A macrocyclic cross-linked anion exchange membrane constructed with host-guest recognition, its preparation method and its application

Abstract

This invention provides a macrocyclic crosslinked anion exchange membrane constructed using host-guest recognition, its preparation method, and its application. First, a large-volume rigid crosslinking agent, CDIC, is synthesized by using a saturated aqueous solution method to include nonpolar molecules via the host-guest molecular recognition of β-cyclodextrin. Second, a membrane-forming material is prepared by first chloromethylating the polymer and then functionalizing it. Finally, CDIC is introduced into the membrane-forming material to promote the formation of microphase separation structures within the membrane, resulting in a macrocyclic crosslinked anion exchange membrane. The anion exchange membrane synthesized by this invention can be applied in the field of electrodialysis water treatment. The preparation process is simple, the raw materials are inexpensive and readily available, and the resulting anion exchange membrane exhibits suitable water absorption and optimal microphase separation structures at a relatively low charged group density, thereby effectively improving the selectivity and ion transport flux of the anion exchange membrane and providing a new preparation strategy for electrodialysis water treatment devices.

Description

TECHNICAL FIELD

[0001] The application is mainly applied to the field of electrodialysis seawater desalination, and the preparation and application research of anion exchange membrane (AEMs) devices used in the process. The electrochemical selectivity of the anion exchange membrane is used to realize the desalination treatment of seawater or brackish water, thereby an innovative preparation method of modified HQPSf-CDIC-x membrane material is proposed. The microphase separation structure of the membrane is optimized by using modified β-cyclodextrin (β-CD), and the desalination treatment of seawater is realized through an electrodialysis device. BACKGROUND

[0002] The world's water resources are becoming increasingly scarce, and this problem will further worsen with the increasing population, climate change, and even nuclear contaminated water discharge into the sea. Therefore, developing a reasonable and effective desalination technology has become the focus of researchers. Current seawater desalination technologies mainly include distillation, freezing, electrodialysis (ED) and reverse osmosis. Electrodialysis has the advantages of convenient installation and operation, lower cost, environmental protection and no pollution in the seawater desalination process, and there is no phase change process in the operation process. In the seawater desalination equipment, electrodialysis is expected to become the mainstream of seawater desalination in the near future. At present, electrodialysis urgently needs high-performance AEMs suitable for electrodialysis devices with excellent ion selectivity, extremely low electrical resistance, excellent stability (mechanical, chemical and thermal stability), and small solute and solvent diffusion coefficient, among which excellent ion selectivity and high ion flux are the most important. Improving the microphase separation microstructure in the membrane is a common method to improve the selectivity and electrical conductivity. V. Yadav et al. in "Long side-chain type partially cross-linked poly(vinylidene fluoride-co-hexafluoropropylene) anion exchange membranes for desalination via electrodialysis" proposed to optimize the microphase separation morphology of the membrane by cross-linking structure, and the optimized AEMs had obvious hydrophilic and hydrophobic phase separation morphology, and had an electrical conductivity of 21.1 mS cm -1 and an electrochemical selectivity of 84%. SUMMARY

[0003] The application discloses a modified method which is simple to operate according to the application defects of the anion exchange membrane for electrodialysis. A macrocyclic hydrophilic crosslinking agent with the function of promoting the aggregation of charged groups is synthesized by a molecular recognition method, and is structured in the membrane by a Menshutkin reaction, so that the microphase separation structure in the membrane is promoted to form, and the difference between the hydrophilic and hydrophobic phases in the membrane is increased. The membrane uses bisphenol A polysulfone (PSf) as a forming material of the AEM, the bisphenol A polysulfone has high hardness and impact strength, is non-toxic, and is resistant to heat, cold and aging, and a quaternary amine group which is resistant to alkali is used as a charged group in the membrane. In the electrodialysis seawater desalination process, the membrane has high current efficiency and lower power consumption.

