CN1817427A - Polymer microporous modification by corona induced grafting technology - Google Patents
Polymer microporous modification by corona induced grafting technology Download PDFInfo
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Abstract
A corona induced grafting method for modifying the millipore polymer membrane to improve its hydrophilicity, anti-pollution performance and biocompatibility includes such steps as corona treating of hydrophibic millipore polymer membrane for 15-120 S to generate the active centers on its surface for inducing polymerization, and immersing it in the hydrophilic olefinic monomer solution at 30-70 deg.C for 0.5-24 hr to form a hydrophilic layer on its surface.
Description
Technical field
The present invention relates to a kind of method of modifying of polymer separation film, provide a kind of corona induced grafting to carry out the method for polymer microporous modification particularly.
Background technology
Membrane separation technique is a kind of new and effective isolation technics, compare with traditional isolation technics, it has outstanding advantages such as separative efficiency height, energy consumption low (no phase transformation), environmental friendliness, is applicable to almost that petrochemical industry/chemical industry, food, pharmacy/medical treatment, dyestuff, natural materials extract and concentrate, the separating of the liquid in each field such as water purification and wastewater treatment, gas medium, purifying and resource reclaim.Because membrane separation technique and energy-conservation, environmental protection, development of resources and the relation that makes full use of are also very close, day by day under the serious situation, the effect of membrane technology more and more obtains attention in world today's energy, shortage of water resources, water and environmental pollution.
The core of membrane separation technique is a separation membrane material.Diffusion barrier includes organic polymeric membrane (being polymer film) and inoranic membrane two big classes, and wherein polymer film accounts for more than 95%.In numerous polymeric film material, the polymer microporous film that is used for ultrafiltration and micro-filtration is research and most widely used one big class film, because this class film has raw material and is easy to get, processes easily film forming, low cost and other advantages, dominate always during their aqueous medium separation in fields such as biological medicine, chemical industry, food, environmental protection, the energy, water treatment, purifying, purification etc. are used.The polymer microporous film of using mainly is that polyethylene, (PE), polypropylene (PP) or Kynoar (PVDF) etc. are the microporous barrier of material at present, the characteristics of these polymeric materials are itself to have very strong hydrophobicity, the problem that when being used for the aqueous medium processing, has two keys: the one, the hydrophobicity of film makes water need higher pressure could see through film, the power consumption height; The 2nd, the hydrophobicity of film causes that easily organic matter and colloid (as protein) adsorb in film surface and fenestra, form film and pollute, and causes the flux of film to reduce.In order to guarantee the carrying out of these film separation processes, need to improve pressure and frequent clean, separative efficiency reduces, and expenses such as energy consumption and cleaning agent improve.At present, hydrophobicity is considered to restrict the main cause that the polymer micro film properties is given full play to always.Owing to contain the polymer surfaces of strong polar group structure such as hydroxyl, amino, sulfonic acid/carboxylic acid group and salt thereof, ability with excellent hydrophilic and opposing protein, organic matter and colloid absorption, therefore by introducing these polar groups on the film surface, the hydrophiling that realizes film is that aqueous medium is handled the important development direction with polymer microporous modification and high performance.
Improve the hydrophilic method of polymer microporous film and mainly contain two kinds, the one, adopt the hydrophilic polymer raw material, make microporous barrier through suitable method, the 2nd, after becoming microporous barrier, employing hydrophobic polymer feedstock production carries out hydrophilic modification again.Since the eighties in 20th century, the method for modifying and the research contents that improve polymer microporous film hydrophily and pollution resistance are mainly the following aspects.
Blend system embrane method: hydrophobic polymer raw material and other hydrophilic polymer are carried out making hydrophilic microporous barrier again after the blend.As patent WO2005032684 report, with PVDF and hydrophilic hydroxy alkyl cellulose blend after phase inversion makes hydrophilic PVDF milipore filter, the raising of the anti-protein-contamination performance of film; Chinese patent CN1093018 discloses a kind of method for preparing haemodialyser usefulness hollow-fibre membrane with cellulose acetate, glycerine and polyethylene glycol melt blending.In patent CN1254308, sulfone polymer and hydrophilic polymer polyvinylpyrrolidone (PVP) are total to casting film, prepared the asymmetric microporous barrier of possess hydrophilic property, film surface average pore size is about 0.1～10 micron; In U.S. Pat 6495043, reported that the diamines blend that polysulfones, polyether sulfone and polyoxyethylene/polyoxypropylene are replaced prepares the method for Hydrophilized porous membrane, membrane aperture is at 0.1～1 micron.The characteristics that blending method prepares hydrophilic porous film are that method is simple, but the compatibility between hydrophilic additive and system membrane polymer, the solvent is relatively poor, the separation and the mechanical performance of film have been influenced, simultaneously, hydrophilic polymer in the blend film also can in use be dissolved out from film, and the hydrophily of film is lost gradually.
