CN101979132A - Method for preparing asymmetric nanofiltration membrane by blending polyether sulfone and sulfonated polysulfone high polymers - Google Patents
Method for preparing asymmetric nanofiltration membrane by blending polyether sulfone and sulfonated polysulfone high polymers Download PDFInfo
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Abstract
The invention discloses a method for preparing an asymmetric nanofiltration membrane by blending polyether sulfone and sulfonated polysulfone high polymers. A blending nanofiltration membrane with an asymmetric structure is prepared in one step by the nanofiltration membrane through a phase transformation method. The method comprises the following steps of: preparing casting membrane liquid, namely mixing the polyether sulfone, the sulfonated polysulfone high polymers, an additive and a solvent to prepare the casting membrane liquid; and forming a membrane by the phase transformation method, wherein the membrane comprises a flat membrane and a hollow fibrous membrane. The interception rate of the nanofiltration membrane to 0.5 to 1.5 g/L sodium chloride and 0.5 to 1.5 g/L sodium sulfate under the operating pressure of between 0.1 and 0.8 MPa is between 20 and 95 percent, the interception rate of the nanofiltration membrane to polyethylene glycol with the relative molecular mass of between 600 and 2,000 is between 40 and 99.9 percent, and the pure water flux of the membrane is between 10 and 250 L/(m2hbar). The asymmetric nanofiltration membrane of the invention has the advantages of high strength and toughness, high compactness resistance, chlorine resistance and high-temperature resistance, and can be applied to aspects of water treatment, wastewater treatment, material separation and the like.
Description
Technical field
The present invention relates to a kind of high-molecular special functional membrane and preparation method thereof, particularly a kind of method that adopts phase inversion directly to prepare NF membrane.
Background technology
Nanofiltration (NF, Nanofiltration) be a kind of pressure drive membrane separation process between counter-infiltration and ultrafiltration, the pore diameter range of NF membrane is about several nanometers, operating pressure is at 0.1MPa～2.0MPa, rejection to monovalent salt is lower, and higher, and be that 200～2000 organic molecule has higher rejection to relative molecular mass to the rejection of divalent salts.Based on these characteristics, the type film more and more is subjected to human concern, and extensive use and electron trade, and dyestuff reclaims, and drinking water is made in wastewater treatment, fruit juice concentrate aspects such as water-oil separating.
Present most of commodity NF membrane belongs to composite nanometer filtering film, but just be coated with the very thin dense layer surface that plays separation function of last layer by interfacial polymerization or direct coating process on a kind of ultrafiltration rete of material, the material of its dense layer surface is different fully with the material of ultrafiltration layer.In general, the NF membrane material on the market is a polyamide, polyimides, and cellulose acetate, SPSF etc., and adopt compound mode to prepare NF membrane.The problem that existing composite nanometer filtering film exists is a little less than the oxidation resistance, pre-treatment is required harsh.Yet SPSF class high polymer has the strong advantage of oxidation resistance, but the NF membrane intensity of preparation is lower.The patent that a lot of relevant SPSF class high polymer NF membrane are abroad arranged at present, Tang etc. utilize nonwoven and polysulfones to prepare the support counterdie, then SPSF is compounded in and prepares SPSF composite nanometer filtering film [US Patent.5853487] on the supporting layer, the SPSF class composite nanometer filtering film NTR-7410 and the NTR-7450 of Japan eastern electrician of day company, pure water flux is 500 L/ (m
2.h) and 92L/ (m
2.h), it is 1000 that the sulfonated polyether sulfone filtering film HYDRACoRe-50 of Hydranautics's preparation holds back relative molecular mass, and Pu Tong etc. have invented sulfonated polyether sulfone filtering film, and membrane flux can reach 150L/m
2H reaches the patent 1288776A of the 95%[People's Republic of China (PRC) to the sodium sulphate rejection].But the preparation about polyether sulfone and the asymmetric NF membrane of SPSF class high polymer blend does not also have relevant report.
We adopt polyether sulfone and SPSF class high polymer blended membrane material based on above consideration, have the NF membrane of unsymmetric structure by the one step preparation of wet method phase separation method.Prepared that water flux is big, the aperture precisely, zero defect, intensity be good, toughness is strong, pressure tightness is stronger, anti-chlorine, resistant to elevated temperatures NF membrane.
