CN109200325B - Preparation method of self-adhesive wound dressing - Google Patents
Preparation method of self-adhesive wound dressing Download PDFInfo
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- CN109200325B CN109200325B CN201811069601.2A CN201811069601A CN109200325B CN 109200325 B CN109200325 B CN 109200325B CN 201811069601 A CN201811069601 A CN 201811069601A CN 109200325 B CN109200325 B CN 109200325B
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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
- A61L15/22—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
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/18—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing inorganic materials
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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
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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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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- 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
- A61L15/46—Deodorants or malodour counteractants, e.g. to inhibit the formation of ammonia or bacteria
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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
- A61L15/58—Adhesives
Abstract
The invention discloses a preparation method of a self-adhesive wound dressing, which comprises the following steps: dispersing a visible light catalytic nano antibacterial material and a block polymer consisting of a nonpolar chain segment and a polar chain segment into a mixed solvent consisting of a nonpolar solvent and a polar solvent to prepare a composite solution; coating the composite solution on a release film, and drying to obtain an antibacterial moisture permeable layer; coating the pressure-sensitive adhesive on the antibacterial moisture-permeable layer, and drying to form a self-adhesive antibacterial moisture-permeable layer; and finally, fixing the seepage absorption material on the self-adhesive antibacterial moisture-permeable layer to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture. The wound dressing prepared by the invention has extremely high moisture permeability and long-acting antibacterial performance, and effectively avoids wound infection; can absorb wound exudate, maintain the moist environment of the wound surface, promote the wound healing and avoid the formation of scars; can be directly adhered to the surface of skin, is simple and convenient to use, and has small irritation to the skin.
Description
Technical Field
The invention relates to the technical field of wound surface antibacterial isolation materials, in particular to a preparation method of a self-adhesive wound dressing.
Background
The ideal wound dressing has the functions of isolating wound, blocking bacteria, controlling wound seepage, promoting healing, etc. With the progress of science and technology, the wound dressing is also developed from the traditional natural gauze to products such as polymer film dressing, seepage absorption type dressing, bioactive dressing and the like, and the diversity requirements of different types and different stages of wounds are met.
The theory of wet healing holds that the moist environment of the wound surface aids in the migration of epithelial cells, which can accelerate wound healing. The dressing with the function of absorbing the seepage has the advantages of absorbing purulent blood and seepage, maintaining moist environment of the wound surface and the like, is particularly suitable for wounds which are difficult to heal, such as moist wound surfaces, infected wound surfaces and the like, and is one of the development directions of wound dressing in the world.
The Chinese patent with the granted publication number of CN 1046324C (application number of 91109194.7) discloses an alginate fabric with high absorption capacity and a preparation method thereof, wherein each gram of the fabric can absorb 25 g of deionized water or 19 g of saline, and the alginate fabric is suitable for wound dressings and burn dressings.
The Chinese patent with the granted publication number of CN 100336564C (application number of 200510018241.X) discloses a chitosan hydrogel burn dressing, and the cross-linking density and the porosity of the chitosan hydrogel burn dressing are in a gradient structure from top to bottom. The burn dressing has good water absorption and biocompatibility, and excellent mechanical properties, and can be used for protecting various wound surfaces and treating burns at any time.
The Chinese patent with the granted publication number of CN 104491914B (application number of 201410826196.X) discloses a porous composite gel-nanofiber oxygen-permeable dressing and a preparation method thereof, wherein collagen nanofibers prepared by an electrostatic spinning method are crosslinked with two high molecular polysaccharides of chitosan and alginic acid to obtain composite gel, and then the composite gel is cooled, freeze-dried and dried to obtain a porous sponge-nanofiber double-layer composite material.
However, the wound dressing has no antibacterial effect, so that wound infection is easy to occur. Although the silver ion dressing has a good spectrum antibacterial effect, silver ions are easy to migrate to a wound surface, and the wound surface healing and wound surface pain are inhibited. Therefore, the novel wound dressing with the functions of antibiosis, water absorption, moisture permeation and oxygen permeation can better meet the special requirements of wound care in the field.
Disclosure of Invention
The invention provides a preparation method of self-adhesive wound dressing, and the prepared wound dressing has high moisture permeability and long-acting antibacterial property.
A method of preparing a self-adhesive wound dressing comprising the steps of:
(1) dispersing a block polymer consisting of a nonpolar chain segment and a polar chain segment into a mixed solvent consisting of a nonpolar solvent and a polar solvent to prepare a polymer solution;
(2) adding a visible light catalytic nano antibacterial material into the polymer solution prepared in the step (1) to prepare a composite solution;
(3) coating the composite solution prepared in the step (2) on a release film to form a composite solution wet film, and drying to obtain an antibacterial moisture permeable layer;
(4) coating the medical pressure-sensitive adhesive on the antibacterial moisture-permeable layer prepared in the step (3) to form a pressure-sensitive adhesive wet film, and drying to form a self-adhesive antibacterial moisture-permeable layer;
(5) and (3) fixing the seepage absorption material on the self-adhesive antibacterial moisture-permeable layer prepared in the step (4) to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture.
