CN101439266A - Surface modification method of polymer microporous film - Google Patents
Surface modification method of polymer microporous film Download PDFInfo
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Abstract
The invention discloses a microporous membrane surface hydrophilic modification method which comprises the following steps: (1) a polymer microporous membrane is pretreated by utilizing anatmospheric dielectric barrier discharge plasma technology; (2) the treated microporous membrane is arranged into the aqueous solution of a water-soluble polymer for dipping to lead the surface of the microporous membrane to absorb a polymer layer; (3) the microporous membrane is crosslinked and solidified under certain temperature. The method has the characteristics of simple technique, convenient operation, quick processing speed, good processing effect, low cost, being not easy to cause environment pollution, energy saving, and the like.
Description
Technical field
The present invention relates to a kind of method of separation membrane surface modification, particularly relate to a kind of method of polymer micro membrane surface modification.
Technical background
Membrane separation technique is widely used in aqueous medium separation, purifying, purification in the fields such as biological medicine, chemical industry, food, the energy, water treatment etc.But membrane material hydrophilicities such as polyethylene, polypropylene, Kynoar are poor, thereby influenced their use.By various physics, chemical method modification being carried out on such microporous barrier surface and given its good hydrophilicity, is the necessary ways of widening its range of application.
Plasma technique has that action effect is good, cleanliness without any pollution, only to material list surface layer generation effect, the bulk properties of material is not had characteristics such as harmful effect, thereby also be a kind of microporous barrier surface modifying method that enjoys favor.Patent WO2003051498-A has reported that utilizing the low pressure plasma technique to handle the film material improves its hydrophily; Patent WO9209357 has reported and has utilized vacuum plasma technology to handle microporous teflon membran changing its hydrophily, and has been used for waste water filtering; Patent WO2007126967 has reported that the normal pressure microwave plasma carries out surface modification to microporous barrier; Patent CN1623639 has reported and has utilized high-energy radiation (plasma, electron beam, Co-60 and ray) that microporous barrier is carried out irradiation to change its surperficial hydrophily under the low pressure of carbon dioxide atmosphere.Though the plasma technique action effect is good, there is inconvenient operation in the modification that the low pressure plasma technique is used for microporous barrier, is unfavorable for that industrialization produces continuously; Corona discharge plasma active particle density is low, and treatment effeciency is not high, and technology is difficult for promoting; Normal pressure microwave discharge plasma energy consumption is big, and very strong radiation is arranged, and safety can not ensure.
The atmospheric dielectric barrier discharge plasma technique is a kind of new plasma technique that occurs in recent years, have discharge the time do not need to vacuumize and under normal pressure, carry out, discharging efficiency height, active particle density height, to material processed efficient height, advantage such as popularization easily, thereby be subjected to extensive concern.But this technology is used for the membrane material surface modification and also has action effect this problem that must solve that decays in time.The method that can keep the modification performance for a long time generally is that functional macromolecule is fixed on material surface by chemical bonding, and wherein glycerol polymerization method has certain advantage.Among the Chinese patent ZL200310108528.2, adopting glycosyl compound is the modify and graft monomer, obtains polymer separation film by this method, and hydrophily and biocompatibility improve, and can keep for a long time.But need form the complexity of increase technology as the glycosyl compound of grafted monomers by glycosyl and material chemical combination such as alkene class, ester class.Among the Chinese patent ZL200310122704.8, adopt that hydrophilic polymer adsorbs, crosslinked method in microporous barrier, significantly improve polymer film hydrophily and biocompatibility.But, influence modification efficiency because the existence of boundary layer between hydrophobic polymer film and the hydrophilic polymer to be adsorbed makes that the absorption of hydrophilic polymer in fenestra is limited.
Summary of the invention
The invention provides a kind of method of polymer micro membrane surface modification, adopt the atmospheric dielectric barrier discharge plasma that hydrophilicity-imparting treatment is carried out on the surface of polymer micro membrane material earlier, again at the big molecule of polymer microporous film surface absorption hydrophily, and it is fixed on the microporous barrier, thereby make polymer microporous film obtain efficient and durable hydrophily by chemical crosslink technique.
A kind of surface modification method of polymer microporous film may further comprise the steps:
(1) with polymer microporous film cleaning, drying;
Polymer microporous film cleans with acetone and removes the impurity that is adsorbed on the film surface 3 times, and vacuum drying at room temperature then also can be taked the alternate manner drying, removes the solvent on polymer microporous film surface.