Summary of the invention
The objective of the invention is to solve existing composite nanometer filtering film exists a little less than the oxidation resistance, pre-treatment is required harsh problem, the preparation method of a kind of polyether sulfone and the asymmetric NF membrane of SPSF class high polymer blend is provided, described NF membrane is by the asymmetric NF membrane of inversion of phases preparation, rejection to sodium chloride and sodium sulphate under 0.1～0.8MPa operating pressure reaches 20%～95%, 40%～99.9%, the film pure water flux reaches 10～250L/ (m to the polyethylene glycol rejection of relative molecular mass 600～2000
2Hbar) a series of NF membrane.
Design of the present invention:
Polyether sulfone is a kind of noncrystalline thermal shrinkage type engineering plastics, its strand alternately is connected in the aromatic structure between the penylene by ether, sulfone, thereby have favorable mechanical performance and hear resistance, non-oxidizability, acid and alkali-resistance, anti-solvent, radiation resistance, but its hydrophily is poor, is difficult to prepare the bigger NF membrane of water flux.SPSF class high polymer good hydrophilic property, antipollution, anti-oxidant, good toughness, but its rigidity deficiency.Adopt these two kinds of materials to carry out blend and can prepare rigidity toughness and have concurrently, hydrophily is good, and antipollution is anti-oxidant, materialization stability and select aspect such as permeability to have the NF membrane of higher performance, and be easy to suitability for industrialized production.
According to above-mentioned conception, the preparation method of polyether sulfone provided by the invention and the asymmetric NF membrane of SPSF class high polymer blend comprises the steps:
1st, the preparation of casting solution: polyether sulfone, SPSF class high polymer, additive and four kinds of components of solvent are hybridly prepared into casting solution (at first solvent are fully mixed with additive, after the stirred for several ten minutes, to put in the mixed solution through the good polyether sulfone of super-dry and SPSF class high polymer again and dissolve, the casting solution that formation is made of polyether sulfone, SPSF class high polymer, solvent and additive is through standby after filtration, the standing and defoaming);
Wherein the mass concentration of polyether sulfone is 0%～35%, SPSF class high polymer mass concentration is 0%～40%, and two kinds of polymer total concentrations are 15wt%～45wt%, and preferred concentration is 20wt%～40wt%, and polyether sulfone and SPSF class high polymer mass ratio are preferably 5:1 ~ 3:2; Additive is at least a in acetone, ether, oxolane, ethylene glycol, butanone, methyl ether, the polyethylene glycol, the additive mass concentration is the aperture that 1%～25%(additive can be regulated NF membrane, pure water flux and rejection), preferred mass concentration is 5%～20%; Solvent is at least a in dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, the dimethyl sulfoxide (DMSO);
2nd, forming film with phase transformation method comprises flat sheet membrane and hollow-fibre membrane;
2.1st, the preparation of flat sheet membrane: above-mentioned casting solution is cast on the bright and clean level and smooth glass plate or on the template in that clean casting film is indoor, utilize stainless steel scraper striking film forming, in temperature preliminary treatment 1～20min under 0～60 ℃ the condition, then glass plate or template are put into 0 ℃～10 ℃ coagulating bath, solidified 12～24 hours, make its freezing film, promptly get dull and stereotyped NF membrane; Or adopt identical process conditions to utilize knifing machine to make film continuously.
2.2nd, the preparation of hollow-fibre membrane: above-mentioned casting solution is injected hollow-fibre membrane spinning liquid groove, spin out hollow fiber nanofiltration membrane by spinning head, the film silk directly enters in 0 ℃～10 ℃ coagulation baths and promptly gets hollow fiber nanofiltration membrane.
More than said SPSF class high polymer be SPSF or sulfonated polyether sulfone, sulfonation degree is 5%～50%, the form of material is divided into sodium type and Hydrogen SPSF class high polymer.
Said coagulating bath is water-bath, or contains organic solvent or wherein a kind of water-bath of inorganic salts, and organic solvent is at least a in dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, the dimethyl sulfoxide (DMSO); Inorganic salts are at least a in sodium chloride, the sodium sulphate.
Advantage of the present invention and good effect:
The used film build method of the present invention is the wet method phase separation method, and the NF membrane of preparation belongs to asymmetric NF membrane, is characterized in that step preparation has the blend NF membrane of unsymmetric structure.Prepared polyether sulfone/SPSF class high polymer NF membrane obviously has the dissymmetrical structure (Fig. 1) of dense layer surface and loose supporting layer.Prepared NF membrane work of separation ergosphere is at the surface and the zero defect (Fig. 2) of film, and other parts are supporting layers of porous, are interconnected between the hole.