[0004] In order to achieve the above-mentioned purpose, the technical scheme adopted by the application is:

[0005] A macrocyclic crosslinking type anion exchange membrane constructed by host-guest recognition, wherein poly sulfone is used as a hydrophobic membrane support material, hydroxyl quaternary amine polysulfone is used as a charged group with ion transmission capacity, and a macrocyclic crosslinking agent of beta-cyclodextrin constructed by host-guest recognition is used as a monomer with the function of promoting the microphase separation morphology.

[0006] A preparation method of a macrocyclic crosslinking type anion exchange membrane constructed by host-guest recognition, which comprises the following steps: firstly, halomethylation and functionalization treatment are performed on a polymer main chain to obtain a functionalized polymer with ion conduction capacity; secondly, beta-cyclodextrin and N,N,N',N'-tetramethyl-1,6-hexanediamine (TMHDA) are used to prepare a macrocyclic crosslinking agent CDIC of beta-cyclodextrin as an inclusion compound by a solution co-precipitation method; then, the CDIC is added into the halomethylated polymer, and hydroxyl quaternization and grafting of the macrocyclic crosslinking agent are performed by a Menshutkin reaction, so that the microphase separation structure in the membrane is promoted to form by the hydrogen bond force between the hydroxyl quaternary amine polysulfone and the beta-cyclodextrin with rich hydroxyl groups; and finally, the anion exchange membrane is prepared by a solution casting method or a doctor blade coating method. The preparation process comprises halomethylation of a polymer main chain, synthesis of an inclusion compound, functionalization of a polymer main chain, introduction of CDIC and membrane casting.

[0007] In the first step, an inclusion compound CDIC is synthesized by host-guest molecular recognition as a macrocyclic crosslinking monomer.

[0008] In the first step, an inclusion compound CDIC is synthesized by host-guest molecular recognition as a macrocyclic crosslinking monomer.

[0009] The solution coprecipitation method was used. β-Cyclodextrin was dissolved in solvent A at 50-60℃, and an equimolar amount of N,N,N',N'-tetramethyl-1,6-hexanediamine (TMHDA) was added. TMHDA replaced the high-energy water inside the cyclodextrin cavity and occupied the cavity. The mixture was stirred for 1-2 hours, and the precipitate was formed in the precipitant. The precipitate was washed with an organic solvent and freeze-dried to obtain the monomer.

[0010] The second step involves preparing functionalized polymers with ion-conducting capabilities.

[0011] 1.1) The polymer is subjected to halomethylation to obtain a polymer with halogen sites:

[0012] The polymer was dissolved in solvent B, and chloromethylating agent and SnCl4 were added. The mixture was reacted at 25-35°C for 5-60 minutes. The reactants were then poured into a precipitant to precipitate, and dried under vacuum to prepare the chloromethylated polymer.

[0013] 1.2) Polymer backbone ionization:

[0014] The polymer obtained in step (2) is dissolved in solvent C, wherein the mass concentration of the polymer is 10-15%, and the reaction temperature of the dissolution reaction is [temperature missing].

[0015] The reaction was carried out at 60–90°C for 20–60 minutes to obtain a halomethylated polymer solution. An ionizing agent was added to the halomethylated polymer solution, and the ionizing agent reacted with the halomethylated polymer in a Mensohin reaction. The reaction was carried out at 60–90°C for 48–72 hours. The polymer was precipitated in a precipitant, washed with an organic solvent, and dried under vacuum to obtain a hydroxyl quaternized polymer (ionized polymer), which is then used to obtain a film-forming material.

[0016] The molar ratio of the halomethylating and ionizing reagents is 1:1.02. The ionizing reagent is N,N-dimethylethanolamine.

[0017] The third step involves adding the inclusion complex CDIC to the hydroxyl quaternized polymer, thus embedding the CDIC structure within the membrane. CDIC promotes the formation of microphase separation structures within the membrane. Specifically:

[0018] The hydroxyl quaternized polymer was dissolved in organic solvent D to obtain a 70% (w / w) hydroxyl quaternized polymer solution. CDIC was added to the hydroxyl polymer solution, and hydroxyl quaternization and grafting with a macrocyclic crosslinking agent were carried out via the Menshutkin reaction. The reaction temperature was 30–40 °C, and the reaction time was 48–72 hours, ensuring uniform mixing of the solution to form a casting solution. β-CD will promote the aggregation of charged groups within the membrane, increase the difference between hydrophilic and hydrophobic phases, and enhance the microphase separation structure within the membrane.

