CN101824160A - Preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane - Google Patents
Preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane Download PDFInfo
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- CN101824160A CN101824160A CN 201010136576 CN201010136576A CN101824160A CN 101824160 A CN101824160 A CN 101824160A CN 201010136576 CN201010136576 CN 201010136576 CN 201010136576 A CN201010136576 A CN 201010136576A CN 101824160 A CN101824160 A CN 101824160A
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Abstract
The invention relates to a preparation method of a chitosan/polyvinyl alcohol/polylactic acid blended porous membrane, which comprises the following steps of: (1) using an acetic acid solution as the solvent to dissolve chitosan at 30-40 DEG C to obtain a chitosan solution of which the weight percentage is 3%; (2) using a dimethyl sulfoxide solution as the solvent to dissolve polyvinyl alcohol at room temperature to obtain a polyvinyl alcohol solution of which the weight percentage is 5%; (3) using deionized water as the solvent to dissolve polyvinyl alcohol at 80-120 DEG C, and stirring until the polyvinyl alcohol is completely dissolved to obtain a polyvinyl alcohol solution of which the weight percentage is 7%; (4) mixing the three solutions based on a certain ratio, stirring for 15-30 minutes at the constant temperature of 20-30 DEG C, standing, and defoaming; and (5) using a freeze drying method to prepare the blended porous membrane. The invention has the advantages of no toxic material in the membrane preparation process, simple membrane preparation device and process, biodegradability and convenient clinical use, and can be used for artificial skins, dressing and the like in the biomedical field.
Description
Technical field
The invention belongs to the preparation field of high molecular polymer blended porous membrane, particularly a kind of preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane.
Background technology
Be used to protect wound, make wound avoid being infected and the artificial skin that dewaters has obtained using widely in the past few decades.Many polymeric membranes and medicine-carrying polymer film are used to biomaterials such as manufacture of intraocular skin.And chitosan is the alkaline polysaccharide of the unique a large amount of existence of nature, wide material sources, and it has good film-forming properties, and modification easily can be introduced various functional groups, makes chitosan and derivative thereof at field of medicaments very wide application prospect be arranged.When chitosan uses as biomaterial, have excellent biological compatibility, nontoxic and affinity is arranged to human body cell, not with humoral response, there is not antigen antibody reaction yet.But, chitosan exists a pair of contradiction as tissue engineering bracket material---biocompatibility and degradation property, and promptly deacetylation is high more, and the biocompatibility of chitosan is good more, but its degradation rate in vivo is slow more, easily causes during the implant into body repair tissue " tissue defects ".
Nontoxic, nonirritant that poly(lactic acid) has has the premium properties of good biocompatibility, biodegradable absorption, intensity height, plasticity-machine-shaping.Its degraded product lactic acid, CO
2And H
2O all is harmless natural small molecules, but single poly-lactic acid material wetting ability is relatively poor, a little less than the cell adhesion power, the simple poly-lactic acid material that uses easily produces aseptic inflammation in human body, need improve the wetting ability and the cell adhesion power of poly-lactic acid material and reduce the aseptic inflammation reaction by relevant modification.
The synthetic macromolecule film forming material especially film forming properties of polyvinyl alcohol is good, and intensity after the film forming and flexility satisfy film moulding and application requiring.But exist because polyvinyl alcohol is a form with polymeric chain, intramolecularly and the intermolecular hydrogen bond that all exists are so though that polyvinyl alcohol has is water-soluble, solvability is not very good.For the requirement of the material that satisfies different purposes, must carry out modification to it.
An important channel of exploitation polymer novel material is that the compound performance by each polymeric constituent of aggregative equilibrium of different materials is eliminated weakness on each one-component performance, obtains comparatively ideal polymer novel material of over-all properties.At present to chitosan is day by day goed deep into as the research of the blending and modifying film of main body, but to its research mainly is to rest on the basis of two kinds of material blend, be chitosan/polyvinyl alcohol blend or chitosan/polylactic acid blend, for example application number is that 200610002664.7 patent is exactly the preparation method about a kind of chitosan/polyvinyl alcohol blend film.And the blended porous membrane of other materials raw material select for use with preparation process in all have certain weak point, for example application number is that the silk-protein that adopts in mineralising silk-protein/polymer composite porous material of 200410003454.0 and preparation method thereof need come unstuck, concentration, the quality of coming unstuck has influence on later process, has improved production cost.
