Method for preparing functionalized addition norbornene polymer through precipitation polymerization and application of functionalized addition norbornene polymer

Abstract

The invention discloses a method for preparing a functionalized addition norbornene polymer through precipitation polymerization and application of the functionalized addition norbornene polymer through precipitation polymerization. Alkane is used as a reaction solvent, so that a norbornene derivative monomer can be well dissolved, and a transition metal catalyst and a cocatalyst also have certain solubility; and the functionalized polynorbornene product obtained by precipitation polymerization can be separated out in the reaction process to form a precipitate. After the precipitation polymerization reaction is finished, other solvents do not need to be added into the reaction system, and the reaction system is directly filtered and collected, so that unreacted monomers and solvents can be directly recycled for the polymerization reaction of the next batch. The functionalized addition polynorbornene obtained by precipitation polymerization can be further processed and functionalized so as to be applied to the field of ion exchange membranes and / or ionomers. The precipitation polymerization method provided by the invention is suitable for large-scale production of polynorbornene, and the solvent use, recovery and separation cost can be remarkably reduced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of functional polymer synthesis, and particularly relates to a method for preparing a functionalized addition norbornene polymer by precipitation polymerization and application. BACKGROUND

[0002] Hydrogen energy is considered as the most potential secondary energy to achieve the "double carbon" goal due to its zero emission, high heat value and renewable cycle. However, to make hydrogen energy "green", the key lies in the electrolysis of water to produce hydrogen by renewable energy, which only consumes water and electricity, and the product is only hydrogen and oxygen, thereby eliminating carbon emissions from fossil fuels at the source. Among the many water electrolysis methods, anion exchange membrane (AEM) water electrolysis technology combines the low cost of alkaline water electrolysis and the high efficiency of PEM water electrolysis: by using a solid-state anion exchange membrane instead of traditional liquid electrolyte, the system can operate stably at a high current density of 1-3 A cm -2 at a lower voltage of 1.8-2.2 V, with fast dynamic response, coupling wind and light fluctuation power sources, and no need for noble metal plating to avoid corrosion, thereby reducing both equipment investment and operation and maintenance costs. As the core component of the electrolytic cell, the stability of AEM has become a key challenge to the further promotion of AEM water electrolysis technology.

[0003] Norbornene and its derivatives contain a [2.2.1] bridged ring structure, and the ring internal olefin has very high reactivity, so it can be used for ring-opening metathesis polymerization and addition polymerization to prepare various functionalized polyolefin materials. The poly-norbornene main chain obtained by ring-opening metathesis polymerization contains double bonds, which is chemically unstable and often requires additional reduction and hydrogenation steps, thereby limiting its application and development. The poly-norbornene obtained by addition polymerization contains a saturated main chain structure, which retains the [2.2.1] bridged ring structure, and has stable chemical properties and high glass transition temperature, so it has been widely used in many fields in recent years. For example, the addition copolymer of norbornene and ethylene is a common cyclic olefin copolymer (COC), which is mainly used in medical packaging and optical resin fields; in addition, homopolymers and copolymers of norbornene derivatives are also used in gas separation membranes, ion exchange membranes and other fields. Its stable all-carbon skeleton and high glass transition temperature also make it one of the most stable AEM polymer skeletons.

[0004] Addition polymerization of norbornene derivatives is usually prepared by solution polymerization with transition metal catalysts (such as titanium, zirconium, hafnium, palladium, nickel, etc. are most common) and co-catalysts. Solution polymerization is a homogeneous polymerization process in which monomers, catalysts, and polymers are all soluble in the solvent during polymerization. The advantage of solution polymerization is that the polymerization mechanism is clear and the polymer structure is accurately controlled. However, in large-scale industrial production, on the one hand, the use of solvents significantly increases the cost of raw materials, and on the other hand, in order to separate the polymerization product from the solvent, a poor solvent is often added to precipitate the polymerization product, and the presence of mixed solvents further limits the recovery and reuse of solvents. For example, in order to ensure good solubility of each raw material component, the preparation of COC is carried out in toluene or halogen-containing solvents by solution polymerization of ethylene and norbornene in the literature and patents disclosed at home and abroad. For example, the patent document with application number CN 117229451 A discloses a process for preparing an ion exchange membrane from addition polymerized norbornene, in which toluene is selected as the solvent for the copolymerization of halogen-containing norbornene and other norbornene derivatives. However, alcohol solvents such as ethanol need to be added after such polymerization, which will waste a large amount of solvent and significantly increase the preparation cost.

