CN116355254A - Preparation method of monovalent selective anion exchange membrane with high permeation flux - Google Patents

Abstract

The invention relates to the field of polymer high polymer materials, and particularly discloses a preparation method of a monovalent anion exchange membrane with high permeation capacity. The side chain type anion exchange membrane prepared by the invention has the advantages of good ion conductivity, good dimensional stability, higher monovalent anion permeation selectivity and the like, and particularly has wide application prospect in the electrodialysis application field.

Description

A kind of preparation method of monovalent selective anion exchange membrane with high permeation flux

technical field

The invention relates to the field of polymer polymer materials, in particular to a preparation method of an anion exchange membrane with high permeability of monovalent anions, and belongs to the field of membrane technology.

Background technique

The improvement of ion precision separation technology is of great significance to the sustainable development of chemical industry production, and can further meet the needs of major national strategic goals of "double carbon" such as energy conservation, emission reduction and transformation and upgrading of traditional industries. Precise ion separation refers to the concentration and recovery of a certain target ion in a specific system. In actual demand, salt production from seawater, lithium extraction from salt lakes, brine refining in the chlor-alkali industry, and recycling of waste acid/alkali in the metallurgical industry all require the separation of ions with the same charge and different valence states. 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, because the main component monovalent/divalent ion membrane allows the permeation of monovalent ions but prevents the permeation of divalent or multivalent ions, has been used in energy conversion, chlor-alkali industrial brine purification, high-salt wastewater recycling, It has shown its unique advantages in the application of waste acid and alkali recycling and salt lake lithium extraction. If the traditional ion membrane in the ordinary electrodialysis membrane stack is partially replaced or a monovalent/divalent ion membrane is added, selective electrodialysis can be constructed. At present, the development of monovalent/divalent ion membrane technology has been greatly improved, but there are still some challenges. (1) The long-term stability is poor. For example, the acid or alkali generated under the action of an electric field can easily destroy the structure of the modified layer and weaken the force between the polyelectrolyte skin layer and the base film, so that the charge repulsion effect on multivalent ions is weakened. (2) The operating current density is low. Selective electrodialysis operates at a lower current, which can be attributed to the lower limiting current density of the mono/divalent ion membrane.

Under the condition of ensuring the appropriate selectivity of the ionic membrane, the spiro ring structure, the fluorenyl Cardo ring structure, the bibendazole structure, etc. are introduced into the main chain, and the twisted folding structure and rigidity are used to prevent the effective stacking of the molecules and prevent the formation of the structure. Relaxation and loss of micropores, thereby creating free volume in the polymer membrane to form micropores (ion channels) to help promote the efficient transmission of monovalent ions, and build a class of structurally stable high permeable flux and selectivity ion exchange membrane.

Contents of the invention

The technical problem solved by the present invention is to provide a method for side chain anion exchange membrane with twisted structure.

In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:

The preparation of step (1) monomer (I):

N,N-Dimethyl-1,3-propanediamine and 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein) were treated under nitrogen atmosphere at 160°C Reflux reaction, prepared 2-(3-(dimethylamine) propane group)-3,3-bis(4-hydroxyphenyl) isoindolinone monomer shown in formula (I);

The preparation of step (2) monomer (II):

Bisphenol A is catalyzed by methanesulfonic acid, under nitrogen atmosphere, and reflux reaction at 160 ° C to prepare 6,6-dihydroxy-3,3,3,3-tetramethyl as shown in formula (II) Base-1,1-spirobisindane monomer;

Step (3) preparation of structural main chain:

2-(3-(dimethylamino)propane)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer represented by formula (I), 4,4'-difluoro Diphenylsulfone monomer and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spirobisindane monomer represented by formula (II) are obtained through solvent co-condensation Amino-phenolphthalein polyaryl ether sulfone, such as formula (III). Among them, 2-(3-(dimethylamino)propanyl)-3,3-bis(4-hydroxyphenyl)isoindolinone and 6,6-dihydroxy-3,3,3,3- The ratio of the total substance amount of tetramethyl-1,1-spirobisindane to the amount of substance of 4,4'-difluorodiphenyl sulfone is 1:1, and the 2-(3-(dimethyl Amino)propanyl)-3,3-bis(4-hydroxyphenyl)isoindolinone monomer and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1-spiro The molar ratio of the bisindane monomer is x: 100-x=100%-60%: 0%-40%; the number average molecular weight Mn of the polyarylethersulfone is 50000-120000.

