CN111499867B - Side chain type random polyether sulphone, preparation method thereof and homogeneous anion exchange membrane - Google Patents
Side chain type random polyether sulphone, preparation method thereof and homogeneous anion exchange membrane Download PDFInfo
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Abstract
The invention discloses a side chain type random polyether sulphone and a preparation method thereofMethods and homogeneous anion exchange membranes. The side chain type random polyarylethersulfone is composed of the following four repeating structural units which are randomly arranged; the number average molecular weight Mn of the side chain type random polyarylethersulfone is 40000-100000; repeating structural unit a:
repeating structural unit B:
repeating structural unit C:
repeating structural unit D:
wherein n is 3 to 12,
Description
Technical Field
The invention relates to the field of composite materials, in particular to side chain type random polyether sulphone, a preparation method thereof and a homogeneous anion exchange membrane prepared from the side chain type random polyether sulphone.
Background
At present, the separation of ions with the same electric property but different valence states in a mixed salt system is an important practical application of the electrodialysis technology. The choice of monovalent selective ionic membranes is crucial for the particular mixed salt system to be separated. However, at present, most commercial ionic membrane products in China are heterogeneous membranes and are mainly used in separation fields such as primary water treatment and the like with relatively low requirements on ion purity. The development of a novel commercialized high-selectivity ionic membrane can reduce the dependence on foreign products and meet the actual requirements of domestic industry, and has important practical significance (Chinese J.chem.Eng.25(2017) 111606-1615; J.Membr.Sci.555(2018) 429-454).
According to the separation mechanism of the pore size sieving effect, the electrostatic repulsion effect or the ion hydration energy difference, the current methods for mainly preparing the ion exchange membrane with the single-multivalent selectivity mainly comprise two methods: the method is characterized in that electrostatic deposition modification and chemical bond grafting modification are utilized to perform crosslinking on the surface of a commercial ionic membrane to form a compact layer or introduce a charge layer. However, the general problems with the preparation of monovalent anion selective ionic membranes using the above surface modification strategies are: (i) the modified layer is unstable; (ii) the selection coefficient is lower
(iii) The membrane surface resistance was high (ACS Sustainable chem. Eng.7(2019) 44429-4442; J.Membr.Sci.599(2020) No. 117818).
From the perspective of molecular design, constructing a homogeneous structure polymer ion membrane with a suitable size ion transfer channel and a stable structure is one of the important strategies to overcome the structural deficiencies of the surface modified separation membrane. However, effective separation of mono/dianions is not achieved by any anion exchange membrane, and the selective separation function of the homogeneous ion membrane requires a certain structural specificity of the polymer used. Homogeneous anion exchange membranes currently reported are relatively few and generally exhibit relatively low monovalent anion permeation flux and selectivity. For example, in an anion exchange membrane prepared using a polyelectrolyte having a structure in which hydrophilic conductive groups are directly connected to hydrophobic main chains, adjacent hydrophilic groups inhibit self-aggregation between the hydrophobic main chains to some extent, resulting in higher water absorption (swelling ratio) and non-through ion channels, while significantly reducing anion selectivity and flux (J.Membr.Sci.553(2018) 43-53; ACS Sustainable chem.Eng.7(2019) 44429-.
Through the structural design and the microstructural regulation of the charged polymer, under proper conditions, the hydrophilic groups/hydrophobic segments are respectively aggregated into Nanoscale micro-phase separation structures to form ion transmission channels (Nanoscale 9(2017) 2942-5258, and Adv. Mater.27(2015) 5280-5295). The ion channel chemical microenvironment (such as the charged type, distribution, quantity and hydrophilicity of functional groups) and the physical microenvironment (such as the size, quantity, distribution and continuity of the nanometer channels) of the ion membrane are cooperatively regulated and controlled to construct the homogeneous structure ion exchange membrane containing the auxiliary ion channel. The constructed auxiliary ion channel is beneficial to the transmission efficiency of the monovalent anion, but inhibits/inhibits the passage of the divalent anion, thereby realizing the high-efficiency separation of the monovalent/divalent anion; and the homogeneous ion exchange membrane structure is favorable for the stability of long-period operation in the electrodialysis process.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a side chain type random polyarylethersulfone, which promotes the formation of continuous microstructure phase separation by embedding a fat chain segment in a main chain, and is favorable for forming a through ion channel; and a flexible auxiliary side chain with hydrophobic/hydrophilic end position is introduced into the same main chain to construct an auxiliary ion channel, which is beneficial to the transmission efficiency of univalent anions and inhibits/inhibits the passing of bivalent anions.
The second technical problem to be solved by the invention is to provide a preparation method of the side chain type random polyarylethersulfone.
The third technical problem to be solved by the invention is to provide a homogeneous anion exchange membrane which has the characteristics of excellent ion conductivity, good chemical stability and mechanical properties, high monovalent anion selectivity, high monovalent anion flux and the like.
