Polymeric anion conducting compounds, their preparation and 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] The present invention provides compounds, particularly polymeric compounds, their preparation methods and the use of these compounds. Applications are in the field of electrochemistry. Due to the anion conducting properties of the disclosed compounds, the materials are suitable for the manufacture of anion conducting membranes. [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 electrolyzer. Such an electrolyzer usually comprises a number of electrochemical cells. Each electrochemical cell comprises two compartments, each of which is equipped with a gas-generating electrode and a membrane separating both compartments. To enable the electrolysis of water, the membrane must be conductive to ions (cations or anions) while being largely impermeable to hydrogen and oxygen gases. The compounds discussed herein are intended to constitute such membranes.

[0003] Since the membranes of electrolyzers are in contact with water, they need to be stable against excessive swelling or deformation (wrinkling) caused by large amounts of water absorption within the polymer structure. Excessive swelling can cause mechanical damage to the membrane and lead to an increase in gas permeability. For safety reasons, gas permeability must be limited; otherwise there is a risk of oxyhydrogen explosion.

[0004] However, measures to increase swelling stability must not compromise the anionic conductivity of the material, as this would result in reduced process efficiency.

[0005] Similar requirements concern membranes used in electrochemical cells that perform other electrochemical processes in aqueous / water-containing environments, examples being fuel cells, redox flow batteries, and batteries used in electrodialysis.

[0006] A polymeric anion-conducting material suitable for preparing membranes to be used in electrolytic cells is known from WO 2019 / 076860. This material is characterized by at least one imidazole and / or imidazolium unit.

[0007] China Patent Publication No. 104829814A discloses a polymer containing quaternized piperidine groups, which is also used to prepare anion exchange membranes.

[0008] A method for preparing a tertiary amine-type polyarylethersulfone(ketone) polymer resin is known from CN 110294845 A. The polymer is used for preparing anion exchange membranes.

[0009] Several anion exchange membranes for water electrolysis are commercially available. A market overview is summarized by Henkensmeier et al.: Henkensmeier, Dirk and Najibah, Malikah and Harms, Corinna and Zitka, Jan and Hnat, 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, Bietigheim-Bissingen 74321, Germany. According to Henkensmeier et al., this membrane is based on a polyaromatic polymer with ether linkages in the main chain and quaternary ammonium groups attached to the main chain.

[0011] The disadvantages of these known materials are high water absorption, excessive swelling, rare and expensive precursors, toxic and highly corrosive solvents, and complex preparation conditions that make them difficult to produce on an industrial scale. Therefore, these known materials have high manufacturing costs. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] International Publication No. 2019 / 076860 Brochure [Patent Document 2] China Patent Application Publication No. 104829814A [Patent Document 3] China Patent Application Publication No. 110294845A Summary of the Invention [Problem to be solved by the invention]

[0013] It is therefore an object of the present invention to provide an easily prepared material with suitable anion conducting properties and controlled swelling, especially in aqueous environments, in which the precursors required for the synthesis of the compound are inexpensive and the synthesis process is suitable for industrial production.

[0014] The currently unpublished international patent application PCT / EP2020 / 070153 discloses a compound of formula (0):

[0015] [ka]

[0016] (In the formula, X is a positively charged nitrogen atom, C 1 and C 2 and is 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 4and at least one aromatic six-membered ring bonded directly 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 polymeric anion-conducting membrane made from a compound containing at least one unit of the formula: ##STR1## This material already meets the above-mentioned requirements. However, the inventors have surprisingly found that this problem can also be solved by the compounds of the present invention described below and claimed in the patent claims.

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

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

[0019] [ka]

[0020] (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, preferably 1 to 6, more preferably 1 or 5 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, preferably with a methyl group, an isopropyl group or a tert-butyl group, more preferably with a methyl group.

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

[0022] The present invention also provides methods for the preparation of such compounds and their use as anion conducting membranes in electrochemical cells.

[0023] The polymers according to the invention have the advantage that they can be prepared in a simple manner, the precursors being similarly inexpensive, and therefore the preparation is cost-effective.

[0024] The membranes produced therefrom have the advantage of having very high mechanical stability and low swelling characteristics accompanied by high dimensional stability. Furthermore, the membranes exhibit very high anion conductivity. Therefore, the compounds of the present invention are well suited for separation active materials comprising membranes used in electrochemical cells carrying out electrochemical processes in aqueous / water-containing environments.

