid acid is added to the above mixed solution as a catalyst, wherein the mass ratio of the sum of the aromatic monomer and the hydrophilic group to the solid acid is 1: (50-100) wt%, the mass ratio of the sum of the aromatic monomer and the hydrophilic group to the solid superacid is 1: (20-60) wt%, and the molar ratio of the sum of the aromatic monomer and the hydrophilic group to the liquid acid is 1: (5-13). After reacting at -4-150°C for 4-72 hours, a dark brown viscous solution is obtained, and then the reaction solution is poured into a solvent to precipitate. Precipitation in the solvent (if a solid acid or solid superacid is used, it must be filtered before precipitation, and the solid acid or solid superacid can be reused), and finally washed with a solution and deionized water until neutral, and dried to obtain a multi-block polymer;

[0151] Furthermore, the reaction solvent includes dichloromethane, n-hexane, tetrahydrofuran, N,N-dimethylformamide; dichloromethane is preferably used in an amount of 3-20 mL.

[0152] Furthermore, the precipitation solvent is one or more of methanol, ethanol, acetonitrile, and n-hexane, and the amount used is 150 to 500 mL;

[0153] (2) Preparation of quaternized polymer: The multi-block polymer obtained in step (1) is dissolved in a solvent, fully dissolved, stirred evenly, and then iodomethane is added to react in the dark; after the reaction is completed, the reaction solution is dropped into a solvent to precipitate a yellow precipitate, which is fully washed, filtered, and dried to obtain a quaternized polymer.

[0154] Furthermore, the solvent used to dissolve the monomer polymer is one or more of ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform, and N,N-dimethylformamide; the amount used is 10 to 100 mL; the solid acid catalyst includes Al2O3 / B2O3, BPO4, H4SiW 12 O 40 , β-type molecular sieve (silicon-aluminum ratio: 6-40), ZSM-5 (silicon-aluminum ratio: 5-40), Y-type molecular sieve (silicon-aluminum ratio: 3-6). Solid superacid catalysts include S2O8 2- / CeO2-RF、Pt-SO4 2- / ZrO2-Al2O3、SO4 2- / ZrO2-NiO / Al2O3、SO4 2- / Fe2O3. Liquid superacids include trifluoroacetic acid, carborane acid, and trifluoromethanesulfonic acid.

[0155] Furthermore, the quaternizing agent includes 1,5-dibromopentane, 1,4-dibromobutane, and iodomethane, and the amount used is 0.5 to 10 mL by volume.

[0156] Furthermore, the temperature of the quaternization reaction is 20 to 120° C., and the time is 12 to 72 hours.

[0157] Furthermore, the solvent used in the precipitation reaction liquid is one or more of methanol, acetonitrile, ether, and ethyl acetate; and the amount used is 100 to 500 mL.

[0158] (3) Preparation of a multi-block dibenzofuran-based polyarylpiperidine anion exchange membrane containing hydrophobic segments: dissolving the quaternized polymer obtained in step (2) in a polar solvent, filtering out impurities after sufficient dissolution to obtain a 5-30 wt% homogeneous anion exchange resin casting solution; forming the casting solution into a membrane using a roll-to-roll automatic casting machine; soaking the membrane in 1 M KOH at 25-80° C. for 12-36 h, drying under vacuum, and then storing the membrane in a vacuum environment for standby use to obtain a multi-block dibenzofuran-based polyarylpiperidine anion exchange membrane containing hydrophobic segments in the hydroxide form.

[0159] Furthermore, the polar solvent used to dissolve the quaternized polymer includes one or more of chloroform, dichloromethane, N,N-dimethylformamide, and dimethyl sulfoxide; the amount used is 15-100 mL; and the solid content of the anion exchange resin homogeneous casting solution is 9-23 wt%.

[0160] The present invention provides an application of a multi-block dibenzofuran-based polyarylpiperidine anion exchange membrane containing hydrophobic segments as described in the above technical solution in the field of hydrogen production by water electrolysis.