In order to solve the technical problem, the invention adopts the following technical scheme:
in a first aspect, the invention provides a side chain type random polyarylether sulfone, which is composed of the following four repeating structural units, wherein the four repeating structural units are arranged randomly; the number average molecular weight Mn of the side chain type random polyether sulphone is 40,000-100,000;
repeating structural unit a:
repeating structural unit B:
repeating structural unit C:
repeating structural unit D:
wherein, n is 3-12,
R1wherein represents the bond to the benzene ring, R2Represents that the bond is linked to N;
and the number of the four repeating structural units A, B, C, D in the structure of the side chain type random polyarylethersulfone is respectively represented by a, b, c and d, the following conditions are satisfied:
(a+b)：(c+d)＝90～0％：10～100％，(a+c)：(b+d)＝10～90％：90～10％。
preferably, (a + c): (b + d) 20-50%: 80-50%, more preferably 40%: 60 percent.
Preferably, n is 6 to 9, and most preferably 6.
Preferably, (a + b): (c + d) ═ 50%: 50 percent.
Most preferably: (a + b): (c + d) 50%: 50%, n ═ 6, (a + c): (b + d) 40%: 60 percent.
In a second aspect, the present invention provides a method for preparing side chain type random polyarylethersulfone, comprising the following steps:
(1) preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS):
the modified 4,4 ' -difluoro diphenyl sulfone shown in the formula (III) is prepared by the Heck reaction of 3,3 ' -dibromo-4, 4 ' -difluoro diphenyl sulfone shown in the formula (II) and 5-hexene-1-alcohol or 5-hexene;
(2) preparation of random polyarylethersulfone:
4,4 ' -difluoro diphenyl sulfone (DFPS), modified 4,4 ' -difluoro diphenyl sulfone (m-DFPS) shown in formula (III), 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA) shown in formula (IV) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF) monomers are subjected to solvent copolycondensation to obtain random polyarylether sulfone, wherein the molar ratio of the total amount of 1, n-bis (4-hydroxyphenyl) alkane and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the total amount of 4,4 ' -difluorodiphenyl sulfone and modified 4,4 ' -difluorodiphenyl sulfone is 1:1, 4,4 ' -difluorodiphenyl sulfone to modified 4,4 ' -difluorodiphenyl sulfone is 90-0%: 10 to 100%, and the molar ratio of 1, n-bis (4-hydroxyphenyl) alkane to 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane is 10 to 90%: 90% -10%;
in the formula (IV), n is defined as formula (I);
(3) preparation of side chain type random polyether sulphone:
using 1-bromo-6-imidazolium salt hexane chain (Br- (CH) shown in formula (V)2)6IM) functional modification of the random polyarylethersulfone obtained in step (2) to obtain-NH on the polymer2Are all converted into-N (R)2)2Obtaining side chain type random polyether sulphone;
preferably, step (1) of the present invention is specifically carried out as follows: weighing a certain amount of 3,3 ' -dibromo-4, 4 ' -difluorodiphenyl sulfone shown in formula (II), 5-hexene-1-ol or 5-hexene, palladium acetate, diphenylphosphine benzene-3-sodium sulfonate and potassium carbonate into a reaction vessel, adding a polar solvent A to dissolve the mixture, heating to 50-100 ℃ under the protection of nitrogen, keeping the temperature for 5-10 hours, cooling to room temperature, and separating and purifying to obtain the modified 4,4 ' -difluorodiphenyl sulfone shown in formula (III).
More preferably, in the step (1), the polar solvent a is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and chloroform.
As a further preference, in the step (1), the separation and purification are carried out as follows: and cooling the reaction solution to room temperature, carrying out rotary evaporation on DMF in the mixed solution, collecting the obtained solid, dissolving the solid in DMS, filtering, dropwise adding the filtrate into chloroform to obtain a precipitate, carrying out crystallization and purification on the precipitate in the mixed solution of water and ethanol, and carrying out vacuum drying at 60-120 ℃ for 10-48 h to obtain the monomer m-DFPS.
Preferably, step (2) of the present invention is specifically carried out as follows: adding 4,4 ' -difluorodiphenyl sulfone (DFPS), modified 4,4 ' -difluorodiphenyl sulfone (m-DFPS) shown in formula (III), 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA) shown in formula (IV) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF) monomers, a polar aprotic solvent B, a salt forming agent potassium carbonate and a water carrying agent into a reaction vessel, stirring and reacting for 3-24 h under the condition of 100-180 ℃ under the protection of nitrogen, and separating and drying after the reaction is finished to obtain the random polyarylether sulfone.
More preferably, in the step (2), the polar aprotic solvent B is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone, and chloroform.
