CN1167494C - Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film - Google Patents
Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film Download PDFInfo
- Publication number
- CN1167494C CN1167494C CNB021309272A CN02130927A CN1167494C CN 1167494 C CN1167494 C CN 1167494C CN B021309272 A CNB021309272 A CN B021309272A CN 02130927 A CN02130927 A CN 02130927A CN 1167494 C CN1167494 C CN 1167494C
- Authority
- CN
- China
- Prior art keywords
- shitosan
- solution
- polysulfones
- film
- polysulfone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention discloses a preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film. The present invention uses chloromethylation polysulfone as a base material, a polysulfone asymmetric ultrafiltration film is prepared through a phase inversion method, the membrane is directly or indirectly in reaction with a chitosan acidic solution through hydrolytic activation, chitosan is coupled, and then a polysulfone-chitosan compound film is formed. The present invention is characterized in that an alkaline water solution is used as hydrolysate in hydrolysis, the hydrolysis temperature is from 50 DEG C to 90 DEG C, a methylol polysulfone film is generated and is directly or indirectly in reaction with the chitosan acidic solution, the chitosan is coupled, and then the polysulfone-chitosan compound film is formed. The polysulfone-chitosan compound asymmetrical ultrafiltration film prepared by the present invention has the advantages of favorable affinity, low nonspecific adsorption, good mechanical strength, ideal hole passage structure and simple preparation method, and can be widely applied to affinity ultrafiltration.
Description
Technical field
The present invention relates to a kind of preparation method of the compound asymmetric milipore filter of polysulfones-shitosan of compatibility, belonged to the technology of preparing of composite hyperfiltration membrane.
Background technology
Affinity ultrafiltration is to utilize the aperture of film with aglucon in being bonded in film surface and duct sample solution to be separated and purify, and it can not only make biological molecules of interest and other molecules obtain to separate, and while part that can be removed solvent, reaches concentrated purpose.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 several chemical modification methods: the polysulfones of inventions such as Klein-hydroxyethylcellulose composite membrane is the phenylol that adopts bis-epoxy alkane activation polysulfones end, introduce epoxy radicals, and then by covalent bond coupling hydroxyethylcellulose [Klein E, Eichholz E and Yeager DH.Affinity membranes prepared fromhydrophilic coatings on microporous polysulfone hollow fibers.Journalof Membrane Science, 1994,90:69-80], this film has improved the hydrophilicity of film largely; Employing chloromethylation-aminations such as Shang Zhenhua and two kinds of approach of acidylate-amination carry out modification to polysulfones, have introduced end-NH
2Base [Shang Zhenhua, Yu Yinian. affinity membrane isolation technics (I)-principle and material. membrane science and technology, 1995,15 (2): 1-11].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 the active group of introducing is single, and does not consider the internal structure of film forming.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the compound asymmetric milipore filter of polysulfones-shitosan of compatibility.The prepared composite membrane of Using such method has a large amount of active group (NH
2Base and-the OH yl), good hydrophilic property, non-specific adsorption is low, blood compatibility is good, mechanical strength height, 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 or 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 is through hydrolytic activation, and direct or indirect and shitosan acid solution reacts, and the coupling shitosan forms polysulfones-chitosan complex film.It is characterized in that: with the 10-30% soda ash aqueous solution is hydrolyzate, hydrolysis temperature is 50-90 ℃, direct and 1-3% shitosan acid solution reacts, the coupling shitosan, form polysulfones-chitosan complex film, or to adopt the solution of bis-epoxy alkane, carbonyl dimidazoles, epoxychloropropane or glutaraldehyde be that activator activates the methylol PS membrane, and the coupling shitosan forms polysulfones-chitosan complex film again.
Above-mentioned bis-epoxy alkane solution is the alkaline ethanol solution of bis-epoxy alkane, and concentration is 5-50%; Carbonyl dimidazoles solution is the acetone soln of carbonyl dimidazoles, and concentration is 0.5-4%; Epoxychloropropane solution is the alkaline aqueous solution of epoxychloropropane, and concentration is 5-60%; Glutaraldehyde solution is a glutaraldehyde water solution, and concentration is 10-50%.
