Preparation method of a high permeation flux univalent selective anion exchange membrane

Abstract

The present invention relates to the field of polymer macromolecular materials, and specifically discloses a preparation method of a monovalent anion high-permeability anion exchange membrane. By regulating the hydrophobic segment, hydrophilic segment and the length of the alkyl chain in the side chain, a hydrophilic-hydrophobic microphase separation is induced in the membrane through side chain grafting to form a continuous ion transport channel, forming an efficient ion transport rate and an excellent selective ion transport channel, so that the membrane has good monovalent anion selectivity. The side chain type anion exchange membrane prepared by the present invention has the advantages of good ion conductivity, good dimensional stability, high monovalent anion permeation selectivity, etc., and particularly has broad application prospects in the field of electrodialysis applications.

Description

Technical Field

[0001] The present invention relates to the field of polymer macromolecular materials, and specifically relates to a preparation method of a monovalent anion high-permeation anion exchange membrane, belonging to the field of membrane technology. Background Art

[0002] The improvement of the level of ion precise separation technology is of great significance to the sustainable development of chemical industrial production, and can further meet the needs of energy conservation, emission reduction and the transformation and upgrading of traditional industries for major national strategic goals such as "dual carbon". Ion precise separation refers to the concentration and recovery of a certain target ion in a specific system. In practical applications, salt production from seawater, lithium extraction from salt lakes, brine refining in the chlor-alkali industry, and resource utilization of waste acid / waste alkali in the metallurgical industry all require the separation of ions with the same charge but different valences. At present, electrodialysis technologies such as ordinary electrodialysis, electrolytic electrodialysis, bipolar membrane electrodialysis, and selective electrodialysis have been applied to material desalination, brine concentration, acid-base concentration, seawater desalination, waste acid-base recovery, etc. Among them, selective electrodialysis, due to the main components, the monovalent / divalent ion exchange membranes that allow the permeation of monovalent ions but block the permeation of divalent or polyvalent ions, has shown its unique advantages in applications such as energy conversion, brine refining in the chlor-alkali industry, resource utilization of high-salt wastewater, resource utilization of waste acid and waste alkali, and lithium extraction from salt lakes. If some of the traditional ion exchange membranes in the ordinary electrodialysis stack are replaced or monovalent / divalent ion exchange membranes are added, selective electrodialysis can be constructed. At present, the development of monovalent / divalent ion exchange membrane technology has achieved a great degree of improvement, but still faces some challenges. (1) Poor long-term stability. For example, the acid or alkali generated under the action of an electric field is likely to damage the structure of the modified layer and weaken the force between the polyelectrolyte skin layer and the base membrane, resulting in a weakened charge repulsion effect on polyvalent ions. (2) Low operating current density. The operating current of selective electrodialysis is relatively low, which can be attributed to the low limiting current density of the monovalent / divalent ion exchange membranes.

[0003] Under the condition of ensuring the appropriate selectivity of the ion exchange membrane, spiro ring structures, fluorene-based Cardo ring structures, biphenyl imidazole structures, etc. are introduced into the main chain. By using the twisted and folded structure and rigidity, the molecules cannot be effectively stacked, preventing the relaxation of the structure and the loss of micropores, so as to generate free volume in the polymer membrane to form micropores (ion channels), thereby assisting in promoting the efficient transmission of monovalent ions and constructing a class of ion exchange membranes with stable structure, high permeation flux and selectivity. Summary of the Invention

[0004] The technical problem solved by the present invention is to provide a method for preparing a side-chain type anion exchange membrane containing a twisted structure.

[0005] To solve the above technical problem, the present invention adopts the following technical solutions:

[0006] Step (1) Preparation of monomer (I):

[0007] N,N-dimethyl-1,3-propanediamine and 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuran-1-one (phenolphthalein) are refluxed at 160 °C under a nitrogen atmosphere to prepare the 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolin-1-one monomer shown in formula (I);

[0008]

[0009] Step (2) Preparation of monomer (II):

[0010] Bisphenol A is refluxed at 160 °C under a nitrogen atmosphere in the presence of methanesulfonic acid catalyst to prepare the 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer shown in formula (II);

[0011]

[0012] Step (3) Preparation of the main chain structure:

[0013] The 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolin-1-one monomer shown in formula (I), 4,4'-difluorodiphenyl sulfone monomer and the 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer shown in formula (II) are subjected to solvent co-polycondensation to obtain a polyarylether sulfone with an amino-phenolphthalein structure in the main chain, as shown in formula (III). Among them, the total molar amount of 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolin-1-one and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane is in a ratio of 1:1 to the molar amount of 4,4'-difluorodiphenyl sulfone. The molar ratio of the 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolin-1-one monomer and the 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer is x:100 - x = 100% - 60%:0% - 40%; the number average molecular weight Mn of the polyarylether sulfone is 50000 - 120000.

[0014]

[0015] Step (4) Alkylation functionalization of the main chain structure and preparation of the anion exchange membrane:

[0016] Dissolve the polyarylethersulfone shown in formula (III) prepared in step (3) in an organic solvent, and then add 1-bromopropane (IV), 1-bromopentane (V), 1-bromoheptane (VI), 1-bromononane (VII), 1,1,1,2,2-pentafluoro-4-iodobutane (VIII), and 1,1,2,2-tetrahydroperfluorohexyl iodide (IX) shown in the following formula according to a molar ratio of 1:1.20 - 1.50, stir for a certain period of time, and let it stand for defoaming to obtain a casting solution. The mass-volume concentration of polyarylethersulfone in the casting solution is 3 - 8%; the organic solvent is one or more of DMF, DMAc, and NMP. Pour the obtained casting solution onto a glass plate, and carry out in-situ reaction and drying at 40 - 200 °C for 12 - 96 h. After cooling, peel off the film from the glass plate in water to obtain an alkyl-functionalized anion exchange membrane, whose structural formula is shown in formula (V), and the thickness is 70 - 150 μm.

[0017]

[0018]

[0019]

[0020] Among them, x: 100% - x = 100% - 60%: 0% - 40%;

[0021] Preferably, step (1) of the present invention is specifically implemented as follows: In a reaction vessel, use N,N-dimethyl-1,3-propanediamine and 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein), under a nitrogen atmosphere, heat to reflux, keep for 12 - 48 h, then cool to room temperature, slowly pour it into an ice-water mixture, and then dropwise add dilute hydrochloric acid. A white precipitate appears. Wash the precipitate with water 5 - 7 times, and dry the precipitate in vacuo at 40 °C for 48 h to obtain the 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer shown in formula (I).

[0022] Further preferably, in step (1), the molar ratio of the N,N-dimethyl-1,3-propanediamine to 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein) is 1.0 - 2.5:1, and most preferably 1.2:1.

[0023] Further preferably, in step (1), the dilute hydrochloric acid solution is an aqueous hydrochloric acid solution with pH = 0 - 1 (most preferably pH = 0).

[0024] As a further preference, in step (1), the separation and purification is carried out as follows: under a nitrogen atmosphere, heat to reflux and maintain for 12 - 48 h, then cool to room temperature, slowly pour into an ice - water mixture, and then drop - wise add dilute hydrochloric acid. A white precipitate appears. Wash the precipitate with water 5 - 7 times, and vacuum - dry the precipitate at 30 - 80 °C (more preferably 50 °C) for 24 - 48 h (more preferably 48 h).

[0025] As a preference, step (2) of the present invention is specifically carried out as follows: in a reaction vessel, use bisphenol A and methanesulfonic acid. Under a nitrogen atmosphere, heat to reflux and maintain for 5 - 10 h, then cool to room temperature, slowly pour into an ice - water mixture. A brown precipitate appears. Wash the precipitate with water 5 - 7 times, and vacuum - dry the precipitate at 50 °C for 24 h to obtain the 6,6 - dihydroxy - 3,3,3,3 - tetramethyl - 1,1 - spirobiindane monomer shown in formula (II).

[0026] As a further preference, in step (2), the molar ratio of the feed of bisphenol A to methanesulfonic acid is 7 - 9:1, and most preferably 8.4:1.

[0027] As a preference, in step (3), the molar ratio of 2 - (3 - (dimethylamino)propyl)-3,3 - bis(4 - hydroxyphenyl)isoindolinone to 6,6 - dihydroxy - 3,3,3,3 - tetramethyl - 1,1 - spirobiindane is 100% - 60%:0% - 40%, and most preferably 100% - 80%:0% - 20%.