[0161] The present invention provides a multi-block dibenzofuran polyarylpiperidine polymer and its preparation method, application, a multi-block dibenzofuran polyarylpiperidine anion exchange membrane containing hydrophobic segments and its application. The multi-block dibenzofuran polyarylpiperidine polymer designed by the present invention has a specific structure. The presence of dibenzofuran in the structure allows the polymer to have larger ion groups and tends to interconnect with the aromatic main chain to form ion channels, accelerating the transmission of anions; it also promotes a more obvious phase separation morphology, thereby more effectively delaying the degradation of AEMs by hydroxide ions; because dibenzofuran is a planar molecule, the ion-dipole interaction between the oxygen atoms and the cationic groups therein also contributes to a certain degree to the filling efficiency. Therefore, the membrane with a high dibenzofuran content has a higher density, and its hydrophilicity increases the flexibility or elongation of the membrane. Furthermore, the presence of 2,2,2-trifluoroacetophenone as a hydrophobic group promotes the concentrated distribution of hydrophobic domains through strong hydrophobic interactions, allowing hydrophilic ionic groups to frequently self-aggregate, forming a distinct microphase-separated structure and building a well-developed ion channel. The present invention also provides a method for preparing a multi-block dibenzofuran-based polyarylpiperidine polymer. This green anion exchange membrane preparation process employs solid acid and solid superacid catalysts, resulting in excellent catalytic performance, a mild catalytic environment, ease of separation and recovery, and multiple reuse, making it environmentally friendly.

[0162] The presence of dibenzofuran in the hydrophobic segment-containing multi-block dibenzofuran polyarylpiperidine anion exchange membrane provided by the present invention is conducive to the formation of ion channels and phase separation morphology, thereby accelerating the transmission of anions and improving electrical conductivity; at the same time, it effectively delays the degradation of AEMs by hydroxide ions and enhances the service life of the membrane. The presence of hydrophobic groups enables strong hydrophobic interactions to promote the centralized distribution of hydrophobic domains, so that hydrophilic ionic groups can frequently self-aggregate to form a distinct microphase separation structure and build a developed ion channel. Moreover, the preparation process adopts a technical route for the green preparation of anion exchange membranes using solid acid and solid superacid catalysts, which has good catalytic effect and is easy to separate and recover. Under the premise of appropriately increasing the reaction temperature and reaction time and selecting a high-boiling point solvent, complete replacement of liquid superacids can be achieved.

[0163] This invention proposes, for the first time, a green method and strategy for preparing anion exchange membranes using solid acids and solid superacid catalysts. The solid acids and solid superacid catalysts used in this invention are easily separated and recovered, allowing for repeated reuse. This technology is both green and environmentally friendly. Notably, at low temperatures, the addition of solid acids can reduce the amount of liquid superacid required by 30%, and the addition of solid superacids can reduce the amount of liquid superacid required by 50%.

[0164] Experimental results show that the multi-block dibenzofuran-containing polyarylpiperidine anion exchange membrane containing hydrophobic segments prepared by the present invention has excellent electrical conductivity (168mS / cm@80℃) and alkali stability (in 80℃, 1M KOH solution, the conductivity retention rate is as high as 93% after 2000h); the alkaline electrolysis membrane electrode assembly (AEMWE) composed of the multi-block dibenzofuran-containing polyarylpiperidine anion exchange membrane containing hydrophobic segments requires only 2.31V for stable operation for 1500h; at the same time, the multi-block dibenzofuran-containing polyarylpiperidine anion exchange membrane containing hydrophobic segments has high mechanical strength, good flexibility, and is not easy to break, making it suitable for industrial cast film formation and realizing industrial application.

[0165] In order to further illustrate the present invention, the following embodiments provide a multi-block dibenzoylmethane polyaryl piperidine polymer and its preparation method, application, an anion exchange membrane and its application in detail. However, it should be understood that these embodiments are implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating processes are provided only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention. The scope of protection of the present invention is not limited to the following embodiments.

[0166] Example 1

[0167] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a hydrophobic segment-containing dibenzofuran polyarylpiperidine polymer material.

[0168] (2) Preparation of quaternized polymer: 3 mmol of a hydrophobic segmented multi-block dibenzofuran-based polyarylpiperidine polymer was added to 20 mL of dimethyl sulfoxide solution. The mixture was stirred at 80°C until dissolved, followed by the addition of 1 mL of iodomethane. The reaction was continued at this temperature in the dark for 60 h. The reaction solution was then added dropwise into ethyl acetate to precipitate a pale yellow honeycomb-like solid. The solid was then washed with ethyl acetate and deionized water for 48 h, respectively. Finally, the quaternized polymer was dried in a vacuum oven at 60°C for 24 h.