According to the invention, the wound dressing prepared by adopting the block polymer consisting of the nonpolar chain segment and the polar chain segment and the antibacterial moisture permeable layer consisting of the visible light catalytic nano antibacterial material has the functions of high-efficiency moisture permeable, continuous antibacterial, isolation protection and the like. The medical pressure-sensitive adhesive can effectively adhere the wound dressing to the skin. The exudate absorption material can absorb exudate and maintain the moist environment of the wound surface. The release film is used as a supporting material and can be peeled off after the dressing is adhered to the skin.
In the step (1), the block polymer composed of the nonpolar chain segment and the polar chain segment is dispersed in the solvent at-20 to 80 ℃, and further preferably, the block polymer composed of the nonpolar chain segment and the polar chain segment is dispersed in the solvent at 0 to 40 ℃.
The monomer forming the nonpolar segment of the block polymer is one or more (including two) of styrene-ethylene, styrene-butadiene, styrene-ethylene-butadiene segment, butadiene, propylene-butadiene, and ethylene-propylene. The molecular weight of the nonpolar chain segment is 800-200000 daltons.
The monomers forming the polar chain segment of the block polymer are one or more than two (including two) of maleic anhydride, fumaric acid, 4-vinyl benzene sulfonic acid and 4-vinyl aniline. The molecular weight of the polar chain segment is 500-2000 daltons.
Further preferably, the block polymer composed of the nonpolar segment and the polar segment is a copolymer composed of styrene-maleic anhydride, a copolymer composed of styrene-ethylene-butadiene and 4-vinylbenzenesulfonic acid, a block polymer composed of butadiene and fumaric acid, or a copolymer composed of styrene, butadiene and maleic anhydride. Among them, the block polymer composed of butadiene and fumaric acid has very excellent high water vapor permeability.
The preparation of the copolymer consisting of styrene-ethylene-butadiene and 4-vinyl benzene sulfonic acid comprises the following steps:
adding a styrene-ethylene-butadiene copolymer into 1, 2-dichloroethane in a reaction kettle at 5-15 ℃ under the protection of nitrogen, stirring until the styrene-ethylene-butadiene copolymer is dissolved, adding chlorosulfonic acid, stirring for reacting for 12-24 hours, adding ethanol for precipitation and washing, and drying to obtain the copolymer consisting of styrene-ethylene-butadiene and 4-vinyl benzene sulfonic acid.
More preferably, under the protection of nitrogen, 20 parts by weight of styrene-ethylene-butadiene copolymer is added into 80 parts by weight of 1, 2-dichloroethane in a reaction kettle at 10 ℃, stirred until dissolved, then 1 part by weight of chlorosulfonic acid is added, stirred and reacted for 18 hours, 200 parts by weight of ethanol is added for precipitation and washing, and drying is carried out, thus obtaining the copolymer consisting of styrene-ethylene-butadiene and 4-vinyl benzene sulfonic acid.
The preparation of the block polymer consisting of butadiene and fumaric acid comprises the following steps:
under the protection of nitrogen, adding liquid polybutadiene into 1, 2-dichloroethane in a reaction kettle at 50-70 ℃, stirring until the polybutadiene is dissolved, adding fumaric acid and azobisisobutyronitrile, stirring for reacting for 16-30 hours, adding ethanol for precipitation and washing, and drying to obtain a block polymer consisting of butadiene and fumaric acid;
more preferably, 16 parts by weight of liquid polybutadiene was added to 85 parts by weight of 1, 2-dichloroethane in a reaction vessel at 60 ℃ under nitrogen protection, and stirred until dissolved. Then adding 4 parts by weight of fumaric acid and 0.1 part by weight of azobisisobutyronitrile, stirring and reacting for 24 hours, adding 300 parts by weight of ethanol for precipitation and washing, and drying to obtain the block polymer consisting of butadiene and fumaric acid.