[0005] In addition to solution polymerization, bulk polymerization, emulsion polymerization, and precipitation polymerization are also common means of polymerization. However, bulk polymerization is not conducive to the transfer of reaction heat, and the polymerization process is difficult to control, so it cannot be applied to the addition polymerization process of highly exothermic norbornene. A method for emulsion polymerization of norbornene is disclosed in the literature (Macromolecules 2007, 40, 8947-8953), although the polymerization reaction is carried out in water, a large amount of emulsifier needs to be introduced during the process, thus increasing the cost of polymer purification. Precipitation polymerization refers to a process in which the monomer is dissolved in the solvent, and the polymerization product is gradually precipitated from the solvent as the reaction proceeds. The main advantage of precipitation polymerization is that the polymer can be separated and purified from the system by simple solid-liquid separation methods (filtration or centrifugation), but the main problem is that the structure of the polymer product is not easy to control, and it is also easy to form completely insoluble polymer products, thus making it impossible to be further processed and applied. For example, a method for addition precipitation polymerization of norbornene is reported in the literature (Macromolecules 2008, 41, 2445-2450), which uses norbornene without substituents that precipitates from the reaction due to poor solubility during polymerization. However, due to the fact that poly-norbornene without substituents is almost insoluble in any solvent and has a very high melting point (> 350°C), the product obtained by precipitation polymerization is almost impossible to be further processed and applied. SUMMARY

[0006] To improve the above technical problems, the present application provides a method for preparing functionalized addition norbornene polymer by precipitation polymerization, which uses alkane as a reaction solvent, so that norbornene derivative monomers can be well dissolved, and transition metal catalysts and co-catalysts also have a certain solubility, and the functionalized poly-norbornene product obtained by precipitation polymerization can be precipitated during the reaction process. After the precipitation polymerization reaction of the present application ends, no other solvent needs to be added to the reaction system, but direct filtration collection is performed, so that the unreacted monomers and solvents can be directly recycled for the next batch of polymerization reaction. The functionalized addition poly-norbornene obtained by the precipitation polymerization of the present application is not soluble in alkane solvents, but can be well dissolved in halogen-containing solvents, toluene and other solvents, so that it can be further processed and functionalized for application in the field of ion exchange membranes and / or ionomers. The precipitation polymerization method of the present application is suitable for large-scale production of poly-norbornene, which can significantly reduce the cost of solvent use, recovery and separation.

[0007] The technical solution of the present application is as follows:

[0008] A method for preparing poly-norbornene, comprising preparing the poly-norbornene by precipitation polymerization of monomer 1 and monomer 2 in an alkane solvent,

[0009] wherein the monomer 1 has the structure shown in the following formula (1);

[0010]

[0011] The monomer 2 has one of the structures shown in the following formula (2), formula (3) or formula (4):

[0012]

[0013] In formula (1), R1 is selected from one of C 1-10 alkyl, C 1-10 alkylene-X, C 2-10 alkenyl; X is halogen;

[0014] R2 is selected from one of H, C 1-10 alkyl, C 1-10 alkylene-X', C 6-14 aryl, C 2-10 alkenyl; X' is halogen.

[0015] According to the present application, the precipitation polymerization is carried out in the presence of transition metal catalysts, ligands and co-catalysts.

[0016] According to the present application, the molar ratio of the transition metal catalysts, ligands and co-catalysts is 1:1:(1-10), for example, 1:1:5.

[0017] As preferred, the total mole ratio of the transition metal catalyst to monomer 1 and monomer 2 is 1:100-1:5000, more preferably 1:1000-1:3000.

[0018] According to the present application, the precipitation polymerization can be homopolymerization or copolymerization.

[0019] According to the present application, the alkane solvent is saturated alkane or cyclic alkane solvent, including but not limited to at least one of n-pentane and its isomers, n-hexane and its isomers, n-heptane and its isomers, n-octane and its isomers, n-decane and its isomers, n-dodecane and its isomers, n-tetradecane and its isomers, cyclohexane, methylcyclohexane, etc.

[0020] According to the present application, the volume ratio of the total moles of monomer 1 and monomer 2 to the alkane solvent is 0.1-3 mmol / mL, more preferably 1-2 mmol / mL.

[0021] According to the present application, the mole ratio of monomer 1 to monomer 2 is 10:0-1:9, preferably (1-8):1.

[0022] According to the present application, the mole content of monomer 1 in the polymerization product can be regulated between 10%-100%. According to the present application, the transition metal catalyst includes but is not limited to at least one of Pd catalyst or Ni catalyst (such as palladium chloride, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, palladium acetate, allylpalladium chloride dimer, (1,5-cyclooctadiene)palladium dichloride, chloro(1,5-cyclooctadiene)methylpalladium, nickel chloride, nickel bromide, bis(1,5-cyclooctadiene)nickel, and bis(triphenylstibine)bis(pentafluorophenyl)nickel, etc.).