(2) polymer microporous film after step (1) processing is placed between two sparking electrodes of dielectric barrier discharge, carry out the atmospheric dielectric barrier discharge plasma and handle, make the polymer microporous film surface generate active group to improve its surperficial polarity;
Described plasma producing apparatus is the high-frequency plasma generator, and the plasma discharge pattern is a large tracts of land dielectric barrier discharge under the normal pressure.Long 20 centimetres, wide 12 centimetres of sparking electrode; Electrode is an aluminium matter parallel-plate, and the dielectric-slab material between the electrode is a pottery, and dielectric-slab is close to the high-low pressure electrode respectively, the adjustable gaps between two sparking electrodes; Electric pole plate has gas port so that logical inert gas; The discharge power of plasma producing apparatus is 0～200 watt; Discharge frequency is 1～15 KHz.
Described atmospheric dielectric barrier discharge plasma treatment conditions are: the distance between two sparking electrodes is 1～5 millimeter; Feed the mist of inert gas and oxygen during discharge, 0.5～10 liter/minute of mixed gas flow; Discharge frequency is 10 KHzs, and discharge power is 80～180 watts, and the processing time is 20～180 seconds.
The described distance that is provided with between two sparking electrodes is preferably 2 millimeters.In the described mist, the volume ratio of inert gas and oxygen is 99/1; Described inert gas is preferably helium or argon gas.
Under atmospheric dielectric barrier discharge plasma treatment conditions of the present invention, can produce evenly, high activity, highdensity glow discharge plasma, reach optimization to guarantee glycerol polymerization efficient.
(3) place the hydrophilic polymer aqueous solution to soak 20～60 minutes the polymer microporous film after step (2) processing, make the microporous barrier surface form the dip-coating polymeric layer; Take out heating after immersion is finished and carry out cross-linking reaction;
The mass percent concentration of the hydrophilic polymer in the described hydrophilic polymer aqueous solution is 1～20%, and hydrophilic polymer can effectively be dissolved in solvent, and controls its moderate viscosity, fully ensures the diffusion free degree of strand; Also contain the chloropharin that accounts for hydrophilic polymer amount 1～5% in the hydrophilic polymer aqueous solution or account for the potassium peroxydisulfate of hydrophilic polymer amount 1～5%, as crosslinking agent, make the hydrophilic polymer molecules chain generation cross-linking reaction that is adsorbed on the polymer microporous film material surface make it immobilized purpose to reach.
Described hydrophilic polymer is preferably shitosan, polyethylene glycol, PVP, polyacrylic acid ethylene oxidic ester, poly hydroxy ethyl acrylate, polyacrylic acid, polyacrylamide, polyvinyl alcohol, polypropylene glycol, to give the polymer microporous film surface good hydrophily; The weight average molecular weight range of hydrophilic polymer keeps the suitable molecular weight of hydrophilic polymer to ensure that it is at the surface immobilized back of polymer microporous film difficult drop-off 5000～20000.
Described soak time is preferably 30 minutes, makes fully absorption hydrophilic polymer of polymer microporous film surface, has improved the efficient of technology again.
Described heating-up temperature is preferably 45 ℃, and described cross-linking reaction time is preferably 4 hours, makes hydrophilic polymer that effective cross-linking reaction take place.
Among the present invention, described polymer microporous film is polyethylene, polypropylene or polyvinylidene fluoride microporous film, and its average pore size is 0.1～1.5 micron, and porosity is 20～85%.
Among the present invention, the shape of described polymer microporous film can be flat plate porous film or hollow fiber microporous membrane, but is not limited only to this.
Preferred scheme is that the thickness of described flat plate porous film is 15～200 microns.The internal diameter of described hollow fiber microporous membrane is that 15～500 microns, external diameter are 100～1800 microns.
The inventive method advantage is:
(1) the dielectric barrier discharge plasma processing is to carry out at normal temperatures and pressures; mild condition, energy consumption is little, efficient is high, security is good, be difficult for causing environmental pollution; it is different from the low pressure plasma method and needs vacuum condition; equipment is simple, can design and produce as required; realize the continuous modification of polymer microporous film easily, have more the scale significance of application.
(2) polymer microporous film is applied after plasma treatment immediately cross-linking modified, with polymer micro membrane material glycerol polymerization modification compare used time short, operation is simpler.
(3) the atmospheric dielectric barrier discharge plasma is only in polymer microporous film surface and fenestra inner surface reaction of formation activated centre, be different from ultraviolet, gamma-radiation irradiation etc. and handle crosslinking technology, this processing method can not destroyed film interpolymer strand, and is little to the damage of film.
