CN102218273B - Preparation method for hydrophilic ultrafiltration membrane - Google Patents
Preparation method for hydrophilic ultrafiltration membrane Download PDFInfo
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- CN102218273B CN102218273B CN 201010148305 CN201010148305A CN102218273B CN 102218273 B CN102218273 B CN 102218273B CN 201010148305 CN201010148305 CN 201010148305 CN 201010148305 A CN201010148305 A CN 201010148305A CN 102218273 B CN102218273 B CN 102218273B
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Abstract
The invention relates to a preparation method for a hydrophilic ultrafiltration membrane. Polyacrylic acid and basement membrane material polymer are alloyed to prepare an ultrafiltration membrane; the dosage of the polyacrylic acid is 2-15 percent of the total mass of the polyacrylic acid and the basement membrane material; the basement membrane material is selected from one or more from polysulfone, polyether sulfone, aromatic polysulfonamide, polyvinylidene fluoride and polyvinyl chloride; and then methoxy polyethylene glycol of carboxyl end group is grafted to the surface of the ultrafiltration membrane through crosslinking and grafting processes. The membrane has excellent anti-pollution and stability. The hydrophilic ultrafiltration membrane is prepared by adopting an alloying-crosslinking-grafting modification method. The preparation method for hydrophilic ultrafiltration membrane is simple to operate, and the prepared ultrafiltration membrane has strong anti-pollution capability, good stability and excellent application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of novel hydrophilic ultrafiltration membrane.
Background technology
Milipore filter is one of polymeric membrane for separation of developing the earliest, the sixties ultrafiltration apparatus just realized industrialization.The commercial Application of milipore filter is very extensive, has become one of Novel chemical unit operations.Ultrafiltration membrane technique is widely used in the various isolation and purification processes of the industries such as electronics, chemical industry, medicine, food.The milipore filter material mainly comprises two kinds of inorganic material film and organic film materials.The engineering plastics such as polysulfones, polyether sulfone, polysulfonamides, polyacrylonitrile, Kynoar, polyvinyl chloride are due to cheap, high mechanical strength, good heat endurance and chemical stability, good filming performance is widely used in the preparation of milipore filter.But these membrane materials are all hydrophobic, and therefore in use membrane pollution problem, especially protein in the lip-deep absorption of film, have seriously affected the separation efficiency of ultrafiltration, have become the bottleneck that the restriction hyperfiltration technique further enlarges application.
Development high-permeability, resistant to pollution milipore filter are the outer researcher of Present Domestic institute problems of concerns.Studies show that to have hydrophilic milipore filter better antifouling property is arranged, therefore, film is carried out the main method that hydrophilic modification is preparation antipollution milipore filter.Main hydrophilic modification method comprises physical blending and surface chemical reaction at present.
Surface chemical reaction can make between modified monomer and milipore filter and form chemical bond, has more practical value.Be used for the further active group of reaction but often lack in the milipore filter material that uses at present, therefore be difficult to carry out chemical reaction.Can adopt the method for blend to add macromolecule modified thing with active group in casting solution, prepare milipore filter by the submergence sedimentation, and then milipore filter is modified.Xu Zhikang prepares milipore filter at Polymer (45:399-407) and the upper report of Biomaterial (26:589-598) with polyacrylonitrile and acrylonitrile/copolymer-maleic anhydride blend, forms the carboxyl with chemical reactivity on the surface of blend film.Then at the polyethylene glycol of blend film surface grafting different molecular weight, improved hydrophily and the contamination resistance of film, studies show that the peg molecule of molecular weight 400 has best antipollution effect.Nguyen proposes in Journal of membrane science (327:78-86) that blend with the photoactive PES of ultraviolet, prepares blended ultrafiltration membrane by the submergence sedimentation in PVDF.Under the condition of ultraviolet radiation, obtain hydrophilic milipore filter at the surface grafting vinyl pyrrolidone of blend film.
Polyacrylic acid is a kind of business-like high molecular polymer, is commonly used to and the milipore filter of polyblend with the preparation functionalization.Nguyen proposes polyacrylic acid and the polysulfones blend with HMW in Journal of membrane science (278:10-18), the milipore filter that preparation has ion-exchange capacity.But because polyacrylic acid is water miscible polymer, can be water-soluble in the preparation of film and use procedure and run off, cause the decline of Ultrafiltration Membrane Separation Character.
