Ion conductive polymer and separator comprising same

Abstract

To provide an ion conductive polymer having improved ion conductivity, and a separation membrane containing the same.SOLUTION: The present disclosure relates to an ion-conducting polymer having a repeat unit comprising a quaternary ammonium and at least one ether group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an ion-conducting polymer and a separation membrane containing the same. [Background technology]

[0002] A separation membrane is generally a barrier between two different substances, allowing a specific substance to pass through selectively. Separation membranes are divided into various types depending on their properties, materials, and form. In the case of ion exchange membranes, they fall into the categories of non-porous membranes, symmetric membranes, single membranes, homogeneous membranes, hydrophilic membranes, charged membranes, and liquid separation membranes.

[0003] Ion exchange membranes are membranes that have the ability to exchange specific ions and are a type of highly efficient separation membrane. When an ion exchange membrane is placed in an electrolyte solution and an electric current is passed through it, the positively or negatively charged functional groups on the membrane's pore walls attract only specific ions with the opposite charge into the membrane's pores, making it electrically neutral. The specific ions bound to the membrane's functional groups pass through the membrane by continuously binding and dissociating with the functional groups.

[0004] Ion exchange membranes are classified into cation exchange membranes (CEM), anion exchange membranes (AEM), and bipolar exchange membranes (BEM) based on their characteristics. Cation exchange membranes are membranes that allow only cations to pass through, with anions having a fixed charge. Anion exchange membranes are membranes that allow only anions to pass through, with cations having a fixed charge. Bipolar exchange membranes have a cation exchange membrane and an anion exchange membrane attached to both sides, and selectively allow both cations and anions to pass through.

[0005] Ion exchange membranes can be used in a variety of fields, including water treatment, chemistry, and energy. Because ion exchange membranes must selectively allow specific charges to pass through, they must have low electrical resistance and high ionic conductivity. Furthermore, ion exchange membranes must have excellent mechanical strength and chemical stability for long-term continuous use. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Korean Patent Publication No. 2018-0100079 Summary of the Invention [Problem to be solved by the invention]

[0007] One object of the present disclosure is to provide an ion-conducting polymer with improved ionic conductivity.

[0008] One object of the present disclosure is to provide a separation membrane with improved ionic conductivity. [Means for solving the problem]

[0009] The ion-conducting polymer according to an exemplary embodiment of the present disclosure has a repeating unit represented by the following Chemical Formula 1: [ka] In chemical formula 1, A + is a quaternary ammonium, B - is an anion, a is an integer between 1 and 3, R 1 is an organic group having 1 to 10 carbon atoms, R 2 is H or an organic group having 1 to 10 carbon atoms, R 3 is an organic group having 1 to 20 carbon atoms and containing at least one alkylene group or arylene group, and Ar is a benzene ring.

[0010] In an exemplary embodiment, the B -may be a monovalent or divalent anion.

[0011] In an exemplary embodiment, the B - may be a halogen anion.

[0012] In an exemplary embodiment, the B - is the bromine anion (Br - ) may also be used.

[0013] In an exemplary embodiment, the R 1 may be a methyl group (-CH3).

[0014] In an exemplary embodiment, the R 2 may be an organic group having 1 to 8 carbon atoms.

[0015] In an exemplary embodiment, the R 3 may be an organic group having 4 to 16 carbon atoms.

[0016] In an exemplary embodiment, the repeating unit represented by Chemical Formula 1 may include at least one of repeating units represented by the following Chemical Formulas 1-1 to 1-5. [ka] [ka] [ka] [ka] [ka]

[0017] In an exemplary embodiment, the OH of the ion-conducting polymer at 25° C. - The ionic conductivity may be 40 mS / cm to 80 mS / cm.

[0018] In a method for producing an ion-conducting polymer according to an exemplary embodiment of the present disclosure, a monomer having a benzene ring substituted with at least one alkoxy group is prepared. The monomer is reacted with an aldehyde under mild acid conditions to obtain a precursor polymer. A quaternary ammonium group is introduced into the precursor polymer to synthesize an ion-conducting polymer having a repeating unit represented by the following Chemical Formula 1: [ka]

[0019] In chemical formula 1, A + is a quaternary ammonium, B - is an anion, a is an integer between 1 and 3, R 1 is an organic group having 1 to 10 carbon atoms, R 2 is H or an organic group having 1 to 10 carbon atoms, R 3 is an organic group having 1 to 20 carbon atoms and containing at least one alkylene group or arylene group, and Ar is a benzene ring.

