CN101912738A - Preparation method of composite separating film with uniform surface apertures - Google Patents
Preparation method of composite separating film with uniform surface apertures Download PDFInfo
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- CN101912738A CN101912738A CN2010102620477A CN201010262047A CN101912738A CN 101912738 A CN101912738 A CN 101912738A CN 2010102620477 A CN2010102620477 A CN 2010102620477A CN 201010262047 A CN201010262047 A CN 201010262047A CN 101912738 A CN101912738 A CN 101912738A
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Abstract
The invention discloses a preparation method of a composite separating film with uniform surface apertures. The method comprises the following steps of: dissolving a polymer to a solvent and preparing a polymer solution; (2) adopting a porous material as a basement membrane; (3) coating the polymer solution obtained in the step (1) on the surface of the basement membrane in a mode of dipping, coating or spraying, and the like; and (4) arranging the basement membrane coated with the polymer solution in an environment at a temperature of 18-35 DEG C under a relative moisture of 60-95 percent to prepare a composite separating film with uniform surface apertures. In the invention, a composite layer with uniform surface apertures is formed on the surface of the porous material by adopting a water-assisted method, and the preparation method has simple operation and short time consumption, can adjust the uniform apertures of the composite separating film and has strong universality and wide application prospects in the field of precise filtration.
Description
Technical field
The present invention relates to the preparation field of diffusion barrier, relate in particular to a kind of preparation method of composite separating film with uniform surface apertures.
Background technology
Many fields such as polymer separation film separates at water treatment, gas, industry filtration have a wide range of applications.Along with the pay attention to day by day of people to environment and resource, membrane separation technique is considered to the crucial common technology of energy-saving and emission-reduction, also is the support technology of sustainable development.Though polymer separation film has obtained extensive use, the part but existing polymer separation film also comes with some shortcomings: for example, pore-size distribution broad, some average pore sizes are nominally 0.2 micron commercialization microporous polypropylene membrane, and the effective aperture may be between 0.05～1.2 micron; Hole shape is irregular, and the diffusion barrier that has is irregular near circular hole, and the diffusion barrier that has is the prolate shape hole.Because micro-filtration and ultra-filtration and separation mainly are based on the aperture and sieve this basic principle, therefore the pore-size distribution broad can cause separation accuracy lower, parting liquid is difficult to reach higher purity, thereby the application of polymer separation film aspect secondary filter is greatly limited.
The method of the polymer separation film of preparation aperture homogeneous mainly contains two kinds at present, and the one, track etching, the 2nd, block copolymer self assembly.Track etching method history is longer, mainly is the way pore-forming that adopts high-energy radiation, and membrane material is Merlon commonly, and its porosity is very low, the highest can only reaching about 20%.The diffusion barrier that method by the block copolymer self assembly prepares the aperture homogeneous is that the development in recent years new technology of getting up is (referring to Ja-Hyoung Ryu, et al.Highly Ordered GoldNanotubes Using Thiols at a Cleavable Block Copolymer Interface.J.Am.Chem.Soc.2009,131:9870-9871.), can reach higher porosity, but the aperture can't be applied to the preparation of the bigger micro-filtration membrane in aperture generally in nanometer range.
