CN1299810C - Method for modifying hydroophilicity of highly active separation membrane made from polymer - Google Patents
Method for modifying hydroophilicity of highly active separation membrane made from polymer Download PDFInfo
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Abstract
The present invention relates to a hydrophilization modification method for polymer separation films. In the method, grafted monomers of a glycosyl-containing compound is firstly coated on the surface of a polymer separation film; a solvent is evaporated; then, the graft polymerization of the grafted monomers is initiated on the surface of the polymer separation film by a radiation method so as to fix the grafted monomers to the surface of the polymer separation film through chemical bonds. After the graft modification by the method, the contact angle of the polymer separation film is greatly declined along with the increase of the graft rate of the glycosyl-containing monomers, which indicates that the hydrophilicity of the film is greatly raised, and the hydrophilicity can be kept for a long time, for example, the surface contact angle of a polypropylene separation film which is not modified is 118 degrees, but the surface contact angle after graft modification by allyl glucose through plasma irradiation can drop to 34 degrees. The protein adsorption amount of the polymer separation film modified by the method is less than that of a film which is not modified. Furthermore, the modified film is easier to clean than the film which is not modified, thereby greatly improving the pollution resistance of films.
Description
Technical field
The present invention relates to a kind of polymer separation film be carried out the method for surface modification, especially relate to the method for the hydrophobic polymer separation membrane material being carried out surface modification.
Background technology
Polyolefin such as polyethylene, polypropylene is the polymeric material that a class is cheap, have excellent chemical stability and heat endurance, polyolefin diffusion barrier prepared therefrom has been widely used in fields such as industry, agricultural, medicine, environmental protection, for energy savings, raise the efficiency, environment purification etc. has been made significant contribution.But polyolefin separation membrane surface hydrophily is poor, easy static electrification, and these shortcomings have restricted further applying of they.The polyolefin separation membrane surface is carried out graft modification, the function of utilization introducing group is improved the deficiency on the film surface property, again both advantages being got up simultaneously, increase new performance, is a kind of simple and efficient ways that enlarges polyolefin diffusion barrier purposes.
Have multiple distinct methods to can be used for the surface modification of polyolefin diffusion barrier, mainly contain: physics cladding process, original position are filled polymerization and glycerol polymerization method.Wherein the physics cladding process is the simplest surface modifying method, promptly use hydrophilizing agent (as alcohol, surfactant, polyelectrolyte complex compound etc.) handle diffusion barrier or the diffusion barrier direct impregnation in Polymer Solution, evaporating solvent then.Though this technology is simple, owing to just fix surface modifier, cause surface modifier easily to run off by physisorption, hydrophily in use descends gradually.It is to add monomer and corresponding initator makes monomer polymerization in the micropore of polyolefin diffusion barrier that original position is filled polymerization, can obtain the functional film material of modification.Compare with preceding two kinds of methods, the glycerol polymerization method has following advantage and is widely used: grafted chain is with chemical bond and film surface bond, thereby can be not dissolved when the material permeance film, can not cause the loss of grafted chain.The basic ideas of glycerol polymerization modification are: utilize the whole bag of tricks to handle the surface of diffusion barrier earlier, produce free radical on its surface, then trigger monomer glycerol polymerization or introducing functional group.The implementation method that the film surface grafting polymeric modification is commonly used is ultraviolet radiation, plasma treatment, high-energy radiation (gamma-radiation radiation, electron beam irradiation etc.) initiation grafting polymerization etc.According to different modification purposes, can on MIcroporous polyolefin film, introduce dissimilar monomers.The grafted monomers of reported in literature mostly is the hydrophilic polar monomer, mainly contains: acrylic acid and methacrylic acid or its salt, acrylamide, acrylate and methacrylate (as methyl propenoic acid glycidyl fat, methacrylic acid ethoxy fat etc.), vinyl acetate resin etc.Though the glycerol polymerization method can be fixed functional group with covalent bond, these processing procedure technologies are more complicated often, and suitability for industrialized production is still had any problem.
Summary of the invention
The present invention mainly be solve that existing polymer separation film hydrophily is poor, water flux is little, easy static electrification, contaminated and complex process easily, be difficult to the technical problem of suitability for industrialized production etc.