[0169] (3) Preparation of a multi-block dibenzofuran-type polyarylpiperidine anion exchange membrane containing hydrophobic segments: Weigh 1 g of a quaternized polymer and dissolve it in 30 mL of dimethyl sulfoxide. After fully dissolving, filter out the impurities to obtain a casting solution; then cast the casting solution in a roll-to-roll automatic casting machine and vacuum dry it at 80°C to form a membrane; rinse the dried and formed membrane with deionized water, remove it, and soak it in 1M KOH solution for 36 hours for ion exchange, and rinse off the surface alkali with deionized water to obtain a multi-block dibenzofuran-type polyarylpiperidine anion exchange membrane containing hydrophobic segments.

[0170] Example 2

[0171] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 20:80 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0172] (2) The other steps are the same as those in Example 1.

[0173] Example 3

[0174] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 30:70 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K₂CO₃ and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block polyarylpiperidine polymer material containing a hydrophobic dibenzofuran segment.

[0175] (2) The other steps are the same as those in Example 1.

[0176] Example 4

[0177] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multiblock polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 40:60 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0178] (2) The other steps are the same as those in Example 1.

[0179] Example 5

[0180] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multiblock polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:3; the molar ratio of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0181] (2) The other steps are the same as those in Example 1.

[0182] Example 6

[0183] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:5; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0184] (2) The other steps are the same as those in Example 1.

[0185] Example 7

[0186] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 7:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0187] (2) The other steps are the same as those in Example 1.

[0188] Example 8

[0189] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 11:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0190] (2) The other steps are the same as those in Example 1.

[0191] Example 9

[0192] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multiblock polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:5. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0193] (2) The other steps are the same as those in Example 1.

[0194] Example 10

[0195] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multiblock polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:10. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. After 48 hours of reaction until the reaction solution became a dark brown viscous liquid, it was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing hydrophobic segments.

[0196] (2) The other steps are the same as those in Example 1.

[0197] Example 11

[0198] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to N,N-dimethylformamide at room temperature in a molar ratio of 10:90 to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Y-type molecular sieves were added at 80°C. The mass ratio of the sum of p-terphenyl and dibenzofuran to the Y-type molecular sieve (silicon-aluminum ratio of 5) was 1:60 wt%. After 72 hours of reaction, until the reaction solution became a dark brown viscous liquid, the Y-type molecular sieve was filtered out and the liquid was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K₂CO₃ and deionized water at 50°C for 24 hours. Finally, the polymer was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer containing hydrophobic segments.

[0199] (2) The other steps are the same as those in Example 1.

[0200] Example 12

[0201] (1) Preparation of polyarylpiperidine multi-block polymer containing hydrophobic segment dibenzofuran: p-terphenyl and dibenzofuran were added to N, N-dimethylformamide at a molar ratio of 10:90 to form a heterogeneous solution at room temperature, and N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added after sufficient stirring. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. SO4 was added at 60℃. 2- / ZrO2, the sum of p-terphenyl and dibenzofuran and SO4 2- The reaction mixture was stirred for 60 hours until the reaction solution became a dark brown viscous liquid. The solid catalyst was then filtered out and the liquid was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M KCO and deionized water at 50°C for 24 hours. Finally, the polymer was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer containing hydrophobic segments.

[0202] (2) The other steps are the same as those in Example 1.

[0203] Example 13

[0204] (1) Preparation of polyarylpiperidine multi-block polymer containing hydrophobic segment dibenzofuran: p-terphenyl and dibenzofuran were added to N, N-dimethylformamide at a molar ratio of 10:90 at room temperature to form a heterogeneous solution, and N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added after sufficient stirring. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Y-type molecular sieve (silicon-aluminum ratio of 5) and SO4 were added at 60℃. 2- / ZrO2(Y type molecular sieve and SO4 2- / ZrO2 mass ratio is 2:1), the total mass of terphenyl and dibenzofuran is equal to the mass of Y-type molecular sieve (silicon aluminum ratio is 5) and SO4 2- The total weight ratio of ZrO2 to ZrO2 was 1:60 wt%. The reaction was continued for 66 hours until the reaction solution became a dark brown viscous liquid. The solid catalyst was then filtered out and the liquid was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, it was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer containing hydrophobic segments.