Crosslinkedly can effectively prevent polyacrylic loss in blend film, Zhao etc. propose to adopt the polyacrylic acid of crosslinked mistake and the milipore filter that polyethersulfone blended preparation has ion-exchange capacity in Journal ofmembrane science (337:266-273), have effectively prevented the loss of polyacrylic acid in milipore filter preparation and use procedure.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of novel antipollution milipore filter.This film has good antipollution and stability.The method process is simple to operation, and mild condition is easily controlled, and is easy to amplify.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of novel antipollution milipore filter first prepares milipore filter with polyacrylic acid and basal lamina material polyblend; Polyacrylic consumption is 2%～15% of polyacrylic acid and basal lamina material gross mass; Basal lamina material is one or more in polysulfones, polyether sulfone, polysulfonamides, polyacrylonitrile, Kynoar, polyvinyl chloride;
And then will hold the poly glycol monomethyl ether of carboxyl to be grafted to the surface of milipore filter through crosslinked and grafting process.
Detailed process is as follows:
1) preparation of poly propenoic acid compound blend film: polyacrylic acid and polymer are dissolved in solvent in required ratio, add perforating agent, mechanical agitation is mixed, after vacuum defoamation on glass plate knifing, gel in deionized water;
Polyacrylic consumption is 2%～15% of polyacrylic acid and basal lamina material gross mass; Polyacrylic acid and the basal lamina material total mass concentration in solvent is 10-25%, and the mass concentration of perforating agent in solvent is 2-20%;
2) grafting of poly propenoic acid compound blend film:
A. blend film is soaked in the aqueous solution that contains amide catalysts and activates 〉=2 hours, again milipore filter is soaked in and carries out crosslinked 〉=2 hour in the polyfunctional amine aqueous solution, then take out in the aqueous solution of the poly glycol monomethyl ether that is dipped in again the end carboxyl and carry out acid amides reaction 〉=2 hours;
Or B. is soaked in milipore filter and carries out crosslinked 〉=2 hour in the polyfunctional amine aqueous solution, and adds amidation catalyst in polyfunctional amine solution; Then take out and carry out acid amides reaction 〉=2 hours in the aqueous solution that is dipped in again the poly glycol monomethyl ether of holding carboxyl, and add amidation catalyst in the aqueous solution of the poly glycol monomethyl ether of holding carboxyl;
The concentration of polyfunctional amine solution is 0.1-100g/l, and the concentration of the poly glycol monomethyl ether of end carboxyl is 0.1-100g/l, and the concentration of amidation catalyst in solution is 0.1-100g/l solution.
The temperature that stirs is 60-120 ℃, and incorporation time is 6-50h; Polyacrylic molecular weight is between 5000-200000; The molecular weight of basal lamina material polymer is between 10000-200000, and solvent is DMF (DMF), DMA (DMAc), the mixture of one or more in 1-METHYLPYRROLIDONE (NMP); Perforating agent is the polyethylene glycol of molecular weight 200-5000, the polyvinylpyrrolidone of molecular weight 30000-100000, ether, acetone, LiCl, SiO
2, Al
2O
3In one or more; Polyfunctional amine as crosslinking agent adopts aromatic series or aliphatic polyfunctional amine;
The aromatic series multi-functional amine compounds is m-phenylene diamine (MPD), p-phenylenediamine (PPD), 1,3,5-three amido benzene, 1,2,4-three amido benzene, 2, one or more in 4-diaminourea methoxybenzene, dimethylphenylene diamine;
The aliphatic polyfunctional amine is ethylenediamine, propane diamine, 1, one or more in the 6-hexamethylene diamine.
The catalyst of acid amides reaction is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl); The graft modification monomer that adopts is the poly glycol monomethyl ether of end carboxyl, and its molecular weight is between 200-5000.
The present invention has following advantage: because the polyacrylic acid to blend has been taked crosslinking Treatment, so improved the stability of polyacrylic acid in blend film inside, provide simultaneously a surface with amido to be used for further surface grafting.Be significantly improved through hydrophily and the antifouling property of surface grafting with caudacoria.The gentle easily control of reaction condition of the present invention, easy to operate and safe.
The specific embodiment
Below in conjunction with embodiment in detail the present invention is described in detail.Adopting the bovine serum albumin (BSA) of 1mg/mL in the present invention is pollutant, and milipore filter is carried out the antifouling property evaluation.