The preparation of the copolymer consisting of styrene, butadiene and maleic anhydride comprises the following steps:
adding a styrene-butadiene copolymer into 1, 2-dichloroethane in a reaction kettle at 70-90 ℃ under the protection of nitrogen, stirring until the styrene-butadiene copolymer is dissolved, adding maleic anhydride and azobisisobutyronitrile, stirring for reacting for 8-16 hours, adding ethanol for precipitation and washing, and drying to obtain a copolymer consisting of styrene, butadiene and maleic anhydride;
more preferably, under the protection of nitrogen, 10 parts by weight of styrene-butadiene copolymer (Yanshan petrochemical SBS 1401) is added into 90 parts by weight of 1, 2-dichloroethane in a reaction kettle at 80 ℃, stirred until dissolved, then 1 part by weight of maleic anhydride and 0.1 part by weight of azobisisobutyronitrile are added, stirred for reaction for 10 hours, 200 parts by weight of ethanol is added for precipitation and washing, and drying is carried out, thus obtaining the copolymer consisting of styrene, butadiene and maleic anhydride.
The mass percentage of the block polymer in the polymer solution is 4 to 20 percent, and more preferably 8 to 12 percent.
In the step (1), the mixed solvent consists of 20-80 vol% of a nonpolar solvent and 20-80 vol% of a polar solvent, more preferably, the solvent consists of 40-80 vol% of a nonpolar solvent and 20-60 vol% of a polar solvent, and most preferably, the solvent consists of 60-70 vol% of a nonpolar solvent and 30-40 vol% of a polar solvent.
The nonpolar solvent is one or more (including two) of n-heptane, n-hexane, cyclohexane and methylcyclohexane, and the polar solvent is one or more (including two) of ethanol, n-propanol, isopropanol, butanol, tetrahydrofuran, ethyl acetate and isopropyl acetate.
In the step (2), the visible light catalytic nano antibacterial material is one of anatase titanium dioxide and zinc oxide.
The particle size of the visible light catalytic nano antibacterial material is 20-150 nm, and preferably 60-120 nm.
The visible light catalytic nano antibacterial material contains one or more of elements such as carbon, nitrogen, tungsten, iron, gold, platinum, cerium, nickel, copper, vanadium and the like, and preferably elements such as nitrogen, tungsten, carbon and the like.
More preferably, the visible light catalytic nano antibacterial material is anatase type nano titanium dioxide containing nitrogen element, anatase type nano titanium dioxide containing tungsten element or anatase type nano titanium dioxide containing carbon element.
The mass percentage of other elements in the visible light catalytic nano antibacterial material is 0.5-5%, and preferably 0.5-3%.
The preparation of the anatase type nano titanium dioxide containing nitrogen element comprises the following steps:
mixing butyl titanate and absolute ethyl alcohol, adding mixed solution of nitric acid, deionized water and absolute ethyl alcohol in batches while stirring, continuously stirring to obtain light yellow sol, drying the light yellow sol, calcining for 1-3 h at 350-450 ℃ in nitrogen atmosphere, and grinding to obtain the anatase type nano titanium dioxide containing nitrogen.
More preferably, 10 parts by weight of butyl titanate and 90 parts by weight of absolute ethyl alcohol are mixed, mixed solution of 1.5 parts by weight of nitric acid, 1.5 parts by weight of deionized water and 8 parts by weight of absolute ethyl alcohol is added in batches under strong stirring, strong stirring is continued for 30min to obtain light yellow sol, the light yellow sol is dried for 12h at 75 ℃, then calcined for 2h at 400 ℃ under nitrogen atmosphere, and milling is carried out to obtain anatase type nano titanium dioxide containing nitrogen element.
The preparation of the anatase type nano titanium dioxide containing tungsten element comprises the following steps:
adding titanium sulfate and sodium tungstate into deionized water in a polytetrafluoroethylene reaction kettle, stirring until the titanium sulfate and the sodium tungstate are dissolved, then reacting for 8-16 h at 160-200 ℃, cooling, filtering, washing with absolute ethyl alcohol, and grinding to obtain anatase type nano titanium dioxide containing tungsten.
More preferably, 10 parts by weight of titanium sulfate and 5 parts by weight of sodium tungstate are added into 85 parts by weight of deionized water in a polytetrafluoroethylene reaction kettle, stirred until dissolved, then reacted at 180 ℃ for 12 hours, cooled, filtered, washed with absolute ethyl alcohol, and milled to obtain the anatase type nano titanium dioxide containing tungsten element.
The preparation of the anatase type nano titanium dioxide containing carbon element comprises the following steps:
under the protection of nitrogen, adding graphene oxide into deionized water, stirring uniformly, adding butyl titanate, stirring for 1-3 hours, adding ethanol for precipitation and washing, drying at 65-85 ℃ for 10-14 hours, calcining at 350-450 ℃ for 1-3 hours under the atmosphere of nitrogen, and grinding to obtain the anatase type nano titanium dioxide containing carbon elements.