The present invention is subjected to the inspiration of biofilm structure, the material with glycosyl of glycolipid is grafted on the diffusion barrier in the cell membrane if we are being similar to, utilization contains glycosyl compound as modified monomer, make the outer surface of diffusion barriers such as polyethylene, polypropylene have one deck glycosyl compound, make it to have the layer structure of similar natural fine after birth, the hydrophily of diffusion barrier and biocompatibility also should possess biomembranous characteristic to a certain extent, might obtain comparatively ideal biological function film.Simultaneously, utilize the hydrophily of glycosyl, expectation can reduce film and pollute.For solve prior art problem, take following technical proposals: earlier the grafted monomers that contains glycosyl compound is coated in the surface of polymer separation film, evaporating solvent; Use of the glycerol polymerization of the method initiation grafting monomer of radiation then, so that grafted monomers is fixed on the surface of polymer separation film by chemical bond at surface of separating film of polymer.
The operating procedure of this polymer separation film hydrophilic modification method is as follows successively:
(1) gets the polymer separation film of aequum, clean with acetone and remove the impurity that is adsorbed on the film surface, vacuum drying at room temperature then 3 times;
(2) grafted monomers that will contain glycosyl compound is coated in the surface of polymer separation film, and at 30 ℃ of following atmospheric evaporation solvents or airing at room temperature;
(3) will carry out radiation treatment by the polymer separation film that (2) obtain;
(4) use washed with de-ionized water 3 times, immerse standing over night in the deionized water again, film is taken out from deionized water, 50 ℃ of following vacuum drying;
(5) the polymer separation film of required hydrophilic modification.
As preferably, described glycosyl is monose and disaccharides such as glucose, galactolipin, mannose, wood sugar, fructose, sucrose, maltose; The described glycosyl compound that contains is mainly the alkene class that combines with above-mentioned glycosyl by chemical bond, ester class etc. and contains glycosyl compound; The described glycosyl compound that contains can be caused by radiation, thereby is grafted to the surface of polymer separation film by graft polymerization reaction; Its percent grafting optimum range is 1-10wt.%, and in this scope, the water flux of Modified Membrane can rise to original 2-10 doubly;
As preferably, the method for described radiation is radiation treatment protocols such as plasma resonance, ultraviolet radiation, corona radiation, gamma-radiation radiation and electron beam irradiation;
As preferably, the polymer separation film material is a hydrophobic polymer material, is mainly polymeric film material such as polyethylene, polypropylene, Kynoar, polyacrylonitrile, polyvinyl chloride, polyether sulfone, PEI, polysulfones.
Described polymer separation film can be the diffusion barrier of types such as dull and stereotyped mould, hollow-fibre membrane or tubular membrane.According to the difference in aperture, diffusion barrier can be micro-filtration membrane, milipore filter or NF membrane.
This method improvement existing surface modifying method, developed simple, effective modified technique, simultaneously, synthetic have the good hydrophily and the modified monomer of biocompatibility, this is the bad key issue of modification good working effect.After the graft modification, water descends with the increase that contains the glycosyl compound percent grafting greatly at the contact angle of surface of separating film of polymer.For example, unmodified polypropylene diffusion barrier contact angle is 118 °, can drop to 34 ° after the modification, illustrate that the hydrophily of grafting caudacoria has had great improvement, and hydrophily can keep for a long time.In addition, the polymer separation film by this method modification will be less than unmodified membrane greatly to the amount of protein adsorption; When protein solution was filtered, unmodified membrane flux peak loss can reach 80%, and Modified Membrane only descends about 40%, and Modified Membrane is than the easier cleaning of unmodified membrane, illustrated by this method the antifouling property of the film effect that has greatly improved.
The specific embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1:
Step 1, the polypropylene hollow fiber micro-filtration membrane of getting aequum, porosity is about 40%, and 0.07 micron of average pore size is cleaned 3 times with acetone, is adsorbed on the film surface impurity to remove.Film after processing vacuum drying at room temperature 3 hours, standby.The pi-allyl glucose of aequum is dissolved in the dimethyl formamide, is made into the solution of variable concentrations.Take by weighing micro-filtration membrane that aequum washed with acetone and be immersed in the pi-allyl glucose solution and spend the night, take out micro-filtration membrane then,, promptly get the micro-filtration membrane that scribbles grafted monomers (glycosyl compound) at 30 ℃ of following atmospheric evaporation solvents;
Step 2 places this micro-filtration membrane that scribbles monomer in the plasma processor chamber, vacuumizes, and it is 60Pa that logical nitrogen is regulated vacuum.Open the plasma processor power supply, open high voltage source after the preheating, under power 100W, carry out plasma resonance and handle.After radiation a period of time, powered-down stops to vacuumize, and micro-filtration membrane is taken out in the plasma processor cavity, uses washed with de-ionized water 3 times, immerses standing over night in the deionized water then, so that remove unreacted monomer and monomer homopolymers.Film is taken out from deionized water, and 50 ℃ of following vacuum drying promptly get the required polypropylene hollow fiber micro-filtration membrane after the graft modification of pi-allyl glucose.Treat to claim its weight after the constant weight, place drier standby then.
