CN103272482B - A kind of batch (-type) Plasma modification method of porous diffusion barrier - Google Patents
A kind of batch (-type) Plasma modification method of porous diffusion barrier Download PDFInfo
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Abstract
The invention provides a kind of batch (-type) Plasma modification method preparing porous diffusion barrier, comprise the steps, conventional ultrafiltration film or microfiltration membranes being fixed on is equipped with in the room-temperature plasma chamber of battery lead plate, under certain vacuum degree condition, gas is introduced chamber, adopt interval glow discharge mode process membrane surface under room temperature, obtain final hydrophily or hydrophobic porous diffusion barrier product.Compare with pulsed room-temperature plasma method of modifying with existing continous way, method of modifying process provided by the invention is simple, controllability is strong and without the need to special installation, significantly can strengthen hydrophily or the hydrophobicity on porous diffusion barrier surface; Made hydrophilic porous diffusion barrier can be widely used in the processes such as ultrafiltration, micro-filtration, dialysis, made hydrophobic porous diffusion barrier can be widely used in the processes such as Membrane Materials, film absorption, membrane extraction, Steam soak, oiliness feed clarification, and made porous diffusion barrier also can be used for the preparation of composite membrane as basement membrane.
Description
Technical field
The present invention relates to a kind of method of modifying of porous diffusion barrier, particularly a kind of method adopting the modified porous separation membrane surface of batch (-type) plasma mode.
Background technology
Novel as one, the efficient fluid separation element operating technology of membrane separation technique, achieves the develop rapidly attracted people's attention in recent years, has been widely used in each department of national economy.Within 2009, comprise world's diffusion barrier market scale of membrane product, device and correlation engineering at about 45,000,000,000 dollars, wherein membrane product about 8,000,000,000 dollars.Domestic, within 2009, be separated membrane product market and be about 6,000,000,000 yuans, add correlation engineering, market scale reaches 25,000,000,000 yuans.
Because of the difference of separate object and separation principle, separation membrane surface is often required to present higher hydrophily or hydrophobicity.Such as, take pressure differential as the ultrafiltration of driving force, microfiltration process and take concentration difference as the dialysis procedure of driving force, porous diffusion barrier surface used needs to present high-hydrophilic to reduce the fouling membrane degree in separation process, raising membrane separating process efficiency; Take temperature difference as the Membrane Materials process of driving force and be that the process need face such as membrane extraction, film absorption, Steam soak of driving force presents high hydrophobicity with concentration difference, to increase the wetting ability of the resistance to feed liquid of diffusion barrier, guarantee that the long-term stability of process is run; In addition, also often wishing that separation membrane surface has the hydrophobicity of height when filtering clarification oiliness feed liquid, being separated resistance to reduce.Therefore, the hydrophilic, hydrophobic property of separation membrane surface and its process efficiency closely related.
Although membrane separation technique is used widely, in order to improve the process efficiency of UF membrane further, the hydrophilic, hydrophobic character how improving film surface is better one of academia and industrial quarters problem of showing great attention to all the time.The hydrophilic, hydrophobic property in film surface is on the one hand from the chemical composition of membrane material itself, and simultaneously also by the impact of membrane superficial tissue pattern, in the middle of both, film surface chemistry forms the function of surface provided the foundation.It is generally acknowledged, when film surfaces hydrophilic (water contact angle is less than 90 degree), the larger then hydrophily of surface roughness is stronger, and in like manner, when film surfaces hydrophobic (water contact angle is greater than 90 degree), the larger then hydrophobicity of surface roughness is stronger.