[0028] As a preference, step (3) of the present invention is specifically carried out as follows: add 4,4'-difluorodiphenyl sulfone, 2 - (3 - (dimethylamino)propyl)-3,3 - bis(4 - hydroxyphenyl)isoindolinone shown in formula (I), 6,6 - dihydroxy - 3,3,3,3 - tetramethyl - 1,1 - spirobiindane shown in formula (II), polar aprotic solvent B, salt - forming agent potassium carbonate, and water - carrying agent into a reaction vessel. Under nitrogen protection, stir and react at 100 - 180 °C for 4 - 24 h. After the reaction is completed, separate and dry to obtain the main - chain polyarylether sulfone.

[0029] As a further preference, in step (3), the polar aprotic solvent B is at least one of N,N - dimethylacetamide, N,N - dimethylformamide, and N - methylpyrrolidone.

[0030] As a further preference, in step (3), the mass dosage of the salt - forming agent potassium carbonate is 5.0 - 6.5 g / 20 mmol based on the amount of substance of 4,4'-difluorodiphenyl sulfone.

[0031] As a further preference, the water - carrying agent is toluene, and the volume ratio of toluene to polar aprotic solvent B is 0.2 - 0.7:1.

[0032] As a further preference, in step (4), the polar solvent C is one or more of dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), and dimethyl sulfoxide (DMSO).

[0033] As a further preference, the conditions for the co-polycondensation reaction are: reacting at 120–145 °C (more preferably 145 °C) for 3–5 h (more preferably 4 h), and then reacting at 145–165 °C (more preferably 165 °C) for 2–4 h (more preferably 3 h).

[0034] As a further preference, in step (3), the separation and drying are carried out as follows: after cooling the reaction solution to room temperature, it is slowly poured into ethanol and stirred to form a precipitate, then the precipitate is collected by filtration, washed several times with ethanol and water, and then vacuum dried at 60–120 °C for 10–48 h to obtain the main-chain polyarylethersulfone.

[0035] As a preference, in step (4), the molar ratio of polyarylethersulfone to 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1,1,1,2,2-pentafluoro-4-iodobutane, and 1,1,2,2-tetrahydroperfluorohexyl iodide is 0.4–1.00:1.

[0036] As a further preference, in step (3), the molar ratio of polyarylethersulfone to 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1,1,1,2,2-pentafluoro-4-iodobutane, and 1,1,2,2-tetrahydroperfluorohexyl iodide is 0.6–1.00:1.

[0037] As a preference, in step (4), the mass-volume concentration of polyarylethersulfone in the casting solution is 5%.

[0038] As a preference, in step (4), the reaction conditions are: reacting at 60 °C for 18–36 h.

[0039] As a further preference, in step (3), the reaction conditions are: reacting at 60 °C for 24 h.

[0040] The side-chain type anion exchange membrane prepared by the present invention has advantages such as good ionic conductivity, good dimensional stability, and high monovalent anion permeation selectivity, and particularly has broad application prospects in the field of electrodialysis applications.

[0041] Compared with the prior art, the advantages of the present invention are as follows:

[0042] (1) A monovalent anion highly permeable anion exchange membrane according to the present invention forms a continuous ion transport channel by regulating the hydrophobic segment, hydrophilic segment, and the length of the alkyl chain in the side chain, and inducing hydrophilic-hydrophobic microphase separation in the membrane through side chain grafting, forming an efficient ion transfer rate and an excellent selective ion transport channel, so that the membrane has good monovalent anion selectivity.

[0043] (2) A monovalent anion highly permeable anion exchange membrane according to the present invention contains an N-ring QA cation due to its rigid and twisted structure, and the molecular chains cannot be effectively stacked, forming a unique ion channel with selective ion transport, having high flux while having good selectivity.

[0044] (3) A monovalent anion highly permeable anion exchange membrane according to the present invention introduces appropriate free volume or micropores in the membrane to reduce the ion conduction resistance in the membrane, achieve relatively high conductivity at a lower IEC, and make the membrane have a lower surface resistance; at the same time, the homogeneous membrane structure formed by the chemical bond between the conductive side chain and the rigid main chain ensures the mechanical stability of the membrane. Detailed implementation manners

[0045] To further illustrate the technical solution of the present invention, the preferred implementation manners of the present invention are described below in conjunction with specific embodiments.

