CN1416944A - Prepn precess of composite asymmetrical affinity polysulfone-hydroxyethyl cellulose ultrafiltering film - Google Patents
Prepn precess of composite asymmetrical affinity polysulfone-hydroxyethyl cellulose ultrafiltering film Download PDFInfo
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- CN1416944A CN1416944A CN 02153350 CN02153350A CN1416944A CN 1416944 A CN1416944 A CN 1416944A CN 02153350 CN02153350 CN 02153350 CN 02153350 A CN02153350 A CN 02153350A CN 1416944 A CN1416944 A CN 1416944A
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Abstract
Asymmetrical polysulfone ultrafiltering membrane is first prepared via phase transferring process using chloromethylated polysulfone as base material and is then hydrolyzed to activate and reacted directly or indirectly with hydroxyethyl cellulose solution to form the composite polysulfone-hydroxyethyl cellulose membrane. The preparation process is characterized by the hydrolysis in alkali water solution at 50-90 deg.c to produce hydroxymethyl polysulfone membrane. The prepared composite asymmetrical polysulfone-hydroxyethyl cellulose membrane has coupled hydroxyethyl cellulose amount up to 90-160 mg to each gram polysulfone membrane. The composite membrane has excellent hydrophilicity, low non-specific adsorption, high mechanical strength and ideal pore structure and may be used widely in affinity ultrafiltration.
Description
Technical field
The present invention relates to the preparation method of the compound asymmetric milipore filter of a kind of compatibility polysulfones-hydroxyethylcellulose, belonged to the technology of preparing of composite hyperfiltration membrane.
Background technology
Polysulfones has superior film forming because of it and good chemical stability has obtained extensive use in hyperfiltration technique, but there is not to be directly used in the functional group of immobilized large biological molecule on hydrophobicity that it is intrinsic and the molecule, make it must not carry out chemical modification to it directly as the medium of affine separation.At present existing five kinds of chemical modification methods: (1) preparation can form film, and copolymer [Klein E with polysulfones derivative of active group and hydrophilicity, Silva L.Hydrophilic semipermeable membranes based on copolymersof acrylonitrile and hydroxyalkyl esters of (meth) acrylic acid.U.S.Patent, 5039420,1992]; (2) alloy polymers of adding possess hydrophilic property energy in the polysulfones solid material is to strengthen its surperficial wettable [Newton AB.Compatible polymer blend composition.U.S.Patent, 4387187,1983]; (3) use amphiphilic polymers and plastic cement, realize that strongly hydrophilic is in conjunction with [Henis JM, Tripodi MK, Stimpson DI.Modified polymeric surfaces and process for preparingsame.U.S.Patent, 4794002,1988]; (4) on the skeleton of polysulfones,, introduce hydrophilic radical [Higuchi A, Iwata N, Nakagawa T.Surface-modified polysulfone hollowfibers:II.Fibers having CH by rudimentary replacement
2CH
2CH
2SO
3-segments and immersed in HCl solution.Journal of Applied Polymer Science, 1990,40:709-717]; (5) by covalent bond in PS membrane surface-coated hydrophilic media [Klein E, Feldhoff PA.Affinity separation with activatedpolyamide microporous membranes.U.S.Patent, 5053133,1984].Said method has all been introduced the active group of some, and has improved the hydrophilicity of film to a certain extent, but activation method is comparatively complicated, and does not consider the internal structure of film forming.
Summary of the invention
The object of the present invention is to provide the preparation method of the compound asymmetric milipore filter of a kind of compatibility polysulfones-hydroxyethylcellulose.That the prepared composite membrane of Using such method has is more-OH base active group, and the good hydrophilicity surface, non-specific adsorption is low, and blood compatibility is good, the mechanical strength height, the pore passage structure ideal, and the preparation method is comparatively simple.This film can be widely used in affinity ultrafiltration and separate.
The present invention is realized by following technical proposals: be base material with the chloromethyl polysulphone, be pore-foaming agent with polyethylene glycol and ethylene glycol monoemethyl ether respectively, with dimethyl formamide, dimethylacetylamide and N-methyl pyrrolidone is solvent, is that coagulating bath prepares the asymmetric milipore filter of polysulfones by phase inversion with the ethanol water of water, 10-50% and the propionic acid aqueous solution of 5-20%.This film process hydrolytic activation, direct or indirect and hydroxyethylcellulose solution reaction, the coupling hydroxyethylcellulose forms polysulfones-hydroxyethylcellulose composite membrane.It is characterized in that: with the 10-30% soda ash aqueous solution is hydrolyzate, hydrolysis temperature is 50-90 ℃, at room temperature direct and 1-3% hydroxyethylcellulose acid solution reacts, the coupling hydroxyethylcellulose, form polysulfones-hydroxyethylcellulose composite membrane, or to adopt the solution of bis-epoxy alkane, carbonyl dimidazoles, epoxychloropropane, three chlorotriazines, glutaraldehyde be that activator activates the methylol PS membrane at 20-90 ℃, and the coupling hydroxyethylcellulose forms polysulfones-hydroxyethylcellulose composite membrane again.
