Preparation method of rigid quaternary ammonium salt side chain polynorbornene and ionic membrane thereof

Abstract

The invention discloses a preparation method of rigid quaternary ammonium salt side chain polynorbornene and an ionic membrane of the rigid quaternary ammonium salt side chain polynorbornene, the raw material of the rigid quaternary ammonium salt side chain polynorbornene at least comprises a rigid ionic monomer, the rigid ionic monomer contains a cyclic quaternary ammonium salt structure, an aromatic ring structure and a norbornene structure, the cyclic quaternary ammonium salt structure is directly connected with the aromatic ring structure, and the aromatic ring structure is directly connected with the norbornene structure. The rigid quaternary ammonium salt side chain polynorbornene ionic membrane prepared from the rigid ionic monomer and the flexible comonomer has excellent alkaline stability, oxidation resistance stability, mechanical property and repeatable processing capacity.

Description

Technical Field

[0001] This invention belongs to the field of anion exchange membrane technology, specifically relating to a rigid quaternary ammonium salt side-chain polynorbornene and its ion exchange membrane preparation method. Background Technology

[0002] Anion exchange membrane electrolysis for hydrogen production (AEMWE) technology is gaining increasing attention and importance in the field of water electrolysis due to its low cost, high hydrogen production capacity, and extremely low hydrogen permeability. The energy efficiency, stability, and safety performance of anion exchange membrane water electrolyzers largely depend on the OH groups in the anion exchange membrane (AEM). - Effective transport capacity, long-term stability, and H2 permeability are key features. Currently, the mainstream structures for AEMs include aryl cyclic amines, polynorbornene, and polyaryl compounds. Among these, polynorbornene polymers (PNB), formed by olefin addition polymerization, have a natural advantage in the strong alkaline and electro-oxidative environments of AEMWEs due to their saturated main chain structure. Furthermore, PNB materials offer significant advantages over aryl cyclic amines in terms of polymer production cost control, as they do not require the use of expensive and difficult-to-process trifluoromethanesulfonic acid.

[0003] Polynorbornene (PNB) materials generally possess high glass transition temperatures and flexible structural control capabilities, and have long been used in AEM materials. However, the fully saturated carbon chain structure of PNB materials results in poor performance in maintaining the mechanical properties of AEM materials, and most materials address this issue by crosslinking. However, the introduction of crosslinking sites introduces new potential degradation sites and also introduces defects in the processability of the material. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing rigid quaternary ammonium salt side-chain polynorbornene and its ion-exchange membrane. The rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membrane has excellent alkaline stability, oxidation resistance, and mechanical properties.

[0005] To achieve the above objectives, a specific embodiment of the present invention provides the following technical solution:

[0006] A rigid quaternary ammonium salt side-chain polynorbornene, wherein the raw material for the rigid quaternary ammonium salt side-chain polynorbornene includes at least a rigid ionic monomer, wherein the rigid ionic monomer contains a cyclic quaternary ammonium salt structure, an aromatic ring structure, and a norbornene structure, wherein the cyclic quaternary ammonium salt structure is directly linked to the aromatic ring structure, and the aromatic ring structure is directly linked to the norbornene structure.

[0007] In one or more embodiments of the present invention, the aromatic ring structure is selected from monobenzene rings and biphenyl rings.

[0008] In one or more embodiments of the present invention, the benzylic position of the aromatic ring structure connected to the cyclic quaternary ammonium salt structure is substituted with methyl or methoxy groups.

[0009] In one or more embodiments of the present invention, the rigid ionic monomer is selected from: , , , , , , .

[0010] In one or more embodiments of the present invention, the raw material for the rigid quaternary ammonium salt side-chain polynorbornene further includes a flexible comonomer, wherein the flexible comonomer is selected from: , , , , , , ;

[0011] in, In this case, x is between 0 and 4.

[0012] In one or more embodiments of the present invention, the rigid quaternary ammonium salt side-chain polynorbornene contains 100%-40% rigid ionic monomers and 0%-60% flexible comonomers.

[0013] Another specific embodiment of the present invention provides the following technical solution:

[0014] A method for preparing rigid quaternary ammonium salt side-chain polynorbornene, the method comprising the following steps:

[0015] At least rigid ionic monomers should be used as raw materials;

[0016] A rigid ionic monomer and a solvent were mixed, and a catalyst was added under an inert atmosphere. The mixture was reacted at 45℃-55℃ for 12-18 hours and then evaporated to obtain rigid quaternary ammonium salt side-chain polynorbornene.

[0017] In one or more embodiments of the present invention, the solvent is at least one of dichloromethane and chloroform, and the catalyst is chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline]palladium.

[0018] Another specific embodiment of the present invention provides the following technical solution:

[0019] A rigid quaternary ammonium salt side-chain polynorbornene ion exchange membrane, wherein the raw material of the rigid quaternary ammonium salt side-chain polynorbornene ion exchange membrane includes at least rigid quaternary ammonium salt side-chain polynorbornene.

[0020] Another specific embodiment of the present invention provides the following technical solution:

[0021] A method for preparing a rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membrane, the method comprising the following steps:

[0022] A rigid quaternary ammonium salt side chain polynorbornene was prepared into a 1%wt-5%wt solution with a solvent. A saturated sodium chloride solution was added dropwise for precipitation and ion exchange. After precipitation, the solution was filtered and dried to obtain the dried product.

[0023] The dried material and solvent were mixed to form a solution, which was then dried to form a film, thus obtaining a rigid quaternary ammonium salt side-chain polynorbornene ion membrane.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] 1. By using coordination polymerization of direct ionic monomers, the complex process and incomplete ionization problems caused by post-ionization are eliminated.

[0026] 2. The mechanical swelling problem of traditional linear PNB materials is solved by adopting a dual-phase separation strategy of hydrophilic-hydrophobic and rigid-flexible phase separation, while taking into account the ability to be repeatedly processed.