[0046] Example 1

[0047] Preparation of monomer (I): Weigh 100 mL (18 mmol) of N,N'-dimethyl-1,3-propanediamine into a reaction vessel, then add 40 g (18 mmol) of 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein). Under a nitrogen atmosphere, heat to reflux and maintain for 48 h, then cool to room temperature, slowly pour into an ice-water mixture, and then dropwise add 0.1 M dilute hydrochloric acid for neutralization. A white precipitate appears. The precipitate is washed 6 times with water and dried in vacuo at 40 °C for 24 h to obtain 2-(3-(dimethylamine)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer shown in formula (I).

[0048] Preparation of monomer (II): Weigh 60 g (263 mmol) of bisphenol A into a reaction vessel, then add 3 g (31 mmol) of methanesulfonic acid. Under a nitrogen atmosphere, heat to reflux and maintain for 5 h, then cool to room temperature, slowly pour into an ice-water mixture. A brown precipitate appears. The precipitate is washed 6 times with water and dried in vacuo at 50 °C for 24 h to obtain 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer shown in formula (II).

[0049] Preparation of the main chain: 5.0804 g (20 mmol) of 4,4'-difluorodiphenyl sulfone and 8.0498 g (20 mmol) of 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer were added to a 250 mL three-necked round-bottom flask equipped with a water separator. Using NMP (80 mL) as the solvent, 5.5 g of K 2 CO 3 and 45 mL of toluene were added as the catalyst and water carrier, respectively. Under a N 2 atmosphere, the reaction was carried out at 155 °C for 6 h and then at 165 °C for 12 h. After the solution was cooled to room temperature, it was poured into 300 mL of ethanol. Under high-speed stirring, a precipitate was flocculated. After filtration and separation, a yellow solid was obtained, which was washed repeatedly with ethanol and water, and dried in vacuo at 80 °C for 24 h to obtain 10.5 g of an alternating structure polyarylether sulfone of 4,4'-difluorodiphenyl sulfone and 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone, with a molecular weight Mn = 78200.

[0050] Preparation of the anion exchange membrane: 5 g of polyarylether sulfone was weighed into a three-necked round-bottom flask and dissolved in 30 mL of NMP solvent. It was magnetically stirred at 80 °C until completely dissolved, and then 0.995 g of 1-bromopropane was added. After stirring, a casting solution was obtained; the casting solution was degassed, and then the degassed casting solution was poured onto a clean glass mold and dried into a film at 80 °C for 24 h to obtain a polyarylether sulfone anion exchange membrane.

[0051] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were tested by the national standard method; the surface resistance, transference number, permeability selectivity, and ion flux of the ion exchange membrane were tested by a self-made device. The results are shown in Table 1. (For the specific test method, see the literature reports: Journal of Membrane Science 574 (2019) 181–195; Journal of Membrane Science 577 (2019) 153–164).

[0052] Example 2

[0053] Preparation of the monomer: The same preparation process as in Example 1 was adopted.

[0054] Preparation of the main chain: The same preparation process as in Example 1 was adopted, except that 5.0804 g (20 mmol) of 4,4'-difluorodiphenyl sulfone, 7.2448 g (18 mmol) of 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer, and 0.6168 g (2 mmol) of 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer were added. After reaction, 10.6 g of polyarylether sulfone with a 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone content of 90% was obtained, and its molecular weight was measured to be a number-average molecular weight of 76,800.

[0055] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 0.9100 g of 1-bromopropane was added. After reaction and drying, a polyarylether sulfone anion exchange membrane was obtained.

[0056] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574 (2019) 181–195; Journal of Membrane Science 577 (2019) 153–164).

[0057] Example 3

[0058] Preparation of the monomer: The same preparation process as in Example 1 was adopted.

[0059] Preparation of the main chain: The same preparation process as in Example 1 was adopted, except that 5.0804 g (20 mmol) of 4,4'-difluorodiphenyl sulfone, 6.4398 g (16 mmol) of 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer, and 1.2337 g (4 mmol) of 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer were added. After reaction, 10.9 g of polyarylether sulfone with a 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone content of 80% was obtained, and its molecular weight was measured to be a number-average molecular weight of 89,700.