[0205] (2) The other steps are the same as those in Example 1.

[0206] Example 14

[0207] (1) Preparation of polyarylpiperidine multi-block polymer containing hydrophobic segment dibenzofuran: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution, and N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added after sufficient stirring. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoroacetic acid, trifluoromethanesulfonic acid and SO4 were added at 20℃. 2- / ZrO2, among which the sum of terphenyl and dibenzofuran and SO4 2- The mass ratio of terphenyl to ZrO₂ was 1:10 wt%. The molar ratio of the sum of p-terphenyl and dibenzofuran to the sum of trifluoroacetic acid and trifluoromethanesulfonic acid was 1:5. The reaction was continued for 60 h until the reaction solution became a dark brown viscous liquid. The solid catalyst was then filtered out and the liquid was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1 M K₂CO₃ and deionized water at 50°C for 24 h, respectively. Finally, the polymer was dried in a vacuum oven at 60°C for 24 h to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer containing hydrophobic segments.

[0208] (2) The other steps are the same as those in Example 1.

[0209] Example 15

[0210] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After sufficient stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoroacetic acid, trifluoromethanesulfonic acid, and Y-type molecular sieve (silicon-aluminum ratio of 5) were added at 20°C. The mass ratio of the sum of p-terphenyl and dibenzofuran to the Y-type molecular sieve was 1:30 wt%. The molar ratio of the sum of p-terphenyl and dibenzofuran to the sum of trifluoroacetic acid and trifluoromethanesulfonic acid was 1:3. The reaction was allowed to proceed for 60 hours until the reaction solution became a dark brown viscous liquid. The solid catalyst was then filtered out and the liquid was poured into methanol to precipitate the crude polymer. The crude polymer was then washed with 1M K₂CO₃ and deionized water at 50°C for 24 hours. Finally, the polymer was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer containing hydrophobic segments.

[0211] (2) The other steps are the same as those in Example 1.

[0212] Example 16

[0213] (1) Preparation of polyarylpiperidine multi-block polymer containing hydrophobic segment dibenzofuran: p-terphenyl and dibenzofuran were added to N, N-dimethylformamide at a molar ratio of 10:90 to form a heterogeneous solution at room temperature, and N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added after sufficient stirring. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Y-type molecular sieve (silicon-aluminum ratio of 5) filtered and cleaned in Example 13 was added at 60°C and SO4 2- / ZrO2. The reaction mixture was allowed to react for 120 hours until it became a dark brown viscous liquid. The crude polymer was then poured into methanol to precipitate. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the polymer was dried in a vacuum oven at 60°C for 24 hours to yield a multi-block dibenzofuran-based polyarylpiperidine polymer containing hydrophobic segments.

[0214] (2) The other steps are the same as those in Example 1.

[0215] Example 17

[0216] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl, dibenzofuran, and 4-benzylbiphenyl were added to dichloromethane at a molar ratio of 90:5:5 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added. The molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl, dibenzofuran, and 4-benzylbiphenyl was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 hours until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the material was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing a hydrophobic segment.

[0217] The other steps are the same as those in Example 1.

[0218] Example 18

[0219] (1) Preparation of a hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymer: p-terphenyl, 1,1-binaphthyl, and dibenzofuran were added to dichloromethane at a molar ratio of 90:5:5 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added. The molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl, 1,1-binaphthyl, and dibenzofuran was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 h until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1M K2CO3 and deionized water at 50°C for 24 h. Finally, the material was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing a hydrophobic segment.

[0220] The other steps are the same as those in Example 1.

[0221] Comparative Example 1

[0222] (1) Preparation of polyarylpiperidine polymer containing hydrophobic segments: p-Terphenyl was added to dichloromethane at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 hours until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the polyaryl piperidine polymer material containing a hydrophobic segment was obtained by drying in a vacuum oven at 60°C for 24 hours.

