Long-term anionic conductive compounds, their preparation and use in electrochemistry

Abstract

The present invention provides compounds, particularly polymer compounds, their preparation methods, and the use of these compounds. It is intended to be used in the field of electrochemistry. Due to the anion conducting properties of the disclosed compounds, the materials are suitable for preparing anion conducting membranes. Therefore, the object of the present invention is to provide a material with stable ion conductivity over a long period of time. The object is to provide a material having a stable ion conductivity over a long period of time, the material being a compound of formula (I): [Formula 1] JPEG2024511718000027.jpg51103 (wherein X is a ketone group or a sulfone group, Z is an entity that contains at least one tertiary carbon atom and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms; Y is a moiety containing at least one nitrogen atom having a positive charge and is bonded to the tertiary carbon atom of Z. The problem is solved by a compound containing 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. They are intended for use in the field of electrochemistry. Due to the anionic conductivity properties of the disclosed compounds, these materials are suitable for the preparation 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 apparatus. Such an electrolytic apparatus typically comprises many electrochemical cells. Each electrochemical cell consists of two compartments, each equipped with a gas-generating electrode and a membrane separating the two compartments. To enable the electrolysis of water, the membrane must be conductive to ions (cations or anions) while being almost impermeable to hydrogen and oxygen gases. The compounds discussed herein are intended to constitute such membranes.

[0003] The membranes used in electrochemical cells must be non-conductive; otherwise, an electrical short circuit will occur between the two electrodes. Therefore, from an electrical standpoint, the membranes must be electrically insulated. However, from an electrochemical standpoint, the membranes in the cell must have low ohmic resistance to ions passing through the membrane from one compartment to another. The ability to allow ions to pass through in an isolated state is called ionic conductivity. In the field of water electrolysis, the anionic conductivity of the anionic conductive membranes used is extremely important.

[0004] The efficiency of an electrochemical cell depends heavily on the ionic conductivity of the membrane. Low ionic conductivity requires more power to produce the desired amount of hydrogen due to resistive losses that cause heat generation. Therefore, providing materials with high ionic conductivity is a major goal in membrane engineering.

[0005] Ionic conductivity is an inherent property of membrane materials. Due to the harsh conditions within electrochemical cells, the molecular structure of membrane materials is subjected to chemical and electrochemical degradation. As a result, the ionic conductivity of membrane materials decreases over time, leading to reduced process efficiency and increased power consumption.

[0006] Therefore, if ionic conductivity is rapidly lost in a short period of time, a film with high initial ionic conductivity is worthless.

[0007] Several anion exchange membranes for water electrolysis are commercially available. A market overview is provided by Henkensmeier et al.: Henkensmeier, Dirk and Najibah, Malikah and Harms, Corinna and Zitka, Jan and Hnat, Jaromir and Bouzek, Karel (2020) Overview: 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 In Section 3.7, Henkensmeier et al. already outlined the need for long-term stability, but they have not been able to identify a membrane that lasts for thousands of hours or more.

[0008] An example of a commercially available anion exchange membrane is a product called fumasep® FAA-3-50, manufactured by FUMATECH BWT GmbH (Bietigheim-Bissingen, Germany, 74321). According to Henkensmeier et al., this membrane is based on a polyaromatic polymer with ether bonds in the main chain and quaternary ammonium groups bonded to the main chain. The inventors themselves confirmed that this membrane completely disintegrates after 120 hours in 2M KOH at 80°C.

[0009] Chinese Patent Application Publication No. 104829814 discloses a polymer containing a quaternized piperidine group. This polymer is also used in the preparation of anion exchange membranes. Long-term stability is not evaluated in Chinese Patent Application Publication No. 104829814.

[0010] A method for preparing tertiary amine type polyaryl ether sulfone (ketone) polymer resins is known from Chinese Patent Application Publication No. 110294845. This polymer is used in the preparation of anion exchange membranes. Although long-term stability is not evaluated in Chinese Patent Application Publication No. 110294845, the following is stated: A polymer prepared using tertiary amine bisphenol monomer (MPDDP) as described in Chinese Patent Application Publication No. 110294845 disintegrated into several small pieces after 1,000 hours in 2M KOH at 80°C.

[0011] A polymer anionic conductive material suitable for preparing membranes 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. While this material exhibits good ionic conductivity, its long-term behavior is not evaluated in International Publication No. 2019 / 076860.

[0012] International Publication No. 2021 / 013694 is formula (0a):

[0013] [Chemical formula]

[0014] (In the formula, X is a component containing a positively charged nitrogen atom bonded to C1 and C2, and is a component bonded to one or two hydrocarbon groups having 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 or 5 carbon atoms through two bonds. Z is a structural element containing at least one aromatic six-membered ring directly bonded to one of the carbon atom bonded to C3 and C4 and an oxygen atom, and 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

[0015] As shown below, this material has already achieved very high ionic conductivity that persists for a considerable time. Even after 2,000 hours in 2M KOH at 80°C, it still retains more than 85% of its initial ionic conductivity. [Prior Art Documents] [Patent Documents]

[0016] [Patent Document 1] Specification of Chinese Patent Application Publication No. 104829814 [Patent Document 2] Specification of Chinese Patent Application Publication No. 110294845 [Patent Document 3] Pamphlet of International Publication No. 2019 / 076860 [Patent Document 4] Pamphlet of International Publication No. 2021 / 013694 [Summary of the Invention] [Problems to be Solved by the Invention]

[0017] However, today, sustainability is no longer simply a matter of energy efficiency, but rather a matter of material sufficiency, making the demand for long-term stability increasingly important.