[0027] 3. Through the design of a double-bridged ring quaternary ammonium salt structure, the rigid quaternary ammonium salt side-chain polynorbornene ion membrane is endowed with extremely high alkaline stability.

[0028] 4. The specially designed aromatic ring structure has a high adsorption energy in the catalyst plane, which effectively improves the oxidation resistance stability. Attached Figure Description

[0029] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0030] Figure 1 This is the 1H NMR spectrum of 8-methyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-oxacyclopropane] of the present invention;

[0031] Figure 2 This is the high-resolution mass spectrum of 8-methyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-oxacyclopropane] of the present invention;

[0032] Figure 3 This is the 1H NMR spectrum of 3,8-dimethyl-8-azabicyclo[3.2.1]oct-3-ol of the present invention;

[0033] Figure 4This is the carbon NMR spectrum of 3,8-dimethyl-8-azabicyclo[3.2.1]oct-3-ol of the present invention;

[0034] Figure 5 This is the high-resolution mass spectrum of 3,8-dimethyl-8-azabicyclo[3.2.1]oct-3-ol of the present invention;

[0035] Figure 6 This is the 1H NMR spectrum of 3-(4-bromophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0036] Figure 7 This is the carbon NMR spectrum of 3-(4-bromophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0037] Figure 8 This is the high-resolution mass spectrum of 3-(4-bromophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0038] Figure 9 This is the 1H NMR spectrum of 3-(4-iodophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0039] Figure 10 This is the carbon NMR spectrum of 3-(4-iodophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0040] Figure 11 This is the high-resolution mass spectrum of 3-(4-iodophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0041] Figure 12 The 1H NMR spectrum of 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane of this invention is shown below.

[0042] Figure 13 The carbon NMR spectrum of 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane of this invention;

[0043] Figure 14 This is the high-resolution mass spectrum of 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane of the present invention;

[0044] Figure 15 This is the 1H NMR spectrum of the NBP-BCQA of this invention;

[0045] Figure 16 This is the carbon NMR spectrum of the NBP-BCQA of this invention;

[0046] Figure 17 This is the high-resolution mass spectrometry of the NBP-BCQA of the present invention;

[0047] Figure 18 This is the 1H NMR spectrum of 5-exo-(4-bromophenyl)bicyclo[2.2.1]hept-2-ene of the present invention;

[0048] Figure 19 The 1H NMR spectrum of 3-(4-((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)phenyl)-8-methyl-8-azabicyclo[3.2.1]oct-3-ol is shown in the figure.

[0049] Figure 20 This is the 1H NMR spectrum of the NB-Hex of this invention;

[0050] Figure 21 This is the 1H NMR spectrum of the NB-Trip of this invention;

[0051] Figure 22 Thermogravimetric spectra of the PNB-40PBCQA-r-60Hex ion membrane, PNB-45PBCQA-r-55Hex ion membrane, PNB-50PBCQA-r-50Hex ion membrane, and PNB-60PBCQA-r-40Hex ion membrane of the present invention are shown.

[0052] Figure 23 The infrared spectra of the PNB-40PBCQA-r-60Hex ion exchange membrane, PNB-45PBCQA-r-55Hex ion exchange membrane, PNB-50PBCQA-r-50Hex ion exchange membrane, and PNB-60PBCQA-r-40Hex ion exchange membrane of the present invention are shown below.

[0053] Figure 24 This is an external image of the PNB-50PBCQA-r-50Hex ion exchange membrane of the present invention;

[0054] Figure 25 The PNB-50PBCQA-50Hex ion exchange membrane of this invention operates at 80℃ with Fenton (3%wt H2O2, 4ppm Fe). 2 + Stability tests were conducted on the reagents, and the morphology was compared with that of the commercial PiperIon membrane.

[0055] Figure 26The PNB-50PBCQA-50Hex ion exchange membrane of this invention operates at 80℃ with Fenton (3%wt H2O2, 4ppm Fe). 2 + Stability testing of reagents, and comparison of infrared spectra before and after the stability test;

[0056] Figure 27 Mechanical property testing of the PNB-40PBCQA-r-60Hex ion exchange membrane, PNB-45PBCQA-r-55Hex ion exchange membrane, PNB-50PBCQA-r-50Hex ion exchange membrane, and PNB-60PBCQA-r-40Hex ion exchange membrane of the present invention.

[0057] Figure 28 This is the polarization curve of the PNB-45PBCQA-r-55Hex ion exchange membrane of the present invention in AEMWE. Detailed Implementation

[0058] To enable those skilled in the art to better understand the technical solutions in this disclosure, the technical solutions in the embodiments of this disclosure are described clearly and completely below. Obviously, the described embodiments are only some embodiments of this disclosure, and not all embodiments. Based on the embodiments in this disclosure, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this disclosure.

[0059] This invention prepares a norbornene monomer with rigid side chains and a double-bridged cyclic quaternary ammonium salt. Anion exchange membranes are then prepared using this monomer, such as 8-azabicyclo[3.2.1]octane, which is directly linked to the rigid aromatic ring norbornene and blocks potential unstable sites at the benzylic position. This monomer is then copolymerized with various norbornenes via Pd-catalyzed coordination polymerization to obtain an AEM material. This AEM material exhibits excellent basic stability, oxidation resistance, high ionic conductivity, and mechanical properties.

[0060] One specific embodiment of the present invention provides a rigid quaternary ammonium salt side-chain polynorbornene, the raw material of which includes at least a rigid ionic monomer. The rigid ionic monomer contains a cyclic quaternary ammonium salt structure, an aromatic ring structure and a norbornene structure. The cyclic quaternary ammonium salt structure is linked to the aromatic ring structure, and the aromatic ring structure is linked to the norbornene structure.

[0061] Specifically, the cyclic quaternary ammonium salt structure and the aromatic ring structure provide rigid side chains for polynorbornene. At the same time, the cyclic quaternary ammonium salt structure can endow polynorbornene with extremely high alkaline stability, thereby improving the performance of polynorbornene.