After 3% pi-allyl glucose grafting, the contact angle of film drops to 34 ° by 118 °.For unmodified polypropylene micro-filtration membrane, can not water be passed through.After the polypropylene micro-filtration membrane was soaked 30min with ethanol, its pure water flux was 0.36 ton/square metre hour under 0.2 kilogram test pressure; The water flux of pi-allyl glucose modified polypropene micro-filtration membrane is 3.4 tons/square metre hours under the same terms.For the unmodified polypropylene micro-filtration membrane, when to filter concentration be 1% the bovine serum albumin aqueous solution, its flux dropped to 28% of original pure water flux, after cleaning with alkali lye, returned to original 62%.For the modified polypropene micro-filtration membrane, the minimizing of filtering flux that bovine serum albumin solution causes is lower about 20 percentage points than unmodified polypropylene micro-filtration membrane, and after cleaning, and flux returns to original more than 80%.
Embodiment 2:
Step 1, the polyethylene hollow fiber micro-filtration membrane (porosity about 55%, 0.25 micron of average pore size) of getting aequum is cleaned 3 times with acetone, is adsorbed on the film surface impurity to remove.Film after processing vacuum drying at room temperature 3 hours, standby.The pi-allyl galactolipin of aequum is dissolved in the dimethyl formamide, is made into the solution of desired concn.Take by weighing polyethylene hollow fiber micro-filtration membrane that aequum washed with acetone and be immersed in the allyl sucrose solution and spend the night, take out the polyethylene hollow fiber micro-filtration membrane then, at 30 ℃ of following atmospheric evaporation solvents.
Step 2 places corona treatment with this polyethylene hollow fiber micro-filtration membrane that scribbles monomer, opens and handles dynamo-electric source, carries out the corona radiation treatment.After radiation a period of time, powered-down takes out film, uses washed with de-ionized water 3 times, immerses standing over night in the deionized water then, so that remove unreacted monomer and monomer homopolymers.Film is taken out from deionized water, must be through the polyethylene hollow fiber micro-filtration membrane after the graft modification of alkene galactite, 50 ℃ of following vacuum drying are treated to claim its weight after the constant weight, place drier standby then.After 2.8% pi-allyl galactolipin grafting, the contact angle of polyethylene hollow fiber micro-filtration membrane drops to 30 ° by original 96 °.Its pure water flux of polyethylene hollow fiber micro-filtration membrane that soaks 30min with ethanol is 0.52 ton/square metre hour under 0.2 kilogram test pressure, and the water flux of pi-allyl galactolipin modified poly ethylene hollow fiber microfiltration membrane is 4.6 tons/square metre hours.
Embodiment 3:
Step 1 is got the poly (ether-sulfone) ultrafiltration membrane (molecular cut off is 50000Dalton) of aequum, cleans 3 times with acetone, is adsorbed on the film surface impurity to remove.Film after processing vacuum drying at room temperature 3 hours, standby.Aequum glucose ethoxy propylene acid esters is dissolved in the deionized water, is made into the solution of variable concentrations.Take by weighing poly (ether-sulfone) ultrafiltration membrane that aequum washed with acetone and be immersed in the glucose ethoxy propylene acid esters solution and spend the night, take out poly (ether-sulfone) ultrafiltration membrane then, at room temperature dry.
