CN102068920A - Asymmetrical polyvinyl chloride dry-wet reversible ultrafiltration/microfiltration membrane, preparation method and application thereof - Google Patents
Asymmetrical polyvinyl chloride dry-wet reversible ultrafiltration/microfiltration membrane, preparation method and application thereof Download PDFInfo
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 51
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 48
- 239000012528 membrane Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000001471 micro-filtration Methods 0.000 title claims abstract description 23
- 230000002441 reversible effect Effects 0.000 title claims abstract description 22
- 238000000108 ultra-filtration Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 20
- 238000005266 casting Methods 0.000 claims abstract description 18
- 230000001112 coagulating effect Effects 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
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- 238000005406 washing Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 16
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 238000001879 gelation Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- -1 polyethylene pyrrolidone Polymers 0.000 claims description 9
- 235000011187 glycerol Nutrition 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 235000013361 beverage Nutrition 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000003827 glycol group Chemical group 0.000 claims description 3
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
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- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an asymmetrical polyvinyl chloride dry-wet reversible ultrafiltration/microfiltration membrane, a preparation method and application thereof, which belong to the field of polymer microporous membranes. The asymmetrical polyvinyl chloride dry-wet reversible ultrafiltration/microfiltration membrane is prepared by the following steps of: striking membrane casting liquid which is prepared from polyvinyl chloride (PVC) serving as a major raw material on a carrier substrate so as to obtain an initial liquid producing membrane; gelling in coagulating liquid consisting of a mixed solvent; washing with water and soaking; and drying so as to obtain a finished membrane. The PVC ultrafiltration/microfiltration membrane prepared by a method has a finger-shaped structure on the surface, highly asymmetrical spongy porous structures on a mold stripping side and inside the membrane, has reversible dryness and wetness membrane performance and high stain resistance, is blocked difficultly, is easy to clean and regenerate, has a pore diameter which is adjustable between 0.01 and 1.0 mu m, is suitable for precision filtration, recycled water treatment, R0 pre-cartridge filtration, terminal precision filtration, tapped water direct drinking filtration, sewage treatment and liquid purification and filtration.
Description
Technical field
The present invention relates to the preparation of membrane material, particularly a kind of asymmetric polyvinyl chloride is done the preparation method of wet reversible surpassing/micro-filtration membrane.
Background technology
Polyvinyl chloride (PVC) is traditional macromolecular material that a kind of chemical stability is good, mechanical strength is high, in China stable industrialization product is arranged, and enough attention have just been obtained from China's film early stage of development, advantages such as its cheap price, strong resistance to acids and bases make it obtain development widely in the membrane separation technique field.But PVC material hydrophily is relatively poor, and the film separative efficiency of making is lower, and contamination resistance is also relatively poor, and the permeation rate difference of dried wet film is very big, preserves after glycerine plasticising so most of product all is the hygrometric state film, to keep membrane pore structure indeformable.Most of research all concentrates on the research of membrane material hydrophilic modifying.Being usually used in improving the hydrophilic method of PVC film at present is to allow PVC and other hydrophilic macromolecule organic matter blend, the blend of report both at home and abroad has vinyl chloride one vinyl acetate (V C-co-VAC) (≈ Sun Bin, Yang Yong, the research of .PVC/VC-co-VAC alloy films such as Song Yujun, the 6th extraordinary applied chemistry academic discussion thesis summary set, Beijing: Chinese Chemical Society, 1997,177-185. ≈ Ma Xingfa, Wei Liping, .PVC/CEVA co-mixing system Study on Compatibility such as Wu Chong light. polymer material science and engineering 1996,12 (2): 136-138. ≈ Bodzek M, Konieczny K.Theinfluence of molecular mass of polyvinylchloride) on the structure and transport characteristics of ultrafiltration membranes.Membrane Sciences.1991,61:131-156.), polymethyl methacrylate (PMMA) polyethylene one acrylonitrile copolymer (SAN), isobutene one copolymer-maleic anhydride (IB-CO-MIL), polyacrylonitrile (PAN), carboxylation polyvinyl chloride (CPVC), polyvinylpyrrolidones (PVP) etc. make the milipore filter that is used under the different condition respectively.Adopt the film of these materials and polychloroethylene blended preparation all to improve the hydrophily of PVC film in varying degrees, but pure water flux is higher under the situation that the overall performance of film equates the rejection of primary standard substance.Xu Zhenliang and Xu Jian disclosure of the Invention a kind of preparation method of high flux polyvinyl chloride hollow fiber ultrafiltration membrane, CN 1415407A; Peng Yuelian etc. have invented the preparation method of the alcoholysate blend film of PVC/ polyvinyl acetaldehyde high polymer blend film and PVC/ alkenyl halide one low-carbon ester copolymer, CN1562451A.In all above-mentioned reports, the wet film performance of PVC/PVP blend is best, and under 95% condition, pure water flux is 658ml/cm2hMPa to the bovine serum albumin rejection; (P.Rameh.Babu, VG Galkar.Preparation, Structure, and Transport Properties of Ultrafiltration poly (vinlychloride) is and Polyvinyl pyrrolidone (PVC)) Blends.App1 polym Sci 1999,73:1i17-1130.).