The surface applied method: coating process is to use hydrophilizing agent to be coated in the microporous barrier surface and gives film with hydrophily.Such as, with dip coating the surfactant solution of nonionic, anionic and amphoteric ion type is coated in the polysulphone super-filter membrane surface, the hydrophily on dry caudacoria surface has improvement in various degree, order by water flux reflection hydrophilic modifying effect is: nonionic＞anionic＞amphoteric ion type (membrane science and technology, 1997,17 (4): 36～41).Patent CN1704152 has described and has a kind ofly adopted solvent evaporation to be separated to combine with dipping coating reshaping method that preparation is hydrophilic, the method for high flux microporous barrier.Chinese patent CN1509804 discloses the hydrophilic composite methods of a kind of PVDF hollow-fibre membrane monolayer surface, makes pvdf membrane surface and hydrophilic composite produce chemical bonding by crosslinking agent, has improved the fastness and the hydrophily of composite membrane.Marianne Nystr m soaks polysulphone super-filter membrane and applies modification in polyelectrolyte polyethyleneimine: amine aqueous solution, utilize between film surface and the protein and to produce coulomb repulsion and reduced the absorption of protein on film, improved antifouling property (the J Membr Sci of film, 1989,44:183～196).The characteristics of surface applied method are that the hydrophilic effect at modification initial stage is good, but the modifier of coating easily comes off from the film surface, and along with service time of film prolongs, hydrophily decays gradually, can not obtain permanent modified effect.
Surface physics facture: adopt ultraviolet light, electron beam, gamma-radiation irradiation, some physical means such as Low Temperature Plasma Treating are handled the polymer microporous film surface, can cause the oxidation reaction or the cross-linking reaction on film surface, generate polar group, thereby improve the wetability of film, strengthen its antifouling property.Such as, during microwave field is following, N
2, He, CO
2, O
2, H
2The O plasma to the surface treatment of PE film after, the film surface has generated polar group, hydrophily improves (Chinese Journal of Chemical Physics, 1997,10 (3): 280～283); Adopt CO
2, NH
3Plasma carries out modification to the PP microporous barrier, and PP film antifouling property in membrane bioreactor is used improves (J Membr Sci, 2005,254:219～227; Sep ﹠amp; Purifi Tech, 2005,45:8～15); With
60Co gamma-rays Dichlorodiphenyl Acetate cellulose (CA) film carries out radiation treatment, and the water penetration of film improves, and the rejection of film is changed little (water technology, 1997,23,10 (6): 315～318).The characteristics of these surface physics factures are that process is simple, but these technology or equipment complexity, otherwise efficient is lower, may destroy the polymer molecular chain in the microporous barrier body simultaneously in the processing procedure, reduces the mechanical strength of film; And because the polar group that forms is little, in use, these groups can be embedded in the motion of polymer segment under the film surface, and the hydrophily of film decays gradually.
The surface grafting method: the surface grafting method is to adopt suitable method to handle polymer microporous film earlier, produces the reactivity point on the film surface, utilizes this active site to cause the glycerol polymerization of hydrophilic monomer in film surface and fenestra then, forms hydrophily grafting layer.This method is the most effectual way that for good and all improves the hydrophily of film, strengthens its anti-protein-contamination performance.The main means that cause surface grafting have: chemistry causes (as ozone treatment), Low Temperature Plasma Treating, ultraviolet light irradiation, high-power electron beam and gamma-rays radiation etc.Such as, Chinese patent CN1640533 discloses the hydrophilic method of modifying of a kind of raising ultra-high molecular mass polyethylene micropore film, adopt ozone treatment to cause vinylacetate (VAc) at film surface grafting, carrying out the saponification hydrolysis, form polyvinyl alcohol (PVA) hydrophilic radical, obtain having excellent hydrophilic and hygroscopic miillpore filter; Improve the hydrophily of film with argon plasma acrylamide triggered (AAm) at the surface grafting of polyether sulfone (PES) film, reduced protein contamination, and the mechanical strength of film decrease (Langmuir, 2003,19:79～85); Put down in writing among the Chinese patent CN1586702 and a kind ofly prepared the method for hydrophily NF membrane, used the ultraviolet irradiation technology to have in strand that grafting has carboxyl, hydroxyl, amino or sulfonic compound on the polymer film of carbonyl or sulfonyl by the surface grafting technology; The monomer solution that Chinese patent CN1539550 will contain glycosyl compound is coated in surface of separating film of polymer, and behind the evaporating solvent, the method trigger monomer of using irradiation has improved the hydrophily of film at film surface grafting.Chinese patent CN1546214 soaks polymer separation film in polyvinylpyrrolidone (PVP) solution, make the PVP of absorption be bonded in separation membrane surface with radiation method or persulfate again, has improved the hydrophily and the biocompatibility of film; The method trigger monomer that uses plasma, glow discharge, gamma-ray irradiation among the Japan Patent JP62193604 is at polymer milipore filter surface grafting, and preparation stimulates the milipore filter that sensitive reaction is arranged to external world.The surface graft modification method can make polymer microporous film have lasting hydrophily and pollution resistance, but ozonisation and Low Temperature Plasma Treating equipment complexity, the running cost height, and security is not good, the low temperature plasma method is difficult for realizing the serialization application owing to carry out under negative pressure; And UV, high energy particle radiation treatment method may cut off polymer molecular chain, destroy the body construction of film, reduce the separating property and the mechanical strength of film.Therefore, need a kind of more suitable, sufacing carries out the surface modification of polymer microporous film efficiently.