Step 2 places metering for 5-35kGy's this poly (ether-sulfone) ultrafiltration membrane that scribbles monomer
60Carry out the gamma-radiation radiation treatment in the Co source.After radiation a period of time, with poly (ether-sulfone) ultrafiltration membrane from
60Co takes out in the source, uses washed with de-ionized water 3 times, immerses standing over night in the deionized water then, so that remove unreacted monomer and homopolymers.Film is taken out from deionized water, 50 ℃ of following vacuum drying, the poly (ether-sulfone) ultrafiltration membrane of hydrophilic modification, treat to claim its weight after the constant weight, place drier standby then.After 2.5% glucose ethoxy propylene acid esters grafting, the contact angle of film drops to 20 ° by 56 °; Cross under the film pressure at 1 kilogram, its pure water flux increases to 2.44 tons/square metre hours by 0.57 ton/square metre hour of unmodified membrane.For unmodified poly (ether-sulfone) ultrafiltration membrane, when to filter concentration be 1% the bovine serum albumin aqueous solution, its flux dropped to 30% of original pure water flux, after cleaning with alkali lye, returned to original 50%.For modified poly (ether-sulfone) ultrafiltration membrane capable, the minimizing of filtering flux that bovine serum albumin solution causes is lower about 65 percentage points than unmodified poly (ether-sulfone) ultrafiltration membrane, and after cleaning, and flux returns to original more than 95%.
Embodiment 4:
Step 1 is got the Kynoar hollow fiber microfiltration membrane of 0.2 micron of aequum average pore size, cleans 3 times with acetone, is adsorbed on the film surface impurity to remove.Film after processing vacuum drying at room temperature 3 hours, standby.Aequum mannose ethoxyl methyl acrylate is soluble in water, be made into the solution of variable concentrations.Take by weighing Kynoar hollow fiber microfiltration membrane that aequum washed with acetone and be immersed in the mannose ethoxyl methyl acrylate solution and spend the night, take out the Kynoar hollow fiber microfiltration membrane then, at room temperature dry.
Step 2 places plasma generator with this Kynoar hollow fiber microfiltration membrane that scribbles monomer, opens and handles dynamo-electric source, carries out plasma radiation and handles.After radiation a period of time, powered-down takes out hollow fiber microfiltration membrane, uses washed with de-ionized water 3 times, immerses standing over night in the deionized water then, so that remove unreacted monomer and monomer homopolymers.Film is taken out from deionized water, and 50 ℃ of following vacuum drying must be through the Kynoar hollow fiber microfiltration membrane after the acrylic ester grafted modification of mannose ethoxyl methyl.Treat to claim its weight after the constant weight, place drier standby then.After the acrylic ester grafted modification of 3.5% mannose ethoxyl methyl, the contact angle of Kynoar hollow fiber microfiltration membrane drops to 31 ° by original 90 °; Cross under the film pressure at 1 kilogram, its pure water flux increases to 1.60 tons/square metre hours by 0.20 ton/square metre hour of unmodified membrane.
Embodiment 5:
Step 1, the polyacrylonitrile hollow fiber ultrafiltration membrane (molecular cut off is 50000Dalton) of getting aequum is cleaned 3 times with acetone, is adsorbed on the film surface impurity to remove.Film after processing vacuum drying at room temperature 3 hours, standby.Aequum is dissolved in the deionization dimethyl formamide styryl glucose, is made into the solution of variable concentrations.Take by weighing polyacrylonitrile hollow fiber ultrafiltration membrane that aequum washed with acetone and be immersed in, take out the polyacrylonitrile hollow fiber ultrafiltration membrane then, at room temperature dry in the styryl glucose solution 3 hours.
Step 2 places corona treatment with this polyacrylonitrile hollow fiber ultrafiltration membrane that scribbles monomer, opens and handles dynamo-electric source, carries out the corona radiation treatment.After radiation a period of time, powered-down takes out film, uses washed with de-ionized water 3 times, immerses standing over night in the deionized water then, so that remove unreacted monomer and monomer homopolymers.Film is taken out from deionized water, one day one night of 50 ℃ of following vacuum drying, must be through to the polyacrylonitrile hollow fiber ultrafiltration membrane after the graft modification of styryl glucose.Treat its weight of weighing after the constant weight, place drier standby then.After the graft modification of 2.8% pair of styryl glucose, the contact angle of polyacrylonitrile hollow fiber ultrafiltration membrane drops to 27 ° by original 68 °; Cross under the film pressure at 1 kilogram, its pure water flux increases to 0.90 ton/square metre hour by 0.15 ton/square metre hour of unmodified membrane.