Test process is as follows: the precompressed 30min under 0.15MPa of elder generation, then the pure water flux J of mensuration milipore filter under 0.1MPa
w1, after the mixing speed ultrafiltration 30min with 400rpm under 0.1MPa, measure and pollute flux J
pThen milipore filter 20min after polluting with washed with de-ionized water repeats above precompressed process, and the pure water flux that redeterminates milipore filter under 0.1MPa is J
w2And with initial pure water flux J
w1Do contrast.The variation of film surface water contact angle before and after the marine JC2000C of company water contact angle measurement instrument test in morning uv photo initiated grafting in employing.The rejection of film adopts the Shimadzu UVmini-1240 of company ultraviolet specrophotometer to measure, and measures respectively per-meate side and the absorbance of holding back side under ultraviolet wavelength 280nm, and corresponding calibration curve obtains the corresponding BSA solution concentration of this absorbance.
The flow recovery rate:
The milipore filter rejection:
In formula:
J
w1Be the pure water flux before Pollution of Ultrafiltration Membrane;
J
w2Be the pure water flux after the milipore filter cleaning;
C
bConcentration for feed side BSA solution;
C
pConcentration for per-meate side BSA solution;
Embodiment 1
Under 80 ℃, with polysulfones 14.7g, polyethylene glycol (PEG400) 6g is dissolved in 69gN, in dinethylformamide (DMF) solution; Under 90 ℃, the 0.3g polyacrylic acid is dissolved in 10gN, in dinethylformamide (DMF) solution.Fully after dissolving, two solution are mixed, stir the casting solution that 48h obtains stable homogeneous under 80 ℃, spread to certain thickness after deaeration on glass plate, in deionized water, gel makes blended ultrafiltration membrane.
Under 4 ℃, blend film is soaked in (4mg/mL, pH=4.7) 4h in the aqueous solution of EDC, take out the film washed with de-ionized water, then be soaked at normal temperatures 1 of 4g/L, react 24h in the 6-hexamethylene diamine.Take out film and be soaked at normal temperatures (carboxyl-mPEG 4mg/mL, EDC4mg/mL, pH=4.7) in the aqueous solution that contains carboxyl-mPEG and EDC, reaction 24h.Use washed with de-ionized water three times after taking out, then be soaked in deionized water.
The flow recovery rate of Modified Membrane is that 81%, BSA rejection is in 94% left and right.
Embodiment 2
Under 80 ℃, with polysulfones 14.4g, polyvinylpyrrolidone (PVP K-30) 6g is dissolved in 69gN, in dinethylformamide (DMF) solution; Under 90 ℃, the 0.6g polyacrylic acid is dissolved in 10gN, in dinethylformamide (DMF) solution.Fully after dissolving, two solution are mixed, stir the casting solution that 48h obtains stable homogeneous under 80 ℃, spread to certain thickness after deaeration on glass plate, in deionized water, gel makes blended ultrafiltration membrane.
Under 4 ℃, blend film is soaked in (4mg/mL, pH=4.7) 4h in the aqueous solution of EDC, take out the film washed with de-ionized water, then be soaked at normal temperatures 1 of 4g/L, react 24h in the 6-hexamethylene diamine.Take out film and be soaked at normal temperatures (carboxyl-mPEG 4mg/mL, EDC4mg/mL, pH=4.7) in the aqueous solution that contains carboxyl-mPEG and EDC, reaction 24h.Use washed with de-ionized water three times after taking out, then be soaked in deionized water.
The flow recovery rate of Modified Membrane is that 87%, BSA rejection is in 96% left and right.
Embodiment 3
Under 80 ℃, with polysulfones 14.1g, polyethylene glycol (PEG400) 6g is dissolved in 69gN, in dinethylformamide (DMF) solution; Under 90 ℃, the 0.9g polyacrylic acid is dissolved in 10gN, in dinethylformamide (DMF) solution.Fully after dissolving, two solution are mixed, stir the casting solution that 48h obtains stable homogeneous under 80 ℃, spread to certain thickness after deaeration on glass plate, in deionized water, gel makes blended ultrafiltration membrane.
Under 4 ℃, blend film is soaked in (8mg/mL, pH=4.7) 4h in the aqueous solution of EDC, take out the film washed with de-ionized water, then be soaked at normal temperatures 1 of 4g/L, react 24h in the 6-hexamethylene diamine.Take out film and be soaked at normal temperatures (carboxyl-mPEG 4mg/mL, EDC4mg/mL, pH=4.7) in the aqueous solution that contains carboxyl-mPEG and EDC, reaction 24h.Use washed with de-ionized water three times after taking out, then be soaked in deionized water.