Step (4) Alkyl functionalization of structural main chain and preparation of anion exchange membrane:

Dissolve the polyarylethersulfone represented by 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-butyliodane (Ⅷ), 1, 1,2,2-Tetrahydroperfluorohexyliodane (IX) was stirred for a certain period of time, and left to stand for degassing to obtain a casting solution. The mass volume concentration of polyarylethersulfone in the casting solution was 3-8%; The above-mentioned organic solvent is one or more of DMF, DMAc, NMP, and the obtained casting solution is poured on a glass plate, and kept at 40-200°C for 12-96 hours to realize in-situ reaction and drying, and after cooling, place it in water The film is peeled off from the glass plate to obtain an alkyl functionalized anion exchange membrane, the structural formula of which is shown in formula (V), and the thickness is 70-150 μm.

Among them, x: 100% - x = 100% ~ 60%: 0% ~ 40%;

As a preference, 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 nitrogen atmosphere, heated to reflux, kept for 12-48h, then cooled to room temperature, slowly poured into ice-water mixture, and then added dropwise dilute hydrochloric acid, white precipitate appeared, precipitated Wash 5 to 7 times with water, and dry the precipitate under vacuum at 40°C for 48 hours to obtain 2-(3-(dimethylamine)propane)-3,3-bis(4-hydroxyphenyl) represented by formula (I) ) isoindolinone monomer.

As a further preference, in step (1), the N,N-dimethyl-1,3-propanediamine and 3,3-bis(4-hydroxyphenyl)-3H-isobenzofuranone ( The molar ratio of phenolphthalein) is 1.0-2.5:1, most preferably 1.2:1.

As a further preference, in step (1), the dilute hydrochloric acid solution is an aqueous hydrochloric acid solution with pH=0-1 (most preferably pH=0).

As a further preference, in step (1), the separation and purification are carried out as follows: under a nitrogen atmosphere, heat to reflux, keep for 12-48h, then cool to room temperature, slowly pour into the ice-water mixture, and then gradually Dilute hydrochloric acid was added dropwise, and a white precipitate appeared. The precipitate was washed with water for 5-7 times, and the precipitate was vacuum-dried at 30-80° C. (more preferably 50° C.) for 24-48 hours (more preferably 48 hours).

As a preference, step (2) of the present invention is specifically implemented as follows: in a reaction vessel, use bisphenol A and methanesulfonic acid, heat to reflux under a nitrogen atmosphere, keep for 5-10h, then cool to room temperature, and slowly pour into the ice-water mixture, a brown precipitate appeared, and the precipitate was washed with water for 5 to 7 times, and the precipitate was vacuum-dried at 50°C for 24 hours to obtain 6,6-dihydroxy-3,3,3,3- Tetramethyl-1,1-spirobisindane monomer.

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

As a preference, in step (3), the 2-(3-(dimethylamino)propanyl)-3,3-bis(4-hydroxyphenyl)isoindolinone and 6,6-dihydroxy - The molar ratio of 3,3,3,3-tetramethyl-1,1-spirobisindane is 100%～60%: 0%～40%, most preferably 100%～80%: 0%～20 %.

As a preference, step (3) of the present invention is specifically implemented as follows: add 4,4'-difluorodiphenyl sulfone and 2-(3-(dimethylamine)propane group represented by formula (I) to the reaction vessel )-3,3-bis(4-hydroxyphenyl)isoindolinone and 6,6-dihydroxy-3,3,3,3-tetramethyl-1,1- Spirobisindane, polar aprotic solvent B, salt-forming agent potassium carbonate and water-carrying agent are stirred and reacted at 100-180°C for 4-24 hours under the protection of nitrogen. After the reaction, the main chain polymer is obtained by separation and drying. Aryl ether sulfone.

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 .

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

As a further preference, 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.

As a further preference, in step (4), the polar solvent C is dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylmethylene One or more of sulfone (DMSO).

As a further preference, the co-condensation reaction conditions are: react at 120-145°C (more preferably 145°C) for 3-5h (more preferably 4h), then react at 145-165°C (more preferably 165°C) for 2-4h ( More preferably 3h).

As a further preference, in step (3), the separation and drying are carried out as follows: after the reaction solution is cooled to room temperature, it is slowly poured into ethanol and stirred to generate a precipitate, and then the precipitate is collected by filtration, washed with ethanol and water for several After the second time, vacuum-dry at 60-120°C for 10-48 hours to obtain the main chain polyarylethersulfone.

