Ionic polynorbornene crosslinked anion exchange membrane and preparation method therefor and use thereof

Abstract

The present invention provides an ionic polynorbornene crosslinked anion exchange membrane and a preparation method therefor and a use thereof. The membrane prepared in the present invention has a smooth and transparent surface, has excellent conductivity, stability and mechanical properties, and can be applied to the fields of fuel cells, electrolyzed water, electrodialysis, acid recovery, etc. The preparation method of the present invention is simple to operate, and fewer polymerization catalysts can be used when combined with a chain transfer agent, thereby reducing costs; and scale-up production and roll-to-roll continuous preparation can be achieved, providing a guarantee for industrial production and application of membranes.

Description

Ionic polynorbornene cross-linked anion exchange membrane and its preparation method and application

[0001] This application claims priority to a prior patent application filed by the applicant with the State Intellectual Property Office of China on March 14, 2024, with patent application number 202410293880X, entitled "Ionic Polynorbornene Cross-linked Anion Exchange Membrane, Preparation Method, and Application Thereof." The entire text of the prior patent application is incorporated herein by reference. Technical Field

[0002] The present invention belongs to the technical field of energy storage and conversion, and in particular relates to an ionic polynorbornene cross-linked anion exchange membrane and a preparation method and application thereof. Background Art

[0003] Compared to devices operating under acidic conditions (such as proton exchange membrane fuel cells [PEMFCs]), alkaline water electrolysis (AEMWEs) and alkaline fuel cells (AEMFCs) offer improved catalyst stability and rapid cathode reaction kinetics under alkaline conditions. The use of non-platinum group metal electrocatalysts can significantly reduce device costs. Anion exchange membranes (AEMs) are key components of electrochemical devices such as AEMWEs and AEMFCs. AEMs consist of a polymer backbone, cations covalently attached to the backbone, and free anions. High-performance AEMs are typically evaluated based on the following criteria: high hydroxide ion conductivity, high mechanical strength, and excellent polymer stability in alkaline media. Currently, synthesizing AEMs with high conductivity and long-term alkaline stability remains a challenge. To achieve a balance between ionic conductivity and stability, chemical crosslinking is an effective strategy for preparing ion exchange membranes. Because the catalyst of ring-opening metathesis polymerization (ROMP) has the characteristics of high activity and wide functional group tolerance, mild polymerization conditions and narrow molecular weight distribution of polymerization products, strong controllability and functional group compatibility, the synthesis of cross-linked AEM through ROMP has become a research hotspot.

[0004] However, these cross-linked AEMs require both covalently linked cationic functional groups and stable chemical crosslinks. There are two main approaches to preparing cross-linked AEMs. One method involves first forming the cross-linked structure and then introducing the cationic functional groups (ACS Appl. Energy Mater. 2019, 2, 2458–2468). To achieve sufficient membrane ionization, this preparation strategy requires the AEMs to be immersed in a solution for a long time (for example, in a trimethylamine aqueous solution for at least 48 hours). This strategy, however, consumes a large amount of solvent and time, making it unsuitable for continuous preparation. Another approach involves first synthesizing the ionic monomers and then polymerizing them. This method can significantly reduce time and solvent costs. This approach has also been reported (J. Am. Chem. Soc. 2009, 131, 12888–12889; Chemical Engineering and Engineering Journal, 2015, 66, 257–262; Chemical Engineering and Engineering Journal, 2015, 66, 338–342). However, the unsaturated bonds in the backbone can lead to dimensional instability in the polymer. Therefore, researchers have resorted to crosslinking the raw material, dicyclopentadiene (DCPD), to maintain stability. This preparation method requires the use of large amounts of Grubbs' catalyst (1,000-10,000 ppm), which increases costs and prevents large-scale, continuous production. Therefore, further research is needed to develop a method that directly polymerizes ionic monomers, which is more cost-effective and can be scaled up and used in a roll-to-roll continuous film production process. Summary of the Invention

[0005] The present invention proposes a method for directly polymerizing norbornene ionic monomers, followed by crosslinking to improve the mechanical stability of the polymer. The present invention first performs ROMP on the ionic norbornene monomers. However, because the polymer backbone obtained by ROMP contains unsaturated double bonds, this can lead to increased water absorption and reduced mechanical strength of the membrane. Therefore, preparing AEMs by crosslinking the double bonds in polynorbornene with polythiols can resolve the trade-off between conductivity and stability. By copolymerizing, the polynorbornene structure contains more active olefin functional groups that can be used for crosslinking. Therefore, in the multi-component copolymer designed in the present invention, monomer 1 is used to provide ionic functional groups, monomer 2 is used to balance the hydrophilicity and hydrophobicity of the polymer and provide sufficient mechanical support for the polymer, and monomer 3 is used to provide more active double bonds for chemical crosslinking.