Sided corona treatment is with respect to processing methods such as high-power electron beam, ultraviolet light irradiation and plasmas, has simple, the atmospheric operation of equipment, advantages such as easy to control, easy grasp, be widely used in the surface treatment of material dense film such as plastics, metal forming, paper, to improve the surface tension of film, improve wetting, printing and character such as bonding.Chinese patent CN1274478 and CN87104611 disclose two kinds of multi-electrode corona treatment plants of handling band shape or fiber rail shape material continuously respectively, are used to print, the preliminary treatment of coating; Chinese patent CN1272860 discloses a kind of at N
2Form in the mist account for 0.01～10% hydrogen, ammonia or its mixture, with volume with the method on polymer dense material surfaces such as corona technical finesse fluoropolymer, Merlon, polyimides, to improve the wetability and the cohesive of material.Japan Patent JP60038441 adopts corona discharge to handle the PE dense film in air atmosphere, again in atmosphere of inert gases and under the existence condition of reducing agent, make hydrophilic monomer (as acrylic acid) carry out glycerol polymerization, improve the dyeability of PE film at film surface.
Characteristics based on corona treatment techniques, for overcoming the problem that exists in aforementioned several polymer microporous film graft-modification method, the present invention has proposed to be different from the technology that the polymer microporous film hydrophilic modification is carried out in the induced grafting of above-mentioned existing methods corona on the basis of system experimentation.
The characteristics of the method that this patent provided are that sided corona treatment is applied in the surface graft modification of polymer microporous film, polymer microporous film after sided corona treatment immerses and has in the monomer solution of hydrophilic radical, under certain operation condition, carry out graft reaction, strand at film surface and fenestra inwall introducing possess hydrophilic property obtains hydrophilic resistant to pollution microporous barrier.The sided corona treatment operation is carried out at normal temperatures and pressures, and industrial easy realization serialization is produced, and can wait length and the character of controlling grafted chain by grafting time, monomeric species, monomer solution concentration, thus the combination property of controlling diaphragm.Polymer microporous film hydrophily after graft modification is significantly improved, and the protein adsorption amount obviously descends.
Summary of the invention
The present invention is directed to the deficiency in the existing polymer microporous film hydrophilic modification technology, provide a kind of corona induced grafting to carry out the method for polymer microporous modification.
It may further comprise the steps:
(1) with polymer microporous film in the indoor sided corona treatment of carrying out of the corona that is full of dry air, form the activated centre of causing double-bond polymerization on film surface and fenestra inwall, the sided corona treatment condition is: dry air charges into 5～30 liters/minute of speed, 20 kilo hertzs of discharge frequencies, 0.5～2 kilowatt of discharge power, 15～120 seconds processing times;
(2) carry out graft polymerization reaction in the solution with immersion hydrophily vinyl monomer of the polymer microporous film after the sided corona treatment and solvent composition, form stable hydrophilic grafting layer on film surface and fenestra inwall, the composition mass percent of hydrophily vinyl monomer solution is: hydrophily vinyl monomer 3～30%, solvent 70～97%, the graft polymerization reaction temperature is 30～70 ℃, and the reaction time is 0.5～24 hour;
(3) polymer microporous film soaked 3～5 hours in 40～60 ℃ mass percentage concentration is 1.0～2.0% sodium hydrate aqueous solution after the glycerol polymerization, soaking and washing in cleaning agent then, dry again, perhaps with the soaking and washing in cleaning agent of the polymer microporous film after the graft modification, dry again, cleaning temperature is 20～60 °, and soak time is 24～48 hours, and baking temperature is 10～60 °.
Described polymer microporous film is polyethylene, polypropylene or polyvinylidene fluoride microporous film;
Polymer microporous film be shaped as flat plate porous film or hollow fiber microporous membrane;
The polymer micro membrane aperture is 0.1～1.5 micron,
The hydrophily vinyl monomer is N-vinylpyrrolidone, acrylic acid, right-vinylbenzenesulfonic acid, right-vinylbenzenesulfonic acid sodium, vinylacetate or allyl acetate;
Solvent be a kind of of water, ethanol or both with any than the mixture of forming.
The invention has the beneficial effects as follows:
Method provided by the invention; sided corona treatment is to carry out in the air atmosphere of normal temperature and pressure; mild condition, energy consumption is little, efficient is high, security is good; be different from the low temperature plasma method and need vacuum condition; equipment is simple, can design and produce as required; realize the continuous modification of microporous barrier easily, have more the scale significance of application.