[0060] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 0.825 g of 1-bromopropane was added. After reaction and drying, an anion exchange membrane was obtained.

[0061] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeability selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0062] Example 4

[0063] Preparation of the monomer: The same preparation process as in Example 1 was used.

[0064] Preparation of the main chain: The same preparation process as in Example 1 was used, except that 5.0804 g (20 mmol) of 4,4'-difluorodiphenyl sulfone, 5.6348 g (14 mmol) of 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer, and 1.851 g (6 mmol) of 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer were added. After the reaction, 11.3 g of polyarylethersulfone with a 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone content of 70% was obtained, and its molecular weight was measured to be a number-average molecular weight of 89700.

[0065] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was used, except that 0.73 g of 1-bromopropane was added. After the reaction and drying, an anion exchange membrane was obtained.

[0066] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeability selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0067] Example 5

[0068] Preparation of the monomer: The same preparation process as in Example 1 was used.

[0069] Preparation of the main chain: The same preparation process as in Example 1 was used.

[0070] Preparation of anion exchange membrane: The same preparation process as in Example 1 was used, except that 1.45 g of 1-bromoheptane was added, and the anion exchange membrane was obtained through reaction and drying.

[0071] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeability selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, please refer to the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0072] Example 6

[0073] Preparation of monomer: The same preparation process as in Example 1 was used.

[0074] Preparation of main chain: The same preparation process as in Example 1 was used.

[0075] Preparation of anion exchange membrane: The same preparation process as in Example 1 was used, except that 2.22 g of 1,1,1,2,2-pentafluoro-4-iodobutane was added, and the anion exchange membrane was obtained through reaction and drying.

[0076] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeability selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, please refer to the literature reports:

[0077] Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0078] Example 7

[0079] Preparation of monomer: The same preparation process as in Example 1 was used.

[0080] Preparation of main chain: The same preparation process as in Example 1 was used.

[0081] Preparation of anion exchange membrane: The same preparation process as in Example 1 was used, except that 3.03 g of 1,1,2,2-tetrahydroperfluorohexyl iodide was added, and the anion exchange membrane was obtained through reaction and drying.

[0082] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574 (2019) 181–195; Journal of Membrane Science 577 (2019) 153–164).

[0083] Example 8

[0084] Preparation of the monomer: The same preparation process as in Example 1 was used.

[0085] Preparation of the main chain: The same preparation process as in Example 2 was used.

[0086] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was used, except that 1.325 g of 1-bromoheptane was added, and the anion exchange membrane was obtained through reaction and drying.

[0087] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574 (2019) 181–195; Journal of Membrane Science 577 (2019) 153–164).

[0088] Example 9

[0089] Preparation of the monomer: The same preparation process as in Example 1 was used.

[0090] Preparation of the main chain: The same preparation process as in Example 2 was used.

[0091] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was used, except that 2.025 g of 1,1,1,2,2-pentafluoro-4-iodobutane was added, and the anion exchange membrane was obtained through reaction and drying.

[0092] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0093] Example 10

[0094] Preparation of the monomer: The same preparation process as in Example 1 was adopted.

[0095] Preparation of the main chain: The same preparation process as in Example 2 was adopted.

[0096] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 2.77 g of 1,1,2,2-tetrahydroperfluorohexyl iodide was added, and the anion exchange membrane was obtained through reaction and drying.

[0097] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0098] Example 11

[0099] Preparation of the monomer: The same preparation process as in Example 1 was adopted.

[0100] Preparation of the main chain: The same preparation process as in Example 3 was adopted.

[0101] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 1.20 g of 1-bromoheptane was added, and the anion exchange membrane was obtained through reaction and drying.

[0102] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports:

[0103] Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0104] Example 12

[0105] Preparation of monomer: The same preparation process as in Example 1 was adopted.

[0106] Preparation of main chain: The same preparation process as in Example 3 was adopted.

[0107] Preparation of anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 1.835 g of 1,1,1,2,2-pentafluoro-4-iodobutane was added, and the anion exchange membrane was obtained through reaction and drying.