As a preference, in step (4), polyarylethersulfone is mixed with 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1,1,1,2,2-pentafluoro The molar ratio of -4-butane iodane to 1,1,2,2-tetrahydroperfluorohexyl iodane is 0.4-1.00:1.

As a further preference, in step (3), polyarylethersulfone is mixed with 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1,1,1,2,2- The molar ratio of pentafluoro-4-butyl iodide to 1,1,2,2-tetrahydroperfluorohexyl iodide is 0.6-1.00:1.

Preferably, in step (4), the mass volume concentration of polyarylethersulfone in the casting solution is 5%.

Preferably, in step (4), the reaction conditions are: react at 60° C. for 18-36 hours.

As a further preference, in step (3), the reaction condition is: react at 60° C. for 24 hours.

The side chain type anion exchange membrane prepared by the invention has the advantages of good ion conductivity, good dimensional stability, high permeation selectivity of monovalent anions, etc., and has broad application prospects in the field of electrodialysis application.

Compared with the prior art, the present invention has the advantages of:

(1) A monovalent anion high permeability anion exchange membrane according to the present invention, by regulating the length of the alkyl chain in the hydrophobic segment and the hydrophilic segment and the side chain, the hydrophilic and hydrophobic membrane is induced in the membrane by the side chain grafting method The microphase separation forms continuous ion transport channels, forming high-efficiency ion transport rates and excellent selective ion transport channels, so that the membrane has good monovalent anion selectivity.

(2) A kind of monovalent anion high permeability anion exchange membrane of the present invention, because its rigidity and twisted structure contain N ring QA cation, molecular chain can not be piled up effectively, and forms the unique ion channel with selective ion transmission in High throughput with good selectivity.

(3) a kind of monovalent anion high permeability anion exchange membrane of the present invention introduces suitable free volume or micropore in the membrane, reduces the ion conduction resistance in the membrane, realizes the relatively high electrical conductivity under lower IEC, makes The film has a low surface resistance; at the same time, the homogeneous film structure formed by the chemical bonds between the conductive side chain and the rigid main chain ensures the mechanical stability of the film.

Detailed ways

In order to further illustrate the technical solution of the present invention, preferred embodiments of the present invention are described below in conjunction with specific examples.

Example 1

Preparation of monomer (I): Weigh 100mL (18mmol) of N,N'-dimethyl-1,3-propanediamine in a reaction vessel, then add 40 grams (18mmol) of 3,3-di( 4-Hydroxyphenyl)-3H-isobenzofuranone (phenolphthalein), under nitrogen atmosphere, heated to reflux for 48h, then cooled to room temperature, slowly poured into ice-water mixture, and then added dropwise 0.1M neutralized with dilute hydrochloric acid, a white precipitate appeared, the precipitate was washed 6 times with water, and the precipitate was vacuum-dried at 40° C. for 24 hours to obtain 2-(3-(dimethylamino)propane)-3 represented by formula (I), 3-bis(4-hydroxyphenyl)isoindolinone monomer.

Preparation of monomer (II): Weigh 60g (263mmol) of bisphenol A in a reaction vessel, then add 3g (31mmol) of methanesulfonic acid, heat to reflux under nitrogen atmosphere, keep for 5h, then cool to Slowly pour into the ice-water mixture at room temperature, a brown precipitate appears, wash the precipitate 6 times with water, and dry the precipitate in vacuum at 50°C for 24 hours to obtain 6,6-dihydroxy-3,3,3 ,3-Tetramethyl-1,1-spirobisindane monomer.

Preparation of the main chain: 5.0804 grams (20mmol) of 4,4'-difluorodiphenyl sulfone and 8.0498 grams (20mmol) of 2-(3-(dimethylamino)propanyl)-3,3-bis( 4-Hydroxyphenyl) isoindolinone monomer was added into a 250mL three-necked round-bottomed flask equipped with a water separator, and NMP ( _80mL ) was used as a solvent, and 5.5 grams of _K2CO3 and 45mL toluene were added simultaneously As catalyst and water carrier. Under _N2 atmosphere, react 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, stirred at high speed, and flocculated to obtain a precipitate. After separation by suction filtration, a yellow solid was obtained, which was repeatedly washed with ethanol and water, and dried in vacuum at 80°C for 24 hours to obtain 10.5 g of 4,4'-difluorodiphenyl sulfone and 2-(3-(dimethylamine) Propanyl)-3,3-bis(4-hydroxyphenyl)isoindolinone alternating structure polyarylethersulfone, its molecular weight Mn=78200.