Lyophilize is to utilize the principle of distillation to carry out a kind of technology of exsiccant, is the material quick freezing at low temperatures that will be dried, and under suitable vacuum environment, makes the water molecules that freezes be directly sublimed into the process of overflowing into water vapour then.Material is in low temperature (frozen state) all the time before drying, ice crystal is uniformly distributed in the material simultaneously, and when the ice distillation, it can stay hole in the exsiccant surplus materials.Sublimation process can not avoided by side effects such as water vapour generation foam, oxidations because of concentration phenomena takes place in dehydration.Dry substance is dried sponge vesicular, and volume is constant substantially, and is very easily water-soluble and restore to the original state.Lyophilize has kept the biological and chemical structure and the active integrity thereof of product to the full extent.Therefore lyophilize is the feasible means of preparation porous-film.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane, this method does not relate to toxicant, membrane equipment and technology are easy, has biodegradability, clinical easy to use, can be used for the artificial skin, dressing in bio-medical field etc.
The preparation method of a kind of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane of the present invention comprises:
(1) is that 1～2% acetum is made the dissolution with solvents chitosan down at 30～40 ℃, obtains weight percentage and be 3% chitosan solution with weight percentage;
(2) at room temperature make the dissolution with solvents poly(lactic acid), obtain weight percentage and be 5% poly(lactic acid) solution with the dimethyl sulphoxide solution of content 〉=99wt%;
(3) under 80～120 ℃, make the dissolution with solvents polyvinyl alcohol, be stirred to it and dissolve fully, make weight percentage and be 7% polyvinyl alcohol solution with deionized water;
(4) above-mentioned three kinds of solution are mixed, stir 15～30min at 20～30 ℃ of following constant temperature, and standing and defoaming, chitosan in the mixing solutions: polyvinyl alcohol: the mass ratio 4～8: 5～1: 1 of poly(lactic acid);
(5) above-mentioned mixing solutions is passed through freeze-drying, make chitosan/polyvinyl alcohol/polylactic acid blended porous membrane.
Chitosan in the described step (1) is medical grade, deacetylation 90%～100%.
The polymerization degree of the polyvinyl alcohol in the described step (3) is 1700, and alcoholysis degree is 88%.
The processing condition of the freeze-drying in the described step (5) are injected metalware for chitosan/polyvinyl alcohol/poly(lactic acid) mixing solutions that will mix, in-80 ℃～-8 ℃ freezing 10～12 hours, vacuum lyophilization is 10～15 hours subsequently.
The purpose of this invention is to provide chitosan/polyvinyl alcohol/polylactic acid blended porous membrane of a kind of permeable, good permeability and preparation method thereof, specifically is to adopt Freeze Drying Technique to have porous, a resilient sponge product with chitosan, polyvinyl alcohol, poly(lactic acid) are synthetic.Made blended porous membrane is the film with micropore, and the form in hole is not of uniform size.What the pore space structure that forms helped cell adheres to, breeds growth, and the high ventilation performance is avoided hydrops, helps wound healing.The present invention has eliminated the film forming defective of one-component, has reached the purpose of three's performance complement.
Beneficial effect
(1) to select chitosan, polyvinyl alcohol, poly(lactic acid) for use be raw material in the present invention, and wide material sources are cheap, pollution-free nontoxic, have biodegradability and good affinity, do not relate to toxicant in film-forming process, and membrane equipment and technology are easy;
(2) nontoxic, the side effect of blend film has biocompatibility, have biodegradability and can not cause environmental pollution, and its degraded product can improve micro-ecological environment in soil, and this blend has reached the purpose of three's performance complement;
(3) utilize Vacuum Freezing ﹠ Drying Technology that three's mixing solutions is made porous-film, obtain a kind of porosity height, hole and distribute and be suitable as the blend film of curable products such as artificial skin, dressing comparatively uniformly.
Description of drawings
Fig. 1 is the SEM figure of blended porous membrane of the present invention.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The 97g weight percent that the 3g chitosan is dissolved in 40 ℃ is in 2% acetum, becomes homogeneous solution.The 5g poly(lactic acid) is dissolved in 25 ℃ 95g (99wt%) dimethyl sulfoxide solution, becomes homogeneous solution.The 7g polyvinyl alcohol is dissolved in 100 ℃ the 93g deionized water, becomes homogeneous solution.Take by weighing 11.2g chitosan solution, 0.6g polyvinyl alcohol solution and 0.84g poly(lactic acid) solution respectively, under 25 ℃, mix, stir 30min, deaeration.The mixing solutions of deaeration is injected flat Stainless Steel Ware, freezing 12 hours in-80 ℃～-8 ℃, vacuum lyophilization can make chitosan: polyvinyl alcohol after 12 hours subsequently: the poly(lactic acid) weight percent is chitosan/polyvinyl alcohol/polylactic acid blended porous membrane of 8: 1: 1.