[0223] (2) Preparation of quaternized polymer: 3 mmol of a polyarylpiperidine polymer containing a hydrophobic segment was weighed and added to 20 mL of dimethyl sulfoxide solution. The mixture was stirred at 80°C until dissolved, and then 1 mL of iodomethane was added. The reaction was continued at this temperature in the dark for 60 h. The reaction solution was then added dropwise into ethyl acetate to precipitate a pale yellow honeycomb solid. The solid was then washed with ethyl acetate and deionized water for 48 h. Finally, the quaternized polymer was dried in a vacuum oven at 60°C for 24 h.

[0224] (3) Preparation of a polyarylpiperidine anion exchange membrane containing a hydrophobic segment: 1 g of the quaternized polymer was weighed and dissolved in 30 mL of dimethyl sulfoxide. After complete dissolution, impurities were filtered to obtain a casting solution. The casting solution was then cast on a roll-to-roll automatic casting machine and dried under vacuum at 80°C to form a membrane. The dried membrane was rinsed with deionized water, removed, and immersed in a 1 M KOH solution for 36 h for ion exchange. The surface alkali was then rinsed with deionized water to obtain a polyarylpiperidine anion exchange membrane containing a hydrophobic segment. Specific performance parameters are shown in Table 1.

[0225] Comparative Example 2

[0226] (1) Preparation of a polyarylpiperidine tetramer containing a hydrophobic segment: Biphenyl was added to dichloromethane at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 hours until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the polyaryl piperidine polymer material containing a hydrophobic segment was obtained by drying in a vacuum oven at 60°C for 24 hours.

[0227] The other steps are the same as those in Comparative Example 1.

[0228] Comparative Example 3

[0229] (1) Preparation of a polyarylpiperidine tetramer containing a hydrophobic segment: Triphenylmethane was added to dichloromethane at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 hours until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the polyaryl piperidine polymer material containing a hydrophobic segment was obtained by drying in a vacuum oven at 60°C for 24 hours.

[0230] The other steps are the same as those in Comparative Example 1.

[0231] Comparative Example 4

[0232] (1) Preparation of a polyarylpiperidine tetramer containing a hydrophobic segment: 1,3,5-triphenylmethane was added to dichloromethane at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone were added. The molar ratio of the sum of N-methyl-4-piperidone and 2,2,2-trifluoroacetophenone to the sum of p-terphenyl and dibenzofuran was 1:1; the molar ratio of N-methyl-4-piperidone to 2,2,2-trifluoroacetophenone was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 hours until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the polyaryl piperidine polymer material containing a hydrophobic segment was obtained by drying in a vacuum oven at 60°C for 24 hours.

[0233] The other steps are the same as those in Comparative Example 1.

[0234] Comparative Example 5

[0235] (1) Preparation of a multi-block polymer of dibenzoylmethane containing hydrophobic segments: p-terphenyl and dibenzoylmethane were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added, with the molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl and dibenzoylmethane being 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C, with the molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzoylmethane being 9:1. The reaction was carried out for 48 hours until the reaction solution became a dark brown viscous liquid. The crude polymer was then poured into methanol to precipitate. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the product was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block polymer of dibenzoylmethane containing hydrophobic segments.

[0236] The other steps are the same as those in Comparative Example 1.

[0237] Comparative Example 6

[0238] (1) Preparation of a multi-block polymer of dibenzoylmethane containing hydrophobic segments: Biphenyl and dibenzoylmethane were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added, with the molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl and dibenzoylmethane being 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C, with the molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzoylmethane being 9:1. The reaction was carried out for 48 hours until the reaction solution became a dark brown viscous liquid. The crude polymer was then poured into methanol to precipitate. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the solution was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block polymer of dibenzoylmethane containing hydrophobic segments.

[0239] The other steps are the same as those in Comparative Example 1.

[0240] Comparative Example 7

[0241] (1) Preparation of a multi-block polymer of dibenzoylmethane containing hydrophobic segments: Triphenylmethane and dibenzoylmethane were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added, with the molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl and dibenzoylmethane being 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C, with the molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzoylmethane being 9:1. The reaction was carried out for 48 hours until the reaction solution became a dark brown viscous liquid. The crude polymer was then poured into methanol to precipitate. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the product was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block polymer of dibenzoylmethane containing hydrophobic segments.