[0006] The technical solutions of the present invention are as follows:

[0007] An ionic polynorbornene, wherein the ionic polynorbornene is obtained by copolymerizing monomer 1, monomer 2 and monomer 3.

[0008] Wherein, monomer 1 has the structure shown in the following formula (1);

[0009] Monomer 2 is selected from one or both of the structures shown in the following formula (2) and formula (3):

[0010] Monomer 3 is selected from one, two or more of the structures shown in formula (4), formula (5), formula (6) or formula (7):

[0011] In formula (1), a is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; X is halogen;

[0012] R1 is selected from H, C 1-10 Alkyl, C 6-14 Aryl, C 2-10 One of the alkenyl groups; R a 、R b 、R c The same or different, independently selected from C 1-10 alkyl;

[0013] In formula (2), R2 and R3 are the same or different and are independently selected from H, C 1-10 Alkyl, C 6-14 One of the aromatic groups;

[0014] In formula (3), p is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, q is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;

[0015] In formula (4), b is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0016] According to the present invention, X is Cl, Br or I.

[0017] According to the present invention, a is selected from 1-8, more preferably 4-6.

[0018] According to the present invention, R1 is selected from H, C 1-6 Alkyl, C 6-14 Aryl, C 2-6 One of the alkenyl groups, preferably H; R a 、R b 、R c The same or different, independently selected from C 1-6 Alkyl groups are, for example, all methyl groups.

[0019] According to the present invention, R2 is selected from H, C 1-6 Alkyl, C 6-14 One of the aryl groups, preferably H.

[0020] According to the present invention, R3 is selected from H, C1-6 Alkyl, C 6-14 One of the aryl groups, preferably H.

[0021] According to the present invention, b is selected from 0, 1, 2, 3, 4, 5 or 6, preferably 0.

[0022] According to the present invention, p is selected from 1, 2, 3, 4, 5 or 6, preferably 1.

[0023] According to the present invention, q is selected from 1, 2, 3, 4, 5 or 6, preferably 1.

[0024] According to the present invention, the molar ratio of the monomer 1 to the sum of the monomer 2 and the monomer 3 is 0.5 to 3:1, preferably 1.1 to 0.9:1.

[0025] According to the present invention, the ionic polynorbornene is a ring-opening polynorbornene directly charged with ions.

[0026] According to the present invention, the ionic polynorbornene has one of the following structural formulas:

[0027] Wherein, x, y, z and m are the molar contents of each monomer respectively;

[0028] R1, R2, R3, R a 、R b 、R c , a, b, p, q have the same definitions as above.

[0029] As an exemplary embodiment of the present invention, the ionic polynorbornene has one of the following structural formulas:

[0030] Wherein, x, y, z and m are the molar contents of each monomer respectively; the molar ratio of x, y, z and m satisfies that the molar ratio of monomer 1 to the sum of monomer 2 and monomer 3 is 0.5 to 3:1.

[0031] The present invention also provides a method for preparing the above-mentioned ionic polynorbornene, comprising the following steps:

[0032] Monomer 1, monomer 2 and monomer 3 as described above are reacted in the presence of a catalyst;

[0033] The catalyst is selected from a Ru catalyst or a W catalyst.

[0034] According to an embodiment of the present invention, the catalyst is selected from at least one of Grubbs I generation catalyst (CAS Registry No. 172222-30-9), Grubbs II generation catalyst (CAS Registry No. 246047-72-3), Grubbs III generation catalyst (CAS Registry No. 357186-58-4), and Hoveyda-Grubbs II generation catalyst (CAS Registry No. 301224-40-8).