The flow recovery rate of Modified Membrane is that 81%, BSA rejection is in 94% left and right.
Embodiment 4
Under 80 ℃, with Kynoar 13.8g, polyethylene glycol (PEG1000) 6g is dissolved in 69gN, in dinethylformamide (DMF) solution; Under 90 ℃, the 1.2g polyacrylic acid is dissolved in 10gN, in dinethylformamide (DMF) solution.Fully after dissolving, two solution are mixed, stir the casting solution that 48h obtains stable homogeneous under 80 ℃, spread to certain thickness after deaeration on glass plate, in deionized water, gel makes blended ultrafiltration membrane.
Under 4 ℃, blend film is soaked in (4mg/mL, pH=4.7) 4h in the aqueous solution of EDC, take out the film washed with de-ionized water, then be soaked at normal temperatures 1 of 4g/L, react 24h in the 6-hexamethylene diamine.Take out film and be soaked at normal temperatures (carboxyl-mPEG 4mg/mL, EDC4mg/mL, pH=4.7) in the aqueous solution that contains carboxyl-mPEG and EDC, reaction 24h.Use washed with de-ionized water three times after taking out, then be soaked in deionized water.
The flow recovery rate of Modified Membrane is that 78%, BSA rejection is in 90% left and right.
Comparative Examples 1
Under 80 ℃, with polysulfones 15g, polyethylene glycol (PEG400) 6g is dissolved in 79gN, makes casting solution in dinethylformamide (DMF) solution, spreads to certain thickness after deaeration on glass plate, and in water, gel makes polysulphone super-filter membrane.
The flow recovery rate of polysulphone super-filter membrane is that 48%, BSA rejection is in 95% left and right.
Comparative Examples 2
Under 80 ℃, with Kynoar 15g, polyethylene glycol (PEG400) 6g is dissolved in 79gN, makes casting solution in dinethylformamide (DMF) solution, spreads to certain thickness after deaeration on glass plate, and in water, gel makes polysulphone super-filter membrane.
The flow recovery rate of polysulphone super-filter membrane is that 45%, BSA rejection is in 90% left and right.
Claims (8)
1. the preparation method of a hydrophilic ultrafiltration membrane is characterized in that:
First polyacrylic acid and basal lamina material polyblend are prepared milipore filter; Polyacrylic consumption is 2%～15% of polyacrylic acid and basal lamina material gross mass; Basal lamina material is one or more in polysulfones, polyether sulfone, polysulfonamides, polyacrylonitrile, Kynoar, polyvinyl chloride;
And then will hold the poly glycol monomethyl ether of carboxyl to be grafted to the surface of milipore filter through crosslinked and grafting process;
The grafting of poly propenoic acid compound blend film:
A. blend film is soaked in the aqueous solution that contains amide catalysts and activates 〉=2 hours, again milipore filter is soaked in and carries out crosslinked 〉=2 hour in the polyfunctional amine aqueous solution, then take out in the aqueous solution of the poly glycol monomethyl ether that is dipped in again the end carboxyl and carry out acid amides reaction 〉=2 hours;
Or B. is soaked in milipore filter and carries out crosslinked 〉=2 hour in the polyfunctional amine aqueous solution, and adds amidation catalyst in polyfunctional amine solution; Then take out and carry out acid amides reaction 〉=2 hours in the aqueous solution that is dipped in again the poly glycol monomethyl ether of holding carboxyl, and add amidation catalyst in the aqueous solution of the poly glycol monomethyl ether of holding carboxyl;
The concentration of polyfunctional amine solution is 0.1-100g/l, and the concentration of the poly glycol monomethyl ether of end carboxyl is 0.1-100g/l, and the concentration of amidation catalyst in solution is 0.1-100g/l solution.
2. according to preparation method claimed in claim 1, it is characterized in that, the detailed process that first polyacrylic acid and basal lamina material polyblend is prepared milipore filter is as follows:
The preparation of poly propenoic acid compound blend film: polyacrylic acid and polymer are dissolved in solvent in required ratio, add perforating agent, mechanical agitation is mixed, after vacuum defoamation on glass plate knifing, gel in deionized water;
Polyacrylic consumption is 2%～15% of polyacrylic acid and basal lamina material gross mass; Polyacrylic acid and the basal lamina material total mass concentration in solvent is 10-25%, and the mass concentration of perforating agent in solvent is 2-20%.
3. according to preparation method claimed in claim 2, it is characterized in that: the temperature of stirring is 60-120 ℃, and incorporation time is 6-50h.