Preferably, under the protection of nitrogen, 5 parts by weight of graphene oxide is added into 95 parts by weight of deionized water, the mixture is stirred uniformly, 10 parts by weight of butyl titanate is added, the mixture is stirred vigorously for 2 hours, 200 parts by weight of ethanol is added for precipitation and washing, the mixture is dried at 75 ℃ for 12 hours, then the mixture is calcined at 400 ℃ for 2 hours under the atmosphere of nitrogen, and the anatase type nanometer titanium dioxide containing carbon elements is obtained by grinding.
The mass percentage of the visible light catalytic nano antibacterial material in the composite solution is 0.05-1%, and preferably 0.05-0.4%.
In the step (3), the release film is one of a polyethylene release film and a polyethylene terephthalate release film, and is preferably a polyethylene terephthalate release film.
The thickness of the release film is 20-100 μm, preferably 25-40 μm.
The surface of the release film is coated with 0.1-0.2 g/m2The silicone oil of (1).
The thickness of the composite solution wet film is 100-400 microns, and preferably 200-300 microns.
The drying temperature is 40-60 ℃, and the drying is preferably 1-3 min at 40-60 ℃.
In the step (4), the pressure-sensitive adhesive is one of water-based polyacrylic acid pressure-sensitive adhesive and water-based polyurethane pressure-sensitive adhesive, and is preferably water-based polyacrylic acid pressure-sensitive adhesive.
The solid content of the pressure-sensitive adhesive is 20-60%, and preferably 40-50%.
The viscosity of the pressure-sensitive adhesive is 100-2000 cP, and preferably 200-800 cP.
The thickness of the pressure-sensitive adhesive wet film is 20-50 mu m, and preferably 30-40 mu m.
The drying temperature of the pressure-sensitive adhesive wet film is 60-90 ℃, preferably 70-80 ℃, and further preferably, the drying is carried out for 2-7 min at 60-80 ℃.
In the step (5), the liquid-permeable absorbing material is one of alginate non-woven fabric, chitosan non-woven fabric, polyurethane foam and polyvinyl alcohol foam, and preferably alginate non-woven fabric and chitosan non-woven fabric.
The seepage absorption amount of the seepage absorption material is 400-6000 g/m2。
The thickness of the seepage absorption material is 0.5-3 mm.
The prepared wound dressing has the functions of antibiosis, water absorption, moisture permeation, oxygen permeation and the like.
Most preferably, a method of making a self-adhesive wound dressing comprises the steps of:
(1) under the protection of nitrogen, 16 parts by weight of liquid polybutadiene (Polyvest 110, Germany) is added into 85 parts by weight of 1, 2-dichloroethane in a reaction kettle at 60 ℃ and stirred until the liquid polybutadiene is dissolved; then adding 4 parts by weight of fumaric acid and 0.1 part by weight of azobisisobutyronitrile, stirring and reacting for 24 hours, adding 300 parts by weight of ethanol for precipitation and washing, and drying to obtain a block polymer consisting of butadiene and fumaric acid;
(2) adding 10 parts by weight of titanium sulfate and 5 parts by weight of sodium tungstate into 85 parts by weight of deionized water in a polytetrafluoroethylene reaction kettle, stirring until the titanium sulfate and the sodium tungstate are dissolved, then reacting for 12 hours at 180 ℃, cooling, filtering, washing with absolute ethyl alcohol, and grinding to obtain anatase type nano titanium dioxide containing tungsten;
(3) weighing 10 parts by weight of a copolymer consisting of butadiene and fumaric acid at 20 ℃ and dispersing the copolymer in a mixed solvent consisting of 70 volume percent of cyclohexane and 30 volume percent of isopropanol to prepare a polymer solution with the mass percent of 10 percent;
(4) weighing 0.05 part by weight of anatase type nano titanium dioxide containing tungsten element, and dispersing in the polymer solution obtained in the step (3) to obtain a composite solution;
(5) the surface of the release film is coated with 0.15g/m2Coating the composite solution prepared in the step (4) on a polyethylene terephthalate release film (DN 508, 30 mu m, southeast of Zhejiang province Co., Ltd.), wherein the thickness of the wet film of the composite solution is 200 mu m, and drying for 1min at 50 ℃ to obtain an antibacterial moisture permeable layer;
(6) coating a water-based acrylic pressure-sensitive adhesive (BLJ-569, Shanghai Baoli chemical industry Co., Ltd.) on the antibacterial moisture-permeable layer prepared in the step (5), wherein the thickness of the pressure-sensitive adhesive wet film is 40 mu m, and drying the pressure-sensitive adhesive wet film for 2min at 80 ℃ to form a self-adhesive antibacterial moisture-permeable layer;
(7) and (3) fixing a chitosan non-woven fabric (Kary medical supplies, Co., Ltd., Yangzhou city) on the self-adhesive antibacterial moisture-permeable layer prepared in the step (6) to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture.
