CN102286184A - Carboxymethyl chitosan/ polyvinyl alcohol porous composite material and preparation method thereof - Google Patents
Carboxymethyl chitosan/ polyvinyl alcohol porous composite material and preparation method thereof Download PDFInfo
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- CN102286184A CN102286184A CN201110170138A CN201110170138A CN102286184A CN 102286184 A CN102286184 A CN 102286184A CN 201110170138 A CN201110170138 A CN 201110170138A CN 201110170138 A CN201110170138 A CN 201110170138A CN 102286184 A CN102286184 A CN 102286184A
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Abstract
The invention relates to a carboxymethyl chitosan/ polyvinyl alcohol porous composite material, which comprises the following raw materials in percentage by weight: 4 to 22 percent of carboxymethyl chitosan, 10 to 30 percent of polyvinyl alcohol, 3 to 5 percent of acetic acid, 5 to 10 percent of inorganic acid, 5 to 10 percent of cross-linking agent, 1 to 5 percent of foaming agent, 0.5 to 2 percent of antibacterial agent, 1 to 5 percent of softening agent and the like. A preparation method for the composite material comprises the following steps of: stirring the polyvinyl alcohol till full dissolution, pouring the dissolved polyvinyl alcohol into the dissolved carboxymethyl chitosan, adding the inorganic acid, the cross-linking agent, the foaming agent, the softening agent and the antibacterial agent, heating the solution to the temperature of between 90 and 100 DEG C, pouring the solution into a die, continuously reacting the solution for 6 to 9 hours at the temperature of between 60 and 100 DEG C, cooling the product, and repeatedly washing the product by using distilled water. The prepared material has the characteristics of good biocompatibility, excellent antibacterial effect, strong solution absorption, biodegradability, good attachment to the skin and the like, is quick in hemostasis, antibacterial and anti-inflammatory, has the function of promoting wound healing, and is suitable for making various wound dressings.
Description
Technical field
The present invention relates to a kind of biomaterial for medical purpose, particularly a kind of cm-chitosan/polyvinyl alcohol with antisepsis and anti-inflammation function is composite porous and preparation method thereof.
Background technology
We know, cm-chitosan has excellent biological compatibility, antibiotic, hemostasis and promotes wound healing, biodegradability and with skin good excellent properties such as attaching are arranged.Cm-chitosan all has a wide range of applications in fields such as wound dressings, hemostatic material, tissue engineering bracket and drug release.But the cm-chitosan mechanical property is relatively poor.
And polyvinyl alcohol is water-soluble synthetic macromolecule, has very strong imbibition ability, simultaneously no leakage.Existing in the market by the various hemostatic materials of modified polyvinyl alcohol material preparation, the haemostatic effect excellence, but the antisepsis and anti-inflammation effect is relatively poor.At present, the report of cm-chitosan/polyvinyl alcohol composite material is less.
Existing hemostatic material or wound dressings also have inorganic antiseptic, as nano-Ag particles, Sulfadiazine Silver, nano zine oxide and nano cupric oxide excellent broad-spectrum sterilization performance are arranged all.Nanometer silver gellike and the dressing of nanometer silver class in the market all has sale.
Summary of the invention
Technical problem to be solved by this invention is the deficiency that overcomes above-mentioned existing hemostatic material or wound dressings, provide a kind of composition reasonable, processing and easy to use, it is composite porous and preparation method thereof to have a cm-chitosan/polyvinyl alcohol of antisepsis and anti-inflammation function.
The technical scheme that the present invention solves the problems of the technologies described above employing is: a kind of cm-chitosan/polyvinyl alcohol is composite porous, it is characterized in that: its raw material is formed and weight proportion is: cm-chitosan 4-22%, polyvinyl alcohol 10-30%, acetic acid 3-5%, mineral acid 5-10%, linking agent 5-10%, whipping agent 1-5%, antiseptic-germicide 0.5-2%, softening agent 1-5%, surplus is a distilled water.
The deacetylation of described cm-chitosan is 80-90%.
The alcoholysis degree of described polyvinyl alcohol is that the polymerization degree is 2000-3800 greater than 80%.