As the effective surface modifying method of one, room-temperature plasma modification technology obtains investigation and application widely in membrane surface modification.According to the difference of air inlet kind, room-temperature plasma processing procedure can give separation membrane surface different hydrophilic, hydrophobic characteristics.Usually, select and the gas of film surface generation hydroxyl, carboxyl, amino isopolarity group can be made to carry out room-temperature plasma modification, the hydrophily on film surface can be increased; And select fluoro-gas, film surface can be made containing phenyl ring gas, long chain alkane gas etc. to produce the gas of low-surface-energy non-polar group, then can improve the hydrophobicity on film surface.Such as, adopt the microporous polypropylene membrane of ammonia room-temperature plasma technical finesse surface hydrophobicity, along with the prolongation in processing time, the water contact angle of Microporous Polypropylene Membrane can be reduced to 53.7 degree (processing time 8min) gradually by 128.2 degree, film surface hydrophilicity significantly increases, and makes the bovine serum albumin(BSA) adsorbance of microporous polypropylene membrane by 180 initial μ g/cm
2be reduced to 120 μ g/cm gradually
2(processing time 8min), effectively improves the pollution capacity of resistance to protein adsorption [ChemicalEngineeringJournal, 145 (2008): 218-224] of hydrophobic microporous polypropylene membrane.And for example, adopt carbon tetrafluoride normal-temperature plasma technology modified poly (ether-sulfone) ultrafiltration membrane capable, by regulating the key parameter such as power, processing time, the water contact angle on poly (ether sulfone) film surface can be increased to about 125 degree by 62 degree, the poly (ether-sulfone) ultrafiltration membrane successful transformation of script surface hydrophilicity is become can be used for the surface hydrophobicity perforated membrane [JournalofMembraneSciences, 407-408 (2012): 164-175] of Membrane Materials desalination.
Usually, for the surface modification of perforated membrane, existing room-temperature plasma processing procedure is general in a continuous mode, film surface chemistry is regulated to form or structure and morphology by changing the key parameter such as gaseous species, sample and electrode distance, Chamber vacuum degree, power, processing time, the hydrophilic, hydrophobic property in film surface needed for acquisition.Although large quantity research report all confirms, above-mentioned continous way room-temperature plasma modification technology can the chemical composition and structure pattern on effective modified membrane surface, but also exist following not enough: along with the prolongation in processing time, the hydrophilic, hydrophobic property in film surface often reaches stationary value, continues to increase the processing time then little on the hydrophilic, hydrophobic property impact of film surface.For above-mentioned carbon tetrafluoride plasma modification poly (ether-sulfone) ultrafiltration membrane [JournalofMembraneSciences, 407-408 (2012): 164-175], when being increased to 5min by 0min when treated, film surface water contact angle significantly improves to 113 degree by 62 degree, but continue to extend the processing time to 40min, film surface water contact angle is only slowly increased to 125 degree by 113 degree; Change film surface water contact angle further if think, can predict and need process longer time, can bring that processing cost increases thus, equipment heating is difficult to control and membrane surface pore structure is tending towards the series of problems such as densified.
In existing room-temperature plasma modification technology, also there is the method adopting pulsed plasma.Sample surfaces process is carried out in the millimicrosecond pulse (glow switch time controling is at millisecond or microsecond range scale) that the method produces plasma by modes such as hollow cathode pipes.Such as, adopt pulsed plasma deposition process can prepare super-hydrophobic Nano microsphere [Chem.Mater., 14 (2002): 4566-4571], adopting during pulsed plasma technology aggregation maleic anhydride to enable polymer retain the function [Chem.Mater., 8 (1996): 37-42] of acid anhydrides better.But so far, not yet have the report adopting the modified porous diffusion barrier of pulsed room-temperature plasma technology, and the enforcement of this technology needs comparatively complicated appointed condition.
Summary of the invention
Can not the deficiency of the hydrophilic, hydrophobic property in wider regulation and control porous diffusion barrier surface for existing continous way room-temperature plasma modification technology, and existing pulsed room-temperature plasma modification technology relies on the deficiency of complex device condition, the invention provides a kind of simple porous diffusion barrier batch (-type) Plasma modification method.Perforated membrane method of modifying process provided by the invention is simple, controllability is strong and without the need to special installation, significantly can strengthen hydrophily or the hydrophobicity on porous diffusion barrier surface; Adopt the made hydrophilic porous diffusion barrier of the present invention can be widely used in the processes such as ultrafiltration, micro-filtration, dialysis, made hydrophobic porous diffusion barrier can be widely used in the processes such as Membrane Materials, film absorption, membrane extraction, Steam soak, oiliness feed clarification, and made porous diffusion barrier also can be used for the preparation of composite membrane as basement membrane.