Above-mentioned bis-epoxy alkane solution is the alkaline ethanol solution of bis-epoxy alkane, and concentration is 5-50%, and preferred concentration is 20-30%; Carbonyl dimidazoles solution is the acetone soln of carbonyl dimidazoles, and concentration is 0.5-4%, and preferred concentration is 1-1.5%; Epoxychloropropane solution is the alkaline aqueous solution of epoxychloropropane, and concentration is 5-60%, and preferred concentration is 20-30%; Three chlorotriazine solution are the alkaline aqueous solution of three chlorotriazines, and concentration is 5-30%, and preferred concentration is 15-25%; Glutaraldehyde solution is a glutaraldehyde water solution, and concentration is 10-50%, and preferred concentration is 20-25%.
The prepared compound anisotropic membrane coupling of the polysulfones-hydroxyethylcellulose hydroxyethylcellulose amount of the present invention reaches: the 90-160mg/g PS membrane, this film has good hydrophilicity, non-specific adsorption is low, mechanical strength is good, the pore passage structure ideal, and the preparation method is comparatively simple, and this film can be widely used in affinity ultrafiltration.
The specific embodiment
Embodiment one:
1. the preparation of chloromethyl polysulphone anisotropic membrane
Get chloromethyl polysulphone and polyethylene glycol places dimethyl formamide, chloromethyl polysulphone/polyethylene glycol is 4/1, and the molecular weight of polyethylene glycol is 600, and 80-85 ℃ was stirred 12 hours down.Then casting solution is placed the lucifuge place to leave standstill 24 hours.Casting solution is fallen on glass plate, and the temperature of glass plate is 50 ℃, with scraper striking film forming, evaporates after 30 seconds, immerses in the distilled water, solidifies 1 hour.The film that will solidify takes out, and with flowing water flushing 24 hours, promptly gets the chloromethyl polysulphone anisotropic membrane with bottom through hole.
2. the preparation of methylol PS membrane
Get the chloromethyl polysulphone film of step 1 preparation, place 15% soda ash solution, 85 ℃ of following constant temperature vibrations 6 hours.Repeatedly change water with distilled water then and cleaned 1 hour, promptly get the methylol PS membrane.
3. the preparation of polysulfones-hydroxyethylcellulose composite membrane
Get the methylol PS membrane of step 2 preparation, be cut into a disk, diameter is 47mm, places 5 milliliter 2% hydroxyethylcellulose aqueous hydrochloric acid solution, at room temperature, vibrates 1 hour.Place 80 ℃ dry 90 minutes of baking oven then.The sodium hydroxide solution of dried film with 0.1M cleaned 1 hour, and cleaned 1 day, promptly get polysulfones-hydroxyethylcellulose composite membrane with a large amount of distilled water.This film coupling hydroxyethylcellulose amount reaches: the 110mg/g PS membrane.
Embodiment two:
Get chloromethyl polysulphone and ethylene glycol monoemethyl ether and place the N-methyl pyrrolidone, chloromethyl polysulphone/ethylene glycol monoemethyl ether is 4/1, and 80-85 ℃ was stirred 15 hours down.Then casting solution is placed the lucifuge place to leave standstill 24 hours.Casting solution is fallen on glass plate, and the temperature of glass plate is 70 ℃, with scraper striking film forming, evaporates after 1 minute, in the propionic acid solution of immersion 10%, solidifies 1 hour.The film that will solidify took out, with flowing water flushing 24 hours.Promptly get the chloromethyl polysulphone anisotropic membrane.
Scheme according to embodiment one prepares the methylol PS membrane.