[0019] Step 4, casting

[0020] The casting solution obtained in the third step is cast into a film on a glass plate or is flow-casted, and is left to stand at 40-50 DEG C for 12-24 hours to obtain the anion exchange membrane.

[0021] Further, the solvent A in the first step is deionized water; the solvent B in the second step 1.1) is dichloromethane; the solvent C in the second step 1.2) is dimethyl sulfoxide, N-methyl pyrrolidone and N,N-dimethylformamide; and the organic solvent D in the third step is N,N-dimethylformamide.

[0022] Further, the precipitant in the first step is acetone; the precipitant in the second step 1.1) is methanol or ethanol; and the precipitant in the second step 1.2) is ethyl acetate.

[0023] Further, the freeze-drying time in the first step is 24-48 hours at a temperature of -80 DEG C.

[0024] Further, the temperature for vacuum drying in the second step 1.1) is 40-100 DEG C for 12-48 hours; and the temperature for vacuum drying in the second step 1.2) is 40-100 DEG C for 12-48 hours.

[0025] Further, the polymer in the second step 1.1) is polysulfone, polyether ether ketone, polyimide or polyphenyl ether, preferably polysulfone.

[0026] The application of the host-guest recognition structure macrocyclic cross-linked anion exchange membrane, which is applied to a electrodialysis seawater desalination device and used as an anion exchange membrane device.

[0027] The application has the following advantages:

[0028] The application fixes the large-volume hydrophilic cyclic structure beta-CD containing rich hydroxyl groups in the membrane through the host-guest molecular recognition physical change process, the rich hydroxyl groups contained can promote the aggregation of cationic groups and increase the ion cluster size, the large-volume hydrophilic property can increase the difference between hydrophilic and hydrophobic phases, these factors can promote the microphase separation structure in the membrane, so that more continuous ion transmission channels appear in the membrane, the new cross-linked anion exchange membrane effectively optimizes the current efficiency value and energy consumption size of the anion exchange membrane in the electrodialysis process under the conditions of low ion exchange capacity and suitable water absorption rate, and the addition amount of CDIC is also important for the performance improvement of the electrodialysis. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 Hydroxyl quaternary ammonium polysulfone obtained from the chloromethyl site left after functionalization in Example 1 1 The H NMR spectrum, in which the abscissa is the chemical shift value ppm.

[0030] Figure 2 Fourier infrared spectrum of the HQPSf-CDIC composite film functionalized in Example 2, the abscissa of the figure is the wave number cm -1 .

[0031] Figure 3 The limit current density diagram of the HQPSf-CDIC-x composite film obtained in Comparative Example 1, Example 1-Example 3, the curves HQPSF-CDIC-0, HQPSF-CDIC-1, HQPSF-CDIC-2, HQPSF-CDIC-3 are the films prepared in Comparative Example 1, Example 1, Example 2, Example 3, respectively, the abscissa of the figure is the voltage value V, and the ordinate is the current density mA cm -1 .

[0032] Figure 4 The current efficiency-energy consumption diagram of the HQPSf-CDIC-x composite film obtained in Comparative Example 1, Example 1-Example 3, the abscissa of the figure is the film name, from left to right HQPSF-CDIC-0, HQPSF-CDIC-1, HQPSF-CDIC-2, HQPSF-CDIC-3 are the films prepared in Comparative Example 1, Example 1, Example 2, Example 3, respectively, the left ordinate is the current efficiency %, and the right ordinate is the energy consumption kWh kg -1 . DETAILED DESCRIPTION

[0033] The content of the application will be described in more detail and more clearly by specific embodiments.