In recent years, the water auxiliary law has been subjected to extensive concern as a kind of method for preparing ordered porous material simply, easily and fast.The water auxiliary law is called steam revulsion or water droplet template again, is template with the condensed water under high humidity environment promptly, on solid substrate preparation pore-size distribution homogeneous, arrange ordered porous thin-film closely.From Francois is membrane material first with the star-shaped polystyrene, (G.Widawski since the acquisition honeycomb porous structure in high humidity environment, M.Rawiso, B.Francois, Self-organizedhoneycomb morphology of star-polymer polystyrene films, Nature, 1994, advantage such as 369:387-389), the water auxiliary law is simple because of its technology, experiment condition is gentle and compound with regular structure is controlled has been subjected to domestic and international researcher's extensive concern.The ordered porous membrane that has prepared amphipathic nature polyalcohol among Japan Patent JP 2002335949, JP2002347107 and the JP 2003128832 by the water auxiliary law can be used as cell culture material and display device; Publication number is to build polymer solution in the Chinese patent application of CN 1869109A at the bottom of the peeling liner, has prepared ordered porous laminated film, has greatly improved the mechanical performance of perforated membrane; Yu Chunling etc. are filmogen with the polyaniline that the 4-DBSA mixes, cellular ordered porous thin-film (Yu Chunling etc. have been prepared with electric conductivity, " the cellular discussion that the preparation of many holes film is arranged and form mechanism of doped polyaniline ", " SCI ", 2004,25:1322-1324); The brave grade with the chloroform of Zhao Xiao is the ordered porous membrane that solvent has prepared lactide-glycolide copolymer, and the influence (Zhao Xiaoyong etc. to membrane pore structure such as membrane material hydrophily, ambient humidity and solution concentration have been studied, the steam auxiliary law prepares the cellular porous film of LA-GA copolymer, " membrane science and technology ", 2004,24:1-6).At present, what the water auxiliary law obtained only is the surface hole defect structure, does not connect, thereby can't form the perforated membrane with isolated by filtration function.
Summary of the invention
The invention provides a kind of preparation method of composite separating film with uniform surface apertures.
A kind of preparation method of composite separating film with uniform surface apertures, basic principle is that the employing porous material is substrate, apply the volatile polymer solution of one deck solvent at porous material surface, in high humidity environment, place a period of time then, promptly making composite separating film with uniform surface apertures, is substrate owing to adopt porous material, can form the surface pore structure of the aperture homogeneous of perforation, the coat of this aperture homogeneous specifically comprises the steps: as the separating layer of composite separating film
1) polymer dissolution that will be used for surperficial pore-forming is configured to polymer solution in solvent;
Described polymer is polystyrene, PLA, cellulose, polysulfones, polyether-ether-ketone, PEI, Merlon, styrol copolymer or polystyrene blend;
Wherein, the comonomer of described styrol copolymer can be selected acrylic acid, methacrylic acid, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate or methyl acrylate etc. for use; The molar content of comonomer is preferably 0.2%～50% in the described styrol copolymer;
First component is a polystyrene in the described polystyrene blend, and second component can be selected polyethylene glycol, PVP, polyvinyl alcohol, polyvinylpyridine or polyacrylic acid etc. for use; The weight percentage of second component is preferably 1%～50% in the described polystyrene blend;
The concentration of described polymer solution is preferably 0.1mg/mL～50mg/mL.
The solvent of described polymer solution is selected according to polymer, and principle is a solvent of selecting for use saturated vapor pressure high, is preferably the mixture of chloroform, carbon disulfide, carrene, toluene, ethyl acetate, oxolane or oxolane and water etc.; Wherein, the volumn concentration of water is preferably 0.5%～10% in the mixture of described oxolane and water;
2) adopting porous material is basement membrane;
Described porous material is made by materials such as polypropylene, polyethylene, polysulfones, polyether sulfone, polyacrylonitrile, polyether-ether-ketone, cellulose, Kynoar, polytetrafluoroethylene (PTFE), polyester or nylon;
Described porous material can be the porous material of different shape, is preferably dull and stereotyped porous material or doughnut porous material;
Described porous material can be the microporous barrier of nonwoven, weaving cloth, phase inversion preparation or the microporous barrier of pulling method preparation according to preparation method's difference;
Described aperture of porous material is preferably 0.1～20 micron;
3) polymer solution that step 1) is made is coated on membrane surface by modes such as dip-coating, coating or sprayings;
4) basement membrane that will be coated with polymer solution was placed 10 seconds～10 minutes in 18 ℃～35 ℃, relative humidity are 60%～95% environment, made composite separating film with uniform surface apertures.
The aperture of described composite separating film is generally 0.05 micron～10 microns.
The present invention has following advantage and beneficial effect:
The present invention adopts the water auxiliary law to form the composite bed of surface apertures homogeneous at porous material surface, make composite separating film with uniform surface apertures, the simple to operate and weak point consuming time of method, the aperture homogeneous of composite separating film is adjustable, highly versatile is with a wide range of applications in the secondary filter field.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the typical composite separating film of embodiment 1 preparation.
