Anion exchange membrane, preparation method therefor and use thereof, integrated electrode and manufacturing method therefor, and electrosorptive deionization device

Abstract

The present invention relates to the technical fields of membrane separation and electrochemistry. Disclosed are an anion exchange membrane, a preparation method therefor and the use thereof, an integrated electrode and a manufacturing method therefor, and an electrosorptive deionization device. The anion exchange membrane comprises a plurality of polyphenylene oxide molecular chains having a structure shown as formula I and a plurality of molecular chains having a structure shown as formula II, wherein Q1 or Q2 is independently a halogen atom or is linked to the molecular chain having the structure shown as formula II to form a bond. The anion exchange membrane uses polyphenylene oxide as a main chain backbone, and the backbone contains a cationic group and long-carbon-chain molecular chains linked to the polyphenylene oxide backbone, such that the anion exchange membrane has excellent thermal stability while achieving high OH- conductivity, stability and excellent durability. In addition, the integrated electrode comprising the anion exchange membrane can remarkably increase the ion transport rate and improve the saturated adsorption capacity of an electrosorption electrode, and when being used in electrosorptive deionization devices, the integrated electrode can remarkably improve the desalination performance of the electrosorptive deionization devices.

Description

Anion exchange membrane, preparation method and application thereof, integrated electrode, preparation method thereof, and electrode adsorption ion removal device

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202410465588.1, filed April 17, 2024, and Chinese Patent Application No. 202410465817.X, filed April 17, 2024, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[0003] The present application relates to the fields of membrane separation technology and electrochemistry, in particular, to an anion exchange membrane, a preparation method and application thereof, an integrated electrode, a preparation method thereof, and an electrode adsorption ion removal device. BACKGROUND

[0004] Due to the non-renewability of fossil fuels and the environmental problems caused by the release of carbon dioxide during their combustion, developing clean energy is an indispensable condition for implementing the national sustainable development strategy. Hydrogen energy, as a renewable energy, is considered the "ultimate energy" of the 21st century due to its high calorific value, diverse sources, abundant reserves, and long-term and large-scale storage characteristics. Electrolysis of water is considered an efficient, clean, and scalable hydrogen production technology. In the existing water electrolysis hydrogen production technology route, from the comprehensive perspective of large-scale, long-life, and low cost, alkaline anion membrane water electrolysis is considered to have unique advantages. On the one hand, compared with commercial alkaline water electrolysis, it can reduce internal resistance, improve current density and energy efficiency; on the other hand, it can use non-noble metal catalysts, overcoming the problem of limited resources and high construction cost due to the use of noble metal catalysts in proton exchange membrane water electrolysis. In the process of alkaline anion membrane water electrolysis, the anion exchange membrane conducts hydroxyl ions from the cathode to the anode while blocking the direct transmission of gas and electrons between the electrodes, which is an extremely important part of the entire water electrolysis system. Therefore, it is of great significance to develop an anion exchange membrane with high performance and easy preparation.

[0005] CN112175217A discloses a method for preparing an anion exchange membrane: the obtained polymer solution is directly cast on a glass plate or a stainless steel plate, pushed flat with a casting knife, then dried at 60-100℃ for 5-24h to form a film, and finally vacuum dried at 80-150℃ for 1-24h to obtain an anion exchange membrane containing a copolymer of arylpiperidine and diketone monomers. CN113851683A discloses a method for preparing an anion exchange membrane: an anion exchange resin is dissolved in a polar solution to form a homogeneous solution of anion exchange resin with a concentration of 3wt%, which is directly cast on a glass plate and dried at 60℃ for 8h to form a film. CN115678073A discloses a method for preparing an anion exchange membrane: the casting solution is cast on a clean glass plate, then vacuum dried at 120℃ for 24h to completely remove the residual solvent, and an I-type thin film anion exchange membrane is obtained. In the literature Journal of Membrane Science, 2008, 310(1-2): 577-585. DOI: 10.1016 / j.memsci.2007.11.039, the casting solution is cast on a glass plate at room temperature and placed at room temperature for 48h, then placed at 80℃ for 24h to completely volatilize the solvent, and an anion exchange membrane is obtained. However, the above-mentioned hot curing technology has the following disadvantages in the preparation of anion exchange membranes: (1) the preparation method is currently based on thermal crosslinking, and the film preparation time is too long; (2) the energy consumption of the membrane preparation process is high; (3) a large amount of organic solvent is needed to prepare the casting solution, which causes serious environmental pollution. Therefore, it is necessary to develop a rapid and simple method for preparing ion exchange membranes.

[0006] Photocuring technology refers to the use of light radiation to induce the polymerization of active components of organic matter, achieving rapid curing of coatings in a short time. Compared with traditional thermal curing technology, the energy of photochemical reaction molecules is much higher than that of thermal chemical reaction molecules, which means that photocuring reaction does not require heating and can achieve coating curing in a few seconds to tens of seconds at room temperature, which is far higher than the rate of thermal curing by ten orders of magnitude. The characteristics of photocuring technology are that all substances in the system participate in the curing reaction and are directly or indirectly converted into a solid film. This means that compared with traditional solvent evaporation solid coatings, zero emission of volatile organic compounds (VOCs) is achieved during photocuring. Overall, photocuring technology has the advantages of high reaction rate, low energy consumption and low pollution. CN111793156A discloses a preparation method of a block anion exchange membrane, which uses visible light to initiate polymerization to synthesize a block polymer with a soft-hard segment structure, and introduces a pyrrole group, a trimethylamine group or a piperidine group into the block polymer. The block anion exchange membrane is prepared by irradiating for 20-45 min. CN116459680A discloses a preparation method of a green photo-polymerization anion exchange membrane. First, brominated self-porous polymer (PIM-Br) and photoinitiator are dissolved in chloromethyl styrene (VBC), then the solution is cast on a glass plate, and the anion exchange membrane is obtained by nucleophilic substitution reaction of bromomethyl in PIM-Br and chloromethyl in VBC with bis-tert-amine group after photo-curing under ultraviolet light irradiation for 20-30 min and direct immersion in bis-tert-amine reagent. Although the above-mentioned patents use photocuring technology, which avoids high energy consumption and complex reaction process, it is still necessary to further shorten the film preparation time and improve the preparation efficiency of the anion exchange membrane. In addition, the same increase and decrease of ion exchange capacity IEC and water absorption greatly limit the application efficiency.

[0007] Capacitive deionization (CDI) is an efficient and environmentally friendly electrochemical water treatment technology that can be used for moderate desalination of salt-containing wastewater. In order to improve the desalination performance of the CDI device, ion exchange membranes are often placed on the surface of the electrode in practical applications to weaken the common ion effect in the adsorption process, reduce the adsorption resistance, and avoid the secondary adsorption of ions by the opposite electrode during the desorption process of CDI.

[0008] In actual operation, the desalination performance of the CDI device is limited by the low adsorption capacity of the electrode. This is because the ion exchange membrane and the adsorption electrode are combined in a physical superposition form, resulting in a large gap between the ion exchange membrane and the electrode, and the actual ion transport distance from the solution to the electrode is long, increasing the mass transfer resistance. Therefore, the heterogeneous structure between the ion exchange membrane and the adsorption electrode is a major bottleneck for the performance improvement of CDI.

[0009] CN109502708A discloses a preparation method of an ion exchange membrane / carbon composite electrode, specifically spraying ion exchange membrane layer slurry to the surface of a carbon electrode, and then heating and curing to obtain an ion exchange membrane / carbon composite electrode, wherein the ion exchange membrane layer slurry is pretreated ion exchange resin and a binder. This method mixes solutions. The composite electrode prepared by this method is still a heterogeneous structure, and the ion exchange resin and the electrode are bonded by the binder. On the one hand, the ion exchange resin in the ion exchange layer is a discontinuous phase, and the ion transport channel density is low; on the other hand, the binder does not have ion exchange function, which increases the contact resistance between the adsorption electrode and the ion exchange resin, and limits the ion transport rate to the adsorption electrode. CN115536114A discloses a membrane capacitive deionization desalination module, which comprises an anode, a cathode and an ion exchange membrane. The cathode comprises a carbon material matrix and a conductive polymer doped with anions B deposited in the carbon material matrix. The electrode prepared by this method can improve its conductivity and the ion transport rate in the electrode, but does not change the heterogeneous structure between the ion exchange membrane and the electrode, and the contact resistance between the electrode and the ion exchange membrane is large, which has limited improvement on the desalination performance. SUMMARY

[0010] The purpose of the present application is to overcome the shortcomings of the prior art, and to provide an anion exchange membrane, a preparation method and application thereof, an integrated electrode, a preparation method thereof, and an electrosorption deionization device. The anion exchange membrane has a polyphenyl ether-containing main chain skeleton, and the skeleton contains cationic groups and long carbon chain molecular chains connected to the polyphenyl ether skeleton, so that the anion exchange membrane has excellent thermal stability, high OH - conductivity, stability and excellent durability. The integrated electrode comprises an electrosorption electrode and an anion exchange functional layer with a specific structure coated on the surface of the electrosorption electrode, which can significantly improve the ion transport rate and the saturation adsorption capacity of the electrosorption electrode. When the integrated electrode is used in an electrosorption deionization device, the desalination performance of the electrosorption deionization device can be significantly improved.

[0011] To achieve the above-mentioned purpose, the first aspect of the present application provides an anion exchange membrane, wherein the anion exchange membrane comprises a polyphenyl ether molecular chain having a structure shown in formula I and a molecular chain having a structure shown in formula II.

[0012] wherein Q1 or Q2 is independently a halogen atom, or is connected to the molecular chain having a structure shown in formula II to form a bond;

[0013] wherein R1 and R2 are independently H or C1-C5 alkyl, R3, R4, R5 and R6 are independently C1-C 10A straight or branched alkyl group, -R9SO3, R9 is C1-C 10 R7 and R8 are each independently a C1-C3 alkylene group; x is 20%-50%, and * represents the connection position of Formula II and Formula I.

[0014] A second aspect of the present invention provides a method for preparing an anion exchange membrane, wherein the preparation method comprises:

[0015] (1) mixing a photocrosslinking agent represented by Formula 1 and / or Formula 2, a halogenated polyphenylene ether represented by Formula 3, and an organic solvent, and reacting the mixture to obtain a solution containing a prepolymer;

[0016] (2) mixing the prepolymer-containing solution with a photoinitiator under light-proof conditions to obtain a casting solution;

[0017] (3) coating the casting solution on a substrate and curing it under light conditions to obtain the anion exchange membrane;

[0018] Among them, R 10 is H or C1-C5 alkyl, R 11 is a C1-C3 alkylene group, R 12 and R 13 Each independently is C1-C 10 A straight or branched alkyl group, -R9SO3, R9 is C1-C 10 Alkylene; R 14 is a C1-C3 alkyl group, X is a monovalent anion; X1 and X2 are each independently H or a halogen atom, and at least one of X1 and X2 is a halogen atom; x is 20%-50%.

[0019] The third aspect of the present invention provides an anion exchange membrane produced by the above-mentioned preparation method.

[0020] A fourth aspect of the present invention provides a use of the above-mentioned anion exchange membrane in a separation process.

[0021] A fifth aspect of the present invention provides an integrated electrode, wherein the integrated electrode comprises an electrosorption electrode and an anion exchange functional layer coated on the surface of the electrosorption electrode;

[0022] Wherein, the anion exchange functional layer is the above-mentioned anion exchange membrane.

[0023] A sixth aspect of the present invention provides a method for preparing an integrated electrode, wherein the preparation method comprises the following steps:

[0024] S1, mixing the photocrosslinking agent shown in formula 1 and / or formula 2, the halogenated polyphenyl ether shown in formula 3 and the organic solvent, and then performing a reaction to obtain a solution containing a prepolymer;

[0025] S2, mixing the solution containing the prepolymer with a photoinitiator under light shielding conditions to obtain a precursor solution;

[0026] S3, vacuum deaerating the precursor solution and then coating the precursor solution on an electrosorption electrode to obtain an electrosorption electrode with a liquid coating layer;

[0027] S4, curing the electrosorption electrode with the liquid coating layer under light irradiation to obtain the integrated electrode;

[0028] wherein R 10 is H or C 1- alkyl, R 11 is C1-C3 alkylene, R 12 and R 13 are each independently C1-C 10 linear or branched alkyl, -R9SO3, R9 is C1-C 10 alkylene; R 14 is C1-C3 alkyl, X is a monovalent anion; X1 and X2 are each independently H or a halogen atom, and at least one of X1 and X2 is a halogen atom; x is 20%-50%.

[0029] The seventh aspect of the present application provides an integrated electrode prepared by the above preparation method.

[0030] The eighth aspect of the present application provides an electrosorption deionization device, wherein the electrosorption deionization device comprises the integrated electrode described above.

[0031] Through the above technical solutions, the anion exchange membrane and the preparation method and application thereof, the integrated electrode and the preparation method thereof, and the electrosorption deionization device provided by the present application have the following beneficial effects:

[0032] The anion exchange membrane provided by the present application takes a polyphenyl ether-containing main chain skeleton, and the skeleton contains a cationic group and a long carbon chain molecular chain connected to the polyphenyl ether skeleton, so that the anion exchange membrane has excellent thermal stability, high OH - conductivity, stability and excellent durability. Specifically, the cationic group contained in the polyphenyl ether skeleton can construct an anion transport channel, thereby enabling the anion exchange membrane to have a high ion exchange rate. The long carbon chain molecular chain connected to the polyphenyl ether skeleton contained in the anion exchange membrane can form dense ion clusters, further improving the OH -The conductivity, and the polyphenyl ether skeleton makes the anion exchange membrane have excellent thermal stability. Finally, the anion exchange membrane not only has excellent ion exchange capacity, mechanical properties, water absorption rate and swelling rate, but also has excellent high temperature resistance and high alkalinity, especially in the field of electrodialysis, seawater desalination has broad application prospect. Specifically, in some embodiments of the present application, the ion exchange capacity of the anion exchange membrane at 25 DEG C is above 0.5 mmol / g, preferably 0.9-2.5 mmol / g, the water absorption rate is above 8.6%, preferably 15.6-154%, the swelling rate is above 7.3%, preferably 8.9-80.6%, the tensile strength is above 0.4 MPa, preferably 1.2-4.8 MPa, the elongation at break is above 1.3%, preferably 2.3-23.6%, the IEC reduction rate after soaking in an alkaline solution with pH = 12 for 24 hours is below 40%, preferably 4.68-20%, the surface Zeta potential is above 28 mV, preferably 45-60 mV.

