Ionic polynorbornene cross-linked anion exchange membrane as well as preparation method and application thereof

Abstract

The invention provides an ionic polynorbornene cross-linked anion exchange diaphragm as well as a preparation method and application thereof. The prepared membrane is smooth and transparent in surface, has excellent conductivity, stability and mechanical performance, and can be applied to the fields of fuel cells, electrolyzed water, electrodialysis, acid recovery and the like. The preparation method provided by the invention is simple to operate, can use less polymerization catalyst in cooperation with the chain transfer agent, reduces the cost, can realize large-scale production and roll-to-roll continuous preparation, and provides guarantee for industrial production and application of the membrane.

Description

Technical Field

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

[0002] Compared with devices operating under acidic conditions (e.g., proton exchange membrane fuel cells [PEMFCs]), alkaline water electrolysis (AEMWE) and alkaline fuel cells (AEMFCs) have better catalyst stability and fast cathode reaction kinetics under alkaline conditions. The use of non-platinum group metal electrocatalysts can significantly reduce equipment costs. Anion exchange membranes (AEMs) are key components of electrochemical devices such as AEMWEs and AEMFCs. AEMs are composed of three parts: a polymer backbone, cations covalently linked to the backbone, and free anions. AEMs with excellent performance usually have the following evaluation criteria: high hydroxide ion conductivity, high mechanical strength, and excellent stability of the polymer in alkaline media. At present, it is still a challenge to synthesize AEMs with high conductivity and long-term alkaline stability. In order to achieve a balance between ionic conductivity and stability, preparing ion exchange membranes by chemical crosslinking is an effective strategy. The synthesis of cross-linked AEMs by ROMP has become a hot topic of research because the catalysts of ring-opening metathesis polymerization (ROMP) have the characteristics of high activity and wide functional group tolerance, mild polymerization conditions, narrow molecular weight distribution of polymerization products, strong controllability and functional group compatibility.

[0003] However, for these cross-linked AEMs, both covalently linked cationic functional groups and stable chemical cross-linking are required. There are two main methods for preparing cross-linked AEMs. One method is to first form a cross-linked structure and then introduce cationic functional groups (ACS Appl. Energy Mater. 2019, 2, 2458-2468). In order to achieve full ionization of the membrane, this preparation strategy requires long-term solution immersion of the AEM (for example, at least 48 hours in a trimethylamine aqueous solution). The disadvantage is that it consumes a lot of solvent and time, which is not conducive to continuous preparation. Another method is to first synthesize ionic monomers and then polymerize them. This method can greatly reduce time and solvent costs. This method has also been reported (J. Am. Chem. Soc. 2009, 131, 12888-12889; Chemical Industry Journal, 2015, 66, 257-262; Chemical Industry Journal, 2015, 66, 338-342), but the disadvantage is that there are unsaturated bonds on the main chain, and there is a problem of unstable polymer size. Therefore, researchers will cross-link the raw material dicyclopentadiene (DCPD) to maintain stability. This preparation method requires the use of a large amount of Grubbs catalyst (1000-10000ppm), which increases the cost of use and fails to achieve large-scale and continuous production. Therefore, it is necessary to further study the direct polymerization of ionic monomers, and the polymerization process is low-cost, and the preparation process can achieve scale-up production and "roll-to-roll" continuous film preparation method. Summary of the invention

[0004] The present invention proposes a method for directly polymerizing norbornene ionic monomers, which are subsequently cross-linked to improve the mechanical stability of the polymer. The present invention first performs ROMP on norbornene monomers with ions. However, since the polymer main chain obtained by ROMP contains unsaturated double bonds, this will lead to increased water absorption and reduced mechanical strength of the membrane. Therefore, the double bonds in polynorbornene are cross-linked with polythiol to prepare AEM, which can solve the trade-off between conductivity and stability. By copolymerization, the structure of polynorbornene contains more active olefin functional groups that can be used for cross-linking. 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 cross-linking.

[0005] The technical solution of the present invention is as follows:

[0006] An ionic polynorbornene, wherein the ionic polynorbornene is obtained by copolymerizing a monomer 1, a monomer 2 and a monomer 3,

[0007] Wherein, monomer 1 has a structure as shown in the following formula (1);

[0008]

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

[0010]

[0011] Monomer 3 is selected from one, two or more of the structures shown in formula (4), formula (5), formula (6) or formula (7):

[0012]

[0013] In formula (1), a is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; X is halogen;

[0014] 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;

[0015] 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;

[0016] 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;

[0017] In formula (4), b is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0018] According to the present invention, X is Cl, Br or I.