[0062] Furthermore, the aromatic ring structure is selected from monophenyl rings and biphenyl rings, and the benzylic position where the aromatic ring structure connects to the cyclic quaternary ammonium salt structure is substituted with a methyl or methoxy group. The substitution of the benzylic position with a methyl or methoxy group enhances the stability of polynorbornene.

[0063] Furthermore, the rigid ionic monomers are selected from: , , , , , , NBP-BCQA-Sb is preferred.

[0064] The raw materials for rigid quaternary ammonium salt side-chain polynorbornene also include flexible comonomers, which are selected from: , , , , , , ;in, In the figure, x is 0-4, with x preferably being 4; the flexible comonomer is preferably NBE-Alk. The flexible comonomer has a heteroatom-free norbornene structure, which, when combined with the rigid ionic monomer, solves the mechanical swelling problem of polynorbornene materials while also ensuring reprocessability.

[0065] Furthermore, in rigid quaternary ammonium salt side-chain polynorbornene, the proportion of rigid ionic monomers is 100%-40%, and the proportion of flexible comonomers is 0%-60%. By adjusting the molar ratio of rigid ionic monomers and flexible comonomers, the performance of polynorbornene can be better optimized.

[0066] Another specific embodiment of the present invention provides a method for preparing rigid quaternary ammonium salt side-chain polynorbornene, which includes the following steps: taking at least a rigid ionic monomer as a raw material; mixing the rigid ionic monomer and a solvent, adding a catalyst under an inert atmosphere, reacting at 45℃-55℃ for 12h-18h, and then drying by rotary evaporation to obtain rigid quaternary ammonium salt side-chain polynorbornene.

[0067] Specifically, the solvent is at least one of dichloromethane and chloroform, preferably dichloromethane; the catalyst is palladium chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline]carbamate. Polynorbornene is a polyolefin catalyzed by active coordination polymerization, using random copolymerization or block copolymerization methods.

[0068] Another specific embodiment of the present invention provides a rigid quaternary ammonium salt side-chain polynorbornene ion membrane, the raw material of which includes at least rigid quaternary ammonium salt side-chain polynorbornene.

[0069] Another specific embodiment of the present invention provides a method for preparing a rigid quaternary ammonium salt side-chain polynorbornene ion exchange membrane, which specifically includes the following steps: preparing a 1%wt-5%wt solution of rigid quaternary ammonium salt side-chain polynorbornene and a solvent, adding a saturated sodium chloride solution dropwise for precipitation and ion exchange, filtering and drying the precipitate to obtain a dried product; mixing the dried product and a solvent to prepare a solution, and then drying it to form a membrane to obtain a rigid quaternary ammonium salt side-chain polynorbornene ion exchange membrane.

[0070] The present invention will be further described in detail below with reference to specific embodiments.

[0071] Unless otherwise stated, all chemicals used in this invention are commercially available, stored at room temperature, and used as received. Solvents and other commercial reagents were purchased from companies such as Leyan, Anengji, Sigma-Aldrich, Yonghua, and Nanshi and used as received.Tropine (532-24-1) purchased from Anage; Trimethyl sulfoxide (1774-47-6) purchased from Anage; Sodium hydride (7646-69-7) purchased from Amethyst; Lithium triethylborohydride (22560-16-3) purchased from Anage; Bromobenzene (108-86-1) purchased from Aladdin; Aluminum trichloride (7446-70-0) purchased from Anage; Sodium iodide (7681-82-5) purchased from 3A; Cuprous iodide (7681-65-4) purchased from Bide; N,N'-Dimethylethylenediamine (110-70-3) purchased from Bide; 1,4-Dioxane (123-91-1) purchased from Anage; Dimethyl sulfoxide (67-68-5) Purchased from Amethyst; Tetrahydrofuran (109-99-9) purchased from Sigma; Norbornene (121-46-0) purchased from Anaiji; Dichlorodiphenylphosphine palladium (13965-03-2) purchased from Bide; Triethylamine (121-44-8) purchased from Anaiji; Formic acid (64-18-6) purchased from Anaiji; N,N-Dimethylformamide (68-12-2) purchased from Inokai; Iodomethane (74-88-4) purchased from Anaiji; N-Methylpyrrolidone (872-50-4) purchased from Inokai; p-Bromoiodobenzene (589-87-7) purchased from Bide; N-tert-Butoxycarbonyl-nortropinone (185099-67-6) Purchased from Bide; 1,4-Dimethylpiperidin-4-ol (10354-61-7) purchased from Block Chemical Technology (Shanghai) Co., Ltd.; 3-Methyl-1-azabicyclo[2.2.2]octane-3-ol (16283-66-2) purchased from Wuhan Kaimeike Chemical Technology Co., Ltd.; 1,5-Dibromopentane (111-24-0) purchased from Anaiji; Cyclopentadiene dimer (77-73-6) purchased from Anaiji; n-Butyllithium (109-72-8) purchased from J&K; Anthracene (120-12-7) purchased from Maclean; 2-Cyclohexyl-5-norbornene (NB-lCH, 185971-98-6) purchased from Wuhan Xinshengyang Biotechnology Co., Ltd.; Bis(1,5-cyclooctadiene)nickel (0) (1295-35-8) Purchased from Bailingwei; Triphenylphosphine (603-35-0) purchased from Anaiji; Norbornene (NBE, 498-66-8) purchased from Maclean; 1,2,3,4,4A,5,8,8A-octahydro-1,4:5,8-dimethylbridged naphthalene (NB-fNBH, 21635-90-5) purchased from Bailingwei; 2-Phenyl-5-norbornene (NB-Ph, 6143-30-2) purchased from Bide.

