CN102653597A - Preparation method of cellulose acetate membrane surface crosslinked chitosan hydrophilic membrane - Google Patents
Preparation method of cellulose acetate membrane surface crosslinked chitosan hydrophilic membrane Download PDFInfo
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- CN102653597A CN102653597A CN2012101413267A CN201210141326A CN102653597A CN 102653597 A CN102653597 A CN 102653597A CN 2012101413267 A CN2012101413267 A CN 2012101413267A CN 201210141326 A CN201210141326 A CN 201210141326A CN 102653597 A CN102653597 A CN 102653597A
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Abstract
The invention provides a preparation method of a cellulose acetate membrane surface crosslinked chitosan hydrophilic membrane and belongs to the technical field of membrane surface modification. A cellulose acetate membrane is activated by an acid solution, and has coupling crosslinking with the acetic acid water solution of the chitosan, so that a hydrophilic membrane material of the cellulose acetate membrane surface crosslinked chitosan can be prepared. The preparation method of the invention is simple in technology, low in cost, natural, and environmentally-friendly. The cellulose acetate membrane modified by the method is good in hydrophillic nature and binding capability, is good in mechanical strength and mechanical toughness, can be widely applicable to the field of biochemistry, molecular biology and environment, such as the immunoassay, the protein and DNA (deoxyribonucleic acid) analysis, the colloidal gold detection card, the absorption and removal of the toxic and harmful substances in the environment such as the environmental hormone and the like, and can be taken as biomedical material due to the improvement of the mold resistance of a cellulose acetate membrane.
Description
Technical field
The invention belongs to technical field of polymer materials, belong to the membrane surface modification technical field.It is simple to relate to a kind of technology, the preparation method of the surface-crosslinked chitosan hydrophilic film of nontoxic CAM.
Background technology
CAM is formed by plain manufacturing of pure vinegar fiber, and it has advantages such as selectivity height, resistance to chlorine is good, filming technology is simple.At present, this film is used for very ideal of biological and aspects such as clinical analysis, aseptic test and flicker measurement.But because chemistry, thermostability, the densification property of CAM are relatively poor, membranous crisp, mechanical property is relatively poor, has seriously limited its range of application and performance.Carried out the development work of the modification CAM of different purposes in recent years, wherein, the physical strength, toughness and the absorption property that improve the FM mould material have become the key of expanding its range of application.Cross-linked modification method is compared with other method of modifying, has to implement simple and can utilize linked advantage separately to overcome the shortcoming of homogeneous membrane.Though; The method of linking agent such as the Z 150PH that adopts at present extensively, LUTARALDEHYDE and FM can improve the mechanical property of CAM to a certain extent; But these linking agents itself are exactly toxic substance, and are harmful, and its effect also is restricted.Therefore, need develop a kind of environmental protection, technology is simple, method of modifying with low cost.
Chitosan is that glycosaminoglycan-chitin that nature extensively exists takes off the product that acetyl obtains under the concentrated base effect.Chitosan has premium propertiess such as good biological activity, biocompatibility, biodegradability and antibiotic, hemostasis, anti-inflammatory; The linear molecule chain structure of chitosan makes it have good film-forming properties, in numerous areas widespread uses such as medicine, food, chemical industry, makeup, water treatment, METAL EXTRACTION and recovery, biochemistry and biomedical engineerings.Chitosan is nontoxic, also obtains easily, is a kind of ideal mould material.Active hydroxyl and amino are arranged in the chitosan macromole, have bigger wetting ability, and have stronger chemical reaction ability, in addition, the distinctive character of chitosan makes the film of its formation have physical strength height, advantages such as good springiness.Do not see at present with the research report of natural polysaccharide chitosan as the cross-linking modified CAM of linking agent.
Summary of the invention
Technical problem to be solved by this invention provides that a kind of technology is simple, natural environmental-protective and the nontoxic cross-linking modified preparation methods of CAM.CAM after the method modification has the good hydrophilicity performance than original CAM according to this, and good mechanical tenacity and bonding properties, and has better anti-microbial effect.
Concrete technical scheme provided by the invention is: (1) is basement membrane with the CAM, makes the film surface hydrolysis with acidic solution, obtains the CAM after the activation, and wash clean is for use; (2) chitosan is processed the acidic aqueous solution of 1-4 ﹪ (quality is than concentration) chitosan, for use; (3) with the acidic aqueous solution of the CAM on surface hydrolytic activation and chitosan 10～50 ℃ of crosslinking reactions, coupled chitosan forms the hydrophilic film material of the surface-crosslinked chitosan of CAM.