[0242] The other steps are the same as those in Comparative Example 1.

[0243] Comparative Example 8

[0244] (1) Preparation of a multi-block polymer of dibenzoylmethane containing hydrophobic segments: 1,3,5-triphenylbenzene and dibenzoylmethane were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added, with the molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl and dibenzoylmethane being 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C, with the molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzoylmethane being 9:1. The reaction was carried out for 48 hours until the reaction solution became a dark brown viscous liquid. The crude polymer was then poured into methanol to precipitate. The crude polymer was then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the product was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block polymer of dibenzoylmethane containing hydrophobic segments.

[0245] The other steps are the same as those in Comparative Example 1.

[0246] Comparative Example 9

[0247] (1) Preparation of hydrophobic segmented dibenzofuran-containing polyarylpiperidine multi-block polymers: 4,4′-trimethylenebis(1-methylpiperidine) and dibenzofuran were added to dichloromethane at a molar ratio of 10:90 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added. The molar ratio of N-methyl-4-piperidone to the sum of 4,4′-trimethylenebis(1-methylpiperidine) and dibenzofuran was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C. The molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was allowed to proceed for 48 h until the reaction solution became a dark brown viscous liquid. The solution was then poured into methanol to precipitate the crude polymer, which was then washed with 1 M K2CO3 and deionized water at 50°C for 24 h. Finally, the material was dried in a vacuum oven at 60°C for 24 hours to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer material containing a hydrophobic segment.

[0248] The other steps are the same as those in Comparative Example 1.

[0249] Comparative Example 10

[0250] (1) Preparation of a polyarylpiperidine multi-block polymer containing hydrophobic segments: p-terphenyl and 4-benzylbiphenyl were added to dichloromethane at a molar ratio of 60:40 at room temperature to form a heterogeneous solution. After thorough stirring, N-methyl-4-piperidone was added, and the molar ratio of N-methyl-4-piperidone to the sum of p-terphenyl and 4-benzylbiphenyl was 1:1. Trifluoromethanesulfonic acid and trifluoroacetic acid were added at 8°C, and the molar ratio of the sum of trifluoromethanesulfonic acid and trifluoroacetic acid to the sum of p-terphenyl and dibenzofuran was 9:1. The reaction was carried out for 48 hours until the reaction solution became a dark brown viscous liquid. The crude polymer was then poured into methanol to precipitate, and then washed with 1M K2CO3 and deionized water at 50°C for 24 hours. Finally, the solution was dried in a vacuum oven at 60°C for 24 hours to obtain a polyarylpiperidine multi-block polymer material containing hydrophobic segments.

[0251] The other steps are the same as those in Comparative Example 1.

[0252] The performance of the anion exchange membranes prepared in the examples of the present invention and the comparative examples was tested.

[0253] Membrane tensile stress test: Anion exchange membrane samples were cut into 1 cm × 5 cm pieces and immersed in deionized water for 36 h. After the surface moisture was wiped off, the membrane samples were tested using a universal material testing machine at 25°C and a tensile rate of 5 mm / min.

[0254] Membrane conductivity test: Anion exchange membrane samples were cut into 1 cm × 5 cm pieces, placed in 1 M KOH solution at 60°C for 24 hours, rinsed with deionized water, and tested using an electrochemical workstation at 80°C.

[0255] Ion exchange capacity test: First, the prepared AEMs were cut into 1 cm × 5 cm rectangles, and the membrane samples were immersed in 1 mol / L NaOH solution for 48 hours and then rinsed with deionized water 3 to 5 times to obtain OH - Form of AEMs. - The AEMs were immersed in 50 mL (V1) of a pre-prepared 0.01 mol / L standard HCl solution and sealed and allowed to stand for 48 hours. The acid-soaked AEMs were rinsed repeatedly and the washing liquid was carefully collected. The dry weight m was measured when the AEMs were dried to a constant weight. Using a back titration method, the remaining HCl solution and washing liquid were titrated with a freshly prepared 0.01 mol / L NaOH standard solution. When the electronic pH meter displayed a reading of 7.0, the volume of the NaOH solution (V2) was recorded. The following formula is the calculation formula for IEC:

[0256]

[0257] Swelling rate test: Cut the anion exchange membrane samples into 1cm×5cm pieces and place them in a vacuum oven. Dry them at 60℃ until the residual solvent and water on the membrane surface are completely removed. Measure the length L of the dried samples. dry (mm). Then, place the membrane in deionized water at 80°C and soak it for 2 hours. Measure the membrane length L after soaking. wet (mm).

