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

Abstract

The present invention discloses a polynorbornene-based cross-linked anion exchange membrane and a preparation method and application thereof, wherein the membrane is prepared by using the following polynorbornene, wherein the polynorbornene is obtained by copolymerizing monomer 1 and monomer 2, wherein monomer 1 has a structure shown in the following formula (1); and monomer 2 has one of the structures shown in the following formula (2), formula (3) or formula (4). The AEM prepared by the present invention has a smooth and transparent surface, excellent electrical conductivity, stability and mechanical properties, overcomes the trade-off problem between electrical conductivity and stability of common AEM, and can be applied in fuel cells, water electrolysis, electrodialysis, acid recovery and other fields.

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 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 alkaline fuel cells (AEMFC), alkaline water electrolysis (AEMWE), acid recovery, wastewater treatment, and carbon dioxide reduction. The alkaline system to which it is applicable has fast cathode reaction kinetics, and non-precious metal catalysts can be used in the process of assembling the equipment, thereby significantly reducing the system cost. However, taking AEMFC as an example, its power density and durability limit its practical application, especially its durability in working environments. According to a technical goal provided by the U.S. Department of Energy, a feasible single-cell AEMFC needs to be above 60°C and have a current density of more than 600mA / cm 2 The voltage drop rate was less than 10% after running for 2000 hours under the conditions of . However, the life of most AEMFCs is still less than 1000 hours. AEM is a key component of AEMFC. It consists of three parts: a polymer backbone, cations covalently linked to the backbone, and free anions. Researchers intend to design and synthesize AEMs with excellent conductivity, mechanical stability, thermal stability, and alkaline stability to improve the durability of AEMFC. In existing technologies, the conductivity and alkaline stability of AEMs are still challenges, especially the trade-off between the two. High conductivity requires a high ion exchange capacity (IEC) to achieve. Too high IEC will cause excessive swelling of the AEM, thereby reducing the stability of the AEM. Summary of the invention

[0003] In order to solve the above technical problems, the present invention proposes a polynorbornene-based cross-linked anion exchange membrane and its preparation method and application. The main chain of polynorbornene is a full carbon-hydrogen main chain without heteroatoms. This structure has excellent thermal stability and chemical stability. However, uncross-linked polynorbornene still cannot effectively inhibit the swelling of AEM (see WO2022026794A1). Therefore, the trade-off between conductivity and stability can be solved by preparing AEM through cross-linking of double bonds in polynorbornene with polythiol; and by copolymerization, the structure of polynorbornene contains both alkyl halides that can be connected to cationic functional groups and olefin functional groups that can be used for cross-linking.

[0004] The technical solution of the present invention is as follows:

[0005] A polynorbornene, wherein the polynorbornene is obtained by copolymerizing a monomer 1 and a monomer 2,

[0006] Wherein, monomer 1 has a structure as shown in the following formula (1);

[0007]

[0008] Monomer 2 has one of the structures shown in the following formula (2), formula (3) or formula (4):

[0009]

[0010] In formula (1), R1 is -C 1-10 Alkylene-X; X is halogen;

[0011] R2 is selected from H, C 1-10 Alkyl, C 1-10 Alkylene-X, C 6-14 Aryl, C 2-10 A type of alkenyl.

[0012] In formula (2), R3 is C 2-10 Alkenyl,

[0013] R4 is selected from H, C 1-10 Alkyl, C 6-14 Aryl, C 2-10 A type of alkenyl.

[0014] According to the present invention, X is Cl, Br or I.

[0015] According to the present invention, R1 is preferably -C 1-6 Alkylene-X.

[0016] According to the present invention, R2 is selected from H, C 1-6 Alkyl, C 1-6 Alkylene-X, C 6-14 Aryl, C 2-6 One of the alkenyl groups, more preferably H.

[0017] According to the present invention, R3 is C 2-6 The alkenyl group is more preferably a vinyl group.

[0018] According to the present invention, R4 is selected from H, C 1-6 Alkyl, C 6-14 Aryl, C 2-6 One of the alkenyl groups, more preferably H.

[0019] According to the present invention, the molar ratio of the monomer 1 to the monomer 2 is 10:1 to 1:10, preferably (1 to 8):1.

[0020] According to the present invention, the polynorbornene is an addition-type polynorbornene or a ring-opening type polynorbornene.