Get a slice methylol PS membrane, diameter 47mm places the acetone soln of 1% carbonyl dimidazoles, and at room temperature, oscillating reactions 1 hour is cleaned 3 times with acetone then, and film was placed 50 ℃ of baking ovens dry 30 minutes.Film after the activation is placed 2% hydroxyethylcellulose alkaline aqueous solution, pH8.4, oscillating reactions 1 hour places 80 ℃ dry 1 hour of baking oven then.The sodium hydroxide solution of dried film with 0.1M cleaned 1 hour, cleaned 1 day, promptly get polysulfones-hydroxyethylcellulose composite membrane with a large amount of distilled water.This film coupling hydroxyethylcellulose amount reaches: the 130mg/g PS membrane.
Embodiment three:
The sodium borohydride of getting 80 milligrams is dissolved among 12 milliliters of 2M NaOH, adds 20 ml waters and 4 milliliters of bis-epoxy alkane.The methylol PS membrane of embodiment one preparation is placed above-mentioned solution, and the vibration activation is 4 hours under the room temperature, cleans 3 times with distilled water then.Film after the activation is placed 2% hydroxyethylcellulose alkaline aqueous solution, and pH11 40 ℃ of down vibrations 5 hours, places 120 ℃ dry 4 hours of baking oven then.The sodium hydroxide solution of dried film with 0.1M cleaned 1 hour, cleaned 1 day, promptly get polysulfones-hydroxyethylcellulose composite membrane with a large amount of distilled water.This film coupling hydroxyethylcellulose amount reaches: the 95mg/g PS membrane.
Embodiment four:
The methylol PS membrane of embodiment one preparation is placed 20% epoxychloropropane solution, and pH11 60 ℃ of activation 10 hours of vibrating down, cleans 3 times with distilled water then.Film after the activation is placed 2% hydroxyethylcellulose alkaline aqueous solution, and pH11 at room temperature vibrated 30 minutes, placed 100 ℃ dry 4 hours of baking oven then.The sodium hydroxide solution of dried film with 0.1M cleaned 1 hour, cleaned 1 day, promptly get polysulfones-hydroxyethylcellulose composite membrane with a large amount of distilled water.This film coupling hydroxyethylcellulose amount reaches: the 90mg/g PS membrane.
Claims (2)
1. the preparation method of the compound asymmetric milipore filter of compatibility polysulfones-hydroxyethylcellulose, this method is base material with the chloromethyl polysulphone, be pore-foaming agent with polyethylene glycol and ethylene glycol monoemethyl ether respectively, with dimethyl formamide, dimethylacetylamide and N-methyl pyrrolidone are solvent, with water, the propionic acid aqueous solution of the ethanol water of 10-50% and 5-20% is coagulating bath, prepare the asymmetric milipore filter of polysulfones by phase inversion, this film is through hydrolytic activation, directly or indirectly and the hydroxyethylcellulose solution reaction, the coupling hydroxyethylcellulose, form polysulfones-hydroxyethylcellulose composite membrane, it is characterized in that: hydrolysis is a hydrolyzate with the 10-30% soda ash aqueous solution, hydrolysis temperature is 50-90 ℃, generate the methylol PS membrane, at room temperature direct and 1-3% hydroxyethylcellulose acid solution reacts, the coupling hydroxyethylcellulose, form polysulfones-hydroxyethylcellulose composite membrane, or employing bis-epoxy alkane, carbonyl dimidazoles, epoxychloropropane, three chlorotriazines, the solution of glutaraldehyde is that activator activates the methylol PS membrane at 20-90 ℃, again with 1-3% hydroxyethylcellulose solution reaction, the coupling hydroxyethylcellulose forms polysulfones-hydroxyethylcellulose composite membrane.
2. by the preparation method of the compound asymmetric milipore filter of the described compatibility polysulfones-hydroxyethylcellulose of claim 1, it is characterized in that: bis-epoxy alkane solution is the alkaline ethanol solution of bis-epoxy alkane, and concentration is 5-50%, and preferred concentration is 20-30%; Carbonyl dimidazoles solution is the acetone soln of carbonyl dimidazoles, and concentration is 0.5-4%, and preferred concentration is 1-1.5%; Epoxychloropropane solution is the alkaline aqueous solution of epoxychloropropane, and concentration is 5-50%, and preferred concentration is 20-30%; Three chlorotriazine solution are the alkaline aqueous solution of three chlorotriazines, and concentration is 5-50%, and preferred concentration is 15-25%; Glutaraldehyde solution is a glutaraldehyde water solution, and concentration is 10-50%, and preferred concentration is 20-25%.