[0034] Comparative Example 1 (without CDIC):

[0035] (1) Preparation of chloromethyl octyl ether (CMOE)

[0036] 500 mL flask was added 100 g of anhydrous CaCl2, 30 g of polyformaldehyde, and mechanically stirred to dissolve, and HCl gas was introduced for 3 hours under ice water bath conditions (concentrated hydrochloric acid and NaCl were added dropwise to concentrated sulfuric acid), the gas supply was stopped, and the stirring was continued for 30 min, and the filtrate was obtained by filtration after standing for 10 hours. It is a chloromethylation reagent.

[0037]

[0038] (2) Preparation of chloromethylated polysulfone

[0039] 125 mL of dichloromethane was dissolved in a 250 mL three-necked flask 5 g of polysulfone (PSf), then 30 mL of CMOE and 1.5 mL of SnCl4 were added. 25℃ reaction for 60 min, a large amount of anhydrous ethanol was precipitated, washed with anhydrous ethanol (3x), and dried at 40℃ under reduced pressure for 48 hours to obtain the CMPSf product.

[0040] (3) Polymer ionization

[0041] 10 g of CMPSf was dissolved in 100 mL of dimethyl sulfoxide, stirred at 60 °C for 60 min to complete dissolution, then 1.96 mL of N, N-dimethyl ethanolamine was added, and reacted at 60 °C for 72 h. Ethyl acetate was precipitated, washed, and dried in a vacuum oven at 40 °C for 48 h to obtain a light yellow HQPSf-Cl product.

[0042] (4) Introduction of large volume crosslinking monomer, casting film and obtaining anion exchange membrane

[0043] 0.7 g of HQPSf-Cl was added to 10 mL of N, N-dimethyl formamide, and a uniform solution was obtained by continuous stirring at 70 °C; then the solution was cast on a glass plate or flow casted into a film, and the glass plate was heated to 40 °C for 24 h for solvent evaporation.

[0044] The anion exchange membrane was obtained by peeling the above film from the glass plate.

[0045] The prepared anion exchange membrane had an ion exchange capacity of 1.524 mmol / g, a water absorption rate of 34.29% at room temperature, a swelling rate of 13.02%, and a current efficiency value of 86.41% and an energy consumption value of 5.17 KWh kg -1 .

[0046] Example 1:

[0047] (1) Preparation of CDIC

[0048] 1 g of β-CD was dissolved in 18.98 mL of deionized water at 50 °C with rapid stirring, 0.15 mL of TMHDA was added, and after continuous stirring at a reduced speed for 1 h at 50 °C, it was cooled to room temperature and placed in a refrigerator at 2 °C for 24 h. After filtration, a small amount of water was washed, and then washed three times in acetone, and a white powder solid was obtained by filtration. After being frozen in a refrigerator for 24 h, it was freeze-dried for 24 h to obtain CDIC.

[0049] (2) Preparation of chloromethyloctyl ether (CMOE)

[0050] 100 g of anhydrous CaCl2, 30 g of polyformaldehyde were added to a 500 mL flask, and dissolved by mechanical stirring. Hydrochloric acid gas was introduced for 3 h under ice water bath conditions (concentrated hydrochloric acid and NaCl were added dropwise with concentrated sulfuric acid), the gas supply was stopped, and stirring was continued for 30 min. After standing for 10 h, the filtrate was obtained by filtration, which was a chloromethylation reagent.

[0051]

[0052] (3) Preparation of chloromethylated polysulfone

[0053] Dissolve 5 g of polysulfone (PSf) in 125 mL of dichloromethane in a 250 mL three-necked flask, then add 30 mL of CMOE and 1.5 mL of SnCl4. React at 28°C for 23 min, a large amount of anhydrous ethanol is precipitated, washed with anhydrous ethanol (3x), and dried at 60°C under reduced pressure for 36 hours to obtain the CMPSf product.

[0054] (4) Polymer ionization

[0055] Dissolve 10 g of CMPSf in 83 mL of dimethyl sulfoxide, stir at 70°C for 40 min until completely dissolved, then add 1.96 mL of N,N-dimethyl ethanolamine, react at 70°C for 64 hours. Precipitate and wash with ethyl acetate, and dry in a vacuum oven at 60°C for 36 hours to obtain a light yellow HQPSf-Cl product.

