CN111499867A - Side chain type random polyether sulfone, preparation method thereof and homogeneous anion exchange membrane - Google Patents
Side chain type random polyether sulfone, 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, a preparation method thereof and a homogeneous anion exchange membrane. The side chain type random polyarylether sulfone is composed of the following four repeating structural units which are arranged randomly; 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 polyarylethersulfone, a preparation method thereof and a homogeneous anion exchange membrane prepared from the side chain type random polyarylethersulfone.
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 of domestic commercial ionic membrane products 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 pore size sieving effect, electrostatic repulsion effect or ionic hydration energy difference, the current methods for mainly preparing the ion exchange membrane with single-multivalence 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, neither anion exchange membrane can achieve effective separation of mono/dianions, 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 in which hydrophilic conductive groups are directly bonded to hydrophobic backbones, adjacent hydrophilic groups inhibit self-aggregation between the hydrophobic backbones 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) 4442).
Through the structural design and the microstructure regulation of the charged polymer, under appropriate conditions, the hydrophilic groups/hydrophobic segments are respectively aggregated into a nano-scale micro-phase separation structure to form an ion transmission channel (Nanoscale 9(2017) 2942-2958; adv. Mater.27(2015) 5280-5295). The ion exchange membrane with the homogeneous structure and the auxiliary ion channel is constructed by cooperatively regulating and controlling the chemical microenvironment (such as the charged type, distribution, quantity and hydrophilicity of functional groups) and the physical microenvironment (such as the size, quantity, distribution, continuity and the like of the nano channel) of the ion channel of the ion exchange membrane. 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 beneficial to forming a through ion channel; and a flexible auxiliary side chain with hydrophobic/hydrophilic end positions is introduced into the same main chain to construct an auxiliary ion channel, so that the transmission efficiency of monovalent anions is improved, and the passage of divalent anions is inhibited.
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 property, high monovalent anion selectivity, high monovalent anion flux and the like.
In order to solve the technical problems, 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 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 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-di (4-hydroxyphenyl) alkane (1, n-DBA) shown in formula (IV) and 2,2 ' -di (3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF) monomers are subjected to solvent copolycondensation to obtain the 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 polyarylethersulfone:
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 polyarylether 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 ' -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, 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 carried out 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 the 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 preferred example, in the step (3), the polar solvent C is one or more of 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 vacuum-drying at 60-120 ℃ for 10-48 h.
The 1, n-bis (4-hydroxyphenoxy) alkane represented by 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 the sodium hydroxide to the 1, n-dibromon 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 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 a 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 beneficial to improve the separation performance of the anion-exchange membrane prepared from the anion-exchange membrane on mono/divalent anions and the flux of 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 random poly (aryl ether sulfone) prepared in example 1 of the present 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 permeate 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 in a 250m L round-bottomed flask, then 150m L concentrated sulfuric acid was added thereto, and stirred and dissolved at 25 ℃ under nitrogen atmosphere, then 14.2 g (0.22mol) of N-bromosuccinimide (NBS) was added in 3 portions, each for 15min, rapidly stirred, kept for 6h, the resulting mixture was poured into ice water (500m L), filtered to obtain a precipitate, then washed with 600m L deionized water and 100m L N-hexane, respectively, finally, crystallized in toluene, and dried under vacuum at 60 ℃ for 12h to obtain 18.3 g of db-DFPS.
Preparation of modified 4,4 ' -difluorodiphenyl sulfone (m-DFPS) 8.0 g (19.4mmol) of 3,3 ' -dibromo-4, 4 ' -difluorodiphenyl sulfone, 3.5 g (41.2mmol) of 1-hexene, 0.262 g (1.07mmol) of palladium acetate, 0.2120 g (0.582mmol) of diphenylphosphinobenzene-3-sulfonic acid sodium salt and 8.3 g (50mmol) of potassium carbonate were weighed, respectively, in a 500m L three-necked round-bottomed flask, then dried DMF and nitrogen were added, heated to 120 ℃ and kept at room temperature for 12 hours, then cooled to room temperature, DMF in the mixed solution was evaporated off, the resulting solid was collected and dissolved in DMS, filtered, the filtrate was dropwise added to chloroform to give a precipitate and purified by crystallization in a mixed solution of water and ethanol, and finally dried under vacuum at 80 ℃ for 12 hours to give 8.5 g of bis (4-fluoro-3- (4- (1-hexene)) sulfone.
Synthesis of 1, n-bis (4-hydroxyphenyl) alkane (1, n-DBA) Hydroquinone (40mmol) and 1, 3' -dibromopropane (10mmol) were charged to a 250m L three-necked round-bottomed flask equipped with a water trap, using ethanol (75m L) as solvent, and 5.5 g of K were simultaneously charged2CO3And 40m of L toluene are respectively used as a catalyst and a water carrying agent, the reaction is carried out for 5h at 60 ℃ in nitrogen atmosphere, after cooling, 30 percent sulfuric acid solution is added to neutralize the redundant alkaline catalyst, the precipitation is precipitated in ethanol, and after washing the precipitation by water, vacuum drying is carried out for 24h at 40 ℃ to obtain the 1, 3' di (4-hydroxyphenyl) alkane monomer.