[0023] According to the present application, the ligand includes but is not limited to phosphine ligand (such as triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, triadamantylphosphine, trimethylphosphine, etc.) and N-heterocyclic carbene (NHC) ligand (such as at least one of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidine and 1,3-bis(2,6-diisopropylphenyl)imidazoline-2-ylidene, etc.).

[0024] According to the present application, the transition metal catalyst, ligand can be added into the reaction system in the form of solution (for example, dissolving the above-mentioned transition metal catalyst and ligand in a solvent to obtain a mixed solution; the solvent is for example selected from at least one of the above-mentioned alkane solvent and halogen-containing solvent (for example, at least one of dichloromethane, trichloromethane, trichloroethane, and chlorobenzene, etc.)) or by synthesizing the corresponding complex of the transition metal catalyst and the ligand after purification and then adding into the reaction system.

[0025] According to the present application, the co-catalyst includes but is not limited to at least one of boron-containing co-agents (such as tris(pentafluorophenyl)boron, lithium tetra(pentafluorophenyl)borate-ethyl ether complex, sodium tetra(3,5-di(trifluoromethyl)phenyl)borate, potassium tetra(3,5-di(trifluoromethyl)phenyl)borate and phenyldimethylammonium tetra(3,5-di(trifluoromethyl)phenyl)borate, etc.

[0026] According to the present application, the X is Cl, Br or I.

[0027] According to the present application, the X' is Cl, Br or I.

[0028] According to the present application, R1 is selected from one of C 1-10 alkyl, C 1-10 alkylene-X, C 2-10 alkenyl, more preferably C 1-6 alkyl, C 1-6 alkylene-X.

[0029] According to the present application, R2 is selected from one of H, C 1-6 alkyl, C 1-6 alkylene-X', C 6-14 aryl, C 2-6 alkenyl, more preferably H.

[0030] According to the present application, the precipitation polymerization reaction is carried out under anhydrous and anaerobic conditions.

[0031] As a preference, the polymerization reaction time according to the present application is 2h-24h, more preferably 4h-12h.

[0032] As a preference, the polymerization reaction temperature according to the present application is 20-100℃, more preferably 40-70℃.

[0033] According to the present application, the method for preparing the polynorbornene comprises:

[0034] Under anhydrous and anaerobic conditions, monomer 1 and monomer 2 are dissolved in an alkane solvent to prepare a monomer solution, while a co-agent is added thereto, then a solution of transition metal catalyst and ligand is added to the monomer solution to carry out a precipitation polymerization reaction, and a precipitate is formed during the reaction, and the precipitate is collected to obtain the polynorbornene.

[0035] In the present application, the product obtained by the precipitation polymerization does not need to be subjected to a settling or washing operation by adding other solvents.

[0036] The present application further provides a polynorbornene prepared by the above preparation method, which has one of the following structural formulae:

[0037]

[0038] wherein n and m are the molar content of monomer 1 and monomer 2, respectively.

[0039] As an exemplary embodiment of the present application, the polynorbornene has one of the following structural formulas:

[0040]

[0041] wherein n and m are the molar content of monomer 1 and monomer 2, respectively.

[0042] The functionalized polynorbornene prepared by the precipitation polymerization of the present application can be dissolved in other organic solvents except alkanes, and thus can be used to prepare high-performance ion exchange membranes.

[0043] The present application also provides a crosslinked membrane prepared from the polynorbornene described above.

[0044] The present application also provides a method for preparing a crosslinked membrane, which comprises a photo-initiated method for preparing a crosslinked membrane and a thermal-initiated method for preparing a crosslinked membrane.

[0045] The photo-initiated method for preparing a crosslinked membrane comprises:

[0046] The polynorbornene, the polythiol and the photo-initiator are mixed in an organic solvent, and the crosslinked membrane is obtained after UV irradiation.

[0047] Alternatively, the thermal-initiated method for preparing a crosslinked membrane comprises:

[0048] The polynorbornene, the polythiol and the thermal initiator are mixed in an organic solvent, and the crosslinked membrane is obtained under heating conditions with the solvent volatilizing.

[0049] Illustratively, the photo-initiated method for preparing a crosslinked membrane comprises: dissolving the polynorbornene, the polythiol and the photo-initiator in an organic solvent, stirring at room temperature until complete dissolution, then pouring the obtained mixture solution into a mold, and performing crosslinking reaction and solvent volatilization under UV irradiation conditions, and obtaining the crosslinked membrane after irradiation. Preferably, the crosslinked membrane is dried again in a vacuum oven to ensure complete volatilization of the solvent.

[0050] Illustratively, the thermal-initiated method for preparing a crosslinked membrane comprises: dissolving the polynorbornene, the polythiol and the thermal initiator in an organic solvent, stirring at room temperature until complete dissolution, then pouring the obtained mixture solution into a mold, and performing crosslinking reaction and solvent volatilization under heating conditions, and obtaining the crosslinked membrane after complete volatilization of the solvent.