[0056] (5) Introduction of large volume crosslinking monomer, casting film and obtaining anion exchange membrane

[0057] Add 0.7 g of HQPSf-Cl to 10 mL of N,N-dimethylformamide, continuously stir at 70°C to obtain a uniform solution; after the solution is naturally cooled to 25°C, add 0.007 g of CDIC pre-dissolved in 2 mL of DMF, stir at 30°C for 72 hours; then cast the solution on a glass plate or flow into a film, and heat the glass plate to 44°C for 20 hours to evaporate the solvent.

[0058] The anion exchange membrane is obtained by removing the above film from the glass plate.

[0059] The prepared anion exchange membrane has an ion exchange capacity of 1.496 mmol / g, a water absorption rate of 38.04% at room temperature, a swelling rate of 10.05%, and an electrodialysis desalination test is performed on the membrane, the current efficiency value is 90.14%, and the energy consumption value is 4.87 KWh kg -1 .

[0060] Example 2:

[0061] (1) Preparation of CDIC

[0062] Dissolve 1.2 g of β-CD in 22.78 mL of deionized water at 55°C with rapid stirring, add 0.18 mL of TMHDA, continue stirring at a reduced speed at 55°C for 1.5 hours, then cool to room temperature, place in a refrigerator at 3°C and stand for 24 hours, filter, wash with a small amount of water, and then wash three times in acetone, filter to obtain white powder solid, freeze in a refrigerator for 36 hours, and freeze dry for 36 hours to obtain CDIC.

[0063] (2) Preparation of chloromethyl octyl ether (CMOE)

[0064] 500mL flask was added 100g anhydrous CaCl2, 30g paraformaldehyde, mechanical stirring to dissolve, ice water bath conditions for 3 hours HCl gas (to the concentrated hydrochloric acid and NaCl drop concentrated sulfuric acid), stop aeration, continue to stir for 30 min, 10 hours standing filter to get the filtrate is chloromethylation reagent.

[0065]

[0066] (3) Preparation of chloromethylated polysulfone

[0067] 250mL three neck flask 125mL dichloromethane dissolved 5g polysulfone (PSf), then added 30mL CMOE and 1.5mL SnCl4. 31 degrees Celsius reaction 41 min, cooling to 30 °C, a large amount of methanol precipitated, methanol washing (3x), drying at 80 °C under reduced pressure for 24 hours, CMPSf product was obtained.

[0068] (4) polymer ionization

[0069] 10g CMPSf dissolved in 77mL N-methyl pyrrolidone, stirring at 80 °C for 30 min to completely dissolved, then added 1.96mL N, N- dimethyl ethanolamine, 80 °C reaction for 56 hours. Ethyl acetate precipitated, washed, dried in a vacuum oven at 80 °C for 24 hours, HQPSf-Cl product was obtained.

[0070] (5) large volume crosslinking monomer introduction, casting film and anion exchange membrane

[0071] 0.7g HQPSf-Cl was added to 10mL N, N-dimethyl formamide, stirring at 70 °C, a homogeneous solution was obtained; after the solution was cooled to 25 °C, 0.014g CDIC was added, which was pre-dissolved in 3mL DMF, and stirring was carried out at 35 °C for 50 hours; then the solution was cast on a glass plate or flow casted into a film, and the glass plate was heated to 46 °C for 16 hours to evaporate the solvent.

[0072] The above film was removed from the glass plate to obtain the anion exchange membrane.

[0073] The prepared anion exchange membrane had an ion exchange capacity of 1.463mmol / g, a room temperature of 39.05%, a swelling rate of 10.40%, and an electrodialysis desalination test was carried out on the membrane, the current efficiency value was 92.04%, and the energy consumption value was 4.68KWh kg -1 .

[0074] Example 3:

[0075] (1) Preparation of CDIC

[0076] Dissolve 1.5 g of β-CD in 27.60 mL of deionized water at 60°C with rapid stirring, add 0.23 mL of TMHDA, continue stirring at 60°C for 2 hours at a reduced speed, cool to room temperature, and place in a refrigerator at 2°C for 24 hours. Filter, rinse with a small amount of water, and then wash three times in acetone. Filter to obtain a white powder, and then place in a refrigerator for 48 hours. Freeze dry for 48 hours to obtain CDIC.