Wherein the described acidic aqueous solution of step (1) is hydrochloric acid, trichoroacetic acid(TCA), phosphoric acid, oxalic acid, formic acid, phenylformic acid, acetate, propionic acid, butenoic acid etc.; Used acidic aqueous solution concentration is 1 ﹪-99 ﹪ (volume by volume concentration).
Wherein the ratio of the acidic solution of CAM after the activation and 1-4 ﹪ (quality is than concentration) chitosan is 1:100-10:100 (mass ratio) in the step (3).
The present invention provides the preparation method of the surface-crosslinked chitosan hydrophilic film of a kind of CAM.After making the CAM activation with acidic solution, to carry out coupling crosslinked with the acetic acid aqueous solution of chitosan, processes the hydrophilic film material of the surface-crosslinked chitosan of CAM.The inventive method technology is simple, and is with low cost, natural environmental-protective.CAM after the method modification has good hydrophilicity performance and bonding properties according to this, and excellent mechanical strength and mechanical tenacity, and has better anti-microbial effect; Can be widely used in biological chemistry and molecular biology and environmental area, concrete like hazardous and noxious substances such as environmental hormone adsorption removal etc. in immunoassay, albumen and DNA analysis, Radioactive colloidal gold test card, the environment; Also can be used as bio-medical material because of the raising of its anti-microbial property.
Embodiment
Embodiment 1: with the aperture is that the CAM (purchasing on the market) of 0.1 μ m is put in hydrolysis in 2 ﹪ (W/W) aqueous hydrochloric acid, and the CAM that activation is good takes out and uses the deionized water wash clean, blots for use.Get in the acetic acid aqueous solution that chitosan 0.1g is dissolved in 50 ﹪ (volume by volume concentration), process the acetic acid soln of 1 ﹪ chitosan (quality is than concentration).With 2 of activation is good CAMs, place the acetic acid aqueous solution of 1 ﹪ chitosan.Under 30 ℃, oscillatory reaction 2 hours.Take out this film, the solution on film surface is blotted, use the deionized water wash clean then, in 80 ℃ of oven dryings 30 minutes, Air drying was preserved, and promptly gets CAM cross-linked chitosan modified hydrophilic property film with film.
The test of CAM counterweight Adsorption Properties for Metal Ions after chitosan crosslinked modification is as follows: the metal ion solution that 10ml is contained different concns is packed in the 10ml centrifuge tube; Sorbent material (the film that above-mentioned modification makes of the equal in quality of in every centrifuge tube, packing into then; Dry weight is 0.01); 12h vibrates under the cover lid, room temperature.The concentration of heavy metal ion is measured by Atomic Absorption Spectroscopy AAS (PerkinElmer instruments AAS800 USA) in the aqueous solution.All test repetitions 3 times are averaged.Cu ionic adsorption amount (q
e) be 0. 4782 mmol/g; Hg ionic adsorption amount (q
e) be 1.3548 mmol/g; Pb ionic adsorption amount (q
e) be 2. 1326mmol/g.
Embodiment 2: with the aperture is that the CAM (purchasing on the market) of 1.5 μ m is put in hydrolysis in 90 ﹪ (W/W) oxalic acid aqueous solution, and the CAM that activation is good takes out and uses the deionized water wash clean, blots for use.Get chitosan 0.15g and be dissolved in 40 ﹪ (volume by volume concentration) acetic acid soln, process the acetic acid aqueous solution of 1.5 ﹪ chitosans (quality is than concentration).With 1 of activation is good CAM, place the acetic acid aqueous solution of 1.5 ﹪ chitosans, under 30 ℃, oscillatory reaction 2 hours.Take out this film, the solution on film surface is blotted, use the deionized water wash clean then, in 80 ℃ of oven dryings 30 minutes, Air drying was preserved, and promptly gets CAM cross-linked chitosan modified hydrophilic property film with film.
The test of CAM counterweight Adsorption Properties for Metal Ions after chitosan crosslinked modification is as follows: the metal ion solution that 10ml is contained different concns is packed in the 10ml centrifuge tube; Sorbent material (the film that above-mentioned modification makes of the equal in quality of in every centrifuge tube, packing into then; Dry weight is 0.01); 12h vibrates under the cover lid, room temperature.The concentration of heavy metal ion is measured by Atomic Absorption Spectroscopy AAS (PerkinElmer instruments AAS800 USA) in the aqueous solution.All test repetitions 3 times are averaged.Cu ionic adsorption amount (q
e) be 0. 7624 mmol/g; Hg ionic adsorption amount (q
e) be 1.8093 mmol/g; Pb ionic adsorption amount (q
e) be 1.0893mmol/g.