[0051] The film-forming method of the present application includes but is not limited to solution casting, spin coating, blade coating or casting.

[0052] According to the present application, the polythiol is selected from at least one of the following compounds:

[0053]

[0054] wherein b is an integer from 0 to 10.

[0055] According to the present application, the photoinitiator is a conventional reagent in the art, for example, phenyl (2,4,6-trimethylbenzoyl) phosphine oxide.

[0056] According to the present application, the thermal initiator is a conventional reagent in the art, for example, azobisisobutyronitrile.

[0057] According to the present application, the organic solvent includes, but is not limited to, chloroform, dichloromethane and tetrahydrofuran.

[0058] According to the present application, the ratio of the molar amount of double bond in the polynorbornene to the molar amount of mercapto group in the polythiol is 1:0.5 to 1:1.5, more preferably 1:0.8 to 1:1.2.

[0059] According to the present application, the content of the total mass of polynorbornene, polythiol and photoinitiator in the solvent is 20 g / mL to 60 g / mL, more preferably 30 g / mL to 40 g / mL.

[0060] According to the present application, the content of the total mass of 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.

[0061] According to the present application, the ultraviolet light irradiation can use an ultraviolet lamp.

[0062] According to the present application, the time of light irradiation (or heating) is 5 min to 240 min, more preferably 30 min to 60 min.

[0063] The present application also provides an anion exchange membrane prepared by the crosslinked membrane described above.

[0064] The present application also provides a preparation method of an anion exchange membrane, which comprises: quaternizing the crosslinked membrane in a quaternization reagent to obtain an anion exchange membrane with negative ions X - ;

[0065] wherein X has the meaning as above.

[0066] According to the present application, the method comprises: quaternizing the crosslinked membrane in a quaternization reagent, and after the reaction is completed, soaking in deionized water for multiple times to remove the residual quaternization reagent on the surface, thereby obtaining an anion exchange membrane with negative ions X- anion exchange membrane (i.e. negative ion is X - AEM).

[0067] According to the present application, the quaternary ammonium reagent includes but is not limited to trimethylamine solution and 1-methylpiperidine. The present application does not particularly limit the concentration of the quaternary ammonium reagent, and the conventional concentration in the art can be used.

[0068] According to the present application, the preparation method of the anion exchange membrane further comprises an ion replacement step: soaking the AEM with negative ion X - in an aqueous NaHCO3 solution to prepare a polynorbornene-based cross-linked anion exchange membrane with negative ion HCO3 - or soaking the AEM with negative ion X - in an aqueous solution containing OH - to prepare a polynorbornene-based cross-linked anion exchange membrane with negative ion OH - .

[0069] Preferably, the aqueous solution containing OH - is, for example, an aqueous NaOH solution or an aqueous KOH solution.

[0070] The present application also provides the use of the above-mentioned anion exchange membrane in the fields of fuel cells, water electrolysis, electrodialysis, acid recovery, etc.

[0071] The present application also provides the use of the above-mentioned polynorbornene in the preparation of ionomers.

[0072] The present application also provides an ionomer prepared from the above-mentioned polynorbornene.

[0073] The present application also provides a preparation method of the above-mentioned ionomer, comprising the following steps: soaking the polynorbornene in an aqueous solution of tertiary amine to perform a quaternary ammonium reaction to obtain the ionomer.

[0074] According to the present application, the preparation method specifically comprises the following steps: soaking the polynorbornene in an aqueous solution of tertiary amine to perform a quaternary ammonium reaction, and removing low-boiling-point residual amine and water by vacuum distillation after the quaternary ammonium reaction to obtain the ionomer.

[0075] According to the present application, the preparation method further specifically comprises the following steps:

[0076] Soaking the above-mentioned polynorbornene in an aqueous solution of tertiary amine, gradually dissolving the product in the aqueous amine solution after the quaternary ammonium reaction, and reacting until the addition copolymer is completely dissolved to obtain a clear and transparent solution; and removing low-boiling-point residual amine and water by vacuum distillation after the reaction to obtain the ionomer.

[0077] The application also provides application of the ionomer in preparation of membrane electrode in the fields of fuel cell and water electrolysis.

[0078] The application also provides a catalytic slurry comprising the ionomer.

[0079] According to the application, the catalytic slurry further comprises a catalyst and a solvent.

[0080] According to the application, the mass ratio of the catalyst and the ionomer is 20:1-1:1, preferably 15:1-5:1.

[0081] According to the application, the concentration of the catalyst is 0.1wt%-5wt%, preferably 0.5wt%-1wt%.

