CN1236844C - Method for preparing hydrophilic microporous material - Google Patents
Method for preparing hydrophilic microporous material Download PDFInfo
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- CN1236844C CN1236844C CN 03115190 CN03115190A CN1236844C CN 1236844 C CN1236844 C CN 1236844C CN 03115190 CN03115190 CN 03115190 CN 03115190 A CN03115190 A CN 03115190A CN 1236844 C CN1236844 C CN 1236844C
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- polyvinyl alcohol
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- microporous barrier
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Abstract
The present invention relates to a preparation method for microporous materials, particularly to a preparation method for hydrophilic microporous materials. The hydrophilic microporous material overcomes the defect that the existing microporous separation materials prepared from hydrophilic materials are easy to block by bioactive substances. The method for preparing hydrophilic microporous materials is characterized in that polyvinyl alcohol and one or a plurality of additives are used as solutes; the solutes are dissolved in a solvent to form a film casting solution; the film casting solution is uniformly coated on a supporting layer; and then the supporting layer is immersed in a gel bath for sedimentation, and a hyperfiltration film is obtained. The hyperfiltration film is mainly used as the separation material and the adsorption material for bioseparation and drug release.
Description
Technical field: the present invention relates to the preparation method of poromerics, particularly polyvinyl alcohol microporous barrier preparation method.
Background technology: poromerics has been widely used.Can make adsorbent, diffusion barrier.At present common micropore parting material is all prepared by hydrophobic material, as polyethylene, and polypropylene, Kynoar, polyimides, polyether sulfone etc.This is because they have good mechanical property and processing characteristics, is convenient to preparation.But hydrophobic polymer has a tangible weakness, and promptly material itself is to bioactivator, as protein, and polysaccharide, microorganisms etc. have very strong suction-operated.The duct that causes like this separating is stopped up by these materials, has weakened separating effect.In order to reduce the absorption of bioactivator on the hydrophobic material surface, usual way is to material surface modifying, as the hydrophilic coating structure of method formation layer of surface of grafting, spraying.Perhaps will prepare poromerics after hydrophilic and the hydrophobic material blend.Also there is not a kind of direct effective method to prepare the polyvinyl alcohol microporous barrier at present, as the polyvinyl alcohol microporous barrier.Polyvinyl alcohol is widely used as infiltration evaporation (evaporation) diffusion barrier, belongs to the what dense film.Its utilization be affinity between its molecule and the hydrone, make it very strong absorption and selectivity be arranged to hydrone.
The end of the year 60 of twentieth century, the method preparation of adopting gel phase to separate are born in the preparation of conventional poromerics, particularly microporous barrier.This method is one of the most frequently used method of industrial production poromerics.Concrete process is with polymer solution, to be immersed in the coagulation bath, mainly form by the what coagulation bath by the poor solvent of polymer, therefore, when polymer solution touches coagulation bath, poor solvent can be diffused in the polymer solution, and the generation that causes being separated finally forms microcellular structure.By the composition of control solution, the composition of coagulation bath and the temperature of gel process, structure and form that can control hole.Adopt the membrane material of this technology preparation to comprise Kynoar, polyimides, polyether sulfone, polysulfones, polyether-ether-ketone etc. at present.Cellulose, polypropylene is fine also to be to use this legal system to be equipped with the hydrophilic material of microcellular structure the earliest.All water insoluble by the above-mentioned all materials of what, therefore the coagulation bath that adopts all is an aqueous systems.And concerning what water wetted material polyvinyl alcohol, adopt aqueous systems by very strong interaction is arranged between what water and the polyvinyl alcohol, form intermolecular hydrogen bonding.Make that polyvinyl alcohol is difficult to be separated, even be separated generation, its pore space structure still can not be kept.Usually polyvinyl alcohol all is to be used as additive, perhaps make face coat, as Chinese patent application numbers 99122946, (applicant wide a rapids refined man of virtue and ability) described the aqueous solution with the polyethenol series amines of side chain amino and has been coated on the polysulphone super-filter membrane as little porous support, then apply the trimesic acid chloride solution, carry out interfacial polycondensation, prepare the method for complex reverse osmosis membrane.US 5,993, and 661 patents have been reported, and the employing inorganic silicon is a pore former, and film after material of preparing mixes, and the method for the micropore of the blend that inorganic silicon prepares shitosan and polyvinyl alcohol is dissolved in dry back with acid.US 5,573, and 668 patents have been reported hydrophilic polymer such as employing polyvinyl alcohol in microporous barrier surface preparation coating, as the method for medicine releasable material.U.S.4,885,086 have reported and adopt the polyvinyl alcohol valence bond to be connected on the method for hollow fiber microporous membrane surface preparation coating.What JP62-277106 adopted is to use the polyvinyl alcohol of ionomer to form hydrophilic coating on the microporous barrier surface.