Again, method provided by the invention, sided corona treatment is only in microporous barrier surface and fenestra inner surface reaction of formation activated centre, be different from ultraviolet, low temperature plasma, gamma-radiation irradiation etc. and handle crosslinking technology, sided corona treatment can not destroyed film interpolymer strand, damage to film is little, and the mechanical performance of modification caudacoria can not be affected.
Again, method provided by the invention, the hydrophilic modifying layer of modification caudacoria surface and fenestra inwall is the hydrophilic side-chains of covalence graft, compare with blending method, surface-coated method and surface physics facture, hydrophilic layer is stable, modification is lasting, the contact angle of water reduces more than 50%, protein adsorption reduces more than 40%, and water flux improves more than 50%.
Again, the method that provides among the present invention, highly versatile, the polymer microporous film or the kind of suitable modification many, form membrane can be a hollow-fibre membrane, also can be flat sheet membrane.
Again, in the method that provides among the present invention, available hydrophily vinyl monomer kind is many, according to the end of selecting hydrophily vinyl monomer kind or post-processing step control grafted chain for use is groups such as hydroxyl, carboxyl, sulfonic group, carboxylate, sulfonate or pyrrolidones, further improve the changeability of membrane superficial tissue, and the ability of follow-up modification or functionalization, widened the scope of application of the inventive method.
In the method that provides among the present invention,, and then can regulate and control the holding back of polymer microporous film after the modification, separating property by the concentration that changes the hydrophily vinyl monomer, the length that the graft polymerization reaction temperature and time can be controlled the hydrophily grafted chain again.
Again, in the method that provides among the present invention, the sided corona treatment of polymer microporous film be may be carried out batchwise, also can carry out continuously.
Description of drawings
Fig. 1 (a) be the induced grafting of PE hollow fiber microporous membrane corona acrylic acid modified before, the electron scanning micrograph of the outer surface of film;
Fig. 1 (b) be the induced grafting of PE hollow fiber microporous membrane corona acrylic acid modified after, the electron scanning micrograph of the outer surface of film;
Before Fig. 2 (a) is the modification of PP hollow fiber microporous membrane corona induced grafting N-vinylpyrrolidone, the electron scanning micrograph of the outer surface of film;
After Fig. 2 (b) is the modification of PP hollow fiber microporous membrane corona induced grafting N-vinylpyrrolidone, the electron scanning micrograph of the outer surface of film;
Fig. 3 (a) be the induced grafting of PVDF flat plate porous film corona right-modification of vinylbenzenesulfonic acid sodium before, the electron scanning micrograph on film surface.
Fig. 3 (b) be the induced grafting of PVDF flat plate porous film corona right-modification of vinylbenzenesulfonic acid sodium after, the electron scanning micrograph on film surface.
The specific embodiment
The method of polymer microporous modification is carried out in a kind of corona induced grafting provided by the invention, is made up of three steps, and the specific embodiment of each step is followed successively by:
1) sided corona treatment of polymer microporous film
Intermittently operated: polymer microporous film is fixed on the sided corona treatment frame in the corona machine cavity, dry air fills into corona treatment cavity with 5～30 liters of/minute flow velocitys, the air gap between control sparking electrode and the corona roller is at 2～3 millimeters, control processing power at 0.5～2 kilowatt by the power adjusting knob, 15～120 seconds processing times.
The drying air temperature that charges into is room temperature (15～40 ℃); Before film carries out sided corona treatment, if the cleannes of film are not enough, clean in the cleaning fluid that available water and ethanol are formed, be lower than 60 ℃ of dryings down again.
Continued operation: the preliminary treatment of polymer microporous film is carried out in service sink that roller is installed and drying tube continuously, and cleaning fluid is ethanol, water or both mixed liquors, and the drying tube temperature is controlled at 50～60 ℃, carries out air blast simultaneously; After the preliminary treatment, banded flat plate porous film is transmitted by corona roller and roller, and the cannulated tunica fibrosa is transmitted by the conveyer that twists at corona machine two ends, by setting speed by the corona gap, control its processing time by the transfer rate of film, the same intermittently operated of sided corona treatment control of process condition.
Optimum condition is: dry air flow rates: 15～20 liters/minute; 0.5～1.5 kilowatt of sided corona treatment power; 30～90 seconds processing times.
Polymer microporous film: the shape of film is selected from flat sheet membrane or the hollow-fibre membrane any one, 0.1～5 micron of average pore size, and the matter material is selected from any one among PE, PP or the PVDF.