[0033] The preparation method provided by the present application realizes solidification and film formation under light conditions, which is 2-3 orders of magnitude faster than traditional heat treatment, avoids high energy consumption and complicated reaction process, and improves the preparation efficiency of the anion exchange membrane.

[0034] In the present application, the integrated electrode comprises an electrosorption electrode and an anion exchange functional layer with a specific structure coated on the surface of the electrosorption electrode. The anion exchange functional layer has a homogeneous structure and contains a large number of active ion exchange groups, which can tightly combine the anion exchange function with the electrode, greatly reduce the mass transfer distance and resistance of ions from the solution to the electrode, greatly improve the mass transfer rate, and improve the exchange capacity of the electrosorption electrode. In particular, when the integrated electrode is used in an electrosorption ion removal device, the desalination performance of the electrosorption ion removal device can be significantly improved, and the energy consumption can be reduced.

[0035] Further, the integrated electrode provided by the present application has a high adsorption capacity for anions (such as chloride ions), and the electrosorption ion removal device containing the integrated electrode has a high desalination rate, and the adsorption rate of the opposite electrode during desorption is low. Specifically, the adsorption capacity of the integrated electrode for anions is 12-20 mg / g, the desalination rate of the electrosorption ion removal device is 43-76%, the adsorption rate of the opposite electrode during desorption is less than or equal to 11%, preferably 2-7%, and the adsorption time can be shortened to 85% of the original, which greatly improves the desalination performance of the electrosorption ion removal device.

[0036] In the preparation method provided by the present application, the integrated electrode is prepared under light conditions, which is 2-3 orders of magnitude faster than traditional heat treatment, avoids high energy consumption and complicated reaction process, and improves the preparation efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure A1 is the NMR of BPPO prepared in Example 1-3. 1 H spectrum.

[0038] Figure A2 is the FTIR spectra of the raw material PPO, BPPO-1 prepared in Preparation Example 1, and the anion exchange membrane prepared in Example A3.

[0039] Figure A3 is the nuclear magnetic resonance of the anion exchange membranes prepared in Example A3 and Comparative Example DA2. 13 C spectrum.

[0040] FIG. A4 is the FTIR spectra of the anion exchange membrane prepared in Example A3 before and after immersion in alkali.

[0041] FIG. A5 is an SEM image of the anion exchange membrane prepared in Example A3 before and after immersion in alkali.

[0042] Figure B1 is a process flow chart for preparing an integrated electrode according to the method of the present invention. DETAILED DESCRIPTION

[0043] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0044] Unless otherwise defined, all terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, preferred methods and materials are now described.

[0045] In the present invention, the ranges of dosage concentration, temperature or other physical or chemical properties or characteristics cover or include the upper and lower limits of the ranges unless otherwise specified.

[0046] A first aspect of the present invention provides an anion exchange membrane, wherein the anion exchange membrane comprises a polyphenylene ether molecular chain having a structure represented by Formula I and a molecular chain having a structure represented by Formula II;

[0047] wherein Q1 or Q2 is independently a halogen atom, or is bonded to a molecular chain having a structure represented by Formula II;

[0048] wherein R1 and R2 are each independently H or C1-C5 alkyl, R3, R4, R5 and R6 are each independently C1-C 10 alkyl, -R9SO3, R9 is C1-C 10 alkylene; R7 and R8 are each independently C1-C3 alkylene; x is 20%-50%, * indicates the position of the connection between formula II and formula I.

[0049] In the present application, the polyphenyl ether molecular chain shown in formula I and the molecular chain having the structure of formula II are long chain structures, each independently comprising a plurality of structures shown in formula I or formula II, and in the present application, only the structure of a fragment in the long molecular chain structure is schematically provided, and the rest of the structure is represented by . In the present application, a plurality of polyphenyl ether molecular chains and a plurality of molecular chains having the structure shown in formula II exist in the anion exchange membrane.

[0050] In the present application, the anion exchange membrane is stored in a salt solution (such as sodium chloride), and the anion Cl - or OH - present in the salt solution can ensure the charge balance of the anion exchange membrane.

[0051] The anion exchange membrane provided by the present application takes polyphenyl ether as the main chain skeleton, and the skeleton contains cationic groups and long carbon chain molecular chains connected to the polyphenyl ether skeleton, so that the anion exchange membrane has excellent thermal stability, high OH - conductivity, stability and excellent durability. Specifically, the long carbon chain molecular chains connected to the polyphenyl ether skeleton can gather to form ion clusters due to the dense ion groups, thereby enabling the anion exchange membrane to have high ion exchange rate, and the polyphenyl ether skeleton enables the anion exchange membrane to have excellent thermal stability. The long carbon chain molecular chains connected to the polyphenyl ether skeleton contained in the anion exchange membrane can form dense ion clusters, further improving the OH - conductivity of the anion exchange membrane. Ultimately, the anion exchange membrane not only has excellent ion exchange capacity, mechanical properties, water absorption rate and swelling rate, but also has excellent high temperature resistance and high alkalinity, and has a broad application prospect in the fields of electrodialysis and seawater desalination.

[0052] In the present application, x refers to the halogenation rate of the halogenated polyphenyl ether. For example, when the halogenated polyphenyl ether is brominated polyphenyl ether, x specifically refers to the bromination rate of the brominated polyphenyl ether, which reflects the proportion of H on the methyl group on the benzene ring in the polyphenyl ether molecular chain shown in formula I being replaced by Q1 or Q2.

[0053] In the present application, the stability refers to the excellent toughness of the anion exchange membrane, which can withstand greater deformation without breaking.

[0054] In the present application, the molecular chain with the structure shown in Formula II refers to the molecular chain formed after the crosslinking agent is subjected to radical polymerization.

[0055] Specifically, the structure of the anion exchange membrane according to the present application is shown in the following schematic diagram:

[0056] In the present application, the C1-C5 alkyl group includes a C1-C5 straight chain alkyl group or a C1-C5 branched chain alkyl group. 10 The C1-C3 alkylene group and the C1-C3 alkylene group each independently include a straight chain alkylene group or a branched chain alkylene group.

[0057] In the present application, x is 20%-50%, for example, can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, and the range consisting of any two values.

[0058] In one specific embodiment of the present application, R1 and R2 are each independently H, CH3 or CH2CH3, R3, R4, R5 and R6 are each independently a C1-C5 straight chain or branched chain alkyl group, -R9SO3; R9 is a C1-C3 alkylene group; R7 and R8 are each independently methylene or ethylene; and x is 30%-40%.

[0059] According to the present application, the polyphenyl ether in the anion exchange membrane is a crosslinked polyphenyl ether.

[0060] According to the present application, the content of the polyphenyl ether molecular chain is 18wt%-95wt% and the content of the molecular chain with the structure shown in Formula II is 5wt%-82wt% based on the total weight of the anion exchange membrane.

[0061] In the present application, when the content of the polyphenyl ether molecular chain and the molecular chain with the structure shown in Formula II in the anion exchange membrane satisfies the above range, the anion exchange membrane can contain sufficient quaternary ammonium salt groups, and can effectively construct efficient ion exchange channels, thereby imparting the anion exchange membrane with good ion exchange capacity.

[0062] In the present application, the content of the polyphenyl ether molecular chain is 18wt%-95wt% based on the total weight of the anion exchange membrane, for example, it can be 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, 42wt%, 44wt%, 46wt%, 48wt%, 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%, 66wt%, 68wt%, 70wt%, 72wt%, 74wt%, 76wt%, 78wt%, 80wt%, 82wt%, 84wt%, 86wt%, 88wt%, 90wt%, 92wt%, 94wt%, 95wt%, and a range consisting of any two values; the content of the molecular chain with the structure shown in formula II is 5wt%-82wt%, for example, it can be 5wt%, 6wt%, 8wt%, 10wt%, 12wt%, 14wt%, 16wt%, 18wt%, 20wt%, 22wt%, 24wt%, 26wt%, 28wt%, 30wt%, 32wt%, 34wt%, 36wt%, 38wt%, 40wt%, 42wt%, 44wt%, 46wt%, 48wt%, 50wt%, 52wt%, 54wt%, 56wt%, 58wt%, 60wt%, 62wt%, 64wt%, 66wt%, 68wt%, 70wt%, 72wt%, 74wt%, 76wt%, 78wt%, 80wt%, 82wt%, and a range consisting of any two values.

[0063] In one specific embodiment of the present application, the content of the polyphenyl ether molecular chain is 31wt%-78wt% based on the total weight of the anion exchange membrane, and the content of the molecular chain with the structure shown in formula II is 22wt%-69wt%.

[0064] According to the present application, the anion exchange membrane has an ion exchange capacity of 0.9-2.5 mmol / g at 25°C; for example, it can be 0.9 mmol / g, 0.95 mmol / g, 1 mmol / g, 1.05 mmol / g, 1.1 mmol / g, 1.15 mmol / g, 1.2 mmol / g, 1.25 mmol / g, 1.3 mmol / g, 1.35 mmol / g, 1.4 mmol / g, 1.45 mmol / g, 1.5 mmol / g, 1.55 mmol / g, 1.6 mmol / g, 1.65 mmol / g, 1.7 mmol / g, 1.75 mmol / g, 1.8 mmol / g, 1.85 mmol / g, 1.9 mmol / g, 1.95 mmol / g, 2 mmol / g, 2.05 mmol / g, 2.1 mmol / g, 2.15 mmol / g, 2.2 mmol / g, 2.25 mmol / g, 2.3 mmol / g, 2.35 mmol / g, 2.4 mmol / g, 2.45 mmol / g, 2.5 mmol / g, and a range between any two values, preferably 1.1-2.5 mmol / g.

[0065] According to the present application, the anion exchange membrane has a water absorption of 15.6%-154.3% at 25°C; for example, it can be 15.6%, 20%, 26.4%, 31.7%, 35.9%, 36.5%, 37.6%, 38.1%, 38.2%, 38.4%, 44.5%, 54.3%, 60%, 84.1%, 124.7%, 125.8%, 127.4%, 150.2%, 154.3%, and a range between any two values, preferably 31.7%-124.7%.

[0066] According to the present application, the anion exchange membrane has a swelling rate of 8.9%-80.6% at 25°C; for example, it can be 8.9%, 10%, 30.2%, 30.4%, 32.1%, 33.8%, 34.3%, 34.5%, 35.4%, 35.6%, 40.6%, 42.1%, 50.3%, 68.7%, 80.6%, and a range between any two values, preferably 30.2%-68.7%.

[0067] According to the present application, the tensile strength of the anion exchange membrane is 1.2-4.7 MPa, for example, it can be 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, and any range consisting of two values, preferably 1.8-4.8 MPa, and the elongation at break is 2.3-23.6%, for example, it can be 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 4%, 4.4%, 4.8%, 5.2%, 5.4%, 5.6%, 6%, 6.4%, 6.8%, 7.2%, 7.6%, 8%, 8.4%, 8.8%, 9.2%, 9.6%, 10%, 12%, 14%, 16%, 18%, 20%, 20.5%, 21%, 21.2%, 21.4%, 21.6%, 21.8%, 22%, 22.2%, 22.4%, 22.6%, 22.8%, 23%, 23.2%, 23.4%, 23.6%, and any range consisting of two values, preferably 3.2-23.6%.

[0068] According to the present application, the anion exchange membrane has a decrease rate of ion exchange capacity at 25°C of 3.6-22.4% after being soaked in an alkaline solution with pH=12 for 24 hours, for example, it can be 3.6%, 4%, 4.4%, 4.6%, 4.8%, 5%, 5.3%, 5.5%, 5.8%, 6%, 6.3%, 6.5%, 6.8%, 7.2%, 7.6%, 8%, 8.5%, 9.1%, 9.5%, 10%, 10.5%, 11%, 11.1%, 11.6%, 12%, 12.5%, 13%, 14%, 14.3%, 15%, 15.5%, 16%, 16.7%, 18%, 18.5%, 19%, 19.5%, 20%, 20.5%, 21%, 21.5%, 22%, 22.4%, and any range consisting of two values, preferably 3.6-11.6%.

[0069] According to the present application, the surface Zeta potential of the anion exchange membrane is 28-60 mV, for example, can be 28 mV, 32 mV, 36 mV, 40 mV, 44 mV, 48 mV, 52 mV, 56 mV, 60 mV, and a range consisting of any two values, preferably 45-60 mV.

[0070] According to the present application, the thickness of the anion exchange membrane is 50-200 μm, for example, can be 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm, and a range consisting of any two values, preferably 100-150 μm.

[0071] According to the present application, the crosslinking density of the anion exchange membrane is 0.4 x 10 -4 -1.9 x 10 -4 mol / cm 3 .

[0072] In the present application, when the crosslinking density of the anion exchange membrane satisfies the above range, it indicates that the structure of the anion exchange membrane is compact and the long carbon chain molecules having the structure shown in Formula II connected to the polyphenyl ether skeleton can form dense ion clusters, providing more ion exchange sites, thereby giving the anion exchange membrane higher OH - conductivity, current density, desalination rate and lower impedance.