[0025] In a preferred embodiment, 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 of 1 to 1,000, preferably an integer of 5 to 500.)

[0028] According to a preferred embodiment of the 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 to each other via 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 components X present have an occurrence of units of formula (IIa), formula (IIb) or formula (IIc) of more than 5%, preferably more than 50%, most preferably more than 90%. This occurrence can be measured, for example, by classical spectroscopy performed according to 01 / 2005:20233 (European Pharmacopoeia 5.0.2.2.33. Nuclear Magnetic Resonance Spectroscopy) in DMSO-d6 as solvent at room temperature. 1 The occurrence rate can be measured by H-NMR. The occurrence rate can be calculated by integrating the area of ​​the corresponding signal and comparing the normalized area of ​​the corresponding signal (peak) with the corresponding number of 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 occurrence rate of the unit of formula (IIa) in the analyzed polymer of Experimental Example 3 is equal to 100% (calculated as 6.003 / 6*100%=100%).

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

[0033] [ka]

[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, more preferably a methyl group.)

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

[0036] [ka]

[0037] (In the formula, M a , M b and M. c are each an integer of 1 to 1,000, and preferably, M a , M b and M. c are integers between 5 and 500.)

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

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] (wherein at least two polymer chains are linked by an aliphatic chain having 1 to 10 carbon atoms (m=1 to 9), M a , M b and M. c are each an integer of 1 to 1,000, preferably M a , M b and M. care each an integer of 5 to 500, and X and Z are each an integer of 0.01 to 0.5, and preferably, X and Z are each an integer of 0.01 to 0.25.

[0044] As can be derived from formula (I), (Ia), (Ib), (IVa)-(IVf) and (Va)-(Vd) and the associated definitions, all of the compounds of the present invention have an aromatic 6-membered ring directly bonded to one of the oxygen atoms, and the aromatic 6-membered ring is substituted at the 3- and 5-positions with the same or different alkyl groups having 1 to 4 carbon atoms.

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

[0046] According to a second preferred variant of the invention, said aromatic 6-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. Thus, the cost of preparation and final compound is low.

[0047] It is yet another object of the present invention to provide processes for the preparation of the compounds of the present invention.

[0048] This object is solved by a process comprising the step of reacting a compound of formula (VI), in which Y is the same or different halogen, preferably fluorine, with one or both compounds selected from formulae (VIIa) and / or (VIIb).

[0049] [ka]

[0050] (In formulae 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.) When compound (VIIa) is used, an additional step (quaternization of the nitrogen atom) is required, which can be easily achieved using an alkylating agent.

[0051] Such a process is very simple to carry out and gives the desired compound.

[0052] Preferably, this reaction step is carried out at a reaction temperature between 100°C and 300°C, more preferably between 125°C and 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 preferred to remove any water formed 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), dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), and N,N-dimethylacetamide (DMAC). Preferably, N,N-dimethylacetamide is used as the solvent.

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

[0056] According to a 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 by one or more halogens or one or more C1-C4-alkyl groups.

[0057] The compounds of the invention may be used for different purposes. Preferably, the compounds of the invention are polymeric and are used as or for the manufacture of anion-conducting membranes. Such uses are further objects of the invention.

[0058] In such a membrane, the compound of the present invention functions as a separation active material due to its excellent anion conducting properties, while being very airtight. In addition to the compound of the present invention, the above-mentioned membrane may contain further materials, such as a porous support (e.g., a textile material or a nonwoven material).

[0059] Due to the engineered properties of the components disclosed herein, anion-conducting membranes made of such materials can be used in electrochemical cells. Accordingly, another embodiment of the present invention is an electrochemical cell having an anion-conducting membrane made of the compounds of the present invention.

[0060] The excellent aqueous stability of the compounds makes the materials suitable for use in electrolysers or fuel cells or redox flow batteries. Thus, preferred embodiments of the electrochemical cells of the present invention are electrolysers, fuel cells, or redox flow batteries, respectively.

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

[0062] Preferably, said electrochemical process is an electrolysis or electrodialysis or an electrochemical process occurring during the operation of a fuel cell or an electrochemical process occurring during the operation of a redox flow battery.