[0072] Synthesis of rigid ionic monomers

[0073] Example 1

[0074]

[0075] Trimethyl sulfoxide (40.4 g, 180 mmol, 1.5 equiv) was added to a dry 500 mL flask, followed by dimethyl sulfoxide (200 mL). Sodium hydride (60%, 7.2 g, 180 mmol, 1.5 equiv) was added in portions, and the mixture was stirred at room temperature for 1 h. Tropine (16.9 g, 120 mmol, 1.0 equiv) was prepared as a dimethyl sulfoxide solution (100 mL), which was added to the flask at room temperature, and the reaction was allowed to proceed overnight at room temperature. After the reaction was complete, the reaction mixture was extracted with dichloromethane and water and evaporated to dryness. The solution was then dried in a vacuum oven at 60 °C to obtain a pale yellow, transparent, oily liquid in 90% yield.

[0076]

[0077] 8-Methyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-oxetane] (10.5 g, 68 mmol, 1.0 equiv) was dissolved in tetrahydrofuran, and triethyllithium borohydride (1.0 M, 90 mL, 89 mmol, 1.3 equiv) was slowly added. The reaction was carried out overnight at room temperature. After the reaction was complete, water was added and stirred. The reaction solution was extracted with ethyl acetate and evaporated to dryness. The solution was dried in a vacuum oven at 80 °C to obtain white needle-like crystals in 95% yield.

[0078]

[0079] 3,8-Dimethyl-8-azabicyclo[3.2.1]octane-3-ol (4.2 g, 27 mmol, 1.0 equiv) was added to a flask and dissolved in bromobenzene (70 mL). Aluminum trichloride powder (10.7 g, 80 mmol, 3.0 equiv) was added in portions, and the mixture was stirred overnight at 50 °C. After the reaction was complete, the reaction was quenched with water, separated by dichloromethane, and evaporated to dryness. Diethyl ether (50 mL) was added, and the mixture was filtered to obtain a white powdery solid in 66% yield.

[0080]

[0081] 3-(4-bromophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane (4.3 g, 14 mmol, 1.0 equiv) was added to a flask, followed by sodium iodide (5.25 g, 34 mmol, 2.4 equiv), cuprous iodide (139 mg, 0.7 mmol, 0.05 equiv), N,N'-dimethylethane-1,2-diamine (0.16 mL, 1.4 mmol, 0.1 equiv), and dioxane (30 mL). The mixture was stirred at 110 °C for 2 days. After the reaction was complete, the mixture was filtered, evaporated to dryness, and dried overnight in a vacuum oven at 80 °C to obtain a light yellow powdery solid with a yield of 95%.

[0082]

[0083] 3-(4-Iodophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane (1.6 g, 5 mmol, 1.0 equiv) was added to a reaction tube, followed by norbornene (2.5 mL, 24 mmol, 5.0 equiv), palladium dichloride dichloride (34 mg, 0.05 mmol, 0.01 equiv), trimethylamine (2.1 mL, 15 mmol, 3.2 equiv), formic acid (0.4 mL, 10 mmol, 2.1 equiv), and N,N'-dimethylformamide (30 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness and dried overnight in a vacuum oven at 80 °C to obtain a white powdery solid with a yield of 95%.

[0084]

[0085] 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane (1.3 g, 4.3 mmol, 1 equiv) was added to a beaker, followed by iodomethane (1.2 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted several times with excess silver hexafluoroantimonate and ethyl acetate to give a white powdery solid in 80% yield.

[0086] Example 2

[0087]

[0088] 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane was prepared according to Example 1. 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane (1.3 g, 4.3 mmol, 1 equiv) was added to a beaker, followed by iodomethane (1.2 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted multiple times with excess silver tetrafluoroborate and ethyl acetate to obtain a white powdery solid in 80% yield.

[0089] Example 3

[0090]

[0091] Norbornene (7.1 g, 75.1 mmol, 3.1 equiv) was added to a reaction tube, followed by p-bromoiodobenzene (7.0 g, 24.4 mmol, 1 equiv), palladium dichloride dichloride (174.8 mg, 0.25 mmol, 0.01 equiv), triethylamine (8.1 g, 78.9 mmol, 3.2 equiv), formic acid (2.4 g, 51.3 mmol, 2.1 equiv), and N,N'-dimethylformamide (10.0 mL). The mixture was stirred at 50 °C for 1 hour, and the solution was purified by petroleum ether column chromatography. The purified solution was evaporated to dryness to obtain a colorless oily liquid in 90% yield.

[0092]

[0093] 5-exo-(4-bromophenyl)bicyclo[2.2.1]hept-2-ene (1.04 g, 4.0 mmol, 1 equiv) was added to a 100 mL flask, followed by tetrahydrofuran (10.0 mL). Butyllithium (1.6 M, 2.8 mL, 4.4 mmol, 1.1 equiv) was added at -78 °C, and the mixture was stirred for 1 hour. A solution of tropinone (0.62 g, 4.4 mmol, 1.1 equiv) in tetrahydrofuran (2.0 mL) was added to the flask, and the reaction was allowed to proceed overnight. After the reaction was complete, the solution was quenched with an aqueous sodium carbonate solution, then extracted with ethyl acetate, and evaporated to dryness to obtain a white solid powder in 75% yield.

[0094]

[0095] 3-(4-((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)phenyl)-8-methyl-8-azabicyclo[3.2.1]oct-3-ol (1.3 g, 4.3 mmol, 1 equiv) was added to a beaker, followed by methyl iodoform (1.2 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted several times with excess silver hexafluoroantimonate and ethyl acetate to give a white powdery solid in 80% yield.

[0096] Example 4

[0097]

[0098] Trimethyl sulfoxide (40.4 g, 180 mmol, 1.5 equiv) was added to a dry 500 mL flask, followed by dimethyl sulfoxide (200 mL). Sodium hydride (60%, 7.2 g, 180 mmol, 1.5 equiv) was added in portions, and the mixture was stirred at room temperature for 1 h. A 100 mL solution of N-tert-butyloxycarbonyl-nortropinone (27.1 g, 120 mmol, 1.0 equiv) was prepared and added to the flask at room temperature. The reaction mixture was allowed to react overnight at room temperature. After the reaction was complete, the reaction mixture was extracted with dichloromethane and water and evaporated to dryness. The solution was then dried in a vacuum oven at 60 °C to obtain a pale yellow, transparent, oily liquid in 90% yield.