[0035] According to an embodiment of the present invention, the method comprises:

[0036] Monomer 1, monomer 2, monomer 3 and an optional chain transfer agent are dissolved in a solvent to prepare a monomer solution, a catalyst is dissolved in a solvent to prepare a catalyst solution, and then the catalyst solution is added to a solution of monomer 3 and an optional chain transfer agent to carry out a polymerization reaction to prepare the ionic polynorbornene.

[0037] According to the preparation method of the present invention, the chain transfer agent is a small molecule olefin, including at least one of 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-hexene, 4-octene, etc.

[0038] According to the preparation method of the present invention, the molar ratio of the monomer 1 to the sum of the monomer 2 and the monomer 3 is 0.5 to 3:1, preferably 1.1 to 0.9:1.

[0039] According to the preparation method of the present invention, the molar ratio of the chain transfer agent to the total amount of monomer 1, monomer 2 and monomer 3 is 1:5-1000, preferably 1:10-100, and more preferably 1:15-20.

[0040] According to the preparation method of the present invention, the solvent is a single solvent or a mixed solvent such as dichloromethane, chloroform, 1,1,2-trichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, or isobutanol. The volume ratio of the total molar number of monomer 1, monomer 2, and monomer 3 to the solvent is 0.1 to 2 mol / L, preferably 0.8 to 1.5 mol / L.

[0041] According to the preparation method of the present invention, the molar ratio of the catalyst to the chain transfer agent is 1:1 to 1000, more preferably 1:1 to 500.

[0042] According to the preparation method of the present invention, the polymerization reaction time is 0.1h to 6h, preferably 0.2h to 0.5h.

[0043] According to the preparation method of the present invention, the polymerization reaction temperature is 20-80°C, preferably 40-60°C.

[0044] According to the preparation method of the present invention, the polymerization reaction is carried out under anhydrous and oxygen-free conditions, such as in a nitrogen atmosphere.

[0045] As an exemplary embodiment of the present invention, the preparation method of the ionic polynorbornene specifically includes:

[0046] dissolving the catalyst in chloroform to prepare a catalyst solution;

[0047] Monomer 1, monomer 2, monomer 3, and optionally a chain transfer agent are dissolved in a mixed solvent of chloroform and n-propanol to prepare a monomer solution, and then the catalyst solution is added to the monomer solution and stirred at 60° C. for 30 minutes to obtain ionic polynorbornene.

[0048] The present invention also provides a cross-linked membrane, wherein the cross-linked membrane is a membrane structure obtained by reacting the ionic polynorbornene and polythiol as described above in the presence of an initiator;

[0049] The polythiol is selected from one of the following structures:

[0050] wherein c is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0051] The present invention also provides a method for preparing the cross-linked film, the method comprising:

[0052] The ionic polynorbornene and polythiol as described above are reacted in the presence of an initiator;

[0053] The initiator is a photoinitiator or a thermal initiator.

[0054] According to the present invention, the method is a photoinitiation method, comprising: mixing the ionic polynorbornene, polythiol and photoinitiator in an organic solvent, and irradiating the mixture with ultraviolet light to obtain the cross-linked film;

[0055] Alternatively, the preparation method is a thermal initiation method, comprising:

[0056] The ionic polynorbornene, polythiol and thermal initiator are mixed in an organic solvent, and the solvent is volatilized while crosslinking under heating conditions to obtain the crosslinked film;

[0057] The photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2-(4-methylbenzyl)-2-(dimethylamino)-1- One, two or more of (4-morpholinophenyl)-1-butanone, 1,1'-(methylenebis-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-1-hexanophenone, bis-2,6-difluoro-3-pyrrolophenyl titanocene, methyl benzoylformate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, or 2-ethylanthraquinone;

[0058] The thermal initiator is one of azobisisobutyronitrile and dibenzoyl peroxide.

[0059] Exemplarily, the method for preparing a cross-linked film by photoinitiation includes: dissolving polythiol and a photoinitiator in an organic solvent, and mixing them evenly with ionic polynorbornene at room temperature, degassing the final polymer, and then scraping the film on a PET substrate, and then under ultraviolet light irradiation, simultaneously carrying out a cross-linking reaction and volatilization of the solvent, and after the irradiation is completed, a cross-linked film is obtained; preferably, the cross-linked film is dried again in a vacuum oven to ensure that the solvent is completely volatilized.

