Polynorbornene interpenetrating polymer network cross-linked anion exchange membrane as well as preparation method and application thereof

Abstract

The invention provides a polynorbornene interpenetrating polymer network cross-linked anion exchange membrane as well as a preparation method and application thereof. According to the invention, the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane is prepared from polynorbornene, allylphenol quaternary ammonium salt and polythiol under the irradiation condition of an ultraviolet lamp. The polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane has a smooth and transparent surface, has excellent conductivity, stability and mechanical properties, overcomes the problem of tradeoff between conductivity and stability of a common AEM, and can be applied to alkaline fuel cell equipment, alkaline electrolyzed water equipment, electrodialysis equipment, waste acid recovery equipment, carbon dioxide reduction equipment 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 and a preparation method and application thereof. Background Art

[0002] Anion exchange membrane (AEM) is widely used in many new energy conversion fields such as anion exchange membrane fuel cell (AEMFC), anion exchange membrane water electrolysis (AEMWE), electrodialysis, waste acid recovery, and carbon dioxide reduction. Compared with cation exchange membranes, the alkaline medium used in anion exchange membranes has fast cathode reaction kinetics, so non-precious metal catalysts can be used, which significantly reduces the system cost. However, taking AEMWE as an example, its current density and durability limit its practical application, especially its durability in working environments. AEM is a key component of AEMWE. It consists of three parts: a polymer backbone, cations covalently bonded to the backbone, and free anions. In existing technologies, the conductivity and alkaline stability of AEM are still challenging, especially the trade-off between the two. High conductivity requires high ion exchange capacity (IEC) to achieve, and too high IEC will lead to excessive swelling of AEM, thereby reducing the dimensional stability, mechanical stability, and alkaline stability of AEM. Traditional cross-linking strategies usually enhance the mechanical properties of AEM, but the ionic conductivity of AEM is reduced.

[0003] Polynorbornene has excellent thermal and chemical stability, but pure polynorbornene AEM still has the problem of brittle film and low mechanical strength. Taking the commercial polynorbornene AEM (Pention series products of Xergy Membranes, USA) as an example, it uses porous PTFE as a substrate to reinforce the polynorbornene polymer. However, incomplete filling of the porous substrate often leads to poor gas barrier properties of the film, which is not suitable for applications in fields 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 for a click reaction, and the cross-linking and solvent volatilization are carried out simultaneously, and the corresponding AEM can be obtained when the solvent is completely volatilized. 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 for 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 AEM, no additional quaternization reaction is required, which eliminates the problem of post-treatment of the membrane; the formation of an interpenetrating polymer network solves the trade-off between the conductivity and stability of 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, 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 with compound A-2 is carried out at 60-80° C. for 1-48 h.

[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 h.

[0023] According to an embodiment of the present invention, the method comprises: in the presence of sodium carbonate or potassium carbonate, compound A-1 and compound A-2 or compound B-2 are subjected to reflux reaction in acetonitrile 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, then removing dichloromethane by rotary evaporation, and finally precipitating with ether, washing, and obtaining the product.

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

[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 or a copolymer thereof represented by formula E:

[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 is independently 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 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 are independently 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 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, and the solvent 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 comprises: 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 crosslinking reaction and volatilization of the solvent under ultraviolet light irradiation conditions, and drying in a vacuum oven after the irradiation is completed.

[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: - 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 method for preparing the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane of the present invention includes but is not limited to: solution casting, spin coating, blade coating or casting.

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

[0062] The present invention also provides the use of the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane as described above 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 uses polynorbornene, allylphenol quaternary ammonium salt and polythiol to prepare a polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane under ultraviolet lamp irradiation conditions. The polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane has a smooth and transparent surface, excellent conductivity, stability and mechanical properties, overcomes the trade-off problem between the conductivity and stability of common AEM, and can be applied to alkaline fuel cells, alkaline water electrolysis, electrodialysis, waste acid recovery, carbon dioxide reduction and other equipment.

[0065] The preparation method of the present invention is a click reaction, which has a fast rate and a short reaction time. After the film is prepared directly using a diene monomer containing a cationic functional group, no additional quaternization reaction is required, thus eliminating the problem of post-treatment of the film, 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 film.

[0066] Definition and explanation of terms

[0067] Partial Substituents The ligation sites are indicated.

[0068] In this document, the term "halogen" refers to fluorine, chlorine, bromine and / or iodine. Correspondingly, the term "halo" refers to fluoro, chloro, bromo and / or iodo.

[0069] The term "C 1-12 "Alkyl" means straight chain and branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. 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 2-6 "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, in the case 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-hexenyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)-pent-1-enyl, (Z)-pent ...1-enyl, (Z)-pent-1-enyl, isopropenyl, 2-hexenyl, (E)-pent-2- -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 The invention can be substituted with vinyl or 1-isopropylvinyl, or a mixture of vinyl and 1-isopropylvinyl. The invention can be substituted with vinyl or 1-isopropylvinyl, or a mixture of vinyl and 1-isopropylvinyl.