[0019] According to the present invention, a is selected from 1-8, more preferably 4-6.

[0020] 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 The alkyl group is, for example, methyl.

[0021] According to the present invention, R2 is selected from H, C 1-6Alkyl, C 6-14 One of the aryl groups, preferably H.

[0022] According to the present invention, R3 is selected from H, C 1-6 Alkyl, C 6-14 One of the aryl groups, preferably H.

[0023] According to the present invention, b is selected from 0, 1, 2, 3, 4, 5 or 6, preferably 0.

[0024] According to the present invention, p is selected from 1, 2, 3, 4, 5 or 6, preferably 1.

[0025] According to the present invention, q is selected from 1, 2, 3, 4, 5 or 6, preferably 1.

[0026] 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.

[0027] According to the present invention, the ionic polynorbornene is a ring-opening polynorbornene directly carrying ions.

[0028] According to the present invention, the ionic polynorbornene has one of the following structural formulas:

[0029]

[0030] Wherein, x, y, z and m are the molar contents of each monomer respectively;

[0031] R1, R2, R3, R a , R b , R c , a, b, p, q have the definitions described above.

[0032] As an exemplary embodiment of the present invention, the ionic polynorbornene has one of the following structural formulas:

[0033]

[0034] Among them, 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.

[0035] The present invention also provides a method for preparing the above-mentioned ionic polynorbornene, comprising the following steps:

[0036] Monomer 1, monomer 2 and monomer 3 as described above are reacted in the presence of a catalyst;

[0037] The catalyst is selected from a Ru catalyst or a W catalyst.

[0038] According to an embodiment of the present invention, 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).

[0039] According to an embodiment of the present invention, the method comprises:

[0040] 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 the solution of monomer 3 and an optional chain transfer agent to carry out a polymerization reaction to prepare the ionic polynorbornene.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] 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, isobutanol, etc. The volume ratio of the total mole 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.

[0045] According to the preparation method of the present invention, the molar ratio of the catalyst to the chain transfer agent is 1:1-1000, more preferably 1:1-500.

[0046] According to the preparation method of the present invention, the polymerization reaction time is 0.1h to 6h, preferably 0.2h to 0.5h.

[0047] According to the preparation method of the present invention, the polymerization reaction temperature is 20 to 80°C, preferably 40 to 60°C.

[0048] 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.

[0049] As an exemplary embodiment of the present invention, the method for preparing the ionic polynorbornene specifically comprises:

[0050] The catalyst is dissolved in chloroform to prepare a catalyst solution;

[0051] 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 an ionic polynorbornene.

[0052] 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;

[0053] The polythiol is selected from one of the following structures:

[0054]

[0055] wherein c is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

[0056] The present invention also provides a method for preparing the cross-linked film as described above, the method comprising:

[0057] The ionic polynorbornene and polythiol as described above are reacted in the presence of an initiator;

[0058] The initiator is a photoinitiator or a thermal initiator.

[0059] According to the present invention, the method is a photoinitiator method, comprising: mixing the ionic polynorbornene, polythiol and photoinitiator in an organic solvent, and obtaining the cross-linked film after irradiation with ultraviolet light;

[0060] Alternatively, the preparation method is a thermal initiation method, comprising:

[0061] 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;

[0062] The photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenyl propiophenone, 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-morpholinylbenzylphenyl)butanone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2-(4-methylbenzyl)-2-(dimethylamino)-1- One, two or more of (4-morpholinophenyl)-1-butanone, 1,1'-(methylenedi-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;

[0063] The thermal initiator is one of azobisisobutyronitrile and dibenzoyl peroxide.

[0064] 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, cross-linking reaction and solvent volatilization are carried out simultaneously, 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.

[0065] Illustratively, the preparation method of the thermally initiated cross-linked film 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, and under heating conditions, cross-linking reaction and solvent volatilization are carried out simultaneously, and after the solvent is completely evaporated, a cross-linked film is obtained.

[0066] The film forming method described in the present invention includes but is not limited to solution casting, spin coating, blade coating or casting.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] According to the present invention, the ultraviolet light irradiation can use an ultraviolet lamp with a wavelength of 365nm.

[0071] According to the present invention, the illumination (or heating) time is 5 min to 240 min, preferably 30 min to 60 min.

[0072] 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.

