Polymeric anionic conductive compounds, their preparation, and their use in electrochemistry

Abstract

The present invention provides a (polymeric) compound and a method for its preparation. The application is in the field of electrochemistry. Due to the anion conducting properties of the disclosed compound, the material is suitable for the production of anion conducting membranes. The aim of the present invention is to provide an easy to produce material with suitable anion conducting properties and controlled swelling. The synthesis shall use inexpensive precursors. The problem is to obtain a compound of formula (I): [Formula 1] TIFF2024503388000034.tif54170 (in the formula, X is at least one nitrogen atom carrying a positive charge, C 1 and C 2 and is bonded via two bonds to one or two hydrocarbon groups having 1 to 12 carbon atoms, Z is C 3 and C 4 and at least one aromatic six-membered ring bonded directly to one of the oxygen atoms, The aromatic six-membered ring is substituted at the 3- and 5-positions with the same or different alkyl groups having 1 to 4 carbon atoms. The problem is solved by providing a compound characterized by at least one unit of

Description

[Technical Field]

[0001] This invention provides compounds, particularly polymer compounds, methods for preparing them, and uses of these compounds. The applications are in the field of electrochemistry. Due to the anionic conductivity properties of the disclosed compounds, these materials are suitable for the production of anionic conductive films. [Background technology]

[0002] One important example of an electrochemical process is the electrolysis of water to obtain molecular hydrogen and molecular oxygen. The electrochemical assembly used to carry out such a process is called an electrolytic cell. Such an electrolytic cell typically comprises a number of electrochemical cells. Each electrochemical cell has two compartments, each compartment equipped with one gas-generating electrode and a membrane separating the two compartments. To enable the electrolysis of water, the membrane needs to be conductive to ions (cations or anions) but almost impermeable to hydrogen and oxygen gases. The compounds discussed herein are intended to constitute such membranes.

[0003] Because the membrane of the electrolytic cell comes into contact with water, it needs to be stable against excessive swelling or deformation (wrinkling) caused by the absorption of large amounts of water within the polymer structure. Excessive swelling can cause mechanical damage to the membrane and lead to increased gas permeability. For safety reasons, gas permeability must be limited; otherwise, there is a risk of oxyhydrogen explosion.

[0004] However, measures to enhance stability against swelling must not impair the anionic conductivity of the material, because this would lead to a decrease in process efficiency.

[0005] Similar requirements apply to membranes used in electrochemical cells that perform other electrochemical processes in aqueous / hydrous environments. Examples include fuel cells, redox flow batteries, and batteries used in electrodialysis.

[0006] A polymeric anionic conductive material suitable for preparing membranes to be used in electrolytic cells is known from International Publication No. 2019 / 076860. This material is characterized by at least one imidazole and / or imidazolium unit.

[0007] Chinese Patent Application Publication No. 104829814A discloses a polymer containing a quaternized piperidine group. This polymer is also used in the manufacture of anion exchange membranes.

[0008] A method for preparing tertiary amine-type polyaryl ethersulfone (ketone) polymer resins is known from Chinese Patent Application Publication No. 110294845A. This polymer is used in the preparation of anion exchange membranes.

[0009] Several anion exchange membranes for water electrolysis are commercially available. An overview of the market is provided by Henkensmeier et al.: Henkensmeier, Dirk and Najibah, Malikah and Harms, Corinna and Zitka, Jan and Hanat, Jaromir and Bouzek, Karel (2020) Abstract: State-of-the-art commercial membranes for anion exchange membrane water electrolysis. Journal of Electrochemical Energy Conversion and Storage, 18(2), 024001. American Society of Mechanical Engineers (ASME). DOI:10.1115 / 1.4047963 ISSN 2381-6872

[0010] An example of a commercially available anion exchange membrane is a product called fumasep® FAA-3-50, manufactured by FUMATECH BWT GmbH (74321 Bietigheim-Bissingen, Germany). According to Henkensmeier et al., this membrane is based on a polyaromatic polymer having ether bonds in the main chain and quaternary ammonium groups bonded to the main chain.

[0011] The disadvantages of these known materials are large water absorption, excessive swelling, rare and expensive precursors, toxic and highly corrosive solvents, and complex preparation conditions that are difficult for industrial-scale production. Therefore, these known materials have high manufacturing costs.