Corona treatment: corona treatment mainly by compositions such as cavity, multiple tooth sparking electrode, sided corona treatment frame (comprise the corona roller, length is 600mm, diameter 30mm), variable voltage variable frequency device, alarms.The cavity both sides are respectively equipped with air inlet and exhaust outlet, adopt valve and gas flowmeter to regulate the flow of air inlet; Multiple tooth sparking electrode can make the film more effective processing in surface, improves and handles intensity; In operation, can select single or double sided corona treatment frame as required for use, the corona roller is surrounded by the thick electrically insulating silicone rubber pipe of 1～2mm, regulates the gap of electrode and corona roller at 2～3 millimeters by the knob on the corona frame; 220 volts of input voltages, 50 hertz of frequencies by the variable voltage variable frequency device, are exported 15 kilovolts, 20 kilo hertzs high-frequency and high-voltage.When handling sample, charge into dry air, open corona polymer film is in the corona discharge in air inlet.
2) graft polymerization reaction: in the polymer microporous film immersion hydrophily vinyl monomer solution of sided corona treatment, carry out graft reaction, monomer solution concentration 3～30wt%, 20～80 ℃ of reaction temperatures, reaction time 0.5～24h.
Optimum condition is: monomer solution concentration 5～20wt%, and 40～70 ℃ of reaction temperatures, reaction time 1～12h simultaneously, need continue to charge into N in the solution
2To remove the oxygen that may end free radical that is dissolved in the solution.
The monomer that is adopted is the hydrophily vinyl monomer of the two keys of band, comprise in N-vinylpyrrolidone, acrylic acid, right-vinylbenzenesulfonic acid sodium, right-vinylbenzenesulfonic acid, vinylacetate or the allyl acetate any one, the solvent of monomer solution can be water, ethanol or both mixtures.
3) post processing of graft modification film: the graft reaction that arrives setting is after the time, with graft polymerization reaction caudacoria soaking and washing in the mixture of ethanol, water or both any ratios, be preferably in and carry out sonic oscillation when cleaning, to remove monomer and the homopolymers that is attached in film surface and the fenestra.
When monomer is the ester time-like, in the last handling process, polymer microporous film uses 1.0～2.0wt% sodium hydrate aqueous solution of 40～60 ℃ to soak 3～5 hours, 40～60 ℃ water logging bubble 1 hour successively after the glycerol polymerization.Can be converted into sodium salt to the hydrolysis of ester group of grafting layer like this.If further, then can make the ester group of grafting layer be converted into carboxyl with 1.0～2.0wt% aqueous hydrochloric acid solution of 20～30 ℃ immersion 2 hours.Film after the cleaning is oven dry below 60 ℃ in baking oven, promptly gets the good polymer microporous film of hydrophily and pollution resistance.
The sign of polymer microporous film after the corona induced grafting modification among the present invention:
Percent grafting (GD): flat sheet membrane and hollow-fibre membrane are all according to formula GD=(W
2-W
1)/W
1* 100% calculates W in the formula
1Be the weight of preliminary treatment caudacoria, W
2Weight for the post processing caudacoria.
Water flux: the water flux of flat sheet membrane is measured and is carried out in the ultrafiltration cup, and mensuration pressure is 0.1MP; The water flux of hollow-fibre membrane is measured and is adopted outer platen press, and mensuration pressure is 0.1MP.
The Static Water contact angle: the hydrophily of the forward and backward polymer microporous film of graft modification characterizes with the Static Water contact angle.Adopt sessile drop method, use the Static Water contact angle that OCA20 contact angle measurement (German Dataphysics Instruments GmbH produces) is measured former film and graft modification film.
Protein adsorption: the static antifouling property of the forward and backward polymer microporous film of graft modification adopts the adsorbance of bovine serum albumin (BSA) on the film surface to characterize.At first, preparation variable concentrations BSA (concentration is respectively 0.1,0.3, and 0.5,0.8,1.2,1.8, phosphate buffer solution (PBS 2.5g/L), PH=7.4), utilize ultraviolet specrophotometer (UV-1601, Shimadzu Corp produces) to measure the absorbance of BSA solution, draw absorbance-BSA concentration standard curve at the 280nm place.Clip 30cm then
2Membrane sample, immerse and to be equipped with in the test tube that 10ml concentration is 0.5g/L BSA phosphate buffer, 24h vibrates 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, measure the variation that the BSA of 280nm place adsorbs the front and back solution absorbance, the adsorbance on the unit are film respectively with ultraviolet specrophotometer according to calibration curve and solution calculation of total BSA.
The invention will be further described below in conjunction with embodiment and accompanying drawing
Embodiment 1:
With 20 length is 10cm polyethylene (PE) hollow fiber microporous membrane (0.85 micron of average pore size, Kaihua membrane technology Co., Ltd., Zhejiang University, Hangzhou city development) be fixed on after weighing on the corona frame of corona treatment and handle, treatment conditions are: dry air charges into speed 5L/min; 26 ℃ of treatment temperatures (room temperature); Corona discharge power 0.5kW.In acrylic acid (AA) aqueous solution that PE hollow-fibre membrane after treatment immerses,, in reactant liquor, continue to feed N in the course of reaction with water-vapo(u)r saturation at 30 ℃ of following graft reactions
2Deoxygenation.When arrive setting the reaction time, the PE doughnut is taken out, with the ultrasonic repeatedly soaking and washing 24h of film, removing unreacted monomer and homopolymers, 60 ℃ of following vacuum drying are weighed after 24 hours and are characterized with 20 ℃ of pure water and ethanol.