More than the patent of Jie Shaoing all is to increase the hydrophily of material by the hydrophilic coating that forms.Because the thickness of coating is restricted, and coating is also destroyed easily, so its hydrophily is also unstable.Another is that polyvinyl alcohol is prepared into gel.But gel is the mixture of polymer and solvent in essence.It is to separate by the open structure in the gel.This is different with diffusion barrier on the ordinary meaning.
Summary of the invention: the technical issues that need to address of the present invention are: reduce the absorption of bioactivator on the poromerics surface, make this poromerics to hydrone very strong adsorptivity and selectivity be arranged, improve the separative efficiency of poromerics.Thinking of the present invention is to adopt non-aqueous system, as the main constituent of coagulation bath.By increasing the repulsive interaction between polyvinyl alcohol and gel component, improved the speed that is separated.Cause the formation of microcellular structure at last.The aperture is in the method for several nanometers to micron.
Technical scheme of the present invention is: polyvinyl alcohol microporous barrier preparation method, it is characterized in that, be solute with polyvinyl alcohol and one or more additives, solute is dissolved in forms casting solution in the solvent, casting solution is coated on the supporting layer uniformly, immerses precipitation gained milipore filter in the coagulation bath again.Said additive is: the mixture that polyethylene glycol, polyvinylpyrrolidone, glucan, NPE, glycerine, ethylene glycol, lithium chloride, potassium permanganate, anhydrous sodium sulfate or these materials are formed; The polyvinyl alcohol weight percentage 50% to 99% in the said solute, and preferably 60% to 90%; Said solvent is: water, methyl-sulfoxide, N, N-dimethylacetylamide, N, dinethylformamide or the mixture of being made up of these materials; Said coagulation bath is the mixture that acetone, oxolane, alcohols, heptane, ethyl acetate, tricresyl phosphate second fat or these materials are formed.Said supporting layer is a glass plate.
The polyvinyl alcohol molecular weight ranges that adopts is between 30,000 to 200,000.The alcoholization degree is 60% to 100% all applicable to this law.In addition also can be with polyvinyl alcohol and polyacrylic acid, polyvinyl pyrrolidone, poly-semi-annular jade pendant styrene, blend such as shitosan.Form mixture, wherein the content of mixture is controlled at below 50% of total solid content, is good between 10% to 20% generally.The selection of polymer solvent is excellent with higher boiling, and the concentration of polymer is controlled between 7% to 30%, and the temperature of operation can be more favourable a little more than room temperature, and temperature is controlled between the 20-40 degree.
Additive in the polymer solution is a surfactant, and the perhaps poor solvent of polyvinyl alcohol is to help pore-forming and film forming.The concentration of additive is controlled at below 10% of polymer.In order to guarantee that polymer fully dissolves, course of dissolution will be controlled at higher temperature, more than 80 degree, and lasting 3-4 hour to form uniform solution.Polymer solution needs before filming through filtering and degasification process, to remove impurity and the bubble in the solution.For avoiding the variation of solution concentration in this process, whole process need is operated under airtight situation.