Batch (-type) Plasma modification method for porous diffusion barrier provided by the invention comprises the steps, porous diffusion barrier is fixed on and is equipped with in the room-temperature plasma chamber of battery lead plate, under certain vacuum degree condition, gas is introduced chamber, under room temperature, adopt interval glow discharge mode process porous diffusion barrier surface to obtain final modified porous diffusion barrier product; Described interval glow discharge mode is: open glow switch 1s ~ 10min when arriving specified requirements, close glow switch 1s ~ 10min(intermittent phase afterwards), and then open glow switch 1s ~ 10min, so repeatedly operate, but total processing time is no more than 120min, preferably total processing time is 10 ~ 30min.
Described specified requirements is that in chamber, vacuum can ensure that room-temperature plasma glow discharge normally occurs, and meanwhile, gas enters the flow general control of chamber at 0.01 ~ 200L/min.
The scientific basis that the present invention proposes batch (-type) room temperature plasma modification method is: split by continuous print glow discharge time, by nucleation process and the particle growth process of compression glow discharge time regulation and control plasma chamber indoor, control gas ionization degree or level of graft polymerization, and reduce the degree of secondary reaction as far as possible; By the batch process increased, complete the supply of gas (or monomer); By regulating the chemical composition and structure pattern of discharge time and intermittent time comprehensive regulation separation membrane surface, change the hydrophilic, hydrophobic characteristic in film surface to a greater degree with this.
Described porous diffusion barrier is surface and section is conventional ultrafiltration film or the microfiltration membranes of loose structure, and the distance between itself and battery lead plate is 1 ~ 10cm.In addition, the present invention can change glow discharge power with reference to passing through in prior art, and takes necessary pretreated method optimizing processing procedure to porous diffusion barrier sample and chamber.Such as, the general preferable range of glow discharge power is 10 ~ 450W; Pure water is adopted repeatedly to rinse 3 ~ 10 times or the mode of Ultrasonic Cleaning 5 ~ 15min is first cleaned in advance to porous diffusion barrier sample, the impurity such as the protection liquid in removing membrane surface and fenestra or dust; The organic solvent cleaning plasma chamber of available heat, or adopt and inert gas passed into chamber and the mode of opening glow discharge cleans plasma cavity.
The present invention conventionally the middle mode of inert gas room-temperature plasma glow discharge that adopts can also carry out pretreatment to porous diffusion barrier sample, and object is cleaning film surface, produces avtive spot or regulate membrane superficial tissue pattern in advance by corrasion at face; Also this kind of preprocessing process can be combined with above-mentioned batch (-type) room-temperature plasma modifying process, form the batch (-type) room-temperature plasma modifying process comprising " inert gas pretreatment, function gas (gas of the present invention) glow discharge, intermittent phase ".
The milipore filter that the macromolecular materials such as described milipore filter and microfiltration membranes are polyether sulfone, polysulfones, Kynoar, polyacrylonitrile, polyvinyl chloride, polyvinyl alcohol, Pioloform, polyvinyl acetal, cellulose acetate, shitosan, polyamide, polyimides, PPSU, polybenzimidazoles ketone, polybenzimidazoles, PAEK, polyether-ether-ketone are made or microfiltration membranes, or the milipore filter made for the inorganic material such as pottery, metal, metal oxide, cellular glass, zeolite or microfiltration membranes; Form membrane can be sheet type, hollow fiber form or tubular type.