[0073] In the present application, the crosslinking density of the anion exchange membrane is 0.4 x 10 -4 -1.9 x 10 -4 mol / cm 3 , for example, can be 0.4 x 10 -4 mol / cm 3 , 0.5 x 10 -4 mol / cm 3 , 0.6 x 10 -4 mol / cm 3 , 0.7 x 10 -4 mol / cm 3 , 0.8 x 10 -4 mol / cm 3 , 0.9 x 10 -4 mol / cm 3 , 1 x 10 -4 mol / cm 3 , 1.1 x 10 -4 mol / cm 3 , 1.2 x 10 -4 mol / cm 3, 1.3×10 -4 mol / cm 3 , 1.4×10 -4 mol / cm 3 , 1.5×10 -4 mol / cm 3 , 1.6×10 -4 mol / cm 3 , 1.7×10 -4 mol / cm 3 , 1.8×10 -4 mol / cm 3 , 1.9×10 -4 mol / cm 3 , and ranges of any two values.

[0074] Furthermore, the cross-linking density of the anion exchange membrane is 0.8×10 -4 -1.6×10 -4 mol / cm 3 .

[0075] According to the present invention, the anion exchange membrane has an OH content of 80°C. - The electrical conductivity is 30-55ms / cm, for example, 30ms / cm, 31ms / cm, 32ms / cm, 33ms / cm, 34ms / cm, 35ms / cm, 36ms / cm, 37ms / cm, 38ms / cm, 39ms / cm, 40ms / cm, 41ms / cm, 42ms / cm, 43ms / cm, 44ms / cm, 45ms / cm, 46ms / cm, 47ms / cm, 48ms / cm, 49ms / cm, 50ms / cm, 51ms / cm, 52ms / cm, 53ms / cm, 54ms / cm, 55ms / cm, and a range consisting of any two values, preferably 40-55ms / cm.

[0076] According to the present invention, the impedance of the anion exchange membrane is 12-18Ω, for example, it can be 12Ω, 13Ω, 14Ω, 15Ω, 16Ω, 17Ω, 18Ω, and a range consisting of any two values, preferably 12-15Ω.

[0077] According to the present invention, the current density of the anion exchange membrane at a voltage of 2.1 V is 470-630 mA·cm -2 , for example, it can be 470mA·cm -2 , 480mA·cm -2 , 490mA·cm -2 , 500mA·cm -2 , 510mA·cm-2 520 mA cm -2 530 mA cm -2 540 mA cm -2 550 mA cm -2 560 mA cm -2 570 mA cm -2 580 mA cm -2 590 mA cm -2 610 mA cm -2 620 mA cm -2 630 mA cm -2 and a range consisting of any two of the values, preferably 530-630 mA cm -2 .

[0078] According to the present application, the anion exchange membrane has a desalination rate of greater than 94% after 45 minutes of electrodialysis, for example, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, 100%, preferably greater than 97%.

[0079] The second aspect of the present application provides a preparation method of an anion photo-crosslinked membrane, wherein the preparation method comprises:

[0080] (1) mixing a photo-crosslinking agent represented by Formula 1 and / or Formula 2, a halogenated polyphenyl ether represented by Formula 3 and an organic solvent, and then performing a reaction to obtain a solution containing a prepolymer;

[0081] (2) mixing the solution containing the prepolymer with a photo initiator under light shielding conditions to obtain a casting solution;

[0082] (3) coating the casting solution on a substrate and performing curing under light irradiation to obtain the anion exchange membrane;

[0083] wherein R 10 is H or C1-C5 alkyl, R 11 is C1-C3 alkylene, R 12 and R 13 are each independently C1-C 10 straight chain or branched alkyl, -R9SO3, R9 is C1-C 10 alkylene; R 14 is C1-C3 alkyl, X is a monovalent anion; X1 and X2 are each independently H or a halogen atom, and at least one of X1 and X2 is a halogen atom; x is 20%-50%.

[0084] In the present application, by reacting the crosslinking agent shown in Formula 1 and / or Formula 2 with the halogenated polyphenyl ether shown in Formula 3, using one-step reaction of tertiary amine and alkyl halide, cationic groups and photoresponsive groups can be simultaneously introduced on the polyphenyl ether skeleton, anion exchange characteristics and photo-crosslinking characteristics are endowed to the film-forming skeleton, anion transport channels can be constructed to obtain high ion exchange rate, at the same time, the halogenated polyphenyl ether can realize the polymerization reaction of the terminal double bond under light irradiation, and the molecular chain with long carbon chain is introduced into the anion exchange membrane, which forms dense ion clusters, so that OH - The conductivity is further improved, and the presence of the polyphenyl ether skeleton ensures that the prepared anion exchange membrane has excellent thermal stability.

[0085] In the present application, x refers to the halogenation rate of the halogenated polyphenyl ether, specifically, the proportion of H in the methyl group on the benzene ring in the halogenated polyphenyl ether shown in Formula 3 being replaced by halogen atoms.

[0086] Further, by controlling the halogenation degree (x value) of the halogenated polyphenyl ether, the content of cationic groups in the polyphenyl ether skeleton of the anion exchange membrane can be controlled, in particular, when the halogenation degree meets the above range, the prepared anion exchange membrane has a suitable crosslinking density, so that the anion exchange membrane has excellent mechanical properties and ion exchange capacity.

[0087] Further, R 10 is H, CH3 or CH2CH3, R 11 is C1-C2 alkyl, R 12 and R 13 are each independently C1-C5 linear or branched alkyl, R 14 is CH3 or CH2CH3, X is a monovalent anion; X1 and X2 are each independently H or Br, and at least one of X1 and X2 is Br; x is 30%-40%.

[0088] In one specific embodiment of the present application, the crosslinking agent is selected from at least one of dimethylaminoethyl methacrylate, 2-methacryloyloxyethyl trimethylammonium chloride, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 2-(diethylamino)ethyl methacrylate and 2-(diisopropylamino)ethyl methacrylate.

[0089] In the present application, when the crosslinking agent is two or more, the amount of each of the two or more crosslinking agents is not particularly limited, as long as the content of the molecular chain having the structure shown in Formula II in the prepared anion exchange membrane meets the limitation of the present application.

[0090] In the present invention, there is no particular limitation on the type of the organic solvent, as long as the brominated polyphenylene ether can be fully dissolved. For example, the organic solvent is at least one selected from N-methylpyrrolidone, tetrahydrofuran, and N,N-dimethylformamide.

[0091] According to the present invention, the halogenated polyphenylene ether is brominated polyphenylene ether.

[0092] According to the present invention, the weight average molecular weight M of the brominated polyphenylene ether is w The range of the present invention is 55000-90000 g / mol, for example, 55000 g / mol, 56000 g / mol, 57000 g / mol, 58000 g / mol, 59000 g / mol, 60000 g / mol, 61000 g / mol, 62000 g / mol, 63000 g / mol, 64000 g / mol, 65000 g / mol, 66000 g / mol, 67000 g / mol, 68000 g / mol, 69000 g / mol, 70000 g / mol, 71000 g / mol, 72000 g / mol / mol, 73000 g / mol, 74000 g / mol, 75000 g / mol, 76000 g / mol, 77000 g / mol, 78000 g / mol, 79000 g / mol, 80000 g / mol, 81000 g / mol, 82000 g / mol, 83000 g / mol, 84000 g / mol, 85000 g / mol, 86000 g / mol, 87000 g / mol, 88000 g / mol, 89000 g / mol, 90000 g / mol, and ranges between any two values.

[0093] In the present invention, there is no particular limitation on the source of the polyphenylene ether, which can be purchased commercially or prepared in-house.

[0094] In one embodiment of the present invention, the brominated polyphenylene ether is prepared according to the following steps:

[0095] S1. In the presence of a solvent and a protective gas, poly (2,6-dimethyl-1,4-phenylene ether) (PPO), a brominating agent, and an initiator are mixed to perform a bromination reaction;

[0096] S2. Cooling the product obtained in step S1, adding an alcohol solution, filtering, washing, purifying, and drying to obtain the brominated polyphenylene ether.

[0097] In the present application, the molar ratio of the poly(2,6-dimethyl-1,4-phenylene ether) (PPO) to the brominating agent is 1:0.5-3, for example, it can be 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, and a range consisting of any two values, and preferably 1:1-2.

[0098] In the present application, the weight average molecular weight of the poly(2,6-dimethyl-1,4-phenylene ether) is 40000-50000 g / mol, for example, it can be 42000 g / mol, 44000 g / mol, 46000 g / mol, 48000 g / mol, 50000 g / mol, and a range consisting of any two values.

[0099] In the present application, the molar ratio of the poly(2,6-dimethyl-1,4-phenylene ether) (PPO) to the initiator is 1:0.05-0.08, for example, it can be 1:0.05, 1:0.06, 1:0.07, 1:0.08, and a range consisting of any two values, and preferably 1:0.06-0.07.

[0100] In the present application, the brominating agent can be a conventional type of brominating agent in the art, for example, N-bromosuccinimide (NBS) and / or 1,3-dibromo-5,5-dimethylhydantoin (DBH).

[0101] In the present application, the initiator can be a conventional type of initiator in the art, for example, it can be azobisisobutyronitrile (AIBN) and / or azobisisoheptyl nitrile (ABVN).

[0102] In the present application, the solvent can be a conventional solvent in the art, for example, chlorobenzene, and the amount of the organic solvent is not particularly limited as long as the poly(2,6-dimethyl-1,4-phenylene ether) (PPO) can be sufficiently dissolved.

[0103] In the present application, the type of the protective gas is not particularly limited, and a conventional type of protective gas in the art can be used, for example, nitrogen.

[0104] In the present application, the conditions of the bromination reaction include that the reaction temperature is 110-140℃, for example, it can be 110℃, 120℃, 130℃, 140℃, and a range consisting of any two values, and the reaction time is 2-4h, for example, it can be 2h, 2.5h, 3h, 3.5h, 4h, and a range consisting of any two values.

[0105] In the present application, the type of alcohol solution is not particularly limited, and a conventional type of alcohol solution, such as a methanol solution, can be used. The amount of alcohol solution is also not particularly limited, as long as it can completely precipitate the brominated polyphenylene ether. In order to further ensure that the brominated polyphenylene ether can be completely precipitated, preferably, the alcohol solution is added in a dropwise manner, and more preferably, it is added dropwise to the product obtained in step S1 at a speed of 20-50 mL / min.

[0106] In the present application, methanol is used to wash the filtered product.

[0107] In the present application, the step of purifying includes redissolving the washed product in a first organic solvent and washing it with a second organic solvent.

[0108] In the present application, the first organic solvent is selected from at least one of chloroform, dichloromethane and tetrahydrofuran. In the present application, the amount of the first organic solvent is 1000-2000 mL with respect to 100 g of the washed product.

[0109] In the present application, the second organic solvent is selected from acetone and / or butanone.

[0110] In the present application, the amount of the second organic solvent is 1000-2000 mL with respect to 100 g of the washed product.

[0111] In one specific embodiment of the present application, the halogenated polyphenylene ether represented by Formula 3 and the organic solvent are mixed to obtain a mixed solution, and the crosslinking agent represented by Formula 1 and / or Formula 2 is added to the mixed solution to obtain a solution containing a prepolymer.

[0112] In the present application, the halogenated polyphenylene ether is mixed with the organic solvent in advance, which can ensure that the halogenated polyphenylene ether is fully dissolved and dispersed in the organic solvent, improve the dispersibility of the halogenated polyphenylene ether in the mixed solution, and further enable the crosslinking agent to fully contact and react with the halogenated polyphenylene ether.

[0113] In the present application, in order to control the dispersibility of the halogenated polyphenylene ether, preferably, the concentration of the halogenated polyphenylene ether in the mixed solution is 5wt%-20wt%, for example, it can be 5wt%, 10wt%, 15wt%, 20wt%, and a range consisting of any two values, and more preferably, it is 5wt%-10wt%.

[0114] According to the present application, the molar ratio of the halomethyl group in the halogenated polyphenylene ether to the crosslinking agent is 1:0.2-65.

[0115] In the present application, when the molar ratio of halomethyl groups in the halogenated polyphenylene ether to the crosslinking agent meets the above range, the crosslinking agent can provide sufficient quaternary ammonium groups to construct efficient ion exchange channels, and thus the anion exchange membrane has good ion exchange capacity.

[0116] In the present application, the molar ratio of halomethyl groups in the halogenated polyphenylene ether to the crosslinking agent is 1:0.2-65, for example, it can be 1:0.2, 1:0.5, 1:1, 1:1.5, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, 1:50, 1:55, 1:60, 1:65, and a range composed of any two values.

[0117] Further, the molar ratio of halomethyl groups in the halogenated polyphenylene ether to the crosslinking agent is 1:1-25.

[0118] According to the present application, the reaction conditions include that the reaction temperature is 15-30℃, and the reaction time is 12-48h.

[0119] In the present application, the reaction is carried out under the above specific conditions, which can make the halogenated polyphenylene ether and the crosslinking agent fully and efficiently undergo halogen substitution reaction, and form a stable and uniform casting solution, without the generation of insoluble particles in the casting solution due to excessive crosslinking.

[0120] In the present application, the reaction conditions include that the reaction temperature is 15-30℃, for example, it can be 15℃, 20℃, 25℃, 30℃, and a range composed of any two values, and the reaction time is 12-48h, for example, it can be 12h, 16h, 20h, 24h, 30h, 34h, 38h, 42h, 46h, 48h, and a range composed of any two values.

[0121] Further, the reaction conditions include that the reaction temperature is 15-25℃, and the reaction time is 12-24h.