Prior Art Documents

Patent Documents

[0012]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0013] [[ID=J1]]Therefore, an object of the present invention is to provide a material that is easy to prepare, particularly having appropriate anion conduction characteristics and controlled swelling properties in an aqueous environment. The precursors required for the synthesis of the compound are inexpensive, and the synthesis process is suitable for industrial production.

[0014] [[ID=3*]]<00001*9>The currently unpublished international patent application PCT / EP2020 / 070153 has the formula (0):

[0015]

Chemical Formula

[0016] (wherein, X is a nitrogen atom with a positive charge, C 4 , 2 , , 3 , 1 and C 2 is bonded to, and is a component containing a nitrogen atom bonded to one or two hydrocarbon groups having 1 to 12, preferably 1 to 6, more preferably 1 or 5 carbon atoms via two bonds, Z is C 3 and C 4A structural element comprising a carbon atom bonded to it and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms, The aromatic ring may be substituted with one or more halogens and / or one or more C1-C4 alkyl groups. The present invention relates to a polymer anion conductive membrane made from a compound containing at least one unit of . This material already satisfies the aforementioned requirements. However, the inventors have surprisingly found that this problem can also be solved by the compound of the present invention, which is described below and also included in the claims.

[0017] Therefore, the present invention provides the compounds defined in the claims and described below.

[0018] The compounds of the present invention are characterized by at least one unit of formula (I).

[0019] [ka]

[0020] (In the formula, X is at least one nitrogen atom with a positive charge, and C 1 and C 2 A component comprising a nitrogen atom bonded to and bonded via two bonds to one or two hydrocarbon groups having 1 to 12, preferably 1 to 6, more preferably 1 or 5 carbon atoms, Z is C 3 and C 4 A structural element comprising a carbon atom bonded to it and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms, The aromatic six-membered ring is substituted at positions 3 and 5 with the same or different alkyl groups having 1 to 4 carbon atoms, preferably a methyl group, an isopropyl group, or a tert-butyl group, more preferably a methyl group.

[0021] Therefore, the compounds of the present invention differ from the compounds of formula (0) in at least the sulfonic acid group.

[0022] The present invention also provides a method for preparing such compounds and a method for using such compounds as an anion-conducting membrane in an electrochemical cell.

[0023] The polymer according to the present invention has the advantage of being able to be prepared by a simple method. The precursor is equally inexpensive. Therefore, the cost-effectiveness of preparation is high.

[0024] The resulting membrane has the advantage of extremely high mechanical stability and low swelling characteristics due to its high dimensional stability. Furthermore, the membrane exhibits very high anionic conductivity. Therefore, the compounds of the present invention are well-suited as separation active materials consisting of membranes used in electrochemical cells that perform electrochemical processes in aqueous / hydrous environments.

[0025] In preferred embodiments, the compounds of the present invention are represented by formula (Ia) or formula (Ib).

[0026] [ka]

[0027] (In the formula, Y is the same or different halogen, preferably fluorine, and M is an integer from 1 to 1,000, preferably an integer from 5 to 500.)

[0028] According to a preferred embodiment of the present invention, component X represents a unit of formula (IIa), formula (IIb), or formula (IIc).

[0029] [ka]

[0030] (In the formula, R1, R2 and R3 are the same or different alkyl groups having 1 to 6 carbon atoms, the two nitrogen atoms are bonded by an aliphatic chain having 1 to 6 carbon atoms (n = 1 to 6), and R1, R2 and R3 are each preferably a methyl group.)

[0031] Most preferably, the component X present has an appearance rate of the unit of formula (IIa), formula (IIb) or formula (IIc) exceeding 5%, preferably exceeding 50%, and most preferably exceeding 90%. This appearance rate is, for example, in DMSO-d6 as a solvent, at room temperature, in accordance with 01 / 2005:20233 (European Pharmacopoeia 5.0.2.2.33. Nuclear Magnetic Resonance Spectroscopy), and is carried out by classical 1 1H-NMR measurement. The appearance rate can be calculated by comparing the integration of the area of the corresponding signal with the normalized area of the corresponding signal (peak) and the number of corresponding protons in the target unit. For example, the unit of formula (IIa) contains 6 hydrogen atoms, and as shown in Figure 2, the normalized area of the corresponding signal (labeled 5) is equal to 6.003. This indicates that the appearance rate of the unit of formula (IIa) in the polymer of experimental example 3 analyzed is equal to 100% (calculated as 6.003 / 6 * 100% = 100%).