Described gas is oxygen, air, nitrogen, water vapour, ammonia, the steam of the acrylic monomer of carboxy-containing acid group is (as acrylic acid, methacrylic acid etc.), containing the steam (as maleic anhydride etc.) of the anhydrides monomer of anhydride group, the steam of the amide-type monomer of amido-containing group is (as acrylamide, N, N-DMAA etc.), the steam of the acrylic ester monomer of hydroxyl and ester group group is (as hydroxypropyl acrylate, hydroxy-ethyl acrylate etc.), containing the steam of the vinylpyridine class monomer of pyridine ring (as 3-vinylpyridine, 4-vinylpridine etc.) or the compound of above-mentioned gas.When adopting above-mentioned gas, hydroxyl, amino or carboxyl isopolarity group can be formed on porous diffusion barrier surface, thus improve the hydrophily on film surface, the hydrophilic porous diffusion barrier product of preparation, can be used for ultrafiltration, micro-filtration, dialysis procedure or as the basement membrane preparing composite membrane.Composite membrane herein refers to modified porous diffusion barrier for basement membrane, by NF membrane, reverse osmosis membrane, gas-permeable membrane, the preferential water permeable membrane of infiltration evaporation prepared by the methods such as coating, curtain coating, interfacial polymerization on basement membrane.
Described gas is the compound of fluoro-gas (as carbon tetrafluoride, perfluoroethane, octafluorocyclobutane etc.), the steam (as perfluorobutyl ethylene, perfluoro decyl ethene etc.) of fluorine-containing vinyl monomer, acrylate containing fluorine or the steam (as perfluoro butyl ethyl propylene acid esters, perfluorooctylethyl group acrylate, perfluoro butyl ethylmethyl acrylate, perfluorooctylethyl group methacrylate etc.) of fluorine-containing methacrylate class monomer, cinnamic steam or above-mentioned gas.When adopting above-mentioned gas, the non-polar group of low-surface-energy can be formed on porous diffusion barrier surface, thus improve the hydrophobicity on film surface, the hydrophobic porous diffusion barrier product of preparation, can be used for Membrane Materials, film absorption, membrane extraction, Steam soak, oiliness feed clarification or as the basement membrane preparing composite membrane.Composite membrane herein refers to modified porous diffusion barrier for basement membrane, the preferential organic matter film thoroughly of the infiltration evaporation that basement membrane is prepared by methods such as coating, curtain coating, interfacial polymerizations.
Described vacuum is to ensure that required vacuum normally occurs in room-temperature plasma glow discharge.In plasma chamber of the present invention, the preferable range of absolute pressure value is 10 ~ 2000Pa.
The flow that described gas enters chamber is 0.01 ~ 200L/min.
After plasma treatment terminates, the present invention usually can conventionally in leave standstill mode cooling processing is carried out to diffusion barrier sample or plasma cavity, the cooling processing time is generally 3 ~ 10min, period close air inlet but maintain described in vacuum condition.After membrane sample to be separated is cooled to room temperature, conventionally can also carry out post processing to it, such as, use pure water rinsing sample 3 ~ 5 times, or adopt the component of mode except striping excess surface of conventional extracting or immersion if desired.
In the present invention, above-mentioned condition can be combined, and prepared hydrophilic porous diffusion barrier can be used for ultrafiltration, micro-filtration, dialysis procedure or the basement membrane as composite membranes such as preparation NF membrane, reverse osmosis membrane, gas-permeable membrane, the preferential water permeable membrane of infiltration evaporation; Prepared hydrophobic porous diffusion barrier can be used for Membrane Materials, film absorptions, membrane extraction, Steam soak, oiliness feed clarification or as the basement membrane preparing the preferential saturating organic matter composite membrane of infiltration evaporation.
Compared with the Plasma modification method of existing porous diffusion barrier, positive progressive effect of the present invention is:
1. can regulate the hydrophilic, hydrophobic property on porous diffusion barrier surface in larger scope, overcome the drawback that in existing continous way room-temperature plasma modifying process, the hydrophilic, hydrophobic property of face tends towards stability with process time lengthening.
2. by regulation and control glow discharge time and intermittent time and total processing time, can comprehensive regulation film surface chemistry the Nomenclature Composition and Structure of Complexes pattern.