The self-adhesive antibacterial moisture permeable layer prepared by the method has the water vapor transmission rate as high as 2845.8 g/(m)224h), the antibacterial performance is as high as 99.9%, the moisture permeability is extremely high, and the long-acting antibacterial performance is realized.
Compared with the prior art, the invention has the following advantages:
firstly, the wound dressing prepared by the invention has extremely high moisture permeability and long-acting antibacterial performance, and effectively avoids wound infection.
The wound dressing prepared by the invention can absorb wound exudate, maintain the moist environment of the wound, promote wound healing and avoid scar formation.
The wound dressing prepared by the invention can be directly adhered to the surface of skin, is simple and convenient to use and has small irritation to the skin.
Drawings
Fig. 1 is a schematic structural view of a self-adhesive wound dressing of the present invention.
Detailed Description
In order to make the objects, technical solutions, creation features and effects of the present invention clearer, the present invention is further explained below. The parts presented in the examples are parts by weight.
Example 1
(1) Under the protection of nitrogen, 20 parts of styrene-ethylene-butadiene copolymer (ba ling petrochemical, SEBS YH-503) is added into 80 parts of 1, 2-dichloroethane in a reaction kettle at 10 ℃, stirred until dissolved, then 1 part of chlorosulfonic acid is added, stirred and reacted for 18 hours, 200 parts of ethanol is added for precipitation and washing, and drying is carried out, thus obtaining the copolymer consisting of styrene-ethylene-butadiene and 4-vinyl benzene sulfonic acid.
(2) Mixing 10 parts by weight of butyl titanate and 90 parts by weight of absolute ethyl alcohol at the temperature of 20 ℃, adding a mixed solution of 1.5 parts by weight of nitric acid, 1.5 parts by weight of deionized water and 8 parts by weight of absolute ethyl alcohol in batches under strong stirring, and continuing to stir for 30min under strong stirring to obtain transparent pale yellow sol. Drying the sol at 75 ℃ for 12h, then calcining the sol at 400 ℃ for 2h in a nitrogen atmosphere, and grinding to obtain the anatase type nano titanium dioxide containing nitrogen.
(3) Weighing 10g of copolymer consisting of styrene-ethylene-butadiene and 4-vinyl benzene sulfonic acid at 20 ℃, and dispersing the copolymer in a mixed solvent consisting of 70 volume percent of cyclohexane and 30 volume percent of isopropanol to prepare a polymer solution with the mass percent of 8 percent;
(4) weighing 0.2g of anatase type nano titanium dioxide containing nitrogen element, and dispersing in the polymer solution obtained in the step (3) to obtain a composite solution;
(5) the surface of the release film is coated with 0.15g/m2And (3) coating the composite solution prepared in the step (4) on a polyethylene terephthalate release film (DN 508, 30 mu m, southeast of Zhejiang province Co., Ltd.), wherein the thickness of the wet film of the composite solution is 200 mu m, and drying at 50 ℃ for 1min to obtain the antibacterial moisture-permeable layer.
(6) Coating a water-based acrylic pressure-sensitive adhesive (BLJ-569, Shanghai Baoli chemical industry Co., Ltd.) on the antibacterial moisture-permeable layer prepared in the step (5), wherein the thickness of the pressure-sensitive adhesive wet film is 40 mu m, and drying the pressure-sensitive adhesive wet film for 2min at 80 ℃ to form a self-adhesive antibacterial moisture-permeable layer;
(7) fixing alginate nonwoven fabric (Kary medical products, Inc. of Yangzhou city) on the self-adhesive antibacterial moisture-permeable layer prepared in the step (6) to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture.
Example 2
(1) Under the protection of nitrogen, 16 parts by weight of liquid polybutadiene (Polyvest 110, Germany) was added to 85 parts by weight of 1, 2-dichloroethane in a reaction vessel at 60 ℃ and stirred until dissolved. Then adding 4 parts by weight of fumaric acid and 0.1 part by weight of azobisisobutyronitrile, stirring and reacting for 24 hours, adding 300 parts by weight of ethanol for precipitation and washing, and drying to obtain the block polymer consisting of butadiene and fumaric acid.
(2) Adding 10 parts by weight of titanium sulfate and 5 parts by weight of sodium tungstate into 85 parts by weight of deionized water in a polytetrafluoroethylene reaction kettle, stirring until the titanium sulfate and the sodium tungstate are dissolved, then reacting for 12 hours at 180 ℃, cooling, filtering, washing with absolute ethyl alcohol, and grinding to obtain the anatase type nano titanium dioxide containing tungsten element.