[0073] The present invention also provides a method for preparing the polynorbornene-based cross-linked anion exchange membrane as described above, comprising:

[0074] As mentioned above, the negative ion is X - The cross-linked membrane was immersed in HCO3 - Preparation of negative ions in aqueous solution is HCO3 - The polynorbornene-based cross-linked anion exchange membrane; or the negative ion is X - The cross-linked membrane was immersed in OH - The negative ion is OH in aqueous solution - Polynorbornene-based cross-linked anion exchange membrane.

[0075] Preferably, the HCO3 - The aqueous solution is, for example, a NaHCO3 aqueous solution.

[0076] Preferably, the OH - The aqueous solution is, for example, an aqueous NaOH solution or an aqueous KOH solution.

[0077] The present invention also provides the application of the above-mentioned ionic polynorbornene-based cross-linked anion exchange membrane in the fields of fuel cells, water electrolysis, electrodialysis, acid recovery, etc.

[0078] Beneficial effects of the present invention:

[0079] (1) The present invention successfully synthesized a ring-opening polynorbornene copolymer directly carrying ions;

[0080] (2) In the present invention, the ionic polynorbornene and polythiol are cross-linked under the action of light initiation or heat initiation to prepare a cross-linked film.

[0081] (3) In the present invention, ionic polynorbornene and polythiol are cross-linked under the action of light initiation or heat initiation to prepare a more stable cross-linked film.

[0082] (4) The AEM prepared by the present invention has a smooth and transparent surface and has excellent electrical conductivity, stability and mechanical properties, which overcomes the trade-off problem between the electrical conductivity and stability of common AEMs and can be used in fuel cells, water electrolysis, electrodialysis, acid recovery and other fields.

[0083] (5) The method for preparing AEM of the present invention is simple to operate. With the help of 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, thus providing a guarantee for the industrial production and application of AEM.

[0084] Definition and explanation of terms

[0085] The term "C 1-10 "Alkyl" means straight chain and branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 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.

[0086] The term "C 2-10 "Alkenyl" means a straight 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 where 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.

[0087] The term "C 6-14 The term "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. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position. BRIEF DESCRIPTION OF THE DRAWINGS

[0088] Figure 1 It is a preparation flow chart of the ionic polynorbornene of the present invention.

[0089] Figure 2 It is a preparation flow chart of the cross-linked ion exchange membrane of the present invention.

[0090] Figure 3 It is NB4C-N in Example 1 + Cl 1 H NMR spectra.

[0091] Figure 4 Example 2 Ionic polynorbornene 1 H NMR spectra.

[0092] Figure 5 This is an appearance picture of the cross-linked film prepared in Example 7.

[0093] Figure 6 This is the FT-IR graph of the cross-linked film in Example 7.

[0094] Figure 7 The cross-linked membrane anion in Example 7 is OH - Conductivity test chart.

[0095] Figure 8 This is the appearance picture of the cross-linked film prepared in Example 12 (wherein, Figure a is the overall morphology of the film; Figure b is the local morphology of the tail of the film). DETAILED DESCRIPTION

[0096] 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.

[0097] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0098] Example 1

[0099]

[0100] This embodiment provides NB4C-N + The synthesis of Cl is prepared as follows:

[0101] As shown in the above process, 20 mmol NB4C-Cl and 20 ml trimethylamine ethanol solution were added to the sealed tube, stirred at 100 °C for 48 hours, and the reaction solution was precipitated with ether and filtered to obtain the product NB4C-N + Cl.

[0102] Example 2

[0103]

[0104] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, VNB and TCD is prepared as follows:

[0105] As shown in the above process, firstly, 0.0003mmol of Grubbs II generation catalyst was dissolved in 100μL of chloroform to prepare a catalyst solution. + Cl, 0.11mmol VNB, and 0.923mmol TCD were dissolved in 1mL of a mixed solvent of chloroform and 1ml of n-propanol, and then the catalyst solution was 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.

[0106] Example 3

[0107]

[0108] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, DCPD and TCD is prepared as follows:

[0109] As shown in the above process, firstly, 0.0001mmol of Grubbs II generation catalyst was dissolved in 100μL of chloroform to prepare a catalyst solution. + Cl, 0.5mmol DCPD, 0.5mmol TCD, and 0.006mmol 1-octene were dissolved in 1mL chloroform and 1ml n-propanol mixed solvent. 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. The final product was obtained.

[0110] Example 4

[0111]

[0112] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, VNB, DCPD and TCD is prepared as follows:

[0113] As shown in the above process, firstly, 0.0003mmol of Grubbs II generation catalyst was dissolved in 100μL of chloroform to prepare a catalyst solution. + Cl, 0.36mmol DCPD, 0.5mmol TCD and 0.11mmol VNB were dissolved in 1mL chloroform and 1ml n-propanol mixed solvent. 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. The final product was obtained.