[0258] The swelling rate of the membrane is calculated as follows:

[0259]

[0260] Conductivity retention rate test: Cut the anion exchange membrane samples into 1cm×5cm pieces and soak them in 1 mol / L NaOH solution at room temperature for 48 hours to ensure that they are completely exchanged into OH - For an anion exchange membrane, remove the membrane from the alkali solution and rinse the surface with deionized water several times to remove any residual alkali. Then, soak the membrane in a 1 mol / L NaOH solution at 80°C. Samples were removed at regular intervals to test their conductivity, ultimately determining the conductivity retention rate after 2000 hours.

[0261] Stability (voltage) test: Cut the anion exchange membrane into 2cm×2cm pieces, place them in 1M KOH solution at 80℃ for 24 hours, and then rinse them with deionized water. Test the membrane electrode under the conditions of 1M KOH, 80℃, 1A / cm 2 , commercially available foamed nickel was used as the anode and cathode catalyst.

[0262] The parameters are shown in Table 1, which shows the performance parameters of the dibenzofuran-based polyarylpiperidine anion exchange membranes prepared in the examples and comparative examples of the present invention.

[0263] Table 1

[0264]

[0265]

[0266] Note: (1) The conductivity retention mentioned in the table refers to the percentage of the membrane's initial conductivity remaining after 2000 hours of storage in 1M KOH at 80°C. (2) The stable voltage refers to the voltage required for the membrane to electrolyze water after 1500 hours of stable operation on the membrane electrode.

[0267] The above describes in detail a hydrophobic segment-containing dibenzofuran-based polyarylpiperidine anion exchange membrane and its applications provided by the present invention. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is intended only to help understand the methods and core concepts of the present invention, including the best mode, and also to enable any person skilled in the art to practice the present invention, including making and using any device or system, and implementing any combined method. It should be noted that, for a person skilled in the art, without departing from the principles of the present invention, several improvements and modifications may be made to the present invention, and such improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be conceived by a person skilled in the art. If these other embodiments have structural elements that are not different from the literal wording of the claims, or if they include equivalent structural elements that are not substantially different from the literal wording of the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A multi-block dibenzofuran polyarylpiperidine polymer, characterized in that: The multi-block dibenzofuran polyarylpiperidine polymer includes a structural unit represented by formula (I): Wherein, x=0.1-0.3, y=0.9-0.7; The Ar is selected from one or more groups represented by formula (1) to formula (9): The R1 is selected from one or more groups represented by formula (10) to formula (14): The R2 is selected from one or more groups represented by formula (15) to formula (17):

2. A method for preparing the multi-block dibenzofuran polyarylpiperidine polymer according to claim 1, characterized in that: The following steps are involved: 1) mixing the Ar monomer, the hydrophilic group monomer and the organic solvent to obtain a solution, and then adding the cationic group monomer and the hydrophobic segment monomer containing the R1 group to obtain a mixed solution; 2) reacting the mixed solution obtained in the above step under the action of an acid catalyst, and then adding a precipitant to precipitate the mixed solution to obtain a multi-block polymer; 3) reacting the multi-block polymer obtained in the above step, the solvent and the quaternary ammonium agent in the dark, and then precipitating the resultant to obtain a multi-block dibenzofuran-based polyarylpiperidine polymer.