(3) Weighing 10 parts by weight of a copolymer consisting of butadiene and fumaric acid at 20 ℃ and dispersing the copolymer in a mixed solvent consisting of 70 volume percent of cyclohexane and 30 volume percent of isopropanol to prepare a polymer solution with the mass percent of 10 percent;
(4) weighing 0.05 part by weight of anatase type nano titanium dioxide containing tungsten element, and dispersing in the polymer solution obtained in the step (3) to obtain a composite solution;
(5) the surface of the release film is coated with 0.15g/m2And (3) coating the composite solution prepared in the step (4) on a polyethylene terephthalate release film (DN 508, 30 mu m, southeast of Zhejiang province Co., Ltd.), wherein the thickness of the wet film of the composite solution is 200 mu m, and drying at 50 ℃ for 1min to obtain the antibacterial moisture-permeable layer.
(6) Coating a water-based acrylic pressure-sensitive adhesive (BLJ-569, Shanghai Baoli chemical industry Co., Ltd.) on the antibacterial moisture-permeable layer prepared in the step (5), wherein the thickness of the pressure-sensitive adhesive wet film is 40 mu m, and drying the pressure-sensitive adhesive wet film for 2min at 80 ℃ to form a self-adhesive antibacterial moisture-permeable layer;
(7) and (3) fixing a chitosan non-woven fabric (Kary medical supplies, Co., Ltd., Yangzhou city) on the self-adhesive antibacterial moisture-permeable layer prepared in the step (6) to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture.
Example 3
(1) 10 parts by weight of a styrene-maleic anhydride copolymer (SMA-EF-80 from Cray Valley, USA) was dispersed in a mixed solvent composed of 60% by volume of methylcyclohexane and 40% by volume of isopropanol at 20 ℃ to prepare a polymer solution of 8% by mass.
(2) Under the protection of nitrogen, 5 parts by weight of graphene oxide is added into 95 parts by weight of deionized water, the mixture is stirred uniformly, 10 parts by weight of butyl titanate is added, the mixture is stirred vigorously for 2 hours, 200 parts by weight of ethanol is added for precipitation and washing, the mixture is dried at 75 ℃ for 12 hours, then the mixture is calcined at 400 ℃ for 2 hours under the atmosphere of nitrogen, and the anatase type nanometer titanium dioxide containing carbon elements is obtained by grinding.
(3) Weighing 0.5 part by weight of anatase type nano titanium dioxide containing carbon element, and dispersing in the polymer solution obtained in the step (1) to obtain a composite solution;
(4) the surface of the release film is coated with 0.15g/m2And (3) coating the composite solution prepared in the step (3) on a polyethylene terephthalate release film (DN 508, 40 mu m, southeast of Zhejiang province Co., Ltd.), wherein the thickness of the composite solution wet film is 300 mu m, and drying at 40 ℃ for 3min to obtain the antibacterial moisture-permeable layer.
(5) Coating a water-based acrylic pressure-sensitive adhesive (BLJ-569, Shanghai Baoli chemical industry Co., Ltd.) on the antibacterial moisture-permeable layer prepared in the step (4), wherein the thickness of the pressure-sensitive adhesive wet film is 30 mu m, and drying the pressure-sensitive adhesive wet film at 70 ℃ for 5min to form a self-adhesive antibacterial moisture-permeable layer;
(6) fixing alginate nonwoven fabric (Kary medical products, Inc. of Yangzhou city) on the self-adhesive antibacterial moisture-permeable layer prepared in the step (5) to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture.
Example 4
(1) In a reaction vessel at 80 ℃ under nitrogen protection, 10 parts by weight of a styrene-butadiene copolymer (Yanshan petrochemical SBS 1401) was added to 90 parts by weight of 1, 2-dichloroethane, and stirred until dissolved. Then adding 1 weight part of maleic anhydride and 0.1 weight part of azobisisobutyronitrile, stirring and reacting for 10 hours, adding 200 weight parts of ethanol for precipitation and washing, and drying to obtain the copolymer consisting of styrene, butadiene and maleic anhydride.
(2) Mixing 10 parts by weight of butyl titanate and 90 parts by weight of absolute ethyl alcohol at the temperature of 20 ℃, adding a mixed solution of 1.5 parts by weight of nitric acid, 1.5 parts by weight of deionized water and 8 parts by weight of absolute ethyl alcohol in batches under strong stirring, and continuing to stir for 30min under strong stirring to obtain transparent pale yellow sol. Drying the sol at 75 ℃ for 12h, then calcining the sol at 400 ℃ for 2h in a nitrogen atmosphere, and grinding to obtain the anatase type nano titanium dioxide containing nitrogen.
