A polynorbornene-based interpenetrating polymer network crosslinked anion exchange membrane, and a preparation method and application thereof

Abstract

The application provides a polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane and a preparation method and application thereof. The polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane is prepared by using polynorbornene, allyl phenol quaternary ammonium salt and polysulfane under the irradiation of an ultraviolet lamp. The polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane is smooth and transparent on the surface, has excellent conductivity, stability and mechanical properties, and overcomes the trade-off problem between the conductivity and stability of common AEMs, and can be applied to alkaline fuel cells, alkaline water electrolysis, electrodialysis, waste acid recovery, carbon dioxide reduction and the like.

Description

Technical Field

[0001] The present invention belongs to the technical field of energy storage and conversion, and specifically relates to a novel polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane, a preparation method thereof, and an application thereof. Background Art

[0002] Anion exchange membranes (AEMs) are widely used in numerous new energy conversion applications, including anion exchange membrane fuel cells (AEMFCs), anion exchange membrane water electrolysis (AEMWEs), electrodialysis, waste acid recovery, and carbon dioxide reduction. Compared to cation exchange membranes, the alkaline media used in AEMs offer rapid cathode reaction kinetics, enabling the use of non-precious metal catalysts, significantly reducing system costs. However, in the case of AEMWEs, their current density and durability limit their practical application, particularly in operating environments. The AEM, a key component of AEMWEs, consists of a polymer backbone, covalently bonded cations, and free anions. Existing technologies for AEMs remain challenging, particularly in terms of their electrical conductivity and alkaline stability, particularly the trade-off between these two. High conductivity requires a high ion exchange capacity (IEC), but excessively high IEC leads to excessive swelling of the AEM, reducing its dimensional, mechanical, and alkaline stability. Traditional cross-linking strategies typically enhance the mechanical properties of the AEMs, but at the expense of reduced ionic conductivity.

[0003] While polynorbornene possesses excellent thermal and chemical stability, pure polynorbornene AEMs still suffer from film brittleness and low mechanical strength. For example, commercial polynorbornene AEMs (such as the Pention series from Xergy Membranes, Inc.) utilize a porous PTFE substrate to reinforce the polynorbornene polymer. However, incomplete filling of the porous substrate often results in poor gas barrier properties, making the film unsuitable for applications such as water electrolysis. Summary of the Invention

[0004] In order to solve the above technical problems, the present invention provides a polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane (AEM) and its preparation method and application. The present invention selects a substituted norbornene polymer containing a terminal double bond in the side chain and a diene containing a cationic functional group and a polythiol to carry out a click reaction. The crosslinking and solvent volatilization are carried out simultaneously, and the corresponding AEM can be obtained after the solvent is completely evaporated. The preparation method of the present invention has the following advantages: the addition polynorbornene has excellent thermal stability and chemical stability; the double bond at the end of the addition polynorbornene provides the possibility of subsequent functionalization, such as thiol-ene click reaction, and the click reaction rate is fast and the time is short; after the diene monomer containing a cationic functional group is prepared to obtain the AEM, no additional quaternization reaction is required, which eliminates the problem of post-processing of the membrane; the formation of the interpenetrating polymer network solves the trade-off between the conductivity and stability of the AEM.

[0005] The present invention first provides a quaternary ammonium salt shown in the following formula A or B:

[0006]

[0007] wherein s and p are the same or different and are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12;

[0008] X and Y are the same or different and are independently halogen.

[0009] According to an embodiment of the present invention, X and Y are Br; s and p are the same or different and are independently 1, 2, 3, 4, 5 or 6.

[0010] According to an embodiment of the present invention, the quaternary ammonium salt shown in formula A or B is selected from the following structures:

[0011]

[0012] The present invention also provides a method for preparing the quaternary ammonium salt represented by the above formula A or B, comprising the following steps:

[0013] Compound A-1 reacts with compound A-2 to obtain a quaternary ammonium salt represented by formula A;

[0014]

[0015] Alternatively, compound A-1 reacts with compound B-2 to obtain a quaternary ammonium salt represented by formula B;

[0016]

[0017] Wherein, s, p, X, and Y have the same definitions as above.

[0018] According to an embodiment of the present invention, the method is carried out in the presence of a carbonate salt, for example, in the presence of sodium carbonate or potassium carbonate.

[0019] According to an embodiment of the present invention, the molar ratio of compound A-1, compound A-2 and carbonate is 1:0.5-1.0:1.0-10.0, for example, 1:0.6-0.9:1.4-8.0.