[0122] According to the present application, the photoinitiator is selected from at least one of radical photoinitiators and / or cationic photoinitiators, preferably selected from at least one of 2-hydroxy-2-methylpropiophenone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, and 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide.

[0123] According to the present application, the amount of the photoinitiator is 3wt%-10wt% based on the total mass of the crosslinking agent and the halogenated polyphenylene ether.

[0124] In the present application, when the amount of the photoinitiator is controlled to meet the above range, the photoinitiator can quickly initiate the chain reaction of free radicals on the crosslinking agent to achieve rapid crosslinking, and a uniform and defect-free anion exchange membrane is obtained.

[0125] In the present application, the amount of the photoinitiator is 3wt%-10wt% based on the total mass of the crosslinking agent and the halogenated polyphenyl ether, for example, it can be 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, and a range consisting of any two values.

[0126] Further, the amount of the photoinitiator is 3wt%-7wt% based on the total mass of the crosslinking agent and the halogenated polyphenyl ether.

[0127] According to the present application, the preparation method further comprises: degassing the casting solution before coating it on the substrate.

[0128] In the present application, the casting solution is coated on the substrate after degassing, and the substrate can provide good mechanical properties for the solidification process of the liquid anion membrane.

[0129] According to the present application, the degassing includes static degassing and / or vacuum degassing.

[0130] According to the present application, the light irradiation conditions include: the intensity of light irradiation is 5-200mW / cm 2 , for example, it can be 5mW / cm 2 , 10mW / cm 2 , 15mW / cm 2 , 20mW / cm 2 , 25mW / cm 2 , 30mW / cm 2 , 35mW / cm 2 , 40mW / cm 2 , 45mW / cm 2 , 50mW / cm 2 , 55mW / cm 2 , 60mW / cm 2 , 65mW / cm 2 , 70mW / cm 2 , 75mW / cm 2 , 80mW / cm 2 , 85mW / cm 2 , 90mW / cm 2 , 95mW / cm 2 , 100mW / cm 2 , 110mW / cm 2 , 120mW / cm 2 , 130mW / cm2 140 mW / cm 2 150 mW / cm 2 160 mW / cm 2 170 mW / cm 2 180 mW / cm 2 190 mW / cm 2 200 mW / cm 2 and any range derived from any two of the foregoing values.

[0131] In the present application, the type of light source for irradiation is not particularly limited and can be a light source commonly used in the art, such as 365 nm ultraviolet light.

[0132] According to the present application, the curing time is 1-35 minutes, for example, can be 1 minute, 3 minutes, 5 minutes, 7 minutes, 9 minutes, 11 minutes, 13 minutes, 15 minutes, 17 minutes, 19 minutes, 21 minutes, 23 minutes, 25 minutes, 27 minutes, 29 minutes, 31 minutes, 33 minutes, 35 minutes, and any range derived from any two of the foregoing values.

[0133] In the present application, the curing is carried out under the above-mentioned specific intensity of irradiation and irradiation time, which improves the curing efficiency while ensuring that the anion exchange membrane does not deform due to excessive crosslinking.

[0134] Further, the irradiation conditions include: the intensity of irradiation is 30-100 mW / cm 2 .

[0135] Further, the curing time is 3-15 minutes.

[0136] The third aspect of the present application provides an anion exchange membrane prepared by the above-mentioned preparation method.

[0137] The fourth aspect of the present application provides a use of the above-mentioned anion exchange membrane in a separation process.

[0138] According to the present application, the separation process includes electrolysis of water to produce hydrogen or seawater desalination.

[0139] The fifth aspect of the present application provides an integrated electrode, wherein the integrated electrode comprises an electrosorption electrode and an anion exchange functional layer coated on the surface of the electrosorption electrode.

[0140] The anion exchange functional layer is the anion exchange membrane provided in the first aspect or the third aspect of the present application.

[0141] In the present application, the integrated electrode comprises an electrosorption electrode and an anion exchange functional layer with a specific structure coated on the surface of the electrosorption electrode, the anion exchange functional layer has a homogeneous structure and contains a large number of active ion exchange groups, which can enable the anion exchange function to be closely combined with the electrode, greatly reduce the mass transfer distance and resistance of ions from the solution to the electrode, greatly improve the mass transfer rate, and improve the ion exchange capacity of the electrosorption point solution. In particular, when the integrated electrode is used in an electrosorption ion removal device, the desalination performance of the adsorption ion removal device can be significantly improved, and the energy consumption can be reduced.

[0142] Specifically, in the present application, the anion exchange functional layer has a polyphenyl ether-containing main chain skeleton, and the skeleton contains cationic groups and long carbon chain molecular chains connected with the polyphenyl ether skeleton, so that the anion exchange functional layer has excellent thermal stability, high OH-conductivity, stability and excellent durability. Specifically, the cationic groups contained in the polyphenyl ether skeleton can construct an anion transport channel, thereby enabling the anion exchange functional layer to have a high ion exchange rate, and the polyphenyl ether skeleton enables the anion exchange functional layer to have excellent thermal stability. The long carbon chain molecular chains connected with the polyphenyl ether skeleton in the anion exchange functional layer can form dense ion clusters, further improve the OH-conductivity in the anion exchange functional layer, and ultimately enable the anion exchange functional layer to not only have excellent ion exchange capacity, mechanical properties, water absorption rate and swelling rate, but also have excellent high-temperature resistance and high-alkali resistance, and has a wide application prospect in the field of electrosorption desalination and seawater desalination. -

[0143] The structure of the anion exchange functional layer in the fifth aspect of the present application is the same as that of the anion exchange membrane in the first aspect or the third aspect of the present application.

[0144] In the present application, the anion exchange functional layer comprises a polyphenyl ether molecular chain with a structure shown in formula I and a molecular chain with a structure shown in formula II;

[0145] wherein Q1 or Q2 is independently a halogen atom or a bond connected with the molecular chain with a structure shown in formula II;

[0146] wherein R1 and R2 are independently H or C1-C5 alkyl, R3, R4, R5 and R6 are independently C1-C 10 alkyl, -R9SO3, R9 is C1-C 10 alkylene; R7 and R8 are independently C1-C3 alkylene; x is 20%-50%; * indicates the connection position of formula II and formula I.

[0147] ​The polyphenyl ether molecular chain of structure I and the molecular chain of structure II in the present application are long chain structures, each independently comprising a plurality of structures of formula I or II, and only a fragment of the long molecular chain structure is schematically provided in the present application, and the rest of the structure is represented by In the present application, a plurality of polyphenyl ether molecular chains and a plurality of molecular chains of structure II are present in the anion exchange membrane.

[0148] In the present application, x refers to the halogenation rate of the halogenated polyphenyl ether, for example, when the halogenated polyphenyl ether is brominated polyphenyl ether, x specifically refers to the bromination rate of the brominated polyphenyl ether, reflecting the proportion of H on the methyl group on the benzene ring in the polyphenyl ether molecular chain of formula I being replaced by Q1 or Q2.

[0149] In the present application, the molecular chain of structure II refers to the molecular chain formed after the crosslinking agent is free radical polymerized.

[0150] Specifically, the structure of the anion exchange functional layer of the present application is schematically as follows:

[0151] In the present application, the C1-C5 alkyl group includes a C1-C5 straight chain alkyl group or a C1-C5 branched chain alkyl group. The C1-C3 alkylene group and the C1-C3 alkylene group each independently include a straight chain alkylene group or a branched chain alkylene group. 10 The C1-C3 alkylene group and the C1-C3 alkylene group each independently include a straight chain alkylene group or a branched chain alkylene group.

[0152] In the present application, x is 20%-50%, for example, it can be 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 36%, 38%, 40%, 42%, 44%, 46%, 48%, 50%, and a range consisting of any two values.

[0153] In one specific embodiment of the present application, R1 and R2 are each independently H, CH3 or CH2CH3, R3, R4, R5 and R6 are each independently a C1-C5 straight chain or branched chain alkyl group, -R9SO3; R9 is a C1-C3 alkylene group; R7 and R8 are each independently methylene or ethylene; and x is 30%-40%.

[0154] In the present application, the polyphenyl ether in the anion exchange functional layer is a crosslinked polyphenyl ether.

[0155] According to the present application, the content of the polyphenyl ether molecular chain is 18wt%-95wt% and the content of the molecular chain of structure II is 5wt%-82wt% based on the total weight of the anion exchange functional layer.

[0156] In the present application, when the content of the polyphenyl ether molecular chain and the molecular chain with the structure shown in formula II in the anion exchange functional layer meets the above range, the anion exchange functional layer can contain sufficient quaternary ammonium salt groups, and the efficient ion exchange channel can be effectively constructed, and the anion exchange membrane is endowed with good ion exchange capacity.

[0157] Further, the content of the polyphenyl ether molecular chain is 31wt%-78wt%, and the content of the molecular chain with the structure shown in formula II is 22wt%-69wt%, based on the total weight of the anion exchange functional layer.

[0158] According to the present application, the thickness of the anion exchange functional layer is 100-200μm, for example, it can be 100μm, 110μm, 120μm, 130μm, 140μm, 150μm, 160μm, 170μm, 180μm, 190μm, 200μm, and the range between any two values.

[0159] In the present application, when the thickness of the anion exchange functional layer meets the above range, the water absorption of the ion exchange group can be inhibited, and the ion migration channel can be established, and the ion exchange capacity of the anion exchange functional layer can be further improved.

[0160] Further, the thickness of the anion exchange functional layer is 100-150μm.

[0161] According to the present application, the electric adsorption electrode is selected from at least one of porous foam carbon electrode, activated carbon electrode, graphene electrode and metal modified electrode.

[0162] According to the present application, the adsorption capacity of the electrode to anion is 12-20mg / g, for example, it can be 12mg / g, 13mg / g, 14mg / g, 15mg / g, 16mg / g, 17mg / g, 18mg / g, 19mg / g, 20mg / g, and the range between any two values.

[0163] In the present application, the anion can be a common anion in the art, for example, the anion is chloride ion.

[0164] The sixth aspect of the present application provides a preparation method of an integrated electrode, wherein the preparation method comprises the following steps:

[0165] S1, mixing the photocrosslinking agent shown in formula 1 and / or formula 2, the halogenated polyphenyl ether shown in formula 3 and the organic solvent, and then reacting to obtain a solution containing prepolymer;

[0166] S2, mixing the solution containing prepolymer with a photoinitiator under light shielding conditions to obtain a precursor solution;

[0167] S3, coating the precursor solution on the electrode after vacuum degassing to obtain an electrode with liquid coating;

[0168] S4, curing the electrode with liquid coating under light conditions to obtain the integrated electrode;

[0169] wherein R 10 is H or C1-C5 alkyl, R 11 is C1-C3 alkylene, R 12 and R 13 are each independently C1-C 10 linear or branched alkyl, -R9SO3, R9 is C1-C 10 alkylene; R 14 is C1-C3 alkyl, X is a monovalent anion; X1 and X2 are each independently H or a halogen atom, and at least one of X1 and X2 is a halogen atom; x is 20%-50%.

[0170] In the present application, in the preparation method of the integrated electrode, the anion exchange functional layer is formed on the surface of the electrode by in-situ polymerization, which can significantly enhance the binding ability between the anion exchange functional layer and the electrode, thereby reducing the contact resistance, providing the transmission rate of ions on the electrode surface, and improving the ion exchange capacity of the electrode. In particular, when the integrated electrode is used in the electrode adsorption ion removal device, the desalination performance of the adsorption ion removal device can be significantly improved, and the energy consumption can be reduced.

[0171] Further, the integrated electrode is prepared under light conditions, which is 2-3 orders of magnitude faster than the traditional heat treatment, avoids high energy consumption and complicated reaction process, and improves the preparation efficiency.

[0172] In the present application, x refers to the halogenation rate of the halogenated polyphenyl ether. For example, when the halogenated polyphenyl ether is brominated polyphenyl ether, x specifically refers to the bromination rate of the brominated polyphenyl ether, which reflects the proportion of H on the methyl group on the benzene ring in the halogenated polyphenyl ether represented by formula 3 being replaced by a halogen atom.

[0173] Further, by controlling the halogenation degree (x value) of the halogenated polyphenyl ether, the content of cationic groups in the polyphenyl ether skeleton of the anion exchange membrane can be controlled. In particular, when the halogenation degree meets the above range, the prepared anion exchange functional layer has a suitable crosslinking density, so that the anion exchange functional layer has excellent mechanical properties and ion exchange capacity.

[0174] Further, R 10 is H, CH3 or CH2CH3, R 12 and R 13each independently is a linear or branched C1-C5 alkyl group, R 14 is CH3or CH2CH3, X is a monovalent anion; X1and X2are each independently H or Br, and at least one of X1and X2is Br; x is 30%-40%.

[0175] In one embodiment of the present application, the photo-crosslinking agent is at least one selected from the group consisting of dimethylaminoethyl methacrylate, 2-methacryloyloxyethyl trimethylammonium chloride, [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide, 2-(diethylamino)ethyl methacrylate, and 2-(diisopropylamino)ethyl methacrylate.

[0176] In the present application, when the photo-crosslinking agent is two or more, the amount of each of the two or more photo-crosslinking agents is not particularly limited, as long as the content of the molecular chain having the structure shown in Formula II in the prepared anion exchange membrane satisfies the limitation of the present application.

[0177] In the present application, the type of the organic solvent is not particularly limited, as long as it can sufficiently dissolve the brominated polyphenyl ether, for example, the organic solvent is at least one selected from the group consisting of N-methylpyrrolidone, tetrahydrofuran, and N,N-dimethylformamide.

