CN1290582C - Biodegradable chitosan slow-release material - Google Patents
Biodegradable chitosan slow-release material Download PDFInfo
- Publication number
- CN1290582C CN1290582C CN 200310107977 CN200310107977A CN1290582C CN 1290582 C CN1290582 C CN 1290582C CN 200310107977 CN200310107977 CN 200310107977 CN 200310107977 A CN200310107977 A CN 200310107977A CN 1290582 C CN1290582 C CN 1290582C
- Authority
- CN
- China
- Prior art keywords
- chitosan
- starch
- present
- polyvinyl alcohol
- slow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a biodegradable chitosan slow-release material which belongs to the field biotechnology. The aim of the present invention is to overcome the defects of chitosan, the present invention provides a chitosan slow-release base material of simple process, rich source, stable performance, acid-alkali resistance and unique structure, and the present invention is suitable for a diffused type control release system. The present invention which takes the chitosan, polyvinyl alcohol and starch as raw materials is composed of work procedures of blending and crosslinking. A product presents a water solution form, which is favorable for environment protection. The present invention has the characteristics of simple process flow, universal device, easy operation, wide purpose, complete biodegradation, rich raw materials, no organic solvent, convenient generalization, easy industrial production realization, etc. The slow-release material of the present invention can be widely applied to the control release of active substances.
Description
Technical field
The present invention relates to a kind of biodegradable chitosan sustained-release material.
Background technology
Sustained release is active substance and base material (normally macromolecular material) to be combined make active substance pass through diffusion way within a certain period of time, be discharged into technology in the environment with a certain speed, it is significant in medical science, biology, agricultural, environmental protection and daily life, more and more causes people's extensive attention.Base material is the research focus always in control release technic, and people are seeking always that preparation is simple, stable performance, cheap, the base material that enriches in the source.Chitosan is a natural organic matter the abundantest on the earth---the product behind the chitin deacetylate is one of natural resources that do not make full use of, and quite similar with cellulose on its structure, the OH of C-2 position is by NH in the cellulose
2It after the replacement chitosan.Chitosan has been widely used in chemical industry, food, medicine and the agricultural.Aspect the exploitation Biodegradable material, chitosan has critical role, and it and cellulose or starch etc. all can form the material that can degrade fully.Because its good film property, gelation, degradability, biocompatibility, chitosan has been widely used in slow controlled-release technology, but owing to contain a large amount of hydrophilic groups, pure chitosan subject matter in actual applications is that bad mechanical property, the fragility of film is big, water-resistance difference and be not suitable for sour environment.Contain amino, hydroxyl on the chitosan main chain,, can improve structure, the performance of chitosan by chemical modification.Flexible polymer polyvinyl alcohol (PVA) is a kind of very unique water solublity polyhydroxy macromolecular material, and intermolecular force is big, has biodegradability and bioaffinity, and is nontoxic to human body, and it has favorable mechanical performance, oil resistant, the energy of anti-the dissolubility.Starch source is abundant, cheap, and all has the complete biodegradable ability in various environment, and its adding can reduce material cost.PVA, starch and chitosan have the good compatibility, by cross-linking agent between chitosan, PVA, starch molecule and intramolecular crosslinked action, can improve the mechanical performance of material, obtain acid resistance and thermostability preferably, and can improve the degradation time of material.Develop thus novel have unique texture and better flexible, that part keeps natural polymer physiologically active and can biodegradable film, macromolecule slow-release material such as gel.Purpose of the present invention is exactly the shortcoming that overcomes chitosan, provides that a kind of technology is simple, the source is abundant, the chitosan sustained-release base material of stable performance, acid and alkali-resistance, and it goes for diffused sustained release system.