Described mineral acid is hydrochloric acid, sulfuric acid, phosphoric acid or their mixture of analytical pure level.
Described linking agent comprise formaldehyde, butyraldehyde, glutaraldehyde, poly aldehyde, epoxy chloropropane, citric acid,
At least a or their mixture in the borax.
The method that described whipping agent is sodium bicarbonate, yellow soda ash, lime carbonate, volatile salt, zinc powder, pressurized air, also can adopt mechanical stirring or mechanical stirring to combine with whipping agent.
Described antiseptic-germicide is an inorganic antiseptic, comprises nano-Ag particles, Sulfadiazine Silver, nano cupric oxide and nano zine oxide or their mixture.
Described softening agent is: polyoxyethylene, polyoxyethylene glycol, tensio-active agent tell literary composition 80, sorbitan monolaurate, polyoxyethylene 20 sorbitan monooleate, emulsification organosilicon wet goods one or more.
The composite porous preparation method of cm-chitosan/polyvinyl alcohol with antisepsis and anti-inflammation function of the present invention is as follows:
(1) cm-chitosan is put into inorganic acid solution, under the temperature of 20-50oC, be stirred to dissolving fully;
(2) polyvinyl alcohol is put into 20-50 ℃ water complete swelling, under churned mechanically effect, be warming up to 80-90 ℃ until dissolving fully;
(3) solution with step (1) and the preparation of (2) step mixes, and under the stirring of machinery, adds mineral acid, whipping agent, softening agent and antiseptic-germicide, continues reaction 6-9 hours between 60-100 ℃, is cooled to room temperature then;
(4) product that step (3) is obtained with distilled water flushing repeatedly;
(5) the product excision forming that step (4) is obtained is prepared into required wound dressings or hemostatic material.
The present invention is because employing cm-chitosan and polyvinyl alcohol are compound, improve the intensity of cm-chitosan by polyvinyl alcohol, against existing technologies, the present invention has following effect: matrix material provided by the invention has the strong but no leakage of good biocompatibility, antibacterial effect excellence, imbibition ability, biodegradable and has characteristics such as good attaching with skin, preparation technology is simple, cost is low, environmental friendliness, suitability for industrialized production simultaneously, can be applicable to do various wound dressingss.
Embodiment
The invention will be further described below by specific embodiment.
A kind of cm-chitosan/polyvinyl alcohol is composite porous, and its raw material is formed and weight proportion is: cm-chitosan 4-22%, polyvinyl alcohol 10-30%, acetic acid 3-5%, mineral acid 5-10%, linking agent 5-10%, whipping agent 1-5%, antiseptic-germicide 0.5-2%, softening agent 1-5%, surplus is for steaming
Heat up in a steamer water.
The deacetylation of described cm-chitosan is 80-90%.The alcoholysis degree of described polyvinyl alcohol is that the polymerization degree is 2000-3800 greater than 80%.Described mineral acid is hydrochloric acid, sulfuric acid, phosphoric acid or their mixture of analytical pure level.Described linking agent comprises at least a or their mixture in formaldehyde, butyraldehyde, glutaraldehyde, poly aldehyde, epoxy chloropropane, citric acid, the borax.The method that described whipping agent is sodium bicarbonate, yellow soda ash, lime carbonate, volatile salt, zinc powder, pressurized air, also can adopt mechanical stirring or mechanical stirring to combine with whipping agent.Described antiseptic-germicide is an inorganic antiseptic, comprises nano-Ag particles, Sulfadiazine Silver, nano cupric oxide and nano zine oxide or their mixture.Described softening agent is: polyoxyethylene, polyoxyethylene glycol, tensio-active agent tell literary composition 80, sorbitan monolaurate, polyoxyethylene 20 sorbitan monooleate, emulsification organosilicon wet goods one or more.
Embodiment 1
Raw material is formed and weight proportion: cm-chitosan 10%, and polyvinyl alcohol 20%, acetic acid 3%, solubility is 37% hydrochloric acid 5%, formaldehyde 5%, sodium bicarbonate 12%, nanometer silver 0.4%, polyoxyethylene 1%, all the other are distilled water.