More preferably, in the step (2), the molar ratio of the 1, n-bis (4-hydroxyphenyl) alkane to the 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane is 20 to 50%: 80% to 50%, most preferably 40%: 60 percent.
As a further preference, in the step (2), the molar ratio of the 4,4 '-difluorodiphenyl sulfone to the modified 4, 4' -difluorodiphenyl sulfone is preferably 50%: 50 percent.
Preferably, in the step (2), the ratio of the amount of potassium carbonate to the total amount of 4,4 '-difluorodiphenyl sulfone and the modified 4, 4' -difluorodiphenyl sulfone is 2 to 5: 1, most preferably 2: 1.
Preferably, 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, the copolycondensation reaction conditions are: the reaction is carried out at 155 ℃ C.for 4 hours, preferably at 155 ℃ C.for 3 hours, and at 165 ℃ C.for 155 ℃ C.for 3 hours.
Further preferably, in the step (2), the separation and drying are performed as follows: and cooling the reaction liquid to room temperature, slowly pouring the reaction liquid into isopropanol, stirring and precipitating, filtering and collecting the precipitate, washing the precipitate with isopropanol and water for several times, and performing vacuum drying at the temperature of 60-120 ℃ for 10-48 hours to obtain the random polyarylether sulfone.
Preferably, step (3) of the present invention is carried out as follows: dissolving the random polyarylethersulfone obtained in the step (2) in a polar solvent C, adding a 1-bromo-6-imidazolium salt hexane chain shown in a formula (V), stirring for 6-18 h at 40-100 ℃, and reacting-NH on a polymer2Conversion to-N (R)2)2And separating and drying the obtained reaction mixture to obtain the side chain type random polyarylether sulfone shown in the formula (I).
As a further preferable example, in the step (3), the polar solvent C is one or more selected from Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO).
As a further preference, in step (3), the molar ratio of random polyarylethersulfone to 1-bromo-6-imidazolium salt hexane chain is 1: 4.2 to 4.5.
As a further preference, in the step (3), the reaction conditions are: reacting at 80 ℃ for 12 h.
Further preferably, in the step (3), the separation and drying are carried out as follows: and cooling the reaction liquid to room temperature, precipitating in ethanol, repeatedly washing with water, and performing vacuum drying at 60-120 ℃ for 10-48 h.
The 1, n-bis (4-hydroxyphenoxy) alkane shown in the formula (IV) can be prepared by a method reported in the literature, and the following preparation method is specifically recommended: dissolving 1, 6-dihydroxyphenol and 1, n-dibromoalkane (n is 3-12) in ethanol, reacting for 3-12 h at 50-100 ℃ under the protection of nitrogen by using sodium hydroxide as a hydrogen extracting agent, and separating and drying the obtained mixture after the reaction to obtain a compound shown as a formula (IV), namely 1, n-di (4-hydroxyphenoxy) alkane. Preferably, the feeding molar ratio of hydroquinone to 1, n-dibromon alkane is 2-6: 1, more preferably 4: 1. the molar ratio of sodium hydroxide to 1, n-dibromonan alkane is preferably 1-2: 1.
the 1-bromo-6-imidazolium salt hexane chain represented by the formula (V) can also be prepared by a method reported in the literature, and the following preparation method is specifically recommended: dissolving 1, 6-dibromohexane and 1-methylimidazole in acetone, reacting at 20-80 ℃ for 12-36 h (preferably refluxing at 40 ℃ for 24h), and separating and drying after the reaction is finished to obtain the product shown in the formula (V). Preferably, the feeding molar ratio of the 1, 6-dibromohexane to the 1-methylimidazole is 2-8: 1, more preferably 4: 1.
the 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS) of the present invention can also be prepared by literature-reported methods, such as: fully dissolving 4, 4' -difluoro diphenyl sulfone in concentrated sulfuric acid at 25 ℃ in a nitrogen atmosphere, then adding N-bromo succinimide (NBS), rapidly stirring, keeping for 6h, separating and drying the obtained mixture to obtain db-DFPS with the structure shown in the formula (II).
In a third aspect, the invention provides a homogeneous anion exchange membrane prepared from a side-chain random polyarylethersulfone of formula (I).
Preferably, the film forming method is a solution casting method.
As a further preference, the solution casting method is carried out as follows: dissolving side chain type random polyarylethersulfone in a mixed solvent of NMP and DMSO to prepare a casting solution with the mass/volume concentration of w/v of 2-20%, casting the casting solution on a glass plate, drying for 12-96 h at 40-200 ℃, cooling, and removing the film from the glass plate in water to obtain the side chain type random polyarylethersulfone anion exchange membrane with the membrane thickness of 70-150 mu m.