[0082] According to the application, the catalyst comprises at least one of NiFe, NiFeCo, Pt / C, PtRu / C, Pt, Pd, Ir, IrO2 and Ru.

[0083] The application also provides a membrane electrode prepared from the catalytic slurry.

[0084] According to the application, the membrane electrode is prepared by spraying the catalytic slurry on a gas diffusion layer and combining an ion exchange membrane. After spraying, the total loading amount of the catalyst and the ionomer is determined by weighing. For example, the total loading amount of the catalyst and the ionomer is 0.5-5mg / cm 2 , preferably 1-3mg / cm 2 .

[0085] According to the application, the gas diffusion layer comprises at least one of carbon paper, carbon felt, porous stainless steel mesh, nickel mesh, nickel felt and nickel foam.

[0086] According to the application, the ion exchange membrane is a membrane material capable of selectively transmitting ions.

[0087] The application also provides an electrolytic cell comprising the membrane electrode.

[0088] The application has the following advantages:

[0089] (1) The application successfully synthesizes a functionalized addition-type polynorbornene-based polymer by performing precipitation polymerization in an alkane solvent.

[0090] (2) The precipitation polymerization reaction of the application only needs simple filtration to obtain the target polynorbornene-based polymer after the reaction is completed, without the need for adding a poor solvent and other sedimentation operations. The synthesis method of the application is simple and easy to operate, significantly reduces the cost, and is suitable for large-scale production of polynorbornene.

[0091] (3) The functionalized poly (norbornene) prepared by the precipitation polymerization of the present application can still be dissolved in other types of solvents, and thus can be further processed and used in the field of high-performance ion exchange membranes, etc. BRIEF DESCRIPTION OF DRAWINGS

[0092] Figure 1 The precipitation polymerization process in Example 3.

[0093] Figure 2 The nuclear magnetic resonance spectrum of the copolymer product in Example 3.

[0094] Figure 3 The gel permeation chromatogram of the copolymer product in Example 3.

[0095] Figure 4 The gel permeation chromatogram of the copolymer product in Example 11.

[0096] Figure 5 The comparison between the powder product of the precipitation polymerization (left) and the sheet product after solution polymerization (right).

[0097] Figure 6 The product appearance of the crosslinked ion exchange membrane prepared using the precipitation polymerization product as the raw material in Example 16.

[0098] Figure 7 The polarization curve of the electrolytic cell assembled in Example 17. DETAILED DESCRIPTION

[0099] The technical solutions of the present application will be further described in detail below in combination with specific examples. It should be understood that the following examples are only illustrative and explanatory of the present application, and should not be interpreted as limiting the scope of protection of the present application. Any technology realized based on the above description of the present application is covered within the scope of protection intended by the present application.

[0100] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0101] Example 1

[0102]

[0103] This example provides the precipitation polymerization homopolymerization of butyl-substituted norbornene (HNB), and the preparation method is as follows:

[0104] First, 30 mmol of HNB monomer and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, and 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane were added to the solution at 60°C. White solid gradually precipitated as the reaction proceeded. When the precipitation stopped increasing (about 8 hours), the solid was collected by suction filtration, and the obtained solid was washed with n-hexane to directly obtain the target product 2.2 g.

[0105] Example 2

[0106]

[0107] This example provides precipitation polymerization homopolymerization of bromopropyl-substituted norbornene (BrNB) as follows:

[0108] First, 30 mmol of BrNB monomer and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex (CAS No. 155543-02-5) were dispersed in 15 mL of n-hexane, and 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane were added to the solution at 60°C. White solid gradually precipitated as the reaction proceeded. When the precipitation stopped increasing (about 8 hours), the solid was collected by suction filtration, and the obtained solid was washed with n-hexane to directly obtain the target product 3.5 g.

[0109] Example 3

[0110]

[0111] This example provides precipitation polymerization copolymerization of BrNB and vinyl norbornene (VNB) as follows:

[0112] First, 15 mmol of BrNB monomer, 15 mmol of VNB, and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, and 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane were added to the solution at 60°C. White solid gradually precipitated as the reaction proceeded. When the precipitation stopped increasing (about 8 hours), the solid was collected by suction filtration, and the obtained solid was washed with n-hexane to directly obtain the target product 2.8 g.

[0113] Example 4

[0114]

[0115] This example provides a precipitation polymerization copolymerization of BrNB and DCPD, the preparation method is as follows:

[0116] Firstly, 15 mmol of BrNB monomer, 15 mmol of DCPD and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, and a mixed solution of 0.012 mmol of chloro(1,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane was added to the solution at 60°C, and white solid gradually precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, and the obtained solid was washed with n-hexane to directly obtain the target product 2.7 g.