[0020] The separation membrane according to the exemplary embodiment includes the ion-conducting polymer described above.

[0021] The device according to the exemplary embodiment includes a positive electrode, a negative electrode facing the positive electrode, and the separator.

[0022] In exemplary embodiments, the device may include a water electrolyzer, a CO2 electrolyzer, a fuel cell, an electrolysis battery, a vanadium flow battery, or the like. [Effects of the Invention]

[0023] Ion-conducting polymers according to exemplary embodiments of the present disclosure can exhibit excellent ionic conductivity.

[0024] The separation membrane according to the exemplary embodiment of the present disclosure may exhibit excellent ion conductivity by including the ion-conducting polymer.

[0025] The ion-conducting polymers and separation membranes of the present disclosure can be widely applied in the field of green technology, such as electric vehicles, battery charging stations, and other battery-based solar and wind power generation.

[0026] In addition, the ion-conducting polymer and separation membrane of the present disclosure can be used in eco-friendly electric vehicles, hybrid vehicles, and the like, which aim to prevent climate change by suppressing air pollution and greenhouse gas emissions. DETAILED DESCRIPTION OF THE INVENTION

[0027] According to an embodiment of the present disclosure, an ion-conducting polymer is provided having repeating units comprising a quaternary ammonium and at least one ether group.

[0028] The ion-conductive polymer can have improved stability and ion conductivity by containing a quaternary ammonium group.

[0029] The ion-conductive polymer contains an ether group, which allows the polymer to be synthesized under mild acid conditions.

[0030] The ion-conductive polymer can improve its physicochemical durability by including a main chain made of a carbon-carbon bond (C—C bond).

[0031] The present disclosure is described in detail below, but by way of example only, and the present disclosure is not limited to the specific embodiments illustratively described.

[0032] The ion-conducting polymer according to an exemplary embodiment of the present disclosure has a repeating unit represented by the following Chemical Formula 1:

[0033] [ka]

[0034] In an exemplary embodiment, A + may be a quaternary ammonium. In an exemplary embodiment, A + may be a substituent containing at least one methyl group. For example, A + may be a quaternary ammonium.

[0035] In the present disclosure, ammonium may also include those in which two different substituents bound to the nitrogen atom are linked to form a ring structure. For example, A + The ammonium salt may be trimethylammonium, triethylammonium, tripropylammonium, tributylammonium, imidazolium, piperidinium, quinuclidinium, or the like.

[0036] In an exemplary embodiment, B - may be an anion. In an exemplary embodiment, B - may be a monovalent or divalent anion. For example, B - When is a divalent anion, two A's located on different chains + There is one B - can be bonded together to form a cross-linked structure.

[0037] In an exemplary embodiment, B - may be a halogen anion. For example, - is the chlorine anion (Cl - ), bromine anion (Br - ), iodine anion (I - ), hydroxide ion (OH - ), sulfate anion (SO4 2- ), carbonate anion (CO3 2- ), bicarbonate anion (HCO3- ), carboxylate anion (RCO2 - ) may also be used.

[0038] In an exemplary embodiment, a may be an integer from 1 to 3. For example, a may be 1 or 3.

[0039] In an exemplary embodiment, the R 1 may be an organic group having 1 to 10 carbon atoms.

[0040] In exemplary embodiments, the organic group may be a substituent containing only carbon and hydrogen, or may be a substituent containing one or more atoms other than carbon and hydrogen, such as nitrogen (N), oxygen (O), phosphorus (P), sulfur (S), etc.

[0041] In an exemplary embodiment, the R 1 may be an organic group having 1 to 6 carbon atoms. For example, 1 may be a methyl group (-CH3).

[0042] In an exemplary embodiment, the ion-conducting polymer having the repeating unit represented by Chemical Formula 1 may include an ether bond in the benzene ring. When the ether bond is included in the benzene ring, the benzene ring is placed in an electron-rich state. This allows the synthesis of the ion-conducting polymer to be carried out under relatively mild acid conditions, rather than under super-strong acid conditions such as triflic acid.

[0043] According to an exemplary embodiment, the mild acid may have a pKa of −7 or greater.

[0044] For example, the mild acid may be methanesulfonic acid, trifluoroacetic acid, nitric acid, sulfuric acid, hydrochloric acid, and the like.