Embodiment 6:
Step 1, the polyvinyl chloride hollow fiber ultrafiltration membrane (molecular cut off is 50000Dalton) of getting aequum is cleaned 3 times with acetone, is adsorbed on the film surface impurity to remove.Film after processing vacuum drying at room temperature 3 hours, standby.Aequum 1-O-methyl-6-O-methacrylic acid glucose ester is dissolved in the deionized water, is made into the solution of variable concentrations.Take by weighing polyacrylonitrile hollow fiber ultrafiltration membrane that aequum washed with acetone and be immersed in 1-O-methyl-6-O-methacrylic acid glucose ester solution and spend the night, take out the polyacrylonitrile hollow fiber ultrafiltration membrane then, at room temperature dry.
Step 2 places corona treatment with this polyacrylonitrile hollow fiber ultrafiltration membrane that scribbles monomer, opens and handles dynamo-electric source, carries out the corona radiation treatment.After radiation a period of time, powered-down takes out milipore filter, uses washed with de-ionized water 3 times, immerses standing over night in the deionized water then, so that remove unreacted monomer and monomer homopolymers.Film is taken out from deionized water, one day one night of 50 ℃ of following vacuum drying, must be through the polyacrylonitrile hollow fiber ultrafiltration membrane after 1-O-methyl-6-O-methacrylic acid glucose ester graft modification.Treat its weight of weighing after the constant weight, place drier standby then.After 2.8%1-O-methyl-6-O-methacrylic acid glucose ester graft modification, the contact angle of polyacrylonitrile hollow fiber ultrafiltration membrane drops to 27 ° by original 68 °; Cross under the film pressure at 1 kilogram, its pure water flux increases to 1.62 tons/square metre hours by 0.25 ton/square metre hour of unmodified membrane.
Claims (5)
1, a kind of method of polymer separation film hydrophilic modification, it is characterized in that this method is the surface that the grafted monomers of glucose, mannose, galactolipin, fructose, sucrose and maltose monose and disaccharides is coated in polymer separation film containing the glycosyl compound glycosyl earlier, evaporating solvent; Use of the glycerol polymerization of the method initiation grafting monomer of radiation then, so that grafted monomers is fixed on the surface of polymer separation film by chemical bond at surface of separating film of polymer.
2, by the method for the described polymer separation film hydrophilic modification of claim 1, its characterization step is as follows successively:
(1) gets the polymer separation film of aequum, clean with acetone and remove the impurity that is adsorbed on the film surface, vacuum drying at room temperature then 3 times;
(2) grafted monomers that will contain glycosyl compound is coated in the surface of polymer separation film, and at 30 ℃ of following atmospheric evaporation solvents or airing at room temperature;
(3) will carry out radiation treatment by the polymer separation film that (2) obtain;
(4) use washed with de-ionized water 3 times, immerse standing over night in the deionized water again, then film is taken out from deionized water, 50 ℃ of following vacuum drying;
(5) the polymer separation film of required hydrophilic modification.
3, the method for polymer separation film hydrophilic modification according to claim 1 and 2 describedly contains the glycosyl compound that contains that glycosyl compound is mainly the alkene class that combines with above-mentioned glycosyl by chemical bond, amine.
4, the method for polymer separation film hydrophilic modification according to claim 1 and 2, the scope of its percent grafting are 1-10wt.%.
5, the method for polymer separation film hydrophilic modification according to claim 1 and 2, the method for its radiation are the radiation treatment protocols of plasma resonance, ultraviolet radiation, corona radiation, gamma-radiation radiation and electron beam irradiation.
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Cited By (1)
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| WO2021036716A1 (en) | 2019-08-23 | 2021-03-04 | 中国石油化工股份有限公司 | Super-wet surface and preparation method therefor and application thereof |
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| CN100366666C (en) * | 2006-05-11 | 2008-02-06 | 复旦大学 | Method for hydrophilic modifying of poly-vinylidene fluoride film |
| CN100431678C (en) * | 2006-11-28 | 2008-11-12 | 浙江大学 | Surface hydrophilicity modification process for separating fluoric polymer film |
| CN100430118C (en) * | 2006-12-27 | 2008-11-05 | 南京工业大学 | Method for persistent hydrophilic modification of polypropylene porous membrane surface |
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| CN106492649B (en) * | 2016-11-16 | 2017-08-25 | 启迪清源（北京）科技有限公司 | Glycosyl modified reverse osmosis composite membrane and preparation method thereof |
| CN109847603A (en) * | 2019-01-24 | 2019-06-07 | 南京工业大学 | A kind of method that surface glycosylation improves polymer separation film hydrophily and pollution resistance |
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