[0178] In the present application, the amount of the organic solvent is not particularly limited, as long as it can sufficiently mix and disperse each component uniformly, for example, the amount of the organic solvent is 20-40 times the halogenated polyphenyl ether.

[0179] According to the present application, the halogenated polyphenyl ether is a brominated polyphenyl ether.

[0180] According to the present application, the weight average molecular weight M w is 55,000-90,000 g / mol.

[0181] In the present application, the source of the polyphenyl ether is not particularly limited, and it can be commercially available or self-made.

[0182] In one embodiment of the present application, the brominated polyphenyl ether is prepared according to the following steps:

[0183] (1) mixing poly-2,6-dimethyl-1,4-phenylene ether (PPO), a brominating reagent, and an initiator in the presence of a solvent and a protective gas, and then performing a bromination reaction;

[0184] (2) cooling the product obtained in step (1), adding an alcohol solution, and then performing filtration, washing, purification, and drying to obtain the brominated polyphenyl ether.

[0185] In the present application, the molar ratio of the poly(2,6-dimethyl-1,4-phenylene ether) (PPO) to the brominating agent is 1:0.5-3, preferably 1:1-2.

[0186] In the present application, the weight average molecular weight of the poly(2,6-dimethyl-1,4-phenylene ether) is 40000-50000 g / mol.

[0187] In the present application, the molar ratio of the poly(2,6-dimethyl-1,4-phenylene ether) (PPO) to the initiator is 1:0.05-0.08, preferably 1:0.06-0.07.

[0188] In the present application, the brominating agent can be a conventional type of brominating agent in the art, such as N-bromosuccinimide (NBS) and / or 1,3-dibromo-5,5-dimethylhydantoin (DBH).

[0189] In the present application, the initiator can be a conventional type of initiator in the art, such as azobisisobutyronitrile (AIBN) and / or azobisisoheptyl nitrile (ABVN).

[0190] In the present application, the solvent can be a conventional solvent in the art, such as chlorobenzene, and the amount of the organic solvent is not particularly limited as long as the poly(2,6-dimethyl-1,4-phenylene ether) (PPO) can be sufficiently dissolved.

[0191] In the present application, the type of the protective gas is not particularly limited, and a conventional type of protective gas in the art, such as nitrogen, can be used.

[0192] In the present application, the conditions of the bromination reaction include a reaction temperature of 110-140°C and a reaction time of 2-4h.

[0193] In the present application, the type of the alcohol solution is not particularly limited, and a conventional type of alcohol solution in the art, such as a methanol solution, can be used. The amount of the alcohol solution is also not particularly limited as long as the brominated polyphenyl ether can be completely precipitated. In order to further ensure that the brominated polyphenyl ether can be completely precipitated, preferably, the alcohol solution is added in a dropwise manner, more preferably, at a speed of 20-50 mL / min to the product obtained in step S1.

[0194] In the present application, the filtered product is washed with methanol.

[0195] In the present application, the step of purification includes redissolving the washed product in a first organic solvent and washing with a second organic solvent.

[0196] In the present application, the first organic solvent is selected from at least one of chloroform, dichloromethane and tetrahydrofuran. In the present application, the amount of the first organic solvent is 1000-2000 mL with respect to 100 g of the washed product.

[0197] In the present application, the second organic solvent is selected from acetone and / or butanone.

[0198] In the present application, the amount of the second organic solvent is 1000-2000 mL with respect to 100 g of the washed product.

[0199] In one embodiment of the present application, the halogenated polyphenyl ether represented by Formula 3 is mixed with an organic solvent to obtain a mixed solution, and the photocrosslinking agent represented by Formula 1 and / or Formula 2 is added to the mixed solution to obtain a solution containing a prepolymer.

[0200] In the present application, the halogenated polyphenyl ether is mixed with an organic solvent in advance, which can ensure that the halogenated polyphenyl ether is fully dissolved and dispersed in the organic solvent, improve the dispersibility of the halogenated polyphenyl ether in the mixed solution, and further enable the photocrosslinking agent to fully contact and react with the halogenated polyphenyl ether.

[0201] In the present application, in order to control the dispersibility of the halogenated polyphenyl ether, preferably, the concentration of the halogenated polyphenyl ether in the mixed solution is 5wt%-20wt%, more preferably 5wt%-10wt%.

[0202] According to the present application, the molar ratio of the halomethyl group in the halogenated polyphenyl ether to the photocrosslinking agent is 1:0.2-65.

[0203] In the present application, when the molar ratio of the halomethyl group in the halogenated polyphenyl ether to the photocrosslinking agent meets the above range, the photocrosslinking agent can provide sufficient quaternary ammonium groups to construct efficient ion exchange channels, and the anion exchange membrane is endowed with good ion exchange capacity.

[0204] Further, the molar ratio of the halomethyl group in the halogenated polyphenyl ether to the photocrosslinking agent is 1:1-25.

[0205] According to the present application, the reaction conditions include a reaction temperature of 15-30℃ and a reaction time of 12-48h.

[0206] In the present application, the reaction is carried out under the above specific conditions, which can enable the halogenated polyphenyl ether and the photocrosslinking agent to fully and efficiently undergo halogen substitution reaction, form a stable and uniform casting solution, and avoid the generation of insoluble particles in the casting solution due to excessive crosslinking.

[0207] Further, the reaction conditions include a reaction temperature of 15-25℃ and a reaction time of 12-24h.

[0208] According to the present application, the photoinitiator is selected from at least one of radical photoinitiators and / or cationic photoinitiators, preferably selected from 2-hydroxy-2-methylpropiophenone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide.

[0209] According to the present application, the amount of the photoinitiator is 3wt%-10wt% based on the total mass of the photocrosslinking agent and the halogenated polyphenyl ether.

[0210] In the present application, when the amount of the photoinitiator is controlled to meet the above range, the photoinitiator can quickly initiate the chain reaction of free radicals on the photocrosslinking agent to achieve rapid crosslinking, and a uniform and defect-free anion exchange membrane is obtained.

[0211] Further, the amount of the photoinitiator is 3wt%-7wt% based on the total mass of the photocrosslinking agent and the halogenated polyphenyl ether.

[0212] According to the present application, in step S2, the vacuum defoaming conditions include that the relative vacuum degree is-80kPa to-90kPa, preferably-82kPa to-88kPa.

[0213] In the present application, the vacuum defoaming method includes static defoaming and / or vacuum defoaming.

[0214] According to the present application, the thickness of the liquid coating is 100-200μm, preferably 100-150μm.

[0215] According to the present application, the light irradiation conditions include that the intensity of the light irradiation is 5-200mW / cm 2 .

[0216] In the present application, the type of light source for light irradiation is not particularly limited, and can be a common light source in the art, for example, 365nm ultraviolet light.

[0217] According to the present application, the curing time is 1-35 minutes.

[0218] In the present application, curing is carried out under the above-mentioned specific intensity of light irradiation and light irradiation time, which can achieve complete curing of the liquid coating while the anion exchange functional layer does not deform.

[0219] Further, the light irradiation conditions include that the intensity of the light irradiation is 30-100mW / cm 2 .

[0220] Further, the curing time is 3-15 minutes.

[0221] According to the present application, the preparation method further comprises: washing the product after solidification.

[0222] In the present application, the product after solidification is washed by deionized water, preferably, the product after solidification is soaked in deionized water for washing.

[0223] The seventh aspect of the present application provides an integrated electrode prepared by the above preparation method.

[0224] The eighth aspect of the present application provides an electrosorption deionization device, wherein the electrosorption deionization device comprises the integrated electrode.

[0225] In the present application, the integrated electrode is included in the electrosorption deionization device, which can significantly improve the desalination performance of the electrosorption deionization device and significantly reduce the energy consumption.

[0226] In the present application, the desalination rate of the electrosorption deionization device of the integrated electrode of the present application can reach 43-76%, the adsorption rate of the opposite electrode during desorption is less than or equal to 11%, preferably 2-7%, and the adsorption time can be shortened to 85% of the original, which greatly improves the desalination performance of the electrosorption deionization device.

[0227] The present application will be described in detail through examples below. In the following examples,

[0228] (1) Ion exchange capacity test method

[0229] The ion exchange capacity of anion exchange membrane is determined by back titration method, and the test temperature is 25°C. The mass of the completely dried membrane to be tested is accurately weighed, and is recorded as W dry . Then the membrane is soaked in 1M NaOH solution with continuous stirring for 24h, mainly to convert Cl - in the membrane to OH - . After taking out the membrane, deionized water is used to clean the surface to ensure that sodium hydroxide is completely removed. Then the membrane is placed in 0.5mol / L HCl solution for 24h. Phenolphthalein is used as an acid-base indicator, and 0.25M NaOH solution is used to titrate the above solution. Each piece of membrane is measured three times, and the average value is taken as the final ion exchange capacity (IEC 0 ). The calculation formula of IEC 0 is as follows:

[0230] Wherein, C H , C OH respectively represent the concentration of hydrochloric acid and sodium hydroxide (mol / L); V H , V OH respectively represent the volume of consumed hydrochloric acid (mL) and the volume of consumed NaOH during titration (mL); Wdry The film quality (g) is represented.

[0231] (2) Alkali stability test method

[0232] The same film is then immersed in an alkaline solution with pH = 12 for 24 hours at a temperature of 25°C, and the film is taken out and the above steps are repeated to determine the ion exchange capacity thereof. The determination is repeated three times for each film, and the average value is taken as the final IEC', and the IEC reduction rate is calculated as follows:

[0233] wherein IEC' is the ion exchange capacity of the film after being immersed in an alkaline solution with pH = 12 for 24 hours at a temperature of 25°C; IEC is the ion exchange capacity of the film before being immersed, at a temperature of 25°C. 0

[0234] (3) Test method for water absorption

[0235] The film to be tested is cut into a regular 1 cm x 2 cm long strip, immersed in deionized water at 25°C for 24 hours, and the water on the surface of the film is wiped off in a wet state, and the mass of the wet film is accurately weighed by an electronic balance, recorded as m1. The film is completely dried using a vacuum oven, and the mass is weighed and recorded as m0. Each film is repeated three times to reduce errors. The calculation formula is as follows:

[0236] wherein m0 and m1 represent the mass of the dry film and the wet film (g), respectively.

[0237] (4) Test method for swelling rate

[0238] At 25°C, the film sample to be tested is cut into a regular 1 cm x 2 cm long strip, and the length of the dry film sample is measured, recorded as l0. The film sample is immersed in deionized water for 24 hours, and the surface water is wiped off, and the length of the film sample is measured, recorded as l1. Each film is repeated three times to reduce errors. The swelling rate (SR) calculation formula is as follows:

[0239] wherein l0 and l1 represent the length of the dry film and the wet film (cm), respectively.

[0240] (5) Mechanical properties - tensile strength, elongation at break: the mechanical properties of the film are tested by an Instron universal testing machine. The test method is to cut the film into a 30 x 10 mm sample in a wet state, and perform a tensile test in a room temperature environment, with the clamps of the universal testing machine clamping the two ends of the film, the tensile rate being 40 mm / min, the clamp spacing being 20 mm, and the force and elongation of the film at break being recorded by the computer.

[0241] (6) Test method for bromination rate ​

[0242] The structure of Preparation Example 1-3 was tested by a German Bruker AVANCE III HD 400MHz nuclear magnetic resonance spectrometer, deuterated chloroform was used as the test solvent, and the bromination rate of Preparation Example 1-3 in different proportions was obtained by calculating the proportion of the integral area of the characteristic peak. The bromination rate (DBM) of Preparation Example 1-3 was calculated by the following formula:

[0243] Wherein, k represents the number of methyl groups in the polyphenyl ether repeating unit; H a ,H a Respectively represent the proton peak integral area of the methyl group and the bromomethyl group on the brominated polyphenyl ether.

[0244] (7) The thickness of the prepared anion exchange membrane and the thickness of the anion functional exchange layer in the integrated electrode were measured by a film thickness measuring instrument.

[0245] (8) The content of the polyphenyl ether molecular chain and the molecular chain of the structure of Formula II in the prepared anion exchange membrane was calculated by the amount of feed:

[0246] (9) Crosslinking density test

[0247] After the prepared anion exchange membrane was vacuum dried at 60°C for 48h, a Newman VTMR20-010V-I nuclear magnetic resonance crosslinking density spectrometer was used. When the membrane sample was placed in the radio frequency coil, the nuclear magnetic resonance method would measure the decay curve of the sample, the software automatically substituted the XLD model according to the curve, and the anisotropy rate q was obtained, and finally the crosslinking density of the sample was calculated: M(t) = A0 + A1exp(-t / t1-qM1t 2 / 2) + A2exp(-t / t1)

[0248] In the formula, M(t) is the transverse relaxation value at test time t, A0 is a fitting parameter (without actual physical meaning), parameters A1 and A2 respectively represent the content of the crosslinked chain part signal and the content of the pendant chain part signal in the total signal (%), t1 is the transverse relaxation time (s), q is the ratio factor between the second moment above the glass transition temperature and the second moment of the rigid lattice, and M1 is the second moment of the rigid lattice (m / s 2 ).

[0249] The fitting of the test results by the above formula can obtain q, and then the relative molecular mass (M c , g / mol) between the crosslinking points is obtained according to the following formula, so as to obtain the crosslinking density (V NMR , mol / cm 3 ):

[0250] In the formula, C is the number of main chain bonds in the repeating unit, Mr is the molar mass (g / mol) within the repeating unit, and n is the number of main chain bonds in the monomer unit. NMR =Aρ / M c

[0251] Where A1 is the content of cross-linked chain signal in the total signal; ρ is the density of the membrane sample (g / cm 3 ).

[0252] (10) Zeta potential test

[0253] The surface charge of the membrane was tested and analyzed using a Zeta potential analyzer (SurPass3, Anton Paar (Shanghai) Trading Co., Ltd.).