[0020] According to an embodiment of the present invention, the molar ratio of compound A-1, compound B-2 and carbonate is 1:0.5-1.0:1.0-10.0, for example, 1:0.6-0.9:1.4-8.0.

[0021] According to an embodiment of the present invention, the reaction of compound A-1 and compound A-2 is carried out at 60-80° C. for 1-48 hours.

[0022] According to an embodiment of the present invention, the reaction of compound A-1 and compound B-2 is carried out at 60-80° C. for 1-48 hours.

[0023] According to an embodiment of the present invention, the method comprises: in the presence of sodium carbonate or potassium carbonate, reacting compound A-1 with compound A-2 or compound B-2 in acetonitrile under reflux for 1-24 hours.

[0024] According to an embodiment of the present invention, the method further includes the steps of cooling the reaction solution to room temperature after the reaction is completed, removing the solvent acetonitrile by rotary evaporation, then dissolving it in dichloromethane, filtering out inorganic salts, and then removing the dichloromethane by rotary evaporation, and finally precipitating it with ether and washing it to obtain the product.

[0025] The present invention also provides use of the quaternary ammonium salt represented by formula A or B in preparing a polynorbornene-based interpenetrating polymer or a polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane.

[0026] The present invention also provides a polynorbornene-based interpenetrating polymer, which is an interpenetrating polymer obtained by a click reaction of polynorbornene, a quaternary ammonium salt represented by formula A and / or B as described above, and a polythiol represented by formula Q;

[0027] The polynorbornene is a homopolymer of norbornene represented by formula E or a copolymer thereof:

[0028]

[0029] In formula E, R is C 2-12 Alkenyl, C 2-12 Alkynyl, C 2-12 Alkyl or halogenated C 1-12 Alkyl; q is the same or different and independently of each other is 1, 2, 3, 4, 5 or 6;

[0030] Selected from

[0031]

[0032] In formula Q, R1 is O hetero C 2-12 Straight chain alkyl, C 1-12 Alkyl, -C 1-6 Alkyl-phenyl-C 1-6 Alkyl-, -phenyl-S-phenyl-, -phenyl-O-phenyl-, phenyl, -(phenyl)s-, 3, 4, 5 or 6 C 1-6 Alkyl-substituted phenyl, or the following structure

[0033]

[0034] a1, a2, a3, b1, b2, b3, c1, c2, c3, c4, d1, d2, d3, d4 are the same or different and are independently selected from 0, 1, 2, 3, 4, 5 or 6; s is 1, 2, 3, 4, 5 or 6; j is 2, 3 or 4.

[0035] According to an embodiment of the present invention, in formula E, R is C 2-6 Alkenyl or C 2-6 Alkyl; q are the same or different and independently of each other are 1, 2 or 3.

[0036] According to an embodiment of the present invention, in formula E, R is not substituted on the carbon-carbon double bond.

[0037] According to an embodiment of the present invention, the polynorbornene is a homopolymer of the following monomers or a copolymer of any two or more monomers:

[0038]

[0039] According to an embodiment of the present invention, the polynorbornene is wherein m is the same or different and is independently 50-1000; n is 50-1000, for example, m is the same or different and is independently 100-800; n is 100-800.

[0040] According to an embodiment of the present invention, formula Q is selected from the structures shown below:

[0041]

[0042] In one embodiment, the polynorbornene-based interpenetrating polymer is an interpenetrating polymer of the following monomers:

[0043] or,

[0044] or,

[0045]

[0046] The present invention provides a method for preparing the polynorbornene-based interpenetrating polymer as described above, comprising:

[0047] The polynorbornene, the quaternary ammonium salt represented by formula A or B, and the polythiol compound represented by formula Q are subjected to a click reaction.

[0048] According to an embodiment of the present invention, the click reaction is carried out in the presence of a photoinitiator; the photoinitiator is selected from phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

[0049] According to an embodiment of the present invention, the molar ratio of the photoinitiator to the allylphenol quaternary ammonium salt is (0.01-0.1):1, for example (0.02-0.08):1.

[0050] According to an embodiment of the present invention, the ratio of the molar amount of double bonds in the polynorbornene, the molar amount of thiol groups in the polythiol and the molar number of allylphenol quaternary ammonium salt is 1:(0.1-2):(0.1-1), for example, 1:(0.3-1.5):(0.2-0.7).

[0051] According to an embodiment of the present invention, the click reaction is irradiated under ultraviolet light for 2-100 minutes, such as 10-60 minutes, such as 30 minutes.