Before the corona induced grafting is acrylic acid modified with modification after ESEM (SEM) photo of PE hollow fiber microporous membrane outer surface pattern see accompanying drawing 1 (a) (b).The performance characterization data of PE hollow-fibre membrane and former film sees Table 1 after the graft modification.
Show behind the 1:PE hollow-fibre membrane grafting AA and the performance of former film control sample
| Numbering | Sided corona treatment time/s | Monomer solution concentration/wt% | Graft reaction time/h | Percent grafting/% | Water flux/Lm -2·h -1 | Contact angle/° | BSA adsorbance/μ gcm -2 |
| Former film | - | - | - | - | 23.5 | 113±3.4° | 131.8 |
| 1-1 # | 15 | 10 | 0.5 | 3.68 | 86.7 | 38±2.2° | 38.5 |
| 1-2 # | 90 | 10 | 1.0 | 6.81 | 117.8 | 39±3.1° | 21.9 |
| 1-3 # | 90 | 5 | 1.0 | 4.94 | 76.4 | 45±1.9° | 25.6 |
| 1-4 # | 90 | 3 | 4.0 | 5.57 | 67.1 | 33±3.0° | 20.7 |
| 1-5 # | 120 | 8 | 5.0 | 6.22 | 94.9 | 35±2.5° | 28.2 |
Embodiment 2:
Clip is cleaned polypropylene (PP) flat plate porous film (0.22 micron of average pore size, the German Membrana company produces) 4 * 8cm of oven dry
2, carry out sided corona treatment after weighing, treatment conditions are: dry air charges into speed 30L/min; 10 ℃ of treatment temperatures (room temperature); Discharge voltage 2.0kW.Film after sided corona treatment immerses the ethanolic solution of allyl acetate, carries out graft reaction under 70 ℃, continues to feed the N with water-vapo(u)r saturation in the course of reaction in reactant liquor
2Set the reaction time when arriving, the 1.5wt% aqueous hydrochloric acid solution that uses 40 ℃ 2.0wt% sodium hydrate aqueous solution to soak 3 hours, 30 ℃ successively the PP flat sheet membrane soaked 2 hours, steeped with 60 ℃ water logging and cleaned 48 hours, and water carries out again, after 10 ℃ of following vacuum drying, weigh and characterize.
The PP flat plate porous film after corona induced grafting acetate propylene is ester modified and the performance characterization data of former film control sample see Table 2.
Performance with former film behind the table 2:PP flat plate porous film grafting allyl acetate compares
| Numbering | Sided corona treatment time/s | Monomer solution concentration/wt% | Graft reaction time/h | Percent grafting/% | Water flux/Lm -2·h -1 | Contact angle/° | BSA adsorbance/μ gcm -2 |
| Former film | - | - | - | - | 38.5 | 118±3.8° | 127.7 |
| 2-1 # | 30 | 10 | 1.0 | 3.57 | 137.1 | 44±2.0° | 37.2 |
| 2-2 # | 60 | 10 | 2.0 | 3.81 | 147.5 | 38±3.6° | 49.9 |
| 2-3 # | 90 | 15 | 2.0 | 4.94 | 159.4 | 37±3.4° | 26.1 |
| 2-4 # | 90 | 30 | 4.0 | 5.19 | 128.1 | 29±4.1° | 21.0 |
Embodiment 3:
To weigh behind 20 length of clip PP hollow fiber microporous membrane (0.15 micron of average pore size, Kaihua membrane technology Co., Ltd., Zhejiang University, Hangzhou city produces) cleaning-drying that is 10cm, the sided corona treatment condition is with embodiment 1.PP hollow-fibre membrane after treatment immerses in N-vinylpyrrolidone (NVP) aqueous solution, at 75 ℃ of following graft reactions, continues to feed the N with water-vapo(u)r saturation in the course of reaction in reactant liquor
2Deoxygenation.When arrive setting the reaction time, the PP doughnut is taken out, with pure water and ethanol with film repeatedly ultrasonic cleaning weigh after 24 hours and characterize 50 ℃ of following vacuum drying again to remove unreacted monomer and homopolymers.
The PP hollow-fibre membrane behind the surface grafting NVP and the performance characterization data of former film reference substance see Table 3, and the outer surface pattern SEM figure of the forward and backward film of graft modification sees accompanying drawing 2 (a) (b).