[0021] According to the present invention, the polynorbornene has one of the following structural formulas:

[0022]

[0023] Wherein, n and m are the molar contents of monomer 1 and monomer 2, respectively.

[0024] As an exemplary embodiment of the present invention, the polynorbornene has one of the following structural formulas:

[0025]

[0026] Wherein, n and m are the molar contents of monomer 1 and monomer 2, respectively.

[0027] The present invention also provides a method for preparing the above-mentioned polynorbornene, wherein the polynorbornene includes addition-type polynorbornene and ring-opening-type polynorbornene;

[0028] The preparation method of the addition type polynorbornene comprises:

[0029] The monomer 1 and the monomer 2 are dissolved in a solvent to prepare a monomer solution, the first catalyst and its auxiliary agent are dissolved in a solvent to prepare a catalyst solution, and then the catalyst solution is added to the monomer solution to carry out a polymerization reaction to prepare the addition-type polynorbornene;

[0030] Alternatively, the preparation method of the ring-opening polynorbornene comprises:

[0031] The monomer 1, the monomer 2 and the chain transfer agent are dissolved in a solvent to prepare a monomer solution, the second catalyst is dissolved in a solvent to prepare a catalyst solution, and then the catalyst solution is added to the monomer solution to carry out a polymerization reaction to prepare the ring-opening polynorbornene.

[0032] According to the present invention, the first catalyst includes but is not limited to a Pd catalyst or a Ni catalyst (such as tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), palladium acetate (Pd(OAc)2), di(triphenylantimony)di(pentafluorophenyl)nickel (Ni(C6F5)2(SbPh3)2)).

[0033] According to the present invention, the auxiliary agent includes at least one of a stabilizer of the first catalyst (such as tricyclohexylphosphine (PCy3)) and a co-catalyst (such as lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex (LiFABA) or sodium tetrakis(3,5-di(trifluoromethyl)phenyl)borate (NaBARF)).

[0034] Preferably, in the method for preparing addition-type polynorbornene, the first catalyst system used is Pd2(dba)3, PCy3 and LiFABA, wherein the molar ratio of Pd2(dba)3, PCy3 and LiFABA is 1:4:4.

[0035] According to the present invention, the molar ratio of monomer 1 to monomer 2 is 10:1 to 1:10, preferably (1 to 8):1.

[0036] According to the present invention, in the preparation of addition-type polynorbornene, the solvent is toluene, wherein the volume ratio of the total mole number of monomer 1 and monomer 2 to the solvent is 0.1-2 mmol / ml, more preferably 0.4-0.6 mmol / ml.

[0037] Preferably, the total molar ratio of the first catalyst to the monomer 1 and the monomer 2 of the present invention is 1:100 to 1:500, more preferably 1:200 to 1:300.

[0038] Preferably, the polymerization reaction time of the present invention is 10 h to 48 h, more preferably 12 h to 40 h.

[0039] Preferably, the polymerization reaction temperature of the present invention is 20-60°C, more preferably 20-30°C.

[0040] Preferably, the polymerization reaction of the present invention is carried out under anhydrous and oxygen-free conditions.

[0041] According to the present invention, the second catalyst includes but is not limited to a Ru catalyst or a W catalyst. For example, the second catalyst is selected from at least one of a Grubbs I generation catalyst (CAS registration number 172222-30-9), a Grubbs II generation catalyst (CAS registration number 246047-72-3), a Grubbs III generation catalyst (CAS registration number 357186-58-4), a Hoveyda-Grubbs II generation catalyst (CAS registration number 301224-40-8), and WCl6.

[0042] According to 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 and the like.

[0043] According to the present invention, in the preparation of the ring-opening polynorbornene, the molar ratio of monomer 1 to monomer 2 is 10:1 to 1:10, preferably (1 to 8):1.

[0044] According to the present invention, the molar ratio of the chain transfer agent to the total amount of monomer 1 and monomer 2 is 1:100 to 1:1000, more preferably 1:200 to 1:500.

[0045] According to the present invention, the solvent is cyclohexane, tetrahydrofuran, or toluene, and the volume ratio of the total mole number of monomer 1 and monomer 2 to the solvent is 0.1-2 mmol / ml, more preferably 0.5-1.5 mmol / ml.

[0046] Preferably, the molar ratio of the second catalyst to the chain transfer agent of the present invention is 1:1 to 1:1000, more preferably 1:10 to 1:500.