3., compared with existing pulsed room-temperature plasma method of modifying, method of modifying process provided by the invention is simple, controllability is strong and without the need to special installation, have more economy.
4. have permanent high-hydrophilic or high hydrophobicity and applicable surface pore structure and skin depth with the porous diffusion barrier product that the inventive method is modified, film applied range, combination property are high, have great economic benefit.
Accompanying drawing explanation
Film surface infrared spectrum figure in Fig. 1 embodiment 1 before and after polyvinylidene fluoride (PVDF) ultrafiltration membrane hydrophilic modifying
The surface Scanning Electron microscope of polyacrylonitrile ultrafiltration film and contact angle photo in Fig. 2 embodiment 2
Surface Scanning Electron microscope in Fig. 3 embodiment 2 after polyacrylonitrile ultrafiltration film hydrophobically modified and contact angle photo
Surface Scanning Electron microscope in Fig. 4 comparative example 2-2 after polyacrylonitrile ultrafiltration film hydrophobically modified and contact angle photo
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described, but the present invention is not limited.
Embodiment 1 hydrophilic modifying prepares milipore filter
The steam of acrylamide is selected to be the hydrophilic modifying that gas carries out polyvinylidene fluoride (PVDF) ultrafiltration membrane.The sheet type polyvinylidene fluoride (PVDF) ultrafiltration membrane (molecular cut off 70kDa) of 5 × 2.5cm is put into YZDO8-2C type room-temperature plasma chamber, distance between sample and battery lead plate is 4cm, opening vacuum system makes absolute pressure in chamber reach 35 ~ 40Pa, open gas sampling valve, after balance 1min, open glow switch 3min(glow discharge power 120w), close glow switch 3min afterwards, so 5 times repeatedly, cool 5min after end, obtain the hydrophilic ultrafiltration membrane of modification.
Fig. 1 is the film surface infrared spectrum figure before and after polyvinylidene fluoride (PVDF) ultrafiltration membrane hydrophilic modifying, and Modified Membrane is at 3217cm
-1and 1678cm
-1there is the characteristic absorption peak of acid amides in place.Measure through contact angle measurement (OCA20, DataPhysicsInstrumentsCo., Germany), the surface water contact angle of original polyvinylidene fluoride (PVDF) ultrafiltration membrane is 78 degree, and the surface water contact angle of embodiment 1 Modified Membrane is down to 35 degree.In addition, adopt the 0.5g/L bovine serum albumin solution albumen static adsorbance to caudacoria before modified to measure, result shows, the albumen static adsorbance of this polyvinylidene fluoride (PVDF) ultrafiltration membrane is 82 μ g/cm before modified
2, Modified Membrane then reduces to 40 μ g/cm
2.
Comparative example 1-1
Select material and the operating condition of embodiment 1, difference is continuous glow discharge 3min.Through measuring, Modified Membrane surface water contact angle is 65 degree, and albumen static adsorbance is 69 μ g/cm
2.
Comparative example 1-2
Select material and the operating condition of embodiment 1, difference is continuous glow discharge 10min.Through measuring, Modified Membrane surface water contact angle is 52 degree, and albumen static adsorbance is 57 μ g/cm
2.
Comparative example 1-3
Select material and the operating condition of embodiment 1, difference is continuous glow discharge 15min.Through measuring, Modified Membrane surface water contact angle is 49 degree, and albumen static adsorbance is 53 μ g/cm
2.
Comparative example 1-4
Select material and the operating condition of embodiment 1, difference is continuous glow discharge 20min.Through measuring, Modified Membrane surface water contact angle is 48 degree, and albumen static adsorbance is 51 μ g/cm
2.
Comparative example 1-5
Select material and the operating condition of embodiment 1, difference is continuous glow discharge 30min.Through measuring, Modified Membrane surface water contact angle is 46 degree, and albumen static adsorbance is 47 μ g/cm
2.
From above-mentioned comparing result, compared with conventional continous way room-temperature plasma method, adopt method of modifying of the present invention can obtain surface hydrophilicity and the stronger modified polyvinylidene fluoride ultrafiltration membrane of stain resistance.