[0254] (11) The weight-average molecular weight of brominated polyphenylene ether was measured by gel permeation chromatography using a Waters 1515 with toluene as the eluent.

[0255] (12) Impedance and current density test

[0256] The voltage and current of the electrolytic cell were controlled by a CHI600E electrochemical workstation. 1 mol / L KOH solution was used as the electrolyte and the test frequency was set to 0.1-10 6 Hz, and the impedance of the membrane was measured by electrochemical impedance spectroscopy. The voltage and current of the electrolytic cell were controlled by an electrochemical workstation. The cathode material was Pt / C and the anode material was IrO2. When conducting polarization curve tests (testing the relationship between current density and voltage), the voltage was set to 2.1V and the scan rate was 0.01V / s. Before each curve recording, the electrolytic cell was reacted according to the set conditions for a period of time, and the reaction was allowed to stabilize. The performance of the homemade anion exchange membrane was compared with that of the commercial anion exchange membrane. The model of the commercial anion exchange membrane used was Sustainion TM Alkaline anion exchange membrane.

[0257] (13) Electrodialysis desalination test

[0258] The electrodialysis desalination performance of anion exchange membranes was tested using an electrodialysis unit (EX-3BT). One liter of 0.3 mol / L sodium sulfate solution was placed in the polarization chamber of the electrodialysis unit, and one liter of 0.2 mol / L sodium chloride solution was placed in the concentration and desalination chambers. The voltage was set to a constant 12V.

[0259] The salt rejection rate R1 of the membrane is calculated as follows:

[0260] Wherein, c0 represents the conductivity of the desalination chamber at the beginning of the experiment (mS / cm), and c1 represents the conductivity of the desalination chamber at the end of the experiment (mS / cm).

[0261] (14) OH - Conductivity test

[0262] The sample was immersed in 1 mol / L KOH solution for 48 h. The immersed sample was washed with ultrapure water to neutral, and the film thickness and film length were measured. The film was installed in a clamp, and the ion conductivity of the film at 80°C was tested by electrochemical impedance spectroscopy (EIS). The test frequency range was set to 10 6 Hz-1 Hz. OH - The conductivity was calculated as follows:

[0263] Wherein, σ is the conductivity, S / cm; a is the distance between the two electrodes, cm, R is the sample impedance, Ω; b is the effective length of the film perpendicular to the electrode, cm; d is the film thickness, cm.

[0264] (15) The chloride ion adsorption capacity of the integrated electrode and the desalination rate of the electro-adsorption device were tested by the method described in the test example.

[0265] (16) Test of the nuclear magnetic resonance carbon spectrum of the film

[0266] The film sample was dried at 60°C for 24 h, ground into uniform particles, and about 10 mg of the test substance was taken for testing. The Bruker-400MHz nuclear magnetic resonance spectrometer was used to analyze the chemical composition structure of the film sample.

[0267] (17) The surface groups of the film were measured by Japan-Shimadzu-IR Tracer 100 type FT-IR.

[0268] (18) The surface and cross-section structure of the film was measured by Hitachi SU1510 scanning electron microscope.

[0269] The following specific examples are used to specifically illustrate the present application. The experimental methods described below, unless otherwise specified, are all laboratory routine methods. The experimental materials described below, unless otherwise specified, can be obtained from commercial channels. All raw materials in the examples and comparative examples are commercially available from the MacLean Company, wherein the poly2,6-dimethyl-1,4-phenylene ether M w is 45000 g / mol.

[0270] The following preparation examples are used to illustrate the preparation of brominated polyphenyl ether

[0271] Preparation Example 1

[0272] Preparation Example 1 9 g of poly 2,6-dimethyl-1,4-phenylene oxide (PPO) was dissolved in 100 mL of chlorobenzene, 9.34 g of N-bromosuccinimide (NBS) and 0.57 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred for 3 h under an oil bath at 135°C while maintaining a nitrogen atmosphere. After the reaction was cooled, it was added dropwise to 1000 mL of methanol to obtain a crude polymer. The polymer was filtered and washed with methanol several times. Subsequently, the obtained crude product was dissolved in 50 mL of chloroform and washed with 200 mL of acetone to obtain a light yellow powder by filtration. Vacuum drying was performed to obtain BPPO-1.

[0273] The bromination rate x of the brominated polyphenylene ether was 35%, M w was 77751 g / mol. The hydrogen nuclear magnetic resonance spectrum analysis of BPPO-1 was performed, and the results are shown in FIG. A1.

[0274] Preparation Example 2

[0275] 12 g of poly 2,6-dimethyl-1,4-phenylene oxide (PPO) was dissolved in 120 mL of chlorobenzene, 7.12 g of N-bromosuccinimide (NBS) and 0.44 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred for 3 h under an oil bath at 135°C while maintaining a nitrogen atmosphere. After the reaction was cooled, it was added dropwise to 1000 mL of methanol to obtain a crude polymer. The polymer was filtered and washed with methanol several times. Subsequently, the obtained crude product was dissolved in 50 mL of chloroform and washed with 200 mL of acetone to obtain a light yellow powder by filtration. Vacuum drying was performed to obtain BPPO-2.

[0276] The bromination rate x of the brominated polyphenylene ether was 20%, M w was 58741 g / mol. The hydrogen nuclear magnetic resonance spectrum analysis of BPPO-2 was performed, and the results are shown in FIG. A1.

[0277] Preparation Example 3

[0278] 12 g of poly 2,6-dimethyl-1,4-phenylene oxide (PPO) was dissolved in 120 mL of chlorobenzene, 16.02 g of N-bromosuccinimide (NBS) and 0.975 g of azobisisobutyronitrile (AIBN) were added, and the reaction was stirred for 3 h under an oil bath at 135°C while maintaining a nitrogen atmosphere. After the reaction was cooled, it was added dropwise to 1000 mL of methanol to obtain a crude polymer. The polymer was filtered and washed with methanol several times. Subsequently, the obtained crude product was dissolved in 50 mL of chloroform and washed with 200 mL of acetone to obtain a light yellow powder by filtration. Vacuum drying was performed to obtain BPPO-3.

[0279] The bromination rate x of the brominated polyphenylene ether was 50%, M w was 87652 g / mol.

[0280] The results of the nuclear magnetic resonance hydrogen spectrum analysis of BPPO-1 to BPPO-3 are shown in Figure A1. The proton peak of the methyl group on BPPO is δ2.1 ppm, and the proton peak of the methylene group on BPPO after being substituted by bromine is δ4.3 ppm. According to the integral area of the proton peaks corresponding to the methyl group and the methylene group on BPPO in the nuclear magnetic resonance hydrogen spectrum, the bromomethylation degrees of the brominated polyphenylene ether prepared in Preparation Example 1-3 are calculated to be 35%, 20%, and 50%, respectively. The higher the bromination rate of the brominated polyphenylene ether is, the more active groups (CH2Br) on the main chain of the polyphenylene ether that can react with the side chain are. 1 The H NMR results show that bromine is successfully grafted onto the poly 2,6-dimethyl-1,4-phenylene ether, and the calculated bromination rate results show that the synthesized BPPO has sufficient active sites for subsequent quaternization reactions.

[0281] Example A1

[0282] (1) The brominated polyphenylene ether BPPO-1 (1 g) was dissolved in N-methyl pyrrolidone to form a 10 wt% solution. Dimethylaminoethyl methacrylate was added, and the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to crosslinking agent was 1:2.4. After a period of reaction, the solution was stirred at 25°C in the dark for 24 h to obtain a solution containing a prepolymer.

[0283] (2) 5 wt% of the photoinitiator 2-hydroxy-2-methylpropiophenone was added to the solution containing the prepolymer, and the solution was stirred at 25°C in the dark for 10 min to obtain a casting solution.

[0284] (3) The casting solution was degassed and then poured onto a glass plate, and a doctor blade was used to obtain a liquid film layer. The liquid film layer was transferred to an ultraviolet lamp for irradiation, and the intensity of the light used for irradiation was 95 mW / cm 2 , and the curing time was 15 min. After peeling off from the glass plate, anion exchange membrane A1 was obtained.

[0285] Example A2

[0286] (1) The brominated polyphenylene ether BPPO-1 (1 g) was dissolved in N-methyl pyrrolidone to form a 10 wt% solution. Dimethylaminoethyl methacrylate was added, and the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to crosslinking agent was 1:4.8. After a period of reaction, the solution was stirred at 25°C in the dark for 24 h to obtain a solution containing a prepolymer.

[0287] (2) 5 wt% of the photoinitiator 2-hydroxy-2-methylpropiophenone was added to the solution containing the prepolymer, and the solution was stirred at 25°C in the dark for 10 min to obtain a casting solution.

[0288] (3) The casting solution was poured onto a glass plate after being degassed, a liquid film layer was obtained by using a doctor blade to scrape the film, and the liquid film layer was transferred to an ultraviolet lamp for irradiation. The intensity of the light used for irradiation was 95 mW / cm 2 , and the curing time was 15 minutes. After being peeled off from the glass plate, an anion exchange membrane A2 was obtained.

[0289] Example A3

[0290] (1) Brominated polyphenyl ether BPPO-1 (1 g) was dissolved in N-methyl pyrrolidone to form a 10 wt% solution. Dimethylaminoethyl methacrylate was added, wherein the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to crosslinking agent was 1:9.5. After a period of reaction, the solution containing the prepolymer was stirred in the dark at 25°C for 24 h to obtain a solution containing the prepolymer;

[0291] (2) 5 wt% of a photoinitiator 2-hydroxy-2-methylpropiophenone was added to the solution containing the prepolymer, and the solution was stirred in the dark for a period of time. The solution was stirred in the dark at 25°C for 10 min to obtain a casting solution.

[0292] (3) The casting solution was poured onto a glass plate after being degassed, a liquid film layer was obtained by using a doctor blade to scrape the film, and the liquid film layer was transferred to an ultraviolet lamp for irradiation. The intensity of the light used for irradiation was 95 mW / cm 2 , and the curing time was 15 minutes. After being peeled off from the glass plate, an anion exchange membrane A3 was obtained.

[0293] Figure A2 shows the infrared spectra of the raw material PPO, BPPO-1 of Preparation Example 1, and the anion exchange membrane of Example A3, respectively. The absorption peaks at 1605 cm -1 and 1470 cm -1 are consistent with the stretching vibration peaks of C=C bonds on the benzene ring skeleton. The absorption peak at 1429 cm -1 is attributed to the asymmetric bending vibration of the methyl group. The corresponding symmetric bending vibration absorption peak of the methyl group is at 1379 cm -1 . The absorption peak at 1306 cm -1 is attributed to the out-of-plane bending vibration of the methyl group. The corresponding absorption peak at 1188 cm -1 represents the asymmetric stretching vibration of C-O-C on the PPO skeleton. The corresponding symmetric stretching vibration absorption peak is in the form of a doublet at 1020 cm -1 and 958 cm -1 . In the infrared spectrum of Preparation Example 1, an absorption peak at 986 cm -1 can be clearly observed. This is because CH2Br containing a strong electron-withdrawing group is grafted in PPO, resulting in the symmetric vibration stretching peak of C-O-C at 986 cm-1 The IR spectrum of Example A3 shows three different peaks at 1670 cm -1 -1, which is a characteristic peak of the photocrosslinking agent. In addition, the IR spectrum of Example A3 shows an absorption peak of O-H in the bound water at 3420 cm -1 -1. The above results all prove the successful preparation of the photocrosslinking anion exchange membrane.

[0294] Example A4

[0295] (1) Brominated polyphenyl ether BPPO-1 (1 g) was dissolved in N-methyl pyrrolidone to form a 10 wt% solution. Dimethylaminoethyl methacrylate was added, and the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to crosslinking agent was 1:14.3. After a period of reaction, the solution was stirred in the dark at 25°C for 24 h to obtain a solution containing a prepolymer.

[0296] (2) 5 wt% of the photoinitiator 2-hydroxy-2-methylpropiophenone was added to the solution containing the prepolymer, and the solution was stirred in the dark for a period of time and then stirred in the dark at 25°C for 10 min to obtain a casting solution.

[0297] (3) The casting solution was degassed and then poured onto a glass plate, and a doctor blade was used to obtain a liquid film layer. The liquid film layer was transferred to an ultraviolet lamp for irradiation, and the intensity of the light used for irradiation was 95 mW / cm 2 -1, and the curing time was 15 min. After peeling from the glass plate, an anion exchange membrane A4 was obtained.

[0298] Example A5

[0299] (1) Brominated polyphenyl ether BPPO-1 (1 g) was dissolved in N-methyl pyrrolidone to form a 10 wt% solution. Dimethylaminoethyl methacrylate was added, and the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to crosslinking agent was 1:19.1. After a period of reaction, the solution was stirred in the dark at 25°C for 24 h to obtain a solution containing a prepolymer.

[0300] (2) 5 wt% of the photoinitiator 2-hydroxy-2-methylpropiophenone was added to the solution containing the prepolymer, and the solution was stirred in the dark for a period of time and then stirred in the dark at 25°C for 10 min to obtain a casting solution.

[0301] (3) The casting solution was degassed and then poured onto a glass plate, and a doctor blade was used to obtain a liquid film layer. The liquid film layer was transferred to an ultraviolet lamp for irradiation, and the intensity of the light used for irradiation was 95 mW / cm 2 -1, and the curing time was 15 min. After peeling from the glass plate, an anion exchange membrane A5 was obtained.

[0302] Example A6

[0303] An anion exchange membrane was prepared according to the method of Example A3, except that brominated polyphenylene oxide BPPO-2 was used instead of brominated polyphenylene oxide BPPO-1, and the amount of dimethylaminoethyl methacrylate was adjusted so that the molar ratio of bromomethyl groups in BPPO to crosslinking agent was 1 :9.5. An anion exchange membrane A6 was prepared.