[0060] Illustratively, the preparation method of the cross-linked film by thermal initiation includes: dissolving polythiol and photoinitiator in an organic solvent, and mixing them evenly with ionic polynorbornene at room temperature, degassing the final polymer, and then scraping the film on a PET substrate. Under heating conditions, the cross-linking reaction and solvent volatilization are carried out simultaneously, and after the solvent is completely evaporated, a cross-linked film is obtained.

[0061] The film forming methods of the present invention include but are not limited to solution casting, spin coating, blade coating or casting.

[0062] According to the present invention, the organic solvent is but not limited to single solvent or mixed solvent such as dichloromethane, chloroform, 1,1,2-trichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, etc.

[0063] According to the present invention, the ratio of the molar amount of double bonds in the polynorbornene to the molar amount of thiol groups in the polythiol is 1:0.5-1.5, preferably 1:0.8-1.2.

[0064] According to the present invention, the total mass content of the ionic polynorbornene, polythiol and initiator in the solvent is 0.1 g / mL to 6 g / mL, preferably 0.1 g / mL to 0.5 g / mL.

[0065] According to the present invention, the ultraviolet light irradiation can use an ultraviolet lamp with a wavelength of 365nm.

[0066] According to the present invention, the illumination (or heating) time is 5 min to 240 min, preferably 30 min to 60 min.

[0067] The present invention also provides an ionic polynorbornene-based cross-linked anion exchange membrane, wherein the ionic polynorbornene-based cross-linked anion exchange membrane is prepared by reacting the cross-linked membrane with an alkaline reagent to exchange the anions of the cross-linked membrane with hydroxyl or HCO3 – Prepared.

[0068] The present invention also provides a method for preparing the polynorbornene-based cross-linked anion exchange membrane as described above, comprising:

[0069] The negative ion is X – The cross-linked membrane was immersed in HCO3 – The negative ion prepared in aqueous solution is HCO3 – Polynorbornene-based cross-linked anion exchange membrane; or the negative ion is X – The cross-linked membrane was immersed in OH – The negative ions prepared in the aqueous solution are OH – Polynorbornene-based cross-linked anion exchange membrane.

[0070] Preferably, the HCO3 – The aqueous solution is, for example, a NaHCO3 aqueous solution.

[0071] Preferably, the OH – The aqueous solution is, for example, a NaOH aqueous solution or a KOH aqueous solution.

[0072] The present invention also provides applications of the ionic polynorbornene-based cross-linked anion exchange membrane in fuel cells, water electrolysis, electrodialysis, acid recovery and other fields.

[0073] Beneficial effects of the present invention:

[0074] (1) The present invention successfully synthesized a ring-opening polynorbornene copolymer directly carrying ions;

[0075] (2) The present invention cross-links ionic polynorbornene and polythiol under the action of light initiation or heat initiation to prepare a cross-linked film.

[0076] (3) The present invention cross-links ionic polynorbornene and polythiol under the action of light initiation or heat initiation to prepare a more stable cross-linked film.

[0077] (4) The AEM prepared by the present invention has a smooth and transparent surface and has excellent electrical conductivity, stability and mechanical properties, overcoming the trade-off between electrical conductivity and stability of common AEMs. It can be applied in fuel cells, water electrolysis, electrodialysis, acid recovery and other fields.

[0078] (5) The method for preparing AEM of the present invention is simple to operate. In combination with a chain transfer agent, less polymerization catalyst can be used, which reduces costs. It can achieve scale-up production and "roll-to-roll" continuous preparation, providing guarantees for the industrial production and application of AEM.

[0079] Definitions and Explanations of Terms

[0080] The term "C 1-10 "Alkyl" means straight chain and branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 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.

[0081] The term "C 2-10 "Alkenyl" means a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, for example, having 2, 3, 4, 5 or 6 carbon atoms (i.e., C 2-6alkenyl), having 2 or 3 carbon atoms (i.e., C 2-3 It is understood that when the alkenyl group contains more than one double bond, the double bonds may be separated from one another or conjugated. The alkenyl group 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, (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-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, (Z)-1-methyl But-2-enyl, (E)-3-methylbut-1-enyl, (Z)-3-methylbut-1-enyl, (E)-2-methylbut-1-enyl, (Z)-2-methylbut-1-enyl, (E)-1-methylbut-1-enyl, (Z)-1-methylbut-1-enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.