4. according to preparation method claimed in claim 2, it is characterized in that: polyacrylic molecular weight is between 5000-200000; The molecular weight of basal lamina material polymer is between 10000-200000, and solvent is DMF (DMF), DMA (DMAc), the mixture of one or more in 1-METHYLPYRROLIDONE (NMP).
5. according to preparation method claimed in claim 2, it is characterized in that:
Perforating agent is the polyethylene glycol of molecular weight 200-5000, the polyvinylpyrrolidone of molecular weight 30000-100000, ether, acetone, LiCl, SiO
2, Al
2O
3In one or more.
6. according to preparation method claimed in claim 1, it is characterized in that: the polyfunctional amine as crosslinking agent adopts aromatic series or aliphatic polyfunctional amine;
The aromatic series multi-functional amine compounds is m-phenylene diamine (MPD), p-phenylenediamine (PPD), 1,3,5-three amido benzene, 1,2,4-three amido benzene, 2, one or more in 4-diaminourea methoxybenzene, dimethylphenylene diamine;
The aliphatic polyfunctional amine is ethylenediamine, propane diamine, 1, one or more in the 6-hexamethylene diamine.
7. according to preparation method claimed in claim 1, it is characterized in that:
The catalyst of acid amides reaction is 1-ethyl-(3-dimethylaminopropyl) carbodiimide hydrochloride (EDCHCl).
8. according to preparation method claimed in claim 1, it is characterized in that: the graft modification monomer that adopts is the poly glycol monomethyl ether of end carboxyl, and its molecular weight is between 200-5000.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443187B (en) * | 2011-10-28 | 2013-03-27 | 湖北工业大学 | Method for preparing porous membrane by using hydrophilic modified inorganic filler as porogenic agent |
| CN105008418B (en) * | 2012-12-21 | 2019-01-15 | 索尔维特殊聚合物意大利有限公司 | Hydrophilic fluorine polymer |
| CN104667768A (en) * | 2013-11-29 | 2015-06-03 | 贵阳时代沃顿科技有限公司 | Preparation method for novel anti-pollution polysulfone flat plate ultrafiltration membrane |
| CN103877873B (en) * | 2014-03-14 | 2016-09-14 | 西北大学 | A kind of preparation method of amphiphilic amino acid modified antipollution hydrophilic polysulfone membrane |
| CN104353371B (en) * | 2014-11-04 | 2017-04-19 | 福建医工设计院有限公司 | Modification method for ultrafiltration membranes, modified ultrafiltration membrane and method adopting ultrafiltration membrane for filtration |
| CN106166450A (en) * | 2016-08-08 | 2016-11-30 | 贵阳时代沃顿科技有限公司 | A kind of high temperature resistant accurate molecular cut off ultrafilter membrane and preparation method thereof |
| CN109289555B (en) * | 2017-07-25 | 2021-12-21 | 中国石油化工股份有限公司 | Ultrafiltration membrane and preparation method and application thereof |
| CN112237853B (en) * | 2020-09-15 | 2022-05-10 | 浙江大学 | Antibacterial and anti-pollution microporous membrane and preparation method thereof |
| CN113018910A (en) * | 2021-03-05 | 2021-06-25 | 中海油节能环保服务有限公司 | Preparation method of novel super-hydrophilic oleophobic membrane |
| CN113019149B (en) * | 2021-04-12 | 2022-06-07 | 泉州师范学院 | Acid-catalyzed COF self-assembled modified ultrafiltration membrane and preparation method thereof |
| CN113731192A (en) * | 2021-08-25 | 2021-12-03 | 中海油节能环保服务有限公司 | Hydrophilic ultrafiltration membrane for oil-water separation and preparation method thereof |
| CN115282791B (en) * | 2022-08-03 | 2024-04-19 | 沈阳工业大学 | Preparation method and application of mixed matrix film based on modified aluminum oxide and Pebax |
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| CN1745885A (en) * | 2005-08-10 | 2006-03-15 | 天津膜天膜工程技术有限公司 | Preparation and its products for composite nanometer filter membrane |
| CN101190401A (en) * | 2007-06-13 | 2008-06-04 | 海南立昇净水科技实业有限公司 | Hydrophilicity kynoar hollow fiber microporous membrane and preparation method thereof |
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| CN1745885A (en) * | 2005-08-10 | 2006-03-15 | 天津膜天膜工程技术有限公司 | Preparation and its products for composite nanometer filter membrane |
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