[0047] Preferably, the polymerization reaction time of the present invention is 0.5h to 6h, more preferably 0.5h to 1h.

[0048] Preferably, the polymerization reaction temperature of the present invention is 20-60°C, more preferably 40-60°C.

[0049] Preferably, the polymerization reaction of the present invention is carried out under anhydrous and oxygen-free conditions.

[0050] According to the present invention, the method further comprises a post-treatment step, wherein after the polymerization reaction is completed, the prepared product is precipitated, washed, and / or dried to prepare the addition-type polynorbornene or ring-opening polynorbornene.

[0051] As an exemplary embodiment of the present invention, the preparation method of the addition-type polynorbornene specifically includes:

[0052] Firstly, tris(dibenzylideneacetone)dipalladium (Pd2(dba)3), tricyclohexylphosphine (PCy3), and lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex (LiFABA) were dissolved in toluene and stirred at room temperature for 1 h to 2 h to prepare a catalyst solution;

[0053] Dissolving monomer 1 and monomer 2 in toluene to prepare a monomer solution;

[0054] Then, the catalyst solution is added to the monomer solution and stirred at room temperature. After the reaction is completed, the product is poured into methanol for precipitation, ultrasonicated, and filtered to obtain a solid product, which is then vacuum dried to obtain addition-type polynorbornene.

[0055] The catalyst solution is filtered through a 0.45 μm filter membrane before use.

[0056] As an exemplary embodiment of the present invention, the preparation method of the ring-opening polynorbornene specifically includes:

[0057] dissolving the second catalyst in toluene or tetrahydrofuran to prepare a catalyst solution;

[0058] The monomer 1, the monomer 2 and the 1-octene are dissolved in a cyclohexane solvent to prepare a monomer solution, and then the catalyst solution is added to the monomer solution and stirred at 50°C; after the reaction is completed, the product is poured into methanol or ethanol for precipitation, ultrasonicated, and filtered to obtain a solid product, which is then vacuum dried to obtain a ring-opening polynorbornene.

[0059] The present invention also provides a cross-linked film, which is prepared by using the polynorbornene.

[0060] The present invention also provides a method for preparing a cross-linked film, the method comprising preparing the cross-linked film by light initiation and preparing the cross-linked film by heat initiation:

[0061] The method for preparing a cross-linked film by photoinitiation comprises:

[0062] The polynorbornene, polythiol and photoinitiator are mixed in an organic solvent, and irradiated with ultraviolet light to obtain the cross-linked film;

[0063] Alternatively, the method for preparing a cross-linked film by thermal initiation comprises:

[0064] The polynorbornene, polythiol and thermal initiator are mixed in an organic solvent, and the cross-linking is carried out while the solvent is volatilized under heating conditions to obtain the cross-linked film.

[0065] Exemplarily, the method for preparing a cross-linked film by photoinitiation includes: dissolving the polynorbornene, polythiol and photoinitiator in an organic solvent, stirring at room temperature until completely dissolved, and then pouring the obtained mixture solution into a mold, and under ultraviolet light irradiation conditions, a cross-linking reaction and solvent volatilization are carried out simultaneously. 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.

[0066] Illustratively, the method for preparing a cross-linked film by thermal initiation includes: dissolving the polynorbornene, polythiol and thermal initiator in an organic solvent, stirring at room temperature until completely dissolved, and then pouring the obtained mixture solution into a mold, and under heating conditions, simultaneously carrying out a cross-linking reaction and volatilization of the solvent, and obtaining a cross-linked film after the solvent is completely volatilized.

[0067] The film forming method described in the present invention includes but is not limited to solution casting, spin coating, blade coating or casting.

[0068] According to the present invention, the polythiol is selected from at least one of the following compounds:

[0069]

[0070] Here, b is an integer from 0 to 10.

[0071] According to the present invention, the photoinitiator is a conventional reagent in the art, for example, phenyl (2,4,6-trimethylbenzoyl) phosphine oxide.

[0072] According to the present invention, the thermal initiator is a conventional reagent in the art, such as azobisisobutyronitrile.

[0073] According to the present invention, the organic solvent includes but is not limited to chloroform, dichloromethane and tetrahydrofuran.

[0074] 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 to 1:1.5, and more preferably 1:0.8 to 1:1.2.

[0075] According to the present invention, the total mass content of the polynorbornene, polythiol and photoinitiator in the solvent is 20 g / mL to 60 g / mL, more preferably 30 g / mL to 40 g / mL.