Preparation of anion-exchange membrane: Weigh 5 grams of polyarylethersulfone into a round-bottomed three-necked flask, dissolve it in 30 mL of NMP solvent, stir it magnetically at 80°C until completely dissolved, then add 0.995 grams of 1-bromopropane, The casting liquid is obtained after stirring; the casting liquid is defoamed, and then the defoamed casting liquid is poured into a clean glass mold, and dried at 80° C. for 24 hours to form a film to obtain a polyarylethersulfone anion exchange membrane.

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

Example 2

Preparation of monomer: the same preparation process as in Example 1 was adopted.

Preparation of the main chain: the same preparation process as in Example 1 was adopted, except that 5.0804 grams (20 mmol) of 4,4'-difluorodiphenyl sulfone and 7.2448 grams (18 mmol) of 2-(3-(di Methylamino) propane) -3,3-bis(4-hydroxyphenyl) isoindolinone monomer and 0.6168 g (2 mmol) of 6,6-dihydroxy-3,3,3,3-tetra Methyl-1,1-spirobisindane monomer, reacted to obtain 10.6 g of 2-(3-(dimethylamino)propane)-3,3-bis(4-hydroxyphenyl)isoindole Polyaryl ether sulfone with a ketone content of 90% has a number average molecular weight of 76,800.

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 0.9100 g of 1-bromopropane was added, and the polyarylethersulfone anion-exchange membrane was obtained through reaction and drying.

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

Example 3

Preparation of monomer: the same preparation process as in Example 1 was adopted.

Preparation of the main chain: the same preparation process as in Example 1 was adopted, except that 5.0804 grams (20 mmol) of 4,4'-difluorodiphenyl sulfone and 6.4398 grams (16 mmol) of 2-(3-(di Methylamino) propane) -3,3-bis(4-hydroxyphenyl) isoindolinone monomer and 1.2337 g (4 mmol) of 6,6-dihydroxy-3,3,3,3-tetra Methyl-1,1-spirobisindane monomer was reacted to obtain 10.9 grams of 2-(3-(dimethylamino)propane)-3,3-bis(4-hydroxyphenyl)isoindole Polyaryl ether sulfone with ketone content of 80% has a molecular weight of 89,700.

Preparation of anion-exchange membrane: adopt the same preparation process as in Example 1, the only difference is that 0.825 grams of 1-bromopropane is added, and anion-exchange membrane is obtained through reaction and drying.

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

Example 4

Preparation of monomer: the same preparation process as in Example 1 was adopted.

Preparation of the main chain: the same preparation process as in Example 1 was adopted, except that 5.0804 grams (20 mmol) of 4,4'-difluorodiphenyl sulfone and 5.6348 grams (14 mmol) of 2-(3-( Dimethylamino) propane) -3,3-di(4-hydroxyphenyl) isoindolinone monomer and 1.851 g (6 mmol) of 6,6-dihydroxy-3,3,3,3- Tetramethyl-1,1-spirobisindane monomer, reacted to obtain 11.3 grams of 2-(3-(dimethylamine)propane)-3,3-bis(4-hydroxyphenyl)isoindane The molecular weight of the polyarylether sulfone with a dorinone content of 70% was 89,700 in number average.

Preparation of anion-exchange membrane: adopt the same preparation process as in Example 1, the only difference is that 0.73 grams of 1-bromopropane is added, and anion-exchange membrane is obtained through reaction and drying.

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

Example 5

Preparation of monomer: the same preparation process as in Example 1 was adopted.

Preparation of the main chain: the same preparation process as in Example 1 was adopted.

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 1.45 grams of 1-bromoheptane was added, and anion-exchange membrane was obtained through reaction and drying.

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

Example 6

Preparation of monomer: the same preparation process as in Example 1 was adopted.

Preparation of the main chain: the same preparation process as in Example 1 was adopted.

Preparation of anion-exchange membrane: the same preparation process as in Example 1 was adopted, the only difference being that 2.22 grams of 1,1,1,2,2-pentafluoro-4-butyliodane was added, and the anion exchange membrane was obtained by reaction and drying membrane.