[0082] The term "C 6-14 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl) such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-14When the aryl group is substituted, it may be monosubstituted or polysubstituted. Furthermore, there is no limitation on the position of substitution, and for example, substitution may be at the ortho, para or meta position. BRIEF DESCRIPTION OF THE DRAWINGS

[0083] FIG1 is a flow chart of the preparation of ionic polynorbornene according to the present invention.

[0084] FIG2 is a flow chart of the preparation of the cross-linked ion exchange membrane of the present invention.

[0085] Figure 3 is NB4C-N in Example 1 + Cl 1 H NMR spectrum.

[0086] Figure 4 is a diagram of the ionic polynorbornene of Example 2. 1 H NMR spectrum.

[0087] FIG5 is an appearance diagram of the cross-linked film prepared in Example 7.

[0088] FIG6 is an FT-IR graph of the cross-linked film in Example 7.

[0089] Figure 7 is a diagram of the cross-linked membrane anion in Example 7 where OH – Conductivity test chart.

[0090] FIG8 is an appearance diagram of the cross-linked film prepared in Example 12 (wherein, FIGa is an overall morphology diagram of the film; and FIGb is a local morphology diagram of the tail of the film). DETAILED DESCRIPTION

[0091] 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.

[0092] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0093] Example 1

[0094] This embodiment provides NB4C-N + The synthesis of Cl is prepared as follows:

[0095] As shown in the above process, 20 mmol NB4C-Cl and 20 ml trimethylamine ethanol solution were added to the sealed tube and stirred at 100 ° C for 48 hours. The reaction solution was precipitated with ether and filtered to obtain the product NB4C-N + Cl.

[0096] Example 2

[0097] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, VNB and TCD is prepared as follows:

[0098] As shown in the above process, 0.0003 mmol of Grubbs II generation catalyst was first dissolved in 100 μL of chloroform to prepare the catalyst solution. + Cl, 0.11 mmol VNB, and 0.923 mmol TCD were dissolved in a mixed solvent of 1 mL chloroform and 1 mL n-propanol. The catalyst solution was then added to the monomer solution, and the mixture was stirred at 60°C for 30 minutes under a nitrogen atmosphere to obtain the final product.

[0099] Example 3

[0100] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, DCPD and TCD is prepared as follows:

[0101] As shown in the above process, 0.0001 mmol of Grubbs II generation catalyst was first dissolved in 100 μL of chloroform to prepare the catalyst solution. + Cl, 0.5 mmol DCPD, 0.5 mmol TCD, and 0.006 mmol 1-octene were dissolved in a mixed solvent of 1 mL chloroform and 1 mL n-propanol. The catalyst solution was then added to the monomer solution, and the mixture was stirred at 60°C for 30 minutes under a nitrogen atmosphere to obtain the final product.

[0102] Example 4

[0103] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, VNB, DCPD and TCD is prepared as follows:

[0104] As shown in the above process, 0.0003 mmol of Grubbs II generation catalyst was first dissolved in 100 μL of chloroform to prepare the catalyst solution. + Cl, 0.36 mmol DCPD, 0.5 mmol TCD, and 0.11 mmol VNB were dissolved in a mixed solvent of 1 mL chloroform and 1 mL n-propanol. The catalyst solution was then added to the monomer solution, and the mixture was stirred at 60°C for 30 minutes under a nitrogen atmosphere to obtain the final product.

[0105] Example 5

[0106] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, VNB, NB-coumarin and TCD is prepared as follows:

[0107] As shown in the above process, 0.0003 mmol of Grubbs II generation catalyst was first dissolved in 100 μL of chloroform to prepare the catalyst solution. + Cl, 0.11 mmol NB-coumarin, 0.89 mmol TCD, and 0.11 mmol VNB were dissolved in a mixed solvent of 1 mL chloroform and 1 mL n-propanol. The catalyst solution was then added to the monomer solution, and the mixture was stirred at 60°C for 30 minutes under a nitrogen atmosphere to obtain the final product.

[0108] Example 6

[0109] As shown in the above process, the cross-linked film was prepared using the polynorbornene in Example 2. The preparation method is as follows:

[0110] The polynorbornene (2 mmol), 1,6-hexanedithiol (0.34 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.24 mmol) prepared in Example 1 were uniformly mixed in a mixed solvent of chloroform and n-propanol. The final polymer was degassed and cast on a PET substrate. Then, under ultraviolet light irradiation, a cross-linking reaction and solvent volatilization were carried out simultaneously. The irradiation was carried out for 30 minutes to obtain a cross-linked film.