[0045] In an exemplary embodiment, the R 2 may be H or an organic group having 1 to 10 carbon atoms.

[0046] In exemplary embodiments, the organic group may be a hydrocarbon group or a hydrocarbon group containing one or more heteroatoms, such as nitrogen (N), oxygen (O), phosphorus (P), or sulfur (S).

[0047] For example, the R 2 may be an organic group having 1 to 8 carbon atoms. 2 may be an organic group having 1 to 6 carbon atoms.

[0048] In an exemplary embodiment, the R 2 may be further substituted with an electron withdrawing group (EWG). The electron withdrawing group may be, for example, a nitro group, a trifluoromethyl group, a cyano group, a fluoro group, or an acyl group. This makes it easier to synthesize the ion-conducting polymer.

[0049] In an exemplary embodiment, the R 3 may be an organic group having 1 to 20 carbon atoms and containing at least one of an alkylene group or an arylene group. 3 may be an organic group having 4 to 16 carbon atoms. 3 may be an organic group having 6 to 14 carbon atoms. 3 may be an organic group having 8 to 12 carbon atoms.

[0050] When a quaternary ammonium ion is directly attached to a benzene ring, the ammonium functionality undergoes bimolecular nucleophilic substitution (S N It can be decomposed by either the S2 reaction or the Hofmann elimination reaction. N 2 reaction occurs, the ammonium functional group becomes OH - The Hoffmann elimination reaction can be reversed to form an alcohol functional group and a tertiary amine. - The ammonium functional group may be attacked by the ammonium group to form a double bond, which may result in decomposition of the ammonium functional group. The decomposition of the ammonium functional group may significantly reduce the mechanical strength and ionic conductivity of the ion-conducting polymer.

[0051] In the present disclosure, the quaternary ammonium ion is R 3 Since it is connected to the benzene ring via OH, the electron withdrawing inductive effect and resonance effect of the benzene ring are reduced, and - This reduces the attack by ammonium salts, thereby preventing the decomposition of the ammonium functional group.

[0052] In an exemplary embodiment, the R 3 The ion-conducting polymer may contain a mixture of aromatic and aliphatic chains, which can further improve the mechanical strength of the ion-conducting polymer.

[0053] In an exemplary embodiment, Ar can be a benzene ring.

[0054] In an exemplary embodiment, the repeating unit represented by Chemical Formula 1 may include at least one of repeating units represented by the following Chemical Formulas 1-1 to 1-5.

[0055] [ka] [ka] [ka] [ka] [ka]

[0056] In an exemplary embodiment, the OH of the ion-conducting polymer at 25° C. - The ionic conductivity may be 40 mS / cm to 80 mS / cm. For example, the OH - The ionic conductivity may be 43 mS / cm to 70 mS / cm, or 45 mS / cm to 65 mS / cm, or 46 mS / cm to 63 mS / cm, or 47 mS / cm to 60 mS / cm.

[0057] In one embodiment according to the present disclosure, a method for producing an ion-conducting polymer is provided.

[0058] First, a monomer having a benzene ring substituted with at least one alkoxy group is prepared.

[0059] The alkoxy group is -(OR 1 ) a Here, a may be an integer of 1 to 3.

[0060] The benzene ring has an R substituted with a halogen at its end. 3 It may be bonded to.

[0061] The monomer is then reacted with an aldehyde under mild acid conditions to obtain a precursor polymer.

[0062] When the monomer is reacted with an aldehyde under mild acid conditions (primary polymerization), a precursor polymer containing the benzene ring in the main chain is obtained.

[0063] The primary polymerization can be carried out in the presence of a mild acid. The mild acid can be any of the mild acids described above. For example, an acid with a pKa of −7 or higher can be used.

[0064] As mentioned above, when a benzene ring contains an ether bond (alkoxy group), the benzene ring is placed in an electron-rich state, which allows the synthesis of ion-conducting polymers to be carried out under relatively mild acid conditions, rather than under super-strong acid conditions such as triflic acid.

[0065] The aldehyde is R 2 -CHO, and after the first polymerization, R 2 is connected to the main chain of the precursor polymer.

[0066] In some embodiments, R 2 may be further substituted with an electron-withdrawing group, which can increase the reactivity of the aldehyde and facilitate the formation of the precursor polymer.