[0076] According to the present invention, the total mass content of the polynorbornene, polythiol and thermal initiator in the solvent is 20 g / mL to 60 g / mL, more preferably 30 g / mL to 40 g / mL.

[0077] According to the present invention, the ultraviolet light irradiation may be performed using an ultraviolet lamp.

[0078] According to the present invention, the illumination (or heating) time is 5 min to 240 min, more preferably 30 min to 60 min.

[0079] The present invention also provides a polynorbornene-based cross-linked anion exchange membrane, and the polynorbornene-based cross-linked anion exchange membrane is prepared by the cross-linked membrane.

[0080] The present invention also provides a method for preparing a polynorbornene-based cross-linked anion exchange membrane, the method comprising:

[0081] The cross-linked membrane is immersed in a quaternizing agent for quaternization to obtain a negative ion X - Polynorbornene-based cross-linked anion exchange membrane;

[0082] Wherein, X has the above meaning.

[0083] According to the present invention, the method comprises: immersing the cross-linked membrane in a quaternary ammonium agent for quaternization, and after the reaction is completed, immersing the cross-linked membrane in deionized water for multiple times to remove the quaternary ammonium agent remaining on the surface, and obtaining a negative ion X - Polynorbornene-based cross-linked anion exchange membrane (i.e., anions are X - of AEM).

[0084] According to the present invention, the quaternary ammonium agent includes but is not limited to trimethylamine solution and 1-methylpiperidine. The present invention does not specifically limit the concentration of the quaternary ammonium agent, and the conventional concentration in the art can be used.

[0085] According to the present invention, the preparation method of the polynorbornene-based cross-linked anion exchange membrane further comprises an ion replacement step: replacing the negative ion with X - AEM was immersed in NaHCO3 aqueous solution to prepare negative ions as HCO3 - The polynorbornene-based cross-linked anion exchange membrane, or the negative ion is X - The AEM was immersed in OH - The negative ion is OH in aqueous solution - Polynorbornene-based cross-linked anion exchange membrane.

[0086] Preferably, the OH - The aqueous solution is, for example, an aqueous NaOH solution or an aqueous KOH solution.

[0087] The present invention also provides the application of the polynorbornene-based cross-linked anion exchange membrane in the fields of fuel cells, water electrolysis, electrodialysis, acid recovery, etc.

[0088] Beneficial effects of the present invention:

[0089] (1) The present invention successfully synthesized polynorbornene copolymers, including addition-type polynorbornene and ring-opening type polynorbornene.

[0090] (2) In the present invention, polynorbornene and polythiol are cross-linked under the action of light initiation or heat initiation to prepare a cross-linked film.

[0091] (3) The present invention immerses the cross-linked membrane in a quaternizing agent for quaternization to obtain AEM.

[0092] (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.

[0093] Definition and explanation of terms

[0094] 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 1-6The 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.

[0095] The term "C 1-10 "Alkylene" refers to C 1-10 An alkyl group that loses one hydrogen.

[0096] 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 2-6 alkenyl), having 2 or 3 carbon atoms (i.e., C 2-3It 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.

[0097] 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 6-14 When 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

[0098] Figure 1 This is a flow chart for the preparation of addition-type polynorbornene.

[0099] Figure 2 This is a flow chart for the preparation of ring-opening polynorbornene.

[0100] Figure 3 It is a flow chart of the preparation of the ion exchange membrane of the present invention.

[0101] Figure 4 This is the appearance of the AEM prepared in Examples 12 and 14-15.

[0102] Figure 5-7 are respectively the polynorbornene in Examples 1-3 1 H NMR spectra.

[0103] Figure 8 This is the FT-IR graph of polynorbornene in Example 1.

[0104] Fig. 9 This is the FT-IR graph of the cross-linked film in Example 6.

[0105] Figure 10-11 They are the thermogravimetric analysis (TGA) graphs of AEM in Examples 11-12, respectively.

[0106] Fig.12 In Example 23, the negative ion is OH - Conductivity test diagram of AEM. DETAILED DESCRIPTION

[0107] 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.

[0108] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0109] Example 1

[0110]

[0111] This embodiment provides an addition copolymerization of BrNB and ENB, and the preparation method is as follows:

[0112] As shown in the above process, first, 0.01mmol Pd2(dba)3), 0.04mmol PCy3 and 0.04mmol LiFABA were dissolved in 4mL toluene and stirred at room temperature for 1h to prepare a catalyst solution. 2.4mmol BrNB and 1.6mmol ENB 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 under a nitrogen atmosphere at room temperature. After the reaction was completed, the mixture was precipitated in methanol, sonicated, and filtered to obtain a light yellow solid, which was vacuum dried.