More preferably, in the mixed solvent of NMP and DMSO, the volume ratio of NMP to DMSO (1 to 3): 1.
the side chain type random polyarylethersulfone anion exchange membrane prepared by the invention has the advantages of excellent ionic conductivity, good chemical stability, high monovalent anion selectivity, high monovalent anion flux and the like, and particularly has wide application prospect in the field of electrodialysis application.
Compared with the prior art, the invention has the advantages that:
(1) the main chain of the side chain type random polyether sulphone is embedded with the fatty chain segment, so that the polarity of partial chain segment of the main chain is changed, the continuous microstructure phase separation is promoted to be formed, and the through ion channel is favorably formed; introducing a flexible auxiliary side chain R with hydrophobic/hydrophilic end position on the same main chain1And R2Regulating and controlling the swelling rate of the ion exchange membrane and constructing an auxiliary ion channel; these structural features are all beneficial to improve the separation performance of the anion-exchange membrane prepared by the structure on the mono/divalent anions and the flux of the monovalent ions.
(2) The preparation method of the side chain type random polyarylethersulfone adopts common chemical raw materials, and is low in price and easy to obtain.
(3) The side chain type random polyarylethersulfone anion exchange membrane prepared by the invention has the advantages of excellent ion conductivity, good chemical stability and mechanical property, high monovalent anion selectivity, high monovalent anion flux and the like, and particularly has a homogeneous structure and a fluorine-containing group anion exchange membrane compared with the traditional surface modified ion exchange membrane, and the stable chemical structure of the anion exchange membrane enables the anion exchange membrane to keep long-period stability in a relatively severe working environment (such as a small amount of acid or alkali solution generated in the electrodialysis process).
Drawings
FIG. 1 shows that the side chain type random poly (aryl ether sulfone) prepared in example 1 of the present invention1H NMR spectrum.
FIG. 2 is an FTIR spectrum of side chain type random polyarylethersulfone obtained in example 1 of this invention.
FIG. 3 shows Cl of the side chain type random poly (aryl ether sulfone) anion membrane prepared in the embodiment 1-2 of the invention–And SO4 2–The permeation flux.
Detailed Description
To further illustrate the technical solutions of the present invention, the following preferred embodiments of the present invention are described in conjunction with specific examples, but it should be understood that the descriptions are only for further illustrating the features and advantages of the present invention, and are not to be construed as limiting the claims of the present invention.
Example 1:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): 25.4 g of 4, 4' -difluorodiphenyl sulfone (0.10mol) was weighed into a 250mL round-bottomed flask, and then 150mL of concentrated sulfuric acid was added and dissolved with stirring at 25 ℃ under a nitrogen atmosphere. Then, 14.2 g (0.22mol) of N-bromosuccinimide (NBS) were added in 3 portions, with 15min intervals each, with rapid stirring, and held for 6 h. The resulting mixture was poured into ice water (500 mL). The precipitate was filtered and washed with 600mL of deionized water and 100mL of n-hexane, respectively. Finally, the product is purified by crystallization from toluene. Vacuum drying at 60 deg.c for 12 hr to obtain db-DFPS 18.3 g.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): 8.0 g (19.4mmol) of 3,3 '-dibromo-4, 4' -difluorodiphenylsulfone, 3.5 g (41.2mmol) of 1-hexene, 0.262 g (1.07mmol) of palladium acetate, 0.2120 g (0.582mmol) of sodium diphenylphosphinobenzene-3-sulfonate and 8.3 g (50mmol) of potassium carbonate were each weighed into a 500mL three-necked round bottom flask, followed by addition of dry DMF. Heating to 120 ℃ under the protection of nitrogen, and keeping for 12 h. Then cooled to room temperature, DMF in the mixed solution was rotary evaporated, the resulting solid was collected and dissolved in DMS, and filtered. The filtrate was added dropwise to chloroform to give a precipitate, which was purified by crystallization from a mixed solution of water and ethanol, and finally dried under vacuum at 80 ℃ for 12 hours to give bis (4-fluoro-3- (4- (1-hexene)) benzene) sulfone in an amount of 8.5 g.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): hydroquinone (40mmol) and 1, 3' -dibromopropane (10mmol) were charged to a 250mL three-necked round-bottomed flask equipped with a trap, with ethanol (75mL) as solvent, and 5.5 g of K2CO3And 40mL of toluene as catalyst and water carrier, respectively. Reacting for 5 hours at 60 ℃ in a nitrogen atmosphere. After cooling, the excess basic catalyst is neutralized by addition of a 30% sulfuric acid solution and precipitated in ethanol. The precipitate was washed with water and dried under vacuum at 40 ℃ for 24h to give the 1, 3' -bis (4-hydroxyphenyl) alkane monomer.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): adding 1.0mmol of 1, 6-dibromohexane into 300mL of acetonitrile in a 500mL three-neck round-bottom flask, heating to 40 ℃, then dropwise adding 6.0mmol of 1-methylimidazole, reacting for 24h, washing the obtained liquid or solid with diethyl ether for multiple times, and then drying in vacuum at 40 ℃ for 24h to obtain the pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: 4,4 ' -Difluorodiphenylsulfone (10mmol), bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone (10mmol), 1,3 ' -bis (4-hydroxyphenyl) alkane (10mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (10mmol) were charged to a 250mL three-necked round bottom flask equipped with a trap, and NMP (75mL) as solvent, along with 5.5 grams of K2CO3And 40mL of toluene as catalyst and water carrier, respectively. At N2The reaction was carried out at 155 ℃ for 4h under an atmosphere and at 165 ℃ for 3 h. After the polymer solution is cooled to room temperature, the polymer solution is poured into 300mL of isopropanol and flocculated under high-speed stirring to obtain a precipitate. Filtering and separating to obtain brown solid, repeatedly washing with isopropanol and water for many times, and vacuum drying at 80 ℃ for 20h to obtain the random polyarylether sulfone with the molar content of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 50%.