Embodiment 2
Take by weighing the chitosan solution of 12.6g, the polyvinyl alcohol solution of 2.7g and the poly(lactic acid) solution of 1.26g respectively, under 25 ℃, mix, stir 30min, deaeration.The mixing solutions of deaeration is injected flat Stainless Steel Ware, under-80 ℃～-8 ℃ condition freezing 12 hours, vacuum lyophilization can make chitosan: polyvinyl alcohol after 12 hours subsequently: the poly(lactic acid) mass ratio is chitosan/polyvinyl alcohol/polylactic acid blended porous membrane of 6: 3: 1.
Embodiment 3
Take by weighing 11.2g chitosan solution, 6g polyvinyl alcohol solution and 1.68g poly(lactic acid) solution respectively, under 25 ℃, mix, stir 30min, deaeration.The mixing solutions of deaeration is injected flat Stainless Steel Ware, under-80 ℃～-8 ℃ condition freezing 12 hours, vacuum lyophilization can make chitosan: polyvinyl alcohol after 12 hours subsequently: the poly(lactic acid) weight percent is chitosan/polyvinyl alcohol/polylactic acid blended porous membrane of 4: 5: 1.
Claims (4)
1. the preparation method of a chitosan/polyvinyl alcohol/polylactic acid blended porous membrane comprises:
(1) is that 1～2% acetum is made the dissolution with solvents chitosan down at 30～40 ℃, obtains weight percentage and be 3% chitosan solution with weight percentage;
(2) at room temperature make the dissolution with solvents poly(lactic acid), obtain weight percentage and be 5% poly(lactic acid) solution with the dimethyl sulfoxide (DMSO) of content 〉=99wt%;
(3) under 80～120 ℃, make the dissolution with solvents polyvinyl alcohol, be stirred to it and dissolve fully, make weight percentage and be 7% polyvinyl alcohol solution with deionized water;
(4) above-mentioned three kinds of solution are mixed, stir 15～30min at 20～30 ℃ of following constant temperature, and standing and defoaming, chitosan in the mixing solutions: polyvinyl alcohol: the mass ratio 4～8: 5～1: 1 of poly(lactic acid);
(5) above-mentioned mixing solutions is passed through freeze-drying, make chitosan/polyvinyl alcohol/polylactic acid blended porous membrane.
2. the preparation method of a kind of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane according to claim 1, it is characterized in that: the chitosan in the described step (1) is medical grade, deacetylation 90%～100%.
3. the preparation method of a kind of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane according to claim 1, it is characterized in that: the polymerization degree of the polyvinyl alcohol in the described step (3) is 1700, alcoholysis degree is 88%.
4. the preparation method of a kind of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane according to claim 1, it is characterized in that: the processing condition of the freeze-drying in the described step (5) are for injecting metalware with chitosan/polyvinyl alcohol/poly(lactic acid) mixing solutions, in-80 ℃～-8 ℃ freezing 10～12 hours, vacuum lyophilization is 10～15 hours subsequently.