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| CN100531872C (en) * | 2007-08-03 | 2009-08-26 | 厦门大学 | Method for preparing polypyrole-polycarbonate composite membrane of fixed load cibacron blue |
| CN1759924B (en) * | 2004-06-25 | 2010-05-05 | 米利波尔公司 | Ultrafiltration membrane and preparation method thereof |
| CN101690870B (en) * | 2005-10-14 | 2012-07-04 | Emd密理博公司 | Ultrafiltration membranes and methods of making and use of ultrafiltration membranes |
| CN104707488A (en) * | 2015-04-03 | 2015-06-17 | 深圳市诚德来实业有限公司 | Hollow fiber composite membrane and preparation method thereof |
| CN105214515A (en) * | 2014-06-30 | 2016-01-06 | 帕尔公司 | Crosslinked cellulose membrane |
| CN105214525A (en) * | 2014-06-30 | 2016-01-06 | 帕尔公司 | Comprise the film (V) of cellulosic material and hydrophilic block copolymer |
| US9394407B2 (en) | 2014-06-30 | 2016-07-19 | Pall Corporation | Hydrophilic block copolymers and membranes prepared therefrom (I) |
| US9718924B2 (en) | 2014-06-30 | 2017-08-01 | Pall Corporation | Hydrophilic block copolymers and membranes prepared therefrom (II) |
| US9962662B2 (en) | 2014-06-30 | 2018-05-08 | Pall Corporation | Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi) |
| CN112657347A (en) * | 2020-12-16 | 2021-04-16 | 杭州科百特科技有限公司 | Regenerated cellulose ultrafiltration membrane and application and preparation method thereof |
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- 2002-11-29 CN CNB021533504A patent/CN1159092C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1759924B (en) * | 2004-06-25 | 2010-05-05 | 米利波尔公司 | Ultrafiltration membrane and preparation method thereof |
| CN101690870B (en) * | 2005-10-14 | 2012-07-04 | Emd密理博公司 | Ultrafiltration membranes and methods of making and use of ultrafiltration membranes |
| CN100531872C (en) * | 2007-08-03 | 2009-08-26 | 厦门大学 | Method for preparing polypyrole-polycarbonate composite membrane of fixed load cibacron blue |
| JP2016027108A (en) * | 2014-06-30 | 2016-02-18 | ポール・コーポレーションＰａｌｌＣｏｒｐｏｒａｔｉｏｎ | Crosslinked cellulosic membranes |
| US9394407B2 (en) | 2014-06-30 | 2016-07-19 | Pall Corporation | Hydrophilic block copolymers and membranes prepared therefrom (I) |
| CN105214525A (en) * | 2014-06-30 | 2016-01-06 | 帕尔公司 | Comprise the film (V) of cellulosic material and hydrophilic block copolymer |
| EP2977100A1 (en) * | 2014-06-30 | 2016-01-27 | Pall Corporation | Membranes comprising cellulosic material and hydrophilic block copolymer |
| EP2985071A1 (en) * | 2014-06-30 | 2016-02-17 | Pall Corporation | Crosslinked cellulosic membranes |
| CN105214525B (en) * | 2014-06-30 | 2018-05-11 | 帕尔公司 | Film (V) comprising cellulosic material and hydrophilic block copolymer |
| US9309367B2 (en) | 2014-06-30 | 2016-04-12 | Pall Corporation | Membranes comprising cellulosic material and hydrophilic block copolymer (V) |
| CN105214515A (en) * | 2014-06-30 | 2016-01-06 | 帕尔公司 | Crosslinked cellulose membrane |
| KR101730519B1 (en) * | 2014-06-30 | 2017-04-26 | 폴 코포레이션 | Crosslinked cellulosic membranes |
| US9718924B2 (en) | 2014-06-30 | 2017-08-01 | Pall Corporation | Hydrophilic block copolymers and membranes prepared therefrom (II) |
| CN105214515B (en) * | 2014-06-30 | 2017-11-14 | 帕尔公司 | The cellulose membrane of crosslinking |
| US9962662B2 (en) | 2014-06-30 | 2018-05-08 | Pall Corporation | Fluorinated polymer and use thereof in the preparation of hydrophilic membranes (vi) |
| CN104707488A (en) * | 2015-04-03 | 2015-06-17 | 深圳市诚德来实业有限公司 | Hollow fiber composite membrane and preparation method thereof |
| CN112657347A (en) * | 2020-12-16 | 2021-04-16 | 杭州科百特科技有限公司 | Regenerated cellulose ultrafiltration membrane and application and preparation method thereof |
| CN112657347B (en) * | 2020-12-16 | 2022-11-29 | 杭州科百特科技有限公司 | Regenerated cellulose ultrafiltration membrane and application and preparation method thereof |
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