Then, dissolving random polyarylethersulfone (3.0mmol) in 20mL NMP, adding 1-bromo-6-methylimidazolium salt-alkane chain (12.6mmol), reacting at 80 ℃ for 12h, cooling, precipitating in ethanol, washing with water for multiple times, and drying to obtain 4.2 g of side chain random polyarylethersulfone with the molar content of 50% of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was determined to be 51200 number average molecular weight.
Using infrared spectroscopy (see FIG. 1) and1the HNMR pattern (see FIG. 2) demonstrates the chemical structure of the side chain type random poly (aryl ether sulfone) prepared.
Examples 1 to 2:
preparing a side chain type random polyether sulphone anion exchange membrane: dissolving 2.8g of side chain type random polyarylethersulfone prepared in example 1 in 60mL of NMP solvent, and magnetically stirring at 80 ℃ until the side chain type random polyarylethersulfone is completely dissolved to obtain a casting solution; and (3) defoaming the membrane casting solution, pouring the defoamed membrane casting solution onto a clean glass mold, and drying at 80 ℃ to form a membrane, so as to obtain the homogeneous side chain random polyarylethersulfone anion exchange membrane with the membrane thickness of 106 micrometers.
The experiment by adopting the national standard method shows that the prepared side chain type random polyether sulphone anion membrane IEC is 1.82mmol g–1Migration number of 0.97, tensile strength of 32.9MPa, Cl–Maximum permeation flux of 7.5X 10–8mol cm–2s–1，Cl–Selectivity (Cl)–/SO4 2–) Is 7.1 (specific test methods see literature reports: journal of Membrane Science 574(2019) 181-195; journal of membrane Science577(2019) 153-.
Example 2:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of a series of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same procedure for preparation of example 1 was followed to give bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure as in example 1 was followed to give a pure 1, 3-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same procedure as in example 1 was followed, except that 1, 3-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol) were charged to give 6.5 g of a side chain random polyarylethersulfone having a molar content of 60% of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was tested to be 63200 in number average molecular weight.
Example 2-2:
preparing a side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 2 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 115 μm by the same preparation process as in example 1-2.
The experiment by adopting the national standard method proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 2.01mmol g–1Migration number of 0.98, tensile strength of 31.6MPa, Cl–Maximum permeation flux of 8.1X 10–8mol cm–2s–1，Cl–Selectivity (Cl)–/SO4 2–) It was 7.8.
Example 3:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same procedure as in example 1 was followed to give bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure as in example 1 was followed to give a pure 1, 3-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same procedure as in example 1 was followed, except that 1, 3-bis (4-hydroxyphenyl) alkane (6mmol) and 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (14mmol) were charged to give 6.8 g of a side chain random polyarylethersulfone having a molar content of 70% of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was determined to be 76200 number average molecular weight.
Example 3-2:
preparing a side chain random polyarylethersulfone anion exchange membrane: the side chain random polyarylethersulfone prepared in the example 3 is prepared into a homogeneous side chain random polyarylethersulfone anion exchange membrane with the membrane thickness of 112 μm by adopting the same preparation process as the example 1-2.
Adoption countryThe experiment of the standard method shows that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 2.18mmol g–1Migration number of 0.97, tensile strength of 30.8MPa, Cl–Osmotic flux of 8.5X 10–8mol cm–2s–1，Cl–(Cl)–/SO4 2–) Was 9.5.
Example 4:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same procedure as in example 1 was followed to give bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure as in example 1 was followed to give a pure 1, 3-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same procedure as in example 1 was followed, except that 1, 3-bis (4-hydroxyphenyl) alkane (4mmol) and 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (16mmol) were charged to give 6.3 g of a side chain random polyarylethersulfone having a molar content of 80% of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was tested to be 87100.
Example 4-2:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 4 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 118 μm by the same preparation process as in example 1-2.