The specific embodiment
By following examples the present invention is done more detailed description, but described embodiment is not construed as limiting the invention.
Embodiment 1
Be solvent with the chloroform earlier, configuration concentration is the polystyrene solution of 20mg/mL, it is 5 microns the dull and stereotyped nonwoven (as basement membrane) of polypropylene surface that the polystyrene solution that makes is evenly coated the aperture, and the polystyrene solution consumption is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 18 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1.2 microns composite separating film, and stereoscan photograph is seen Fig. 1.
Embodiment 2
Be solvent with ethyl acetate earlier, configuration concentration is the PLA solution of 20mg/mL, it is 5 microns polyester flat nonwoven (as basement membrane) surface that the PLA solution that makes is evenly coated the aperture, and the PLA solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1 micron composite separating film.
Embodiment 3
Is solvent with toluene earlier, configuration concentration is the cellulose solution of 20mg/mL, and it is 5 microns the dull and stereotyped nonwoven (as basement membrane) of cellulose surface that the cellulose solution that makes is evenly coated the aperture, and the cellulose solution consumption is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 2.2 microns composite separating film.
Embodiment 4
Be solvent with the chloroform earlier, configuration concentration is the polysulfones solution of 50mg/mL, the polysulfones solution that makes is evenly coated polysulfones flat plate porous film (Millipore commercially available prod) (as the basement membrane) surface that the aperture is 0.22 micron phase inversion preparation, and the polysulfones solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 10 seconds in 35 ℃, relative humidity are 60% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.2 micron composite separating film.
Embodiment 5
Be solvent with the chloroform earlier, configuration concentration is the polysulfones solution of 50mg/mL, the polysulfones solution that makes is evenly coated polyether sulfone flat plate porous film (Japan filter paper company commercially available prod) (as basement membrane) surface that the aperture is 0.2 micron phase inversion preparation, and the polysulfones solution usage is approximately 60 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 20 seconds in 25 ℃, relative humidity are 60% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.1 micron composite separating film.
Embodiment 6
Be solvent with the carrene earlier, configuration concentration is the polyether-ether-ketone solution of 40mg/mL, the polyether-ether-ketone solution that makes is evenly coated polyether-ether-ketone flat plate porous film (Japan filter paper company commercially available prod) (as basement membrane) surface that the aperture is 0.1 micron phase inversion preparation, and the polyether-ether-ketone solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 20 seconds in 25 ℃, relative humidity are 60% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.05 micron composite separating film.
Embodiment 7
Be solvent with the chloroform earlier, configuration concentration is the polyetherimide amine aqueous solution of 20mg/mL, the polyetherimide amine aqueous solution that makes is evenly coated polyacrylonitrile flat plate porous film (as the basement membrane) surface that the aperture is 2 microns phase inversion preparation, and the PEI solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.8 micron composite separating film.
The preparation process of polyacrylonitrile flat plate porous film is as follows: be that 50,000 polyacrylonitrile is dissolved in the 90g maleic anhydride with the 10g molecular weight under 160 ℃, insulation 6 as a child was cooled to 20 ℃ immediately, used methanol extraction then, drying.
Embodiment 8
Be solvent with the chloroform earlier, configuration concentration is the polycarbonate solution of 20mg/mL, it is 5 microns the dull and stereotyped nonwoven (as basement membrane) of nylon surface that the polycarbonate solution that makes is evenly coated the aperture, and the polycarbonate solution consumption is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.7 micron composite separating film.
Embodiment 9
Be solvent with the chloroform earlier, configuration concentration is the styrol copolymer solution of 30mg/mL, and wherein comonomer is an acrylic acid, and the comonomer mole percent is 2%.The styrol copolymer solution that makes is evenly coated polyvinylidene fluoride flat plate porous film (Millipore company commercially available prod) (as basement membrane) surface that the aperture is 0.1 micron phase inversion preparation, and the styrol copolymer solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 1 minute in 25 ℃, relative humidity are 65% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.05 micron composite separating film.