[0099]

[0100] 16.3 g (68 mmol, 1.0 equiv) of tert-butyl-8-azaspiro[bicyclo[3.2.1]octane-3,2′-epoxyethylene]-8-carboxylic acid ester was dissolved in tetrahydrofuran, and triethyllithium borohydride (1.0 M, 90 mL, 89 mmol, 1.3 equiv) was slowly added. The reaction was carried out overnight at room temperature. After the reaction was completed, water was added and stirred. The reaction solution was extracted with ethyl acetate and evaporated to dryness. The solution was dried in a vacuum oven at 80 °C to obtain white needle-like crystals in 95% yield.

[0101]

[0102] 6.5 g (27 mmol, 1.0 equiv) of tert-butyl-3-hydroxy-3-methyl-8-azabicyclo[3.2.1]octane-8-carboxylic acid ester was added to a flask and dissolved in bromobenzene (70 mL). Aluminum trichloride powder (10.7 g, 80 mmol, 3.0 equiv) was added in portions, and the mixture was stirred overnight at 50 °C. After the reaction was complete, the reaction was quenched with water, separated by dichloromethane, and evaporated to dryness. Diethyl ether (50 mL) was added, and the mixture was filtered to obtain a white powdery solid in 66% yield.

[0103]

[0104] tert-Butyl-3-(4-bromophenyl)-3-methyl-8-azabicyclo[3.2.1]octane-8-carboxylic acid ester (5.3 g, 14 mmol, 1.0 equiv) was added to a flask, followed by sodium iodide (5.25 g, 34 mmol, 2.4 equiv), cuprous iodide (139 mg, 0.7 mmol, 0.05 equiv), N,N'-dimethylethane-1,2-diamine (0.16 mL, 1.4 mmol, 0.1 equiv), and dioxane (30 mL). The mixture was stirred at 110 °C for 2 days. After the reaction was complete, the mixture was filtered, evaporated to dryness, and dried overnight in a vacuum oven at 80 °C to obtain a light yellow powdery solid in 95% yield.

[0105]

[0106] 2.2 g (5 mmol, 1.0 equiv) of tert-butyl-3-(4-iodophenyl)-3-methyl-8-azabicyclo[3.2.1]octane-8-carboxylic acid ester was added to a reaction tube, followed by norbornene (2.5 mL, 24 mmol, 5.0 equiv), palladium dichloride dichloride (34 mg, 0.05 mmol, 0.01 equiv), trimethylamine (2.1 mL, 15 mmol, 3.2 equiv), formic acid (0.4 mL, 10 mmol, 2.1 equiv), and N,N'-dimethylformamide (30 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness and dried overnight in a vacuum oven at 80 °C to obtain a white powdery solid in 95% yield.

[0107]

[0108] tert-Butyl-3-[4-[(1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl]phenyl]-3-methyl-8-azabicyclo[3.2.1]octane-8-carboxylic acid ester (1.7 g, 4.3 mmol, 1 equiv) was added to a beaker, concentrated hydrochloric acid was added, and the mixture was stirred vigorously to precipitate in diethyl ether and filtered. Subsequently, 1,5-dibromopentane (2.0 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL) were added, and the mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted several times with excess silver tetrafluoroborate and ethyl acetate to give a white powdery solid in 80% yield.

[0109] Example 5

[0110]

[0111] 1,4-Dimethylpiperidin-4-ol (3.5 g, 27 mmol, 1.0 equiv) was added to a flask and dissolved in bromobenzene (70 mL). Aluminum trichloride powder (10.7 g, 80 mmol, 3.0 equiv) was added in portions, and the mixture was stirred overnight at 50 °C. After the reaction was complete, the reaction was quenched with water, separated by dichloromethane, and evaporated to dryness. Diethyl ether (50 mL) was added, and the mixture was filtered to obtain a white powdery solid in 66% yield.

[0112]

[0113] 4-(4-bromophenyl)-1,4-dimethylpiperidine (3.8 g, 14 mmol, 1.0 equiv) was added to a flask, followed by sodium iodide (5.25 g, 34 mmol, 2.4 equiv), cuprous iodide (139 mg, 0.7 mmol, 0.05 equiv), N,N'-dimethylethane-1,2-diamine (0.16 mL, 1.4 mmol, 0.1 equiv), and dioxane (30 mL). The mixture was stirred at 110 °C for 2 days. After the reaction was complete, the mixture was filtered, evaporated to dryness, and dried overnight in a vacuum oven at 80 °C to obtain a light yellow powdery solid in 95% yield.

[0114]

[0115] 4-(4-iodophenyl)-1,4-dimethylpiperidine (4.5 g, 14 mmol, 1.0 equiv) was added to a reaction tube, followed by norbornene (2.5 mL, 24 mmol, 5.0 equiv), palladium dichloride dichloride (34 mg, 0.05 mmol, 0.01 equiv), trimethylamine (2.1 mL, 15 mmol, 3.2 equiv), formic acid (0.4 mL, 10 mmol, 2.1 equiv), and N,N'-dimethylformamide (30 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness and dried overnight in a vacuum oven at 80 °C to obtain a white powdery solid in 95% yield.

[0116]

[0117] 3-[4-(bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3,8-dimethyl-8-azabicyclo[3.2.1]octane (1.2 g, 4.3 mmol, 1 equiv) was added to a beaker, followed by iodomethane (1.2 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted several times with excess silver tetrafluoroborate and ethyl acetate to give a white powdery solid in 80% yield.

[0118] Example 6

[0119]

[0120] 3-Methyl-1-azabicyclo[2.2.2]octane-3-ol (3.8 g, 27 mmol, 1.0 equiv) was added to a flask and dissolved in bromobenzene (70 mL). Aluminum trichloride powder (10.7 g, 80 mmol, 3.0 equiv) was added in portions, and the mixture was stirred overnight at 50 °C. After the reaction was complete, the reaction was quenched with water, separated by dichloromethane, and evaporated to dryness. Diethyl ether (50 mL) was added, and the mixture was filtered to give a white powdery solid in 66% yield.