[0304] Example A7

[0305] An anion exchange membrane was prepared according to the method of Example A3, except that brominated polyphenylene oxide BPPO-3 was used instead of brominated polyphenylene oxide BPPO-1, and the amount of dimethylaminoethyl methacrylate was adjusted so that the molar ratio of bromomethyl groups in BPPO to crosslinking agent was 1 :9.5. An anion exchange membrane A7 was prepared.

[0306] Example A8

[0307] An anion exchange membrane was prepared according to the method of Example A3, except that 2-methacryloyloxyethyl trimethylammonium chloride was used instead of dimethylaminoethyl methacrylate, and the amount of 2-methacryloyloxyethyl trimethylammonium chloride was adjusted so that the molar ratio of BPPO to crosslinking agent was 1 :9.5. An anion exchange membrane A8 was prepared.

[0308] Example A9

[0309] An anion exchange membrane was prepared according to the method of Example A3, except that [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide was used instead of dimethylaminoethyl methacrylate, and the amount of [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide was adjusted so that the molar ratio of bromomethyl groups in BPPO to crosslinking agent was 1 :9.5. An anion exchange membrane A9 was prepared.

[0310] Example A10

[0311] An anion exchange membrane was prepared according to the method of Example A3, except that the intensity of the light was 180 mW / cm 2 . An anion exchange membrane A10 was prepared.

[0312] Example A11

[0313] An anion exchange membrane was prepared according to the method of Example A3, except that the time for curing was 1.5 minutes. An anion exchange membrane A11 was prepared.

[0314] Example A12

[0315] An anion exchange membrane was prepared according to the method of Example A3, except that the amount of dimethylaminoethyl methacrylate was changed so that the molar ratio of bromomethyl groups in the BPPO to crosslinking agent was 1 :0.4. An anion exchange membrane A12 was produced.

[0316] Example A13

[0317] An anion exchange membrane was prepared according to the method of Example A3, except that the amount of dimethylaminoethyl methacrylate was changed so that the molar ratio of bromomethyl groups in the BPPO to crosslinking agent was 1 :39. An anion exchange membrane A13 was produced.

[0318] Example A14

[0319] An anion exchange membrane was prepared according to the method of Example A3, except that dimethylaminoethyl methacrylate and 2-methacryloyloxyethyl trimethylammonium chloride were added in a mixed reaction, and the total amount of dimethylaminoethyl methacrylate and 2-methacryloyloxyethyl trimethylammonium chloride was such that the molar ratio of bromomethyl groups in the BPPO to crosslinking agent was 1 :9.5. An anion exchange membrane A14 was produced. In the molecular chain of the structure shown in Formula II, the content of the structural unit from dimethylaminoethyl methacrylate was 49.8 mol%, and the content of the structural unit from 2-methacryloyloxyethyl trimethylammonium chloride was 50.2 mol%.

[0320] Example A15

[0321] An anion exchange membrane was prepared according to the method of Example A3, except that dimethylaminoethyl methacrylate, 2-methacryloyloxyethyl trimethylammonium chloride, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide were added in a mixed reaction, and the amount of dimethylaminoethyl methacrylate, 2-methacryloyloxyethyl trimethylammonium chloride, and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide was such that the molar ratio of bromomethyl groups in the BPPO to crosslinking agent was 1 :9.5. An anion exchange membrane A15 was produced. In the molecular chain of the structure shown in Formula II, the content of the structural unit from dimethylaminoethyl methacrylate was 33.1 mol%, the content of the structural unit from 2-methacryloyloxyethyl trimethylammonium chloride was 33.4 mol%, and the content of the structural unit from [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide was 33.5 mol%.

[0322] Example A16

[0323] An anion exchange membrane was prepared according to the method of Example A3, except that the amount of dimethylaminoethyl methacrylate was changed so that the molar ratio of bromomethyl groups in BPPO to crosslinking agent was 1 :0.1. An anion exchange membrane A16 was prepared.

[0324] Example A17

[0325] An anion exchange membrane was prepared according to the method of Example A3, except that the amount of dimethylaminoethyl methacrylate was changed so that the molar ratio of BPPO to crosslinking agent was 1 :78. An anion exchange membrane A17 was prepared.

[0326] Comparative Example DA1

[0327] Brominated polyphenylene oxide BPPO-1 (1 g) was dissolved in N-methylpyrrolidone to form a 10 wt% solution. 0.029 g of N,N,N,N-tetramethylethylenediamine was added, and the solution was stirred at room temperature for 48 h. The resulting reaction product was precipitated in petroleum ether, filtered and washed several times to obtain a crosslinked polymer. The polymer was dissolved in N-methylpyrrolidone to form a 20 wt% casting solution.

[0328] The casting solution was degassed and poured onto a glass plate, and a doctor blade was used to obtain a liquid membrane layer.

[0329] The liquid membrane layer was transferred to an oven at 80°C for 12 h to obtain an anion exchange membrane DA1 with a solid surface.

[0330] Comparative Example DA2

[0331] (1) Brominated polyphenylene oxide BPPO-1 (1 g) was dissolved in N-methylpyrrolidone to form a 10 wt% solution. Dimethylaminoethyl methacrylate was added, and the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to crosslinking agent was 1 :9.5. After a period of reaction, the solution was stirred at 25°C in the dark for 24 h to obtain a casting solution.

[0332] (2) The casting solution was degassed and poured onto a glass plate, and a doctor blade was used to obtain a liquid membrane layer. The liquid membrane layer was transferred to an oven at 80°C for 24 h to obtain an anion exchange membrane DA2 with a solid surface. Figure A3 shows the nuclear magnetic resonance 13 spectra of the anion exchange membranes of Comparative Example DA2 and Example A3. The nuclear magnetic resonance spectra of Example A3 and Comparative Example DA2 were similar because the main chain skeletons of the two were the same. Because the side chain of Comparative Example DA2 had an un-crosslinked carbon-carbon double bond, the conjugation effect of the benzene ring in the main chain caused the peak to move to a high field, i.e., a sp 2 hybrid peak of the carbon-carbon double bond appeared at δ 177 ppm. In Example A3, no sp 2The hybrid peak indicates that under the action of the photoinitiator, the ultraviolet light can open the carbon-carbon double bond and further crosslink in a short time, i.e. the conversion rate of the carbon-carbon double bond is higher. Figure A3 shows that the film forming method of thermal curing or photocuring does not affect the main chain structure (Formula I) of the anion exchange membrane BPPO, and only affects the side chain structure of the anion exchange membrane, i.e. the anion exchange membrane prepared by the thermal curing method does not contain the structure described in Formula II.

[0333] The structure and performance of the anion exchange membranes prepared in the examples and comparative examples were tested, and the results are shown in Table 1.

[0334] Table 1

[0335] Note that the content of the molecular chain formed after polymerization of N,N,N,N-tetramethyl ethylenediamine; ** the side chain of comparative example DA2 does not contain the structure of Formula II.

[0336] Table 1 continued

[0337] Table 1 continued

[0338] As can be seen from the above table, compared with the thermal cured anion exchange membranes DA1, DA2 and the commercial anion exchange membrane, the anion exchange membranes A1-A17 provided by the present application have relatively high ion exchange capacity, water absorption, swelling rate, mechanical property, alkali resistance, OH -Conductivity, current density, desalination rate, and lower impedance and ion exchange capacity reduction. Because the molecules are in the ground state in thermal chemical reactions and in the excited state in photochemical reactions, the energy of the photochemical reaction molecules is much higher than that of the thermal chemical reaction, so the photo-curing method can quickly excite the carbon-carbon double bonds in the casting solution to achieve free radical type crosslinking, and a solid film layer is obtained. In the case where the molar ratio of bromomethyl to crosslinking agent in BPPO is the same, the conversion rate of carbon-carbon double bonds in the casting solution can be greatly improved by the photo-curing method, so that the crosslinking density of the ion exchange membranes A1-A17 prepared by the present application is higher than that of the ion exchange membranes DA1 and DA2 prepared by thermal curing. When the molar ratio of halomethyl to the crosslinking agent in the halogenated polyphenyl ether is within the preferred range, the film structure prepared by the photo-curing method is more compact and the long carbon chain molecules connected to the polyphenyl ether skeleton can form dense ion clusters, giving the ion exchange membranes A1-A5 better mechanical properties and ion selectivity. When the molar ratio of bromomethyl to crosslinking agent in BPPO is 1:9.5, the crosslinking density of the photo-cured anion exchange membrane is A3>A7>A6, indicating that the brominated polyphenyl ether (BPPO-1) with a bromination degree of 57% is selected, which can provide an appropriate number of active groups (CH2Br) on the main chain skeleton for grafting with the crosslinking agent, and has sufficient active sites for subsequent quaternization reaction, so that the ion exchange membrane A3 has a more compact film structure and further forms dense cation clusters, ultimately giving it good ion selectivity, suitable swelling degree, higher mechanical strength and OH - Conductivity and current density, lower impedance and higher desalination rate. Moreover, in terms of curing time, the photo-cured anion exchange membrane is significantly shorter than the thermal-cured anion exchange membrane in film preparation time, and reduces energy consumption.

[0339] Figure A4 is the FTIR spectrum of the anion exchange membrane prepared in Example A3 before and after soaking in alkali. After soaking Example A3 in an alkali solution with pH=12 and temperature of 80℃ for 100 hours, the infrared spectrum of the membrane did not change significantly.

[0340] Figure A5 is the SEM image of the anion exchange membrane prepared in Example A3 before and after soaking in alkali. Among them, Figure (a) and Figure (b) are respectively the surface SEM image and the cross-sectional SEM image of the anion exchange membrane before soaking in alkali, Figure (c) and Figure (d) are respectively the surface SEM image and the cross-sectional SEM image of the anion exchange membrane after soaking in alkali. After soaking Example A3 in an alkali solution with pH=12 and temperature of 80℃ for 100 hours, the morphology of the membrane did not change significantly. As can be seen from Figures A4 and A5, Example A3 has good alkali resistance at 80℃.

[0341] Table 2

[0342] Note: refers to the assumption that BPPO-1 is fully involved in the reaction, the weight of the ion exchange membrane obtained in Example 1-5 step (3) is W m (g), wherein, W BPPO-1 refers to the mass (g) of brominated polyphenyl ether.

[0343] As can be seen from Table 2, the weight gain of the membranes of Examples A1-A5 increases with the increase of the crosslinking agent content, while the weight gain of the membrane of Comparative Example DA2 is not obvious. From the macroscopic point of view, it is proved that the photo-curing method can quickly excite the carbon-carbon double bonds in the casting solution to realize free radical type crosslinking in a short time, and the conversion rate of carbon-carbon double bonds in the casting solution can be greatly improved by the photo-curing method, so that the crosslinking density of the ion exchange membrane A1-A5 prepared by photo-curing is higher than that of the ion exchange membrane DA2 prepared by thermal curing.

[0344] Example B1

[0345] S1: 1g of BPPO-1 is dissolved in 9g of N-methylpyrrolidone, dimethylaminoethyl methacrylate is added, and the amount of dimethylaminoethyl methacrylate is such that the molar ratio of bromomethyl in BPPO to photo-crosslinking agent is 1:9.5, and the solution containing the prepolymer is obtained by stirring at 25°C for 12 hours;

[0346] S2, 5wt% of 2-hydroxy-2-methylpropiophenone is added to the solution containing the prepolymer, and the solution is stirred at 25°C for 10 minutes in the dark to obtain a precursor solution.

[0347] S3, the precursor solution is vacuum degassed, the vacuum degree is-80kPa; the degassed precursor solution is scraped onto the activated carbon electrode, and the scraper thickness is set to 150μm to obtain an electrode with a liquid coating.

[0348] S4, the electrode with a liquid coating is placed under a UV lamp for irradiation, the irradiation intensity of the UV lamp is 95mW / cm 2 , and the irradiation time is 15 minutes.

[0349] S5, the cured electrode is immersed in deionized water for cleaning to obtain an integrated electrode B1.

[0350] Example B2

[0351] The integrated electrode is prepared according to the method of Example B1, except that:

[0352] Step S4: the intensity of light is 180mW / cm 2 .

[0353] An integrated electrode B2 is prepared.

[0354] Example B3

[0355] An integrated electrode was prepared according to the method of Example B1, except that:

[0356] Step S4: The time for irradiation curing was 1.5 minutes.

[0357] An integrated electrode B3 was prepared.

[0358] Comparative Example DB1

[0359] Step 1 : Preparation of precursor solution. 1 g of BPPO-1 was dissolved in 9 g of N-methyl pyrrolidone, 0.029 g of N,N,N,N-tetramethyl ethylenediamine was added, and the solution was stirred at room temperature for 48 h. The obtained reactant was precipitated in petroleum ether, filtered and washed several times to obtain a cross-linked polymer, and the polymer was dissolved in N-methyl pyrrolidone to form a 20 wt% precursor solution.

[0360] Step 2: Blade coating. The precursor solution prepared in Step 1 was vacuum degassed at a vacuum degree of -80 kPa, and the degassed precursor solution was blade coated on an activated carbon electrode with a blade thickness of 150 pm to obtain an electrode with a liquid coating.

[0361] Step 3: Thermal curing. The activated carbon electrode with a liquid coating was placed in a vacuum oven and cured at 110 °C for 8 hours.

[0362] Step 4: Washing. The cured electrode was immersed and washed in deionized water to obtain an integrated electrode DB1.

[0363] Comparative Example DB2

[0364] An anion exchange membrane A3 was simply covered and paired with a commercially available activated carbon electrode to obtain an electrode DB2.