[0067] Next, a quaternary ammonium group is introduced into the precursor polymer to synthesize an ion-conducting polymer having a repeating unit represented by Chemical Formula 1 above.

[0068] A quaternary ammonium group can be introduced into the side chain of the benzene ring to exhibit ionic conductivity.

[0069] According to an embodiment of the present disclosure, there is provided a separation membrane including the ion-conducting polymer.

[0070] In an exemplary embodiment, the separation membrane can be manufactured by laminating ion-conducting polymer membranes having a repeating unit represented by Chemical Formula 1.

[0071] According to an embodiment of the present disclosure, there is provided a device including the separation membrane. The device may include a positive electrode, a negative electrode facing the positive electrode, and the separation membrane. Devices according to exemplary embodiments may include water electrolysis devices, CO electrolysis devices, fuel cells, electrolysis batteries, vanadium flow batteries, etc.

[0072] Examples are presented below to aid in understanding the present invention, but these examples are merely illustrative of the present invention and do not limit the scope of the appended claims. It will be apparent to those skilled in the art that various changes and modifications to the examples are possible within the scope and technical spirit of the present invention, and it is natural that such changes and modifications also fall within the scope of the appended claims.

[0073] Production Example 1: Monomer Production (1) Production of Monomer 1 (A-1) 50 mL of dichloromethane, anisole (5 g, 46 mmol), and aluminum chloride (6.78 g, 51 mmol) were added to a 100 mL two-necked round-bottom flask, and the mixture was stirred in an ice bath to prepare a mixed solution.

[0074] 6-bromohexanoyl chloride (10.4 g, 49 mmol) was added to the prepared mixed solution using a syringe pump over 2 hours, and 85 mL of 1 M aqueous hydrochloric acid was added. After the reaction was completed, the aqueous layer was removed using a separatory funnel and washed with 1 M aqueous sodium hydroxide. After washing, the aqueous layer was removed, and the organic solvent layer was dried over anhydrous magnesium sulfate. The organic solvent was removed using a vacuum concentrator to obtain a solid.

[0075] A 100 mL round-bottom flask was charged with triethylsilane (16.1 g, 139 mmol), trifluoroacetic acid (5.3 g, 46 mmol), and the solid. The round-bottom flask was equipped with a reflux condenser and stirred at 85°C for 24 hours. After stirring, the mixture was cooled in an ice bath and 53 mL of 1 M aqueous sodium hydroxide solution was added. After the reaction was completed, the aqueous layer was removed using a separatory funnel, and the organic solvent layer was dried over anhydrous magnesium sulfate and purified by column chromatography to produce 11.1 g of Monomer 1 (A-1) represented by the following chemical formula 2-1. [ka]

[0076] (2) Production of Monomer 2 (A-2) A 100 mL two-necked round-bottom flask was charged with 30 mL of dichloromethane, 1,3,5-trimethoxybenzene (3 g, 18 mmol), and aluminum chloride (2.85 g, 21 mmol), and the mixture was stirred in an ice bath to prepare a mixed solution.

[0077] 6-bromohexanoyl chloride (4.57 g, 21 mmol) was added to the prepared mixed solution using a syringe pump over 2 hours, and 45 mL of 1 M aqueous hydrochloric acid was added. After the reaction was completed, the aqueous layer was removed using a separatory funnel and washed with 1 M aqueous sodium hydroxide. After washing, the aqueous layer was removed, and the organic solvent layer was dried over anhydrous magnesium sulfate. The organic solvent was removed using a vacuum concentrator to obtain a solid.

[0078] A 100 mL round-bottom flask was charged with triethylsilane (6.1 g, 52 mmol), trifluoroacetic acid (1.98 g, 17 mmol), and the solid. The round-bottom flask was equipped with a reflux condenser and stirred at 85°C for 24 hours. After stirring, the mixture was cooled in an ice bath, and 53 mL of 1 M aqueous sodium hydroxide solution was added. After the reaction was completed, the aqueous layer was removed using a separatory funnel, and the organic solvent layer was dried over anhydrous magnesium sulfate and purified by column chromatography to produce 3.65 g of Monomer 2 (A-2) represented by the following chemical formula 2-2. [ka]

[0079] (3) Production of Monomer 3 (A-3) 75 mL of dichloromethane, 4-methoxybiphenyl (5 g, 27 mmol), and aluminum chloride (3.98 g, 30 mmol) were added to a 100 mL two-necked round-bottom flask, and the mixture was stirred in an ice bath to prepare a mixed solution.

