CN114106401B - Porous chitosan membrane and preparation method and application thereof - Google Patents
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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
- A61L31/146—Porous materials, e.g. foams or sponges
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Abstract
The invention discloses a porous chitosan membrane and a preparation method and application thereof. Pure chitosan or chitosan and other polymers are mixed and dissolved into solution, and then the chitosan solution is frozen and solidified. And (3) injecting a low-melting-point thawing coagulant into the frozen chitosan solution, wherein the thawing coagulant comprises, by mass, 1% -10% of strong alkali, 1% -10% of inorganic salt, 50% -90% of an organic solvent and the balance of water. The thawing coagulant can still melt the ice crystal structure below-0 ℃, and simultaneously makes the chitosan macromolecules undergo ionic crosslinking solidification, so that the space framework structure of the chitosan macromolecules is reserved, and the porous chitosan membrane is formed. The porous chitosan membrane has uniform pore structure, good mechanical properties, liquid absorption and moisture retention, and biocompatibility, and can be applied to facial masks, wound dressings, surgical anti-adhesion membranes or cell scaffolds. The preparation method provided by the invention has the advantages of simple required equipment and process and high pore-forming efficiency, and is suitable for large-scale processing.
Description
Technical Field
The invention belongs to the field of natural polymer materials, and particularly relates to a porous chitosan membrane and a preparation method and application thereof.
Background
Chitosan is a natural product of deacetylation of chitin, is the only alkaline high molecular polysaccharide in nature, and has rich sources. The chitosan has good biocompatibility, biodegradability, natural antibacterial property and molding processability. Chitosan has been processed into materials such as fibers, films, hydrogels, sponges, and the like, and has been widely used in the industries of foods, textiles, medicines, 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, etc. The chitosan film has wide application value and can be used for beauty and health care products, medical and health products, food packaging materials and the like. Patent CN102317878A discloses a preparation method of a chitosan-based antibacterial film material, which comprises the steps of mixing a chitosan solution with povidone iodine, and drying at 40 ℃ to obtain a compact-structure antibacterial film. Patent CN111518296A discloses a preparation method of chitosan membrane material, which comprises the steps of dissolving chitosan by a weak alkaline aqueous solvent system, regenerating and solidifying, cleaning, drying and forming a 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 the three polymer solutions to form the porous membrane. From the prior art, chitosan films are mostly prepared by drying methods and hydrogel methods, and the mechanical property, the liquid absorption property or the cell adhesion property of the chitosan films are not ideal. While the porous structure membrane helps to improve its wicking properties and cell adhesion. The existing chitosan porous membrane is mainly prepared by a freeze drying method, has poor mechanical properties and low preparation efficiency. If the pore-forming method of the chitosan film is improved, the mechanical property of the porous chitosan film is improved, and the application of the porous chitosan film in the fields of beauty 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 the mixed solution thereof, the macromolecules are in a frozen state, and the ice crystals are uniformly distributed in the chitosan or the mixed solution. And (3) injecting a low-melting-point thawing coagulant to gradually melt ice crystals, and solidifying chitosan and other polymers under the action of ions to maintain a space frame structure so as to form a porous chitosan film. In order to achieve the above purpose, the invention adopts the following technical scheme:
a porous chitosan membrane and a preparation method and application thereof comprise the following steps:
s1, mixing pure chitosan or chitosan and other polymers, dissolving the mixture in dilute acid to prepare a chitosan solution, wherein the other polymers are one or more of gelatin, polyvinyl alcohol, polylactic acid, carboxymethyl cellulose, hydroxypropyl cellulose and water-soluble starch;
s2, spreading the chitosan solution obtained in the step S1, and putting the chitosan solution into a temperature of minus 20 ℃ to freeze and solidify;
s3, preparing a thawing coagulant, and dissolving strong alkali, inorganic salt, an organic solvent and water into a transparent solution, wherein the strong alkali 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 thawing coagulant obtained in the S3 into the frozen chitosan solution obtained in the S2, and continuously standing at the temperature of minus 0 ℃ or below to enable the chitosan solution to be crosslinked and solidified while thawing;
s5, taking out the chitosan film obtained in the step S4, rinsing with small soda water, cleaning with pure water, and drying to obtain the porous chitosan film.
Further, the concentration of the chitosan in the 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 hydrochloric acid, acetic acid or glutamic acid solution with the mass fraction of 1% -3%.
Further, the casting thickness of the chitosan solution in the step S2 is 2mm or less, and the freezing and solidifying time is 2-12 h.
Further, the mass concentration of each component in the thawing and coagulating agent in the S3 is 1% -10% of strong alkali, 1% -10% of inorganic salt, 50% -95% of organic solvent and the balance of water.
And further, the volume usage of the thawing and solidifying agent injected into the S3 is 3-10 times of the volume of the chitosan solution, and the thawing and solidifying time is 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 yet another aspect, the invention provides the use of a porous chitosan film as described above, wherein porous chitosan films of different thickness can be used in a facial mask, wound dressing, surgical anti-adhesion film or cell scaffold.
The invention has the beneficial effects that:
1) Compared with a freeze drying method, the preparation method provided by the invention improves the pore-forming method of the porous chitosan film, and does not need a severe vacuum environment, but only needs a conventional freezing environment; the pore-forming mechanism is changed from ice crystal sublimation to ice crystal dissolution, so that the pore-forming efficiency is greatly improved.
2) The method disclosed by the invention ensures that chitosan and other macromolecules are gradually crosslinked and solidified by liquefied ions in a frozen state, so that a good porous frame structure is maintained, and the mechanical properties of the porous chitosan film are greatly improved.
3) The porous chitosan membrane prepared by the method has good biocompatibility, liquid absorption and moisture retention, high porosity and stable mechanical property, and is suitable for facial masks, dressing, anti-adhesion membranes, cell scaffolds and the like.
4) The preparation method provided by the invention has the advantages of simple process conditions of required equipment, improved film forming efficiency and contribution to large-scale processing.
Drawings
FIG. 1 is a flow chart of the preparation of a porous chitosan membrane.
Detailed Description
The invention is described in further detail below in connection with specific examples, which are provided merely to illustrate the method of the invention and do not limit the invention in any way.
Example 1
0.2g of chitosan was dissolved in 10mL of 2% glutamic acid solution, and the mixture was allowed to stand for 1 hour. 0.5mL of chitosan solution was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 0.5mm, and then the sample dish was placed in a freezer and frozen at-20℃for 3 hours. Further, a thawing coagulant was prepared, and 5g of sodium hydroxide, 1g of anhydrous sodium carbonate, 80g of absolute ethanol, 10g of glycerin and 4g of water were mixed and dissolved by stirring at room temperature. Then, 2.5mL of thawing coagulant was injected into the frozen chitosan solution, and the frozen chitosan solution was thawed and crosslinked at-0℃for 6 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and drying by blowing at 20 ℃. The thickness of the obtained porous chitosan film is about 0.5mm, and the porous chitosan film is soft and porous. The porous chitosan film has water absorption rate of more than 40 times of self weight, and good liquid absorption and moisture preservation effects, and can be used for facial masks and surgical anti-adhesion films.
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 was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 2mm, and then the sample dish was placed in a freezer and frozen at-20℃for 12 hours. Further, a thawing coagulant was prepared, and 10g of potassium hydroxide, 5g of anhydrous sodium acetate, 70g of anhydrous methanol, 5g of polyethylene glycol 200 and 10g of water were mixed and dissolved by stirring at room temperature. Then, 20mL of thawing coagulant was injected into the frozen chitosan solution, and allowed to thaw and crosslink at-20℃for 12 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and vacuum drying at 50 ℃. The thickness of the obtained porous chitosan film is about 2mm, and the porous chitosan film is soft and porous. The porous chitosan film has water absorption rate up to 50 times of its own weight, and good effects of absorbing and keeping moisture, and can be used for wound dressing, hemostatic sponge or cell scaffold.
Example 3
0.1g of chitosan and 0.5g of gelatin were dissolved in 10mL of 1% strength acetic acid solution, and vacuum deaeration was performed for 2 hours. 0.2mL of chitosan solution was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 0.2mm, and then the sample dish was placed in a freezer and frozen at-80℃for 2 hours. A thawing coagulant was prepared, and 3g of lithium hydroxide, 10g of anhydrous ammonium sulfate, 50g of dimethyl sulfoxide, 10g of ethylene glycol, and 27g of water were mixed and dissolved by stirring at room temperature. Then, 0.6mL of thawing coagulant was injected into the frozen chitosan solution, and the frozen chitosan solution was thawed and crosslinked at-0℃for 2 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and vacuum drying at 20 ℃. The obtained porous chitosan has a film thickness of about 0.2mm, is soft and porous, has good liquid absorption and moisture preservation effects, and can be used for facial masks, artificial skin or cell scaffolds.
Example 4
0.3g of chitosan and 1g of hydroxypropyl methylcellulose were dissolved in 10mL of a glutamic acid solution having a concentration of 3%, and vacuum defoamed for 3 hours. 1mL of chitosan solution was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 1mm, and then the sample dish was put into a freezer and frozen at-20℃for 5 hours. In addition, a thawing coagulant was prepared, 8g of sodium hydroxide, 5g of sodium citrate, 60g of isopropyl alcohol, 5g of N, N-dimethylformamide, 2g of glycerin and 20g of water were mixed and dissolved by stirring at room temperature. Then, 8mL of thawing coagulant was injected into the frozen chitosan solution, and allowed to thaw and crosslink at-20℃for 8 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and vacuum drying at 20 ℃. The obtained porous chitosan has a film thickness of about 1mm, is soft and porous, has good imbibition and moisture preservation effects, and can be used for masks, surgical anti-adhesion films or cell scaffolds.
Example 5
0.2g of chitosan and 0.8g of polyvinyl alcohol were dissolved in 10mL of a 2% hydrochloric acid solution, and vacuum deaeration was performed for 3 hours. 0.5mL of chitosan solution was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 0.5mm, and then the sample dish was placed in a freezer and frozen at-80℃for 2 hours. Further, a thawing coagulant was prepared, and 5g of potassium hydroxide, 10g of anhydrous sodium citrate, 40g of anhydrous ethanol, 10g of dimethyl sulfoxide and 35g of water were mixed and dissolved by stirring at room temperature. Then, 5mL of thawing coagulant was injected into the frozen chitosan solution, and allowed to thaw and crosslink at-20℃for 12 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and vacuum drying at 25 ℃. The obtained porous chitosan has a film thickness of about 0.5mm, is soft and porous, has good liquid absorption and moisture preservation effects, and can be used for facial masks, wound dressings, artificial skin or cell scaffolds.
Example 6
0.3g of chitosan and 0.7g of water-soluble starch are dissolved in 10mL of acetic acid solution with concentration of 3%, and vacuum defoaming is carried out for 6 hours. 1mL of chitosan solution was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 1mm, and then the sample dish was placed in a freezer and frozen at-20℃for 8 hours. Further, a thawing coagulant was prepared, and 7g of potassium hydroxide, 5g of anhydrous sodium phosphate, 50g of N, N-dimethylacetamide, 20g of polyethylene glycol 600 and 18g of water were mixed and dissolved by stirring at room temperature. Then, 10mL of thawing coagulant was injected into the frozen chitosan solution, and allowed to thaw and crosslink at-20℃for 12 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and vacuum drying at 50 ℃. The obtained porous chitosan has a film thickness of about 1mm, is soft and porous, has good liquid absorption and moisture preservation effects, 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% strength acetic acid solution, and vacuum deaeration was performed for 3 hours. 0.5mL of chitosan solution was poured into a flat-bottom sample dish, the sample dish was cast flat to a thickness of 0.5mm, and then the sample dish was placed in a freezer and frozen at-20℃for 5 hours. Further, a thawing coagulant was prepared, and 1g of sodium hydroxide, 10g of anhydrous calcium chloride, 80g of absolute ethanol, 3g of glycerin and 6g of water were mixed and dissolved by stirring at room temperature. Then, 5mL of thawing coagulant was injected into the frozen chitosan solution, and allowed to thaw and crosslink at-0℃for 6 hours. And then taking out the porous chitosan membrane, rinsing with 5% sodium bicarbonate solution, cleaning with pure water, and vacuum drying at 30 ℃. The obtained porous chitosan has a film thickness of about 0.5mm, is soft and porous, has good imbibition and moisture preservation effects, and can be used for masks, wound dressings or surgical anti-adhesion films.
Claims (7)
1. The preparation method of the porous chitosan membrane is characterized by comprising the following steps of:
s1, mixing pure chitosan or chitosan and other polymers, dissolving the mixture in dilute acid to prepare a chitosan solution, wherein the other polymers are one or more of gelatin, polyvinyl alcohol, polylactic acid, carboxymethyl cellulose, hydroxypropyl cellulose and water-soluble starch;
s2, spreading the chitosan solution obtained in the step S1, and putting the chitosan solution into a temperature below minus 20 ℃ for freezing and solidification;
s3, preparing a low-melting-point thawing coagulant, and dissolving strong base, inorganic salt and organic solvent in water, wherein the mass concentration of each component is respectively 1% -10% of strong base, 1% -10% of inorganic salt and 50% -95% of organic solvent; the strong alkali 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 and sodium phosphate, and the organic solvent is one or more of ethanol, methanol, isopropanol, acetone, dimethyl sulfoxide, glycerol, glycol, polyethylene glycol 200-600, N-dimethylformamide and N, N-dimethylacetamide;
s4, injecting the thawing coagulant obtained in the S3 into the frozen chitosan solution obtained in the S2, and continuously standing at the temperature below 0 ℃ to enable the chitosan solution to be cross-linked and solidified while being thawed;
s5, taking out the chitosan film obtained in the step S4, rinsing with small soda water, cleaning with pure water, and drying to obtain the porous chitosan film.
2. The preparation method of the porous chitosan membrane according to claim 1, wherein the concentration of the chitosan in S1 is 0.01-0.04 g/mL, the concentration of the other polymers is 0-0.1 g/mL, and the dilute acid is hydrochloric acid, acetic acid or glutamic acid solution with the mass fraction of 1% -3%.
3. The method for preparing a porous chitosan film according to claim 1, wherein the casting thickness of the chitosan solution in S2 is 2mm or less, and the freeze-setting time is 2 to 12 hours.
4. The method for preparing a porous chitosan film according to claim 1, wherein the volume of the thawing and solidifying agent injected into the S3 in the S4 is 3-10 times of the volume of the chitosan solution, and the thawing and solidifying time is 2-12 hours at the temperature below 0 ℃.
5. The method for preparing a porous chitosan film according to claim 1, wherein the drying method in S5 is air drying or vacuum drying, and the temperature is 20-50 ℃.
6. A porous chitosan membrane prepared according to the preparation method of any one of claims 1 to 5.
7. The use of a porous chitosan film according to claim 6, wherein said porous chitosan film is used for the preparation of a facial mask, a wound dressing, a surgical anti-adhesion film or a cell scaffold.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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