[0018] Therefore, the object of the present invention is to provide a material that has stable ionic conductivity over a long period of time.

[0019] The currently unpublished European patent application No. 21152487.1 focuses on mechanical stability and is suited to a different problem. This unpublished application contains at least one formula (0b):

[0020] [ka]

[0021] (In the formula, X is a component comprising at least one positively charged nitrogen atom bonded to C1 and C2, 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 a structural element comprising carbon atoms bonded to C3 and C4, and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms, wherein the aromatic ring has positions 3 and 5 substituted with the same or different C1-C4 alkyl groups, preferably a methyl group, an isopropyl group, or a tert-butyl group, more preferably a methyl group. In a preferred embodiment, component X of formula (0b) includes a positively charged nitrogen atom bonded to an adjacent component by a single aliphatic chain. This relates to compounds characterized by the unit of [unit].

[0022] The inventors discovered an improved compound in which the decrease in ionic conductivity over time is slower. Therefore, the recently discovered compounds solve the aforementioned problems and thus constitute the subject matter of the present invention. These compounds according to the present invention are described below and in the claims. [Means for solving the problem]

[0023] Equation (I):

[0024] [ka]

[0025] (In the formula, X is a ketone group or a sulfone group, Z is a component comprising at least one tertiary carbon atom and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms. Y is a component containing at least one positively charged nitrogen atom, bonded to the tertiary carbon atom of Z. The compound of the present invention comprising at least one unit of .

[0026] Therefore, compared to the conventional compounds described above, the compounds of the present invention are characterized by at least one tertiary carbon atom in the structural element Z to which the constituent Y is bonded. Compared to conventional materials with similar chemical properties, the compounds of the present invention achieve better long-term stability of ionic conductivity.

[0027] According to a preferred embodiment of the present invention, the compound is of formula (Ia) or formula (Ib):

[0028] [ka]

[0029] (In the formula, V is the same or different halogen, preferably fluor, and M is an integer from 1 to 1000, most preferably from 5 to 500. When M is 1, the compound is considered a monomer. When M is greater than 1, the compound of the present invention is considered a polymer.) It is represented as follows.

[0030] According to a preferred embodiment of the present invention, component Y is defined by formula (IIa), formula (IIb), or formula (IIc):

[0031] [ka]

[0032] (In the formula, n represents the number of carbon atoms in the aliphatic chain, which is 0 to 9, preferably 0 to 5. R1, R2, and R3 are the same or different alkyl groups having 1 to 9 carbon atoms, preferably each being a methyl group.) It represents the unit.

[0033] According to a preferred embodiment of the present invention, the component Y present in the compound represents a unit of formula (IIa), formula (IIb), or formula (IIc) having an appearance rate of more than 5%, preferably more than 50%, and most preferably more than 90%. This appearance rate is measured, for example, in triduterio(triduteriomethylsulfonyl)methane (DMSO-d6) as a solvent at room temperature in accordance with classical spectroscopy 01 / 2005:20233 (European Pharmacopoeia 5.0.2.2.33. Nuclear Magnetic Resonance Spectroscopy). 1 It can be measured by 1H-NMR. The occurrence rate can be calculated by integrating the area of ​​the corresponding signal and comparing the normalized area (peak) of the corresponding signal with the number of corresponding protons within the target unit.

[0034] According to a more preferred embodiment of the present invention, component Z is given by formula (III):

[0035] [ka]

[0036] (In the formula, R4, R5, R6, and R7 are the same or different C1-C4 alkyl groups, preferably a methyl group, an isopropyl group, or a tert-butyl group, respectively, and more preferably a methyl group, respectively.) It represents the unit.

[0037] Six preferred embodiments of the compounds of the present invention are given by formulas (IVa) to (IVf):

[0038] [ka] TIFF0007879874000008.tif173162

[0039] (In formulas (IVa) to (IVf), n represents the number of carbon atoms in the aliphatic chain, and is 0 to 9, preferably 0 to 5, M a M b and M c Each of these is an integer between 1 and 1,000, preferably between 5 and 500. It is represented by at least one of the following.

[0040] 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 contain an aromatic six-membered ring, the aromatic six-membered ring of which is directly bonded to one of the oxygen atoms, and the 3rd and 5th positions are substituted with the same or different C1-C4 alkyl groups.

[0041] 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. Preferred alkyl groups are selected from the list consisting of methyl, isopropyl, and tert-butyl. The most preferred alkyl group is methyl.

[0042] 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. Precursor materials for preparing such compounds are inexpensive. Therefore, the cost of preparation and the final compound is not very high.

[0043] Another object of the present invention is to provide a method for producing the compound of the present invention. The purpose of this is, (a) Equation (VIa) or Equation (VIb):

[0044] [ka]

[0045] (In the formula, V is the same or different halogen, preferably fluor.) Prepare a first free body containing at least one of the compounds, (b) Formula (VIIa), formula (VIIb), formula (VIIc), or formula (VIId):

[0046] [ka] TIFF0007879874000011.tif67112

[0047] Prepare a second free body containing at least one compound selected from the following: (c) React the first free product with the second free product, (d) This can be solved by a method comprising the step of obtaining at least one compound of the present invention.

[0048] Such methods are very easy to implement and yield the desired compounds. Compounds (VIa) and (VIb) (precursors in the first free body) are commercially available. Compounds according to formulas (VIIa), (VIIb), (VIIc), or (VIId) (precursors in the second free body) can be prepared by classical organic chemistry. The reaction routines are derived from Experimental Examples 1, 8, 15, and 18, respectively.

