CN114106401A - Porous chitosan membrane and preparation method and application thereof - Google Patents
Porous chitosan membrane and preparation method and application thereof Download PDFInfo
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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Abstract
The invention discloses a porous chitosan membrane and a preparation method and application thereof. Mixing pure chitosan or chitosan with other macromolecules, dissolving to obtain a solution, and freezing and solidifying the chitosan solution. Injecting a low-melting-point thawing coagulant into the frozen chitosan solution, wherein the thawing coagulant comprises 1-10% by mass of strong base, 1-10% by mass of inorganic salt, 50-90% by mass of an organic solvent and the balance of water. The thawing coagulator can still melt the ice crystal structure below-0 ℃, and simultaneously, chitosan macromolecules are subjected to ion crosslinking and solidification, and the space frame structure of the chitosan macromolecules is reserved, so that the porous chitosan membrane is formed. The porous chitosan membrane has uniform pore structure, good mechanical property, imbibition and moisture retention property and biocompatibility, and can be applied to facial masks, wound dressings, operation anti-adhesion membranes or cytoskeletons. The preparation method of the invention has the advantages of simple required equipment and process, high hole forming efficiency and suitability for large-scale processing.
Description
Technical Field
The invention belongs to the field of natural high polymer materials, and particularly relates to a porous chitosan membrane and a preparation method and application thereof.
Background
The chitosan is a natural product of deacetylation of chitin, is the only basic high molecular polysaccharide in the nature, and has rich sources. The chitosan has good biocompatibility, biodegradability, natural antibacterial property and molding processability. Chitosan has been processed into fibers, films, hydrogels, sponges and other materials, and has been widely applied in the industries of food, textile, medicine, chemical industry and the like. In order to improve the properties of the material, chitosan is often blended with other polymers, such as gelatin, polyvinyl alcohol, cellulose derivatives, and the like. The chitosan film has wide application value and can be used for beauty and health care products, medical and sanitary products, food packaging materials and the like. Patent CN102317878A discloses a preparation method of a chitosan-based antibacterial membrane material, which comprises the steps of mixing a chitosan solution with povidone iodine, drying at 40 ℃ and drying to obtain an antibacterial membrane with a compact structure. Patent CN111518296A discloses a method for preparing chitosan membrane material, which comprises dissolving chitosan in weak alkaline aqueous solvent system, regenerating and solidifying, cleaning, drying and forming membrane. Patent CN101824160A discloses a preparation method of chitosan/polyvinyl alcohol/polylactic acid blended porous membrane, which is to blend three polymer solutions and freeze-dry them into porous membrane. In the prior art, chitosan membranes are mostly prepared by a drying method and a hydrogel method, and the mechanical properties, the imbibition performance or the cell adhesion of the chitosan membranes are not ideal. And the porous structure membrane is helpful to improve the imbibition performance and cell adhesion. The existing chitosan porous membrane is mainly prepared by adopting a freeze-drying method, and has poor mechanical properties and low preparation efficiency. If the pore-forming method of the chitosan film can be improved, the mechanical property of the porous chitosan film can be improved, and the application of the porous chitosan film in the fields of beauty treatment and health care, medical treatment and health, cell scaffolds and the like can be promoted.
Disclosure of Invention
The invention aims to solve the technical problems and provides a porous chitosan membrane and a preparation method and application thereof. The invention pre-freezes and solidifies chitosan or its mixed solution, the macromolecule is in frozen state, the ice crystal is distributed in it evenly. Injecting low melting point defreezing coagulant to melt the ice crystal gradually, and curing chitosan and other polymer under the action of ion to maintain the space frame structure and form porous chitosan film. In order to achieve the purpose, the invention adopts the technical scheme that:
a porous chitosan film and a preparation method and application thereof comprise the following steps:
s1, mixing pure chitosan or chitosan and other macromolecules, dissolving the mixture in dilute acid to prepare a chitosan solution, wherein the other macromolecules are one or more of gelatin, polyvinyl alcohol, polylactic acid, carboxymethyl cellulose, hydroxypropyl cellulose and water-soluble starch;
s2, casting and spreading the chitosan solution obtained in the step S1, and freezing and solidifying at the temperature of-20 ℃;
s3, preparing a thawing coagulator, dissolving strong base, inorganic salt, an organic solvent and water into a transparent solution, wherein the strong base is any one of sodium hydroxide, lithium hydroxide and potassium hydroxide, the inorganic salt is one or more of sodium sulfate, ammonium sulfate, sodium carbonate, calcium chloride, sodium nitrate, calcium nitrate, sodium acetate, sodium phosphate and sodium citrate, and the organic solvent is one or more of ethanol, methanol, isopropanol, acetone, dimethyl sulfoxide, glycerol, ethylene glycol, polyethylene glycol 200-600, N-dimethylformamide and N, N-dimethylacetamide;
s4, injecting the unfreezing coagulant obtained in the step S3 into the frozen chitosan solution obtained in the step S2, and continuously standing at the temperature of-0 ℃ or below to enable the chitosan solution to be unfrozen and crosslinked and solidified;
and S5, taking out the chitosan membrane obtained in the step S4, rinsing with sodium bicarbonate water, washing with pure water, and drying to obtain the porous chitosan membrane.
Further, the concentration of the chitosan in S1 is 0.01-0.04 g/mL, the concentration of any other polymer is 0-0.1 g/mL, and the dilute acid is a hydrochloric acid, acetic acid or glutamic acid solution with the mass fraction of 1% -3%.
Further, in S2, the casting thickness of the chitosan solution is 2mm or less, and the freezing and solidifying time is 2-12 h.
Further, the mass concentration of each component in the thawing coagulator S3 is 1% -10% of strong base, 1% -10% of inorganic salt, 50% -95% of organic solvent and the balance of water.
Furthermore, the volume of the thawing coagulator injected into S3 in S4 is 3-10 times of the volume of the chitosan solution, and the thawing coagulator has the thawing coagulation time of 2-12 hours below-0 ℃.
Further, the drying method in S5 is air blast drying or vacuum drying, and the temperature is 20-50 ℃.
On the other hand, the invention provides the porous chitosan membrane prepared by the preparation method of the porous chitosan membrane.
In another aspect, the present invention provides an application of the above porous chitosan membrane, wherein the porous chitosan membranes with different thicknesses can be used in facial masks, wound dressings, anti-adhesion membranes for surgery or cytoskeletons.
The invention has the beneficial effects that:
1) compared with a freeze drying method, the preparation method provided by the invention improves a pore-forming method of the porous chitosan membrane, does not need harsh vacuum environment, and only needs conventional freezing environment; the pore-forming mechanism is changed from ice crystal sublimation pore-forming into ice crystal dissolution pore-forming, so that the pore-forming efficiency is greatly improved.
2) The method disclosed by the invention ensures that the chitosan and other macromolecules are gradually crosslinked and solidified by liquefied ions in a frozen state, maintains a good porous frame structure, and greatly improves the mechanical properties of the porous chitosan membrane.
3) The porous chitosan membrane prepared by the method has good biocompatibility, imbibition and moisture retention, high porosity and stable mechanical property, and is suitable for the aspects of facial masks, dressings, anti-adhesion membranes, cell scaffolds and the like.
4) The preparation method provided by the invention has the advantages of simple equipment and process conditions, improved film forming efficiency and contribution to large-scale processing.
Drawings
FIG. 1 is a flow chart of a method for preparing a porous chitosan membrane.
Detailed Description
The invention is described in further detail below with reference to specific examples, which are provided only for illustration of the process of the invention and are not intended to limit the invention in any way.
Example 1
0.2g of chitosan was dissolved in 10mL of 2% glutamic acid solution, and the solution was left to stand for deaeration for 1 hour. 0.5mL of chitosan solution was poured into a flat bottom sample dish, which was cast flat to a thickness of 0.5mm, and then the dish was frozen in a freezer at-20 ℃ for 3 hours. Separately, a thawing coagulant was prepared by mixing 5g of sodium hydroxide, 1g of anhydrous sodium carbonate, 80g of anhydrous ethanol, 10g of glycerin, and 4g of water, and dissolving them under stirring at room temperature. Then, 2.5mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-0 ℃ for 6 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, then washing the porous chitosan membrane by using pure water, and then blowing and drying the porous chitosan membrane at 20 ℃. The obtained porous chitosan film has a thickness of about 0.5mm, and is soft and porous. The porous chitosan membrane has water absorption rate of 40 times of the dead weight, good imbibition and moisture retention effects, and can be used as facial mask and anti-adhesion membrane for operation.
Example 2
0.4g of chitosan was dissolved in 10mL of a 3% hydrochloric acid solution and vacuum defoamed for 6 hours. 2mL of chitosan solution is poured into a flat-bottom sample dish, the flat-bottom sample dish is made to be flat by casting, the thickness of the flat-bottom sample dish is 2mm, and then the sample dish is put into a refrigerator to be frozen for 12 hours at the temperature of minus 20 ℃. Separately, a thawing coagulant was prepared by mixing 10g of potassium hydroxide, 5g of anhydrous sodium acetate, 70g of anhydrous methanol, 5g of polyethylene glycol 200 and 10g of water, and dissolving them under stirring at room temperature. Then, 20mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-20 ℃ for 12 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, washing the porous chitosan membrane by using pure water, and drying the porous chitosan membrane at 50 ℃ in vacuum. The obtained porous chitosan film has a thickness of about 2mm, and is soft and porous. The porous chitosan membrane has water absorption rate of over 50 times of the self weight, has good imbibition and moisture retention effects, and can be used in wound dressing, hemostatic sponge or cell scaffold.
Example 3
0.1g of chitosan and 0.5g of gelatin were dissolved in 10mL of 1% acetic acid solution and vacuum defoamed for 2 hours. 0.2mL of chitosan solution was poured into a flat bottom sample dish, which was cast flat to a thickness of 0.2mm, and then the dish was frozen in a freezer at-80 ℃ for 2 h. Separately, a thawing coagulant was prepared by mixing 3g of lithium hydroxide, 10g of anhydrous ammonium sulfate, 50g of dimethyl sulfoxide, 10g of ethylene glycol and 27g of water, and dissolving the mixture by stirring at room temperature. Then, 0.6mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-0 ℃ for 2 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, washing the porous chitosan membrane by using pure water, and drying the porous chitosan membrane in vacuum at 20 ℃. The obtained porous chitosan membrane has a thickness of about 0.2mm, is soft and porous, has good imbibing and moisturizing effects, and can be used for facial masks, artificial skin or cytoskeleton.
Example 4
0.3g of chitosan and 1g of hydroxypropyl methylcellulose were dissolved in 10mL of 3% glutamic acid solution and vacuum defoamed for 3 hours. 1mL of chitosan solution is poured into a flat-bottom sample dish, the flat-bottom sample dish is made to be flat by tape casting, the thickness of the flat-bottom sample dish is 1mm, and then the sample dish is put into a refrigerator to be frozen for 5 hours at the temperature of minus 20 ℃. Separately, a thawing coagulant was prepared by mixing 8g of sodium hydroxide, 5g of sodium citrate, 60g of isopropyl alcohol, 5g N, N-dimethylformamide, 2g of glycerin, and 20g of water, and dissolving them under stirring at room temperature. Then, 8mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-20 ℃ for 8 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, washing the porous chitosan membrane by using pure water, and drying the porous chitosan membrane in vacuum at 20 ℃. The obtained porous chitosan membrane has a thickness of about 1mm, is soft and porous, has good imbibing and moisturizing effects, and can be used as facial mask, anti-adhesion membrane for operation or cytoskeleton.
Example 5
0.2g of chitosan and 0.8g of polyvinyl alcohol were dissolved in 10mL of a 2% hydrochloric acid solution and vacuum defoamed for 3 hours. 0.5mL of chitosan solution was poured into a flat bottom sample dish, which was cast flat to a thickness of 0.5mm, and then the dish was frozen in a freezer at-80 ℃ for 2 h. Separately, a thawing coagulant was prepared by mixing 5g of potassium hydroxide, 10g of anhydrous sodium citrate, 40g of anhydrous ethanol, 10g of dimethyl sulfoxide and 35g of water, and dissolving the mixture under stirring at room temperature. Then, 5mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-20 ℃ for 12 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, washing the porous chitosan membrane by using pure water, and drying the porous chitosan membrane in vacuum at 25 ℃. The obtained porous chitosan membrane has a thickness of about 0.5mm, is soft and porous, has good imbibing and moisturizing effects, and can be used for facial masks, wound dressings, artificial skin or cytoskeletons.
Example 6
0.3g of chitosan and 0.7g of water-soluble starch are dissolved in 10mL of 3% acetic acid solution, and vacuum defoamation is carried out for 6 h. 1mL of chitosan solution is poured into a flat-bottom sample dish, the flat-bottom sample dish is made to be flat by tape casting, the thickness of the flat-bottom sample dish is 1mm, and then the sample dish is put into a refrigerator to be frozen for 8 hours at the temperature of minus 20 ℃. In addition, a thawing coagulant was prepared by mixing 7g of potassium hydroxide, 5g of anhydrous sodium phosphate, 50g N, N-dimethylacetamide, 20g of polyethylene glycol 600, and 18g of water, and dissolving them under stirring at room temperature. Then, 10mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-20 ℃ for 12 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, washing the porous chitosan membrane by using pure water, and drying the porous chitosan membrane at 50 ℃ in vacuum. The obtained porous chitosan membrane has a thickness of about 1mm, is soft and porous, has good effects of absorbing liquid and keeping moisture, and can be used for facial masks, wound dressings or artificial skin.
Example 7
0.2g of chitosan and 0.3g of gelatin were dissolved in 10mL of 2% acetic acid solution and vacuum defoamed for 3 hours. 0.5mL of chitosan solution was poured into a flat bottom sample dish, which was cast flat to a thickness of 0.5mm, and then the dish was frozen in a freezer at-20 ℃ for 5 hours. Separately, a thawing coagulant was prepared by mixing 1g of sodium hydroxide, 10g of anhydrous calcium chloride, 80g of anhydrous ethanol, 3g of glycerin, and 6g of water, and dissolving them under stirring at room temperature. Then, 5mL of thawing coagulant was injected into the frozen chitosan solution, and was thawed and cross-linked at-0 ℃ for 6 hours. And then, taking out the porous chitosan membrane, rinsing the porous chitosan membrane by using a 5% sodium bicarbonate solution, washing the porous chitosan membrane by using pure water, and drying the porous chitosan membrane at 30 ℃ in vacuum. The obtained porous chitosan membrane has a thickness of about 0.5mm, is soft and porous, has good effects of absorbing liquid and keeping moisture, and can be used as facial mask, wound dressing or operation anti-adhesion membrane.
Claims (8)
1. A preparation method of a porous chitosan membrane is characterized by comprising the following steps:
s1, mixing pure chitosan or chitosan and other macromolecules, dissolving the mixture in dilute acid to prepare a chitosan solution, wherein the other macromolecules are one or more of gelatin, polyvinyl alcohol, polylactic acid, carboxymethyl cellulose, hydroxypropyl cellulose and water-soluble starch;
s2, casting and spreading the chitosan solution obtained in the step S1, and freezing and solidifying at the temperature of-20 ℃;
s3, preparing a thawing coagulator, dissolving strong base, inorganic salt, an organic solvent and water into a transparent solution, wherein the strong base is any one of sodium hydroxide, lithium hydroxide and potassium hydroxide, the inorganic salt is one or more of sodium sulfate, ammonium sulfate, sodium carbonate, calcium chloride, sodium nitrate, calcium nitrate, sodium acetate, sodium phosphate and sodium citrate, and the organic solvent is one or more of ethanol, methanol, isopropanol, acetone, dimethyl sulfoxide, glycerol, ethylene glycol, polyethylene glycol 200-600, N-dimethylformamide and N, N-dimethylacetamide;
s4, injecting the unfreezing coagulant obtained in the step S3 into the frozen chitosan solution obtained in the step S2, and continuously standing at the temperature of-0 ℃ or below to enable the chitosan solution to be unfrozen and crosslinked and solidified;
and S5, taking out the chitosan membrane obtained in the step S4, rinsing with sodium bicarbonate water, washing with pure water, and drying to obtain the porous chitosan membrane.
2. The method for preparing a porous chitosan membrane according to claim 1, wherein the chitosan concentration of S1 is 0.01-0.04 g/mL, the concentration of any other polymer is 0-0.1 g/mL, and the dilute acid is a hydrochloric acid, acetic acid or glutamic acid solution with a mass fraction of 1% -3%.
3. The method according to claim 1, wherein the casting thickness of the chitosan solution in S2 is 2mm or less, and the freezing and solidifying time is 2-12 h.
4. The method for preparing a porous chitosan membrane according to claim 1, wherein the mass concentration of each component in the thawing coagulating agent of S3 is 1% -10% of strong base, 1% -10% of inorganic salt, 50% -95% of organic solvent, and the balance of water.
5. The method for preparing a porous chitosan membrane according to claim 1, wherein the volume of the thawing coagulant injected in S3 in S4 is 3-10 times of the volume of the chitosan solution, and the thawing coagulation time is 2-12 h at-0 ℃.
6. The method for preparing a porous chitosan membrane according to claim 1, wherein the drying method in S5 is air drying or vacuum drying, and the temperature is 20-50 ℃.
7. A porous chitosan membrane, characterized by being produced according to the production method of claims 1 to 6.
8. The use of a porous chitosan membrane according to claim 7, wherein the porous chitosan membrane can be used in a mask, a wound dressing, a surgical anti-adhesion membrane or a cytoskeleton.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02225539A (en) * | 1989-02-27 | 1990-09-07 | Fuji Spinning Co Ltd | Production of porous chitosan molding |
| US20080242850A1 (en) * | 2006-03-28 | 2008-10-02 | Korea Atomic Energy Research Institute | Method of producing chitosan scaffold having high tensile strength and chitosan scaffold produced using the method |
| CN102258801A (en) * | 2011-06-27 | 2011-11-30 | 武汉纺织大学 | Sponge calcium alginate medical dressing, and preparation method |
| CN103992501A (en) * | 2014-05-23 | 2014-08-20 | 东华大学 | Preparation method of citric acid grafted chitosan hydrogel |
| CN107057108A (en) * | 2017-04-24 | 2017-08-18 | 北京大学口腔医学院 | Controllable chitosan material of a kind of structure and performance and preparation method thereof |
| CN107118385A (en) * | 2017-06-20 | 2017-09-01 | 杭州英健生物科技有限公司 | A kind of preparation method and its product of medical alginate sponge or pectin sponge |
| CN110585474A (en) * | 2019-09-29 | 2019-12-20 | 青岛大学附属医院 | Preparation method of marine organism polysaccharide-based composite sponge, composite sponge and application |
| CN111662464A (en) * | 2020-07-23 | 2020-09-15 | 南京工业大学 | Preparation method of chitosan/sodium alginate double-network hydrogel |
| CN113480772A (en) * | 2021-06-24 | 2021-10-08 | 中山大学 | Preparation method of nano-cellulose-chitosan-based room-temperature aerogel |
-
2021
- 2021-12-03 CN CN202111466713.3A patent/CN114106401B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02225539A (en) * | 1989-02-27 | 1990-09-07 | Fuji Spinning Co Ltd | Production of porous chitosan molding |
| US20080242850A1 (en) * | 2006-03-28 | 2008-10-02 | Korea Atomic Energy Research Institute | Method of producing chitosan scaffold having high tensile strength and chitosan scaffold produced using the method |
| CN102258801A (en) * | 2011-06-27 | 2011-11-30 | 武汉纺织大学 | Sponge calcium alginate medical dressing, and preparation method |
| CN103992501A (en) * | 2014-05-23 | 2014-08-20 | 东华大学 | Preparation method of citric acid grafted chitosan hydrogel |
| CN107057108A (en) * | 2017-04-24 | 2017-08-18 | 北京大学口腔医学院 | Controllable chitosan material of a kind of structure and performance and preparation method thereof |
| CN107118385A (en) * | 2017-06-20 | 2017-09-01 | 杭州英健生物科技有限公司 | A kind of preparation method and its product of medical alginate sponge or pectin sponge |
| CN110585474A (en) * | 2019-09-29 | 2019-12-20 | 青岛大学附属医院 | Preparation method of marine organism polysaccharide-based composite sponge, composite sponge and application |
| CN111662464A (en) * | 2020-07-23 | 2020-09-15 | 南京工业大学 | Preparation method of chitosan/sodium alginate double-network hydrogel |
| CN113480772A (en) * | 2021-06-24 | 2021-10-08 | 中山大学 | Preparation method of nano-cellulose-chitosan-based room-temperature aerogel |
Non-Patent Citations (1)
| Title |
|---|
| 徐梦洁等: "双交联聚乙烯醇/海藻酸钠水凝胶的制备与表征", 《高分子材料科学与工程》 * |
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