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

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

[0065] Experimental Example 1: Synthesis of piperidine-containing polymer (VIIa) A 500 mL three-neck flask equipped with an internal thermometer, heating and magnetic stirrer and reflux condenser was charged with 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. The solution was then heated to 90° C. with stirring. Over the reaction time, a significant portion of the product precipitated. After 40 hours, the reaction mass was cooled to room temperature. The crystallized precipitate was filtered off, washed three times with small amounts 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., dissolving the suspended solids. The 4,4-bis-(4-hydroxy-3,5-dimethyl-phenyl)-1-methyl-piperidine monomer (VIIa) was precipitated by adding ammonia solution. After cooling to room temperature, it was filtered off, the filter cake was washed with water three times and dried overnight in vacuum at 40° C. The chemical structure of monomer (VIIa) is: 1 This was confirmed by H-NMR. 1 The H-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-neck 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 Example 1, 12.72 g (0.05 mol) of 4,4'-difluorodiphenylsulfone, 180 mL of N,N-dimethylacetamide, and 15.21 g (0.011 mol) of finely ground K2CO3 were mixed at room temperature under nitrogen for 1 hour. The temperature of the reaction mixture was then increased to 120°C and the water formed was removed using a column for 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 increased to 165°C. After 20 hours, the oil bath was turned off and the viscous reaction product was cooled and 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] Example 3: Quaternization of the piperidine-containing polymer of Example 2 10 g of the polymer of 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, and the polymer solution was stirred at 30° C. for 24 hours to quaternize the polymer. The chemical structure of the quaternized piperidine-containing polymer of Experimental Example 3 is shown below. 1 This was confirmed by H-NMR. 1 The H-NMR spectrum is shown in Figure 2. DMSO-d6 was used as the solvent.

[0068] Example 4: Film casting of the piperidine-containing polymer of Example 3 The solution of the quaternized polymer from Example 3 was used directly for the preparation of the membrane. The required amount of the polymer solution was taken with a syringe and applied directly onto 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 over the glass plate at a speed of 5 mm / sec. The applied wet layer was pre-dried at room temperature under N2 atmosphere for 24 hours, and then finally dried at 60°C under vacuum for 6 hours.

[0069] Example 5: Synthesis of spiro-containing monomer (VIIb) In a 2 L three-neck flask equipped with a magnetic stirrer, temperature control and condenser, 36 g (0.26 mol) of K2CO3 was dissolved in 150 mL of EtOH. Then, 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-neck flask. The temperature was then adjusted to 35°C. A solution of 92 g (0.40 mol) of 1,5-dibromopentane in 150 mL of EtOH was then 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 in a rotary evaporator. During the concentration process, the added amount of 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 h. The mixture was cooled to room temperature and mixed with 200 g of water three times. It was then distilled at a pressure of 1 kPa (10 mbar) to remove the volatile substances. The spiro-containing monomer (VIIb) partially solidified and was recrystallized twice in a 25% by volume mixture of EtOH and water. Finally, it was dried overnight in vacuum at 40 °C. The chemical structure of monomer (VIIb) is shown below. 1This was confirmed by H-NMR. 1 The H-NMR spectrum is shown in Figure 3. DMSO-d6 was used as the solvent.

[0071] Example 6: Synthesis of spiro-containing polymers The synthesis was carried out in a 250 mL three-neck 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 beginning of the synthesis, 4.89 g (0.01 mol) of the spiro-containing monomer (VIIb) from Example 5, 2.54 g (0.01 mol) of 4,4'-difluorodiphenylsulfone, 45 mL of N,N-dimethylformamide, and 3.03 g (0.022 mol) of finely ground K2CO3 were mixed at room temperature under nitrogen for 1 hour. The temperature of the reaction mixture was then increased to 120°C and the water formed was removed using a column for 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 increased to 154°C. After 20 hours, the oil bath was turned off and the viscous reaction product was cooled and poured into cold water. The precipitated product was washed with hot water three times 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 of Example 6 is shown below. 1 This was confirmed by H-NMR. 1 The H-NMR spectrum is shown in Figure 4. DMSO-d6 was used as the solvent.

[0072] Example 7: Film casting of the spiro-containing polymer of Example 6 5 g of the polymer of 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 applied directly onto 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 over the glass plate at a speed of 5 mm / sec. The applied wet layer was pre-dried at room temperature under N2 atmosphere for 24 hours, and then finally dried at 60°C under vacuum for 6 hours.