[0049] Preferably, this reaction step is carried out at a temperature of 100°C to 300°C, more preferably 125°C to 175°C. Most preferably, the reaction step is carried out at a temperature at which the reaction mixture boils, preferably with stirring. Most preferably, the reaction step is carried out under an inert gas atmosphere, preferably under a nitrogen atmosphere. Preferably, the water produced is removed at the top of the reaction vessel.

[0050] The reaction step is preferably carried out in the presence of a base such as KOH, NaOH, K2CO3, or Na2CO3. The preferred base is K2CO3.

[0051] The reaction 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.

[0052] 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 or chloromethane. If alkylation is performed, this step is carried out chronologically before obtaining the compound of the present invention. In this case, the compound of the present invention prepared is an alkylated compound.

[0053] As described above, all compounds of the present invention contain an aromatic six-membered ring, the aromatic six-membered ring of which is directly bonded to one of the oxygen atoms, and the 3rd and 5th positions are substituted with the same or different C1-C4 alkyl groups. According to a first modification of the present invention, the aromatic six-membered ring is further substituted with one or more halogens and / or one or more C1-C4 alkyl groups. According to a second preferred modification of the present invention, the aromatic six-membered ring is not further substituted with one or more halogens and / or one or more C1-C4 alkyl groups.

[0054] In order to realize both variations of the compound of the present invention in the preparation method of the present invention, a precursor, i.e., a compound of formula (VIa) or (VIb) or (VIIa) or (VIIb) or (VIIc) or (VIId), is appropriately selected.

[0055] According to the first modification, the aromatic ring of these compounds (precursors) is further substituted with one or more halogens and / or one or more C1-C4 alkyl groups, the alkyl group being selected from a list consisting of methyl, isopropyl, and tert-butyl, which are preferred alkyl groups, with methyl being the most preferred alkyl group.

[0056] According to the second variation, the aromatic rings of these compounds (precursors) are not further substituted with one or more halogens and / or one or more C1-C4 alkyl groups.

[0057] The compounds of the present invention can be used for a variety of purposes. Preferably, the compounds of the present invention are polymers and are used as an anionic conductive membrane, or at least 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 substance due to its long-term stable anion conductivity, while also exhibiting extremely high airtightness. In addition to the compound of the present invention, the above membrane may include further materials, such as a porous support (e.g., a fabric or nonwoven fabric).

[0059] Thanks to the designed properties of the components disclosed herein, an anionic conductive membrane containing such materials can be used in electrochemical cells. Accordingly, another embodiment of the present invention is an electrochemical cell having an anionic conductive membrane, the anionic conductive membrane containing the compound of the present invention.

[0060] Due to the specific mechanical and chemical 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, electrolytic cells, fuel cells, or redox flow batteries.

[0061] Performing 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 electrolysis, electrodialysis, an electrochemical process performed during the operation of a fuel cell, or an electrochemical process performed during the operation of a redox flow battery.

[0063] Further details of the present invention can be derived from experimental examples and accompanying drawings, the latter of which are shown below. [Brief explanation of the drawing]

[0064] [Figure 1] This is the 1H-NMR spectrum of monomer (VIIa). [Figure 2] This is the 1H-NMR spectrum of the quaternized piperidine-containing polymer from Experimental Example 3. [Figure 3] This is the 1H-NMR spectrum of the quaternized piperidine-containing polymer from Experimental Example 6. [Figure 4] This is the 1H-NMR spectrum of monomer (VIIb). [Figure 5] This is the 1H-NMR spectrum of a quaternized piperidine-containing polymer from Experimental Example 10. [Figure 6] This is the 1H-NMR spectrum of a quaternized piperidine-containing polymer from Experimental Example 13. [Figure 7] This is the 1H-NMR spectrum of monomer (VIIc). [Figure 8] This is the 1H-NMR spectrum of a spiro-containing polymer from Experimental Example 16. [Figure 9] This is the 1H-NMR spectrum of monomer (VIId). [Figure 10] This is the 1H-NMR spectrum of a quaternized piperidine-containing polymer from Experimental Example 20. [Figure 11] This is the 1H-NMR spectrum of a quaternized piperidine-containing polymer from Experimental Example 23. [Examples]

[0065] Experimental Example 1: Example 1: Synthesis of piperidine-containing monomer (VIIa) The synthesis of piperidine-containing monomer (VIIa) was carried out in two steps according to reaction scheme 1 (step 1) and reaction scheme 2 (step 2).

[0066] [ka]

[0067] A mixture of 227.2 g (662.778 mmol) of methoxymethyl-triphenyl-phosphine chloride in 1.3 L of dry THF was placed in a 6 L three-necked round-bottom flask equipped with a thermometer, dropping funnel, mechanical stirrer, ice bath, and N2 atmosphere, and cooled to 0°C. A solution of 99.16 g (883.704 mmol) of potassium tert-butoxide in 900 mL of dry tetrahydrofuran (THF) was added dropwise, and the reaction mixture was stirred at room temperature for 30 minutes. After 30 minutes, the reaction mixture was cooled to 0°C, and a solution of 50 g (441.852 mmol) of 1-methylpiperidine-4-one in 900 mL of dry THF was added dropwise to the reaction mixture. The mixture was stirred at room temperature overnight. The reaction mixture was divided into two batches (Batch 1 and Batch 2). Batch 1 was poured into 1 L of ice water and extracted with 5 × 200 mL of dichloromethane (DCM). The complex organic layer was washed with brine, dried over MgSO4, and the solvent was removed under vacuum to obtain 45.25 g of crude material. Column chromatography using silica as the stationary phase and DCM / methanol (+1%NH3) as the mobile phase was used for purification to obtain 24.89 g of intermediate 1 (55% yield).