[0080] 6-Bromohexanoyl chloride (6.08 g, 28 mmol) was added to the prepared mixed solution using a syringe pump for 2 hours, and 50 mL of 1 M aqueous hydrochloric acid was added. After the reaction was completed, the aqueous layer was removed using a separatory funnel and washed with 1 M aqueous sodium hydroxide. After washing, the aqueous layer was removed, and the organic solvent layer was dried over anhydrous magnesium sulfate. The organic solvent was removed using a vacuum concentrator to obtain a solid.

[0081] A 100 mL round-bottom flask was charged with triethylsilane (12.6 g, 109 mmol), trifluoroacetic acid (6.2 g, 54 mmol), and the solid. A reflux condenser was attached to the round-bottom flask, and the mixture was stirred at 85°C for 24 hours. After stirring, the mixture was cooled in an ice bath, and 60 mL of 1 M aqueous sodium hydroxide solution was added. After the reaction was completed, the aqueous layer was removed using a separatory funnel, and the organic solvent layer was dried over anhydrous magnesium sulfate and purified by column chromatography to produce 6.20 g of Monomer 3 (A-3) represented by the following chemical formula 2-3. [ka]

[0082] Production Example 2: Polymer Production (1) Production of Polymer 1 (B-1) A 25 mL round-bottom flask was charged with 14.8 mL of chloroform, 1.8 mL of methanesulfonic acid, 0.24 g of paraformaldehyde (equivalent to 8 mmol of formaldehyde), and 2 g of A-1 (7 mmol). A reflux condenser was attached to the round-bottom flask, and the mixture was refluxed at 85°C for 2 hours. After refluxing, the mixture was cooled to room temperature (25°C) and poured into 200 mL of methanol to precipitate a solid. The precipitated solid was filtered, washed twice with 50 mL of methanol, and dried in an oven to produce 1.9 g of Polymer 1 (B-1) represented by the following formula 3-1. [ka]

[0083] (2) Production of Polymer 2 (B-2) A 25 mL round-bottom flask was charged with 12.0 mL of chloroform, 1.5 mL of methanesulfonic acid, 0.20 g of paraformaldehyde (equivalent to 7 mmol of formaldehyde), and 2 g of A-2 (6 mmol). A reflux condenser was attached to the round-bottom flask, and the mixture was refluxed at 85°C for 2 hours. After refluxing, the mixture was cooled to room temperature (25°C), and 200 mL of methanol was added to precipitate a solid. The precipitated solid was filtered, washed twice with 50 mL of methanol, and dried in an oven to produce 1.6 g of polymer 2 (B-2) represented by the following formula 3-2. [ka]

[0084] (3) Production of Polymer 3 (B-3) A 25 mL round-bottom flask was charged with 14.8 mL of chloroform, 1.8 mL of methanesulfonic acid, benzaldehyde (0.77 g, 7 mmol), and A-1 (2 g, 7 mmol). The round-bottom flask was equipped with a reflux condenser and refluxed at 85°C for 2 hours. After refluxing, the mixture was cooled to room temperature (25°C) and 200 mL of methanol was added to precipitate a solid. The precipitated solid was filtered, washed twice with 50 mL of methanol, and dried in an oven to produce 2.3 g of polymer 3 (B-3) represented by the following formula 3-3. [ka]

[0085] (4) Preparation of Polymer 4 (B-4) A 25 mL round-bottom flask was charged with 14.8 mL of chloroform, 1.8 mL of methanesulfonic acid, 1.09 g (7 mmol) of 4-nitrobenzaldehyde, and 2 g (7 mmol) of A-1. A reflux condenser was attached to the round-bottom flask, and the mixture was refluxed at 85°C for 2 hours. After refluxing, the mixture was cooled to room temperature (25°C), and 200 mL of methanol was added to precipitate a solid. The precipitated solid was filtered, washed twice with 50 mL of methanol, and dried in an oven to produce 3.0 g of polymer 4 (B-4), represented by the following chemical formula 3-4. [ka]

[0086] (5) Production of Polymer 5 (B-5) A 25 mL round-bottom flask was charged with 11.5 mL of chloroform, 1.44 mL of methanesulfonic acid, paraformaldehyde (0.61 g, equivalent to 20 mmol of formaldehyde), and A-3 (2 g, 6 mmol). The round-bottom flask was equipped with a reflux condenser and refluxed at 85°C for 2 hours. After reflux, the mixture was cooled to room temperature (25°C) and 200 mL of methanol was added to precipitate a solid. The precipitated solid was filtered, washed twice with 50 mL of methanol, and dried in an oven to produce 1.7 g of polymer 5 (B-5) represented by the following chemical formula 3-5.