[0113] Example 2

[0114]

[0115] This embodiment provides an addition copolymerization of BrNB and DCPD, and the preparation method is as follows:

[0116] As shown in the above process, first, 0.01mmol Pd2(dba)3), 0.04mmol PCy3 and 0.04mmol LiFABA were dissolved in 4mL toluene and stirred at room temperature for 1h to prepare a catalyst solution. 2.67mmol BrNB and 1.33mmol 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 under a nitrogen atmosphere 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.

[0117] Example 3

[0118]

[0119] This embodiment provides an addition copolymerization of BrNB and TCPD, and the preparation method is as follows:

[0120] As shown in the above process, first, 0.01mmol Pd2(dba)3), 0.04mmol PCy3 and 0.04mmol LiFABA were dissolved in 4mL toluene and stirred at room temperature for 1h to prepare a catalyst solution. 2.4mmol BrNB and 1.6mmol TCPD 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 under a nitrogen atmosphere. After the reaction was completed, the mixture was precipitated in methanol, ultrasonicated, and filtered to obtain a light yellow solid, which was then dried in vacuo.

[0121] Example 4

[0122]

[0123] This embodiment provides a ring-opening copolymerization of BrNB and DCPD, and the preparation method is as follows:

[0124] As shown in the above process, first, 0.001mmol of Grubbs II generation catalyst was dissolved in 1mL of toluene to prepare a catalyst solution. 2.67mmol of BrNB, 1.33mmol of DCPD, and 0.01mmol of 1-octene were dissolved in 40mL of cyclohexane to prepare a monomer solution. Then, the catalyst solution was added to the monomer solution, and the mixture was stirred at 50°C under a nitrogen atmosphere for 1h. After the reaction was completed, the mixture was poured into ethanol for precipitation, sonicated, and filtered to obtain a solid product, which was then vacuum dried.

[0125] Example 5

[0126]

[0127] This embodiment provides a ring-opening copolymerization of BrNB and TCPD, and the preparation method is as follows:

[0128] As shown in the above process, first, 0.001mmol of Grubbs II generation catalyst was dissolved in 1mL of toluene to prepare a catalyst solution. 2.67mmol of BrNB, 1.33mmol of TCPD, and 0.01mmol of 1-octene were dissolved in 40mL of cyclohexane to prepare a monomer solution. Then, the catalyst solution was added to the monomer solution, and the mixture was stirred at 50°C under a nitrogen atmosphere for 1h. After the reaction was completed, the mixture was poured into ethanol for precipitation, sonicated, and filtered to obtain a solid product, which was then dried in vacuo.

[0129] Example 6

[0130]

[0131] As shown in the above process, the cross-linked film is prepared using the polynorbornene in Example 1, and the preparation method is as follows:

[0132] The addition-type polynorbornene (0.8 mmol), 3,6-dioxa-1,8-octanedithiol (0.16 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 to obtain a crosslinked film.

[0133] Example 7

[0134]

[0135] As shown in the above process, the cross-linked film is prepared using the polynorbornene in Example 1, and the preparation method is as follows:

[0136] The addition-type polynorbornene (0.8 mmol), 1,6-hexanedithiol (0.16 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 to obtain a crosslinked film.

[0137] Example 8

[0138]

[0139] 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:

[0140] The addition-type polynorbornene (0.75 mmol), 1,6-hexanedithiol (0.125 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.01 mmol) prepared in Example 2 were dissolved in 5 mL of chloroform and stirred at room temperature until completely dissolved. The mixture solution was then poured into a mold and subjected to simultaneous cross-linking reaction and solvent volatilization under ultraviolet light irradiation conditions. The mixture was irradiated for 30 min and then dried again in a vacuum oven to obtain a cross-linked film.

[0141] Example 9

[0142]

[0143] As shown in the above process, the cross-linked film is prepared using the polynorbornene in Example 4, and the preparation method is as follows:

[0144] The ring-opening polynorbornene (0.75 mmol), 1,6-hexanedithiol (0.5 mmol) and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (0.01 mmol) prepared in Example 4 were dissolved in 5 mL of chloroform and stirred at room temperature until completely dissolved. The mixture solution was then poured into a mold and subjected to simultaneous cross-linking reaction and solvent volatilization under ultraviolet light irradiation conditions for 30 min. The mixture was then dried again in a vacuum oven to obtain a cross-linked film.