Also have, wet film is difficult to aseptic storage transportation, and when package group was dressed up filter, glycerine influenced the sealing intensity of filter, and promptly first compressive resistance is lower.The dry state film can thoroughly address the above problem, but up to the present, nobody can prepare the dried wet reversible non-plasticizing dry state PVC of film properties and surpass/micro-filtration membrane.
Summary of the invention
The objective of the invention is to overcome above-mentioned defective, provide a kind of high asymmetric polyvinyl chloride do wet reversible super/micro-filtration membrane and preparation method, solved existing phase inversion with the film of the method preparation and prepared spongy pore structure microporous barrier because of easily obstruction, flow depletion are rapidly, easy cleaning does not influence the problem in service life.The present invention can be used as the membrane material of aspects such as drinks, beverage, water treatment.
The objective of the invention is to be achieved through the following technical solutions: a kind of asymmetric polyvinyl chloride is done wet reversible surpassing/micro-filtration membrane, it is characterized in that: it is to be the casting solution that primary raw material is made with PVC, according to mass ratio: PVC: pore former: additive: solvent=8～21%: 1～7%: 1～10%: 65～90%; On carrier substrate, scrape and make the nascent liquid film that thickness is 80～600 μ m, gelation in the solidification liquid that mixed solvent is formed then, washing and dipping, drying;
Described pore former is selected from least a in polyethylene pyrrolidone PVP, polyethylene glycol PEG, lauryl alcohol ether sodium sulfate AES or the dodecyl sodium sulfate;
Described additive is water, glycerine, ethylene glycol or diethylene glycol ether;
Described solvent is N, N '-dimethylacetylamide DMAC, N, N '-dimethyl formamide DMF or N-methyl pyrrolidone NMP;
Described mixed solvent is a kind of and water among DMAC, DMF or the NMP or a kind of the mixing in the glycol water.
A kind of asymmetric polyvinyl chloride is done the preparation method of wet reversible surpassing/micro-filtration membrane, and it is characterized in that: it may further comprise the steps:
1) casting solution preparation: with mass concentration is 8～21% PVC, 1～7% pore former, 1～10% additive and 65～90% solvent, 20～75 ℃ of stirrings 20～50 hours down, after dissolving full and uniformly; 20～200 mesh sieves filter, and afterwards, deaeration is 1～30 hour in a vacuum, fully removes air, obtains casting solution;
2) the nascent liquid film of striking, and in air prevapourising: with 10～70 ℃ of slakings of casting solution constant temperature after 24～48 hours, spreading to thickness on glass, stainless steel or polyester flat carrier is the nascent liquid film of 80～600 μ m, and is that 10～40 ℃, relative humidity are to stop 50～150 seconds in 60～98% the air in temperature;
3) gelation: will immerse in 0～60 ℃ the coagulating bath, through nascent liquid film on the carrier until the demoulding of gel mould nature at air evaporation;
4) solid film post processing: solidify fully and from the gel mould that carrier is peeled off, immerse in 10～60 ℃ the pure water lixiviate residual solvent and additive more than three times, each 10 minutes, in pure water, flood 24～72 hours more at last after, room temperature is dried naturally.
The molecular weight of described PVC is 2 * 10
4～5 * 10
5
The molecular weight of described pore former is 2 * 10
3～2 * 10
6, comprise polyethylene pyrrolidone PVP, or polyethylene glycol PEG, or the lauryl alcohol ether sodium sulfate, or dodecyl sodium sulfate is a kind of, or both or three's mixture.