(4) surface of the polymer microporous film after the modification and fenestra inwall are endowed the hydrophilic modifying layer, the hydrophilic modifying layer is good with the compatibility between the polymer microporous film base material, hydrophilic layer is stable, modification is lasting, the contact angle of water reduces more than 40%, protein adsorption reduces more than 70%, and water flux improves more than 70%.
Description of drawings
Fig. 1 is a plasma treatment procedure schematic diagram of the present invention.
Wherein, 1 is pending polymer micro membrane material; 2 is plasma generator; 3 is wireway, and mist imports from this wireway; 4 is sparking electrode; 5 is dielectric-slab; 6 is winder.
The specific embodiment
The explanation of plasma treatment
In conjunction with the accompanying drawings 1, article on plasma body processing procedure of the present invention is described:
Pending polymer micro membrane material 1 through between the sparking electrode 4 of plasma device, is wound in an automatic winding machine 6 again.This automatic winding machine 6 can carry out online rolling with the polymer microporous film after handling, and comes the Trace speed of telomerized polymer microporous barrier by the rotating speed of regulating Scroll.
The distance of regulating between two sparking electrodes 4 is 1～5 millimeter, feeds mist earlier, and the regulation and control intake velocity is 0.5～10 liter/minute; Open power supply then, the switch of the plasma generator 2 that closes, regulating plasma discharge power is 80～180 watts, makes to produce uniform plasma.In the time of between the polymer microporous film process plasma discharge electrode 4, its surface obtains handling.Regulate the rotating speed of Scroll, making polymer microporous film Trace speed (transfer rate) is 3.3～30 meters/minute, passes through winder 5 rollings then.Can guarantee that like this plasma treatment time at 20～180 seconds, is handled the polymer microporous film surface fully.
Embodiment 1: atmospheric plasma is handled polyethylene flat sheet membrane modified technique.
Raw material: polyethylene flat sheet membrane (25 microns of thickness, average pore size are 0.4 micron, porosity 20%); Be used for the aqueous solution (shitosan is 6% in the mass percentage concentration of solution, shitosan weight average molecular weight 8000～10000) of the shitosan of film surface dip-coating, wherein also contain chloropharin in the aqueous solution of shitosan, the quality of chloropharin is 5% of a chitosan mass.
After the polyethylene flat sheet membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polyethylene flat sheet membrane after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is argon gas and oxygen (volume ratio is 99/1), and intake velocity is 4 liters/minute; Plasma discharge power is 150 watts, and the Trace speed of film is 20 meters/minute, and plasma treatment time is about 30 seconds.Polyethylene flat sheet membrane that again will be after plasma treatment immersed in the chitosan aqueous solution 30 minutes, took out back 45 ℃ of dryings in baking oven, promptly carried out cross-linking reaction 4 hours under this temperature.
Embodiment 2: atmospheric plasma is handled polyethylene hollow fiber film modified technique
Raw material: polyethylene hollow fiber film (100 microns of internal diameters, 500 microns of external diameters, average pore size is 0.8 micron, porosity 40%), (polyethylene glycol is 8% in the solution mass percentage concentration to be used for the aqueous solution of polyethylene glycol of film surface dip-coating, weight average molecular weight 18000～20000), wherein also contain chloropharin in the aqueous solution of polyethylene glycol, the quality of chloropharin is 3% of a polyethylene glycol quality.
After the polyethylene hollow fiber film cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polyethylene hollow fiber film after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is argon gas and oxygen (volume ratio is 99/1), and intake velocity is 4 liters/minute; Plasma discharge power is 150 watts, and the Trace speed of film is 20 meters/minute, and plasma treatment time is about 30 seconds.Again the polyethylene hollow fiber film after plasma treatment is immersed the polyethylene glycol aqueous solution 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 3: atmospheric plasma is handled polypropylene flat sheet membrane modified technique.
Raw material: polypropylene flat sheet membrane (200 microns of thickness, average pore size is 1 micron, porosity 60%), (PVP is 12% in the solution mass percentage concentration to be used for the aqueous solution of PVP of film surface dip-coating, the weight average molecular weight 15000～18000 of PVP), wherein contain potassium peroxydisulfate in the aqueous solution of PVP, the quality of potassium peroxydisulfate is 4% of a PVP quality.