The thickness, ion exchange capacity, tensile strength and swelling rate of the prepared monovalent anion selective anion exchange membrane were tested by the national standard method; the surface resistance, transfer number, permeability selectivity and ion exchange membrane were tested by the self-made device flux. The results are shown in Table 1. (see the literature report for the specific test method:

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

Example 7

Preparation of monomer: the same preparation process as in Example 1 was adopted.

Preparation of the main chain: the same preparation process as in Example 1 was adopted.

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 3.03 grams of 1,1,2,2-tetrahydroperfluorohexyliodane was added, and anion-exchange membrane was obtained through reaction and drying.

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

Example 8

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 1.325 grams of 1-bromoheptane was added, and anion-exchange membrane was obtained through reaction and drying.

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

Example 9

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, the only difference being that 2.025 grams of 1,1,1,2,2-pentafluoro-4-butyliodane was added, and the anion exchange membrane was obtained by reaction and drying membrane.

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

Example 10

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 2.77 grams of 1,1,2,2-tetrahydroperfluorohexyliodane was added, and the anion-exchange membrane was obtained through reaction and drying.

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

Example 11

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

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

The thickness, ion exchange capacity, tensile strength and swelling rate of the prepared monovalent anion selective anion exchange membrane were tested by the national standard method; the surface resistance, transfer number, permeability selectivity and ion exchange membrane were tested by the self-made device flux. The results are shown in Table 1. (see the literature report for the specific test method:

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

Example 12

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: the same preparation process as in Example 1 was adopted, the only difference being that 1.835 grams of 1,1,1,2,2-pentafluoro-4-butyliodane was added, and the anion exchange membrane was obtained by reaction and drying membrane.

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

Example 13

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 2.505 grams of 1,1,2,2-tetrahydroperfluorohexyliodane was added, and anion-exchange membrane was obtained through reaction and drying.

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

Example 14

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

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

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

Example 15

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, the only difference being that 1.63 grams of 1,1,1,2,2-pentafluoro-4-butyliodane was added, and the anion exchange membrane was obtained by reaction and drying membrane.

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

Example 16

Preparation of monomer: the same preparation process as in Example 1 was adopted.

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

Preparation of anion-exchange membrane: The same preparation process as in Example 1 was adopted, except that 2.225 grams of 1,1,2,2-tetrahydroperfluorohexyliodane was added, and anion-exchange membrane was obtained through reaction and drying.

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

Table 1.

Claims (10)

1. The preparation method of the monovalent selective anion exchange membrane with high permeation flux is characterized by comprising the following steps:

preparation of monomer (I) in step (1):

the N, N-dimethyl-1, 3-propylene diamine and 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) are subjected to reflux reaction at 160 ℃ in the nitrogen atmosphere to prepare a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I);

step (2) preparation of monomer (II):

bisphenol A is introduced into a methane sulfonic acid to be catalyzed, and is subjected to reflux reaction at 160 ℃ in the nitrogen atmosphere to prepare a 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan monomer shown in a formula (II);

preparation of the structural main chain in the step (3):

the method comprises the steps of performing solvent copolycondensation on a 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer, a 4,4' -difluoro diphenyl sulfone monomer and a 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindan monomer shown in a formula (II) to obtain polyarylether sulfone with a main chain containing an amino-phenolphthalein structure, wherein the structural formula is shown in a formula (III); wherein the ratio of the total amount of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone and 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane to the amount of 4,4' -difluorodiphenyl sulfone is 1:1, and the molar ratio of 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer to 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer is x:

100-x=100% -60%: 0% -40%; the number average molecular weight Mn=50000-120000 of the polyarylethersulfone;

step (4) preparation of an alkyl functionalized and anion exchange membrane of a structural main chain:

dissolving the polyarylethersulfone represented by the formula (III) prepared in the step (3) in a polar solvent C, and then according to a molar ratio of 1:1.20 to 1.50 of 1-bromopropane shown in a formula (IV), 1-bromopentane shown in a formula (V), 1-bromoheptane shown in a formula (VI), 1-bromononane shown in a formula (VII), 1, 2-pentafluoro-4-Ding Dian alkane shown in a formula (VIII) and 1, 2-tetrahydroperfluorohexane shown in a formula (IX) are respectively added, and stirring for a certain period of time, standing and defoaming are carried out to obtain a casting solution, wherein the mass volume concentration of polyarylethersulfone in the casting solution is 3 to 8 percent; the organic solvent is one or more of DMF, DMAc, NMP, the obtained casting film liquid is poured on a glass flat plate, in-situ reaction and drying are realized by keeping the casting film liquid at 40-200 ℃ for 12-96 hours, after cooling, the film is removed from the glass flat plate in water, and the alkyl functionalized anion exchange membrane is obtained, the structural formula of which is shown in the formula (V V), and the thickness of which is 70-150 mu m;

wherein x:100% -x=100% -60%: 0% -40%.

2. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: the step (1) is specifically implemented as follows: in a reaction vessel, N-dimethyl-1, 3-propylene diamine and 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) are used, heated to reflux under nitrogen atmosphere, kept for 12-48H, cooled to room temperature, slowly poured into an ice-water mixture, then diluted hydrochloric acid is gradually added dropwise, white precipitation appears, the precipitation is washed with water for 5-7 times, and the precipitation is dried in vacuum at 30-80 ℃ for 24-48H to obtain the 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone monomer shown in the formula (I).

3. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 2, wherein: in the step (1), the feeding mole ratio of the N, N-dimethyl-1, 3-propylene diamine to the 3, 3-bis (4-hydroxyphenyl) -3H-isobenzofuranone (phenolphthalein) is 1.0-2.5:1, and most preferably 1.2:1; the dilute hydrochloric acid solution is an aqueous hydrochloric acid solution with a ph=0-1, and most preferably with a ph=0.

4. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 2, wherein: in step (1), the precipitate is more preferably dried under vacuum at 50℃for 48 hours.

5. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: the step (2) is specifically carried out by heating bisphenol A and methane sulfonic acid to reflux in a reaction vessel under nitrogen atmosphere, maintaining for 5-10h, cooling to room temperature, slowly pouring into an ice-water mixture, washing the precipitate with water for 5-7 times, and vacuum drying the precipitate at 50 ℃ for 24h to obtain the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane monomer shown in the formula (II).

6. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 5, wherein: in the step (2), the feeding mole ratio of bisphenol A to methane sulfonic acid is as follows

7-9:1, most preferably 8.4:1.

7. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: the step (3) is specifically implemented as follows: adding 4,4' -difluoro diphenyl sulfone, 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone shown in a formula (I) and 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane shown in a formula (II), a polar aprotic solvent B, a salifying agent potassium carbonate and a water-carrying agent into a reaction container, stirring and reacting for 4-24 hours under the protection of nitrogen at 100-180 ℃, and separating and drying after the reaction is finished to obtain the main chain polyarylethersulfone.

8. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 7, wherein: in the step (3), the molar ratio of the 2- (3- (dimethylamine) propane) -3, 3-bis (4-hydroxyphenyl) isoindolinone to the 6, 6-dihydroxy-3, 3-tetramethyl-1, 1-spirobiindane is preferably 100% -80%: 0% -20%;

the polar aprotic solvent B is at least one of N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone; the mass dosage of the salifying agent potassium carbonate is 5.0-6.5g/20mmol based on the mass of 4,4' -difluorodiphenyl sulfone; the water-carrying agent is toluene, and the volume ratio of toluene to the polar aprotic solvent B is 0.2-0.7:1;

in the step (3), the mass ratio of the polyarylethersulfone to the 1-bromopropane, 1-bromopentane, 1-bromoheptane, 1-bromononane, 1, 2-pentafluoro-4-Ding Dian and 1, 2-tetrahydroperfluorohexane-iodoane is 0.6-1.00 respectively: 1.

9. the method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 7, wherein: the copolycondensation reaction conditions in the step (3) are as follows: reacting at 120-145 ℃, more preferably 145 ℃ for 3-5 hours, more preferably 4 hours, and further reacting at 145-165 ℃, more preferably 165 ℃ for 2-4 hours, more preferably 3 hours;

in the step (3), the separation and drying are carried out as follows: cooling the reaction liquid to room temperature, slowly pouring the reaction liquid into ethanol, stirring to generate precipitate, filtering, collecting the precipitate, washing the precipitate with ethanol and water for several times, and vacuum drying at 60-120 ℃ for 10-48 h to obtain the main chain polyarylethersulfone.

10. The method for preparing a monovalent selective anion exchange membrane with high permeation flux according to claim 1, wherein: in the step (4), the polar solvent C is one or more of Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO); the mass volume concentration of the polyarylethersulfone in the casting solution is 5%; the reaction conditions are as follows: the reaction is carried out for 18 to 36 hours at the temperature of 60 ℃.