Described additive is a kind of of water, glycerine, ethylene glycol or diethylene glycol ether.
Described solvent is N, N '-dimethylacetylamide DMAC, N, N '-dimethyl formamide DMF or N-methyl pyrrolidone NMP.
The described striking liquid film of coming into being, and the prevapourising condition is in air:
Casting solution: 20～40 ℃;
Carrier: stainless steel;
Air themperature: 20～30 ℃;
Relative air humidity: 55～95%;
The time of staying: 50^120 second;
Nascent liquid film optimum thickness: 150～200 μ m.
The composition of described coagulating bath: comprise first component and second component, the mass content of first component is 0～90%; Residue is second component,
Wherein:
First component is a solvent, and solvent comprises DMAC, DMF or NMP;
Second component comprises water or glycol water, and the percentage composition of ethylene glycol is 0-50%.
The condition of described gelation:
First component is DMAC or DMF, 0%～85%;
Second component is glycol water or water, 15～85%;
Temperature: 0～40 ℃;
Time: 2～10 minutes.
Described asymmetric polyvinyl chloride is done the membrane material of wet reversible surpassing/micro-filtration membrane as drinks, beverage, water treatment.
The invention has the beneficial effects as follows:
A gelation different from the past prepares the method for polymeric membrane, the present invention is to provide a kind of meteorological surface evaporation initial set and liquid phase gel phase and transform the method that combines, and room temperature dry naturally obtain PVC super/micro-filtration membrane, the film top layer has finger-shaped, demoulding side is the high asymmetric apertures structure in spongy hole, has solved existing phase inversion and has prepared spongy pore structure microporous barrier because of easily obstruction, flow depletion are rapidly, easy cleaning does not influence the problem in service life.
Again, the inversion of phases method of first gel of a kind of low temperature and high relative humidity gas evaporation that provides among the present invention and the combination of liquid phase gel phase, obtain PVC super/the micro-filtration membrane top layer has finger-shaped, demoulding side and innerly is the high asymmetric apertures structure in spongy hole, have voidage high in, still have higher intensity.
Again, in method provided by the invention, by adjusting casting solution, coagulation bath composition prescription and filming technology condition, as evaporating temperature and humidity, evaporation time, coagulation bath temperature and gel time, and dry condition naturally, can prepare pore size and do wet reversible surpassing/micro-filtration membrane at the high asymmetric polyvinyl chloride (PVC) of 0.01～1.0 μ m.
Again, in the method provided by the invention, adopt additive and pore former blend in casting solution, can by realize simultaneously in the preparation process high asymmetric polyvinylchloride super/the micro-filtration membrane performance is done wet reversible.
Synthetically, do wet reversible surpassing/micro-filtration membrane by the high asymmetric polyvinylchloride that the invention provides the method preparation, the top layer have finger-shaped, demoulding side and film inner for high asymmetric apertures structure, the film properties in spongy hole especially be suitable as liquor, beer, beverage accurate do wet reversible, should not stop up, easy cleaning regenerates, and resistance to soiling is good, the aperture can be adjusted between 0.01～1.0 μ m, and security personnel's filtration, terminal secondary filter, running water are directly drunk the membrane material that filtration, sewage disposal and fluid purification filter before filtration, middle water treatment, the RO.
Description of drawings
Fig. 1 is the high asymmetric finger-shaped pore structure sem photographs of 50 μ m sections of the present invention.
Fig. 2 is 10 μ m film surface pore structure sem photographs of the present invention.
The specific embodiment
A kind of asymmetric polyvinyl chloride provided by the invention do wet reversible super/micro-filtration membrane, it is to be the casting solution that primary raw material is made with PVC, according to mass ratio: PVC: pore former: additive: solvent=8～21%: 1～7%: 1～10%: 65～90%; On carrier substrate, scrape and make the nascent liquid film that thickness is 80～600 μ m, gelation in the solidification liquid that mixed solvent is formed then, washing and dipping, drying;
Described pore former is selected from least a in polyethylene pyrrolidone PVP, polyethylene glycol PEG, lauryl alcohol ether sodium sulfate AES or the dodecyl sodium sulfate;
Described additive is water, glycerine, ethylene glycol or diethylene glycol ether;
Described solvent is N, N '-dimethylacetylamide DMAC, N, N '-dimethyl formamide DMF or N-methyl pyrrolidone NMP;
Described mixed solvent is a kind of and water among DMAC, DMF or the NMP or a kind of the mixing in the glycol water.