[0108] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using the national standard method; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0109] Example 13

[0110] Preparation of monomer: The same preparation process as in Example 1 was adopted.

[0111] Preparation of main chain: The same preparation process as in Example 3 was adopted.

[0112] Preparation of anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 2.505 g of 1,1,2,2-tetrahydroperfluorohexyl iodide was added, and the anion exchange membrane was obtained through reaction and drying.

[0113] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using the national standard method; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0114] Example 14

[0115] Preparation of monomer: The same preparation process as in Example 1 was adopted.

[0116] Preparation of the main chain: The same preparation process as in Example 4 was adopted.

[0117] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 1.065 g of 1-bromoheptane was added, and the anion exchange membrane was obtained through reaction and drying.

[0118] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0119] Example 15

[0120] Preparation of monomer: The same preparation process as in Example 1 was adopted.

[0121] Preparation of the main chain: The same preparation process as in Example 4 was adopted.

[0122] Preparation of the anion exchange membrane: The same preparation process as in Example 1 was adopted, except that 1.63 g of 1,1,1,2,2-pentafluoro-4-iodobutane was added, and the anion exchange membrane was obtained through reaction and drying.

[0123] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were experimentally tested using national standard methods; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested using a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574(2019)181–195; Journal of Membrane Science 577(2019)153–164).

[0124] Example 16

[0125] Preparation of monomer: The same preparation process as in Example 1 was adopted.

[0126] Preparation of the main chain: The same preparation process as in Example 4 was adopted.

[0127] Preparation of anion exchange membrane: The same preparation process as in Example 1 was used, except that 2.225 g of 1,1,2,2-tetrahydroperfluorohexyl iodide was added. After reaction and drying, an anion exchange membrane was obtained.

[0128] The thickness, ion exchange capacity, tensile strength, and swelling ratio of the prepared monovalent anion-selective anion exchange membrane were tested by the national standard method; the surface resistance, transference number, permeation selectivity, and ion flux of the ion exchange membrane were tested by a self-made device. The results are shown in Table 1. (For the specific test methods, see the literature reports: Journal of Membrane Science 574 (2019) 181–195; Journal of Membrane Science 577 (2019) 153–164).

[0129]

[0130] Table 1.

Claims

1. A preparation method of a high-permeation-flux monovalent-selective anion exchange membrane, characterized in that it includes the following steps: Step (1) Preparation of monomer (I): N,N-dimethyl-1,3-propanediamine and 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein) are refluxed under a nitrogen atmosphere at 160 °C to prepare 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer shown in formula (I); Step (2) Preparation of monomer (II): Bisphenol A is refluxed under the catalysis of methanesulfonic acid in a nitrogen atmosphere at 160 °C to prepare 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer shown in formula (II); Step (3) Preparation of the main chain structure: The 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer shown in formula (I), 4,4'-difluorodiphenyl sulfone monomer and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer shown in formula (II) are co-polycondensed in a solvent to obtain a polyarylether sulfone with an amino-phenolphthalein structure in the main chain, and the structural formula is as shown in formula (Ⅲ); wherein, the total molar amount of 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane is in a ratio of 1:1 to the molar amount of 4,4'-difluorodiphenyl sulfone, and the molar ratio of the 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobiindane monomer is x: 100 - x = 80% - 60%: 20% - 40%; the number-average molecular weight Mn of the polyarylether sulfone is 50000 - 120000; Step (4) Alkylation functionalization of the main chain structure and preparation of the anion exchange membrane: The polyarylether sulfone shown in formula (Ⅲ) prepared in step (3) is dissolved in a polar solvent C, and then one of the compounds shown in formula (IV) - formula (IX) is added. The molar ratio of the polyarylether sulfone to one of the compounds shown in formula (IV) - formula (IX) is 0.4 - 1.00:

1. After stirring for a certain period of time and standing for defoaming, a casting solution is obtained. The mass-volume concentration of the polyarylether sulfone in the casting solution is 3 - 8%; the polar solvent C is one or more of DMF, DMAc, and NMP. The obtained casting solution is poured onto a glass plate and in-situ reaction and drying are carried out at 40 - 200 °C for 12 - 96 h. After cooling, the film is peeled off from the glass plate in water to obtain an alkyl-functionalized anion exchange membrane, and its structural formula is as shown in formula (V V), with a thickness of 70 - 150 μm; wherein, x: 100% - x = 80% - 60%: 20% - 40%.

