CN102653597B - 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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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.Relate to a kind of technique simple, the preparation method of the surface-crosslinked chitosan hydrophilic film of nontoxic cellulose acetate membrane.
Background technology
Cellulose acetate membrane is made by pure vinegar fiber element and is formed, and it has the advantages such as selectivity is high, resistance to chlorine good, filming technology is simple.At present, this film is ideal for aspects such as biological and clinical analysis, aseptic test and flicker measurements.But because chemistry, thermostability, the densification of cellulose acetate membrane are relatively poor, membranous crisp, mechanical property is relatively poor, has seriously limited its range of application and performance.Carried out in recent years the development work of the modification cellulose acetate membrane of different purposes, wherein, the physical strength, toughness and the absorption property that improve the cellulose acetate mould material have become the key of expanding its range of application.Cross-linked modification method is compared with other method of modifying, has implement simple and can utilize linked advantage separately to overcome the shortcoming of homogeneous membrane.Although, the method of the linking agent such as the polyvinyl alcohol that adopts at present extensively, glutaraldehyde and cellulose acetate can improve the mechanical property of cellulose acetate membrane to a certain extent, but these linking agents itself are exactly toxic substance, and are harmful, and its effect also is restricted.Therefore, need to develop a kind of environmental protection, technique 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 the 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 widespread uses of numerous areas such as medicine, food, chemical industry, makeup, water treatment, METAL EXTRACTION and recovery, biochemistry and biomedical engineerings.Chitosan is nontoxic, also easily obtains, and is a kind of desirable mould material.Active hydroxyl and amino are arranged in the chitosan macromole, have larger wetting ability, and have stronger chemical reaction ability, in addition, it is high that the distinctive character of chitosan makes the film of its formation have physical strength, the advantages such as good springiness.Have no at present with the research report of natural polysaccharide chitosan as the cross-linking modified cellulose acetate membrane of linking agent.
Summary of the invention
Technical problem to be solved by this invention is to provide that a kind of technique is simple, natural environmental-protective and the nontoxic cross-linking modified material preparation method of cellulose acetate membrane.Cellulose acetate membrane after the method modification has good wetting ability performance than original cellulose acetate membrane 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) makes the film surface hydrolysis take cellulose acetate membrane as basement membrane with acidic solution, the cellulose acetate membrane after being activated, and wash clean, stand-by; (2) chitosan is made the acidic aqueous solution of 1-4 ﹪ (quality is than concentration) chitosan, stand-by; (3) with the acidic aqueous solution of the cellulose acetate membrane on surface hydrolytic activation and chitosan 10～50 ℃ of crosslinking reactions, coupled chitosan forms the hydrophilic film material of the surface-crosslinked chitosan of cellulose acetate membrane.
Wherein the described acidic aqueous solution of step (1) is hydrochloric acid, trichoroacetic acid(TCA), phosphoric acid, oxalic acid, formic acid, phenylformic acid, acetic acid, propionic acid, butenoic acid etc.; Acidic aqueous solution concentration used is 1 ﹪-99 ﹪ (volume by volume concentration).
Wherein in step (3), the ratio of the acidic solution of the cellulose acetate membrane after activation and 1-4 ﹪ (quality is than concentration) chitosan is 1:100-10:100 (mass ratio).
The invention provides the preparation method of the surface-crosslinked chitosan hydrophilic film of a kind of cellulose acetate membrane.After making cellulose acetate membrane activation with acidic solution, to carry out coupling crosslinked with the acetic acid aqueous solution of chitosan, makes the hydrophilic film material of the surface-crosslinked chitosan of cellulose acetate membrane.The inventive method technique is simple, and is with low cost, natural environmental-protective.Cellulose acetate membrane after the method modification has good wetting ability performance and bonding properties according to this, and good 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 as hazardous and noxious substances such as environmental hormone adsorption removal etc. in immunoassay, albumen and DNA analysis, colloidal-gold detecting-card, environment; Also can be used as bio-medical material because of the raising of its anti-microbial property.
Embodiment
Embodiment 1: the aperture cellulose acetate membrane (purchasing on market) that is 0.1 μ m is put in 2 ﹪ (W/W) aqueous hydrochloric acid is hydrolyzed, the cellulose acetate membrane that activation is good is taken out and is used the deionized water wash clean, blots stand-by.Get in the acetic acid aqueous solution that chitosan 0.1g is dissolved in 50 ﹪ (volume by volume concentration), make the acetic acid solution of 1 ﹪ chitosan (quality is than concentration).With 2 of the cellulose acetate membrane that activated, be placed in 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, then use the deionized water wash clean, in 80 ℃ of oven dryings 30 minutes, Air drying was preserved, and namely gets cellulose acetate membrane cross-linked chitosan modified hydrophilic film with film.