After the polypropylene flat sheet membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polypropylene flat sheet membrane after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is argon gas and oxygen (volume ratio is 99/1), and intake velocity is 10 liters/minute; Plasma discharge power is 80 watts, and the Trace speed of film is 30 meters/minute, and plasma treatment time is about 20 seconds.Again the polypropylene flat sheet membrane after plasma treatment is immersed the PVP aqueous solution 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 4: atmospheric plasma is handled the polypropylene hollow fiber membrane modified technique.
Raw material: polypropylene hollow fiber membrane (15 microns of internal diameters, 100 microns of external diameters, average pore size is 0.6 micron, porosity 60%), (the polyacrylic acid ethylene oxidic ester is 5% in the mass percentage concentration of solution to be used for the aqueous solution of polyacrylic acid ethylene oxidic ester of film surface dip-coating, the weight average molecular weight 12000～15000 of polyacrylic acid ethylene oxidic ester), wherein contain chloropharin in the aqueous solution of polyacrylic acid ethylene oxidic ester, the quality of chloropharin is 3% of a polyacrylic acid ethylene oxidic ester quality.
After polypropylene hollow fiber membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polypropylene hollow fiber membrane after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is argon gas and oxygen (volume ratio is 99/1), and intake velocity is 4 liters/minute; Plasma discharge power is 150 watts, and the Trace speed of film is 3.3 meters/minute, and plasma treatment time is about 180 seconds.Again the polypropylene hollow fiber microporous membrane after plasma treatment is immersed polyacrylic acid glycidol aqueous solution of ester 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 5: atmospheric plasma is handled polypropylene flat sheet membrane modified technique.
Raw material: polypropylene flat sheet membrane (100 microns of thickness, average pore size is 0.4 micron, porosity 60%), (poly hydroxy ethyl acrylate is 6% in the mass percentage concentration of solution to be used for the aqueous solution of poly hydroxy ethyl acrylate of film surface dip-coating, the weight average molecular weight 8000～10000 of poly hydroxy ethyl acrylate), wherein contain chloropharin in the aqueous solution of poly hydroxy ethyl acrylate, the quality of chloropharin is 3% of a poly hydroxy ethyl acrylate quality.
After the polypropylene flat sheet membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polypropylene flat sheet membrane after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is helium and oxygen (volume ratio is 99/1), and intake velocity is 0.5 liter/minute; Plasma discharge power is 180 watts, and the Trace speed of film is 15 meters/minute, and plasma treatment time is about 40 seconds.Again the polypropylene flat sheet membrane after plasma treatment is immersed the poly hydroxy ethyl acrylate aqueous solution 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 6: atmospheric plasma is handled polyvinylidene fluoride flat film modified technique.
Raw material: polyvinylidene fluoride flat film (80 microns of thickness, average pore size is 0.6 micron, porosity 40%), (polyacrylic acid is 20% in the mass percentage concentration of solution to be used for the polyacrylic aqueous solution of film surface dip-coating, polyacrylic weight average molecular weight 18000～20000), contain chloropharin in the wherein polyacrylic aqueous solution, the quality of chloropharin is 3% of a polyacrylic acid quality.
After the polyvinylidene fluoride flat film cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polyvinylidene fluoride flat film after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is argon gas and oxygen (volume ratio is 99/1), and intake velocity is 5 liters/minute; Plasma discharge power is 180 watts, and the Trace speed of film is 15 meters/minute, and plasma treatment time is about 40 seconds.Again the polyvinylidene fluoride flat film after plasma treatment is immersed the polyacrylic acid aqueous solution 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 7: atmospheric plasma is handled Kynoar hollow-fibre membrane modified technique.
Raw material: Kynoar hollow-fibre membrane (500 microns of internal diameters, 1800 microns of external diameters, average pore size is 1.5 microns, porosity 85%), (polyacrylamide is 12% in the mass percentage concentration of solution to be used for the aqueous solution of polyacrylamide of film surface dip-coating, the weight average molecular weight 10000～12000 of polyacrylamide), wherein contain chloropharin in the aqueous solution of polyacrylamide, the quality of chloropharin is 3% of a polyacrylamide quality.