[0052] According to an embodiment of the present invention, the click reaction is carried out in a solvent, which includes but is not limited to chloroform, dichloromethane and tetrahydrofuran.

[0053] According to an embodiment of the present invention, the volume ratio of the total mass of polynorbornene, polythiol and photoinitiator to the solvent in the click reaction is 20 g / mL to 60 g / mL, preferably 30 g / mL to 40 g / mL.

[0054] According to an embodiment of the present invention, the method includes: dissolving polynorbornene, a quaternary ammonium salt represented by formula A or B, a polythiol represented by formula Q, and a photoinitiator in a solvent, stirring at room temperature until completely dissolved, then pouring the mixture solution into a mold, and simultaneously performing a cross-linking reaction and volatilization of the solvent under ultraviolet light irradiation conditions. After the irradiation is completed, drying in a vacuum oven.

[0055] The present invention also provides a polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane, which is a polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane, wherein the quaternary ammonium anion of the polynorbornene-based interpenetrating polymer is replaced by OH - or HCO3 -structure.

[0056] The present invention also provides a method for preparing the above polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane, comprising: placing the above polynorbornene-based interpenetrating polymer in a hydroxyl-containing - or HCO3 - Soak in a solution of alkali metal salt.

[0057] According to an embodiment of the present invention, the OH-containing - or HCO3 - The alkali metal salt is sodium hydroxide, potassium hydroxide or sodium bicarbonate.

[0058] According to an embodiment of the present invention, the OH-containing - or HCO3 - The concentration of the alkali metal salt solution is 0.5M-5M, for example 1M-3M.

[0059] According to an embodiment of the present invention, the soaking time is 6-24 hours.

[0060] The methods for preparing the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane of the present invention include but are not limited to: solution casting, spin coating, blade coating or casting.

[0061] According to an embodiment of the present invention, the temperature of the casting film is room temperature.

[0062] The present invention also provides the application of the above-mentioned polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane in the fields of anion exchange membrane fuel cells (AEMFC), anion exchange membrane water electrolysis (AEMWE), electrodialysis, waste acid recovery, and carbon dioxide reduction new energy conversion.

[0063] Beneficial effects of the present invention

[0064] The present invention utilizes polynorbornene, allylphenol quaternary ammonium salt, and polythiol under ultraviolet light irradiation to prepare a polynorbornene-based interpenetrating polymer network crosslinked anion exchange membrane. The polynorbornene-based interpenetrating polymer network crosslinked anion exchange membrane has a smooth and transparent surface and excellent conductivity, stability, and mechanical properties. This overcomes the trade-off between conductivity and stability commonly encountered in AEMs and can be used in alkaline fuel cells, alkaline water electrolysis, electrodialysis, waste acid recovery, and carbon dioxide reduction equipment.

[0065] The preparation method of the present invention is a click reaction with a fast reaction rate and a short reaction time. After the membrane is directly prepared using a diene monomer containing a cationic functional group, no additional quaternization reaction is required, thus eliminating the problem of post-processing of the membrane, making the preparation method simpler and reducing the reaction cost. In addition, the formation of an interpenetrating polymer network solves the trade-off problem between the conductivity and mechanical properties of the membrane.

[0066] Definitions and Explanations of Terms

[0067] Some substituents Indicates the connection site.

[0068] As used herein, the term "halogen" refers to fluorine, chlorine, bromine and / or iodine. Accordingly, the term "halo" refers to fluoro, chloro, bromo and / or iodo.

[0069] The term "C 1-12 "Alkyl" means straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, "C 1-6 The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0070] The term "C 2-12 "Alkenyl" is understood to mean a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2 to 12 carbon atoms, optionally "C 2-6 Alkenyl". "C 2-6 "Alkenyl" is understood to mean optionally a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2, 3, 4, 5, 6 carbon atoms, in particular 2 or 3 carbon atoms ("C 2-3"alkenyl"), it being understood that where the alkenyl contains more than one double bond, the double bonds may be separated from one another or conjugated. The alkenyl is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl. -enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-enyl -methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl 1-ethylprop-1-enyl, 1-propylvinyl or 1-isopropylvinyl.