Performance with former film behind the table 3:PP hollow fiber microporous membrane graft N VP compares
| Numbering | Sided corona treatment time/s | Monomer solution concentration/wt% | Graft reaction time/h | Percent grafting/% | Water flux/Lm -2·h -1 | Contact angle/° | BSA adsorbance/μ gcm -2 |
| Former film | - | - | - | - | 18.5 | 125±3.2° | 123.6 |
| 3-1 # | 30 | 10 | 5.0 | 3.96 | 167.1 | 64±2.2° | 57.3 |
| 3-2 # | 60 | 10 | 10.0 | 4.81 | 188.0 | 58±2.9° | 35.1 |
| 3-3 # | 90 | 15 | 24.0 | 4.94 | 153.9 | 55±3.0° | 49.6 |
| 3-4 # | 120 | 20 | 5.0 | 5.57 | 199.1 | 46±3.7° | 25.9 |
| 3-5 # | 120 | 15 | 5.0 | 5.23 | 157.4 | 39±1.9° | 37.5 |
Embodiment 4:
Kynoar (PVDF) flat plate porous film (self-control, 1.5 microns of average pore sizes) that adopts the solution phase inversion to make is carried out solvent exchange 24h successively in absolute ethyl alcohol and n-hexane, the cleaning-drying back clipping plane is long-pending to be 4 * 8cm
2Film, weigh.The sided corona treatment condition is: dry air charges into speed 20L/min; 28 ℃ of treatment temperatures (room temperature); Corona discharge power 1.2kW.Pvdf membrane after sided corona treatment immerses in right-vinylbenzenesulfonic acid sodium (NaSS) aqueous solution, at 70 ℃ of following graft reactions, continues to feed the N with water-vapo(u)r saturation in the course of reaction in reactant liquor
2Deoxygenation.Set the reaction time when arriving, will weigh behind the PVDF microporous barrier taking-up cleaning-drying and characterize.
The corona induced grafting is right-and PVDF flat plate porous film behind the vinylbenzenesulfonic acid sodium and the performance characterization data of former film see Table 4, and the surface topography SEM figure of the forward and backward film of graft modification sees accompanying drawing 3 (a) (b).
The grafting of table 4:PVDF flat plate porous film is right-vinylbenzenesulfonic acid sodium after and the performance of former film control sample
| Numbering | Sided corona treatment time/s | Monomer solution concentration/wt% | Graft reaction time/h | Percent grafting/% | Water flux/Lm -2·h -1 | Contact angle/° | BSA adsorbance/μ gcm -2 |
| Former film | - | - | - | - | 56.1 | 95±1.8° | 157.0 |
| 4-1 # | 45 | 10 | 5.0 | 3.10 | 834.9 | 44±3.5° | 71.4 |
| 4-2 # | 60 | 10 | 8.0 | 4.19 | 753.9 | 39±2.5° | 36.5 |
| 4-3 # | 90 | 15 | 5.0 | 4.84 | 921.7 | 38±4.1° | 43.8 |
To adopt thermally induced phase separation make PE flat plate porous film (self-control, 0.1 micron of average pore size) in ethanol and pure water repeatedly ultrasonic cleaning for several times, the certain area (4 * 8cm of clip after the vacuum drying
2) film, weigh, carry out sided corona treatment again, treatment conditions are: dry air charges into 17 ℃ of speed 20L/min treatment temperatures (room temperature); Sided corona treatment power 0.8kW.Film after sided corona treatment immerses in the aqueous solution of right-vinylbenzenesulfonic acid (SS), at 70 ℃ of following graft reactions, continues to feed the N with water-vapo(u)r saturation in the course of reaction in mixed liquor
2Deoxygenation.When arrive setting the reaction time, the PE microporous barrier is taken out, weigh behind the cleaning-drying and characterize.
Grafting is right-and the performance characterization of the forward and backward PE film of vinylbenzenesulfonic acid modification the results are shown in Table 5.