[0071] The term "C 2-12The term "alkynyl" is understood as meaning a linear or branched monovalent hydrocarbon radical which contains one or more triple bonds and has 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 which contains one or more triple bonds and has 2, 3, 4, 5, 6 carbon atoms, in particular 2 or 3 carbon atoms ("C2-C3-alkynyl"). The alkynyl radical is, 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, 2-methyl -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-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-ynyl, 2 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 term “halo” and “C 1-12 "Alkyl" has the above definition. The substitution is on the same carbon atom or on different carbon atoms. 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 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 scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions 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 included in the scope 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 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, ultrasonicated, and filtered to obtain a yellow solid, which was vacuum dried. The M of the obtained polymer was 1.34W. 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, ultrasonicated, and filtered to obtain a light yellow solid, which was vacuum dried. The M of the obtained polymer was 1.347 W / m. n It is 43.5kDa.

[0089] Example 3

[0090]

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

[0092] First, under the condition of excess potassium carbonate (1g), allyl bromide (10mmol) and o-allyl phenol (50mmol) were added to acetonitrile, refluxed at 70°C, and the reaction time was 24h. After the reaction was completed, it was cooled to room temperature, the inorganic salts were filtered out, and the filtrate was dried. Then the obtained filtrate was reacted in a nitrogen environment at 200°C for 12h. After the reaction was completed, it was cooled to room temperature, the mixture solution was dissolved in petroleum ether and extracted with sodium hydroxide aqueous solution, the aqueous phase was collected and neutralized with acid to neutrality, and then extracted with methyl tert-butyl ether, the organic phase was collected and purified by column with 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 monobromide quaternary ammonium salt (9mmol) were added to acetonitrile, refluxed at 70°C, and the reaction time was 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 film 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 crosslinking reaction and solvent volatilization simultaneously under ultraviolet light irradiation conditions. The mixture was irradiated for 30 min and 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 film prepared by cross-linking an addition copolymer of HNB and DCPD with all-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 subjected to crosslinking reaction and solvent volatilization simultaneously under ultraviolet light irradiation conditions. The mixture was irradiated for 30 min and then dried again in a vacuum oven.

[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, and 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 subjected to crosslinking reaction and solvent volatilization simultaneously under ultraviolet light irradiation conditions. The mixture was irradiated for 30 min and then dried again in a vacuum oven.

[0109] Example 8

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

[0111] The negative ion prepared in Example 5-7 is 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 24 h to prepare negative ions 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 Example 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 of OH is 7.8mS / cm. - The conductivity is 72.5mS / cm, and OH - The 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 Figure 5 shown.

[0117] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope 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. The quaternary ammonium salt according to claim 1, characterized in that X and Y are Br; s and p are the same or different and are independently 1, 2, 3, 4, 5 or 6; Preferably, the quaternary ammonium salt represented by formula A or B is selected from the following structures:

3. The method for preparing the quaternary ammonium salt of formula A or B according to claim 1 or 2, characterized in that: 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 in claim 1 or 2; Preferably, the process is carried out in the presence of a carbonate salt.

4. 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 claim 1 or 2, and a polythiol represented by formula Q; The polynorbornene is a homopolymer of norbornene or a copolymer thereof represented by formula E: 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 is independently 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, -(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 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.

5. The polynorbornene-based interpenetrating polymer according to claim 4, characterized in that: In formula E, R is C 2-6 Alkenyl or C 2-6 Alkyl; q are the same or different and are independently 1, 2 or 3.

6. The polynorbornene-based interpenetrating polymer according to claim 4 or 5, characterized in that: The polynorbornene is a homopolymer of the following monomers or a copolymer of any two or more monomers: Preferably, the polynorbornene is wherein m is the same or different and is independently 50-1000; n is 50-1000; Preferably, formula Q is selected from the structures shown below: Preferably, the polynorbornene-based interpenetrating polymer is an interpenetrating polymer of the following monomers: or, or, 7. The method for preparing the polynorbornene-based interpenetrating polymer according to any one of claims 4 to 6, characterized in that: include: Conducting a click reaction of the polynorbornene according to any one of claims 4 to 6, the quaternary ammonium salt represented by formula A or B, and the polythiol compound represented by formula Q; Preferably, the click reaction is carried out in the presence of a photoinitiator; the photoinitiator is selected from phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; Preferably, 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; Preferably, 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).

8. 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 4 to 6 is replaced by OH - or HCO3 - structure.

9. The method for preparing the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane according to claim 8, characterized in that: include: The polynorbornene-based interpenetrating polymer according to any one of claims 4 to 6 is added to a hydroxyl group - or HCO3 - Soak in a solution of alkali metal salt.

10. Application of the polynorbornene-based interpenetrating polymer network cross-linked anion exchange membrane according to claim 8 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.

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