Embodiment 10
Be solvent with carbon disulfide earlier, configuration concentration is the styrol copolymer solution of 50mg/mL, and wherein comonomer is a methacrylic acid, and the comonomer mole percent is 2%.The styrol copolymer solution that makes is evenly coated polypropylene flat plate porous film (Nuclepore company commercially available prod) (as basement membrane) surface that the aperture is 0.4 micron pulling method preparation, and the styrol copolymer solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 1 minute in 25 ℃, relative humidity are 65% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.3 micron composite separating film.
Embodiment 11
Be solvent with the chloroform earlier, configuration concentration is the styrol copolymer solution of 20mg/mL, and wherein comonomer is a hydroxyethyl methacrylate, and the comonomer mole percent is 0.2%.It is 4 microns the dull and stereotyped nonwoven (as basement membrane) of polyethylene surface that the styrol copolymer solution that makes is evenly coated the aperture, and the styrol copolymer solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1.1 microns composite separating film.
Embodiment 12
Be solvent with carbon disulfide earlier, configuration concentration is the styrol copolymer solution of 0.1mg/mL, and wherein comonomer is a hydroxyethyl methacrylate, and the comonomer mole percent is 2%.It is 20 microns the dull and stereotyped weaving of polyacrylonitrile cloth (as basement membrane) surface that the styrol copolymer solution that makes is evenly coated the aperture, and the styrol copolymer solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 10 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 10 microns composite separating film.
Embodiment 13
Be solvent with the chloroform earlier, configuration concentration is the styrol copolymer solution of 30mg/mL, and wherein comonomer is a dimethylaminoethyl methacrylate, and the comonomer mole percent is 2%.The styrol copolymer solution that makes is evenly coated polytetrafluoroethylene (PTFE) flat plate porous film (Nuclepore company commercially available prod) (as basement membrane) surface that the aperture is 1 micron pulling method preparation, and the styrol copolymer solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.8 micron composite separating film.
Embodiment 14
Be solvent with the chloroform earlier, configuration concentration is the styrol copolymer solution of 50mg/mL, and wherein comonomer is a methyl acrylate, and the comonomer mole percent is 50%.It is 0.2 micron polypropylene hollow fiber microporous membrane (as basement membrane) surface that the styrol copolymer solution that makes is evenly coated the aperture, and the styrol copolymer solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 20 seconds in 25 ℃, relative humidity are 60% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.15 micron composite separating film.
Embodiment 15
Be solvent with oxolane/water earlier, wherein the percentage by volume of water is 0.5%, and configuration concentration is the polystyrene blend solution of 30mg/mL, and wherein second component is a polyethylene glycol, and the percetage by weight of second component is 50%.It is 5 microns the dull and stereotyped nonwoven (as basement membrane) of polypropylene surface that the polystyrene blend solution that makes is evenly coated the aperture, and the polystyrene blend solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.7 micron composite separating film.
Embodiment 16
Be solvent with the oxolane earlier, configuration concentration is the polystyrene blend solution of 30mg/mL, and wherein second component is a polyethylene glycol, and the percetage by weight of second component is 50%.It is 5 microns the dull and stereotyped nonwoven (as basement membrane) of polypropylene surface that the polystyrene blend solution that makes is evenly coated the aperture, and the polystyrene blend solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1 micron composite separating film.
Embodiment 17
Be solvent with the chloroform earlier, configuration concentration is the polystyrene blend solution of 20mg/mL, and wherein second component is a PVP, and the percetage by weight of second component is 30%.It is 5 microns the dull and stereotyped nonwoven (as basement membrane) of polypropylene surface that the polystyrene blend solution that makes is evenly coated the aperture, and the polystyrene blend solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1.3 microns composite separating film.
Embodiment 18
Be solvent with oxolane/water earlier, wherein the percentage by volume of water is 2%, and configuration concentration is the polystyrene blend solution of 20mg/mL, and wherein second component is a polyvinyl alcohol, and the percetage by weight of second component is 10%.It is 5 microns the dull and stereotyped nonwoven (as basement membrane) of polypropylene surface that the polystyrene blend solution that makes is evenly coated the aperture, and the polystyrene blend solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 0.9 micron composite separating film.