[0073] Example 8: Quaternization of piperidine-containing polymers using (2-bromoethyl)-trimethylammonium bromide Five grams of the polymer of Experimental Example 2 was dissolved in 20 mL of N,N-dimethylacetamide over one hour with stirring at 60° C., and simultaneously, 4.46 g of (2-bromoethyl)-trimethylammonium bromide was dissolved 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 shown below. 1 This was confirmed by H-NMR. 1 The H-NMR spectrum is shown in Figure 5. DMSO-d6 was used as the solvent.

[0074] Example 9: Film casting of the piperidine-containing polymer of Example 8 The solution of the quaternized polymer from Example 8 was used directly for the preparation of the membrane. The required amount of the polymer solution was taken with a syringe and applied directly onto 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 over the glass plate at a speed of 5 mm / sec. The applied wet layer was pre-dried at room temperature under N2 atmosphere for 24 hours, and then finally dried at 60°C under vacuum for 6 hours.

[0075] Example 10: Partial quaternization of the piperidine-containing polymer of Example 2 5 g of the polymer of Experimental Example 2 was dissolved in 20 mL of N,N-dimethylacetamide over 1 hour with stirring at 60° C., and simultaneously, 0.25 mL of iodomethane was dissolved in 5 mL of N,N-dimethylacetamide. After the polymer solution was cooled 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] Example 11: Crosslinking and film casting of the polymer of 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 for another 10 min at 30° C. and directly used for film casting. The required amount of polymer solution was taken with a syringe and applied directly onto a glass plate preheated to 40° C. through a 1 μm PTFE filter. For coating the glass plate, a doctor blade applicator was automatically moved across the glass plate at a speed of 5 mm / s. The wet layer after coating was covered with a metal cover to slow down the evaporation of the solvent. The coated glass plate was heated in an oven at 80° C. for 48 h. Finally, the film was dried under vacuum at 60° C. for 6 h without a metal cover. The obtained film was insoluble in DMSO-d6.

[0077] Experimental Example 12: Membrane Ion Exchange The membranes prepared in Examples 4, 7, 9 and 11 were subjected to ion exchange. The membrane samples were placed in a fresh portion of 1M KOH solution at 60°C for 1 hour three times, and then in a fresh portion of 1M KOH solution at 60°C for 24 hours. The membrane samples were then rinsed with deionized water and placed in a fresh portion of deionized water at 60°C for 1 hour three times. The membrane samples were then stored overnight at 60°C in the fresh portion of deionized water, and finally rinsed with deionized water at room temperature. The commercially available anion exchange membrane FAA-3-50 was also 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 of Example 12 was measured by impedance spectroscopy (EIS) in a conventional four-electrode configuration. The membrane sample was mounted in a commercially available BT-112 cell (Bekk Tech LLC) by passing two outer Pt wires under the sample and two middle Pt wires over the sample. The BT-112 cell was mounted between two PTFE plates and filled with deionized water. The temperature of the deionized water was controlled by a water bath and deionized water was constantly pumped through the cell. The membrane resistance (R membrane ) was calculated by substituting the acquired EIS spectra using the widely used R(RC) Randles type equivalent circuit.

[0079] The ionic conductivity (σ) of the membrane sample is given by equation (1). σ = L / (R membrane *A) (1) where 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 average ± standard deviation was calculated. A commercial anion exchange membrane, FAA-3-50, was also 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 of Example 12 (three samples for each membrane tested) were used for the measurement of water uptake (WU). All samples were dried in a vacuum oven at 40° C. and 2.5 kPa (25 mbar) for 24 hours, then cooled to room temperature in a desiccator and weighed. For the measurement of water uptake, the membrane samples were stored in deionized water at 25° C. for 24 hours. Each sample was subsequently weighed again. For this purpose, the 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 (WU) is calculated using equation (2). WU=(m wet -m dry ) / m dry *100% (2) In the formula, m wet is the mass of the sample after swelling, m dry is the mass of the sample after drying. The commercially available anion exchange membrane FAA-3-50 was also tested in the same manner. The measurement results are shown in Table 1.

[0081] Experimental Example 15: Measurement of Dimensional Stability (DS) Ion exchange membrane samples from Example 12 (three samples per each membrane tested) were used for the measurement of dimensional stability (DS). All samples were dried in a vacuum oven at 40°C and 2.5 kPa (25 mbar) 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 the 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, the 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 ), width (DS w ), and thickness (DS t The swelling behavior of the sintered body (hereinafter referred to as sintered body) was calculated using equation (3). DSx=(x wet -x dry ) / x dry *100% (3) In the formula, x wet is the length, width or thickness of the sample after swelling, and x dry is the length, width or thickness of the sample after drying. The DS value is (DS l +DS w +DS t The measurement results are shown in Table 1.