After the Kynoar hollow-fibre membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polyvinylidene fluoride flat film after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is helium and oxygen (volume ratio is 99/1), and intake velocity is 6 liters/minute; Plasma discharge power is 180 watts, and the Trace speed of film is 15 meters/minute, and plasma treatment time is about 40 seconds.Kynoar hollow-fibre membrane after plasma treatment is immersed polyacrylamide solution 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 8: atmospheric plasma is handled polyacrylonitrile flat plate porous film modified technique
Raw material: polyacrylonitrile flat sheet membrane (120 microns of thickness, average pore size is 0.4 micron, porosity 40%), (polyvinyl alcohol is 5% in the mass percentage concentration of solution to be used for the aqueous solution of polyvinyl alcohol of film surface dip-coating, the weight average molecular weight 18000～20000 of polyvinyl alcohol), wherein contain chloropharin in the aqueous solution of polyvinyl alcohol, the quality of chloropharin is 1% of a polyvinyl alcohol quality.
After the polyacrylonitrile flat sheet membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polyacrylonitrile flat sheet membrane after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is helium and oxygen (volume ratio is 99/1), and intake velocity is 3 liters/minute; Plasma discharge power is 180 watts, and the Trace speed of film is 15 meters/minute, and plasma treatment time is about 40 seconds.Again the polyacrylonitrile flat sheet membrane after plasma treatment is immersed polyvinyl alcohol water solution 30 minutes, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carried out cross-linking reaction 4 hours.
Embodiment 9: atmospheric plasma is handled polyacrylonitrile hollow-fibre membrane modified technique.
Raw material: polyacrylonitrile hollow-fibre membrane (100 microns of internal diameters, 500 microns of external diameters, average pore size is 0.8 micron, porosity 40%), (polypropylene glycol is 8% in the mass percentage concentration of solution to be used for the aqueous solution of polypropylene glycol of film surface dip-coating, the weight average molecular weight 15000～18000 of polypropylene glycol), wherein contain chloropharin in the aqueous solution of polypropylene glycol, the quality of chloropharin is 2% of a polypropylene glycol quality.
After the polyacrylonitrile hollow-fibre membrane cleaned 3 times with acetone, vacuum drying at room temperature 3 hours.Then the polyacrylonitrile hollow-fibre membrane after above-mentioned processing is carried out the atmospheric dielectric barrier discharge plasma and handle, treatment conditions are: the gap between the sparking electrode 4 is 2 millimeters; Mist is helium and oxygen (volume ratio is 99/1), and intake velocity is 3 liters/minute; Plasma discharge power is 180 watts, and the Trace speed of film is 15 meters/minute, and plasma treatment time is about 40 seconds.To after plasma treatment, immerse the polypropylene glycol aqueous solution 30 minutes by the polyacrylonitrile hollow-fibre membrane again, take out back 45 ℃ of dryings in baking oven, promptly under this temperature, carry out cross-linking reaction 4 hours.
Performance test
Polymer microporous film to the hydrophilic modification that obtains among each embodiment carries out performance test according to the following steps:
Water flux: the water flux of flat sheet membrane is measured and is carried out in the ultrafiltration cup, and measuring pressure is 1 atmospheric pressure; The water flux of hollow-fibre membrane is measured and is adopted outer platen press, and measuring pressure is 1 atmospheric pressure.
The Static Water contact angle: the hydrophily on polymer microporous film surface characterizes with the Static Water contact angle before and after the modification, and the room temperature during the contact angle test is 20 ℃.Adopt sessile drop method, use the Static Water contact angle that OCA20 contact angle measurement (German Dataphysics Instru-ments GmbH produces) is measured former film and Modified Membrane.
Protein adsorption: the static antifouling property of polymer microporous film adopts the adsorbance of bovine serum albumin (BSA) on the film surface to characterize before and after the modification.(concentration is respectively 0.1 at first to dispose variable concentrations BSA, 0.3,0.5,0.8,1.2,1.8,2.5 (PBS pH=7.4), utilizes ultraviolet specrophotometer (UV-1601 to phosphate buffer solution grams per liter), Shimadzu Corp produces) measure the absorbance of BSA solution in 280 nanometers, draw absorbance-BSA concentration standard curve.The membrane sample of 30 square centimeters of clips immerses and is equipped with in the test tube that 10 ml concns are 0.5 grams per liter BSA phosphate buffer then, and vibration is 24 hours in 30 ℃ water bath with thermostatic control.After absorption is finished with the abundant flushing membrane of quantitative deionized water, flushing liquor and adsorption liquid merge, do not measure the variation that 280 nanometers BSA adsorb the front and back solution absorbance, the adsorbance on the unit are film with the score of ultraviolet spectrometry degree according to calibration curve and solution calculation of total BSA.