[0145] Example 10

[0146]

[0147] 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:

[0148] The addition-type polynorbornene (0.75 mmol), 1,6-hexanedithiol (0.125 mmol) and azobisisobutyronitrile (0.01 mmol) prepared in Example 2 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 heated to 70°C for thermal crosslinking reaction and solvent volatilization. The mixture was heated for 2 hours and then dried again in a vacuum oven to obtain a crosslinked film.

[0149] Examples 11-15

[0150] The cross-linked membranes obtained in Examples 6-10 were respectively immersed in a 35 wt% trimethylamine aqueous solution for quaternization, immersed at room temperature for 2 days, and then immersed in deionized water for multiple times to remove the residual trimethylamine on the surface to obtain anions of Br - AEM. Figure 4 This is the appearance of the AEM prepared in Examples 12, 14-15, from Figure 4 It can be seen that the surface of AEM is smooth and transparent, has good flexibility and can be bent.

[0151] Examples 16-20

[0152] Ion replacement: The anions in Examples 11-15 were replaced by Br - The AEM was immersed in NaHCO3 aqueous solution to prepare the negative ion HCO3 - AEM.

[0153] Examples 21-25

[0154] The negative ions in Examples 11-15 are Br - The AEM was immersed in NaOH aqueous solution to prepare the negative ions OH - AEM.

[0155] Test Case 26

[0156] The AEM prepared in Examples 16-20 and 21-25 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).

[0157]

[0158] In Example 16, the negative ion is HCO3 - The conductivity of AEM at room temperature is 10.2 mS / cm.

[0159] In Example 21, the negative ion is OH -The conductivity of AEM at 40°C is 107.5 mS / cm, and the conductivity at 90°C is 190.8 mS / cm.

[0160] In Example 17, the negative ion is HCO3 - The conductivity of AEM at room temperature is 10.1 mS / cm.

[0161] In Example 22, the negative ion is OH - The conductivity of AEM at 40°C is 112.1 mS / cm, and the conductivity at 90°C is 194.6 mS / cm.

[0162] In Example 18, the negative ion is HCO3 - The conductivity of AEM at room temperature is 14.2 mS / cm.

[0163] Fig.12 In Example 23, the negative ion is OH - The conductivity test diagram of AEM, in Example 23, the negative ion is OH - The conductivity of AEM is 119 mS / cm at 40°C and 213.9 mS / cm at 90°C.

[0164] 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. A polynorbornene, characterized in that: The polynorbornene is obtained by copolymerizing monomer 1 and monomer 2. Wherein, monomer 1 has a structure as shown in the following formula (1); Monomer 2 has one of the structures shown in the following formula (2), formula (3) or formula (4): In formula (1), R1 is -C 1-10 Alkylene-X; X is halogen; R2 is selected from H, C 1-10 Alkyl, C 1-10 Alkylene-X, C 6-14 Aryl, C 2-10 A type of alkenyl. In formula (2), R3 is C 2-10 Alkenyl, R4 is selected from H, C 1-10 Alkyl, C 6-14 Aryl, C 2-10 A type of alkenyl.

2. The polynorbornene according to claim 1, characterized in that The X is Cl, Br or I.

3. The polynorbornene according to claim 1, characterized in that R1 is -C 1-6 Alkylene-X.

4. The polynorbornene according to claim 1, characterized in that R2 is selected from H, C 1-6 Alkyl, C 1-6 Alkylene-X, C 6-14 Aryl, C 2-6 A type of alkenyl.

5. The polynorbornene according to claim 1, characterized in that R3 is C 2-6 Alkenyl.

6. The polynorbornene according to claim 1, characterized in that R4 is selected from H, C 1-6 Alkyl, C 6-14 Aryl, C 2-6 A type of alkenyl.

7. The polynorbornene according to claim 1, characterized in that The molar ratio of monomer 1 to monomer 2 is 10:1 to 1:10; The polynorbornene is an addition-type polynorbornene or a ring-opening type polynorbornene.

8. The polynorbornene according to claim 1, characterized in that The polynorbornene has one of the following structural formulas: Wherein, n and m are the molar contents of monomer 1 and monomer 2, respectively.