Cm-chitosan is put into the container that aqueous acetic acid is housed mix, under 20-50 ℃ temperature, be stirred to dissolving fully; The water of polyvinyl alcohol being put into 20-50 ℃ is poured a certain amount of hydrochloric acid into then to molten fully, is warming up to 60-100 ℃, under churned mechanically effect until dissolving fully; Be poured in the container that fills the carboxymethyl chitosan sugar aqueous solution, stir, be warming up to 60-100 ℃, formaldehyde, sodium bicarbonate, nano-Ag particles, polyoxyethylene are put into the above mixed solution container of Sheng, under mechanical stirring, feed the pressurized air of low pressure, continue reaction 6h at 60-100 ℃, be cooled to room temperature, with distilled water repetitive scrubbing, vacuum-drying.Product is cut into corresponding shape, prepare required sample.
Embodiment 2
Raw material is formed and weight proportion: cm-chitosan 15%, and polyvinyl alcohol 25%, acetic acid 3%, solubility is 37% hydrochloric acid 5%, glutaraldehyde 8%, whipping agent 2%, antiseptic-germicide 0.5%, softening agent 2%, all the other are distilled water.
Cm-chitosan is put into the container that aqueous acetic acid is housed mix, under 20-50 ℃ temperature, be stirred to dissolving fully; The water of polyvinyl alcohol being put into 20-50 ℃ falls then to molten fully
Go into a certain amount of hydrochloric acid, be warming up to 60-100 ℃, under churned mechanically effect until fully the dissolving; Be poured in the container that fills the carboxymethyl chitosan sugar aqueous solution, stir, be warming up to 60-100 ℃, glutaraldehyde, bicarbonate of ammonia, nano-Ag particles, emulsification organic silicone oil are put into the above mixed solution container of Sheng, under mechanical stirring, at 60-100 ℃ of continuation reaction 6h, be cooled to room temperature, with distilled water repetitive scrubbing, vacuum-drying.Product is cut into corresponding shape, prepare required sample.
Embodiment 3
Raw material mass mixture ratio: cm-chitosan 22%, polyvinyl alcohol 30%, acetic acid 3%.Sulfuric acid 10%, Paraformaldehyde 96 5%, whipping agent 3%, antiseptic-germicide 0.8%, softening agent 3%, all the other are distilled water.
Cm-chitosan is put into the container that aqueous acetic acid is housed mix, under 20-50 ℃ temperature, be stirred to dissolving fully; The water of polyvinyl alcohol being put into 20-50 ℃ is poured a certain amount of sulfuric acid into then to molten fully, is warming up to 60-100 ℃, under churned mechanically effect until dissolving fully; Be poured in the container that fills the carboxymethyl chitosan sugar aqueous solution, stir, be warming up to 60-100 ℃, glutaraldehyde, bicarbonate of ammonia and Sulfadiazine Silver particle, emulsification organic silicone oil are put into the above mixed solution container of Sheng, under mechanical stirring, at 60-100 ℃ of continuation reaction 6h, be cooled to room temperature, with distilled water repetitive scrubbing, vacuum-drying.Product is cut into corresponding shape, prepare required sample.
Embodiment 4
Raw material mass mixture ratio: cm-chitosan 4%, polyvinyl alcohol 20%, acetic acid 5%, solubility is 37% hydrochloric acid 10%, citric acid 10%, whipping agent 5%, antiseptic-germicide 0.8%, softening agent 4%, all the other are distilled water.
Cm-chitosan is put into the container that aqueous acetic acid is housed mix, under 20-50 ℃ temperature, be stirred to dissolving fully; The water of polyvinyl alcohol being put into 20-50 ℃ is poured a certain amount of hydrochloric acid into then to molten fully, is warming up to 60-100 ℃, under churned mechanically effect until dissolving fully; Be poured in the container that fills the carboxymethyl chitosan sugar aqueous solution, stir, be warming up to 60-100 ℃, citric acid, yellow soda ash and nano granular of zinc oxide, Sodium dodecylbenzene sulfonate are put into the above mixed solution container of Sheng, under mechanical stirring, at 60-100 ℃ of continuation reaction 6h, be cooled to room temperature, with distilled water repetitive scrubbing, vacuum-drying.Product is cut into corresponding shape, prepare required sample.