[0365] Comparative Example DB3

[0366] Step 1 : Preparation of precursor solution. 1 g of BPPO-1 was dissolved in 9 g of N-methyl pyrrolidone, and dimethylaminoethyl methacrylate was added, wherein the amount of dimethylaminoethyl methacrylate was such that the molar ratio of BPPO to cross-linking agent was 1 :9.5. After a period of reaction, the solution was stirred at 25 °C in the dark for 24 h to obtain a precursor solution.

[0367] Step 2: Blade coating. The precursor solution prepared in Step 1 was vacuum degassed at a vacuum degree of -80 kPa, and the degassed precursor solution was blade coated on an activated carbon electrode with a blade thickness of 150 pm to obtain an electrode with a liquid coating.

[0368] Step 3: Thermal curing. The activated carbon electrode with a liquid coating was placed in a vacuum oven and cured at 80 °C for 24 hours.

[0369] Step 4: cleaning. The solidified electrode was immersed in deionized water for cleaning, to obtain the integrated electrode DB3.

[0370] The content of each molecular chain in the anion exchange functional layer and the thickness of the anion exchange functional layer of the integrated electrode of the examples and the comparative examples were tested, and the results are shown in Table 3.

[0371] Table 3

[0372] Note: refers to the content of the molecular chain formed after polymerization of N,N,N,N-tetramethyl ethylenediamine; ** the side chain of comparative example DB3 does not contain the structure of formula II.

[0373] Test example

[0374] An electrosorption deionization device was assembled for testing, the anode of which used the integrated electrode prepared in the examples and the comparative examples, and the cathode of which used a commercially available activated carbon electrode, to test the desalination performance thereof on a salt-containing solution.

[0375] Another reference example was set, in which the anode and the cathode of the electrosorption deionization device both used commercially available activated carbon electrodes.

[0376] The size of the activated carbon electrode was 6 cm x 9 cm.

[0377] The test conditions were as follows: the water sample used for testing was 500 mL of a sodium chloride solution, the initial conductivity of which was 1500 μs·cm -1 , and the test voltage was 1.5 V.

[0378] The test process was as follows: (1) the mass of the anode electrode was weighed, denoted as M; (2) a peristaltic pump was used to circulate the sodium chloride solution in the electrosorption deionization device, and the voltage was turned on to start the adsorption process; (3) after a period of time of adsorption, the conductivity of the sodium chloride solution was tested, denoted as the product water conductivity C1, and the time was denoted as the operation time t1; (4) the power was turned off, and a reverse voltage was applied to the device to perform the desorption operation; (5) after a period of time of desorption, the conductivity of the sodium chloride solution was tested, denoted as the concentrated water conductivity C2.

[0379] The electrode adsorption capacity Q (mg / g) was calculated according to the formula , and the results are shown in Table 4;

[0380] The desalination rate a1 was calculated according to the formula , and the results are shown in Table 4;

[0381] The adsorption rate of the opposite electrode during desorption was calculated according to the formula , and the results are shown in Table 4.

[0382] Table 4

[0383] As can be seen from Table 4, the integrated electrode prepared by the present application comprises an anion exchange functional layer with a specific structure, so that the adsorption capacity of the electrode to anions (such as chloride ions) is higher.

[0384] In addition, the electric adsorption ion removal device comprising the integrated electrode of the present application has a shorter time to reach saturated adsorption under the same operation, is more conducive to improving the ion transmission rate, and improves the desalination performance of the electric adsorption ion removal device.

[0385] The integrated electrode prepared by the present application has a high adsorption capacity to anions (such as chloride ions), and the electric adsorption ion removal device comprising the integrated electrode has a high desalination rate and a low adsorption rate to the opposite electrode during desorption. Specifically, the adsorption capacity of the integrated electrode to anions is 12-20 mg / g, the desalination rate of the electric adsorption ion removal device is 43-76%, the adsorption rate to the opposite electrode during desorption is less than or equal to 11%, preferably 2-7%, the adsorption time can be shortened to 85% of the original, and the desalination performance of the electric adsorption ion removal device is greatly improved.

Claims

1. An anion exchange membrane, characterized by, The anion exchange membrane includes polyphenyl ether molecular chains having a structure shown in Formula I and molecular chains having a structure shown in Formula II; wherein Q1 or Q2 is independently a halogen atom or a bond connected to a molecular chain having a structure shown in Formula II; wherein R1and R2are each independently H or C1-C5alkyl, R3, R4, R5, and R6are each independently C1-C 10 alkyl, -R9SO3, R9is C1-C 10 alkylene; R7and R8are each independently C1-C3alkylene; x is 20%-50%, * indicates the position of attachment of Formula II to Formula I.

2. The anion exchange membrane according to claim 1, wherein, R1 and R2 are independently H, CH3 or CH2CH3, R3, R4, R5 and R6 are independently C1-C5 linear or branched alkyl, -R9SO3; R9 is C1-C3 alkylene; R7 and R8 are independently methylene or ethylene; and x is 30%-40%.

3. The anion exchange membrane according to claim 1 or 2, wherein, The polyphenyl ether in the anion exchange membrane is a crosslinked polyphenyl ether; Preferably, the content of the polyphenyl ether molecular chain is 18wt%-95wt% and the content of the molecular chain having a structure shown in Formula II is 5wt%-82wt% based on the total weight of the anion exchange membrane.

4. The anion exchange membrane according to any one of claims 1 to 3, wherein, The ion exchange capacity of the anion exchange membrane at 25℃ is 0.9-2.5mmol / g; Preferably, the water absorption of the anion exchange membrane at 25℃ is 15.6%-154.3%; Preferably, the swelling rate of the anion exchange membrane at 25℃ is 8.9%-80.6%; Preferably, the tensile strength of the anion exchange membrane is 1.2MPa-4.7MPa and the elongation at break is 2.3%-23.6%; Preferably, the decrease rate of the ion exchange capacity of the anion membrane at 25℃ after being soaked in an alkaline solution with pH=12 for 24 hours is 3.6%-22.4%; Preferably, the surface Zeta potential of the anion exchange membrane is 28-60mV; Preferably, the cross-linking density of the anion exchange membrane is 0.4 x 10 -4 -1.9 x 10 -4 mol / cm 3 ; Preferably, the anion exchange membrane has an OH - Electrical conductivity is 30-55 ms / cm; Preferably, the impedance of the anion exchange membrane is 12-18Ω; Preferably, the anion exchange membrane has a current density of 470-630 mA-cm at a voltage of 2.1 V -2 ; Preferably, the desalination rate of the anion exchange membrane is greater than 94% when electro-dialysis for 45min.

5. A method for producing an anion exchange membrane, characterized by, The preparation method comprises: (1) mixing a photo-crosslinking agent shown in Formula 1 and / or Formula 2, a halogenated polyphenyl ether shown in Formula 3 and an organic solvent, and then performing a reaction to obtain a solution containing a prepolymer; (2) mixing the solution containing the prepolymer with a photo-initiator under light-proof conditions to obtain a casting solution; (3) coating the casting solution on a substrate, and curing under light to obtain the anion exchange membrane; wherein R 10 is H or C1-C5 alkyl, R 11 is C1-C3 alkylene, R 12 and R 13 are each independently C1-C 10 straight chain or branched alkyl, -R9SO3, R9 being C1-C 10 alkylene; R 14 is C1-C3 alkyl, X is a monovalent anion; X1and X2are each independently H or a halogen atom, and at least one of X1and X2is a halogen atom; x is 20%-50%.

6. The production method according to claim 5, wherein R 10 is H, CH3, or CH2CH3, R 12 and R 13 each independently is C1-C5 linear or branched alkyl, R 14 is CH3or CH2CH3, X is a monovalent anion; X1and X2each independently is H or Br, and at least one of X1and X2is Br; x is 30% - 40%.

7. The production method according to claim 5 or 6, wherein The organic solvent is selected from at least one of N-methyl pyrrolidone, tetrahydrofuran and N,N-dimethylformamide; Preferably, the halogenated polyphenylene ether is a brominated polyphenylene ether, preferably the brominated polyphenylene ether has a Mw w of 55000 to 90000 g / mol; Preferably, the halogenated polyphenyl ether shown in Formula 3 and the organic solvent are mixed to obtain a mixed solution, and then the photo-crosslinking agent shown in Formula 1 and / or Formula 2 is added to the mixed solution to perform a reaction to obtain the solution containing the prepolymer; Preferably, the concentration of the halogenated polyphenyl ether in the mixed solution is 5wt%-20wt%.

8. The method of making according to any one of claims 5-7, wherein, The molar ratio of the halomethyl in the halogenated polyphenyl ether to the photo-crosslinking agent is 1:0.2-65, preferably 1:1-25; Preferably, the reaction conditions comprise a reaction temperature of 15-30℃ and a reaction time of 12-48h.

9. The method of making according to any one of claims 5-8, wherein, The photo-initiator is selected from at least one of a free radical type photo-initiator and / or a cationic type photo-initiator, preferably selected from at least one of 2-hydroxy-2-methylpropiophenone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide. Preferably, the amount of the photoinitiator is 3wt%-10wt% based on the total mass of the photocrosslinking agent and the halogenated polyphenyl ether.

10. The method of making according to any one of claims 5-9, wherein, The preparation method further comprises: The casting solution is coated on a substrate after being degassed; Preferably, the degassing comprises static degassing and / or vacuum degassing.

11. The method of making according to any one of claims 5-10, wherein, The light conditions include: the intensity of the light is 5-200 mW / cm 2 , preferably 30-100 mW / cm 2 ; Preferably, the curing time is 1-35 minutes, preferably 3-15 minutes.

12. The anion exchange membrane prepared by the preparation method of any one of claims 5-11.

13. Use of the anion exchange membrane of any one of claims 1-4 and 12 in a separation process.

14. Use according to claim 13, wherein, The separation process comprises electrolysis of water to produce hydrogen or desalination of seawater.

15. An integrated electrode, characterized by The integration comprises an electrosorption electrode and an anion exchange functional layer coated on the surface of the electrosorption electrode; The anion exchange functional layer is the anion exchange membrane of any one of claims 1-4 and 12.

16. The integrated electrode of claim 15, wherein, The thickness of the anion exchange membrane is 100-200μm, preferably 100-150μm.

17. The integrated electrode of claim 15 or 16, wherein, The electrosorption electrode is selected from at least one of a porous foam carbon electrode, an activated carbon electrode, a graphene electrode and a metal modified electrode.

18. The integrated electrode of any of claims 15-17, wherein, The adsorption capacity of the electrode for anions is 12-20mg / g.

19. A method of making an integrated electrode, comprising: The preparation method comprises the following steps: S1, mixing a photocrosslinking agent shown in formula 1 and / or formula 2, a halogenated polyphenyl ether shown in formula 3 and an organic solvent, and then reacting to obtain a solution containing a prepolymer; S2, mixing the solution containing the prepolymer with a photoinitiator under light shielding conditions to obtain a precursor solution; S3, coating the precursor solution on an electrosorption electrode after vacuum degassing to obtain an electrosorption electrode with a liquid coating layer; S4. solidifying the electro-adsorptive electrode with the liquid coating under light conditions to obtain the integrated electrode; wherein R 10 is H or C1-C5 alkyl, R 11 is C1-C3 alkylene, R 12 and R 13 are each independently C1-C 10 straight chain or branched alkyl, -R9SO3, R9 being C1-C 10 alkylene; R 14 is C1-C3 alkyl, X is a monovalent anion; X1and X2are each independently H or a halogen atom, and at least one of X1and X2is a halogen atom; x is 20%-50%.

20. The method of making according to claim 19, wherein, The organic solvent is selected from at least one of N-methylpyrrolidone, tetrahydrofuran and N,N-dimethylformamide; Preferably, the halogenated polyphenylene ether is a brominated polyphenylene ether, preferably the brominated polyphenylene ether has a Mw w of 55 000 to 90 000 g / mol; Preferably, the halogenated polyphenyl ether shown in formula 3 and the organic solvent are mixed to obtain a mixed solution, and the photocrosslinking agent shown in formula 1 and / or formula 2 is added to the mixed solution to react to obtain the solution containing the prepolymer; Preferably, the concentration of the halogenated polyphenyl ether in the mixed solution is 5wt%-20wt%.

21. The method of manufacturing according to claim 19 or 20, wherein, The molar ratio of halomethyl in the halogenated polyphenyl ether to the photocrosslinking agent is 1:0.2-65, preferably 1:1-25; Preferably, the reaction conditions include a reaction temperature of 15-30℃ and a reaction time of 12-48h.

22. The method of making according to any one of claims 19-21, wherein, The photoinitiator is selected from at least one of a free radical type photoinitiator and / or a cationic type photoinitiator, preferably selected from at least one of 2-hydroxy-2-methylpropiophenone, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide and 2,4,6-trimethylbenzoyl-di(p-tolyl) phosphine oxide; Preferably, the amount of the photoinitiator is 3wt%-10wt% based on the total mass of the photocrosslinking agent and the halogenated polyphenyl ether.

23. The method of making according to any one of claims 19-22, wherein, The vacuum degassing conditions include a relative vacuum degree of-80kPa to-90kPa; Preferably, the thickness of the liquid coating layer is 100-200μm.

24. The method of making according to any one of claims 19-23, wherein, The light conditions include: the intensity of the light is 5-200 mW / cm 2 , preferably 30-100 mW / cm 2 ; Preferably, the curing time is 1-35 minutes, preferably 3-15 minutes. Preferably, the preparation method further comprises: washing the product after solidification.

25. An integrated electrode produced by the preparation method of any one of claims 19-24.

26. An electrosorption deionization device, comprising: The electro-adsorption deionization device comprises the integrated electrode of any one of claims 15-18 and 25.

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