[0121]

[0122] 3-(4-bromophenyl)-3-methyl-1-azabicyclo[2.2.2]octane (3.9 g, 14 mmol, 1.0 equiv) was added to a reaction tube, followed by norbornene (2.5 mL, 24 mmol, 5.0 equiv), palladium dichloride dichloride (34 mg, 0.05 mmol, 0.01 equiv), trimethylamine (2.1 mL, 15 mmol, 3.2 equiv), formic acid (0.4 mL, 10 mmol, 2.1 equiv), and N,N'-dimethylformamide (30 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness and dried overnight in a vacuum oven at 80 °C to obtain a white powdery solid with a yield of 95%.

[0123]

[0124] 3-(4-iodophenyl)-3-methyl-1-azabicyclo[2.2.2]octane (4.6 g, 14 mmol, 1.0 equiv) was added to a reaction tube, followed by norbornene (2.5 mL, 24 mmol, 5.0 equiv), palladium dichloride dichloride (34 mg, 0.05 mmol, 0.01 equiv), trimethylamine (2.1 mL, 15 mmol, 3.2 equiv), formic acid (0.4 mL, 10 mmol, 2.1 equiv), and N,N'-dimethylformamide (30 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness and dried overnight in a vacuum oven at 80 °C to obtain a white powdery solid with a yield of 95%.

[0125]

[0126] 3-[4-((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)phenyl]-3-methyl-1-azabicyclo[2.2.2]octane (1.3 g, 4.3 mmol, 1 equiv) was added to a beaker, followed by iodomethane (1.2 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted several times with excess silver tetrafluoroborate and ethyl acetate to give a white powdery solid in 80% yield.

[0127] Example 7

[0128]

[0129] 3-(4-bromophenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane (4.3 g, 14 mmol, 1.0 equiv) and 5-exo-(4-bromophenyl)bicyclo[2.2.1]hept-2-ene (3.10 g, 14.0 mmol, 1 equiv) were added, followed by bis-(1,5-cyclooctadiene)nickel (3.8 g, 14.0 mmol, 1 equiv), PPh3 (1.8 g, 7.0 mmol, 0.5 equiv), and DMF (15 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was purified by dichloromethane column chromatography and dried at 80 °C to obtain a pale yellow solid.

[0130]

[0131] 3-(4'-((1R,2S,4R)-bicyclo[2.2.1]hept-5-en-2-yl)-4-biphenyl)-3,8-dimethyl-8-azabicyclo[3.2.1]octane (1.7 g, 4.3 mmol, 1 equiv) was added to a beaker, followed by iodomethane (1.2 g, 8.7 mmol, 2 equiv) and N-methylpyrrolidone (10 mL). The mixture was stirred overnight at 50 °C. After the reaction was complete, the solution was evaporated to dryness. Water was added, and the mixture was extracted several times with excess silver tetrafluoroborate and ethyl acetate to give a white powdery solid in 80% yield.

[0132] Synthesis of flexible comonomers

[0133] Example 8

[0134]

[0135] Cyclopentadiene dimer (6.0 g, 45.4 mmol, 1 equiv) was added to a 350 mL flask, followed by 6-bromo-1-hexene (24.0 mL, 180.0 mmol, 4 equiv). The reaction was carried out at 200 °C for 3 days. After the reaction was completed, the sample was distilled under reduced pressure at -730 mmHg, with the fraction at 114–112 °C, yielding the desired product in 89% yield.

[0136] Example 9

[0137]

[0138] Anthracene (8.8 g, 28.1 mmol, 1 equiv) was added to a flask, followed by norbornene (22.7 g, 245.8 mmol, 5 equiv). The flask was sealed under nitrogen atmosphere and reacted at 185 °C for 3 days. After the reaction was complete, the product was purified by petroleum ether column chromatography to give a white solid in 80% yield.

[0139] Synthesis of rigid quaternary ammonium salt side-chain polynorbornene

[0140] Example 10

[0141]

[0142] The rigid ionic monomer and the flexible comonomer were added together to a reaction tube (1.5 mmol, 160 equiv). The proportion of the rigid ionic monomer (n) was 1.0 mmol, and the proportion of the flexible comonomer (m) was 0.5 mmol. A dichloromethane solution (7.5 mL) was added, and under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added. The reaction was carried out overnight at 50 °C to obtain a brownish-yellow suspension. The suspension was evaporated to dryness to obtain the desired polymer product in 95% yield.

[0143] Example 11

[0144]

[0145] The flexible comonomer was added to a reaction tube, followed by 7.5 mL of dichloromethane solution. Under nitrogen atmosphere, palladium chloride [(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ion] (5.3 mg, 9.4 μmol, 1.0 equiv) was added. The reaction was carried out at room temperature for 5 hours, yielding a yellow viscous solution. Under nitrogen atmosphere, a rigid ionic monomer (1.5 mmol, 160 equiv) was then added. The proportion of the rigid ionic monomer (n) was 1.0 mmol, and the proportion of the flexible comonomer (m) was 0.5 mmol. The reaction was carried out overnight at 50 °C, yielding a brownish-yellow suspension. The suspension was evaporated to dryness to obtain the desired polymer product, with a yield of 95%.

[0146] Example 12

[0147]

[0148] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBP-BCQA-Sb (418.7 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a brownish-yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50PBCQA-r-50Hex, with a yield of 95%.

[0149] Example 13

[0150] The preparation method of rigid quaternary ammonium salt side chain polynorbornene in this embodiment is basically the same as that in Example 12, except for the addition ratio of raw materials: NBP-BCQA-Sb is 335.0 mg, 0.6 mmol, 64 equiv; NB-Hex is 160.5 mg, 0.9 mmol, 96 equiv, and the resulting polymer product is denoted as PNB-40PBCQA-r-60Hex.