[0068] 16 g (0.113 mol) of intermediate 1 was placed in a three-necked flask (500 mL capacity) equipped with a thermometer, dropping funnel, mechanical stirrer, and N2 atmosphere. 37.4 g (0.306 mol) of 2,6-dimethylphenol solution in 170 mL of acetonitrile was added dropwise at 10°C. 26 mL (0.34 mol) of trifluoroacetic acid (TFA) was then added dropwise, followed by 12 mL (0.136 mol) of trifluoromethanesulfonic acid. The resulting solution was stirred overnight at room temperature. The reaction mixture was evaporated under vacuum. The crude residue was treated with diethyl ether (Et2O, 300 mL) and stirred overnight at room temperature. The solid was filtered, washed with Et2O (100 mL), and dried under high vacuum at 45°C. The TFA salt of the obtained product was converted to a free base by dissolving it in 90 mL of acetonitrile, followed by the addition of 6 mL of water and basicization with 10% aqueous ammonia to a pH of approximately 8. As a result, a white precipitate was formed. The precipitate was collected by filtration, washed with 10 mL of water, and dried under vacuum. The obtained white solid was dissolved in 1 L of methanol, concentrated under vacuum until the solution became cloudy, and stored at room temperature. The crystallized solid was separated by vacuum filtration and dried under vacuum. Normal-phase column chromatography was used for purification to obtain 24.97 g (yield 62%) of piperidine-containing monomer (VIIa). The chemical structure of monomer (VIIa) is as follows: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 1. Triduterio(triduteriomethylsulfonyl)methane (DMSO-d6) was used as the solvent.

[0069] 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 condenser with adjustable return rate and condensate removal. At the start of the synthesis, 10.61 g (0.03 mol) of piperidine-containing monomer (VIIa) from Experimental Example 1, 6.55 g (0.03 mol) of 4,4'-difluorobenzophenone (VIa), 165 mL of N,N-dimethylacetamide, and 9.12 g (0.066 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 10 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 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 14.64 g (91.8%).

[0070] 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 while stirring at 60°C for 1 hour. After cooling the polymer solution to 30°C, 2.5 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 from Experimental Example 3 is as follows: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 2. DMSO-d6 was used as the solvent.

[0071] Experimental Example 4: Film casting of piperidine-containing polymer from Experimental Example 3 The quaternized polymer solution from Experimental Example 3 was directly used for the preparation of the membrane. The required amount of the polymer solution was collected with a syringe and directly applied through a 1-μm polytetrafluoroethylene (PTFE) filter onto a glass plate preheated to 40°C. To coat the glass plate, an applicator equipped with a doctor blade was made to run automatically on the glass plate at a speed of 5 mm / second. The applied wet layer was pre-dried at room temperature for 24 hours under a nitrogen atmosphere and finally dried at 60°C for 6 hours under vacuum.

[0072] Experimental Example 5: Synthesis of Piperidine-Containing Polymer The synthesis was carried out in a 500-mL three-necked flask equipped with an oil bath, a mechanical stirrer, a distillation head condenser with an adjustable reflux rate and condensate removal, and a packed column. At the beginning of the synthesis, 10.61 g (0.03 mol) of the piperidine-containing monomer (VIIa) from Experimental Example 1, 7.63 g (0.03 mol) of 4,4'-difluorodiphenyl sulfone (VIb), 165 mL of N,N-dimethylacetamide, and 9.12 g (0.066 mol) of finely powdered K2CO3 were mixed under a nitrogen atmosphere at room temperature over 1 hour. Then, the temperature of the reaction mixture was raised to 120°C, and the water generated was removed over 4 hours using the column. After 4 hours, an additional 10 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 poured into cold water. The precipitated product was washed three times with hot water and dried under vacuum at 40°C over 48 hours. The yield was 15.21 g (89.3%).

[0073] Experimental Example 6: Quaternization of the Piperidine-Containing Polymer of Example 5 10 g of the polymer from Experimental Example 5 was dissolved in 40 mL of N,N-dimethylacetamide while stirring at 60°C for 1 hour. After cooling the polymer solution to 30°C, 2.5 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 from Experimental Example 6 was 1 confirmed by 1H-NMR. 1The 1H-NMR spectrum is shown in Figure 3. DMSO-d6 was used as the solvent.

[0074] Experimental Example 7: Film casting of piperidine-containing polymer from Experimental Example 6 The quaternized polymer solution from Experimental Example 3 was used directly for film preparation. 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 equipped with a doctor blade was moved over the plate at a speed of 5 mm / second. The applied wet layer was pre-dried in an N2 atmosphere at room temperature for 24 hours, and finally dried under vacuum at 60°C for 6 hours.

[0075] Experimental Example 8: Synthesis of piperidine-containing monomer (VIIb) The synthesis of the piperidine-containing monomer (VIIb) was carried out in three steps according to reaction scheme 3 (step 1), reaction scheme 4 (step 2), and reaction scheme 5 (step 3).

[0076] [ka]

[0077] A 6N HCl aqueous solution was added to batch 2 of Experimental Example 1 to adjust the pH to 1. The reaction mixture was stirred with 1.5 L of Et2O for 30 minutes. The organic phase was then separated, and the aqueous phase was extracted again with 1 L of Et2O. The resulting aqueous phase was basicized with 3N NaOH to approximately pH 10 and extracted with DCM (3 × 1 L). The organic phase was separated, concentrated to dryness, and 45.5 g of crude product (intermediate 2) was obtained.