[0032] According to a more preferred embodiment of the present invention, the component Z of the compound represents a unit of formula (III).

[0033]

Chemical formula

[0034] (In the formula, R4, R5, R6 and R7 are the same or different alkyl groups having 1 to 4 carbon atoms, and R4, R5, R6 and R7 are each preferably a methyl group, an isopropyl group or a tert-butyl group, and more preferably a methyl group.)

[0035] Six preferred embodiments of the compounds of the present invention are represented by at least one of formula (IVa) to formula (IVf).

[0036] [ka]

[0037] (In the formula, M a M b and M c Each of these is an integer between 1 and 1,000, preferably M a M b and M c These are integers between 5 and 500.

[0038] Even more preferred compounds are crosslinked compounds represented by at least one of formulas (Va) to (Vd).

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] (In the formula, at least two polymer chains are linked by aliphatic chains having 1 to 10 carbon atoms (m=1 to 9), M a M b and M c Each of these is an integer between 1 and 1,000, preferably M a M b and M c(where each is an integer between 5 and 500, and X and Z are each between 0.01 and 0.5, preferably between 0.01 and 0.25.)

[0044] As can be derived from formulas (I), (Ia), (Ib), (IVa) to (IVf), and (Va) to (Vd), and related definitions, all compounds of the present invention have an aromatic six-membered ring directly bonded to one of the oxygen atoms, and the aromatic six-membered ring is substituted at positions 3 and 5 with the same or different alkyl groups having 1 to 4 carbon atoms.

[0045] According to a first modification of the present invention, the above aromatic six-membered ring is further substituted with one or more halogens and / or one or more C1-C4 alkyl groups.

[0046] According to a second preferred modification of the present invention, the above aromatic six-membered ring is not further substituted with one or more halogens and / or one or more C1-C4 alkyl groups. The precursor materials for preparing such compounds are inexpensive. Therefore, the cost of preparation and the final compound is not very high.

[0047] Another object of the present invention is to provide a method for preparing the compounds of the present invention.

[0048] This objective is achieved by a method comprising the step of reacting a compound of formula (VI) (wherein Y is the same or different halogen, preferably fluorine) with one or both compounds selected from formula (VIIa) and / or (VIIb).

[0049] [ka]

[0050] (In formulas VI, VIIa, and VIIb, the aromatic ring may be further substituted with one or more halogens and / or one or more C1-C4 alkyl groups.) If compound (VIIa) is used, an additional step (quaternization of the nitrogen atom) is required, which can be easily performed using an alkylation reagent.

[0051] Such a process can be carried out very easily, and the desired compound can be obtained.

[0052] Preferably, this reaction step is carried out at a reaction temperature of 100°C to 300°C, more preferably 125°C to 175°C. Most preferably, this reaction step is carried out at a temperature at which the reaction mixture is boiling, preferably with stirring. Most preferably, this reaction step is carried out under an inert gas atmosphere, preferably under a nitrogen atmosphere. It is preferable to remove all the water produced at the top of the reaction vessel.

[0053] This reaction step is preferably carried out in the presence of a base such as KOH, NaOH, K2CO3, or Na2CO3. The preferred base is K2CO3.

[0054] This reaction step is carried out in the presence of an organic solvent. Preferred solvents are selected from the list consisting of N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC). Preferably, N,N-dimethylacetamide is used as the solvent.

[0055] Preferably, the method according to the present invention includes a step of using an alkylating reagent, preferably a methylating reagent. The preferred methylating agent used is iodomethane.

[0056] According to the preferred preparation method of the present invention, the aromatic rings in the compounds of formula (VI), formula (VIIa), and formula (VIIb) are not further substituted with one or more halogens or one or more C1-C4 alkyl groups.

[0057] The compounds of the present invention may be used for different purposes. Preferably, the compounds of the present invention are polymers and are used as an anionic conductive membrane or in the manufacture of anionic conductive membranes. Such uses are further objectives of the present invention.

[0058] Within such a membrane, the compound of the present invention functions as a separation active material due to its excellent anion conductivity, while also being highly airtight. In addition to the compound of the present invention, the aforementioned membrane may also contain further materials, such as a porous support (e.g., fabric material or nonwoven material).