[0117] Example 5

[0118] Similar to Example 3, firstly, 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of heptane, and a mixed solution of 0.012 mmol of chloro(1,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of heptane was added to the solution at 60°C, and white solid gradually precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, and the obtained solid was washed with n-hexane to directly obtain the target product 2.8 g.

[0119] Example 6

[0120] Similar to Example 3, firstly, 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of octane, and a mixed solution of 0.012 mmol of chloro(1,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of octane was added to the solution at 60°C, and white solid gradually precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, and the obtained solid was washed with n-hexane to directly obtain the target product 2.7 g.

[0121] Example 7

[0122] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane mixture at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation did not increase anymore (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, the target product was obtained directly 2.2 g.

[0123] Example 8

[0124] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of sodium tetra(3,5-di(trifluoromethyl)phenyl)borate were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane mixture at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation did not increase anymore (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, the target product was obtained directly 1.3 g.

[0125] Example 9

[0126] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of potassium tetra(pentafluorophenyl)borate were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of triphenylphosphine in 2 mL of n-hexane mixture at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation did not increase anymore (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, the target product was obtained directly 0.8 g.

[0127] Example 10

[0128] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of tricyclohexylphosphine in 2 mL of n-hexane mixture at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation did not increase anymore (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, the target product was obtained directly 2.7 g.

[0129] Example 11

[0130] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of tri-tert-butylphosphine in 2 mL of n-hexane mixture solution at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, directly obtained the target product 2.7 g.

[0131] Example 12

[0132] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of tri-tert-butylphosphine in 2 mL of n-hexane mixture solution at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, directly obtained the target product 2.7 g.

[0133] Example 13

[0134] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of tri-tert-butylphosphine in 2 mL of n-hexane mixture solution at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, directly obtained the target product 2.7 g.

[0135] Example 14

[0136] Similar to Example 3, first 15 mmol of BrNB monomer, 15 mmol of VNB and 0.03 mmol of lithium tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL of n-hexane, to the solution was added 0.012 mmol of chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol of tri-tert-butylphosphine in 2 mL of n-hexane mixture solution at 60 °C, gradually white solid precipitated as the reaction proceeded. When the precipitation no longer increased (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, directly obtained the target product 2.7 g.

[0137] Example 15

[0138] Example 3 was scaled up: first 300 mmol BrNB monomer, 300 mmol VNB and 0.6 mmol lithium-tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 300 mL n-hexane, to the solution was added 0.24 mmol chloro(l,5-cyclooctadiene)methyl palladium and 0.24 mmol triphenylphosphine in 40 mL n-hexane at 60 °C, as the reaction proceeded white solid precipitated gradually. When the precipitation did not increase anymore (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, the target product was obtained directly 56.1 g.

[0139] Comparative Example 1

[0140] Similar to Example 3, first 15 mmol BrNB monomer, 15 mmol VNB and 0.03 mmol lithium-tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL toluene, to the solution was added 0.012 mmol chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol triphenylphosphine in 2 mL toluene at 60 °C, as the reaction proceeded the color gradually darkened and the solution gradually became viscous. After the reaction was allowed to proceed for 8 hours, the reaction was cooled to room temperature, 200 mL anhydrous ethanol was added to the reaction to precipitate, flaky solid was obtained, the obtained solid was collected by filtration and washed with ethanol, the target product was obtained after vacuum suction dry 4.4 g.

[0141] Comparative Example 2

[0142]

[0143] This example provides the precipitation polymerization of homopolymerization of dicyclopentadiene (DCPD), the preparation method is as follows:

[0144] First 30 mmol DCPD monomer and 0.03 mmol lithium-tetra(pentafluorophenyl)borate-ethyl ether complex were dispersed in 15 mL n-hexane, to the solution was added 0.012 mmol chloro(l,5-cyclooctadiene)methyl palladium and 0.012 mmol triphenylphosphine in 2 mL n-hexane at 60 °C, as the reaction proceeded white solid precipitated gradually. When the precipitation did not increase anymore (about 8 hours), the solid was collected by suction filtration, the obtained solid was washed by n-hexane, the target product was obtained directly 2.8 g.

[0145] Test Example 1

[0146] The solubility of the samples in Examples 1 to 15 and Comparative Examples 1 and 2 in tetrahydrofuran at room temperature (whether they can be completely dissolved at a concentration of 1 mg / mL) was determined, and the samples that could be dissolved were subjected to gel permeation chromatography for molecular weight analysis to analyze the molecular weight (instrument: Agilent 1260 Infinity II, tetrahydrofuran mobile phase, 40°C, flow rate: 0.3 mL / min, differential detector, polystyrene standard as molecular weight reference).