Embodiment 2 hydrophobically modified prepares Membrane Materials film
Argon gas and carbon tetrafluoride gas is selected to carry out the hydrophobically modified of polyacrylonitrile ultrafiltration film.The sheet type polyacrylonitrile ultrafiltration film (molecular cut off 20kDa) of 5 × 3cm is put into YZDO8-2C type room-temperature plasma chamber, distance between sample and battery lead plate is 5cm, opening vacuum system makes absolute pressure in chamber reach 850 ~ 1000Pa, open argon inlet valve, after balance 1min, open glow switch 5min(glow discharge power 40w), close glow switch 5min afterwards, then argon inlet valve is closed, open carbon tetrafluoride intake valve, after balance 1min, open glow switch 5min(glow discharge power 100w), close glow switch 5min afterwards, so 3 times repeatedly, 5min is cooled after end, obtain the hydrophobic film distillation film of modification.
Fig. 2 and Fig. 3 is the surface Scanning Electron microphotograph before and after polyacrylonitrile ultrafiltration film hydrophobically modified respectively, and wherein embedded figure is its water contact angle photo.The surface water contact angle of original polyacrylonitrile ultrafiltration film is 55 degree, and the surface water contact angle of embodiment 2 Modified Membrane is increased to 155 degree.(material liquid is the sodium-chloride water solution of the 3.5wt% of 80 DEG C to the desalting performance of the film after adopting conventional vacuum Membrane Materials process measurement before modified, film downstream vacuum is 95kPa), result shows, original polyacrylonitrile ultrafiltration film is because having comparatively strongly hydrophilic, saline solution penetrates fenestra, cannot be applied to Membrane Materials desalination processes; The Modified Membrane that this embodiment obtains may be used for Membrane Materials desalination processes, and membrane flux is 70kg/m
2h, salt rejection rate reaches 99.98%.
Comparative example 2-1
Select material and the operating condition of embodiment 2, difference is the continuous glow discharge 15min when carbon tetrafluoride air inlet.Through measuring, Modified Membrane surface water contact angle is 120 degree, flux of membrane distillation 65kg/m
2h, salt rejection rate is 96.5%.
Comparative example 2-2
Select material and the operating condition of embodiment 2, difference is the continuous glow discharge 30min when carbon tetrafluoride air inlet.Through measuring, Modified Membrane surface water contact angle is 125 degree, flux of membrane distillation 63kg/m
2h, salt rejection rate is 99.2%.Fig. 4 is the surface Scanning Electron microphotograph of the modified hydrophobic film that this comparative example obtains, and wherein embedded figure is water contact angle photo.
From above-mentioned comparing result, compared with conventional continous way room-temperature plasma method, adopt method of modifying of the present invention can obtain surface hydrophobic and Membrane Materials desalting performance stronger modified polyacrylonitrile hydrophobic membrane distillation film.
Claims (8)
1. the batch (-type) Plasma modification method of a porous diffusion barrier, it is characterized in that comprising the steps, porous diffusion barrier is fixed on and is equipped with in the room-temperature plasma chamber of battery lead plate, under certain vacuum degree condition, gas is introduced chamber, under room temperature, adopt interval glow discharge mode process porous diffusion barrier surface to obtain final modified porous diffusion barrier product; Described interval glow discharge mode is: open glow switch 1s ~ 10min when arriving specified requirements, close glow switch 1s ~ 10min afterwards, and then open glow switch 1s ~ 10min, so repeatedly operate, but total processing time is no more than 120min; Described specified requirements is that in chamber, vacuum can ensure that room-temperature plasma glow discharge normally occurs.
2. method of modifying according to claim 1, described porous diffusion barrier is surface and section is conventional ultrafiltration film or the microfiltration membranes of loose structure, and the distance between itself and battery lead plate is 1 ~ 10cm.