[0078] In a four-necked flask (6 L capacity) equipped with a thermometer, dropping funnel, mechanical stirrer, ice bath, and N2 atmosphere, 259.84 g (0.758 mol) of methoxymethyl-triphenyl-phosphine chloride was suspended in 1.55 L of dry THF and cooled to 0°C. To this suspension, a solution of 127.58 g (1.137 mol) of potassium tert-butoxide in 1 L of THF was added dropwise. The resulting solution was stirred at room temperature for 1 hour. The reaction mixture was cooled to 0°C, and a solution of 45.5 g of the crude product (intermediate 2) in 780 mL of THF was added to the reaction mixture. The resulting reaction mixture was stirred at room temperature overnight. The reaction mixture was poured into 3 L of ice-cold water and extracted with 3 L of DCM × 3 until the aqueous phase product was no longer visible. The complex organic phase was washed with brine, dried over MgSO4, and concentrated under vacuum. Column chromatography using silica as the stationary phase and DCM / methanol (+1%NH3) as the mobile phase was used for purification to obtain 52.89 g of intermediate 3.

[0079] 47.5 g (0.306 mol) of intermediate 3 was placed in a three-necked flask (500 mL capacity) equipped with a thermometer, dropping funnel, mechanical stirrer, ice bath, and N2 atmosphere. 101 g (0.827 mol) of 2,6-dimethylphenol solution in 230 mL of acetonitrile was added dropwise at 10°C. 70 mL (0.919 mol) of TFA was then added dropwise, followed by 32 mL (0.367 mol) of trifluoromethanesulfonic acid. The resulting solution was stirred overnight at room temperature. The reaction mixture was concentrated to dryness under vacuum, and the resulting crude product was stirred with 1 L of Et2O. The Et2O filtrate was transferred to a decanter, and another 1 L of Et2O was added. The viscous solid was filtered, washed with Et2O (500 mL), and dried under vacuum. The brown solid was stirred in 300 mL of ethyl acetate for 30 minutes. The off-white solid was filtered, washed with ethyl acetate (100 mL), and dried under high vacuum to obtain an off-white solid. The TFA salt of the obtained product was suspended in 100 mL of water and neutralized with 200 mL of 25% NH3 to convert it to a free base, and the piperidine-containing monomer (VIIb) precipitated as a white solid. The obtained product was dried overnight under vacuum, and 20.67 g of the product was purified by normal-phase column chromatography to obtain 12.13 g (yield 59%) of piperidine-containing monomer (VIIb). The chemical structure of monomer (VIIb) is as follows: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 4. DMSO-d6 was used as the solvent.

[0080] Experimental Example 9: 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 condenser with adjustable return rate and condensate removal. At the start of the synthesis, 11.03 g (0.03 mol) of piperidine-containing monomer (VIIb) from Experimental Example 8, 6.55 g (0.03 mol) of 4,4'-difluorobenzophenone (VIa), 165 mL of N,N-dimethylacetamide, and 9.12 g (0.066 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 10 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 the mixture was 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 15.14 g (92.4%).

[0081] Experimental Example 10: Quaternization of the piperidine-containing polymer from Experimental Example 9 10 g of the polymer from Experimental Example 9 was dissolved in 40 mL of N,N-dimethylacetamide while stirring at 60°C for 1 hour. After cooling the polymer solution to 30°C, 2.5 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 from Experimental Example 10 is as follows: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 5. DMSO-d6 was used as the solvent.

[0082] Experimental Example 11: Membrane casting of piperidine-containing polymer from Experimental Example 10 The quaternized polymer solution from Experimental Example 3 was used directly for film preparation. 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 equipped with a doctor blade was moved over the plate at a speed of 5 mm / second. The applied wet layer was pre-dried in an N2 atmosphere at room temperature for 24 hours, and finally dried under vacuum at 60°C for 6 hours.

[0083] Experimental Example 12: 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 condenser with adjustable return rate and condensate removal. At the start of the synthesis, 11.03 g (0.03 mol) of piperidine-containing monomer (VIIb) from Experimental Example 8, 7.63 g (0.03 mol) of 4,4'-difluorodiphenylsulfone (VIb), 165 mL of N,N-dimethylacetamide, and 9.12 g (0.066 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 10 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 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 15.39 g (88.1%).

[0084] Experimental Example 13: Quaternization of piperidine-containing polymers from Experimental Example 12 10 g of the polymer from Experimental Example 12 was dissolved in 40 mL of N,N-dimethylacetamide while stirring at 60°C for 1 hour. After cooling the polymer solution to 30°C, 2.5 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 from Experimental Example 10 is as follows: 1 This was confirmed by 1H-NMR. 1The 1H-NMR spectrum is shown in Figure 6. DMSO-d6 was used as the solvent.

[0085] Experimental Example 14: Membrane casting of piperidine-containing polymer from Experimental Example 13 The quaternized polymer solution from Experimental Example 13 was used directly for film preparation. 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 equipped with a doctor blade was moved over the plate at a speed of 5 mm / second. The applied wet layer was pre-dried in an N2 atmosphere at room temperature for 24 hours, and finally dried under vacuum at 60°C for 6 hours.

[0086] Experimental Example 15: Synthesis of spiro-containing monomer (VIIc) The synthesis of the spiro-containing monomer (VIIc) was carried out in four steps according to reaction schemes 6 (step 1), 7 (step 2), 8 (step 3), and 9 (step 4). Intermediate 4 was synthesized according to the exact same procedure as the synthesis of monomer (VIIb), but the synthesis was started with 1-benzylpiperidine-4-one instead of 1-methylpiperidine-4-one.