2. The preparation method of the high-permeation-flux monovalent-selective anion exchange membrane according to claim 1, characterized in that: Step (1) is specifically implemented as follows: In a reaction vessel, N,N-dimethyl-1,3-propanediamine and 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein) are used. Under a nitrogen atmosphere, it is heated to reflux and maintained for 12 - 48 h, and then cooled to room temperature. It is slowly poured into an ice-water mixture, and then dilute hydrochloric acid is added dropwise. A white precipitate appears. The precipitate is washed with water 5 - 7 times, and the precipitate is vacuum dried at 30 - 80 °C for 24 - 48 h to obtain the 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer shown in formula (I).

3. The preparation method of the high-permeability flux monovalent selective anion exchange membrane according to claim 2, characterized in that: In step (1), the molar ratio of the feed of N,N-dimethyl-1,3-propanediamine to 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein) is 1.0 - 2.5:1; the dilute hydrochloric acid solution is an aqueous hydrochloric acid solution with pH = 0 - 1.

4. The preparation method of the high-permeability flux monovalent selective anion exchange membrane according to claim 2, characterized in that: In step (1), the precipitate is vacuum dried at 50 °C for 48 h.

5. The preparation method of the high-permeability flux monovalent selective anion exchange membrane according to claim 1, characterized in that: Step (2) is specifically implemented as follows: In a reaction vessel, bisphenol A and methanesulfonic acid are used. Under a nitrogen atmosphere, it is heated to reflux and maintained for 5 - 10 h, and then cooled to room temperature. It is slowly poured into an ice-water mixture, and a brown precipitate appears. The precipitate is washed with water 5 - 7 times, and the precipitate is vacuum dried at 50 °C for 24 h to obtain the 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane monomer shown in formula (II).

6. The preparation method of the high-permeability flux monovalent selective anion exchange membrane according to claim 5, characterized in that: In step (2), the molar ratio of the feed of bisphenol A to methanesulfonic acid is 7 - 9:

1.

7. The preparation method of the high-permeability flux monovalent selective anion exchange membrane according to claim 1, characterized in that: Step (3) is specifically implemented as follows: 4,4'-Difluorodiphenyl sulfone, 2-(3-(dimethylamino)propyl)-3,3-bis(4-hydroxyphenyl)isoindolinone shown in formula (I), and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane shown in formula (II), polar aprotic solvent B, salt-forming agent potassium carbonate, and water-carrying agent are added to a reaction vessel. Under nitrogen protection, it is stirred and reacted at 100 - 180 °C for 4 - 24 h. After the reaction is completed, the main-chain polyarylether sulfone is obtained through separation and drying.

8. The preparation method of the high-permeability flux monovalent selective anion exchange membrane according to claim 7, characterized in that: In step (3), the polar aprotic solvent B is at least one of N,N-dimethylacetamide, N,N-dimethylformamide, and N-methylpyrrolidone; the mass dosage of the salt-forming agent potassium carbonate is 5.0 - 6.5 g / 20 mmol based on the amount of substance of 4,4'-difluorodiphenyl sulfone; the water-carrying agent is toluene, and the volume ratio of the toluene to the polar aprotic solvent B is 0.2 - 0.7:

1.

9. The method for preparing a high permeation flux monovalent selective anion exchange membrane according to claim 7, characterized in that: the conditions for the co-polycondensation reaction in step (3) are: reacting at 120 - 145 °C for 3 - 5 h; in step (3), the separation and drying are carried out as follows: after cooling the reaction solution to room temperature, slowly pour it into ethanol and stir to produce a precipitate, then filter to collect the precipitate, wash it several times with ethanol and water, and then vacuum dry it at 60 - 120 °C for 10 - 48 h to obtain the main chain polyarylether sulfone.

10. The method for preparing a high permeation flux monovalent selective anion exchange membrane according to claim 1, characterized in that: in step (4), the mass-volume concentration of the polyarylether sulfone in the casting solution is 5%; the reaction conditions are: reacting at 60 °C for 18 - 36 h.

Images