[0071] The term "C 2-12The term "alkynyl" is understood as meaning a linear or branched monovalent hydrocarbon radical containing one or more triple bonds and having 2 to 12 carbon atoms, optionally a "C2-C6-alkynyl" radical. The term "C2-C6-alkynyl" is understood as optionally meaning a linear or branched monovalent hydrocarbon radical containing one or more triple bonds and having 2, 3, 4, 5, 6 carbon atoms, in particular 2 or 3 carbon atoms ("C2-C3-alkynyl"). Such alkynyl radicals are, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, -ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, 1-methylpent-2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1 ...2-ynyl, 4-methylpent-1-ynyl, 3-methylpent-1-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4-ynyl, 2-methylpent-3-ynyl, 1-methylpent-3-ynyl, 4-methylpent-2-ynyl, In some embodiments, the alkynyl group is ethynyl, prop-1-ynyl or prop-2-ynyl.

[0072] The term "halogenated C 1-12 "Alkyl" means C 1-12 In the case where the H on the alkyl group is optionally substituted by 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 halogens, the “halogen” and “C 1-12 "Alkyl" has the above definition. The substitution is substituted on the same carbon atom or on different carbon atoms. Optionally "halogenated C 1-6 Alkyl". The "halogenated C 1-12 "Alkyl" is, for example, trifluoromethyl.

[0073] The term "O hetero 2-12 "Linear alkyl" means C 2-12 The C on the straight chain alkyl group is optionally substituted by 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 O. Preferably, "1, 2, 3 or 4 O hetero C 2-12 Straight chain alkyl". BRIEF DESCRIPTION OF THE DRAWINGS

[0074] Figure 1 It is 1.6-diallylphenol quaternary ammonium salt 1 H NMR spectrum.

[0075] Figure 2 This is the infrared spectrum of the AEM obtained in Example 5.

[0076] Figure 3 The anion obtained after the AEM prepared in Example 5 is soaked in NaHCO3 is HCO3 - Image of AEM.

[0077] Figure 4 The anion obtained after the AEM prepared in Example 5 is soaked in NaHCO3 is HCO3 - Mechanical properties test results of AEM.

[0078] Figure 5 The anion obtained after the AEM prepared in Example 5 is soaked in NaHCO3 is HCO3 - TGA curve of AEM. DETAILED DESCRIPTION

[0079] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0080] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0081] Example 1

[0082]

[0083] This embodiment provides an addition homopolymerization of VNB, and the preparation method is as follows:

[0084] First, 0.01mmol Pd2(dba)3, 0.04mmol PCy3 and 0.04mmol lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex (LiFABA) were dissolved in 4mL toluene and stirred at room temperature for 1h to prepare a catalyst solution. 3mmol VNB was dissolved in 4mL toluene to prepare a monomer solution. The catalyst solution was then filtered with a 0.45μm filter membrane and added to the monomer solution, and the mixture was stirred at room temperature. After the reaction was completed, the mixture was precipitated in methanol, sonicated, and filtered to obtain a yellow solid, which was vacuum dried. The M of the obtained polymer was 0.01mmol. n It is 37.5kDa.

[0085] Example 2

[0086]

[0087] This embodiment provides an addition copolymerization of HNB and DCPD, and the preparation method is as follows:

[0088] First, 0.01mmol Pd2(dba)3, 0.04mmol PCy3 and 0.04mmol lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex (LiFABA) were dissolved in 4mL toluene and stirred at room temperature for 1h to prepare a catalyst solution. 1.5mmol HNB and 1.5mmol DCPD were dissolved in 4mL toluene to prepare a monomer solution. The catalyst solution was then filtered with a 0.45μm filter membrane and added to the monomer solution, and the mixture was stirred at room temperature. After the reaction was completed, the mixture was precipitated in methanol, sonicated, and filtered to obtain a light yellow solid, which was vacuum dried. The M of the obtained polymer was 0.01mmol. n It is 43.5kDa.

[0089] Example 3

[0090]

[0091] This example provides the synthesis of 2,6-diallylphenol, and the preparation method is as follows:

[0092] First, allyl bromide (10 mmol) and o-allylphenol (50 mmol) were added to acetonitrile in the presence of an excess of potassium carbonate (1 g). The mixture was refluxed at 70°C for 24 hours. After the reaction was complete, the mixture was cooled to room temperature, the inorganic salts were filtered off, and the filtrate was dried. The resulting filtrate was then reacted in a nitrogen atmosphere at 200°C for 12 hours. After the reaction was complete, the mixture was cooled to room temperature, dissolved in petroleum ether, and extracted with aqueous sodium hydroxide. The aqueous phase was collected, neutralized with acid to neutrality, and then extracted with methyl tert-butyl ether. The organic phase was collected and purified by column chromatography using petroleum ether and ethyl acetate to obtain 2,6-diallylphenol.