[0059] Thanks to the designed properties of the components disclosed herein, an anion-conducting membrane made of such materials can be used in an electrochemical cell. Therefore, another embodiment of the present invention is an electrochemical cell having an anion-conducting membrane made of the compound of the present invention.

[0060] Due to the excellent water stability of this compound, this material is suitable for use in electrolytic cells, fuel cells, or redox flow batteries. Therefore, preferred embodiments of the electrochemical cell of the present invention are, respectively, an electrolytic cell, a fuel cell, or a redox flow battery.

[0061] The implementation of an electrochemical process using the electrochemical cell of the present invention is another embodiment of the present invention.

[0062] Preferably, the electrochemical process described above is an electrolysis, electrodialysis, or electrochemical process that occurs during the operation of a fuel cell, or an electrochemical process that occurs during the operation of a redox flow battery.

[0063] Further details of the present invention can be derived from experimental examples and the accompanying drawings. [Brief explanation of the drawing]

[0064] [Figure 1] 1H-NMR spectrum of monomer (VIIa) [Figure 2] 1H-NMR spectrum of the quaternized piperidine-containing polymer from Experimental Example 3 [Figure 3] 1H-NMR spectrum of monomer (VIIb) [Figure 4] 1H-NMR spectrum of the spiro-containing polymer in Experimental Example 6 [Figure 5] 1H-NMR spectrum of the piperidine-containing polymer quaternized with (2-bromoethyl)-trimethylammonium bromide in Experimental Example 8 [Examples]

[0065] Experimental Example 1: Synthesis of piperidine-containing monomer (VIIa) In a 500 mL three-necked flask equipped with an internal thermometer, heating element, magnetic stirrer, and reflux condenser, 150 g of acetic acid, 17 g (0.15 mol) of N-methylpiperidone, 49 g (0.40 mol) of 2,6-dimethylphenol, and 30 g of concentrated hydrochloric acid were supplied. The solution was then heated to 90°C with stirring. Over time, a considerable portion of the product precipitated. After 40 hours, the reaction mixture was cooled to room temperature. The crystallized precipitate was filtered off, washed three times with a small amount of acetic acid, and suspended in a mixture of 250 g of water and 400 g of ethanol. The suspension was then heated to 80°C to dissolve the suspended solid. By adding ammonia solution, 4,4-bis-(4-hydroxy-3,5-dimethylphenyl)-1-methylpiperidine monomer (VIIa) was precipitated. After cooling to room temperature, the mixture was filtered off, the filtered cake was washed three times with water, and dried overnight in a vacuum at 40°C. The chemical structure of monomer (VIIa) is: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 1. DMSO-d6 was used as the solvent.

[0066] Experimental Example 2: Synthesis of piperidine-containing polymers The synthesis was carried out in a 500 mL three-necked flask equipped with an oil bath, a mechanical stirrer, and a packed column with a distillation head cooler with adjustable return rate and condensate removal. At the start of the synthesis, 16.98 g (0.05 mol) of the piperidine-containing monomer (VIIa) from Experimental Example 1, 12.72 g (0.05 mol) of 4,4'-difluorodiphenyl sulfone, 180 mL of N,N-dimethylacetamide, and 15.21 g (0.011 mol) of finely ground K2CO3 were mixed under a nitrogen atmosphere at room temperature for 1 hour. The temperature of the reaction mixture was then raised to 120 °C, and the resulting water was removed using a column over 4 hours. After 4 hours, an additional 18 mL of N,N-dimethylacetamide was added to the reaction mixture, and the temperature of the reaction mixture was raised to 165 °C. After 20 hours, the heating of the oil bath was stopped, the viscous reaction product was cooled, and it was placed in cold water. The precipitated product was washed three times with hot water and dried under vacuum at 40°C for 48 hours. The yield was 25.53 g (92.2%).

[0067] Experimental Example 3: Quaternization of the piperidine-containing polymer from Experimental Example 2 10 g of the polymer from Experimental Example 2 was dissolved in 40 mL of N,N-dimethylacetamide over 1 hour with stirring at 60°C. The polymer solution was cooled to 30°C, and then 2.8 mL of iodomethane was added dropwise to the polymer solution. The polymer solution was stirred at 30°C for 24 hours to quaternize the polymer. The chemical structure of the quaternized piperidine-containing polymer from Experimental Example 3 is as follows: 1 Confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 2. DMSO-d6 was used as the solvent.