[0147]

[0148] Example 16

[0149]

[0150] As shown in the above scheme, an ion exchange membrane was prepared using the poly(norbornene) copolymer powder prepared in Example 3, and the preparation method was as follows:

[0151] The addition-type poly(norbornene) prepared in Example 3 (0.8 mmol) and 3,6-dioxa-1,8-octanedithiol (0.16 mmol) and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (0.01 mmol) were dissolved in 5 mL of chloroform, and stirred at room temperature until completely dissolved. Then, the mixture solution was poured into a mold, and crosslinking reaction and solvent evaporation were simultaneously performed under ultraviolet lamp irradiation. Irradiation was performed for 30 min, and then the crosslinked membrane was dried again in a vacuum oven to obtain a crosslinked membrane.

[0152] The obtained crosslinked membrane was immersed in a 35 wt% aqueous trimethylamine solution for quaternization, and after immersion at room temperature for 2 days, it was immersed in deionized water several times to remove the residual trimethylamine on the surface to obtain an AEM having Br - as the negative ion. The AEM was immersed in an aqueous NaHCO3 solution to obtain an AEM having HCO3 - as the negative ion.

[0153] Figure 6 A photograph of the appearance of the AEM prepared in this example.

[0154] Comparative Example 3

[0155] As shown in the above scheme, an ion exchange membrane was prepared using the poly(norbornene) copolymer prepared in Comparative Example 1, and the preparation method was as follows:

[0156] The addition type poly-norbornene (0.8 mmol) prepared in Comparative Example 1 and 3,6-dioxa-1,8-octanedithiol (0.16 mmol) and phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide (0.01 mmol) were dissolved in 5 mL of chloroform, stirred at room temperature until completely dissolved, and then the mixture solution was poured into a mold, and crosslinking reaction and solvent evaporation were simultaneously performed under UV irradiation. After irradiation for 30 min, the crosslinked membrane was dried again in a vacuum oven to obtain a crosslinked membrane.

[0157] The obtained crosslinked membrane was immersed in a 35 wt% aqueous trimethylamine solution to perform quaternization, and after immersion at room temperature for 2 days, the surface residual trimethylamine was removed by immersing in deionized water several times to obtain an AEM having Br - as a negative ion. The AEM was immersed in an aqueous NaHCO3 solution to obtain an AEM having HCO3 - as a negative ion.

[0158] Test Example 2

[0159] The AEMs prepared in Example 16 and Comparative Example 3 were subjected to conductivity tests. Specifically, the conductivity was measured using electrochemical impedance spectroscopy to measure the resistance of the membrane, and then the AEM conductivity was calculated using Equation (1).

[0160]

[0161] The AEM having HCO3 - as a negative ion in Example 16 had a conductivity of 15.6 mS / cm at room temperature.

[0162] The AEM having Br - as a negative ion in Example 16 was immersed in an aqueous NaOH solution of 1 mol / L to replace it with an AEM having OH - as a negative ion, and had a conductivity of 109.2 mS / cm at 40℃ and a conductivity of 205.8 mS / cm at 90℃.

[0163] The AEM having HCO3 - as a negative ion in Comparative Example 3 had a conductivity of 10.4 mS / cm at room temperature.

[0164] The AEM having Br - as a negative ion in Comparative Example 3 was immersed in an aqueous NaOH solution of 1 mol / L to replace it with an AEM having OH - as a negative ion, and had a conductivity of 99.5 mS / cm at 40℃ and a conductivity of 188.1 mS / cm at 90℃.

[0165] Example 17

[0166]

[0167] The present example provides the quaternization of the addition polynorbornene copolymer powder obtained by precipitation polymerization, and the preparation method is as follows:

[0168] As shown in the above flow, the addition polynorbornene copolymer in Example 3 was soaked in an aqueous trimethylamine solution (30 wt%) at room temperature for 48 hours. As the quaternization reaction proceeded, the product gradually dissolved in the aqueous trimethylamine solution after being formed. The reaction was continued until the addition polynorbornene copolymer was completely dissolved to obtain a clear and transparent solution. After the reaction was completed, the trimethylamine was removed by rotary evaporation at 40°C, and then the water was removed by vacuum drying at 60°C to obtain the ionomer.

[0169] A membrane electrode (MEA) was prepared using the catalyst-coated substrate method, and the specific method was as follows: the anode catalyst was NiFe, the anode substrate was nickel foam, the cathode catalyst was Pt / C, the cathode substrate was carbon paper, and the cross-linked polynorbornene-based ion exchange membrane was from Example 16. In the process of spraying, the composition of the catalyst slurry was as follows: the amount of catalyst was 180 mg, the amount of ionomer prepared in the present example was 18 mg, the amount of propanol was 15 mL, and the amount of water was 3 mL. The catalyst slurry was sprayed onto the anode substrate and the cathode substrate, respectively, and the total loading amount of the catalyst and the ionomer in the catalyst slurry was 1.3 mg / cm 2 .