[0093] Example 4

[0094]

[0095] This embodiment provides the synthesis of allylphenol quaternary ammonium salt, and the preparation method is as follows:

[0096] Under the condition of excess potassium carbonate (2g, 14mmol), 2,6-diallylphenol (10mmol) and monobromo quaternary ammonium salt (9mmol) were added to acetonitrile and refluxed at 70°C for 24h. After the reaction was completed, it was cooled to room temperature, the solvent acetonitrile was removed by rotary evaporation, and then dissolved in dichloromethane, the inorganic salt was filtered out, and the dichloromethane was removed by rotary evaporation. Finally, it was precipitated with ether and washed to obtain allylphenol quaternary ammonium salt. 1 HNMR spectrum Figure 1 shown.

[0097] Example 5

[0098]

[0099] This embodiment provides a cross-linked membrane prepared by cross-linking a VNB addition homopolymer with a full carbon dithiol, and the preparation method is as follows:

[0100] The addition-type polynorbornene homopolymer (0.6 mmol), 1,6-hexanedithiol (0.5 mmol), allylphenol quaternary ammonium salt (0.4 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.01 mmol) prepared in Example 1 were dissolved in 5 mL of chloroform and stirred at room temperature until completely dissolved. The mixture solution was then poured into a mold and subjected to simultaneous cross-linking reaction and solvent volatilization under ultraviolet light irradiation for 30 minutes. The mixture was then dried again in a vacuum oven. The infrared spectrum thereof was as follows: Figure 2 shown.

[0101] Example 6

[0102]

[0103] This embodiment provides a cross-linked membrane prepared by cross-linking an HNB and DCPD addition copolymer with a full carbon dithiol, and the preparation method is as follows:

[0104] The addition-type polynorbornene copolymer prepared in Example 2 (0.5 mmol), 1,6-hexanedithiol (0.5 mmol), allylphenol quaternary ammonium salt (0.4 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.01 mmol) were dissolved in 6 mL of chloroform and stirred at room temperature until completely dissolved. The mixture solution was then poured into a mold and irradiated with ultraviolet light for 30 min to allow the cross-linking reaction and solvent volatilization to proceed simultaneously.

[0105] Example 7

[0106]

[0107] This embodiment provides a cross-linked film prepared by cross-linking a VNB addition homopolymer with an oxygen-containing dithiol. The preparation method is as follows:

[0108] The polynorbornene homopolymer (0.75 mmol), 3,6-dioxa-1,8-octanedithiol (0.5 mmol), allylphenol quaternary ammonium salt (0.4 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.01 mmol) prepared in Example 1 were dissolved in 6 mL of chloroform and stirred at room temperature until completely dissolved. The mixture solution was then poured into a mold and irradiated with ultraviolet light for 30 min to allow the cross-linking reaction and solvent volatilization to proceed simultaneously.

[0109] Example 8

[0110] This example provides ion exchange of the cross-linked membranes prepared in Examples 5-7. The preparation method is as follows:

[0111] The negative ions prepared in Example 5-7 are Br - The AEM was immersed in 1M NaHCO3 aqueous solution for 24h to prepare negative ions as HCO3 - AEM. The negative ion is Br - The AEM was immersed in 1M NaOH aqueous solution for 24h to prepare the negative ion OH - AEM. Figure 3 The anion obtained after AEM is soaked in NaHCO3 is HCO3 - AEM.

[0112] Example 9

[0113] This example provides the conductivity of the AEM prepared in Examples 5-8. The specific method is as follows: The conductivity test uses electrochemical impedance spectroscopy to measure the resistance of the membrane, and then calculates the conductivity using formula (1).

[0114]

[0115] After the membrane prepared in Example 5 was soaked by the method of Example 8, the prepared AEM was HCO3 at room temperature. - The conductivity is 7.8mS / cm. At 40℃, OH - The conductivity is 72.5mS / cm, and at 90℃, OH - The electrical conductivity is 120.4mS / cm,

[0116] After the membrane prepared in Example 5 was soaked by the method of Example 8, the mechanical properties of the prepared AEM were as follows: Figure 4 As shown, the TGA curve is as Figure 5 shown.

[0117] The above describes the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. Quaternary ammonium salt represented by formula A or B: in, s and p are the same or different and are independently 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12; X and Y are the same or different and are independently halogen.

2. quaternary ammonium salt according to claim 1, is characterized in that, X and Y are Br; s and p are the same or different and independently represent 1, 2, 3, 4, 5 or 6.