The experiment by adopting the national standard method proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 2.32mmol g–1Migration number of 0.97, tensile strength of 29.1MPa, Cl–Maximum permeation flux of 9.5X 10–8mol cm–2s–1，Cl–Selectivity (Cl)–/SO4 2–) It was 11.9.
Example 5:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same procedure as in example 1 was followed to give bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): hydroquinone (40mmol) and 1, 6-dibromohexane (10mmol) were charged to a 250mL three-necked round-bottomed flask equipped with a trap, with ethanol (75mL) as solvent, and 5.5 g of K were added2CO3And 40mL of toluene as catalyst and water carrier, respectively. Reacting for 5 hours at 60 ℃ in a nitrogen atmosphere. After cooling, the excess basic catalyst was neutralized by addition of a 30% sulfuric acid solution and precipitated in ethanol. The precipitate was washed with water and dried under vacuum at 40 ℃ for 24h to give the 1, 6-bis (4-hydroxyphenyl) alkane monomer.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to give pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: using the same preparation process as in example 1, using 4,4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone (10mmol), 1, 6-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol), 8.6 g of a side chain random polyarylether sulfone having a molar content of 60% of 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane were obtained. The molecular weight was tested to be 98600 number average molecular weight.
Example 5-2:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 5 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 116 μm by the same preparation process as in example 1-2.
The side manufactured can be found by adopting a national standard method through experimental measurementThe IEC of the chain type random polyether sulphone anion membrane is 1.99mmol g–1Migration number of 0.97, tensile strength of 33.4MPa, Cl–Maximum permeation flux of 10.5X 10–8mol cm– 2s–1，Cl–(Cl)–/SO4 2–) Was 12.3.
Example 6:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedures as in example 1 were carried out to obtain db-DFPS.
Preparation of a series of modified 4, 4' -difluorodiphenyl sulfones (m-DFPS): the same procedure for preparation of example 1 was followed to give bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): hydroquinone (40mmol) and 1, 9-dibromohexane (10mmol) were charged to a 250mL three-necked round-bottomed flask equipped with a water trap, with ethanol (75mL) as solvent, and 5.5 g of K were added2CO3And 40mL of toluene as catalyst and water carrier, respectively. Reacting for 5 hours at 60 ℃ in a nitrogen atmosphere. After cooling, excess basic catalyst was neutralized by addition of a 30% sulfuric acid solution and precipitated in ethanol. The precipitate was washed with water and dried under vacuum at 40 ℃ for 24 hours to give a 1, 9-bis (4-hydroxyphenyl) alkane monomer.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same preparation as in example 1 was carried out using 4,4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (1-hexene)) benzene) sulfone (10mmol), 1, 9-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol) to give 5.6 g of a side chain random polyarylether sulfone having a molar content of 60% 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was tested to be 54600 number average molecular weight.
Example 6 to 2
Preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 6 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 115 μm by the same preparation process as in example 1-2.
The experiment by adopting the national standard method shows that the prepared side chain type random polyether sulphone anion membrane IEC is 1.96mmol g–1Migration number of 0.98, tensile strength of 33.9MPa, Cl–Maximum permeation flux of 10.2X 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) Was 10.3.
Example 7:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same procedure for preparation of example 1 was followed to give bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): hydroquinone (40mmol) and 1, 12-dibromohexane (10mmol) were charged to a 250mL three-necked round-bottomed flask equipped with a water trap, with ethanol (75mL) as solvent, and 5.5 g of K were added2CO3And 40mL of toluene as catalyst and water carrier, respectively. Reacting for 5h at 60 ℃ in a nitrogen atmosphere. After cooling, excess basic catalyst was neutralized by addition of a 30% sulfuric acid solution and precipitated in ethanol. The precipitate was washed with water and dried under vacuum at 40 ℃ for 24h to give the 1, 12-bis (4-hydroxyphenyl) alkane monomer.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to give pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same procedure as in example 1 was followed, using 4,4 '-difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (1-hexene)) benzene) sulfone (10mmol), 1, 12-bis (4-hydroxyphenyl) alkane (8mmol) and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol), to give 6.1 g of a side chain random polyarylether sulfone having a molar content of 60% 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was tested to be 72100 number average molecular weight.
Example 7-2
Preparing a side chain type random polyether sulphone anion exchange membrane: the side chain random polyarylethersulfone prepared in example 7 is prepared into a homogeneous side chain random polyarylethersulfone anion-exchange membrane with a membrane thickness of 114 μm by the same preparation process as example 1.
The experiment of the national standard method shows that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.93mmol g–1Migration number of 0.98, tensile strength of 32.8MPa, Cl–Maximum permeation flux of 9.7X 10–8mol cm–2s–1，Cl–(Cl)–/SO4 2–) And was 9.5.