Experimental result before and after the microporous modification is as follows:
Claims (8)
1, a kind of surface modification method of polymer microporous film may further comprise the steps:
(1) with polymer microporous film cleaning, drying;
(2) polymer microporous film after step (1) processing is placed between two sparking electrodes of dielectric barrier discharge, carrying out the atmospheric dielectric barrier discharge plasma handles, wherein the distance between two sparking electrodes is 1～5 millimeter, feed inert gas and oxygen mixed gas during discharge, 0.5～10 liter/minute of mixed gas flow, discharge frequency is 10 KHzs, and discharge power is 80～180 watts, and the processing time is 20～180 seconds;
(3) place the hydrophilic polymer aqueous solution to soak 20～60 minutes the polymer microporous film after step (2) processing, take out heating after immersion is finished and carry out cross-linking reaction;
The mass percent concentration of hydrophilic polymer is 1～20% in the described hydrophilic polymer aqueous solution, and contains chloropharin or the potassium peroxydisulfate that accounts for hydrophilic polymer amount 1～5%.
2, surface modification method of polymer microporous film as claimed in claim 1 is characterized in that: the inert gas described in the step (2) is helium or argon gas, and the volume ratio of inert gas and oxygen is 99/1.
3, surface modification method of polymer microporous film as claimed in claim 1 is characterized in that: the hydrophilic polymer described in the step (3) is shitosan, polyethylene glycol, PVP, polyacrylic acid ethylene oxidic ester, poly hydroxy ethyl acrylate, polyacrylic acid, polyacrylamide, polyvinyl alcohol or polypropylene glycol.
4, surface modification method of polymer microporous film as claimed in claim 3 is characterized in that: the weight average molecular weight of described hydrophilic polymer is 5000～20000.
5, surface modification method of polymer microporous film as claimed in claim 1 is characterized in that: the soak time described in the step (3) is 30 minutes, and the temperature of heating is 45 ℃, and cross-linking reaction time is 4 hours.
6, surface modification method of polymer microporous film as claimed in claim 1, it is characterized in that: described polymer microporous film is polyethylene, polypropylene, polyacrylonitrile or polyvinylidene fluoride microporous film, its average pore size is 0.1～1.5 micron, and porosity is 20～85%.
7, surface modification method of polymer microporous film as claimed in claim 1 is characterized in that: described polymer microporous film is a flat plate porous film, and the thickness of flat plate porous film is 15～200 microns.
8, surface modification method of polymer microporous film as claimed in claim 1 is characterized in that: described polymer microporous film is a hollow fiber microporous membrane, and the internal diameter of hollow fiber microporous membrane is 15～500 microns, and external diameter is 100～1800 microns.
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| CN103285743A (en) * | 2013-06-28 | 2013-09-11 | 厦门建霖工业有限公司 | Hydrophilization modification method for polyvinyl chloride alloy ultrafiltration membrane |
| CN103831027A (en) * | 2014-02-28 | 2014-06-04 | 东华大学 | Method for improving pollution resistance of PVDF (polyvinylidene fluoride) porous membrane based on plasmas technology |
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| CN103861465A (en) * | 2014-03-21 | 2014-06-18 | 东华大学 | Method for modifying surface super-hydrophilicity of hydrophobic separation membrane material |
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| CN104209009A (en) * | 2014-08-26 | 2014-12-17 | 东华大学 | Interface-crosslinking-based method for improving pollution resistance performance of hydrophobic microporous membrane |
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| CN107927528A (en) * | 2017-07-24 | 2018-04-20 | 中国科学院过程工程研究所 | It is a kind of to be used to remove Biomimetic membranes of aflatoxin and preparation method thereof and processing method |
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| CN109092078A (en) * | 2018-09-13 | 2018-12-28 | 上海恩捷新材料科技有限公司 | The processing method and modified poly ethylene seperation film of polyethylene seperation film |
| CN109126483A (en) * | 2018-09-30 | 2019-01-04 | 上海恩捷新材料科技有限公司 | A kind of method of polyethene microporous membrane surface hydrophilic modification and the modified polyethylene film formed by it |
| CN109248569A (en) * | 2018-10-19 | 2019-01-22 | 上海恩捷新材料科技有限公司 | A kind of seperation film and preparation method thereof |
| CN112852011A (en) * | 2021-01-09 | 2021-05-28 | 西安交通大学 | Surface modification method for realizing honeycomb micropore structure on surface of high polymer material |
| CN112852011B (en) * | 2021-01-09 | 2022-04-22 | 西安交通大学 | Surface modification method for realizing honeycomb micropore structure on surface of high polymer material |
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