Prepared NF membrane is that the sodium chloride of 0.5g/L～1.5g/L and the rejection of sodium sulphate reach 20%～95% to concentration under 0.1～0.8MPa operating pressure, in 40%～99.9% scope, the film pure water flux reaches 10～250L/ (m to the polyethylene glycol rejection of relative molecular mass 600～2000
2H), have that water flux is big, the aperture is accurate, intensity is high, pressure tightness is strong, and anti-chlorine is high temperature resistant, characteristics such as antipollution.Can be applicable to water treatment, wastewater treatment, aspects such as feed separation.
Description of drawings
Fig. 1 is the cross-sectional scans electromicroscopic photograph figure of ether sulfone of the present invention and a kind of embodiment of the asymmetric NF membrane of SPSF class high polymer blend (embodiment 2);
Fig. 2 is the film function tunic surface scan electromicroscopic photograph figure of ether sulfone of the present invention and a kind of embodiment of the asymmetric NF membrane of SPSF class high polymer blend (embodiment 2).
The specific embodiment
Below provide specific embodiments of the invention, but the present invention is not subjected to the restriction of embodiment:
Embodiment 1
The 55g dimethylacetylamide is joined in the 250mL there-necked flask, adding 15g acetone fully mixes, add polyether sulfone 18g again, sulfonation degree is 10% sodium type SPSF 12g, carry out stirring and dissolving under the room temperature, the weight ratio that is made into polyether sulfone and SPSF is 3:2, and the polymer total concentration is 30wt%, additive concentration is the casting solution of 15wt%, filters the airtight standing and defoaming in back.
Humidity in the casting film chamber is controlled at 40%, temperature is controlled at 25 ℃ in the casting film chamber, in the casting film chamber of cleaning with deaeration completely casting solution be cast on the bright and clean glass plate, with scraping the stainless steel scraper striking film forming that slot thickness is 0.25mm, put into temperature rapidly and be 4 ℃ the water-bath of solidifying, wait to solidify 24 and as a child took out, after water fully cleans it is stored in the preservation liquid, promptly get the said NF membrane of the present invention.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 20.3L/ (m
2H), be 89.5% to the sodium sulphate rejection of 1g/L, be 39.1% to the sodium chloride rejection of 1g/L, be 800 to the PEG800(relative molecular mass) rejection is 99%, is 600 to the PEG600(relative molecular mass) rejection is 81.6%.
Embodiment 2
The preparation condition of casting solution adopts the 180g dimethylacetylamide, 45g acetone with embodiment 1, polyether sulfone 45g, sulfonation degree is 10% sodium type SPSF 30g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
Humidity in the casting film chamber is controlled at 40%, and temperature is controlled at 25 ℃ in the casting film chamber, and the casting solution for preparing is poured in the material fluid bath, use conventional doughnut manufacturing installation, spinning doughnut condition is: core flow velocity 10ml/min, core liquid temp are 25 ℃, and coagulation bath temperature is 7 ℃.The spinning hollow fiber nanofiltration membrane immerses gel taking-up in 24 hours in the coagulating bath, after water fully cleans it is stored in the preservation liquid, promptly gets the said NF membrane of the present invention.
According to the film properties evaluation method of routine, utilize the evaluation of hollow-fibre membrane evaluating apparatus.At pressure is 0.5MPa, and feed temperature is under 25 ℃, and the pure water flux of this film is 54.0 L/ (m
2H), be 78.0% to the sodium sulphate rejection of 1g/L, be 34.8% to the sodium chloride rejection of 1g/L, be 800 to the PEG800(relative molecular mass) rejection is 98.8%, is 600 to the PEG600(relative molecular mass) rejection is 80.6%.
Embodiment 3
The preparation condition of casting solution adopts the 55g dimethylacetylamide, 15g acetone with embodiment 1, polyether sulfone 18g, sulfonation degree is 10% Hydrogen SPSF 12g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 30wt%, and the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 50.5 L/ (m
2H), be 76.5% to the sodium sulphate rejection of 1g/L, be 28.5% to the sodium chloride rejection of 1g/L, be 800 to the PEG800(relative molecular mass) rejection is 95.6%, is 600 to the PEG600(relative molecular mass) rejection is 72.6%.
Embodiment 4
The preparation condition of casting solution adopts the 60g dimethylacetylamide, 15g acetone with embodiment 1, polyether sulfone 21g, sulfonation degree is 50% sodium type SPSF 4g, the mass ratio of polyether sulfone and SPSF is 5:1, the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 17.9 L/ (m
2H), be 54.5% to the sodium sulphate rejection of 1g/L, be 25.3% to the sodium chloride rejection of 1g/L, be 2000 to the PEG2000(relative molecular mass) rejection is 92.3%, is 1000 to the PEG1000(relative molecular mass) rejection is 85.6%.