[0087] [ka]

[0088] Manufacturing Example 3: Manufacturing of separation membrane Example 1 1.45 mL of N-methylpyrrolidone and 0.25 g of B-1 were added to a 20 mL glass vial and stirred at room temperature (25°C). After B-1 was completely dissolved, 0.17 g of N,N-dimethylcyclohexylamine was added and stirred at 80°C for 24 hours. After stirring, the mixture was cooled to room temperature (25°C), poured into a Petri dish, and dried in an oven at 80°C for 24 hours to produce a separator (C-1) made from a polymer having a repeating unit represented by Chemical Formula 1-1. Regarding C-1 1 H-nuclear magnetic resonance spectroscopy ( 1 H-Nuclear Magnetic Resonance, 1 The results of H-NMR are shown below. 1 H-NMR (DMSO-d6, ppm):7.3(br,2H),4.0(br,2H),3.8(br,3H),3.6-3.2(br,9H),2.6-2.5(br,2H),2.0-1.0(br,18H)

[0089] Example 2 2.12 mL of N-methylpyrrolidone and 0.25 g of B-2 were added to a 20 mL glass vial and stirred at room temperature (25°C). After B-2 was completely dissolved, 0.28 g of an aqueous trimethylamine solution (28 wt%) was added and stirred at 80°C for 24 hours. After stirring, the solution was cooled to room temperature (25°C), poured into a Petri dish, and dried in an oven at 80°C for 24 hours to produce a separator (C-2) made from a polymer having a repeating unit represented by Chemical Formula 1-2. Regarding C-2 1 The results of H-nuclear magnetic resonance spectroscopy are shown below. 1 H-NMR(DMSO-d6,ppm):3.9(br,2H),3.8(br,9H),3.3-3.2(br,11H),2.7-2.6(br,2H),2.0-1.0(br,8H)

[0090] Example 3 1.38 mL of N-methylpyrrolidone and 0.25 g of B-3 were placed in a 20 mL glass vial and stirred at room temperature (25°C). After B-3 was completely dissolved, 0.10 g of 1-methylimidazole was added and stirred at 80°C for 24 hours. After stirring, the mixture was cooled to room temperature (25°C), poured into a Petri dish, and dried in an oven at 80°C for 24 hours to produce a separator (C-3) made from a polymer having a repeating unit represented by chemical formula 1-3. Regarding C-3 1 The results of H-nuclear magnetic resonance spectroscopy are shown below. 1 H-NMR(DMSO-d6,ppm):8.92(br,1H),7.9-7.0(br,9H),5.48(br,1H),5.01(br,2H),3.9-3.7(br,6H),2.64(br,2H),2.1-1.2(br,8H)

[0091] Example 4 1.83 mL of N-methylpyrrolidone and 0.25 g of B-4 were placed in a 20 mL glass vial and stirred at room temperature (25°C). After B-4 was completely dissolved, 0.21 g of an aqueous trimethylamine solution (28 wt%) was added and stirred at 80°C for 24 hours. After stirring, the mixture was cooled to room temperature (25°C), poured into a Petri dish, and dried in an oven at 80°C for 24 hours to produce a separator (C-4) made from a polymer having a repeating unit represented by Chemical Formula 1-4. Regarding C-4 1 The results of H-nuclear magnetic resonance spectroscopy are shown below. 1 H-NMR(DMSO-d6,ppm):8.16(br,2H),7.5-7.0(br,4H),5.50(br,1H),3.78(br,3H),3.5-3.0(br,11H),2.66(br,2H),1.8-1.2(br,8H)

[0092] Example 5 1.44 mL of N-methylpyrrolidone, 1.44 g of dimethyl sulfoxide, and 0.25 g of B-5 were added to a 20 mL glass vial and stirred at room temperature (25°C). After B-5 was completely dissolved, 0.1 g of N-methylpiperidine was added and stirred at 80°C for 24 hours. After stirring, the mixture was cooled to room temperature (25°C), poured into a Petri dish, and dried in an oven at 80°C for 24 hours to produce a separator (C-5) made from a polymer having a repeating unit represented by formula 1-5. Regarding C-5 1 The results of H-nuclear magnetic resonance spectroscopy are shown below. 1 H-NMR(DMSO-d6,ppm):7.8-7.0(br,6H),4.0-3.8(br,5H),3.4-3.0(br,9H),2.63(br,2H),2.0-1.0(br,14H)

[0093] Comparative Example 1 Dioxide materials' Sustainion® X37-50 Grade RT product was used.