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102605467A (en) * | 2012-03-02 | 2012-07-25 | 北京化工大学 | Method for preparing composite polyelectrolyte fiber membrane by utilizing freeze-drying way |
| CN102697600A (en) * | 2012-05-19 | 2012-10-03 | 江苏百得医疗器械有限公司 | Medical absorbable anti-adhesion membrane |
| CN102850574A (en) * | 2012-09-26 | 2013-01-02 | 华东理工大学 | Method for preparing ordered-structure porous polymer material based on directional crystallization technology |
| CN103172896A (en) * | 2011-12-22 | 2013-06-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Porous membrane, and preparation method and application thereof |
| CN103520765A (en) * | 2013-11-06 | 2014-01-22 | 中国科学院长春应用化学研究所 | Method for preparing wound hemostasis dressing |
| CN106176295A (en) * | 2016-08-26 | 2016-12-07 | 李冬琼 | The preparation method of oil absorbing polymer paper |
| CN106176294A (en) * | 2016-08-26 | 2016-12-07 | 李冬琼 | The preparation technology of oil-Absorbing Sheets |
| CN107261866A (en) * | 2017-08-10 | 2017-10-20 | 武汉纺织大学 | A kind of preparation method of through hole membrane for water treatment |
| CN107261867A (en) * | 2017-08-10 | 2017-10-20 | 武汉纺织大学 | A kind of preparation method of super water-purifying filter film |
| CN107447281A (en) * | 2017-08-10 | 2017-12-08 | 武汉纺织大学 | A kind of preparation method of oil phase polymeric hollow fiber array material |
| CN107441963A (en) * | 2017-08-10 | 2017-12-08 | 武汉纺织大学 | A kind of preparation method of aqueous phase polymeric hollow fiber array material |
| CN107519847A (en) * | 2017-08-10 | 2017-12-29 | 武汉纺织大学 | A kind of preparation method of heavy metal ion adsorbed film |
| CN109734939A (en) * | 2019-01-20 | 2019-05-10 | 成都大学 | A method of preparation food-grade polylactic acid film is dissolved using glacial acetic acid |
| CN110302010A (en) * | 2019-06-10 | 2019-10-08 | 苏州晶俊新材料科技有限公司 | A kind of multiple trauma dressing and its quick molding method with two-way function |
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| CN114044834A (en) * | 2021-11-02 | 2022-02-15 | 千芝雅(湖北)卫生用品有限公司 | Polylactic acid fiber and application thereof in adult incontinence nursing pad |
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| CN103172896A (en) * | 2011-12-22 | 2013-06-26 | 上海纳米技术及应用国家工程研究中心有限公司 | Porous membrane, and preparation method and application thereof |
| CN103172896B (en) * | 2011-12-22 | 2015-04-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Porous membrane, and preparation method and application thereof |
| CN102605467A (en) * | 2012-03-02 | 2012-07-25 | 北京化工大学 | Method for preparing composite polyelectrolyte fiber membrane by utilizing freeze-drying way |
| CN102605467B (en) * | 2012-03-02 | 2014-10-29 | 北京化工大学 | Method for preparing composite polyelectrolyte fiber membrane by utilizing freeze-drying way |
| CN102697600A (en) * | 2012-05-19 | 2012-10-03 | 江苏百得医疗器械有限公司 | Medical absorbable anti-adhesion membrane |
| CN102850574A (en) * | 2012-09-26 | 2013-01-02 | 华东理工大学 | Method for preparing ordered-structure porous polymer material based on directional crystallization technology |
| CN102850574B (en) * | 2012-09-26 | 2013-12-25 | 华东理工大学 | Method for preparing ordered-structure porous polymer material based on directional crystallization technology |
| CN103520765A (en) * | 2013-11-06 | 2014-01-22 | 中国科学院长春应用化学研究所 | Method for preparing wound hemostasis dressing |
| CN106176295A (en) * | 2016-08-26 | 2016-12-07 | 李冬琼 | The preparation method of oil absorbing polymer paper |
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| CN107441963A (en) * | 2017-08-10 | 2017-12-08 | 武汉纺织大学 | A kind of preparation method of aqueous phase polymeric hollow fiber array material |
| CN107519847A (en) * | 2017-08-10 | 2017-12-29 | 武汉纺织大学 | A kind of preparation method of heavy metal ion adsorbed film |
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| CN107261867B (en) * | 2017-08-10 | 2019-09-24 | 武汉纺织大学 | A kind of preparation method of super water-purifying filter film |
| CN109734939A (en) * | 2019-01-20 | 2019-05-10 | 成都大学 | A method of preparation food-grade polylactic acid film is dissolved using glacial acetic acid |
| CN109734939B (en) * | 2019-01-20 | 2021-03-02 | 成都大学 | Method for preparing food-grade polylactic acid film by dissolving glacial acetic acid |
| CN110302010A (en) * | 2019-06-10 | 2019-10-08 | 苏州晶俊新材料科技有限公司 | A kind of multiple trauma dressing and its quick molding method with two-way function |
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| CN114044834A (en) * | 2021-11-02 | 2022-02-15 | 千芝雅(湖北)卫生用品有限公司 | Polylactic acid fiber and application thereof in adult incontinence nursing pad |
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Application publication date: 20100908 |