Embodiment 5
The preparation condition of casting solution is with embodiment 1, adopt the 60g dimethylacetylamide, the 15g oxolane, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, and the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.1MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 95.2 L/ (m
2H), be 2000 to the PEG2000(relative molecular mass) rejection is 93.1%, is 1000 to the PEG1000(relative molecular mass) rejection is 74.2%.
Embodiment 6
The preparation condition of casting solution adopts the 41.4g dimethylacetylamide, 5g acetone with embodiment 1, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 35wt%, and the additive mass concentration is 7% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 10.3L/ (m
2H), be 79.2% to the sodium sulphate rejection of 1g/L, be 33.5% to the sodium chloride rejection of 1g/L, be 1000 to the PEG1000(relative molecular mass) rejection is more than 99%, is 800 to the PEG800(relative molecular mass) rejection is 89.9%.
Embodiment 7
The preparation condition of casting solution adopts the 60g dimethylacetylamide, 15g acetone with embodiment 1, polyether sulfone 20g, sulfonation degree is 30% sodium type SPSF 5g, the mass ratio of polyether sulfone and SPSF is 4:1, the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 111.5L/ (m
2H), be 2000 to the PEG2000(relative molecular mass) rejection is 96%, is 1000 to the PEG1000(relative molecular mass) rejection is 87.9%.
Embodiment 8
The preparation condition of casting solution adopts the 55g dimethylacetylamide, 20g acetone with embodiment 1, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 25wt%, and the additive mass concentration is 20% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 78.4L/ (m
2H), be 78.0% to the sodium sulphate rejection of 1g/L, be 27.2% to the sodium chloride rejection of 1g/L, be 1000 to the PEG1000(relative molecular mass) rejection is 98.9%, is 800 to the PEG800(relative molecular mass) rejection is 84.1%.
Embodiment 9
The preparation condition of casting solution is with embodiment 1, adopt the 30g dimethyl formamide, the 30g dimethylacetylamide, 15g acetone, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 86.3L/ (m
2H), be 68.2% to the sodium sulphate rejection of 1g/L, be 21.5% to the sodium chloride rejection of 1g/L, be 1000 to the PEG1000(relative molecular mass) rejection is more than 99%, is 800 to the PEG800(relative molecular mass) rejection is 80.9%.
Embodiment 10
The preparation condition of casting solution adopts the 60g dimethylacetylamide, the 15g ether with embodiment 1, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 143.5L/ (m
2H), be 55.5% to the sodium sulphate rejection of 1g/L, be 25.0% to the sodium chloride rejection of 1g/L, be 1000 to the PEG1000(relative molecular mass) rejection is 96.7%, is 800 to the PEG800(relative molecular mass) rejection is 79.1 %.
Embodiment 11
The preparation condition of casting solution adopts the 60g dimethylacetylamide, 15g acetone with embodiment 1, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, the polymer total concentration is 25wt%, and the additive mass concentration is 15% formula of casting.
Humidity in the casting film chamber is controlled at 40%, temperature is controlled at 25 ℃ in the casting film chamber, in the casting film chamber of cleaning with deaeration completely casting solution be cast on the bright and clean glass plate, with scraping the stainless steel scraper striking film forming that slot thickness is 0.25mm, putting into environment temperature is 60 ℃ drying oven, takes out after 7 minutes, put into temperature rapidly and be 4 ℃ the water-bath of solidifying, treat that gel 24 as a child took out, after water fully cleans it is stored in the preservation liquid, promptly get the said NF membrane of the present invention.
According to the film properties evaluation method of routine, be 0.8MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 22.4L/ (m
2H), be 95.0% to the sodium sulphate rejection of 1g/L, be 32.8% to the sodium chloride rejection of 1g/L, be 800 to the PEG800(relative molecular mass) rejection is 98.4%, is 600 to the PEG600(relative molecular mass) rejection is 72.6%.
Embodiment 12
The preparation condition of casting solution is with embodiment 1, adopt 47g N-methyl pyrrolidone, 28g acetone, polyether sulfone 15g, sulfonation degree is 10% sodium type SPSF 10g, the mass ratio of polyether sulfone and SPSF is 3:2, and the polymer total concentration is 25wt%, and the additive mass concentration is 28% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 86.3L/ (m
2H), be 68.2% to the sodium sulphate rejection of 1g/L, be 21.5% to the sodium chloride rejection of 1g/L, be 1000 to the PEG1000(relative molecular mass) rejection is more than 99%, is 800 to the PEG800(relative molecular mass) rejection is 80.9%.