(3) Weighing 10 parts by weight of a copolymer consisting of styrene, butadiene and maleic anhydride at 20 ℃ and dispersing the copolymer in a mixed solvent consisting of 60% by volume of n-heptane and 40% by volume of n-propanol to prepare a polymer solution with the mass percent of 12%;
(4) weighing 0.2 part by weight of anatase type nano titanium dioxide containing nitrogen element, and dispersing in the polymer solution obtained in the step (3) to obtain a composite solution;
(5) the surface of the release film is coated with 0.15g/m2And (3) coating the composite solution prepared in the step (4) on a polyethylene terephthalate release film (DN 508, 25 mu m, southeast of Zhejiang province Co., Ltd.), wherein the thickness of the wet film of the composite solution is 300 mu m, and drying at 60 ℃ for 1min to obtain the antibacterial moisture-permeable layer.
(6) Coating a water-based acrylic pressure-sensitive adhesive (BLJ-569, Shanghai Baoli chemical industry Co., Ltd.) on the antibacterial moisture-permeable layer prepared in the step (5), wherein the thickness of the pressure-sensitive adhesive wet film is 40 mu m, and drying the pressure-sensitive adhesive wet film at 60 ℃ for 7min to form a self-adhesive antibacterial moisture-permeable layer;
(7) and (3) fixing a chitosan non-woven fabric (Kary medical supplies, Co., Ltd., Yangzhou city) on the self-adhesive antibacterial moisture-permeable layer prepared in the step (6) to obtain the self-adhesive wound dressing capable of absorbing seepage and resisting bacteria and moisture.
The water vapor permeability and antibacterial performance of examples 1-4 were tested according to the standards of section 2 of breathable film dressing water vapor permeability of YYT 0471.2-2004 test method for contact wound dressing, and methods and evaluations for testing the antibacterial performance of photocatalytic antibacterial materials and products under visible light irradiation of GBT 30706 and 2014, and the results are shown in the following tables.
TABLE 1 Water vapor Transmission and antimicrobial Properties of the examples
As shown in fig. 1, the absorbable, anti-bacterial and moisture-permeable self-adhesive wound dressing of the present invention comprises a release film 1, an anti-bacterial and moisture-permeable layer 2 disposed on the release film 1, a pressure-sensitive adhesive layer 3 disposed on the anti-bacterial and moisture-permeable layer 2, and a liquid-permeable absorbing material 4 disposed on the pressure-sensitive adhesive layer 3, wherein the anti-bacterial and moisture-permeable layer 2 and the pressure-sensitive adhesive layer 3 form a self-adhesive anti-bacterial and moisture-permeable layer.
The foregoing shows and describes the general principles and features of the present invention, together with the advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. A method of preparing a self-adhesive wound dressing, comprising the steps of:
(1) dispersing a block polymer consisting of a nonpolar chain segment and a polar chain segment into a mixed solvent consisting of a nonpolar solvent and a polar solvent to prepare a polymer solution;
the monomer for forming the nonpolar chain segment of the block polymer is one or more than two of styrene-ethylene, styrene-butadiene, styrene-ethylene-butadiene segment, butadiene, propylene-butadiene and ethylene-propylene;
the monomer for forming the polar chain segment of the block polymer is one or more than two of maleic anhydride, fumaric acid, 4-vinyl benzene sulfonic acid and 4-vinyl aniline;
the mixed solvent consists of 20-80% by volume of a nonpolar solvent and 20-80% by volume of a polar solvent;
the nonpolar solvent is one or more than two of n-heptane, n-hexane, cyclohexane and methylcyclohexane, and the polar solvent is one or more than two of ethanol, n-propanol, isopropanol, butanol, tetrahydrofuran, ethyl acetate and isopropyl acetate;
(2) adding a visible light catalytic nano antibacterial material into the polymer solution prepared in the step (1) to prepare a composite solution;
(3) coating the composite solution prepared in the step (2) on a release film to form a composite solution wet film, and drying to obtain an antibacterial moisture permeable layer;
(4) coating the medical pressure-sensitive adhesive on the antibacterial moisture-permeable layer prepared in the step (3) to form a pressure-sensitive adhesive wet film, and drying to form a self-adhesive antibacterial moisture-permeable layer;
(5) and (3) fixing the seepage absorption material on the self-adhesive antibacterial moisture permeable layer prepared in the step (4) to obtain the self-adhesive wound dressing.
2. The method for preparing a self-adhesive wound dressing according to claim 1, wherein in step (1), the block polymer composed of a nonpolar segment and a polar segment is a copolymer composed of styrene-ethylene-butadiene and 4-vinylbenzenesulfonic acid, a block polymer composed of butadiene and fumaric acid or a copolymer composed of styrene, butadiene and maleic anhydride;
the mass percentage of the block polymer in the polymer solution is 4-20%.