Cellulose acetate membrane counterweight metal biosorption performance test 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 then packing in every centrifuge tube, dry weight is 0.01), 12h vibrates under cover lid, room temperature.In the aqueous solution, the concentration of heavy metal ion is measured by Atomic Absorption Spectroscopy AAS (PerkinElmer instruments AAS800 USA).All tests repeat 3 times, average.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: the aperture cellulose acetate membrane (purchasing on market) that is 1.5 μ m is put in 90 ﹪ (W/W) oxalic acid aqueous solution is hydrolyzed, the cellulose acetate membrane that activation is good is taken out and is used the deionized water wash clean, blots stand-by.Get chitosan 0.15g and be dissolved in 40 ﹪ (volume by volume concentration) acetic acid solution, make the acetic acid aqueous solution of 1.5 ﹪ chitosans (quality is than concentration).With 1 of the cellulose acetate membrane that activated, be placed in 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, then use the deionized water wash clean, in 80 ℃ of oven dryings 30 minutes, Air drying was preserved, and namely gets cellulose acetate membrane cross-linked chitosan modified hydrophilic film with film.
Cellulose acetate membrane counterweight metal biosorption performance test 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 then packing in every centrifuge tube, dry weight is 0.01), 12h vibrates under cover lid, room temperature.In the aqueous solution, the concentration of heavy metal ion is measured by Atomic Absorption Spectroscopy AAS (PerkinElmer instruments AAS800 USA).All tests repeat 3 times, average.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: the aperture cellulose acetate membrane (purchasing on market) that is 3 μ m is put in 50 ﹪ (W/W) the phenylformic acid aqueous solution is hydrolyzed, the cellulose acetate membrane that activation is good is taken out and is used the deionized water wash clean, blots stand-by.Get chitosan 0.2g and be dissolved in 30 ﹪ (volume by volume concentration) acetic acid solution, make the acetic acid aqueous solution of 4 ﹪ chitosans (quality is than concentration).With 1 of the cellulose acetate membrane that activated, be placed in 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, then use the deionized water wash clean, in 80 ℃ of oven dryings 30 minutes, Air drying was preserved, and namely gets cellulose acetate membrane cross-linked chitosan modified hydrophilic film with film.
Cellulose acetate membrane counterweight metal biosorption performance test 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 then packing in every centrifuge tube, dry weight is 0.01), 12h vibrates under cover lid, room temperature.In the aqueous solution, the concentration of heavy metal ion is measured by Atomic Absorption Spectroscopy AAS (PerkinElmer instruments AAS800 USA).All tests repeat 3 times, average.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 cellulose acetate membrane after 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 test method and antibacterial effect " standard code, the bacteriologic test bacterial classification is streptococcus aureus ATCC 6538 (gram-positive microorganism) and colon bacillus 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 example 3 gained modification cellulose acetate membrane
| Sample | Streptococcus aureus | Colon bacillus | 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 |
Cellulose acetate membrane after chitosan crosslinked modification, all has obvious antibacterial effect to gram sun bacterium, Gram-negative bacteria and fungi as can be seen from the table.
Claims (3)
1. the preparation method of the surface-crosslinked chitosan hydrophilic film of cellulose acetate membrane, it is characterized in that carrying out according to following step: (1) makes the film surface hydrolysis take cellulose acetate membrane as basement membrane with acidic aqueous solution, the cellulose acetate membrane after being activated, wash clean, stand-by; (2) chitosan is made quality than the acidic aqueous solution of concentration 1-4 ﹪ chitosan, stand-by; (3) with the acidic aqueous solution of the cellulose acetate membrane on surface hydrolytic activation and chitosan 10～50 ℃ of crosslinking reactions, coupled chitosan forms the hydrophilic film material of the surface-crosslinked chitosan of cellulose acetate membrane.
2. the preparation method of the surface-crosslinked chitosan hydrophilic film of cellulose acetate membrane 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, acetic acid, propionic acid, butenoic acid; Acidic aqueous solution volume by volume concentration used is 1 ﹪-99 ﹪.
3. the preparation method of the surface-crosslinked chitosan hydrophilic film of cellulose acetate membrane according to claim 1 is characterized in that the mass ratio that in step (3) wherein, the cellulose acetate membrane after activation and quality are the acidic solution of 1-4 ﹪ chitosan than concentration is 1:100-10:100.
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| 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 |
| 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 |
| CN109456503B (en) * | 2017-09-06 | 2021-06-25 | 中国海洋大学 | Milt DNA/chitosan blend film and preparation method thereof |
| CN108003363B (en) * | 2017-10-17 | 2020-10-23 | 齐鲁工业大学 | Preparation method of NTAA (N-terminal-N-acetyl-N-terminal) -modified cellulose membrane |
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