[0087] [ka] TIFF0007879874000015.tif68151

[0088] In a three-necked round-bottom flask (1000 mL capacity) equipped with a thermometer, dropping funnel, mechanical stirrer, ice bath, and N2 atmosphere, 20 g (45.1 mmol) of intermediate 4 was dissolved in 451 mL of DCM, and 18.4 g (270.5 mmol) of imidazole was added. The mixture was carefully evacuated and refilled with N2 (3 times). The reaction mixture was cooled in an ice bath, and 16.31 g (108.2 mmol) of tert-butyldimethylchlorosilane (TBDMSCl) in 20 mL of DCM was added dropwise to the reaction mixture. After the addition, cooling was stopped, and the reaction mixture was stirred overnight at room temperature to form a white precipitate. The reaction mixture was quenched with 200 mL of saturated NH4Cl solution, 200 mL of water was added, and then extracted with 600 mL of DCM. The aqueous phase was washed with 300 mL of DCM, the complex organic layer was washed twice with 400 mL of water, then washed with 400 mL of brine, dried over MgSO4, filtered, and the solvent was removed under reduced pressure. The crude product was purified by normal-phase column chromatography to obtain 24.92 g (65% yield) of intermediate 5.

[0089] In a three-necked round-bottom flask (1,000 mL capacity) equipped with a mechanical stirrer, N2 atmosphere, and H2 atmosphere, 24.7 g (36.7 mmol) of intermediate 5 was dissolved in 150 mL of DCM / methanol (3 / 1) under N2. To the mixture, 4.45 g of Pd / C (10%, 50% wet) was added, and the atmosphere was changed to H2 (3 times). The reaction mixture was stirred overnight at room temperature under an H2 atmosphere. After 24 hours, an additional 3 g of Pd / C (10%, 50% wet) was added to the reaction mixture, and the reaction mixture was stirred under H2 at room temperature for another 24 hours. The crude product was filtered twice through Celite and washed with DCM (100 mL). The filtrate was evaporated to obtain 21 g (crude yield 69%) of intermediate 6.

[0090] In a three-necked round-bottom flask (1 L capacity) equipped with a thermometer, mechanical stirrer, ice bath, and N2 atmosphere, 21 g (36.1 mmol) of intermediate 6 was suspended in 500 mL of acetonitrile, and 35.3 g (108.2 mmol) of Cs2CO3 was added all at once. The reaction mixture was cooled to 0°C, and 10 g (43.3 mmol) of 1,5-dibromopentane was added all at once. The reaction mixture was stirred at 0°C for 2 hours, then stirred overnight at room temperature. After reacting for a total of 24 hours at room temperature, an additional 3 g of 1,5-dibromopentane and 5 g of Cs2CO3 were added to the reaction mixture. The reaction mixture was then evacuated with N2 (3 times) and stirred for a further 6 hours at room temperature. The reaction mixture was filtered off by gravity through filter paper, evaporated, precipitated in Et2O, filtered, and dried under high vacuum to obtain 18.17 g (yield 69%) of intermediate 7.

[0091] In a three-necked round-bottom flask (1 L capacity) equipped with a thermometer, dropping funnel, mechanical stirrer, ice bath, and N2 atmosphere, 186 mL of methanol was added, and 5.7 mL of acetyl bromide was added dropwise at 0°C. To this mixture, 17 g (23.25 mmol) of intermediate 7 in 50 mL of methanol was added dropwise at 0°C. The reaction mixture was stirred overnight at room temperature. After reacting for a total of 24 hours, the reaction mixture was evaporated, followed by precipitation in Et2O, filtered, and dried under high vacuum to obtain 12.35 g of crude product. Purification by reverse-phase column chromatography under neutral conditions yielded 5.51 g (yield 44%) of spiro-containing monomer (VIIc). The chemical structure of monomer (VIIc) is as follows: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 7. DMSO-d6 was used as the solvent.

[0092] Example 16: Synthesis of spiro-containing polymer 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 condenser with adjustable return rate and condensate removal. At the start of the synthesis, 5.02 g (0.01 mol) of spiro-containing monomer (VIIc) from Experimental Example 15, 2.18 g (0.01 mol) of 4,4'-difluorobenzophenone (VIa), 70 mL of N,N-dimethylformamide, and 3.04 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 resulting 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 5.48 g (85.6%). The chemical structure of the spiro-containing polymer from Experimental Example 16 is 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 8. DMSO-d6 was used as the solvent.

[0093] Experimental Example 17: Film casting of spiro-containing polymer from Experimental Example 16 5 g of the polymer from Experimental Example 16 was dissolved in 20 mL of N,N-dimethylformamide while stirring at 60°C for 1 hour. 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 equipped with a doctor blade was moved over the glass plate at a speed of 5 mm / second. The applied wet layer was pre-dried in an N2 atmosphere at room temperature for 24 hours, and finally dried under vacuum at 60°C for 6 hours.