[0068] Experimental Example 4: Membrane casting of the piperidine-containing polymer from Experimental Example 3 The quaternary polymer solution from Experimental Example 3 was used directly for film preparation. The required amount of polymer solution was taken with a syringe and applied directly to a glass plate preheated to 40°C through a 1 μm PTFE filter. To coat the glass plate, an applicator with a doctor blade was automatically moved across the plate at a speed of 5 mm / second. The wet layer after application was pre-dried at room temperature under an N2 atmosphere for 24 hours, and then final dried under vacuum at 60°C for 6 hours.

[0069] Experimental Example 5: Synthesis of spiro-containing monomer (VIIb) In a 2L three-necked flask equipped with a magnetic stirrer, temperature control device, and condenser, 36 g (0.26 mol) of K2CO3 was dissolved in 150 mL of EtOH. Next, 57.3 g (0.40 mol) of 1,4-dioxa-8-azaspiro[4,5]decane was dissolved in 800 mL of EtOH and transferred to the three-necked flask. The temperature was then adjusted to 35°C. Subsequently, a solution of 92 g (0.40 mol) of 1,5-dibromopentane dissolved in 150 mL of EtOH was added dropwise over 12 hours. After 70 hours, the reaction product was cooled to room temperature, the precipitated KBr was filtered off, and the solution was concentrated using a rotary evaporator. During the concentration process, the added KBr crystallized and was filtered off. The filtrate solidified at temperatures below 80°C, so it was filtered and used as one of the extracts for the synthesis of spiro-containing monomer (VIIb) without further purification.

[0070] In a 500 mL round-bottom flask equipped with a magnetic stirrer and an oil bath, 51.5 g (0.177 mol) of the above molecule, 0.44 mol of 2,6-dimethylphenol, 20 g (0.21 mol) of methanesulfonic acid, 1 g of water, and 0.90 g (0.005 mol) of sodium 3-mercapto-1-propanesulfonate were stirred at 100 °C for 70 hours. The mixture was cooled to room temperature and mixed three times with 200 g of water. Then, it was distilled at a pressure of 1 kPa (10 millibars) to remove volatile substances. The spiro-containing monomer (VIIb) partially solidified and was recrystallized twice in a 25 vol% mixture of EtOH and water. Finally, it was dried overnight at 40 °C in a vacuum. The chemical structure of monomer (VIIb) is 1Confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 3. DMSO-d6 was used as the solvent.

[0071] Experimental Example 6: Synthesis of Spiro-containing Polymers The synthesis was carried out in a 250 mL three-necked flask equipped with an oil bath, a mechanical stirrer, and a packed column with a distillation head cooler with adjustable return rate and condensate removal. At the start of the synthesis, 4.89 g (0.01 mol) of the spiro-containing monomer (VIIb) from Experimental Example 5, 2.54 g (0.01 mol) of 4,4'-difluorodiphenyl sulfone, 45 mL of N,N-dimethylformamide, and 3.03 g (0.022 mol) of finely ground K2CO3 were mixed under a nitrogen atmosphere at room temperature for 1 hour. The temperature of the reaction mixture was then raised to 120 °C, and the generated water was removed using a column over 4 hours. After 4 hours, an additional 5 mL of N,N-dimethylformamide was added to the reaction mixture, and the temperature of the reaction mixture was raised to 154 °C. After 20 hours, the heating of the oil bath was stopped, the viscous reaction product was cooled, and poured into cold water. The precipitated product was washed three times with hot water and dried under vacuum at 40°C for 48 hours. The yield was 6.21 g (88.3%). The chemical structure of the spiro-containing polymer in Experimental Example 6 is 1 Confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 4. DMSO-d6 was used as the solvent.

[0072] Experimental Example 7: Membrane casting of the spiro-containing polymer from Experimental Example 6 5 g of the polymer from Experimental Example 6 was dissolved in 20 mL of N,N-dimethylformamide over 1 hour with stirring at 60°C. The required amount of polymer solution was taken with a syringe and directly applied to a glass plate preheated to 40°C through a 1 μm PTFE filter. To coat the glass plate, an applicator with a doctor blade was automatically moved across the plate at a speed of 5 mm / second. The wet layer after application was pre-dried at room temperature under an N2 atmosphere for 24 hours, and then final dried under vacuum at 60°C for 6 hours.