Coagulation bath can contain a spot of salt and crosslinking agent (adopting the twain-aldehyde compound compound) etc.Both are not that pore-forming is necessary for the back, but in order to keep pore structure.The temperature of control coagulation bath is in room temperature or below the room temperature, and is proper between the 0-25 degree.And that the temperature of polymer solution is controlled between the 20-40 degree is proper.The polymer solution coating is exposed to the airborne time to be no more than 1 minute for good before being immersed in coagulation bath.The thickness of coating can arrive several millimeters for a hundreds of micron.Depend on different application scenarios.
Milipore filter need carry out crosslinked post processing, and crosslinking agent adopts the twain-aldehyde compound compound, preferred glutaraldehyde.
The invention has the beneficial effects as follows: owing to directly adopt water wetted material to prepare poromerics, make bioactivator, as protein, polysaccharide, microorganisms etc. can't be adsorbed in the micropore, have improved greatly and have filtered and the efficient of separating, and have very strong anti-pollution ability.Also are better than the hydrophilic coating that grafting and spraying form in effect and service life.
Description of drawings
Fig. 1 is the cross section electromicroscopic photograph of the embodiment of the invention 1 polyvinyl alcohol microporous barrier
Fig. 2 is the cross section electromicroscopic photograph of the embodiment of the invention 2 polyvinyl alcohol microporous barriers
The specific embodiment: embodiment 1 adopts polyvinyl alcohol (available from Shanghai Chemical Plant), and molecular weight ranges is 8-10 ten thousand, and the alcoholization degree is 88%.The DMF solution of preparation 15% adds a spot of surfactant NPE, and content is 1% of polymer.After the solution filtration degassing, maintain 30 degree and on glass plate, film down, the thickness of film is 350 microns.Stopped for 5 seconds, coating was immersed in the coagulation bath 10 minutes.The main component of coagulation bath is 60% ethanol, 20% butanols, 10% heptane, 10% ethyl acetate.After the taking-up, dry rapidly under hot-air.Place then under the glutaraldehyde steam and under 60 degree, carried out cross-linking reaction 30 minutes.The electromicroscopic photograph that adopts ESEM to measure its cross section is seen Fig. 1.Record that pure water flux is 150L/h.m under 0.1 atmospheric pressure
2
Embodiment 2, adopt polyvinyl alcohol (available from Shanghai Chemical Plant), and molecular weight ranges is 12-14 ten thousand, and the alcoholization degree is 75%.The DMAc solution of preparation 15% adds a spot of surfactant NPE, and content is the % of polymer.After the solution filtration degassing, maintain 30 degree and on glass plate, film down, the thickness of film is 350 microns.Stopped for 5 seconds, coating was immersed in the coagulation bath 10 minutes.The main component of coagulation bath is 50% ethanol, 30% butanols, 5% heptane, 15% oxolane, and 0.1% glutaraldehyde.After the taking-up, dry rapidly under hot-air.Place then under the glutaraldehyde steam and under 60 degree, carried out cross-linking reaction 30 minutes.Adopt ESEM to measure its cross section electromicroscopic photograph and see Fig. 2.Record that pure water flux is 140L/h.m under 0.1 atmospheric pressure
2
Embodiment 3: solvent adopts water, and additive is a polyvinylpyrrolidone, and content is 4% of polymer, and all the other are identical with embodiment 1.
Embodiment 4: solvent adopts water, methyl-sulfoxide, N, N-dimethylacetylamide, N, the mixture that dinethylformamide is formed, additive are the mixture of glycerine, ethylene glycol, lithium chloride, potassium permanganate, anhydrous sodium sulfate composition, content is 7% of polymer, and all the other are identical with embodiment 1.