Embodiment 19
Be solvent with oxolane/water earlier, wherein the percentage by volume of water is 20%, and configuration concentration is the polystyrene blend solution of 20mg/mL, and wherein second component is a polyvinylpyridine, and the percetage by weight of second component is 10%.With the aperture is that 5 microns polyester flat nonwoven (as basement membrane) is immersed in the above-mentioned polystyrene blend solution and takes out after about 1 minute, the basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1.1 microns composite separating film.
Embodiment 20
Be solvent with the chloroform earlier, configuration concentration is the polystyrene blend solution of 20mg/mL, and wherein second component is a polyacrylic acid, and the percetage by weight of second component is 1%.It is 5 microns the dull and stereotyped nonwoven (as basement membrane) of polypropylene surface that the polystyrene blend solution that makes evenly is sprayed at the aperture, and the polystyrene blend solution usage is approximately 100 milliliters of/square metre basement membranes.The basement membrane that will be coated with polymer solution was then placed 3 minutes in 25 ℃, relative humidity are 85% environment, promptly made hole, surface apertures homogeneous and aperture with perforation and be 1.5 microns composite separating film.
Claims (10)
1. the preparation method of a composite separating film with uniform surface apertures comprises the steps:
1) with polymer dissolution in solvent, be configured to polymer solution;
Described polymer is polystyrene, PLA, cellulose, polysulfones, polyether-ether-ketone, PEI, Merlon, styrol copolymer or polystyrene blend;
Wherein, the comonomer of described styrol copolymer is acrylic acid, methacrylic acid, hydroxyethyl methacrylate, dimethylaminoethyl methacrylate or methyl acrylate;
First component is a polystyrene in the described polystyrene blend, and second component is polyethylene glycol, PVP, polyvinyl alcohol, polyvinylpyridine or polyacrylic acid;
2) adopting porous material is basement membrane;
Described porous material is made by polypropylene, polyethylene, polysulfones, polyether sulfone, polyacrylonitrile, polyether-ether-ketone, cellulose, Kynoar, polytetrafluoroethylene (PTFE), polyester or nylon material;
3) polymer solution that step 1) is made is coated on membrane surface by the mode of dip-coating, coating or spraying;
4) basement membrane that will be coated with polymer solution was placed 10 seconds～10 minutes in 18 ℃～35 ℃, relative humidity are 60%～95% environment, made composite separating film with uniform surface apertures.
2. the preparation method of composite separating film with uniform surface apertures according to claim 1 is characterized in that, the concentration of described polymer solution is 0.1mg/mL～50mg/mL.
3. the preparation method of composite separating film with uniform surface apertures according to claim 1 and 2, it is characterized in that, described polymer solution with the mixture of chloroform, carbon disulfide, carrene, toluene, ethyl acetate, oxolane or oxolane and water as solvent.
4. the preparation method of composite separating film with uniform surface apertures according to claim 3 is characterized in that, the volumn concentration of water is 0.5%～10% in the mixture of described oxolane and water.
5. the preparation method of composite separating film with uniform surface apertures according to claim 1 is characterized in that, in the step 1), the molar content of comonomer is 0.2%～50% in the described styrol copolymer.
6. the preparation method of composite separating film with uniform surface apertures according to claim 1 is characterized in that, in the step 1), the weight percentage of second component is 1%～50% in the described polystyrene blend.
7. the preparation method of composite separating film with uniform surface apertures according to claim 1 is characterized in that step 2) in, described porous material is the microporous barrier of nonwoven, weaving cloth, phase inversion preparation or the microporous barrier of pulling method preparation;
Described porous material be shaped as flat sheet membrane or doughnut.
8. the preparation method of composite separating film with uniform surface apertures according to claim 1 is characterized in that, the aperture of described porous material is 0.1 micron 20 microns.
9. according to the composite separating film with uniform surface apertures of the preparation method of each described composite separating film with uniform surface apertures of claim 1～8 preparation.
10. composite separating film with uniform surface apertures according to claim 9 is characterized in that, the aperture of described composite separating film is 0.05 micron～10 microns.