[0094] Experimental Example 18: Synthesis of amine-containing monomer (VIId) A solution of 138.05 g (1.13 mol) of 2,6-dimethylphenol in 500 mL of acetic acid was placed in a 2 L three-necked round-bottom flask equipped with a thermometer, dropping funnel, mechanical stirrer, and N2 atmosphere. 500 mL of concentrated aqueous HCl and 74.59 g (0.56 mol) of 2,2-dimethoxy-N,N-dimethylethaneamine were added dropwise. The reaction mixture was stirred overnight at room temperature, and an additional 250 mL of concentrated aqueous HCl was added after 24 hours of reaction. The reaction mixture was stirred overnight at room temperature. After a total of 48 hours of reaction, it was concentrated directly to dryness under vacuum, mixed with 1.5 L of water, and sonicated for 30 minutes. The solid product was collected by filtration, washed with water, then suspended in 500 mL of acetonitrile, and concentrated under vacuum to obtain 97 g of crude product. 40 g of this crude product was then purified by reverse-phase column chromatography to obtain 30.8 g of the pure product as the HCl salt. Subsequently, the mixture was suspended in 700 mL of 25% ammonia solution and stirred overnight at room temperature to convert it to the free amine form. The resulting solid was collected by filtration, washed with water, and directly freeze-dried to obtain 25.03 g (yield 63%) of amine-containing monomer (VIId). The chemical structure of monomer (VIId) is shown below. 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 9. DMSO-d6 was used as the solvent.

[0095] The same reaction conditions can be applied to the synthesis of similar monomers with different aliphatic chain lengths n. For example, when using 3,3-dimethoxy-N,N-dimethyl-1-propanamine, n becomes 2.

[0096] Experimental Example 19: Synthesis of amine-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 condenser with adjustable return rate and condensate removal. At the start of the synthesis, 9.4 g (0.03 mol) of the amine-containing monomer (VIId) from Experimental Example 18, 6.55 g (0.03 mol) of 4,4'-difluorobenzophenone (VIa), 150 mL of N,N-dimethylacetamide, and 9.12 g (0.066 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 10 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 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 13.36 g (90.6%).

[0097] Experimental Example 20: Quaternization of the amine-containing polymer from Example 19 10 g of the polymer from Experimental Example 19 was dissolved in 40 mL of N,N-dimethylacetamide while stirring at 60°C for 1 hour. After cooling the polymer solution to 30°C, 2.5 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 amine-containing polymer from Experimental Example 20 is as follows: 1 This was confirmed by 1H-NMR. 1 The 1H-NMR spectrum is shown in Figure 10. DMSO-d6 was used as the solvent.

[0098] Experimental Example 21: Film casting of amine-containing polymers from Example 20 The quaternized polymer solution from Experimental Example 20 was used directly for film preparation. 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 equipped with a doctor blade was moved over the plate at a speed of 5 mm / second. The applied wet layer was pre-dried in an N2 atmosphere at room temperature for 24 hours, and finally dried under vacuum at 60°C for 6 hours.

[0099] Experimental Example 22: Synthesis of amine-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, 9.4 g (0.03 mol) of the amine-containing monomer (VIId) from Experimental Example 18, 7.63 g (0.03 mol) of 4,4'-difluorodiphenylsulfone (VIb), 160 mL of N,N-dimethylacetamide, and 9.12 g (0.066 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 10 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 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 13.87 g (87.6%).

[0100] Experimental Example 23: Quaternization of the amine-containing polymer from Experimental Example 22 10 g of the polymer from Experimental Example 22 was dissolved in 40 mL of N,N-dimethylacetamide while stirring at 60°C for 1 hour. After cooling the polymer solution to 30°C, 2.5 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 from Experimental Example 6 is as follows: 1 This was confirmed by 1H-NMR. 1The 1H-NMR spectrum is shown in Figure 11. DMSO-d6 was used as the solvent.

[0101] Experimental Example 24: Film casting of amine-containing polymers from Experimental Example 23 The quaternized polymer solution from Experimental Example 23 was used directly for film preparation. 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 equipped with a doctor blade was moved over the plate at a speed of 5 mm / second. The applied wet layer was pre-dried in an N2 atmosphere at room temperature for 24 hours, and finally dried under vacuum at 60°C for 6 hours.

[0102] Experimental Example 25: Ion exchange in hydroxide-form membranes The membrane prepared in Example 4 of International Publication No. 2021 / 013694 (referred to as membrane #1), the membrane prepared in Experimental Example 11 of this specification (referred to as membrane #2), the membrane prepared in Experimental Example 17 of this specification (referred to as membrane #3), the polymer membrane prepared using the tertiary amine bisphenol monomer (MPDDP) described in Chinese Patent Application Publication No. 110294845 under reaction conditions similar to those in Experimental Example 2 of this specification (referred to as membrane #4), and the commercially available anion exchange membrane FAA-3-50 were ion-exchanged using the following procedure: Six samples (40 × 40 mm) of each membrane were placed in a fresh 1 M KOH solution at 60°C for 1 hour three times, followed by 24 hours in a fresh 1 M KOH solution at 60°C. Afterward, the membrane samples were rinsed with deionized water and placed in a fresh deionized water solution at room temperature for 1 hour three times. Finally, the membrane samples were stored overnight in a fresh deionized water solution at room temperature.

[0103] Experimental Example 26: Decomposition of film samples in 2M KOH at 80°C All samples from Experimental Example 25 (six samples of each membrane type per bottle) were placed in 250 mL capacity bottles made of thick PTFE material with airtight screw caps, filled with 2 M KOH solution, and placed in a drying cabinet at 80°C for 2,000 hours. After that, the samples were rinsed with deionized water, and the ionic conductivity of each sample was measured.