[0073] Experimental Example 8: Quaternization of piperidine-containing polymers using (2-bromoethyl)-trimethylammonium bromide 5 g of the polymer from Experimental Example 2 was dissolved in 20 mL of N,N-dimethylacetamide over 1 hour with stirring at 60°C, while simultaneously dissolving 4.46 g of (2-bromoethyl)-trimethylammonium bromide in 10 mL of N,N-dimethylacetamide. The (2-bromoethyl)-trimethylammonium bromide solution was added dropwise to the polymer solution, and the polymer solution was stirred at 100°C for 48 hours to quaternize the polymer. The chemical structure of the piperidine-containing polymer quaternized with (2-bromoethyl)-trimethylammonium bromide is as follows: 1 Confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 5. DMSO-d6 was used as the solvent.

[0074] Experimental Example 9: Membrane casting of the piperidine-containing polymer from Experimental Example 8 The quaternary polymer solution from Experimental Example 8 was used directly for film preparation. The required amount of polymer solution was taken with a syringe and applied directly to a glass plate preheated to 40°C through a 1 μm PTFE filter. To coat the glass plate, an applicator with a doctor blade was automatically moved across the plate at a speed of 5 mm / second. The wet layer after application was pre-dried at room temperature under an N2 atmosphere for 24 hours, and then final dried under vacuum at 60°C for 6 hours.

[0075] Experimental Example 10: Partial quaternization of the piperidine-containing polymer from Experimental Example 2 5 g of the polymer from Experimental Example 2 was dissolved in 20 mL of N,N-dimethylacetamide over 1 hour while stirring at 60°C. Simultaneously, 0.25 mL of iodomethane was dissolved in 5 mL of N,N-dimethylacetamide. After cooling the polymer solution to 30°C, the iodomethane solution was added dropwise to the polymer solution, and the polymer solution was stirred at 30°C for 24 hours to partially quaternize the polymer.

[0076] Experimental Example 11: Crosslinking and membrane casting of the polymer from Experimental Example 10 0.15 g of 1,6-diiodohexane was dissolved in 5 mL of N,N-dimethylacetamide and added dropwise to the polymer solution of Example 10. The polymer solution was stirred further at 30°C for 10 minutes and used directly for film casting. The required amount of polymer solution was taken with a syringe and applied directly to a glass plate preheated to 40°C through a 1 μm PTFE filter. To coat the glass plate, an applicator with a doctor blade was used to automatically move the glass plate at a speed of 5 mm / second. The wet layer after coating was covered with a metal cover to slow the evaporation of the solvent. The coated glass plate was heated in an oven at 80°C for 48 hours. Finally, the film was dried under vacuum at 60°C for 6 hours without the metal cover. The resulting film was insoluble in DMSO-d6.

[0077] Experimental Example 12: Ion Exchange in Membranes The membranes prepared in Experimental Examples 4, 7, 9, and 11 were subjected to ion exchange. The membrane samples were placed in a fresh 1M KOH solution at 60°C for 1 hour three times, and then in a fresh 1M KOH solution at 60°C for 24 hours. After that, the membrane samples were rinsed with deionized water and placed in a fresh deionized water at 60°C for 1 hour three times. Subsequently, the membrane samples were stored overnight in a fresh deionized water at 60°C, and finally, rinsed with deionized water at room temperature. A commercially available anion exchange membrane, FAA-3-50, was subjected to ion exchange in the same manner.

[0078] Experimental Example 13: Measurement of Ionic Conductivity (IC) The ionic conductivity (IC) of the ion-exchange membrane sample in Experimental Example 12 was measured by impedance spectroscopy (EIS) using a conventional four-electrode configuration. The membrane sample was fixed to a commercially available BT-112 cell (Bekk Tech LLC). To do this, two outer Pt wires were passed under the sample and two intermediate Pt wires were passed over the sample. The BT-112 cell was fixed between two PTFE plates and filled with deionized water. The temperature of the deionized water was controlled using a water bath, and the deionized water was continuously pumped into the cell. Membrane resistance (R membrane The calculation was performed by replacing the acquired EIS spectrum with a widely used R(RC)Randles equivalent circuit.