Table 5: the PE microporous barrier grafting that thermally induced phase separation makes is right-vinylbenzenesulfonic acid after and the performance of former film reference substance relatively
| Numbering | Sided corona treatment time/s | Monomer solution concentration/wt% | Graft reaction time/h | Percent grafting/% | Water flux/Lm -2·h -1 | Contact angle/° | BSA adsorbance/μ gcm -2 |
| Former film | - | - | - | - | 23.4 | 120±1.6° | 168.0 |
| 5-1 # | 30 | 10 | 8.0 | 2.97 | 182.7 | 58±1.9° | 68.5 |
| 5-2 # | 30 | 10 | 4.0 | 2.09 | 171.6 | 61±2.9° | 76.1 |
| 5-3 # | 60 | 5 | 4.0 | 2.68 | 207.9 | 47±3.7° | 55.9 |
| 5-4 # | 90 | 5 | 5.0 | 3.94 | 225.4 | 43±3.5° | 45.7 |
| 5-5 # | 120 | 8 | 5.0 | 3.76 | 173.9 | 40±1.9° | 76.9 |
| 5-6 # | 120 | 8 | 2.0 | 4.24 | 186.9 | 42±2.0° | 58.2 |
Embodiment 6
With length is PVDF hollow fiber microporous membrane (0.15 micron of the average pore size of 20m, Tianjin MoTian Membrane Engineering Technology Co., Ltd's production) successively soak, carry out sufficient solvent exchange to remove remaining solvent and the soluble additive of possibility in the striping with ethanol and n-hexane.Under the traction of electronic roller, the PVDF hollow-fibre membrane is stablized by pre-processing device (comprising service sink and drying tube) by setting speed, and cleaning fluid is a water, and the drying tube temperature is 50 ℃.Under the roller transmission, make hollow-fibre membrane pass through corona treatment then, carry out twisted simultaneously.The sided corona treatment condition is: dry air charges into speed 20L/min; 25 ℃ of treatment temperatures (room temperature); Sided corona treatment power 1.6kW.Pvdf membrane after the sided corona treatment is immersed in vinylacetate (VAc) solution, and solvent is the mixture of second alcohol and water, and both volume ratios are 1: 1, at 65 ℃ of following graft reaction 1h, continues in the course of reaction to feed with steam and the saturated N of ethanol in reactant liquor
2Set the reaction time when arriving, the 1.5wt% aqueous hydrochloric acid solution that uses 60 ℃ 1.0wt% sodium hydrate aqueous solution to soak 5 hours, 25 ℃ successively the pvdf membrane behind the graft reaction soaked 2 hours, steeping 24,60 ℃ of following vacuum drying of cleaning with 40 ℃ water logging again characterized after 24 hours.
The PVDF hollow fiber microporous membrane after continuous sided corona treatment, VAc grafting, hydrolysis and the performance characterization data of former membrane sample see Table 6.
Performance with former membrane sample after the modification of table 6:PVDF hollow fiber microporous membrane compares
| Numbering | Sided corona treatment time/s | Monomer solution concentration/wt% | Graft reaction time/h | Percent grafting/% | Water flux/Lm -2·h -1 | Contact angle/° | BSA adsorbance/μ gcm -2 |
| Former film | - | - | - | - | 34.9 | 118±3.9° | 197 |
| 6-1 # | 90 | 10 | 2.0 | 5.08 | 172.9 | 49±3.5° | 88.5 |
| 6-2 # | 90 | 15 | 2.0 | 4.96 | 185.6 | 58±4.1° | 64.9 |
| 6-3 # | 120 | 20 | 1.0 | 6.59 | 197.0 | 47±1.5° | 75.0 |
Claims (6)
1, the method for polymer microporous modification is carried out in a kind of corona induced grafting, it is characterized in that, may further comprise the steps:
(1) with polymer microporous film in the indoor sided corona treatment of carrying out of the corona that is full of dry air, form the activated centre of causing double-bond polymerization on film surface and fenestra inwall, the sided corona treatment condition is: dry air charges into 5～30 liters/minute of speed, 20 kilo hertzs of discharge frequencies, 0.5～2 kilowatt of discharge power, 15～120 seconds processing times;
(2) carry out graft polymerization reaction in the solution with immersion hydrophily vinyl monomer of the polymer microporous film after the sided corona treatment and solvent composition, form stable hydrophilic grafting layer on film surface and fenestra inwall, the composition mass percent of hydrophily vinyl monomer solution is: hydrophily vinyl monomer 3～30%, solvent 70～97%, the graft polymerization reaction temperature is 30～70 ℃, and the reaction time is 0.5～24 hour;
(3) polymer microporous film soaked 3～5 hours in 40～60 ℃ mass percentage concentration is 1.0～2.0% sodium hydrate aqueous solution after the glycerol polymerization, soaking and washing in cleaning agent then, dry again, perhaps with the soaking and washing in cleaning agent of the polymer microporous film after the graft modification, dry again, cleaning temperature is 20～60 °, and soak time is 24～48 hours, and baking temperature is 10～60 °.
2, the method for polymer microporous modification is carried out in a kind of corona induced grafting according to claim 1, it is characterized in that described polymer microporous film is polyethylene, polypropylene or polyvinylidene fluoride microporous film.
3, the method for polymer microporous modification is carried out in a kind of corona induced grafting according to claim 1, it is characterized in that, described polymer microporous film be shaped as flat plate porous film or hollow fiber microporous membrane.
4, the method for polymer microporous modification is carried out in a kind of corona induced grafting according to claim 1, it is characterized in that described polymer micro membrane aperture is 0.1～1.5 micron.
5, the method for polymer microporous modification is carried out in a kind of corona induced grafting according to claim 1, it is characterized in that described hydrophily vinyl monomer is N-vinylpyrrolidone, acrylic acid, right-vinylbenzenesulfonic acid, right-vinylbenzenesulfonic acid sodium, vinylacetate or allyl acetate.
6, the method for polymer microporous modification is carried out in a kind of corona induced grafting according to claim 1, it is characterized in that, described solvent be a kind of of water, ethanol or both with any than the mixture of forming.
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