Embodiment 3: with the aperture is that the CAM (purchasing on the market) of 3 μ m is put in hydrolysis in 50 ﹪ (W/W) the phenylformic acid aqueous solution, and the CAM that activation is good takes out and uses the deionized water wash clean, blots for use.Get chitosan 0.2g and be dissolved in 30 ﹪ (volume by volume concentration) acetic acid soln, process the acetic acid aqueous solution of 4 ﹪ chitosans (quality is than concentration).With 1 of activation is good CAM, place the acetic acid aqueous solution of 4 ﹪ chitosans, under 30 ℃, oscillatory reaction 2 hours.Take out this film, the solution on film surface is blotted, use the deionized water wash clean then, in 80 ℃ of oven dryings 30 minutes, Air drying was preserved, and promptly gets CAM cross-linked chitosan modified hydrophilic property film with film.
The test of CAM counterweight Adsorption Properties for Metal Ions after chitosan crosslinked modification is as follows: the metal ion solution that 10ml is contained different concns is packed in the 10ml centrifuge tube; Sorbent material (the film that above-mentioned modification makes of the equal in quality of in every centrifuge tube, packing into then; Dry weight is 0.01); 12h vibrates under the cover lid, room temperature.The concentration of heavy metal ion is measured by Atomic Absorption Spectroscopy AAS (PerkinElmer instruments AAS800 USA) in the aqueous solution.All test repetitions 3 times are averaged.Cu ionic adsorption amount (q
e) be 1. 2637 mmol/g; Hg ionic adsorption amount (q
e) be 0.9812 mmol/g; Pb ionic adsorption amount (q
e) be 2. 3270mmol/g.
Experimental example: the CAM after the above modification has also been estimated its anti-microbial property.Anti-microbial property is tested by the testing method of " QB/T 2591-2003 antibiotic plastic anti-microbial property TP and antibacterial effect " standard code; The bacteriologic test bacterial classification is streptococcus aureus ATCC 6538 (gram-positive microorganism) and ETEC ATCC 25922 (Gram-negative bacteria), and fungi check bacterial classification is Candida albicans ATCC 10231.
The anti-microbial property of table 1 embodiment 1, example 2 and routine 3 gained modification CAMs
| Sample | Streptococcus aureus | ETEC | Candida albicans |
| Example 1 antibacterium rate (mildew grade) | 99% | 98% | 0 grade |
| Example 2 antibacterium rates (mildew grade) | 98% | 99% | 1 grade |
| Example 3 antibacterium rates (mildew grade) | 99% | 99% | 1 grade |
From table, can find out CAM after chitosan crosslinked modification, gram sun bacterium, Gram-negative bacteria and fungi are all had tangible antibacterial effect.
Claims (3)
1. the preparation method of the surface-crosslinked chitosan hydrophilic film of CAM; It is characterized in that carrying out according to following step: (1) is basement membrane with the CAM, makes the film surface hydrolysis with acidic solution, obtains the CAM after the activation; Wash clean, for use; (2) chitosan is processed the acidic aqueous solution of quality than concentration 1-4 ﹪ chitosan, for use; (3) with the acidic aqueous solution of the CAM on surface hydrolytic activation and chitosan 10～50 ℃ of crosslinking reactions, coupled chitosan forms the hydrophilic film material of the surface-crosslinked chitosan of CAM.
2. the preparation method of the surface-crosslinked chitosan hydrophilic film of CAM according to claim 1 is characterized in that wherein the described acidic aqueous solution of step (1) is hydrochloric acid, trichoroacetic acid(TCA), phosphoric acid, oxalic acid, formic acid, phenylformic acid, acetate, propionic acid, butenoic acid; Used acidic aqueous solution volume by volume concentration is 1 ﹪-99 ﹪.