Above-mentioned shitosan acid solution is the hydrochloric acid solution of shitosan, the acetic acid solution of shitosan or the phosphoric acid solution of shitosan.
The prepared compound anisotropic membrane of polysulfones-shitosan of the present invention has good hydrophilicity, and non-specific adsorption is low, and 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.
Description of drawings
Fig. 1 is the electromicroscopic photograph of the compacted zone surface texture of methylol PS membrane of the present invention
Fig. 2 is the electromicroscopic photograph of the support layer surface structure of methylol PS membrane of the present invention
Fig. 3 is the electromicroscopic photograph of the section structure of methylol PS membrane of the present invention
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-chitosan complex film
Get the methylol PS membrane of step 2 preparation, be cut into a disk, diameter is 47mm, places 5 milliliter 2% shitosan acetic acid solution, and the concentration of acetic acid solution is 1% (volume).At room temperature, vibration is 1 hour.Place 80 ℃ dry 90 minutes of baking oven then.Dried film was cleaned 1 hour with 1% acetic acid solution, and, promptly get polysulfones-chitosan complex film with a large amount of distilled water cleaning 1 day.
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 methylol PS membrane and polysulfones-chitosan complex film.
Embodiment three:
The sodium borohydride of getting 80 milligrams is dissolved among 12 milliliters of 2MNaOH, 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% shitosan acetic acid solution, and the concentration of acetate is 10% (volume), 40 ℃ of down vibrations 5 hours, places 120 ℃ dry 4 hours of baking oven then.Dried film was cleaned 1 hour with 1% acetic acid solution,, promptly get polysulfones-chitosan complex film with a large amount of distilled water cleaning 1 day.
Claims (3)
1. polysulfones-the shitosan of a compatibility is answered the preparation method of an asymmetric milipore filter, 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 or 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, direct or indirect and shitosan acid solution reacts, the coupling shitosan, form polysulfones-chitosan complex film, 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, direct and 1-3% shitosan acid solution reacts, the coupling shitosan, form polysulfones-chitosan complex film, or employing bis-epoxy alkane, carbonyl dimidazoles, the solution of epoxychloropropane or glutaraldehyde is that activator activates the methylol PS membrane, react with 1-3% shitosan acid solution again, the coupling shitosan forms polysulfones-chitosan complex film.
2. press the preparation method of the compound asymmetric milipore filter of polysulfones-shitosan of the described compatibility 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%; Carbonyl dimidazoles solution is the acetone soln of carbonyl dimidazoles, and concentration is 0.5-4%; Epoxychloropropane solution is the alkaline aqueous solution of epoxychloropropane, and concentration is 5-60%; Glutaraldehyde solution is a glutaraldehyde water solution, and concentration is 10-50%.
3. press the preparation method of the compound asymmetric milipore filter of polysulfones-shitosan of the described compatibility of claim 1, it is characterized in that: the shitosan acid solution is the hydrochloric acid solution of shitosan, the acetic acid solution of shitosan or the phosphoric acid solution of shitosan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021309272A CN1167494C (en) | 2002-09-17 | 2002-09-17 | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021309272A CN1167494C (en) | 2002-09-17 | 2002-09-17 | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1413761A CN1413761A (en) | 2003-04-30 |
| CN1167494C true CN1167494C (en) | 2004-09-22 |
Family
ID=4746514
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021309272A Expired - Fee Related CN1167494C (en) | 2002-09-17 | 2002-09-17 | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1167494C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100531872C (en) * | 2007-08-03 | 2009-08-26 | 厦门大学 | Method for preparing polypyrole-polycarbonate composite membrane of fixed load cibacron blue |