[0151] Example 14

[0152] The preparation method of rigid quaternary ammonium salt side chain polynorbornene in this embodiment is basically the same as that in Example 12, except for the addition ratio of raw materials: NBP-BCQA-Sb is 376.9 mg, 0.675 mmol, 72 equiv; NB-Hex is 147.1 mg, 0.825 mmol, 88 equiv; the resulting polymer product is denoted as PNB-45PBCQA-r-55Hex.

[0153] Example 15

[0154] The preparation method of rigid quaternary ammonium salt side chain polynorbornene in this embodiment is basically the same as that in Example 12, except for the addition ratio of raw materials: NBP-BCQA-Sb is 502.5 mg, 0.9 mmol, 96 equiv; NB-Hex is 106.9 mg, 0.6 mmol, 64 equiv; the resulting polymer product is denoted as PNB-60PBCQA-r-40Hex.

[0155] Example 16

[0156]

[0157] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBP-BCQA-B (418.7 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a pale yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product in 95% yield.

[0158] Example 17

[0159]

[0160] The flexible comonomer NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) was added to a reaction tube, followed by 7.5 mL of dichloromethane solution. Under nitrogen atmosphere, palladium chloride [(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added. The reaction was carried out at room temperature for 5 hours, yielding a yellow viscous solution. Under nitrogen atmosphere, the rigid ionic monomer NBPO-BCQA-Sb (430.7 mg, 0.75 mmol, 80 equiv) was added (total monomer 1.5 mmol, 160 equiv). The reaction was carried out overnight at 50 °C, yielding a dark brownish-yellow suspension. The suspension was evaporated to dryness to obtain the desired polymer, designated PNB-50PBCQA-b-50Hex, with a yield of 90%.

[0161] Example 18

[0162]

[0163] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBPO-BCQA-Sb (430.7 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, palladium chloride [(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the reaction was carried out overnight at 50 °C to obtain a brownish-yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50POBCQA-r-50Hex, with a yield of 95%.

[0164] Example 19

[0165]

[0166] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBP-SBCQA-Sb (460.7 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a pale yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50PSBCQA-r-50Hex, with a yield of 90%.

[0167] Example 20

[0168]

[0169] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBP-Pip-Sb (399.2 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a pale yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50PPip-r-50Hex, with a yield of 90%.

[0170] Example 21

[0171]

[0172] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBP-Qui-Sb (408.9 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a pale yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50PQui-r-50Hex, with a yield of 90%.

[0173] Example 22

[0174]

[0175] NB-Hex (133.7 mg, 0.75 mmol, 80 equiv) and NBBP-BCQA-Sb (475.8 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50BPBCQA-r-50Hex, with a yield of 85%.

[0176] Example 23

[0177]

[0178] NB-fNBH (120.2 mg, 0.75 mmol, 80 equiv) and NBP-BCQA-Sb (418.7 mg, 0.75 mmol, 80 equiv) were added to a dichloromethane solution (7.5 mL). Under nitrogen atmosphere, chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline ide]palladium (5.3 mg, 9.4 μmol, 1.0 equiv) was added, and the mixture was reacted overnight at 50 °C to obtain a brownish-yellow suspension. The suspension was evaporated to dryness to obtain the desired polymerization product, designated PNB-50PBCQA-r-50fNBH, with a yield of 95%.

[0179] Preparation of rigid quaternary ammonium salt side-chain polynorbornene ion membranes

[0180] Rigid quaternary ammonium salt side-chain polynorbornene powder was mixed with dimethyl sulfoxide to prepare a 3% wt solution. This solution was then added dropwise to a saturated sodium chloride aqueous solution and stirred vigorously overnight to exchange the counterion for chloride ions. The mixture was filtered and dried. The dried polymer was then reconstituted into a 3% wt dimethyl sulfoxide solution and dried in 10 mL of a 4.5 cm diameter tetrafluoroethylene dish at 80 °C to form a membrane with a thickness of 80 μm (±5 μm), yielding a rigid quaternary ammonium salt side-chain polynorbornene ion exchange membrane. The polymer material after membrane formation can be purified by immersion in a relevant ion-exchange aqueous solution.

[0181] The obtained rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membrane was subjected to the following tests:

[0182] Testing of ion exchange membrane swelling and water absorption: The ion exchange membrane with chloride ion as the counterion was cut into strips of 1 cm * 5 cm. The ion exchange membrane was immersed in deionized water at room temperature or 80 °C for 24 h. The changes in mass (water absorption rate WU), length (in-plane swelling rate SRin-plane), and membrane thickness (transmembrane swelling rate SRthrough-plane) before and after immersion were measured. Three sets of measurements were performed in parallel to obtain the final data.

[0183] Testing the conductivity of the ion exchange membrane: The ion exchange membrane with hydroxide ions as the counterion was washed with water and cut into strips of 1 cm * 5 cm. Using a thin-film four-electrode fixture, its electrochemical impedance R (Ω), membrane thickness d (cm), mold length L (cm), and membrane width W (cm) were measured. The conductivity data σ = L / (R*W*d) (mS / cm) was calculated.

[0184] Ion exchange capacity (IEC) test of ion-exchange membrane: Measured using molar titration, an ion-exchange membrane with chloride ions as the counterion (dry mass mdry (g)) was immersed overnight in a sodium nitrate aqueous solution. The membrane was then removed, and the immersion solution was titrated using silver nitrate solution (concentration CAg (mmol / mL)) as the titrant and potassium chromate solution as the indicator. The volume of silver nitrate used (VAg (mL)) was obtained, and the experimental value of the ion exchange capacity was calculated: IEC = CAg*VAg / mdry (mmol / g). The theoretical value of the ion exchange capacity is calculated based on the polymerization reaction feed ratio.