9. The method for preparing polynorbornene according to any one of claims 1 to 8, characterized in that: The preparation of the polynorbornene includes the preparation of addition-type polynorbornene and ring-opening-type polynorbornene; The preparation method of the addition type polynorbornene comprises: The monomer 1 and the monomer 2 are dissolved in a solvent to prepare a monomer solution, the first catalyst and its auxiliary agent are dissolved in a solvent to prepare a catalyst solution, and then the catalyst solution is added to the monomer solution to carry out a polymerization reaction to prepare the addition-type polynorbornene; Alternatively, the preparation method of the ring-opening polynorbornene comprises: The monomer 1, the monomer 2 and the chain transfer agent are dissolved in a solvent to prepare a monomer solution, the second catalyst is dissolved in a solvent to prepare a catalyst solution, and then the catalyst solution is added to the monomer solution to carry out a polymerization reaction to prepare the ring-opening polynorbornene.

10. The preparation method according to claim 9, characterized in that: The first catalyst is a Pd catalyst or a Ni catalyst.

11. The preparation method according to claim 10, characterized in that: The first catalyst is selected from at least one of tris(dibenzylideneacetone)dipalladium, palladium acetate, and di(triphenylantimony)di(pentafluorophenyl)nickel.

12. The preparation method according to claim 9, characterized in that: The auxiliary agent includes at least one of a stabilizer and an auxiliary catalyst for the first catalyst.

13. The preparation method according to claim 9, characterized in that: The stabilizer of the first catalyst is tricyclohexylphosphine; The co-catalyst is selected from lithium tetrakis(pentafluorophenyl)borate-ethyl ether complex or sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

14. The preparation method according to claim 9, characterized in that: The total molar ratio of the first catalyst to monomer 1 and monomer 2 is 1:100 to 1:500; The second catalyst is a Ru catalyst or a W catalyst.

15. The preparation method according to claim 14, characterized in that: The second catalyst is selected from at least one of Grubbs I generation catalyst, Grubbs II generation catalyst, Grubbs III generation catalyst, Hoveyda-Grubbs II generation catalyst, and WCl6.

16. The preparation method according to claim 9, characterized in that: 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, and 4-octene.

17. The preparation method according to claim 9, characterized in that: The molar ratio of the chain transfer agent to the total amount of monomer 1 and monomer 2 is 1:100 to 1:1000; The molar ratio of the second catalyst to the chain transfer agent is 1:1 to 1:1000.

18. A cross-linked film, characterized in that: The cross-linked film is prepared by using the polynorbornene described in any one of claims 1 to 8.

19. The method for preparing a cross-linked film according to claim 18, characterized in that: The method comprises preparing a cross-linked film by light initiation and preparing a cross-linked film by heat initiation: The method for preparing a cross-linked film by photoinitiation comprises: The polynorbornene, polythiol and photoinitiator are mixed in an organic solvent, and irradiated with ultraviolet light to obtain the cross-linked film; Alternatively, the method for preparing a cross-linked film by thermal initiation comprises: The polynorbornene, polythiol and thermal initiator are mixed in an organic solvent, and the cross-linking is carried out while the solvent is volatilized under heating conditions to obtain the cross-linked film.

20. A polynorbornene-based cross-linked anion exchange membrane, characterized in that: The polynorbornene-based cross-linked anion exchange membrane is prepared by the cross-linked membrane according to claim 18.

21. The method for preparing the polynorbornene-based cross-linked anion exchange membrane according to claim 20, characterized in that: The method comprises: The cross-linked membrane is immersed in a quaternizing agent for quaternization to obtain a negative ion X - Polynorbornene-based cross-linked anion exchange membrane; Wherein, X has the above meaning.

22. The method for preparing a cross-linked film according to claim 21, characterized in that: The preparation method of the polynorbornene-based cross-linked anion exchange membrane further comprises an ion replacement step: replacing the negative ion with X - AEM was immersed in NaHCO3 aqueous solution to prepare negative ions as HCO3 - The polynorbornene-based cross-linked anion exchange membrane, or the negative ion is X - The AEM was immersed in OH - The negative ion is OH in the aqueous solution - Polynorbornene-based cross-linked anion exchange membrane.

23. Use of the polynorbornene-based cross-linked anion exchange membrane according to claim 20 in the fields of fuel cells, water electrolysis, electrodialysis or acid recovery.

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