3. The preparation method according to claim 2, characterized in that The Ar monomer includes one or more of biphenyl, p-terphenyl, m-terphenyl, triphenylmethane, 4-benzylbiphenyl, binaphthyl, erene, 4,4′-trimethylenebis(1-methylpiperidine) and 1,3,5-triphenylbenzene; The hydrophilic group monomer includes dibenzofuran; The organic solvent includes one or more of dichloromethane, n-hexane, tetrahydrofuran and N,N-dimethylformamide; The molar ratio of the Ar monomer to the hydrophilic group monomer is 1:(1-100); The cationic group monomer includes N-methyl-4-piperidone; The hydrophobic segment monomer containing the R1 group includes one or more of 1,1,1-trifluoroacetone, 2,2,2-trifluoroacetophenone, benzoyltrifluoroacetone, 7-bromo-1,1,1-trifluoro-2-heptanone and ethyl 3,3,3-trifluoropyruvate; The molar ratio of the cationic group monomer to the hydrophobic segment monomer containing the R1 group is 1:(1-15).

4. The preparation method according to claim 2, characterized in that The ratio of the total molar number of the Ar monomer and the hydrophilic group monomer to the total molar number of the cationic group monomer and the hydrophobic segment monomer containing the R1 group is 1:(1-10); In the mixed solution, the mass concentration of the sum of all monomers is 5% to 50%; The acid catalyst includes solid acid and liquid acid; The solid acid includes Al2O3 / B2O3, BPO4, H4SiW 12 O 40 , one or more of β-type molecular sieve, ZSM-5 and Y-type molecular sieve; The acid catalyst also includes a solid superacid; The solid superacid includes S2O8 2- / CeO2-RF、Pt-SO4 2- / ZrO2-Al2O3、SO4 2- / ZrO2-NiO / Al2O3 and SO4 2- / Fe2O3 one or more; The liquid acid includes one or more of trifluoroacetic acid, carborane acid and trifluoromethanesulfonic acid.

5. The preparation method according to claim 2, characterized in that The mass ratio of the total mass of the Ar monomer and the hydrophilic group monomer to the solid acid is 100:(50-100); The mass ratio of the total mass of the Ar monomer and the hydrophilic group monomer to the solid superacid is 100:(20-60); The molar ratio of the total molar number of the Ar monomer and the hydrophilic group monomer to the liquid acid is 1:(5-13); The reaction temperature is -4 to 150°C; the reaction temperature when only organic liquid acid is used is -4 to 100°C; the reaction temperature when only solid acid is used is 60 to 150°C; the reaction temperature when solid acid and organic liquid acid are used in combination is 10 to 60°C; The reaction time is 4 to 72 hours; The precipitant includes one or more of methanol, ethanol, acetonitrile and n-hexane; The method further comprises the steps of solution washing and water washing after the precipitation.

6. The preparation method according to claim 2, characterized in that The quaternizing agent includes one or more of 1,5-dibromopentane, 1,4-dibromobutane and iodomethane; The solvent includes one or more of ethyl acetate, dimethyl sulfoxide, dichloromethane, chloroform and N,N-dimethylformamide; The temperature of the light-proof reaction is 20 to 120°C; The light-avoidance reaction time is 12 to 72 hours; The solvent used in the precipitation reaction solution in step 3) includes one or more of methanol, acetonitrile, diethyl ether and ethyl acetate; The multi-block dibenzofuran polyarylpiperidine polymer is specifically a multi-block dibenzofuran polyarylpiperidine polymer containing a hydrophobic segment.

7. Use of the multi-block dibenzofuran polyarylpiperidine polymer according to claim 1 or the multi-block dibenzofuran polyarylpiperidine polymer prepared by the preparation method according to any one of claims 2 to 6 in anion exchange membranes.

8. An anion exchange membrane, characterized in that The anion exchange membrane is a multi-block dibenzofuran polyarylpiperidine anion exchange membrane; The anion exchange membrane includes an alkalized multi-block dibenzofuran polyarylpiperidine polymer; The multi-block dibenzofuran polyarylpiperidine polymer is the multi-block dibenzofuran polyarylpiperidine polymer according to claim 1 or the multi-block dibenzofuran polyarylpiperidine 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 multi-block dibenzofuran polyarylpiperidine anion exchange membrane is prepared by the following steps: A multi-block dibenzofuran polyarylpiperidine 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 immersed in a potassium hydroxide solution and dried to obtain a multi-block dibenzofuran polyarylpiperidine anion exchange membrane in the hydroxide form; The concentration of the anion exchange resin homogeneous solution is 5wt% to 30wt%; The soaking time is 12 to 36 hours; The soaking temperature is 25-80°C.

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

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