[0077] (2) Preparation of chloromethyloctyl ether (CMOE)

[0078] Add 100 g of anhydrous CaCl2 and 30 g of paraformaldehyde to a 500 mL flask, and dissolve with mechanical stirring. Bubble in HCl gas (add concentrated sulfuric acid dropwise to concentrated hydrochloric acid and NaCl) for 3 hours under ice water bath conditions. Stop bubbling, continue stirring for 30 min, and then let stand for 10 hours. Filter to obtain a filtrate, which is a chloromethylation reagent.

[0079]

[0080] (3) Preparation of chloromethylated polysulfone

[0081] Dissolve 5 g of polysulfone (PSf) in 125 mL of dichloromethane in a 250 mL three-necked flask, and then add 30 mL of CMOE and 1.5 mL of SnCl4. React at 35°C for 5 min, and then wash with a large amount of methanol (3x). Dry at 100°C under reduced pressure for 12 hours to obtain a CMPSf product.

[0082] (4) Polymer ionization

[0083] Dissolve 10 g of CMPSf in 67 mL of N,N-dimethylformamide, and then add 1.96 mL of N,N-dimethyl ethanolamine. React at 90°C for 48 hours. Precipitate with ethyl acetate, wash, and dry in a vacuum oven at 100°C for 12 hours to obtain a light yellow HQPSf-Cl product.

[0084] (5) Introduction of a large volume of crosslinking monomer, casting of a film, and obtaining an anion exchange membrane

[0085] Add 0.7 g of HQPSf-Cl to 10 mL of N,N-dimethylformamide, and then stir at 70°C to obtain a uniform solution. After the solution is naturally cooled to 25°C, add 0.021 g of CDIC that has been previously dissolved in 4 mL of DMF, and then stir at 40°C for 48 hours. Then, cast the solution on a glass plate or flow cast into a film, and then heat the glass plate to 50°C for 12 hours to evaporate the solvent.

[0086] Remove the film from the glass plate to obtain an anion exchange membrane.

[0087] The prepared anion exchange membrane has an ion exchange capacity of 1.455 mmol / g, a water absorption rate of 42.33% at room temperature, and a swelling rate of 11.08%. The membrane is subjected to electrodialysis desalination test, and the current efficiency value is 90.01% and the energy consumption value is 4.88 kWh / kg -1 .

[0088] Composite membrane material characterization:

[0089] The nuclear magnetic resonance spectrometer 1 H-NMR and Fourier infrared spectrometer ATR are used to characterize the functional groups of the composite membrane and the modified composite membrane. Material characterization result analysis

[0090] It can be seen from the characteristic functional group characterization of CDIC of Example 1 that the signal at 2.01 ppm (a) belongs to the methyl group, and the signals at 2.06 ppm (b), 1.28 ppm (c) and 1.16 ppm (d) belong to the methylene (-CH2-) group of THMDA. The signals of β-CD in CDIC are 1 H-NMR signals are 5.64 ppm (OH-2), 5.58 ppm (OH-3), 4.74 ppm (1), 4.36 ppm (OH-6), 3.65-3.43 ppm (3, 4, 5) and 3.22-3.16 ppm (2). The above results show that CDIC has all the signals of β-CD, the signal of the tertiary amine methyl substituent group of TMHDA (1.99 ppm) and the weak methylene proton peak (2.07 ppm). It shows the successful synthesis of CDIC.

[0091] It can be seen from the characteristic functional group characterization of the CMPSf composite membrane of Comparative Example 1 and the modified HQPSf-CDIC composite membrane of Examples 1-3 that the modified HQPSf-CDIC composite membrane has a characteristic peak of the ether bond (C-O-C) of β-CD at 1034 cm -1 , which indicates that the anion exchange membrane is modified.