3. The quaternary ammonium salt according to claim 1 or 2, wherein The quaternary ammonium salt shown in formula A is selected from the following structures:

4. The quaternary ammonium salt according to claim 1 or 2, wherein The quaternary ammonium salt shown in B is selected from the following structures:

5. The method for preparing the quaternary ammonium salt of formula A or B according to any one of claims 1 to 4, wherein The steps include: Compound A-1 reacts with compound A-2 to obtain a quaternary ammonium salt represented by formula A; Alternatively, compound A-1 reacts with compound B-2 to obtain a quaternary ammonium salt represented by formula B; Wherein, s, p, X, and Y have the definitions as described in any one of claims 1 to 4; The reaction is carried out in the presence of a carbonate salt.

6. A polynorbornene-based interpenetrating polymer, which is an interpenetrating polymer obtained by a click reaction of polynorbornene, a quaternary ammonium salt represented by formula A and / or B according to any one of claims 1 to 4, and a polythiol represented by formula Q; The polynorbornene is Or a homopolymer of norbornene represented by formula E or a copolymer thereof: In formula E, R is C 2-12 Alkenyl, C 2-12 Alkynyl, C 2-12 Alkyl or halogenated C 1-12 Alkyl; q is the same or different and independently of each other is 1, 2, 3, 4, 5 or 6; Selected from In formula Q, R1 is O hetero C 2-12 Straight chain alkyl, C 1-12 Alkyl, -C 1-6 Alkyl-phenyl-C 1-6 Alkyl-, -phenyl-S-phenyl-, -phenyl-O-phenyl-, -(phenyl)s-, 3, 4, 5 or 6 C 1-6 Alkyl-substituted phenyl, or the following structure: a1, a2, a3, b1, b2, b3, c1, c2, c3, c4, d1, d2, d3, d4 are the same or different and are independently selected from 0, 1, 2, 3, 4, 5 or 6; s is 1, 2, 3, 4, 5 or 6; j is 2, 3 or 4.

7. The polynorbornene-based interpenetrating polymer according to claim 6, characterized in that: In formula E, R is C 2-6 Alkenyl or C 2-6 Alkyl; q are the same or different and independently of each other are 1, 2 or 3.

8. The polynorbornene-based interpenetrating polymer according to claim 6 or 7, characterized in that: The polynorbornene is a homopolymer of the following monomers or a copolymer of any two or more monomers:

9. The polynorbornene-based interpenetrating polymer according to claim 6 or 7, characterized in that: The polynorbornene is wherein m is the same or different and is independently 50-1000; and n is 50-1000.

10. The polynorbornene-based interpenetrating polymer according to claim 6 or 7, characterized in that: Formula Q is selected from the following structures:

11. The polynorbornene-based interpenetrating polymer according to claim 6 or 7, characterized in that: The polynorbornene-based interpenetrating polymer is an interpenetrating polymer of the following monomers: or, or, wherein m is the same or different and is independently 100-800; and n is 100-800.

12. The method for preparing the polynorbornene-based interpenetrating polymer according to any one of claims 6 to 11, characterized in that: include: The polynorbornene according to any one of claims 6 to 11, the quaternary ammonium salt represented by formula A or B, and the polythiol compound represented by formula Q are subjected to a click reaction.

13. The preparation method according to claim 12, characterized in that The click reaction is carried out in the presence of a photoinitiator; the photoinitiator is selected from phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide.

14. The preparation method according to claim 12, characterized in that The molar ratio of the photoinitiator to the quaternary ammonium salt represented by formula A or B is (0.01-0.1):

1.

15. The preparation method according to claim 12, characterized in that The ratio of the molar amount of double bonds in the polynorbornene, the molar amount of thiol groups in the polythiol compound represented by formula Q, and the molar number of the quaternary ammonium salt represented by formula A or B is 1:(0.1-2):(0.1-1).

16. A polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane, wherein the quaternary ammonium anion of the polynorbornene-based interpenetrating polymer according to any one of claims 6 to 11 is replaced by OH - or HCO3 - structure.

17. The method for preparing the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane according to claim 16, characterized in that: include: The polynorbornene-based interpenetrating polymer according to any one of claims 6 to 11 is added to a substrate containing OH - or HCO3 - Soak in a solution of alkali metal salt.

18. Application of the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane according to claim 16 in the fields of anion exchange membrane fuel cells, anion exchange membrane water electrolysis, electrodialysis, waste acid recovery, and carbon dioxide reduction new energy conversion.

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