[0079] The ionic conductivity (σ) of the film sample is obtained by equation (1). σ = L / (R membrane *A) (1) In the formula, L is the distance between the Pt wires (5 mm), and A is the area of ​​the membrane sample between the two outer Pt wires. Each measurement was repeated for three samples per membrane, and the mean ± standard deviation was calculated. A commercially available anion exchange membrane, FAA-3-50, was tested in the same manner. The measurement results are shown in Table 1.

[0080] Experimental Example 14: Measurement of Water Absorption (WU) The ion-exchange membrane samples from Experimental Example 12 (three samples per tested membrane) were used to measure water absorption (WU). All samples were dried in a vacuum oven at 40°C and 2.5 kPa (25 mmbar) for 24 hours, then cooled to room temperature in a desiccator and weighed. To measure water absorption, the membrane samples were stored in deionized water at 25°C for 24 hours. Subsequently, the weight of each sample was measured again. For this purpose, adhering water was removed from the membrane using filter paper. Each measurement was repeated three times, and the mean ± standard deviation was calculated. The water absorption capacity (WU) can be calculated from equation (2). WU=(m wet -m dry ) / m dry *100% (2) In the formula, m wet m is the mass of the sample after swelling. dry This is the mass of the sample after drying. A commercially available anion exchange membrane, FAA-3-50, was tested using the same method. The measurement results are shown in Table 1.

[0081] Experimental Example 15: Measurement of Dimensional Stability (DS) The ion-exchange membrane samples from Experimental Example 12 (three samples per tested membrane) were used to measure dimensional stability (DS). All samples were dried in a vacuum oven at 40°C and 2.5 kPa (25 mmbar) for 24 hours, and then cooled to room temperature in a desiccator. Parameters such as length, width, and thickness of the samples were measured. To measure swelling behavior, the membrane samples were stored in deionized water at 25°C for 24 hours. Subsequently, the length, width, and thickness of the samples were measured again. For this purpose, adhering water was removed from the membrane using filter paper. Each measurement was repeated three times, and the mean ± standard deviation was calculated. Length (DS l (called), width (DS w (called), and thickness (DS t The swelling behavior of (called) was calculated using equation (3). DSx=(x wet -x dry ) / x dry *100% (3) In the formula, x wet x is the length, width, or thickness of the sample after swelling. dry is the length, width, or thickness of the sample after drying. The DS value is (DS l +DS w +DS t The calculation is performed using the formula ) / 3. A commercially available anion exchange membrane, FAA-3-50, was also tested using the same method. The measurement results are shown in Table 1.

[0082] [Table 1]

[0083] Table 1: Experimental data obtained according to Experimental Examples 13-15 using the membrane from Experimental Example 4 (labeled as Membrane 1), the membrane from Experimental Example 7 (labeled as Membrane 2), the membrane from Experimental Example 9 (labeled as Membrane 3), the membrane from Experimental Example 11 (labeled as Membrane 4), and the commercially available anion exchange membrane FAA-3-50 (labeled as FAA-3-50).

[0084] FAA-3-50 is an anion exchange membrane commercially available from FUMATECH BWT GmbH (74321 Bietigheim-Bissingen, Germany).

[0085] Table 1 shows that the membrane according to the present invention exhibits up to twice the ionic conductivity compared to the commercially available anion-conducting membrane FAA-3-50, in addition to at least three times better dimensional stability and up to twice as little water absorption.

Claims

1. Equation (I): 【Chemistry 1】 (In the formula, X is at least one nitrogen atom with a positive charge, and C １ and C ２ A component comprising a nitrogen atom bonded to one or two hydrocarbon groups having 1 to 12 carbon atoms via two bonds, Z is C ３ and C ４ A structural element comprising a carbon atom bonded to it and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms, The aforementioned aromatic six-membered ring is substituted at positions 3 and 5 with the same or different alkyl groups having 1 to 4 carbon atoms. A compound containing at least one unit of .

2. Equation (Ia): 【Chemistry 2】 Or formula (Ib): 【Transformation 3】 (In the formula, Y is the same or different halogens, and M is an integer between 1 and 1,000.) The compound according to claim 1, represented as shown.