A kind of asymmetric polyvinyl chloride is done the preparation method of wet reversible surpassing/micro-filtration membrane, and it may further comprise the steps:
1) casting solution preparation: with mass concentration is 8～21% PVC, 1～7% pore former, 1～10% additive and 65～90% solvent, 20～75 ℃ of stirrings 20～50 hours down, after dissolving full and uniformly; 20～200 mesh sieves filter, and afterwards, deaeration is 1～30 hour in a vacuum, fully removes air, obtains casting solution;
2) the nascent liquid film of striking, and in air prevapourising: with 10～70 ℃ of slakings of casting solution constant temperature after 24～48 hours, spreading to thickness on glass, stainless steel or polyester flat carrier is the nascent liquid film of 80～600 μ m, and is that 10～40 ℃, relative humidity are to stop 50～150 seconds in 60～98% the air in temperature;
3) gelation: will immerse in 0～60 ℃ the coagulating bath, through nascent liquid film on the carrier until the demoulding of gel mould nature at air evaporation;
4) solid film post processing: solidify fully and from the gel mould that carrier is peeled off, immerse in 10～60 ℃ the pure water lixiviate residual solvent and additive more than three times, each 10 minutes, in pure water, flood 24～72 hours more at last after, room temperature is dried naturally.
The molecular weight of described PVC is 2 * 10
4～5 * 10
5
The molecular weight of described pore former is 2 * 10
3～2 * 10
6, comprise polyethylene pyrrolidone PVP, or polyethylene glycol PEG, or the lauryl alcohol ether sodium sulfate, or dodecyl sodium sulfate is a kind of, or both or three's mixture.
Described additive is a kind of of water, glycerine, ethylene glycol or diethylene glycol ether.
Described solvent is N, N '-dimethylacetylamide DMAC, N, N '-dimethyl formamide DMF or N-methyl pyrrolidone NMP.
The described striking liquid film of coming into being, and the prevapourising condition is in air:
Casting solution: 20～40 ℃;
Carrier: stainless steel;
Air themperature: 20～30 ℃;
Relative air humidity: 55～95%;
The time of staying: 50^120 second;
Nascent liquid film optimum thickness: 150～200 μ m.
The composition of described coagulating bath: comprise first component and second component, the mass content of first component is 0～90%; Residue is second component,
Wherein:
First component is a solvent, and solvent comprises DMAC, DMF or NMP;
Second component comprises water or glycol water, and the percentage composition of ethylene glycol is 0-50%.
The condition of described gelation:
First component is DMAC or DMF, 0%～85%;
Second component is glycol water or water, 15～85%;
Temperature: 0～40 ℃;
Time: 2～10 minutes.
Described asymmetric polyvinyl chloride is done the membrane material of wet reversible surpassing/micro-filtration membrane as drinks, beverage, water treatment.
Being the embodiment that high asymmetric polyvinyl chloride (PVC) is done wet reversible surpassing/micro-filtration membrane preparation below, is every implementation condition of embodiment in the tabulation, and the implementation step of all embodiment is all identical with aforementioned implementation step.
Every implementation condition of embodiment 1 is as shown in Table 1:
Table one
Primary raw material: PVC is a Tianjin Bohai Sea group Tianjin Chemical Plant, and PEG is 20000, Shanghai chemical reagents corporation of Chinese Medicine group; DMAC is Shanghai Jingwei Chemical Co., Ltd..
Every implementation condition of embodiment 2 is as shown in Table 2:
Table two
Every implementation condition of embodiment 3 is as shown in Table 3:
Table three
Wherein: PVP, K90, Shanghai chemical reagents corporation of Chinese Medicine group; Other raw materials are with embodiment 1.Every implementation condition of embodiment 4 is as shown in Table 4:
Table four
Raw material is with embodiment 3.
Among each embodiment, polyethers mocks the microporous barrier structures of samples and the performance situation sees Table five, wherein:
The water flux test is the sample of φ 10cm with diameter, tests under 1m water column static pressure;
Membrane aperture and voidage are measured: mercury injection method, instrument: DEM09500 type mercury injection apparatus, MicromecriticsInstrument Corp, the U.S.