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| CN105013354A (en) * | 2014-04-30 | 2015-11-04 | 华北电力大学 | Composite membrane used for gathering water vapor in smoke of thermal power plant and preparation method thereof |
| CN105085782A (en) * | 2015-07-17 | 2015-11-25 | 中国石油天然气股份有限公司 | Polystyrene methyl acrylate and synthetic method therefor and application thereof |
| CN105482139A (en) * | 2016-01-18 | 2016-04-13 | 浙江工业大学 | Preparation method of porous polystyrene thin-film material with uniform pore diameters |
| WO2017012152A1 (en) * | 2015-07-20 | 2017-01-26 | 北京工业大学 | Method for rapid and environmentally friendly preparation of dense separation membrane |
| CN106512755A (en) * | 2016-10-11 | 2017-03-22 | 新疆蓝山屯河能源有限公司 | Molecular weight narrowing ultrafiltration membrane, preparation method, PTMEG molecular weight narrowing method and application thereof |
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| CN103904274A (en) * | 2012-12-28 | 2014-07-02 | 海洋王照明科技股份有限公司 | Electrochemical power source diaphragm and preparation method thereof, and electrochemical cell or capacitor |
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| CN103113613B (en) * | 2013-01-30 | 2014-07-02 | 浙江大学 | Preparation method of self-supporting through-type polyelectrolyte ordered porous membrane |
| CN105013354A (en) * | 2014-04-30 | 2015-11-04 | 华北电力大学 | Composite membrane used for gathering water vapor in smoke of thermal power plant and preparation method thereof |
| CN105085782A (en) * | 2015-07-17 | 2015-11-25 | 中国石油天然气股份有限公司 | Polystyrene methyl acrylate and synthetic method therefor and application thereof |
| WO2017012152A1 (en) * | 2015-07-20 | 2017-01-26 | 北京工业大学 | Method for rapid and environmentally friendly preparation of dense separation membrane |
| CN105482139A (en) * | 2016-01-18 | 2016-04-13 | 浙江工业大学 | Preparation method of porous polystyrene thin-film material with uniform pore diameters |
| CN107789988A (en) * | 2016-08-31 | 2018-03-13 | 山东东岳高分子材料有限公司 | Hollow fiber composite membrane of ultra-thin active layer and preparation method thereof |
| CN106512755A (en) * | 2016-10-11 | 2017-03-22 | 新疆蓝山屯河能源有限公司 | Molecular weight narrowing ultrafiltration membrane, preparation method, PTMEG molecular weight narrowing method and application thereof |
| CN106512755B (en) * | 2016-10-11 | 2019-12-13 | 新疆蓝山屯河能源有限公司 | Narrowing molecular weight ultrafiltration membrane, preparation method thereof, method for narrowing molecular weight of PTMEG and application |
| CN110227350A (en) * | 2018-01-08 | 2019-09-13 | 淮阴师范学院 | A kind of application of the modified PVDF ultrafiltration membrane of attapulgite in protein solution filtration |
| CN110227350B (en) * | 2018-01-08 | 2022-01-28 | 淮阴师范学院 | Application of attapulgite modified PVDF ultrafiltration membrane in protein solution filtration |
| CN111135732A (en) * | 2019-12-26 | 2020-05-12 | 厦门大学 | Fluorine-containing polymer film and preparation method and application thereof |
| CN111346522A (en) * | 2020-02-16 | 2020-06-30 | 武汉纺织大学 | Polyvinyl alcohol-ethylene copolymer honeycomb porous membrane and preparation method thereof |
| CN111346522B (en) * | 2020-02-16 | 2021-10-01 | 武汉纺织大学 | Polyvinyl alcohol-ethylene copolymer honeycomb porous membrane and preparation method thereof |
| CN112456432A (en) * | 2020-08-26 | 2021-03-09 | 北京航空航天大学 | Method for preparing surface micro-nano dents based on liquid drop dissolution |
| CN112456432B (en) * | 2020-08-26 | 2022-10-11 | 北京航空航天大学 | Method for preparing surface micro-nano dents based on liquid drop dissolution |
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