3. The aforementioned component X is given by equation (IIa): 【Chemistry 4】 【Transformation 5】 Or formula (IIc): 【Transformation 6】 (In the formula, R １ , R ２ and R ３ (These are identical or distinct alkyl groups having 1 to 6 carbon atoms, with two nitrogen atoms linked by an aliphatic chain formed of 1 to 6 carbon atoms (n = 1 to 6).) The compound according to claim 1, which indicates the unit of.

4. The compound according to claim 3, wherein the constituent X present in the compound has an occurrence rate of more than 5% of the units of formula (IIa), formula (IIb), or formula (IIc) determined according to (i) and (ii) below. (i) First, the compound of formula (I) is subjected to 1H-NMR measurement in DMSO-d6 as a solvent at room temperature in accordance with 01 / 2005:20233 (European Pharmacopoeia 5.0.2.2.

33. Nuclear Magnetic Resonance Spectroscopy), and the proton integral value is analyzed. (ii) Next, in the analysis results of the obtained proton integral values, assume that 100% of the constituent X were units of equation (IIa), equation (IIb), or equation (IIc), calculate the proton integral value corresponding to that unit, calculate the percentage of the measured proton integral value corresponding to the units of equation (IIa), equation (IIb), or equation (IIc) relative to the calculated value, and define it as the occurrence rate.

5. The aforementioned component Z is given by equation (III): 【Transformation 7】 (wherein, R ４ , R ５ , R ６ and R ７ are the same or different alkyl groups having 1 to 4 carbon atoms.) The compound according to claim 1, which indicates the unit of.

6. Formula (IVa): 【Transformation 8】 , formula (IVb): 【Chemistry 9】 , formula (IVc): 【Chemistry 10】 , formula (IVd): 【Chemistry 11】 , formula (IVe): 【Chemistry 12】 Equation (IVf): 【Chemistry 13】 (In the formula, M ａ M ｂ M ｃ (Each of these is an integer between 1 and 1,000.) The compound according to claim 1, represented by at least one of the following.

7. Equation (Va): 【Chemistry 14】 , formula (Vb): 【Chemistry 15】 , formula (Vc): 【Chemistry 16】 , formula (Vd): 【Chemistry 17】 (In the formula, at least two polymer chains are linked by aliphatic chains having 1 to 10 carbon atoms (m = 1 to 9), Ma, Mb, and Mc are integers from 1 to 1,000, and X and Z are from 0.01 to 0.5.) The compound according to claim 1, represented by at least one of the following.

8. The aromatic six-membered ring, which is directly bonded to one of the oxygen atoms and substituted at the 3rd and 5th positions with the same or different alkyl groups having 1 to 4 carbon atoms, is one or more halogens and / or one or more C １ ~C ４ - The compound according to claim 1, further substituted with an alkyl group.

9. The aromatic six-membered ring, which is directly bonded to one of the oxygen atoms and substituted at the 3rd and 5th positions with the same or different alkyl groups having 1 to 4 carbon atoms, is one or more halogens and / or one or more C １ ~C ４ - The compound according to claim 1, which is not further substituted with an alkyl group.

10. Equation (VI): [Chemistry 18] (In the formula, Y is the same or different halogen.) The compound of formula (VIIa): 【Chemistry 19】 and / or formula (VIIb): 【Chemistry 20】 (In the formula, the aromatic ring is one or more halogens and / or one or more C １ ~C ４ (It may be further substituted with an alkyl group.) A method for preparing the compound according to claim 1, comprising the step of reacting it with one or both compounds selected from the following.

11. The method according to claim 10, comprising the step of using an alkylating reagent.

12. The aromatic ring in the compounds of formulas (VI), (VIIa), and (VIIb) is one or more halogens or one or more C １ ~C ４ - The method according to claim 10, wherein no further substitution with alkyl groups is performed.

13. Use of the compound according to claim 1 as an anion conductive film or for manufacturing an anion conductive film.

14. An electrochemical cell having an anionic conductive membrane containing at least one of the compounds described in claim 1.

15. The electrochemical cell according to claim 14, which is a component of an electrolytic cell, fuel cell, or redox flow battery.

16. An electrochemical process can be carried out using the electrochemical cell described in claim 14.

17. An implementation of the electrochemical process according to claim 16, which is an electrochemical process that occurs during the operation of electrolysis or electrodialysis or a fuel cell, or an electrochemical process that occurs during the operation of a redox flow battery.

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