Embodiment 13
The preparation condition of casting solution adopts the 60g dimethylacetylamide with embodiment 1,15g acetone, and the sodium type SPSF 25g of sulfonation degree 10%, polymer concentration is 25wt%, the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 81.6L/ (m
2H), be 52.6% to the sodium sulphate rejection of 1g/L, be 18.6% to the sodium chloride rejection of 1g/L, be 1000 to the PEG1000(relative molecular mass) rejection is 94.2%, is 800 to the PEG800(relative molecular mass) rejection is 66.8%.
Embodiment 14
The preparation condition of casting solution adopts the 75g dimethylacetylamide with embodiment 1, the sodium type SPSF 25g of sulfonation degree 10%, and polymer concentration is 25wt%, non-additive formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 100.6L/ (m
2H), be 2000 to the PEG2000(relative molecular mass) rejection is 54.9%, is 1000 to the PEG1000(relative molecular mass) rejection is 0%.
Comparative Examples 1
The preparation condition of casting solution adopts the 55g dimethylacetylamide with embodiment 1,15g acetone, and polyether sulfone 25g, polymer concentration are 25wt%, the additive mass concentration is 15% formula of casting.
The preparation condition of film is with embodiment 1.
According to the film properties evaluation method of routine, be 0.5MPa at pressure, feed temperature is under 25 ℃, the pure water flux of this film is 0.8L/ (m
2H), be 2000 to the PEG2000(relative molecular mass) rejection is 50.7%, is 1000 to the PEG1000(relative molecular mass) rejection is 8.1%.
The membrane flux that SPSF is not added in Comparative Examples 1 explanation is very little, and very low to the PEG rejection.
Claims (6)
1. polyether sulfone and the asymmetric NF membrane preparation method of SPSF class high polymer blend is characterized in that this method comprises:
1st, the preparation of casting solution: polyether sulfone, SPSF class high polymer, additive and four kinds of components of solvent are hybridly prepared into casting solution;
Wherein the mass concentration of polyether sulfone is 0%～35%, and SPSF class high polymer mass concentration is 0%～40%, and two kinds of polymer total concentrations are 15wt%～45wt%; Additive is at least a in acetone, ether, oxolane, ethylene glycol, butanone, methyl ether, the polyethylene glycol, and the additive mass concentration is 1%～25%; Solvent is at least a in dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, the dimethyl sulfoxide (DMSO);
2nd, forming film with phase transformation method comprises flat sheet membrane and hollow-fibre membrane;
2.1st, the preparation of flat sheet membrane: above-mentioned casting solution is cast on the bright and clean level and smooth glass plate or on other templates in that clean casting film is indoor, utilize stainless steel scraper striking film forming, in temperature preliminary treatment 1～20min under 0～60 ℃ the condition, then glass plate or template are put into 0 ℃～10 ℃ coagulating bath, solidified 12～24 hours, make its freezing film, promptly get dull and stereotyped NF membrane; Or adopt identical process conditions to utilize knifing machine to make film continuously;
2.2nd, the preparation of hollow-fibre membrane: above-mentioned casting solution is injected hollow-fibre membrane spinning liquid groove, spin out hollow fiber nanofiltration membrane by spinning head, the film silk directly enters in 0 ℃～10 ℃ coagulation baths and promptly gets hollow fiber nanofiltration membrane.
2. method according to claim 1, it is characterized in that the 2.1st step coagulating bath before, be preliminary treatment 1～20min under 0-60 ℃ the condition in temperature.
3. method according to claim 1 is characterized in that the mass ratio of said polyether sulfone and SPSF class high polymer is preferably 5:1 ~ 3:2.
4. method according to claim 1 is characterized in that said SPSF class high polymer is SPSF or sulfonated polyether sulfone, and sulfonation degree is 5%～50%, and the form of material is divided into sodium type and Hydrogen SPSF class high polymer.
5. according to the described method of claim 1, it is characterized in that the additive mass concentration preferred 5%～20% in the casting solution.
6. according to each described method in the claim 1 to 5, it is characterized in that, said coagulating bath is water-bath, or containing organic solvent or wherein a kind of water-bath of inorganic salts, organic solvent is at least a in dimethyl formamide, dimethylacetylamide, N-methyl pyrrolidone, the dimethyl sulfoxide (DMSO); Inorganic salts are at least a in sodium chloride, the sodium sulphate.
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