3. The method of preparing the self-adhesive wound dressing according to claim 2, wherein the preparation of the copolymer consisting of styrene-ethylene-butadiene and 4-vinylbenzenesulfonic acid comprises:
adding a styrene-ethylene-butadiene copolymer into 1, 2-dichloroethane in a reaction kettle at 5-15 ℃ under the protection of nitrogen, stirring until the styrene-ethylene-butadiene copolymer is dissolved, adding chlorosulfonic acid, stirring for reacting for 12-24 hours, adding ethanol for precipitation and washing, and drying to obtain a copolymer consisting of styrene-ethylene-butadiene and 4-vinyl benzene sulfonic acid;
the preparation of the block polymer consisting of butadiene and fumaric acid comprises the following steps:
under the protection of nitrogen, adding liquid polybutadiene into 1, 2-dichloroethane in a reaction kettle at the temperature of 50-70 ℃, stirring until the polybutadiene is dissolved, adding fumaric acid and azodiisobutyronitrile, stirring for reacting for 16-30 hours, adding ethanol for precipitation and washing, and drying to obtain a block polymer consisting of butadiene and fumaric acid;
the preparation of the copolymer consisting of styrene, butadiene and maleic anhydride comprises the following steps:
under the protection of nitrogen, adding a styrene-butadiene copolymer into 1, 2-dichloroethane in a reaction kettle at the temperature of 70-90 ℃, stirring until the styrene-butadiene copolymer is dissolved, adding maleic anhydride and azobisisobutyronitrile, stirring for reacting for 8-16 hours, adding ethanol for precipitating and washing, and drying to obtain the copolymer consisting of styrene, butadiene and maleic anhydride.
4. The method for preparing the self-adhesive wound dressing according to claim 1, wherein in the step (2), the visible light catalytic nano antibacterial material is one of anatase titanium dioxide and zinc oxide.
5. The method for preparing the self-adhesive wound dressing according to claim 1, wherein in the step (2), the visible light catalytic nano antibacterial material is anatase type nano titanium dioxide containing nitrogen element, anatase type nano titanium dioxide containing tungsten element or anatase type nano titanium dioxide containing carbon element.
6. The method of preparing the self-adhesive wound dressing according to claim 5, wherein the preparation of the nano anatase titanium dioxide containing nitrogen comprises:
mixing butyl titanate and absolute ethyl alcohol, adding a mixed solution of nitric acid, deionized water and absolute ethyl alcohol in batches under stirring, continuously stirring to obtain light yellow sol, drying the light yellow sol, calcining for 1-3 hours at 350-450 ℃ under a nitrogen atmosphere, and grinding to obtain anatase type nano titanium dioxide containing nitrogen;
the preparation of the anatase type nano titanium dioxide containing tungsten element comprises the following steps:
adding titanium sulfate and sodium tungstate into deionized water in a polytetrafluoroethylene reaction kettle, stirring until the titanium sulfate and the sodium tungstate are dissolved, then reacting for 8-16 h at 160-200 ℃, cooling, filtering, washing with absolute ethyl alcohol, and grinding to obtain anatase type nano titanium dioxide containing tungsten;
the preparation of the anatase type nano titanium dioxide containing carbon element comprises the following steps:
under the protection of nitrogen, adding graphene oxide into deionized water, stirring uniformly, adding butyl titanate, stirring for 1-3 hours, adding ethanol for precipitation and washing, drying at 65-85 ℃ for 10-14 hours, calcining at 350-450 ℃ for 1-3 hours under the atmosphere of nitrogen, and grinding to obtain the anatase type nano titanium dioxide containing carbon elements.
7. The method for preparing the self-adhesive wound dressing according to claim 1, wherein in the step (2), the mass percentage of the visible light catalytic nano antibacterial material in the composite solution is 0.05-1%.
8. The method for preparing the self-adhesive wound dressing according to claim 1, wherein in the step (3), the release film is one of a polyethylene release film and a polyethylene terephthalate release film;
the thickness of the composite solution wet film is 100-400 mu m;
the drying temperature is 40-60 ℃.
9. The method for preparing the self-adhesive wound dressing according to claim 1, wherein in the step (4), the pressure-sensitive adhesive is one of a water-based polyacrylic acid pressure-sensitive adhesive and a water-based polyurethane pressure-sensitive adhesive;
the thickness of the wet film of the pressure-sensitive adhesive is 20-50 mu m;
the drying temperature of the pressure-sensitive adhesive wet film is 60-90 ℃.
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| JP2003010306A (en) * | 2001-06-28 | 2003-01-14 | Nitto Denko Corp | Medical tacky adhesive tape or sheet |
| CN1638819A (en) * | 2001-07-03 | 2005-07-13 | 宝洁公司 | Film-forming compositions for protecting skin from body fluids and articles made therefrom |
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