[0092] Through the limiting current density test of the CMPSf composite membrane of Comparative Example 1 and the modified HQPSf-CDIC-x composite membrane of Examples 1-3, it can be seen from the test results that the HQPSf-CDIC-x membranes all have higher current density values, which indicates that they have excellent electrochemical selectivity, indicating that they can work at higher current-voltage.

[0093] Through the electrodialysis seawater desalination test of the CMPSf composite membrane of Comparative Example 1 and the modified HQPSf-CDIC-x composite membranes of Examples 1-3, it can be seen from the test results that the HQPSf-CDIC-x membranes all have higher current efficiency values and lower energy consumption values than the base membranes, indicating that the structure of the large-volume cross-linked anion exchange membrane and the electrodialysis performance advantage are obvious.

[0094] The above examples only express the embodiments of the present application, but cannot be understood as the limitation of the scope of the patent of the present application. It should be pointed out that, for those skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which all belong to the protection scope of the present application.

Claims

1. A method for preparing a host-guest recognition constructed macrocyclic crosslinked anion exchange membrane, characterized by, The preparation method comprises the following steps: first, preparing a β-cyclodextrin macrocyclic crosslinking agent CDIC as an inclusion compound; second, performing halomethylation and functionalization treatment on a polymer main chain to obtain a functionalized polymer having ion conduction capability; third, adding the CDIC into the functionalized polymer to obtain a casting solution, and performing hydroxyl quaternary amination and grafting of the macrocyclic crosslinking agent to promote the formation of a microphase separation structure in the membrane; and fourth, preparing an anion exchange membrane through the casting solution. In the first step, the β-cyclodextrin macrocyclic crosslinking agent CDIC is synthesized as a macrocyclic crosslinking monomer. In the second step, the functionalized polymer having ion conduction capability is prepared. In step 2.1, the polymer is subjected to halomethylation treatment to obtain a polymer connected with halogen sites. In step 2.2, the polymer main chain is ionized. In the third step, the inclusion compound CDIC is added into the hydroxyl quaternary aminated polymer, and the CDIC is arranged in the membrane, so that the CDIC can promote the formation of a microphase separation structure in the membrane. In the fourth step, the casting is performed. In step 2.2, the molar ratio of the halomethylated polymer to the ionization reagent is 1:1.02, and the ionization reagent is N,N-dimethylethanolamine. In the first step, the solvent A is deionized water; in step 2.1, the solvent B is dichloromethane; in step 2.2, the solvent C is dimethyl sulfoxide, N-methyl pyrrolidone and N,N-dimethylformamide; and in the third step, the organic solvent D is N,N-dimethylformamide. In the first step, the precipitant is acetone; in step 2.1, the precipitant is methanol or ethanol; and in step 2.2, the precipitant is ethyl acetate. ​ ​ 2. The method of claim 1, wherein the host-guest recognition construction is a macrocyclic cross-linked anion exchange membrane. ​ 3. The method of claim 1, wherein the host-guest recognition construction is a macrocyclic cross-linked anion exchange membrane. ​ 4. The method of claim 1, wherein the host-guest recognition construction is a macrocyclic crosslinked anion exchange membrane. ​ 5. The method of claim 1, wherein the host-guest recognition construction is a macrocyclic cross-linked anion exchange membrane. The freezing drying time in the first step is 24-48 hours, and the temperature is -80 DEG C. The temperature of vacuum drying in step 2.1 is 40-100 DEG C, and the time is 12-48 hours; the temperature of vacuum drying in step 2.2 is 40-100 DEG C, and the time is 12-48 hours.

6. The method of claim 1, wherein the method is characterized by: The polymer in step 2.1 is polysulfone, polyether ether ketone, polyimide or polyphenyl ether.

7. A host-guest recognition constructed macrocyclic cross-linked anion exchange membrane, characterized by, The preparation method is prepared by any one of claims 1-6.

8. Use of the host-guest recognition constructed macrocyclic cross-linked anion exchange membrane according to claim 7, characterized in that, The host-guest recognition constructed macrocyclic cross-linked anion exchange membrane is applied to the field of electrodialysis water treatment.

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