[0114] Example 5

[0115]

[0116] This embodiment provides NB4C-N + The ring-opening copolymerization of Cl, VNB, NB-coumarin and TCD is prepared as follows:

[0117] As shown in the above process, firstly, 0.0003mmol of Grubbs II generation catalyst was dissolved in 100μL of chloroform to prepare a catalyst solution. + Cl, 0.11mmol NB-coumarin, 0.89mmol TCD and 0.11mmol VNB were dissolved in 1mL chloroform and 1ml n-propanol mixed solvent. 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. The final product was obtained.

[0118] Example 6

[0119]

[0120] As shown in the above process, the cross-linked film is prepared using the polynorbornene in Example 2, and the preparation method is as follows:

[0121] 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 a film was scraped on a PET substrate. Then, under ultraviolet light irradiation, a cross-linking reaction and solvent volatilization were carried out simultaneously, and the film was irradiated for 30 minutes to obtain a cross-linked film.

[0122] Example 7

[0123]

[0124] As shown in the above process, the cross-linked film was prepared using the polynorbornene in Example 5, and the preparation method was as follows:

[0125] 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 a film was scraped on a PET substrate. Then, under ultraviolet light irradiation, a cross-linking reaction and solvent volatilization were carried out simultaneously, and the film was irradiated for 30 minutes to obtain a cross-linked film.

[0126] Embodiment 8-9

[0127] Ion replacement: The negative ions in Examples 6-7 were replaced by Cl - The AEM was immersed in NaHCO3 aqueous solution to prepare the negative ion HCO3 - AEM.

[0128] Embodiment 10-11

[0129] The negative ions in Examples 6-7 are Cl - The AEM was immersed in a NaOH aqueous solution to prepare the AEM whose negative ion was OH-.

[0130] Example 12

[0131]

[0132] As shown in the above process, the cross-linked membrane is prepared on a large scale using the methods of Example 5 and Example 7. The preparation method is as follows:

[0133] As shown in the above process, firstly, 0.2 mmol of Grubbs II generation catalyst was dissolved in 1 mL of chloroform to prepare a 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. A norbornene polymer was obtained.

[0134] Then, 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 on a PET substrate. Then, under ultraviolet light irradiation, a cross-linking reaction and solvent volatilization were carried out simultaneously. The cross-linking film was irradiated for 30 minutes to obtain a cross-linked film.

[0135] Test Example 1

[0136] The AEM prepared in Examples 8-9 and 10-11 was 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).

[0137]

[0138] In Example 8, the negative ion is HCO3 - The conductivity of AEM at room temperature is 11 mS / cm.

[0139] In Example 9, the negative ion is HCO3 - The conductivity of AEM at room temperature is 9.7 mS / cm.

[0140] The conductivity of the AEM in Example 10 whose negative ions are OH- is 62 mS / cm at 40°C and 110 mS / cm at 80°C.

[0141] The conductivity of the AEM in Example 11 whose negative ions are OH- is 52 mS / cm at 40°C and 104 mS / cm at 80°C.

[0142] The above is an exemplary description of the embodiments of the present invention. However, the protection scope of the present invention is not limited to the above embodiments. Any modification, equivalent substitution, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope 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 a structure as 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, 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: 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: The 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 film is a film structure obtained by using the ionic polynorbornene and polythiol described in 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, characterized in that: Reacting the ionic polynorbornene according to any one of claims 1 to 3 with polythiol in the presence of an initiator; The initiator is a photoinitiator or a thermal initiator; Preferably, the method is a photoinitiator 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: The ionic polynorbornene according to any one of claims 1 to 3, polythiol and a thermal initiator are mixed in an organic solvent, and the solvent is volatilized while crosslinking under heating conditions to obtain the crosslinked film; The photoinitiator is selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4-(2-hydroxyethoxy)-2-methylphenyl propiophenone, 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-morpholinylbenzylphenyl)butanone, 4-benzoyl-4'-methyl-diphenyl sulfide, 2-(4-methylbenzyl)-2-(dimethylamino)-1- One, two or more of (4-morpholinophenyl)-1-butanone, 1,1'-(methylenedi-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 anions X - 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 in claim 6 is X - The cross-linked membrane was immersed in HCO3 - Preparation of negative ions in aqueous solution is HCO3 - The polynorbornene-based cross-linked anion exchange membrane; or the negative ion is X - The cross-linked membrane was immersed in OH - The negative ion is OH in aqueous solution - 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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