[0104] Experimental Example 27: Measurement of Ionic Conductivity (IC) The ionic conductivity (IC) of ion-exchange membrane samples from Experimental Examples 25 and 26 was measured by impedance spectroscopy (EIS) using a conventional four-electrode configuration. The membrane samples were mounted in a commercially available BT-112 cell (Bekk Tech LLC). As a result, two outer Pt wires were positioned below the sample, and two midpoint Pt wires were positioned above 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 continuously pumped into the cell. The membrane resistance (R) was measured. membrane The EIS was calculated by fitting the acquired EIS spectrum using a widely used R(RC) Landrus equivalent circuit.

[0105] The ionic conductivity (σ) of the film sample can be 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 six samples for each membrane, and the mean ± standard deviation was calculated. The commercially available anion exchange membrane FAA-3-50 was also tested using the same method. Furthermore, the IC of natural membrane samples (undissolved samples of the membrane in its as-prepared state) from Experimental Example 25 was measured as a control for comparison. Table 1 summarizes all the measurement results. The normalized initial IC represents the normalized IC of the natural film sample (the undegraded film sample in its as-prepared state), while the residual normalized IC represents the IC of the sample after degradation over 2,000 hours.

[0106] [Table 1]

[0107] Table 1: Experimental data obtained from the membrane of Example 4 (indicated as membrane #1) in International Publication No. 2021 / 013694, the membrane of Experimental Example 11 (indicated as membrane #2) in this specification, the membrane of Example 17 (indicated as membrane #3) in this specification, a polymer membrane (indicated as membrane #4) prepared using tertiary amine bisphenol monomer (MPDDP) described in Chinese Patent Application Publication No. 110294845 under reaction conditions similar to those in Experimental Example 2 in this specification, and Experimental Examples 25 to 27 using the commercially available anion exchange membrane FAA-3-50 manufactured by FUMATECH BWT GmbH. *Membrane 4 decomposed into several small pieces after 1,000 hours in 2M KOH at 80°C. **The FAA-3-50 film was completely decomposed after 120 hours in 2M KOH at 80°C.**

[0108] Table 1 shows that the film according to the present invention exhibits a higher residual normalized IC value than conventional films. Therefore, the compounds of the present invention will maintain their ionic conductivity for a long period of time.

Claims

1. Equation (I): 【Chemistry 1】 (In the formula, X is a ketone group or a sulfonyl group, Z is a component comprising at least one tertiary carbon atom and at least one aromatic six-membered ring directly bonded to one of the oxygen atoms. Y is a component containing at least one positively charged nitrogen atom, which is bonded to the tertiary carbon atom of Z. A compound containing at least one unit of .

2. Formula (Ia) or Formula (Ib): 【Chemistry 2】 (In the formula, V is the same or different halogen, and M is an integer between 1 and 1000.) The compound according to claim 1, represented as shown.

3. The aforementioned component Y is given by formula (IIa), formula (IIb), or formula (IIc): 【Transformation 3】 (In the formula, n represents the number of carbon atoms in the aliphatic chain, and ranges from 0 to 9. R １ , R ２ and R ３ (These are identical or different alkyl groups having 1 to 9 carbon atoms.) The compound according to claim 1, which represents a unit of .

4. The compound according to claim 1, wherein the structural element Y present in the compound represents a unit of formula (IIa), formula (IIb), or formula (IIc) having an occurrence rate of more than 5%.

5. The aforementioned component Z is given by equation (III): 【Chemistry 4】 (In the formula, R ４ , R ５ , R ６ and R ７ (These are identical or different alkyl groups having 1 to 4 carbon atoms.) The compound according to claim 1, which represents a unit of .

6. Formula (IVa) to formula (IVf): 【Transformation 5】 (In the formula, n represents the number of carbon atoms in the aliphatic chain, which is 0 to 9, and M ａ , M ｂ and M ｃ are each an integer of 1 to 1,000.) The compound according to claim 1, represented by at least one of the following.

7. The aromatic six-membered ring directly bonded to one of the oxygen atoms comprises 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.

8. The aromatic six-membered ring directly bonded to one of the oxygen atoms comprises 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.

9. (a) Equation (VIa) or Equation (VIb): 【Transformation 6】 (In the formula, V is the same or different halogen.) Prepare a first free body containing at least one of the compounds, (b) Formula (VIIa), formula (VIIb), formula (VIIc), or formula (VIId): 【Transformation 7】 Prepare a second free body containing at least one compound selected from the following: (c) The first free body and the second free body are reacted, (d) A method for preparing the compound according to claim 1, for obtaining at least one of the compounds according to claim 1.

10. The method according to claim 9, characterized in that the alkylating reagent is used in at least one step.

11. At least one of the compounds of formula (VIa), formula (VIb), formula (VIIa), formula (VIIb), formula (VIIC), or formula (VIID) is prepared as the first or second free body, The aromatic ring of the aforementioned compound contains one or more halogens and / or one or more C １ ~C ４ - The method according to claim 9 for preparing the compound according to claim 7, which is further substituted with an alkyl group.

12. At least one compound from formula (VIa), formula (VIb), formula (VIIa), formula (VIIb), formula (VIIC), or formula (VIID) is prepared as either the first or second free body, The aromatic ring of the aforementioned compound contains one or more halogens and / or one or more C １ ~C ４ - The method according to claim 9 for preparing the compound according to claim 8, which is not further substituted with an alkyl group.

13. Use of the compound according to claim 1 as an anionic conductive film, or for the manufacture of an anionic conductive film.

14. An electrochemical cell having an anion-conducting membrane containing at least one compound according to 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 embodiment of the electrochemical process according to claim 16, wherein the electrochemical process is electrolysis, or electrodialysis, or an electrochemical process performed during the operation of a fuel cell, or an electrochemical process performed during the operation of a redox flow battery.

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