[0111] Example 7

[0112] As shown in the above process, the cross-linked film was prepared using the polynorbornene in Example 5. The preparation method is as follows:

[0113] The polynorbornene (2 mmol), 1,10-decanedithiol (0.05 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.0003 mmol) prepared in Example 4 were uniformly mixed in a mixed solvent of chloroform and n-propanol. The final polymer was degassed and cast on a PET substrate. Then, under ultraviolet light irradiation, a cross-linking reaction and solvent volatilization were carried out simultaneously. The irradiation was carried out for 30 minutes to obtain a cross-linked film.

[0114] Examples 8-9

[0115] Ion replacement: replace the negative ions in Examples 6-7 with Cl –The AEM was immersed in NaHCO3 aqueous solution to prepare the negative ion HCO3 – AEM.

[0116] Examples 10-11

[0117] The negative ions in Examples 6-7 are Cl - The AEM was immersed in NaOH aqueous solution to prepare the negative ions OH – AEM.

[0118] Example 12

[0119] As shown in the above process, the cross-linked membrane was prepared on a large scale using the methods of Example 5 and Example 7. The preparation method is as follows:

[0120] As shown in the above process, 0.2 mmol of Grubbs II generation catalyst was first dissolved in 1 mL of chloroform to prepare the catalyst solution. + Cl, 0.067 mol NB-coumarin, 0.55 mol TCD, and 0.044 mol VNB were dissolved in a mixed solvent of 0.5 L chloroform and 0.5 L n-propanol. The catalyst solution was then added to the monomer solution, and the mixture was stirred at 60°C for 30 minutes under a nitrogen atmosphere. This yielded a norbornene polymer.

[0121] 1,10-Decanedithiol (0.03 mol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (2 mmol) were added to the polymer and mixed evenly in a mixed solvent of chloroform and n-propanol. The final polymer was degassed and scraped onto a PET substrate. Then, under ultraviolet light irradiation, a cross-linking reaction and solvent volatilization were carried out simultaneously. The irradiation was performed for 30 minutes to obtain a cross-linked film.

[0122] Test Example 1

[0123] The AEM prepared in Examples 8-9 and 10-11 were subjected to conductivity testing. 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).

[0124] In Example 8, the negative ion is HCO3 – The conductivity of AEM at room temperature is 11 mS / cm.

[0125] In Example 9, the negative ion is HCO3 – The electrical conductivity of the AEM at room temperature is 9.7 mS / cm.

[0126] In Example 10, the negative ion is OH – The conductivity of the AEM is 62 mS / cm at 40°C and 110 mS / cm at 80°C.

[0127] In Example 11, the negative ion is OH – The conductivity of the AEM is 52 mS / cm at 40°C and 104 mS / cm at 80°C.

[0128] The above is an exemplary description of the embodiments of the present invention. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. An ionic polynorbornene, characterized in that: The ionic polynorbornene is obtained by copolymerizing monomer 1, monomer 2 and monomer 3. Wherein, monomer 1 has the structure shown in the following formula (1); Monomer 2 is selected from one or both of the structures shown in the following formula (2) and formula (3): Monomer 3 is selected from one, two or more of the structures shown in formula (4), formula (5), formula (6) or formula (7): In formula (1), a is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; X is halogen; R1 is selected from H, C 1-10 Alkyl, C 6-14 Aryl, C 2-10 One of the alkenyl groups; R a 、R b 、R c The same or different, independently selected from C 1-10 alkyl; In formula (2), R2 and R3 are the same or different and are independently selected from H, C 1-10 Alkyl, C 6-14 One of the aromatic groups; In formula (3), p is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and q is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; In formula (4), b is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

2. The ionic polynorbornene according to claim 1, characterized in that Said X is Cl, Br or I; Preferably, a is selected from 1-8; Preferably, R1 is selected from H, C 1-6 Alkyl, C 6-14 Aryl, C 2-6 One of the alkenyl groups; Preferably, R a 、R b 、R c The same or different, independently selected from C 1-6 alkyl; Preferably, R2 is selected from H, C 1-6 Alkyl, C 6-14 One of the aromatic groups; Preferably, R3 is selected from H, C 1-6 Alkyl, C 6-14 One of the aromatic groups; Preferably, b is selected from 0, 1, 2, 3, 4, 5 or 6; Preferably, p is selected from 1, 2, 3, 4, 5 or 6; Preferably, q is selected from 1, 2, 3, 4, 5 or 6; Preferably, the molar ratio of the monomer 1 to the sum of the monomer 2 and the monomer 3 is 0.5 to 3:

1.