[0094] Comparative Example 2 Dioxide materials' Sustainion® X37-50 Grade T product was used.

[0095] Experimental example: Evaluation of ionic conductivity of separation membrane The membrane samples of Examples 1 to 5 and Comparative Examples 1 and 2 were cut into a size of 1 cm×3 cm and fixed between Pt electrodes of a Conductivity Clamp (BT-110, Scribner).

[0096] The ionic conductivity (σ) of the anion exchange membrane was measured at room temperature (25°C) and in triple distilled water. -The membrane resistance (R) was measured by the 4-point probe method using an impedance analyzer (VSP-3e, Biologics) in the frequency range of 0.1 kHz to 1 MHz. The thickness (T) of the membrane sample was measured using a micrometer.

[0097] The ionic conductivity (σ) was calculated using the following formula 1. The results are shown in Table 1 below.

[0098]

number

[0099] In Equation 1, R is the membrane resistance (Ω), A is the cross-sectional area of ​​the membrane sample (cm 2 ), L is the distance between the electrodes (cm), W is the width of the membrane sample (cm), and T is the thickness of the membrane sample (cm).

[0100] [Table 1]

[0101] From Table 1, the OH values ​​of Examples 1 to 5 - The ionic conductivity of the OH films of Comparative Examples 1 and 2 was - It can be confirmed that the ionic conductivity is superior to that of the ionic conductivity.

Claims

1. An ion-conducting polymer having a repeating unit represented by the following chemical formula 1: 【Chemistry 1】 (In chemical formula 1, A ＋ is a quaternary ammonium, B － is an anion, a is an integer from 1 to 3, R １ is an organic group having 1 to 10 carbon atoms, R ２ is H or an organic group having 1 to 10 carbon atoms, R ３ is an organic group having 1 to 20 carbon atoms containing at least one alkylene group or arylene group, and Ar is a benzene ring.

2. B － The ion-conducting polymer according to claim 1 , wherein is a monovalent or divalent anion.

3. B － The ion-conducting polymer according to claim 1 , wherein is a halogen anion.

4. B － is the bromine anion (Br － 4. The ion-conducting polymer according to claim 3, wherein

5. The R １ is a methyl group (-CH ３ 2. The ion-conducting polymer according to claim 1, wherein

6. The R ２ is an organic group having 1 to 8 carbon atoms.

7. The R ３ is an organic group having 4 to 16 carbon atoms.

8. The ion-conducting polymer according to claim 1, wherein the repeating unit represented by Chemical Formula 1 includes at least one of repeating units represented by the following Chemical Formulas 1-1 to 1-5. 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 【Transformation 6】

9. The OH of the ion-conductive polymer at 25°C － 2. The ion-conducting polymer according to claim 1, wherein the ion conductivity is 40 mS / cm to 80 mS / cm.

10. providing a monomer having a benzene ring substituted with at least one alkoxy group; reacting the monomer with an aldehyde under mild acid conditions to obtain a precursor polymer; and introducing a quaternary ammonium group into the precursor polymer to synthesize an ion-conducting polymer having a repeating unit represented by the following chemical formula 1: 【Transformation 7】 (In chemical formula 1, A ＋ is a quaternary ammonium, B － is an anion, a is an integer from 1 to 3, R １ is an organic group having 1 to 10 carbon atoms, R ２ is H or an organic group having 1 to 10 carbon atoms, R ３ is an organic group having 1 to 20 carbon atoms containing at least one alkylene group or arylene group, and Ar is a benzene ring.

11. A separation membrane comprising the ion-conducting polymer according to claim 1.

12. A positive electrode and a negative electrode facing the positive electrode; and the separation membrane of claim 11.

13. The device includes a water electrolysis device, a CO ２ 13. The device of claim 12, comprising an electrolyzer, a fuel cell, an electrolytic cell, or a vanadium flow battery.

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