Embodiment 5: additive is the mixture that polyethylene glycol, glucan are formed, and content is 5% of polymer, and the main component of coagulation bath is 60% ethanol, 20% butanols, 10% heptane, 10% tricresyl phosphate second fat.All the other with
Embodiment 1 is identical.
Embodiment 6: the main component of coagulation bath is 60% ethanol, 20% acetone, 10% heptane, 10% tricresyl phosphate second fat.All the other are identical with embodiment 1.
Claims (8)
1, the preparation method of polyvinyl alcohol microporous barrier, it is characterized in that, with molecular weight ranges is between 30,000 to 200,000, the alcoholization degree is that the poor solvent of 60% to 100% polyvinyl alcohol and one or more surfactants or polyvinyl alcohol is a solute, the polyvinyl alcohol weight percentage is 50% to 99% in the solute, the concentration of the poor solvent of surfactant or polyvinyl alcohol is controlled at below 10% of polyvinyl alcohol weight, it is water that solute is dissolved in solvent, methyl-sulfoxide, N, the N-dimethylacetylamide, N, form casting solution in dinethylformamide or the mixture formed by these materials, solution temperature is controlled at more than 80 degree, duration is 3-4 hour, be coated on casting solution on the supporting layer uniformly, coating temperature is the 20-40 degree, immerse precipitation gained milipore filter in the coagulation bath again, the coagulation bath temperature is controlled at the 0-25 degree, and preparation process is operated in closed environment.
2, the preparation method of polyvinyl alcohol microporous barrier according to claim 1, it is characterized in that the poor solvent of said surfactant or polyvinyl alcohol is: the mixture that polyethylene glycol, polyvinylpyrrolidone, glucan, NPE, glycerine, ethylene glycol, lithium chloride, potassium permanganate, anhydrous sodium sulfate or these materials are formed.
3, the preparation method of polyvinyl alcohol microporous barrier according to claim 1 is characterized in that, the polyvinyl alcohol weight percentage is 60% to 90% in the solute.
4, the preparation method of polyvinyl alcohol microporous barrier according to claim 1 is characterized in that, said coagulation bath is the mixture that acetone, oxolane, alcohols, heptane, ethyl acetate, tricresyl phosphate second fat or these materials are formed.
5, the preparation method of polyvinyl alcohol microporous barrier according to claim 1 is characterized in that, said supporting layer is a glass plate.
6, the preparation method of polyvinyl alcohol microporous barrier according to claim 1 is characterized in that, casting solution needs before filming through filtering and the degassing.
7, the preparation method of polyvinyl alcohol microporous barrier according to claim 1 is characterized in that, milipore filter need carry out crosslinked post processing, and crosslinking agent adopts the twain-aldehyde compound compound.
8, the preparation method of polyvinyl alcohol microporous barrier according to claim 7 is characterized in that, crosslinking agent is a glutaraldehyde.
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| CN 03115190 CN1236844C (en) | 2003-01-27 | 2003-01-27 | Method for preparing hydrophilic microporous material |
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| CN 03115190 CN1236844C (en) | 2003-01-27 | 2003-01-27 | Method for preparing hydrophilic microporous material |
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| CN1236844C true CN1236844C (en) | 2006-01-18 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598531A (en) * | 2018-01-24 | 2018-09-28 | 辽宁石油化工大学 | A kind of dibenzo 18 is preced with the preparation method of 6 grafting polyvinyl alcohol microporous barriers |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109603570A (en) * | 2018-10-26 | 2019-04-12 | 德蓝水技术股份有限公司 | The modified method of polytetrafluoroethylhollow hollow fiber hydrophilic microporous membrane |
| CN110652889A (en) * | 2019-09-23 | 2020-01-07 | 杭州佰迈医疗科技有限公司 | Microporous filter membrane based on release layer and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108598531A (en) * | 2018-01-24 | 2018-09-28 | 辽宁石油化工大学 | A kind of dibenzo 18 is preced with the preparation method of 6 grafting polyvinyl alcohol microporous barriers |
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