3. method of modifying according to claim 1, described gas be oxygen, air, nitrogen, water vapour, ammonia, the steam of acrylic monomer of carboxy-containing acid group, the acrylic ester monomer of steam, hydroxyl and the ester group group containing the steam of the anhydrides monomer of anhydride group, the amide-type monomer of amido-containing group steam, containing the steam of vinylpyridine class monomer of pyridine ring or the compound of above-mentioned gas.
4. method of modifying according to claim 3, the acrylic monomer of described carboxy-containing acid group is acrylic or methacrylic acid; The described anhydrides monomer containing anhydride group is maleic anhydride; The described anhydrides monomer containing anhydride group is acrylamide or N,N-DMAA; The acrylic ester monomer of described hydroxyl and ester group group is hydroxypropyl acrylate or hydroxy-ethyl acrylate; The described vinylpyridine class monomer containing pyridine ring is 3-vinylpyridine or 4-vinylpridine.
5. utilize the hydrophilic porous diffusion barrier product that in claim 1,2,3,4 prepared by any one method of modifying, for ultrafiltration, micro-filtration, dialysis procedure or as the basement membrane preparing composite membrane.
6. method of modifying according to claim 1, described gas is the compound of fluoro-gas, the steam of fluorine-containing vinyl monomer, the steam of acrylate containing fluorine monomer, cinnamic steam or above-mentioned gas.
7. method of modifying according to claim 6, described fluoro-gas is carbon tetrafluoride or perfluoroethane or octafluorocyclobutane; Described fluorine-containing vinyl monomer is perfluorobutyl ethylene or perfluoro decyl ethene; Described acrylate containing fluorine monomer is perfluoro butyl ethyl propylene acid esters or perfluorooctylethyl group acrylate or perfluoro butyl ethylmethyl acrylate or perfluorooctylethyl group methacrylate.
8. utilize hydrophobic porous diffusion barrier product prepared by any one method of modifying in claim 1,2,6,7, for Membrane Materials, film absorption, membrane extraction, Steam soak, oiliness feed clarification or as the basement membrane preparing composite membrane.
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| CN105688687B (en) * | 2016-02-29 | 2018-09-04 | 江苏久朗高科技股份有限公司 | The preparation process of double-hydropholic film |
| CN105648770B (en) * | 2016-03-25 | 2018-04-13 | 广州拜费尔空气净化材料有限公司 | A kind of preparation method of super hydrophobic surface |
| CN107998687B (en) * | 2017-12-08 | 2019-12-27 | 刘丁菡 | Preparation method of intelligent oil-water separation material |
| CN109280205B (en) * | 2018-10-26 | 2020-11-27 | 南京科技职业学院 | Preparation method of polytetrafluoroethylene double-hydrophobic membrane |
| CN110404412B (en) * | 2019-07-31 | 2021-11-23 | 常州航爵医药科技有限公司 | Molecular sieve membrane for separating ethanol solution pervaporation water and preparation method thereof |
| CN115079317A (en) * | 2021-03-12 | 2022-09-20 | 江苏菲沃泰纳米科技股份有限公司 | Goggles with hydrophilic antifogging film layer and film coating method |
| CN113413932B (en) * | 2021-06-29 | 2023-03-14 | 郑州大学 | Hydrophobic modification method of microfluidic chip material |
| CN115337790B (en) * | 2022-07-15 | 2023-10-20 | 上海工程技术大学 | Preparation method of super-hydrophilic polyethersulfone separation membrane and separation membrane prepared by same |
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| CN1557533A (en) * | 2004-01-16 | 2004-12-29 | 上海蓝景膜技术工程有限公司 | Low-temperature plasma grafting infiltration vaporization membrane and its preparing method |
| CN101439266A (en) * | 2008-11-25 | 2009-05-27 | 浙江大学 | Surface modification method of polymer microporous film |
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| CN1557533A (en) * | 2004-01-16 | 2004-12-29 | 上海蓝景膜技术工程有限公司 | Low-temperature plasma grafting infiltration vaporization membrane and its preparing method |
| CN101439266A (en) * | 2008-11-25 | 2009-05-27 | 浙江大学 | Surface modification method of polymer microporous film |
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