3. The ionic polynorbornene according to claim 1 or 2, characterized in that The ionic polynorbornene has one of the following structural formulas: Wherein, x, y, z and m are the molar contents of each monomer respectively; R1, R2, R3, R a 、R b 、R c , a, b, p, q have the definitions given in claim 1 or 2.

4. The method for preparing the ionic polynorbornene according to any one of claims 1 to 3, characterized in that: The steps include: Monomer 1, monomer 2 and monomer 3 according to any one of claims 1 to 3 are reacted in the presence of a catalyst; The catalyst is selected from a Ru catalyst or a W catalyst.

5. The preparation method according to claim 4, characterized in that The catalyst is selected from at least one of Grubbs I generation catalyst (CAS registration number 172222-30-9), Grubbs II generation catalyst (CAS registration number 246047-72-3), Grubbs III generation catalyst (CAS registration number 357186-58-4), and Hoveyda-Grubbs II generation catalyst (CAS registration number 301224-40-8).

6. A cross-linked film, characterized in that The cross-linked membrane is a membrane structure obtained by using the ionic polynorbornene and polythiol according to any one of claims 1 to 3 in the presence of an initiator; The polythiol is selected from one of the following structures: wherein c is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

7. The method for preparing a cross-linked film according to claim 6, wherein: reacting the ionic polynorbornene according to any one of claims 1 to 3 and polythiol in the presence of an initiator; The initiator is a photoinitiator or a thermal initiator; Preferably, the method is a photoinitiation method, comprising: mixing the ionic polynorbornene according to any one of claims 1 to 3, polythiol and a photoinitiator in an organic solvent, and irradiating the mixture with ultraviolet light to obtain the cross-linked film; Alternatively, the preparation method is a thermal initiation method, comprising: Mixing the ionic polynorbornene according to any one of claims 1 to 3, polythiol and a thermal initiator in an organic solvent, and volatilizing the solvent while crosslinking under heating conditions to obtain the crosslinked film; The photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylpropiophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2-(4-methylbenzyl)-2-(dimethylamino)-1- One, two or more of (4-morpholinophenyl)-1-butanone, 1,1'-(methylenebis-4,1-phenylene)bis[2-hydroxy-2-methyl-1-propanone], 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-1-hexanophenone, bis-2,6-difluoro-3-pyrrolophenyl titanocene, methyl benzoylformate, benzophenone, 4-methylbenzophenone, 4-phenylbenzophenone, 4-chlorobenzophenone, methyl o-benzoylbenzoate, ethyl 4-dimethylaminobenzoate, isooctyl p-dimethylaminobenzoate, 4,4'-bis(diethylamino)benzophenone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, or 2-ethylanthraquinone; The thermal initiator is one of azobisisobutyronitrile and dibenzoyl peroxide.

8. An ionic polynorbornene-based cross-linked anion exchange membrane, characterized in that: The ionic polynorbornene-based cross-linked anion exchange membrane is prepared by reacting the cross-linked membrane according to claim 6 with an alkaline reagent to exchange the anion X of the cross-linked membrane. – Hydroxyl or HCO3 – Prepared.

9. The method for preparing the ionic polynorbornene-based cross-linked anion exchange membrane according to claim 8, characterized in that: include: The negative ion according to claim 6 is X – The cross-linked membrane was immersed in HCO3 – The negative ion prepared in aqueous solution is HCO3 – Polynorbornene-based cross-linked anion exchange membrane; or the negative ion is X – The cross-linked membrane was immersed in OH – The negative ions prepared in the aqueous solution are OH – Polynorbornene-based cross-linked anion exchange membrane.

10. Use of the ionic polynorbornene-based cross-linked anion exchange membrane according to claim 8 in the fields of fuel cells, water electrolysis, electrodialysis, and acid recovery.

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