1-bromo-6-imidazolium salt hexane chain (Br- (CH)2)6-IM) Synthesis 1.0mmol of 1, 6-dibromohexane was added to a three-necked round-bottomed flask of 500m L in acetonitrile of 300m L, respectively, heated to 40 ℃ and 6.0mmol of 1-methylimidazole was added dropwise thereto and reacted for 24 hours, and the resulting liquid or solid was washed with diethyl ether several times and then dried under vacuum at 40 ℃ for 24 hours to obtain pure 1-bromo-6-methylimidazolium salt-alkane.
Preparation of side chain random polyarylethersulfones 4,4 ' -difluorodiphenyl sulfone (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 250m L three-necked round-bottomed flask equipped with a water trap, NMP (75m L) as solvent and 5.5 g K were simultaneously charged2CO3And 40m L toluene as catalyst and water carrier, respectively, in N2Reacting at 155 deg.C for 4h and at 165 deg.C for 3h under the atmosphere, cooling the polymer solution to room temperature, pouring into 300m L isopropanol, stirring at high speed, flocculating to obtain precipitate, and filteringAnd (3) obtaining a brown solid after separation, repeatedly washing the brown solid with isopropanol and water for many times, and drying the brown solid in vacuum at the temperature of 80 ℃ for 20 hours to obtain the random polyarylether sulfone with the molar content of the 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 50 percent.
Then, dissolving random polyarylethersulfone (3.0mmol) in 20m L 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 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 50%, wherein the molecular weight is tested to be 51200.
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:
the preparation of the side chain type random polyarylethersulfone anion exchange membrane comprises the steps of dissolving 2.8g of the side chain type random polyarylethersulfone prepared in the example 1 in 60m L NMP solvent, magnetically stirring the solution at 80 ℃ until the solution is completely dissolved to obtain a membrane casting solution, defoaming the membrane casting solution, pouring the defoamed membrane casting solution into a clean glass mold, and drying the membrane casting solution at 80 ℃ to form a membrane, so that the homogeneous side chain type random polyarylethersulfone anion exchange membrane is obtained, wherein the membrane thickness of the homogeneous side chain type random polyarylethersulfone anion exchange membrane is 106 mu m.
The experiment by adopting the national standard method proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.82mmol g–1Migration number of 0.97, tensile strength of 32.9MPa, Cl–Maximum permeate flux of 7.5 × 10–8mol cm–2s–1，Cl–Selectivity (Cl)–/SO4 2–) Is 7.1 (see literature reports for specific test methods: journal of membrane science 574(2019) 181-195; journal of Membrane Science577(2019) 153- "164).
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 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): 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:
preparation of 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 permeate flux of 8.1 × 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 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 (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:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 3 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 112 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 2.18mmol g–1Migration number of 0.97, tensile strength of 30.8MPa, Cl–Permeate flux of 8.5 × 10–8mol cm–2s–1，Cl–Selectivity (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 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 (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 permeate flux of 9.5 × 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 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, 6-dibromohexane (10mmol) were charged in a 250m L three-necked round-bottomed flask equipped with a water separator, with ethanol (75m L) as solvent and 5.5 g of K2CO3And 40m of L toluene are respectively used as a catalyst and a water carrying agent, the reaction is carried out for 5h at 60 ℃ in nitrogen atmosphere, after cooling, 30 percent sulfuric acid solution is added to neutralize the redundant alkaline catalyst, the precipitation is precipitated in ethanol, and after washing the precipitation by water, vacuum drying is carried out for 24h at 40 ℃ to obtain 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 obtain 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 experiment of the national standard method shows that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.99mmol g–1Migration number of 0.97, tensile strength of 33.4MPa, Cl–Maximum permeate flux of 10.5 × 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) Was 12.3.