[0185] The properties of rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membranes prepared using PNB-40PBCQA-r-60Hex, PNB-45PBCQA-r-55Hex, PNB-50PBCQA-r-50Hex, and PNB-60PBCQA-r-40Hex materials are shown in Table 1, and the thermogravimetric spectra are as follows. Figure 22 As shown, the infrared spectrum is as follows Figure 23 As shown.

[0186] Table 1. Performance of rigid quaternary ammonium salt side-chain polynorbornene ion exchange membranes

[0187]

[0188] As shown in Table 1, the rigid quaternary ammonium salt side-chain polynorbornene ion membrane prepared using PNB-45PBCQA-r-55Hex exhibits high ionic conductivity (80℃, σ OH- It has a strength of 142 mS / cm and exhibits a low swelling rate, making it the optimal ion exchange membrane.

[0189] The rigid quaternary ammonium salt side-chain polynorbornene ion exchange membrane prepared using PNB-50PBCQA-r-50Hex was selected (see appearance image). Figure 24 As shown), the commercial PiperIon membrane was used as a comparison, and the test was conducted at 80℃ with Fenton (3%wt H2O2, 4ppm Fe). 2+ The stability of the reagent, comparison of appearance images and infrared spectra before and after the test, for example. Figure 25 and Figure 26 As shown in the figure, the rigid quaternary ammonium salt side-chain polynorbornene ion membrane of the present invention exhibits less change in appearance compared to the commercial membrane PiperIon, demonstrating higher stability.

[0190] Rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membranes prepared using PNB-40PBCQA-r-60Hex, PNB-45PBCQA-r-55Hex, PNB-50PBCQA-r-50Hex, and PNB-60PBCQA-r-40Hex materials were tested for their mechanical properties as follows: Figure 27 As shown in the figure, the ratio of NBP-BCQA-Sb and NB-Hex used in the preparation process affects the mechanical properties of the ion exchange membrane. As a flexible comonomer, increasing the proportion of NB-Hex can improve the toughness of the ion exchange membrane and enhance its tensile properties. As a rigid ionomer, NBP-BCQA-Sb, by adjusting its ratio and combining it with the flexible comonomer, can significantly improve the mechanical properties of the ion exchange membrane.

[0191] A rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membrane prepared using PNB-45PBCQA-r-55Hex was selected, and its performance in an alkaline water electrolysis tank was tested. The cathode catalyst was Pt / Ru / C, the anode catalyst was Fe / Ni, the alkaline electrolyte was 1 M KOH, and the temperature was 80 ℃. The test results are as follows. Figure 28As shown in the figure, the rigid quaternary ammonium salt side-chain polynorbornene ion membrane exhibits excellent water electrolysis performance.

[0192] It will be apparent to those skilled in the art that this disclosure is not limited to the details of the exemplary embodiments described above, and that this disclosure can be implemented in other specific forms without departing from the spirit or essential characteristics of this disclosure. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of this disclosure is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within this disclosure.

[0193] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A rigid quaternary ammonium salt side-chain polynorbornene, characterized in that, The raw material for the rigid quaternary ammonium salt side-chain polynorbornene includes at least a rigid ionic monomer, wherein the rigid ionic monomer contains a cyclic quaternary ammonium salt structure, an aromatic ring structure, and a norbornene structure, wherein the cyclic quaternary ammonium salt structure is directly linked to the aromatic ring structure, and the aromatic ring structure is directly linked to the norbornene structure.

2. The rigid quaternary ammonium salt side-chain polynorbornene according to claim 1, characterized in that, The aromatic ring structure is selected from monobenzene rings and biphenyl rings.

3. The rigid quaternary ammonium salt side-chain polynorbornene according to claim 2, characterized in that, The benzylic position of the aromatic ring structure connected to the cyclic quaternary ammonium salt structure is substituted with methyl or methoxy groups.

4. The rigid quaternary ammonium salt side-chain polynorbornene according to claim 1, characterized in that, The rigid ionic monomer is selected from: , , , , , , .

5. The rigid quaternary ammonium salt side-chain polynorbornene according to claim 1, characterized in that, The raw material for the rigid quaternary ammonium salt side-chain polynorbornene also includes a flexible comonomer, which is selected from: , , , , , , ; in, In this case, x is between 0 and 4.

6. The rigid quaternary ammonium salt side-chain polynorbornene according to claim 5, characterized in that, In the rigid quaternary ammonium salt side-chain polynorbornene, the proportion of rigid ionic monomers is 100%-40%, and the proportion of flexible comonomers is 0%-60%.

7. A method for preparing rigid quaternary ammonium salt side-chain polynorbornene according to claim 1, characterized in that, The preparation method includes the following steps: At least rigid ionic monomers should be used as raw materials; The rigid ionic monomer and solvent were mixed, and a catalyst was added under an inert atmosphere. The mixture was reacted at 45℃-55℃ for 12-18 hours and then evaporated to obtain rigid quaternary ammonium salt side-chain polynorbornene.

8. The method for preparing rigid quaternary ammonium salt side-chain polynorbornene according to claim 7, characterized in that, The solvent is at least one of dichloromethane and chloroform, and the catalyst is palladium chloro[(η³-1-phenyl-2-propen-1-yl)][1,3-bis(2,4,6-trimethylphenyl)-2-imidazoline] 9. A rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membrane, characterized in that, The raw material of the rigid quaternary ammonium salt side-chain polynorbornene ion membrane includes at least the rigid quaternary ammonium salt side-chain polynorbornene as described in claim 1.

10. A method for preparing a rigid quaternary ammonium salt side-chain polynorbornene ion-exchange membrane according to claim 9, characterized in that, The preparation method includes the following steps: A 1%wt-5%wt solution of rigid quaternary ammonium salt side chain polynorbornene and solvent was prepared, and a saturated sodium chloride solution was added dropwise for precipitation and ion exchange. After precipitation, the solution was filtered and dried to obtain the dried product. The dried material and solvent were mixed to form a solution, which was then dried to form a film, thus obtaining a rigid quaternary ammonium salt side-chain polynorbornene ion membrane.

Images