Embodiment 5
Raw material mass mixture ratio: cm-chitosan 20%, polyvinyl alcohol 20%, acetic acid 4%, solubility is
37% hydrochloric acid 10%, butyraldehyde 7%, whipping agent 2%, antiseptic-germicide 1%, softening agent 2.5%, all the other are distilled water.
Cm-chitosan is put into the container that aqueous acetic acid is housed mix, under 20-50 ℃ temperature, be stirred to dissolving fully; The water of polyvinyl alcohol being put into 20-50 ℃ is poured a certain amount of hydrochloric acid into then to molten fully, is warming up to 60-100 ℃, under churned mechanically effect until dissolving fully; Be poured in the container that fills the carboxymethyl chitosan sugar aqueous solution, stir, be warming up to 60-100 ℃, butyraldehyde, bicarbonate of ammonia and nano-Ag particles, emulsification organic silicone oil are put into the above mixed solution container of Sheng, under mechanical stirring, at 60-100 ℃ of continuation reaction 6h, be cooled to room temperature, with distilled water repetitive scrubbing, vacuum-drying.Product is cut into corresponding shape, prepare required sample.
Claims (9)
1. a cm-chitosan/polyvinyl alcohol is composite porous, it is characterized in that: its raw material is formed and weight proportion is: cm-chitosan 4-22%, polyvinyl alcohol 10-30%, acetic acid 3-5%, mineral acid 5-10%, linking agent 5-10%, whipping agent 1-5%, antiseptic-germicide 0.5-2%, softening agent 1-5%, surplus is a distilled water.
2. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: the deacetylation of cm-chitosan is 80-90%.
3. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: the alcoholysis degree of polyvinyl alcohol is that the polymerization degree is 1000-3800 greater than 80%.
4. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: described acid solution is hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid or their mixture of analytical pure level.
5. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: described linking agent is at least a or their mixture in formaldehyde, butyraldehyde, glutaraldehyde, poly aldehyde, epoxy chloropropane, citric acid, the borax.
6. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: described whipping agent is sodium bicarbonate, yellow soda ash, lime carbonate, volatile salt, zinc powder, pressurized air.
7. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: described antiseptic-germicide is an inorganic antiseptic.
8. cm-chitosan/polyvinyl alcohol according to claim 1 is composite porous, it is characterized in that: softening agent is that polyoxyethylene, polyoxyethylene glycol, tensio-active agent are told one or more of literary composition 80, sorbitan monolaurate, polyoxyethylene 20 sorbitan monooleate, emulsification organic silicone oil.
9. composite porous preparation method of the described cm-chitosan/polyvinyl alcohol of claim 1 is characterized in that:
(1) cm-chitosan is put into inorganic acid solution, under the temperature of 20-50oC, be stirred to dissolving fully;
(2) polyvinyl alcohol is put into 20-50 ℃ water complete swelling, under churned mechanically effect, be warming up to 80-90 ℃ until dissolving fully;
(3) solution with step (1) and the preparation of (2) step mixes, under the stirring of machinery,
Add mineral acid, whipping agent, softening agent and antiseptic-germicide, between 60-100 ℃, continue reaction 6-9 hours, be cooled to room temperature then;
(4) product that step (3) is obtained with distilled water flushing repeatedly;
(5) the product excision forming that step (4) is obtained is prepared into required wound dressings or hemostatic material.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007334A (en) * | 2012-12-24 | 2013-04-03 | 南通大学 | Liquid wound repairing film and preparation method thereof |