Table five
At last, it is also to be noted that what more than enumerate only is specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion one that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (10)
- An asymmetric polyvinyl chloride do wet reversible super/micro-filtration membrane, it is characterized in that: it is to be the casting solution that primary raw material is made with PVC, according to mass ratio: PVC: pore former: additive: solvent=8～21%: 1～7%: 1～10%: 65～90%; On carrier substrate, scrape and make the nascent liquid film that thickness is 80～600 μ m, gelation in the solidification liquid that mixed solvent is formed then, washing and dipping, drying;Described pore former is selected from least a in polyethylene pyrrolidone PVP, polyethylene glycol PEG, lauryl alcohol ether sodium sulfate AES or the dodecyl sodium sulfate;Described additive is water, glycerine, ethylene glycol or diethylene glycol ether;Described solvent is N, N '-dimethylacetylamide DMAC, N, N '-dimethyl formamide DMF or N-methyl pyrrolidone NMP;Described mixed solvent is a kind of and water among DMAC, DMF or the NMP or a kind of the mixing in the glycol water.
- An asymmetric polyvinyl chloride do wet reversible super/preparation method of micro-filtration membrane, it is characterized in that: it may further comprise the steps:1) casting solution preparation: with mass concentration is 8～21% PVC, 1～7% pore former, 1～10% additive and 65～90% solvent, 20～75 ℃ of stirrings 20～50 hours down, after dissolving full and uniformly; 20～200 mesh sieves filter, and afterwards, deaeration is 1～30 hour in a vacuum, fully removes air, obtains casting solution;2) the nascent liquid film of striking, and in air prevapourising: with 10～70 ℃ of slakings of casting solution constant temperature after 24～48 hours, spreading to thickness on glass, stainless steel or polyester flat carrier is the nascent liquid film of 80～600 μ m, and is that 10～40 ℃, relative humidity are to stop 50～150 seconds in 60～98% the air in temperature;3) gelation: will immerse in 0～60 ℃ the coagulating bath, through nascent liquid film on the carrier until the demoulding of gel mould nature at air evaporation;4) solid film post processing: solidify fully and from the gel mould that carrier is peeled off, immerse in 10～60 ℃ the pure water lixiviate residual solvent and additive more than three times, each 10 minutes, in pure water, flood 24～72 hours more at last after, room temperature is dried naturally.
- 3. preparation method according to claim 2 is characterized in that: the molecular weight of described PVC is 2 * 10 4～5 * 10 5
- 4. preparation method according to claim 2 is characterized in that: the molecular weight of described pore former is 2 * 10 3～2 * 10 6, comprise polyethylene pyrrolidone PVP, or polyethylene glycol PEG, or the lauryl alcohol ether sodium sulfate, or dodecyl sodium sulfate is a kind of, or both or three's mixture.
- 5. preparation method according to claim 2 is characterized in that: described additive is a kind of of water, glycerine, ethylene glycol or diethylene glycol ether.
- 6. preparation method according to claim 2 is characterized in that: described solvent is N, N '-dimethylacetylamide DMAC, N, N '-dimethyl formamide DMF or N-methyl pyrrolidone NMP.
- 7. preparation method according to claim 2 is characterized in that: the described striking liquid film of coming into being, and the prevapourising condition is in air:Casting solution: 20～40 ℃;Carrier: stainless steel;Air themperature: 20～30 ℃;Relative air humidity: 55～95%;The time of staying: 50^120 second;Nascent liquid film optimum thickness: 150～200 μ m.
- 8. preparation method according to claim 2 is characterized in that: the composition of described coagulating bath: comprise first component and second component, the mass content of first component is 0～90%; Residue is second component,Wherein:First component is a solvent, and solvent comprises DMAC, DMF or NMP;Second component comprises water or glycol water, and the percentage composition of ethylene glycol is 0-50%.
- 9. preparation method according to claim 2 is characterized in that: the condition of described gelation:First component is DMAC or DMF, 0%～85%;Second component is glycol water or water, 15～85%;Temperature: 0～40 ℃;Time: 2～10 minutes.
- 10. the described asymmetric polyvinyl chloride of claim 1 is done the application of wet reversible surpassing/micro-filtration membrane, it is characterized in that it is used as the membrane material of drinks, beverage, water treatment.
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