| CN102120148B (en) * | 2011-01-19 | 2013-05-29 | 天津大学 | Preparation method for composite film of chitosan/sulfonated polyethersulfone and polyethersulfone and application thereof |
| CN103041714B (en) * | 2011-10-13 | 2015-01-21 | 中国科学院化学研究所 | Composite ultrafiltration membrane of modified chitosan composite electrostatic spinning nanofiber and preparation method of composite ultrafiltration membrane |
| CN102828392B (en) * | 2012-09-12 | 2015-01-21 | 苏州大学 | Hydrophilic antibacterial composite nano fibrous membrane and preparation method thereof |
| CN103406033B (en) * | 2013-09-09 | 2015-10-21 | 南京大学 | The preparation method of chitosan-polysulfonehollow hollow fiber membrane |
| CN106943901B (en) * | 2017-05-12 | 2019-05-21 | 中南大学 | The modified biocompatibility PS membrane and preparation method thereof of sulfonation hydroxypropyl chitosan |
| CN109316983B (en) * | 2018-11-07 | 2021-01-15 | 中南大学 | Sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof |
| CN109316986B (en) * | 2018-11-07 | 2021-09-21 | 中南大学 | Acrylic acid and sulfonated dihydroxypropyl chitosan modified polysulfone membrane and preparation method thereof |
| CN111467978B (en) * | 2020-03-03 | 2022-03-22 | 贵州省材料产业技术研究院(贵州省复合改性聚合物材料工程技术研究中心、国家复合改性聚合物材料工程技术研究中心) | Method for preparing chitosan crosslinked styrene maleic anhydride/polyether sulfone composite nanofiltration membrane |
| CN113087312B (en) * | 2021-04-30 | 2022-08-30 | 河南鑫安利职业健康科技有限公司 | Chemical wastewater treatment process based on PSF-g-CS polymer microfiltration membrane |
-
2002
- 2002-09-17 CN CNB021309272A patent/CN1167494C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1413761A (en) | 2003-04-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1167494C (en) | Preparation method of affinity polysulfone-chitosan compound asymmetrical ultrafiltration film | |
| CN100363482C (en) | Method for immobilizing lipase using microstructure in hydrophilic/ hydrophobic composite membrane | |
| Bolto et al. | Crosslinked poly (vinyl alcohol) membranes | |
| US5059659A (en) | Surface treatments to impart hydrophilicity | |
| CN1159092C (en) | Prepn precess of composite asymmetrical affinity polysulfone-hydroxyethyl cellulose ultrafiltering film | |
| CN102260662B (en) | Carrier for immobilized enzyme and application thereof and the carrier for being fixed with enzyme | |
| CN110404421B (en) | Preparation method of Janus polyvinylidene fluoride (PVDF) separation membrane | |
| SE452469B (en) | MATERIALS CONSISTING OF A CROSS-BONDED CARBOXYL-GROUPED POLYSACCHARIDE AND PROCEDURE IN THE PREPARATION OF THE SAME | |
| KR20190113538A (en) | Enzyme-based membrane with antifouling activity for water treatment and method for manufacturing thereof | |
| US4872982A (en) | Composite semipermeable membranes and method of making same | |
| CN110354898B (en) | Functionalized polyvinyl alcohol catalytic composite membrane and preparation method thereof | |
| CN112354379A (en) | Preparation method of polytetrafluoroethylene reverse osmosis membrane with lasting and stable filtration and separation performance | |
| Marpani et al. | In situ formation of a biocatalytic alginate membrane by enhanced concentration polarization | |
| CN1189236C (en) | Preparation method of nylon-shell glycan compound film for affinity microfilter | |
| WO1993016117A1 (en) | Water-soluble cellulose derivative and biocompatible material | |
| CN102115921A (en) | Glycosylated nanofiber membrane and preparation method and application thereof | |
| US4976869A (en) | Composite semipermeable membranes and method of making same | |
| CN111632499B (en) | Preparation method of high-flux water filtering membrane based on polyester non-woven fabric | |
| KR20080063960A (en) | Composite membrane reactor immobilized microorganism and system for hydrogen production | |
| JPS6244962B2 (en) | ||
| JP3225272B2 (en) | Filtration membrane and method for preparing the same | |
| JP2008062119A (en) | Filter medium, its manufacturing method, filtration treatment device, and filtration treatment method | |
| CN106512749B (en) | It is a kind of for the two-sided modified seperation film of blood purification and its preparation, application method | |
| CN1194179A (en) | Chemical modification of microporous nylon film and preparation of affinity film with histidine ligand | |
| CN1236844C (en) | Method for preparing hydrophilic microporous material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |