CN110448714B - Moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing and preparation method thereof - Google Patents
Moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing and preparation method thereof Download PDFInfo
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
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- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
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- A61L15/42—Use of materials characterised by their function or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/425—Porous materials, e.g. foams or sponges
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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Abstract
The invention belongs to the technical field of medical products, and relates to a chitosan/sodium alginate interwoven dressing with moisture absorption and bacteriostasis functions and a preparation method thereof. The invention discloses a preparation method of a chitosan/sodium alginate interwoven dressing with moisture absorption and bacteriostasis, which comprises the steps of freeze-drying a chitosan solution into a chitosan foam bracket material, spreading a sodium alginate solution on the surface of the chitosan foam bracket material to enable the sodium alginate solution to permeate into a porous structure of a chitosan bracket, and immersing the chitosan/sodium alginate interwoven dressing into a calcium chloride solution for cross-linking reaction after freeze-drying to obtain the chitosan/sodium alginate interwoven dressing. The chitosan/sodium alginate interwoven dressing prepared by the preparation method can effectively absorb wound secretion and inhibit bacterial growth, and the whole dressing is easy to remove.
Description
Technical Field
The invention belongs to the technical field of medical products, and particularly relates to a chitosan/sodium alginate interwoven dressing with moisture absorption and bacteriostasis functions and a preparation method thereof.
Background
The rectal cancer is one of the clinical common digestive tract malignant tumors, and the abdominal-perineum combined rectal cancer radical operation (Miles operation for short) is the main method for treating the rectal cancer by the existing operation, can effectively improve the survival rate, but has large wound surface of perineum wound after operation, more secretion, easy infection, slow and difficult healing, and increases the pain and the economic burden of patients. Present traditional body surface hemostasis dressing is dry dressing like cotton gauze etc. and the ubiquitous performance of stanching fast is not good, and the wound dehydration is serious, easily glues even wound, and is poor to tissue fluid and blood imbibition performance, and wound healing time is long, appears secondary damage easily during the change, and the bacterium easily pierces through, and it is frequent to change, the big scheduling problem of work load of changing dressings. The other wet therapy for treating the incision is to clean the incision by using normal saline, currently, the foam silver dressing is applied to sterilize, resist infection and absorb seepage, and most of the dressings have good sterilization capability but poor seepage absorption at present.
Chitosan is a basic polysaccharide in nature, and is a primary derivative of chitin deacetylation. The chitosan has good antibacterial effect, and can inhibit the growth of common bacteria and fungi on wound surface. The chitosan wound dressing has good air permeability, and compared with the traditional wound dressing, the wound tissue can obtain enough oxygen partial pressure, so that the growth and the repair of epithelial tissues are facilitated, meanwhile, the excessive proliferation of fibroblasts can be inhibited, and the scar reaction is reduced. At present, chitosan-coated hemostatic sponges and hemostatic gauze are applied to emergency hemostasis and surgical operations. But chitosan itself is not able to absorb moisture.
Therefore, the dressing with the advantages of good antibacterial performance, efficient absorption of secretion, promotion of wound healing, easy removal and the like is developed, and the dressing has important significance for clinical application of the dressing in healing of perineal wounds after Miles operation of rectal cancer.
Disclosure of Invention
In view of the above, the invention aims to provide a chitosan/sodium alginate interwoven dressing with moisture absorption and bacteriostasis functions and a preparation method thereof.
In order to solve the technical problems, the invention provides a preparation method of a moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing, which comprises the following steps:
1) adding chitosan into the acetic acid solution to prepare a chitosan solution;
2) freezing and drying the chitosan solution obtained in the step 1) to obtain a chitosan scaffold;
3) soaking the chitosan scaffold obtained in the step 2) in an alkaline solution, and then washing and freeze-drying to obtain a chitosan foam scaffold material;
4) adding sodium alginate into water to prepare a sodium alginate aqueous solution, spreading the sodium alginate aqueous solution on the surface of the chitosan foam-shaped support material prepared in the step 3), standing for 12-24 h, and freeze-drying to obtain a chitosan/sodium alginate composite;
5) and (3) immersing the chitosan/sodium alginate compound obtained in the step 4) into a calcium chloride solution for crosslinking reaction, and freeze-drying to obtain the chitosan/sodium alginate interwoven dressing.
Preferably, the mass ratio of the chitosan to the sodium alginate is 1: 0.5-1.
Preferably, the concentration of the chitosan solution in the step 1) is 0.03-0.06 g/mL.
Preferably, the temperature of the freeze drying in the step 2) is-20 to 0 ℃.
Preferably, the alkaline solution in step 3) is a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, the concentration of the alkaline solution in the step 3) is 0.02-0.05 g/mL, and the freeze-drying temperature is-20-0 ℃.
Preferably, the thickness of the chitosan foam-shaped bracket material is 5-10 mm.
Preferably, the concentration of the sodium alginate aqueous solution in the step 4) is 0.02-0.03 g/mL, and the freeze-drying temperature is-20-0 ℃.
Preferably, the concentration of the calcium chloride solution in the step 5) is 0.02-0.05 g/mL, the time of the crosslinking reaction is 5-20 min, and the freeze-drying temperature is-20-0 ℃.
The invention also provides the moisture-absorbing bacteriostatic chitosan/sodium alginate interwoven dressing prepared by the preparation method.
Compared with the prior art, the chitosan/sodium alginate interwoven dressing is prepared by preparing a chitosan bracket from a chitosan solution, soaking the chitosan bracket in an alkaline solution to obtain a chitosan foam bracket material, spreading a sodium alginate aqueous solution on the surface of the chitosan foam bracket material to obtain a chitosan/sodium alginate composite, soaking the chitosan/sodium alginate composite in a calcium chloride solution for crosslinking reaction, and freeze-drying. The chitosan and the sodium alginate both have good biocompatibility, the chitosan and the sodium alginate are interwoven together through physical action by adopting a freeze-drying support mode, chemical modification and chemical reaction of biological materials are avoided, the biocompatibility of the materials is ensured, the operation is simple, the reaction condition is mild, the prepared dressing has a good antibacterial effect, a good absorption function on secretion of wounds is realized, the healing of the wounds is facilitated, the whole dressing is easy to remove due to the support structure, the adhesion of the wounds is not easy, and the application value of the dressing for nursing the perineum after the Miles colorectal cancer operation is high.
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Fig. 1 is a scanning electron microscope image of the moisture-absorbing bacteriostatic chitosan/sodium alginate interwoven dressing provided by embodiment 1 of the invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
The invention provides a preparation method of a moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing, which comprises the following steps:
1) adding chitosan into the acetic acid solution to prepare a chitosan solution;
2) freezing and drying the chitosan solution obtained in the step 1) to obtain a chitosan scaffold;
3) soaking the chitosan scaffold obtained in the step 2) in an alkaline solution, and then washing and freeze-drying to obtain a chitosan foam scaffold material;
4) adding sodium alginate into water to prepare a sodium alginate aqueous solution, spreading the sodium alginate aqueous solution on the surface of the chitosan foam-shaped support material prepared in the step 3), standing for 12-24 h, and freeze-drying to obtain a chitosan/sodium alginate composite;
5) and (3) immersing the chitosan/sodium alginate compound obtained in the step 4) into a calcium chloride solution for crosslinking reaction, and freeze-drying to obtain the chitosan/sodium alginate interwoven dressing.
Specifically, the chitosan is added into the acetic acid solution to prepare the chitosan solution. Chitosan is a basic polysaccharide in nature, is a primary derivative of chitin deacetylation, and has good biocompatibility. The chitosan has good antibacterial effect, and can inhibit the growth of common bacteria and fungi on wound surface. Since chitosan can only be dissolved in an acidic solution, chitosan is first dissolved in an acetic acid solution to obtain a chitosan solution. In order to disperse more uniformly, the invention adopts chitosan powder. The source of chitosan powder in the present invention is not limited, and may be a commercially available product known to those skilled in the art, and the concentration of the acetic acid solution in the present invention should not be too high, and is preferably 0.02g/mL of acetic acid solution. The concentration of the chitosan solution prepared by the method is preferably 0.03-0.06 g/mL, and more preferably 0.05 g/mL.
And after obtaining the chitosan solution, freezing and drying the chitosan solution to obtain the chitosan scaffold. Specifically, the chitosan solution can be added into a mold for freeze drying, the freeze drying temperature is preferably-20-0 ℃, more preferably-20 ℃, and the freeze drying time is preferably 3 hours.
And after the chitosan scaffold is obtained, soaking the chitosan scaffold in an alkaline solution, and then washing and freeze-drying to obtain the chitosan foam scaffold material. The alkaline solution in the present invention is preferably a sodium hydroxide solution or a potassium hydroxide solution, and the purpose is to neutralize the acetic acid solution for dissolving chitosan with the alkaline solution. The concentration of the alkaline solution is preferably 0.02-0.05 g/mL, and more preferably 0.05 g/mL. After neutralization, the chitosan foam stent material is soaked in pure water and washed, the excessive sodium hydroxide is dissolved and diffused, the water is changed for several times, the pH value of the soaked water is measured to be 7, and the condition that the excessive alkali does not exist is shown. And then freeze-drying, wherein the freeze-drying temperature is preferably-20-0 ℃, more preferably-20 ℃, and the freeze-drying time is preferably 3 h. The thickness of the chitosan foam-shaped bracket material prepared by the invention is preferably 5-10 mm.
And (3) after the chitosan foam-shaped support material is obtained, adding sodium alginate into water to prepare a sodium alginate aqueous solution, spreading the sodium alginate aqueous solution on the surface of the chitosan foam-shaped support material prepared in the step (3), standing for 12-24 h, and freeze-drying to obtain the chitosan/sodium alginate composite. The source of sodium alginate in the present invention is not limited and may be commercially available as is well known to those skilled in the art. The sodium alginate provided by the invention has high swelling property, and can effectively absorb secretion.
In the invention, the concentration of the prepared sodium alginate solution is preferably 0.02-0.03 g/mL. The mass ratio of the sodium alginate to the chitosan is preferably 1: 0.5-1. And after obtaining the sodium alginate solution, spreading the sodium alginate solution on the surface of the chitosan foam-shaped scaffold material, and standing for 12-24 hours until the sodium alginate solution permeates into the porous structure of the chitosan scaffold. The standing time is more preferably 12 hours. The freeze-drying temperature is-20-0 ℃, the freeze-drying time is preferably-20 ℃, and the freeze-drying time is preferably 3 hours.
And after the chitosan/sodium alginate compound is obtained, immersing the chitosan/sodium alginate compound into a calcium chloride solution for crosslinking reaction, and freeze-drying to obtain the chitosan/sodium alginate interwoven dressing. In the invention, the concentration of the calcium chloride solution is preferably 0.02-0.05 g/mL, more preferably 0.03g/mL, and the time of the crosslinking reaction is preferably 5-20 min, more preferably 10 min. The freeze-drying temperature is preferably-20-0 ℃, more preferably-20 ℃, and the freeze-drying time is preferably 3 h.
Sodium alginate is a byproduct after extracting iodine and mannitol from brown algae such as kelp or gulfweed, and its molecules are connected by a (1 → 4) bond between beta-D-mannuronic acid (M) and alpha-L-guluronic acid (alpha-L-guluronic acid, G). The sodium alginate aqueous solution has high viscosity, can quickly form gel under extremely mild conditions, and has Ca2+Na on G unit when present+With Ca2+Ion exchange reaction occurs, and G units are stacked to form a cross-linked network structure, so that the hydrogel is formed. The gel forming condition of the sodium alginate is mild, and the inactivation of active substances such as sensitive medicines, proteins, cells, enzymes and the like can be avoided. The macromolecular structure of calcium alginate contains a large amount of hydrophilic functional groups such as hydroxyl, carboxyl and the like, and the amorphous area in a cross-linked network structure (egg box structure) formed by calcium ion cross-linked sodium alginate is larger, and the swelling property is goodAnd thus has high water absorption performance.
The invention also provides the chitosan/sodium alginate interwoven dressing prepared by the preparation method.
For further understanding of the present invention, the following examples are provided to illustrate the preparation method of the chitosan/sodium alginate interwoven dressing for moisture absorption and bacteriostasis, and the scope of the present invention is not limited by the following examples.
Example 1
Adding chitosan powder into 0.02g/mL acetic acid aqueous solution, and stirring overnight at room temperature to prepare 0.05g/mL chitosan aqueous solution; adding 6mL of the chitosan aqueous solution into a mold, freezing at-20 ℃, and then freeze-drying by using a freeze dryer; soaking in 0.05g/mL sodium hydroxide solution for 3 hours to neutralize acetic acid, washing off excessive sodium hydroxide with pure water until pH is 7, freezing at-20 deg.C, and lyophilizing with a lyophilizer for 3h to obtain porous chitosan foam scaffold; adding sodium alginate powder into water to prepare 0.02g/mL sodium alginate aqueous solution; spreading 7.5mL of sodium alginate aqueous solution on the chitosan scaffold washed to be neutral and freeze-dried, standing for 12 hours until the sodium alginate solution permeates into the porous structure of the chitosan scaffold, freezing at-20 ℃, freeze-drying by using a freeze dryer, immersing in 0.03g/mL of calcium chloride solution, performing crosslinking reaction for 10min, freezing again at-20 ℃, and freeze-drying by using the freeze dryer to obtain the chitosan/sodium alginate interwoven dressing.
FIG. 1 is a scanning electron microscope image of the chitosan/sodium alginate interwoven dressing. As shown in figure 1, the whole dressing presents a loose and porous mechanism, and the structure is favorable for enhancing the moisture absorption performance of the whole dressing, and simultaneously, the chitosan and the sodium alginate are tightly combined with each other in an interweaving way through stronger physical action. Tests show that the bacteriostatic effect of the dressing reaches over 99 percent, and the dressing can absorb 20 grams of pure water per gram on average.
Example 2
Adding chitosan powder into 0.02g/mL acetic acid aqueous solution, and stirring overnight at room temperature to prepare 0.05g/mL chitosan aqueous solution; adding 3mL of the chitosan aqueous solution into a mold, freezing at-20 ℃, and then freeze-drying by using a freeze dryer; soaking in 0.05g/mL sodium hydroxide solution for 3 hours to neutralize acetic acid, washing off excessive sodium hydroxide with pure water until pH is 7, freezing at-20 deg.C, and lyophilizing with a lyophilizer for 3h to obtain porous chitosan foam scaffold; adding sodium alginate powder into water to prepare 0.03g/mL sodium alginate aqueous solution; spreading 5mL of sodium alginate aqueous solution on the chitosan scaffold washed to be neutral and freeze-dried, standing for 12 hours until the sodium alginate solution permeates into the porous structure of the chitosan scaffold, freezing at-20 ℃, then freeze-drying by using a freeze dryer, immersing in 0.03g/mL of calcium chloride solution for crosslinking for 10min, freezing again at-20 ℃, and freeze-drying by using the freeze dryer to prepare the chitosan/sodium alginate interwoven dressing.
Tests show that the bacteriostatic effect of the dressing reaches over 99 percent, and the dressing can absorb 26 grams of pure water per gram on average.
Comparative example 1
Adding chitosan powder into 0.02g/mL acetic acid aqueous solution, and stirring overnight at room temperature to prepare 0.05g/mL chitosan aqueous solution; adding 3mL of the chitosan aqueous solution into a mold, freezing at-20 ℃, and then freeze-drying by using a freeze dryer; and soaking in 0.05g/mL sodium hydroxide solution for 3 hours to neutralize acetic acid, washing off excessive sodium hydroxide with pure water until the pH value is 7, freezing at the temperature of-20 ℃, and freeze-drying for 3 hours by using a freeze dryer to prepare the loose and porous chitosan dressing.
Tests show that the bacteriostatic effect of the chitosan dressing reaches over 99 percent, but the water absorption performance of the chitosan dressing is poorer than that of the chitosan dressing in examples 1-3.
Comparative example 2
Dissolving sodium alginate powder in water to prepare 0.03g/mL sodium alginate aqueous solution; adding 5mL of sodium alginate aqueous solution into a mold, freezing at-20 ℃, freeze-drying by using a freeze dryer, immersing into 0.03g/mL of calcium chloride solution, crosslinking for 10min, freezing again at-20 ℃, and freeze-drying for 3h by using the freeze dryer to obtain the sodium alginate dressing.
Tests show that the sodium alginate dressing per gram can absorb 18 grams of pure water averagely, has better water absorption performance, but has poorer bacteriostatic effect than the dressing prepared in examples 1-3.
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of a moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing is characterized by comprising the following steps:
1) adding chitosan into the acetic acid solution to prepare a chitosan solution; the concentration of the chitosan solution is 0.03-0.06 g/mL;
2) freezing and drying the chitosan solution obtained in the step 1) to obtain a chitosan scaffold;
3) soaking the chitosan scaffold obtained in the step 2) in a sodium hydroxide solution for 3 hours, then washing away redundant sodium hydroxide with pure water until the pH value is 7, and freeze-drying to obtain a chitosan foam scaffold material; the concentration of the sodium hydroxide solution is 0.02-0.05 g/mL;
4) adding sodium alginate into water to prepare a sodium alginate aqueous solution, spreading the sodium alginate aqueous solution on the surface of the chitosan foam-shaped support material prepared in the step 3), standing for 12-24 h, and freeze-drying to obtain a chitosan/sodium alginate composite; the concentration of the sodium alginate aqueous solution is 0.02-0.03 g/mL;
5) immersing the chitosan/sodium alginate compound obtained in the step 4) into a calcium chloride solution for crosslinking reaction, and freeze-drying to obtain the chitosan/sodium alginate interwoven dressing; the concentration of the calcium chloride solution is 0.02-0.05 g/mL, and the time of the cross-linking reaction is 5-20 min.
2. The preparation method of the moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing as claimed in claim 1, wherein the mass ratio of the chitosan to the sodium alginate is 1: 0.5-1.
3. The preparation method of the moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing according to claim 1, wherein the temperature of the freeze drying in the step 2) is-20-0 ℃.
4. The preparation method of the moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing according to claim 1, wherein in the step 3), the freeze-drying temperature is-20-0 ℃.
5. The preparation method of the moisture-absorbing bacteriostatic chitosan/sodium alginate interwoven dressing as claimed in claim 1, wherein the thickness of the chitosan foamed scaffold material is 5-10 mm.
6. The preparation method of the moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing according to claim 1, wherein in the step 4), the freeze-drying temperature is-20-0 ℃.
7. The preparation method of the moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing according to claim 1, wherein in the step 5), the freeze-drying temperature is-20-0 ℃.
8. The moisture-absorbing and bacteriostatic chitosan/sodium alginate interwoven dressing prepared by the preparation method of any one of claims 1-7.
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| US5836970A (en) * | 1996-08-02 | 1998-11-17 | The Kendall Company | Hemostatic wound dressing |
| CN1380109A (en) * | 2002-04-17 | 2002-11-20 | 苗九昌 | Chitosan collagen and calcium alginate compounded spongy biological dressing and its preparation process |
| CN1810298A (en) * | 2006-01-17 | 2006-08-02 | 武汉理工大学 | Bacteriostatic porous polyelectrolyte material and its prepn process |
| CN106110383A (en) * | 2016-07-07 | 2016-11-16 | 浙江大学 | A kind of chitosan alginate dressing and freeze-drying process thereof |
| CN106110367A (en) * | 2016-07-29 | 2016-11-16 | 北京化工大学常州先进材料研究院 | Based on natural polymer MULTILAYER COMPOSITE medical dressing and preparation method thereof |
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| WO2009106642A1 (en) * | 2008-02-29 | 2009-09-03 | Coloplast A/S | Biosynthetic cartilaginous matrix and methods for their production |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5836970A (en) * | 1996-08-02 | 1998-11-17 | The Kendall Company | Hemostatic wound dressing |
| CN1380109A (en) * | 2002-04-17 | 2002-11-20 | 苗九昌 | Chitosan collagen and calcium alginate compounded spongy biological dressing and its preparation process |
| CN1810298A (en) * | 2006-01-17 | 2006-08-02 | 武汉理工大学 | Bacteriostatic porous polyelectrolyte material and its prepn process |
| CN106110383A (en) * | 2016-07-07 | 2016-11-16 | 浙江大学 | A kind of chitosan alginate dressing and freeze-drying process thereof |
| CN106110367A (en) * | 2016-07-29 | 2016-11-16 | 北京化工大学常州先进材料研究院 | Based on natural polymer MULTILAYER COMPOSITE medical dressing and preparation method thereof |
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