Example 6:
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 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 in a 250m L three-necked round-bottomed flask equipped with a water separator, with ethanol (75m L) as solvent and 5.5 g of K2CO3And 40m of L toluene are respectively used as a catalyst and a water carrier, reacted for 5h at 60 ℃ in a nitrogen atmosphere, cooled, added with 30 percent sulfuric acid solution to neutralize the redundant alkaline catalystAnd 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: using the same preparation process as in example 1, 4 ' -difluorodiphenyl sulfone (10mmol), bis (4-fluoro-3- (4- (1-hexene)) phenyl) sulfone (10mmol), 1, 9-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol) were used to prepare 5.6 g of a side chain random polyarylether sulfone having a molar content of 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 60%. 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 proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.96mmol g–1Migration number of 0.98, tensile strength of 33.9MPa, Cl–Maximum permeate flux of 10.2 × 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) Is 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 in a 250m L three-necked round-bottomed flask equipped with a water separator, using ethanol (75m L) as solvent,5.5 g of K are added simultaneously2CO3And 40m of L toluene are respectively used as a catalyst and a water carrying agent, the reaction is carried out for 5h at 60 ℃ in nitrogen atmosphere, after cooling, 30 percent sulfuric acid solution is added to neutralize the redundant alkaline catalyst, the precipitation is precipitated in ethanol, and after washing the precipitation by water, vacuum drying is carried out for 24h at 40 ℃ to obtain 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 obtain 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, 12-bis (4-hydroxyphenyl) alkane (8mmol) and 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol), 6.1 g of a side chain random polyarylether sulfone having a molar content of 2, 2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane of 60% was obtained. The molecular weight was tested to be 72100 number average molecular weight.
Example 7-2
Preparing a side chain type random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 7 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 114 μm by the same preparation process as in 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 permeate flux of 9.7 × 10–8mol cm–2s–1，Cl–Selectivity (Cl)–/SO4 2–) Was 9.5.
Example 8:
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) 8.0 g (19.4mmol) of 3,3 ' -dibromo-4, 4 ' -difluorodiphenyl sulfone, 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 weighed respectively in a three-necked round bottom flask of 500m L, then heated to 120 ℃ under protection of dry DMF and nitrogen and kept for 12h, then cooled to room temperature, DMF in the mixed solution was rotary-distilled off, the resulting solid was collected and dissolved in DMS, filtered, the filtrate was added to chloroform to give a precipitate and purified by dropwise crystallization in a mixed solution of water and ethanol, and finally dried under vacuum at 80 ℃ for 12h to give bis (4-fluoro-3- (4- (5-hexen-1-ol)) sulfone 9.5 g.
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: 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:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 8 was prepared into a homogeneous side chain random poly (aryl ether sulfone) anion exchange membrane with a membrane thickness of 119 μm by the same preparation process as in example 1-2.
The experiment of the national standard method shows that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.99mmol g–1Migration number of 0.97, tensile strength of 30.9MPa, Cl–Maximum permeate flux of 10.7 × 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) 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 used in example 5 was followed to obtain 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 obtain 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, 6-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol), 7.8 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 81200.
Example 9-2:
preparation of side chain random polyarylethersulfone anion exchange membrane: the side chain random poly (aryl ether sulfone) prepared in example 9 was prepared into a homogeneous side chain random poly (aryl ether sulfone) 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 proves that the prepared side chain type random polyarylethersulfone anionic membrane IEC is 1.96mmol g–1Migration number of 0.98, tensile strength of 29.5MPa, Cl–Maximum permeate flux of 11.8 × 10–8mol cm– 2s–1，Cl–Selectivity (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 process as in example 8 was adopted, 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: 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, 9-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 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane were obtained. The molecular weight was tested to be 78400 number average molecular weight.
Example 10-2:
preparation of 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 permeate flux of 11.1 × 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: 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, 12-bis (4-hydroxyphenyl) alkane (8mmol) and 2,2 ' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane (12mmol), 8.8 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 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 permeate flux of 10.2 × 10–8mol cm– 2s–1，Cl–Selectivity (Cl)–/SO4 2–) Is 10.9.
Claims (10)
1. A side chain type random polyarylether sulphone is composed of the following four repeating structural units which are arranged randomly; 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) 20-50%: 80-50%, preferably 40%: 60 percent.
3. The side-chain random polyarylethersulfone of claim 1, wherein: n is 6 to 9, and most preferably 6.
4. The side-chain random polyarylethersulfone of claim 1, wherein: (a + b): (c + d) 50%: 50 percent.
5. The side-chain random polyarylethersulfone of claim 1, wherein: (a + b): (c + d) 50%: 50%, n ═ 6, (a + c): (b + d) 40%: 60 percent.
6. A process for the preparation of the side-chain random polyarylethersulfone of 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% -10%;
in the formula (IV), n is defined as formula (I);
(3) preparation of side chain type random polyarylethersulfone:
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 polyarylether sulphone;
7. the method of claim 6, 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.
8. The method of claim 7, wherein: in the step (2), the polar aprotic solvent B is at least one of N, N-dimethylacetamide, N-dimethylformamide, N-methylpyrrolidone and trichloromethane.
9. The method of claim 7, 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 ℃.
10. A homogeneous anion exchange membrane made from the side-chain random polyarylethersulfone of claim 1.
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| CN110756230A (en) * | 2019-08-30 | 2020-02-07 | 浙江工业大学 | Preparation method of polyether sulphone anion exchange membrane with homogeneous cross-linked structure |
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| CN110756230A (en) * | 2019-08-30 | 2020-02-07 | 浙江工业大学 | Preparation method of polyether sulphone anion exchange membrane with homogeneous cross-linked structure |
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