[0170] The catalyst sheet was cut into a size of 2.0 cm×2.0 cm, the effective area of the electrolytic cell was 2.0 cm×2.0 cm, and the concentration of the electrolyte KOH aqueous solution was 1.0 M. Using a battery test bench and a temperature control device, a voltage of 1.3 V-2.1 V was applied at 60°C, the current at the corresponding voltage was measured, and a polarization curve was drawn, as shown in Figure 7 . 2 .

[0171] The above describes the embodiments of the present application. However, the present application is not limited to the above-described embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A process for the preparation of a polynorbornene, characterized in that, The monomer 1 and the monomer 2 are prepared by precipitation polymerization in an alkane solvent to obtain the polynorbornene shown, The monomer 1 has the structure shown in the following formula (1); The monomer 2 has one of the structures shown in the following formula (2), formula (3) or formula (4): In formula (1), R1is selected from one of C 1-10 alkyl, C 1-10 alkylene-X, C 2-10 alkenyl; X is halogen; R2is selected from one of H, C 1-10 alkyl, C 1-10 alkylene-X', C 6-14 aryl, C 2-10 alkenyl; X' is halogen.

2. The production method according to claim 1, wherein The precipitation polymerization is carried out in the presence of a transition metal catalyst, a ligand and a cocatalyst; And / or, the molar ratio of the transition metal catalyst, the ligand and the cocatalyst is 1:1:(1-10); And / or, the total molar ratio of the transition metal catalyst to the monomer 1 and the monomer 2 is 1:100-1:5000, more preferably 1:1000-1:3000; And / or, the alkane solvent includes but is not limited to at least one of n-pentane and its isomers, n-hexane and its isomers, n-heptane and its isomers, n-octane and its isomers, n-decane and its isomers, n-dodecane and its isomers, n-tetradecane and its isomers, cyclohexane, methylcyclohexane and the like; And / or, the volume ratio of the total moles of the monomer 1 and the monomer 2 to the alkane solvent is 0.1-3 mmol / mL, more preferably 1-2 mmol / mL; And / or, the molar ratio of the monomer 1 to the monomer 2 is 10:0-1:9, preferably (1-8):1; And / or, the transition metal catalyst includes but is not limited to at least one of Pd catalysts or Ni catalysts (such as palladium chloride, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, palladium acetate, allylpalladium chloride dimer, (1,5-cyclooctadiene)palladium dichloride, chloro(1,5-cyclooctadiene)methylpalladium, nickel chloride, nickel bromide, bis(1,5-cyclooctadiene)nickel and bis(triphenylstibine)bis(pentafluorophenyl)nickel and the like); And / or, the ligand includes but is not limited to at least one of phosphine ligands (such as triphenylphosphine, tricyclohexylphosphine, tri-tert-butylphosphine, trisadamantylphosphine, trimethylphosphine and the like) and N-heterocyclic carbene (NHC) ligands (such as 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidine and 1,3-bis(2,6-diisopropylphenyl)imidazoline-2-ylidene and the like); And / or, the cocatalyst includes but is not limited to at least one of boron-containing cocatalysts (such as tris(pentafluorophenyl)boron, lithium tetra(pentafluorophenyl)borate-ethyl ether complex, sodium tetra(3,5-di(trifluoromethyl)phenyl)borate, potassium tetra(3,5-di(trifluoromethyl)phenyl)borate and phenyldimethylammonium tetra(3,5-di(trifluoromethyl)phenyl)borate and the like); And / or, the polymerization reaction time is 2h-24h, more preferably 4h-12h; And / or, the polymerization reaction temperature is 20-100℃, more preferably 40-70℃.

3. A crosslinked membrane, characterized in that, The crosslinked membrane is prepared from the polynorbornene prepared by the preparation method of claim 1 or 2.

4. An anion exchange membrane, characterized by, The anion exchange membrane is prepared from the crosslinked membrane of claim 3.

5. Application of the polynorbornene prepared by the preparation method of claim 1 or 2 in the preparation of ionomers.

6. An ionomer characterized by, which is prepared by the production method according to claim 1 or 2.

7. The method of preparing an ionomer of claim 6, characterized in that, The production method comprises the following steps: soaking the polynorbornene prepared by the production method according to claim 1 or 2 in an aqueous solution of a tertiary amine, and performing a quaternary ammonium reaction to obtain the ionomer.

8. A catalytic slurry characterized by, which comprises the ionomer according to claim 6.

9. A membrane electrode characterized by, which is prepared by the catalytic slurry according to claim 8.

10. An electrolytic cell characterized by, which comprises the membrane electrode according to claim 9.

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