Example 8:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedures as in example 1 were carried out to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): 8.0 g (19.4mmol) of 3,3 '-dibromo-4, 4' -difluorodiphenylsulfone, 4.2 g (41.9mmol) of 5-hexen-1-ol, 0.262 g (1.07mmol) of palladium acetate, 0.2120 g (0.582mmol) of diphenylphosphinobenzene, sodium 3-sulfonate and 8.3 g (50mmol) of potassium carbonate were each weighed into a 500mL three-necked round-bottomed flask, and then dried DMF was added. Heating to 120 ℃ under the protection of nitrogen, and keeping for 12 h. Then cooled to room temperature, DMF in the mixed solution was rotary evaporated, the resulting solid was collected and dissolved in DMS, and filtered. The filtrate was added dropwise to chloroform to give a precipitate, which was purified by crystallization from a mixed solution of water and ethanol, and finally dried under vacuum at 80 ℃ for 12 hours to give 9.5 g of bis (4-fluoro-3- (4- (5-hexen-1-ol)) phenyl) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure as in example 1 was followed to give a pure 1, 3-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to give pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: using the same preparation process as in example 1, using 4,4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone (10mmol), 1, 3-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol), 7.1 g of a side chain random polyarylether sulfone having a molar content of 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was obtained. The molecular weight was tested to be 98600 number average molecular weight.
Example 8-2:
preparing a side chain random polyarylethersulfone anion exchange membrane: the side chain random polyarylethersulfone prepared in the example 8 is prepared into a homogeneous side chain random polyarylethersulfone anion exchange membrane with the membrane thickness of 119 μm by adopting the same preparation process as the example 1-2.
The experiment by adopting the national standard method shows that the prepared side chain type random polyether sulphone anion membrane IEC is 1.99mmol g–1Migration number of 0.97, tensile strength of 30.9MPa, Cl–Maximum permeation flux of 10.7X 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) It was 11.8.
Example 9:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same preparation process as in example 8 was adopted, except for using 9.8 g of bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure as in example 5 was followed to give a pure 1, 6-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to give pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same preparation as in example 1 was carried out using 4,4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone (10mmol), 1, 6-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol) to give 7.8 g of a side chain random polyarylether sulfone having a molar content of 60% 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was measured to be 81200.
Example 9-2:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random polyarylethersulfone prepared in example 9 was prepared into a homogeneous side chain random polyarylethersulfone anion exchange membrane with a membrane thickness of 117 μm by the same preparation process as in example 1-2.
The experiment by adopting the national standard method shows that the prepared side chain type random polyether sulphone anion membrane IEC is 1.96mmol g–1Migration number of 0.98, tensile strength of 29.5MPa, Cl–Maximum permeation flux of 11.8X 10–8mol cm– 2s–1，Cl–(Cl)–/SO4 2–) It was 15.9.
Example 10:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same preparation as in example 8 was used, except for using 8.9 g of bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure used in example 5 was followed to obtain a pure 1, 9-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same preparation as in example 1 was carried out using 4,4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone (10mmol), 1, 9-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol) to give 8.6 g of a side chain random polyarylether sulfone having a molar content of 60% of 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was tested to be 78400 number average molecular weight.
Example 10-2:
preparing a side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 10 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 110 μm by the same preparation process as in example 1-2.
The experiment by adopting the national standard method proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.94mmol g–1Migration number of 0.99, tensile strength of 30.2MPa, Cl–Maximum permeation flux of 11.1X 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) Was 12.6.
Example 11:
preparation of 3,3 '-dibromo-4, 4' -difluorodiphenyl sulfone (db-DFPS): the same procedure as in example 1 was followed to obtain db-DFPS.
Preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS): the same preparation process as in example 8 was adopted, except for using 9.4 g of bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA): the same procedure used in example 5 was followed to obtain a pure 1, 12-bis (4-hydroxyphenyl) alkane.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-synthesis of IM): the same procedure as in example 1 was followed to obtain pure 1-bromo-6-methylimidazolium salt-alkane chain.
Preparation of side chain random polyarylethersulfone: the same preparation as in example 1 was carried out using 4,4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (5-hexen-1-ol)) benzene) sulfone (10mmol), 1, 12-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol) to give 8.8 g of a side chain random polyarylether sulfone having a molar content of 60% 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane. The molecular weight was tested to be 69900 number average molecular weight.
Example 11-2:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 11 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 110 μm by the same preparation process as in example 1-2.
The experiment by adopting the national standard method proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.91mmol g–1Migration number of 0.99, tensile strength of 29.1MPa, Cl–Maximum permeation flux of 10.2X 10–8mol cm– 2s–1，Cl–(Cl)–/SO4 2–) Is 10.9.
Claims (14)
1. A side chain type random polyarylethersulfone is composed of the following four repeating structural units which are randomly arranged; the number average molecular weight Mn of the side chain type random polyarylethersulfone is 40,000-100,000;
repeating structural unit a:
repeating structural unit B:
repeating structural unit C:
repeating structural unit D:
wherein n is 3 to 12,
R1wherein represents the bond to the benzene ring, R2Represents that the bond is linked to N;
and the number of the four repeated structural units A, B, C, D in the structure of the side chain type random polyarylethersulfone is respectively represented by a, b, c and d, and the following conditions are met:
(a+b)：(c+d)＝90～0％：10～100％，(a+c)：(b+d)＝10～90％：90～10％。
2. the side-chain random polyarylethersulfone of claim 1, wherein: (a + c): (b + d) is 20 to 50%: 80-50%.
3. The side-chain random polyarylethersulfone of claim 2, wherein: (a + c): (b + d) 40%: 60 percent.
4. The side-chain random polyarylethersulfone of claim 1, wherein: n is 6 to 9.
5. The side-chain random polyarylethersulfone of claim 4, wherein: n is 6.
6. The side-chain random polyarylethersulfone of claim 1, wherein: (a + b): (c + d) 50%: 50 percent.
7. The side-chain random polyarylethersulfone of claim 1, wherein: (a + b): (c + d) 50%: 50%, n ═ 6, (a + c): (b + d) 40%: 60 percent.
8. A process for the preparation of a side-chain random polyarylethersulfone according to claim 1, comprising the steps of:
(1) preparation of modified 4, 4' -difluorodiphenyl sulfone (m-DFPS):
the modified 4,4 ' -difluoro diphenyl sulfone shown in the formula (III) is prepared by the Heck reaction of 3,3 ' -dibromo-4, 4 ' -difluoro diphenyl sulfone shown in the formula (II) and 5-hexene-1-alcohol or 5-hexene;
(2) preparation of random polyarylethersulfone:
carrying out solvent copolycondensation on 4,4 '-difluorodiphenyl sulfone (DFPS), modified 4, 4' -difluorodiphenyl sulfone shown in a formula (III), 1, n-bis (4-hydroxyphenyl) alkane shown in a formula (IV) and 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane monomers to obtain the random polyarylether sulfone, wherein the molar ratio of the total mass of the 1, n-bis (4-hydroxyphenyl) alkane and the 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane to the total mass of the 4,4 '-difluorodiphenyl sulfone and the modified 4, 4' -difluorodiphenyl sulfone is 1:1, 4,4 '-difluorodiphenyl sulfone to the modified 4, 4' -difluorodiphenyl sulfone is 90-0%: 10 to 100%, and the molar ratio of 1, n-bis (4-hydroxyphenyl) alkane to 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane is 10 to 90%: 90 to 10 percent;
in the formula (IV), n is as defined in the formula (I);
(3) preparation of side chain type random polyether sulphone:
the random polyarylether sulphone prepared in the step (2) is functionally modified by using a 1-bromo-6-imidazolium salt hexane chain shown in a formula (V) to enable-NH on the polymer2Are all converted into-N (R)2)2Obtaining side chain type random polyether sulphone;
9. the method of claim 8, wherein: the step (2) is specifically implemented as follows: adding 4,4 ' -difluoro diphenyl sulfone, modified 4,4 ' -difluoro diphenyl sulfone shown in a formula (III), 1, n-bis (4-hydroxyphenyl) alkane and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane monomer shown in a formula (IV), a polar aprotic solvent B, a salt forming agent potassium carbonate and a water carrying agent into a reaction vessel, stirring and reacting for 3-24 h under the protection of nitrogen at 100-180 ℃, and separating and drying after the reaction is finished to obtain the random polyarylether sulfone.
10. The method of claim 9, wherein: in the step (2), the polar aprotic solvent B is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and trichloromethane.
11. The method of claim 9, wherein: in the step (2), the copolycondensation reaction conditions are as follows: the reaction is carried out for 4h at the temperature of 120-155 ℃ and then for 3h at the temperature of 155-165 ℃.
12. A homogeneous anion exchange membrane made from the side-chain random polyarylethersulfone of claim 1.
13. The homogeneous anion exchange membrane of claim 12 wherein: the film preparation method is a solution casting method, and the solution casting method is implemented as follows: dissolving side chain type random polyarylethersulfone in a mixed solvent of NMP and DMSO to prepare a casting solution with the mass/volume concentration of 2-20%, casting the casting solution on a glass plate, drying at 40-200 ℃ for 12-96 h, cooling, and then taking off the membrane from the glass plate in water to obtain the homogeneous anion exchange membrane with the membrane thickness of 70-150 mu m.
14. The homogeneous anion exchange membrane of claim 13, wherein: in the mixed solvent of the NMP and the DMSO, the volume ratio of the NMP to the DMSO (1-3) is as follows: 1.
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