3. the preparation method of the surface-crosslinked chitosan hydrophilic film of CAM according to claim 1 is characterized in that the CAM after the activation and quality in the step (3) wherein are that the mass ratio of the acidic solution of 1-4 ﹪ chitosan is 1:100-10:100 than concentration.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105461953A (en) * | 2016-01-04 | 2016-04-06 | 东北林业大学 | Preparation method of nanometer antibacterial composite membrane based on self-assembling technology |
| CN106574929A (en) * | 2014-07-25 | 2017-04-19 | 贝克顿·迪金森公司 | Analyte test strip assays, and test strips and kits for use in practicing the same |
| CN106905553A (en) * | 2017-02-27 | 2017-06-30 | 昆明理工大学 | A kind of cellulose acetate membrane material material of biological polyoses LBL self-assembly modification and preparation method thereof |
| CN108003363A (en) * | 2017-10-17 | 2018-05-08 | 齐鲁工业大学 | A kind of preparation method of NTAA modified celluloses film |
| CN108211826A (en) * | 2018-02-13 | 2018-06-29 | 温州莲华环保科技有限公司 | A kind of forward osmosis membrane and preparation method thereof |
| CN109156776A (en) * | 2018-10-09 | 2019-01-08 | 安徽铜陵天门白姜食品有限责任公司 | A kind of sweet and sour ginger preparation method of bacteriostasis, preservation |
| CN109156514A (en) * | 2018-10-09 | 2019-01-08 | 安徽铜陵天门白姜食品有限责任公司 | A kind of sweet and sour ginger starch based antimicrobials and preparation method thereof |
| CN109456503A (en) * | 2017-09-06 | 2019-03-12 | 中国海洋大学 | A kind of milt DNA/chitosan blend film and preparation method thereof |
| CN112426801A (en) * | 2020-09-09 | 2021-03-02 | 江苏恰瑞生物科技有限公司 | Preparation method of filter medium material |
| CN114181015A (en) * | 2021-12-30 | 2022-03-15 | 中农金瑞肥业有限公司 | Composite slow-release compound fertilizer special for wheat and preparation method thereof |
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| CN1631498A (en) * | 2004-10-29 | 2005-06-29 | 中国海洋大学 | Method for preparing compound nanometer filtering membrane of chitosan sulfate-high molecule polymer |
Non-Patent Citations (1)
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106574929A (en) * | 2014-07-25 | 2017-04-19 | 贝克顿·迪金森公司 | Analyte test strip assays, and test strips and kits for use in practicing the same |
| CN105461953B (en) * | 2016-01-04 | 2018-08-07 | 东北林业大学 | The preparation method of nano-antibacterial composite membrane based on self-assembling technique |
| CN105461953A (en) * | 2016-01-04 | 2016-04-06 | 东北林业大学 | Preparation method of nanometer antibacterial composite membrane based on self-assembling technology |
| CN106905553A (en) * | 2017-02-27 | 2017-06-30 | 昆明理工大学 | A kind of cellulose acetate membrane material material of biological polyoses LBL self-assembly modification and preparation method thereof |
| CN109456503A (en) * | 2017-09-06 | 2019-03-12 | 中国海洋大学 | A kind of milt DNA/chitosan blend film and preparation method thereof |
| CN109456503B (en) * | 2017-09-06 | 2021-06-25 | 中国海洋大学 | Milt DNA/chitosan blend film and preparation method thereof |
| CN108003363A (en) * | 2017-10-17 | 2018-05-08 | 齐鲁工业大学 | A kind of preparation method of NTAA modified celluloses film |
| CN108211826A (en) * | 2018-02-13 | 2018-06-29 | 温州莲华环保科技有限公司 | A kind of forward osmosis membrane and preparation method thereof |
| CN109156776A (en) * | 2018-10-09 | 2019-01-08 | 安徽铜陵天门白姜食品有限责任公司 | A kind of sweet and sour ginger preparation method of bacteriostasis, preservation |
| CN109156514A (en) * | 2018-10-09 | 2019-01-08 | 安徽铜陵天门白姜食品有限责任公司 | A kind of sweet and sour ginger starch based antimicrobials and preparation method thereof |
| CN112426801A (en) * | 2020-09-09 | 2021-03-02 | 江苏恰瑞生物科技有限公司 | Preparation method of filter medium material |
| CN114181015A (en) * | 2021-12-30 | 2022-03-15 | 中农金瑞肥业有限公司 | Composite slow-release compound fertilizer special for wheat and preparation method thereof |
| CN114181015B (en) * | 2021-12-30 | 2022-11-15 | 中农金瑞肥业有限公司 | Composite slow-release compound fertilizer special for wheat and preparation method thereof |
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