[0082] [Table 1]

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

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

[0085] From Table 1 it can be seen that the membranes according to the invention exhibit up to two times higher ionic conductivity combined with at least three times better dimensional stability and up to two times less water absorption compared to the commercially available anion conducting membrane FAA-3-50.

Claims

1. Formula (I): 【Chemistry 1】 (In the formula, X is at least one nitrogen atom having a positive charge, C １ and C ２ and a nitrogen atom bonded through 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 directly bonded 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. A compound containing at least one unit of

2. Formula (Ia): 【Chemistry 2】 or formula (Ib): 【Transformation 3】 (wherein Y is the same or different halogen, and M is an integer from 1 to 1,000.) The compound according to claim 1, represented by:

3. The component X is represented by formula (IIa): 【Chemistry 4】 【Transformation 5】 Or formula (IIc): 【Transformation 6】 (In the formula, R １ , R ２ and R ３ are the same or different alkyl groups having 1 to 6 carbon atoms, and the two nitrogen atoms are connected by an aliphatic chain formed of 1 to 6 carbon atoms (n=1 to 6).

2. The compound of claim 1, wherein the compound represents a unit of:

4. The compound according to claim 3, wherein the component X present in the compound has an occurrence rate of units of formula (IIa), formula (IIb) or formula (IIc) greater than 5%, as determined according to the following (i) and (ii): (i) First, the compound of formula (I) is subjected to 1 H-NMR measurement carried out 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) to analyze the proton integral value. (ii) Next, in the analysis results of the obtained proton integral values, it is assumed that 100% of the constituent element X is a unit of formula (IIa), formula (IIb), or formula (IIc), and the integral value of the proton corresponding to the unit in this case is calculated. The percentage of the integral value of the actually measured proton corresponding to the unit of formula (IIa), formula (IIb), or formula (IIc) relative to the calculated value is calculated and used as the occurrence rate.

5. The component Z is represented by formula (III): 【Transformation 7】 (In the formula, R ４ , R ５ , R ６ and R ７ are the same or different alkyl groups having 1 to 4 carbon atoms.

2. The compound of claim 1, wherein the compound represents a unit of:

6. Formula (IVa): 【Transformation 8】 , formula (IVb): 【Chemistry 9】 , formula (IVc): 【Chemistry 10】 , formula (IVd): 【Chemistry 11】 , formula (IVe): 【Chemistry 12】 , formula (IVf): 【Chemistry 13】 (In the formula, M ａ , M ｂ , M ｃ are each an integer from 1 to 1,000.

2. The compound of claim 1, represented by at least one of:

7. Formula (Va): 【Chemistry 14】 , formula (Vb): 【Chemistry 15】 , formula (Vc): 【Chemistry 16】 , formula (Vd): 【Chemistry 17】 (wherein at least two polymer chains are connected by an aliphatic chain having 1 to 10 carbon atoms (m=1 to 9), Ma, Mb, and Mc are each integers of 1 to 1,000, and X and Z are each 0.01 to 0.5.) 2. The compound of claim 1, represented by at least one of:

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

10. Formula (VI): [Chemistry 18] wherein Y is the same or different halogen. with a compound of formula (VIIa): 【Chemistry 19】 and / or formula (VIIb): 【Chemistry 20】 wherein the aromatic ring is substituted with one or more halogens and / or one or more C １ ~C ４ - may be further substituted with an alkyl group.

10. A method for preparing a compound of claim 1, comprising reacting with one or both compounds selected from:

11. 11. The method of claim 10, comprising using an alkylating agent.

12. The aromatic ring in the compounds of formula (VI), (VIIa) and (VIIb) may be one or more halogens, or one or more C １ ~C ４ 11. The method of claim 10, wherein the alkyl group is not further substituted.

13. 10. Use of a compound according to claim 1 as or for the preparation of an anion-conducting membrane.

14. 10. An electrochemical cell having an anion-conducting membrane comprising at least one compound according to claim 1.

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

16. 15. Conducting an electrochemical process using the electrochemical cell of claim 14.

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

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