| CN103316377A (en) * | 2013-06-27 | 2013-09-25 | 华南理工大学 | Beta-cyclodextrin/carboxymethyl chitosan medical dressing and preparation method thereof |
| CN104258451A (en) * | 2014-05-19 | 2015-01-07 | 山东省医疗器械研究所 | Grafted chitosan hemostatic dressing with three-dimensional multi-network structure and preparation method of grafted chitosan hemostatic dressing |
| WO2015187103A1 (en) * | 2014-05-21 | 2015-12-10 | Punyanitya Sittiporn | Surgical hemostatic based rice starch |
| CN105251034A (en) * | 2015-11-11 | 2016-01-20 | 中国人民解放军第四军医大学 | Novel self-expanding composite material with hemostatic and anti-infectious effects and preparation method |
| CN106344951A (en) * | 2016-07-26 | 2017-01-25 | 青岛琛蓝海洋生物工程有限公司 | Hemostatic anti-adhesion bio-membrane and preparation method thereof |
| CN108498851A (en) * | 2018-04-19 | 2018-09-07 | 江苏理工学院 | A kind of hydrogel material and preparation method thereof |
| CN110201216A (en) * | 2019-07-24 | 2019-09-06 | 中国人民解放军陆军军医大学第二附属医院 | One kind is for through and through wound rapid hemostatic material and preparation method thereof |
| CN111744054A (en) * | 2020-07-20 | 2020-10-09 | 哈尔滨乾佰纳生物药业有限公司 | Antibacterial wound surface dressing capable of promoting healing and preparation method thereof |
| CN115624645A (en) * | 2022-11-05 | 2023-01-20 | 河南驼人贝斯特医疗器械有限公司 | Polyvinyl alcohol foam and preparation method thereof |
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2011
- 2011-06-23 CN CN201110170138A patent/CN102286184A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103007334B (en) * | 2012-12-24 | 2014-11-19 | 南通大学 | Liquid wound repairing film and preparation method thereof |
| CN103007334A (en) * | 2012-12-24 | 2013-04-03 | 南通大学 | Liquid wound repairing film and preparation method thereof |
| CN103316377A (en) * | 2013-06-27 | 2013-09-25 | 华南理工大学 | Beta-cyclodextrin/carboxymethyl chitosan medical dressing and preparation method thereof |
| CN104258451A (en) * | 2014-05-19 | 2015-01-07 | 山东省医疗器械研究所 | Grafted chitosan hemostatic dressing with three-dimensional multi-network structure and preparation method of grafted chitosan hemostatic dressing |
| WO2015187103A1 (en) * | 2014-05-21 | 2015-12-10 | Punyanitya Sittiporn | Surgical hemostatic based rice starch |
| CN105251034B (en) * | 2015-11-11 | 2019-03-01 | 中国人民解放军第四军医大学 | It is a kind of hemostasis, anti-infectious surface of a wound composite material |
| CN105251034A (en) * | 2015-11-11 | 2016-01-20 | 中国人民解放军第四军医大学 | Novel self-expanding composite material with hemostatic and anti-infectious effects and preparation method |
| CN106344951A (en) * | 2016-07-26 | 2017-01-25 | 青岛琛蓝海洋生物工程有限公司 | Hemostatic anti-adhesion bio-membrane and preparation method thereof |
| CN106344951B (en) * | 2016-07-26 | 2019-04-19 | 青岛琛蓝海洋生物工程有限公司 | A kind of bleeding stopping and adherence preventing biomembrane and preparation method thereof |
| CN108498851A (en) * | 2018-04-19 | 2018-09-07 | 江苏理工学院 | A kind of hydrogel material and preparation method thereof |
| CN110201216A (en) * | 2019-07-24 | 2019-09-06 | 中国人民解放军陆军军医大学第二附属医院 | One kind is for through and through wound rapid hemostatic material and preparation method thereof |
| CN111744054A (en) * | 2020-07-20 | 2020-10-09 | 哈尔滨乾佰纳生物药业有限公司 | Antibacterial wound surface dressing capable of promoting healing and preparation method thereof |
| CN111744054B (en) * | 2020-07-20 | 2021-05-25 | 哈尔滨乾佰纳生物药业有限公司 | Antibacterial wound surface dressing capable of promoting healing and preparation method thereof |
| CN115624645A (en) * | 2022-11-05 | 2023-01-20 | 河南驼人贝斯特医疗器械有限公司 | Polyvinyl alcohol foam and preparation method thereof |
| CN115624645B (en) * | 2022-11-05 | 2024-02-27 | 河南驼人贝斯特医疗器械有限公司 | Polyvinyl alcohol foam and preparation method thereof |
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