Summary of the invention
The invention provides a kind of biodegradable chitosan sustained-release material, the primary raw material and the content of slow-release material are as follows:
Chitosan 0.97%
Starch 19.38%
Polyvinyl alcohol 2.42%
Glycerol 0.61%
Tween 80 0.13%
Formaldehyde 1.98%
Ammonium chloride 0.05%
Or
Chitosan 1.70%
Starch 48.70%
Polyvinyl alcohol 6.09%
Glycerol 1.22%
Biformyl 1.39%
Or
Chitosan 1.03%
Starch 12.02%
Polyvinyl alcohol 1.88%
Glycerol 0.43%
Glutaraldehyde 0.18%
Or
Chitosan 0.33%
Starch 33.00%
Polyvinyl alcohol 6.28%
Glycerol 1.01%
Tween 80 0.27%
Formaldehyde 2.10%
Ammonium chloride 0.10%
In reactor, be 2～5 with above-mentioned raw material at pH, temperature is under 75～100 ℃, keeps reaction 1～2 hour, promptly gets product;
Wherein: each components contents by weight percentage; Described deacetylating degree of chitosan is greater than 75%; The alcoholysis degree of described polyvinyl alcohol is 85～100%, the degree of polymerization is 1000～1700.
Optimal technical scheme is as follows:
Chitosan is dissolved in 50 ℃ 2% aqueous acetic acid, be mixed with 2～4% chitosan solution; With starch and water with the ratio of volume ratio 10/90 at 85 ℃ of following gelatinizing 30min, make starch gelatinization liquid; Chitosan solution, starch gelatinization liquid, polyvinyl alcohol, glycerol, Tween 80 are mixed by the described content of claim 1, at pH is 2～5, stirring is warming up to 90～100 ℃, make transparent glue, add formaldehyde, Biformyl or glutaraldehyde, keep reaction 1～1.5h, add a spot of ammonium chloride again, keep reaction 10～20min, make slow-release material.
The present invention has following characteristics:
(1) raw material is chitosan, PVA, starch, and the source is abundant, absolutely degraded.
(2) cheaper than pure chitosan material price, the excellent and acid and alkali resistance of mechanical performance, intensity height.
(3) adjust proportioning raw materials and can be fit to different purposes, product is an aqueous solution, helps environmental conservation.
(4) technological process is simple, and Device-General is easy to grasp and not with an organic solvent, is convenient to promote and realize suitability for industrialized production.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1: add 100 liter of 2% chitosan aqueous acetic acid, 80 kilograms of starch gelatinization liquid, 10 kilograms of PVA, 2 liters of glycerol, 0.5 liter of Tween 80,210 premium on currency in 500 liters of reactors, transfer PH to be about 3, heat temperature raising to 95 ℃ under stirring state, treat to add when solution becomes transparence 10 liters of formaldehyde, keep the temperature stirring reaction 1 hour, and added 0.2 kilogram of NH
4Cl continues to stir discharging 10 minutes.(this is solution-stabilized, atomization is better, can be used as the film coating liquid of granule or lamellar active substance.)
Embodiment 2: 175 liter of 4% chitosan aqueous acetic acid of adding, 200 kilograms of starch gelatinization liquid, 25 kilograms of PVA, 4 liters of glycerol, accent PH are about 3 in 500 liters of reactors, heat temperature raising to 95 ℃ under stirring state, treat to add when solution becomes transparence 5 liters of Biformyls, kept the temperature stirring reaction 1 hour, cooling.(add water-soluble actives, stir, liquid is applied in corrosion resistant plate or the dish, dry, section, broken or promptly get slow release product in the Squeezinggranulator pelletize.)
Embodiment 3: add 100 liter of 3% chitosan aqueous acetic acid, 5.5 kilograms of PVA, 35 kilograms of starch gelatinization liquid in 500 liters of reactors, 1 liter of glycerol, 150 premium on currency, transfer PH to be about 5, heat temperature raising to 95 ℃ under stirring state, treat to add when solution becomes transparence 0.5 liter of glutaraldehyde, keep the temperature stirring reaction 1 hour, and be cooled to room temperature.(add 0.5 kilogram of xanthan gum and stir, be prepared into kind of a clothing agent.Then 4 kilograms of soybean seed are mixed with the agent of 1 kilogram of kind clothing, room temperature is air-dry to get final product.)
Embodiment 4: add 50 liter of 2% chitosan aqueous acetic acid, 100 kilograms of starch gelatinization liquid, 19 kilograms of PVA, 2.5 liters of glycerol, 0.8 liter of Tween 80,130 premium on currency in 500 liters of reactors, transfer PH to be about 3, heat temperature raising to 95 ℃ under stirring state, treat to add when solution becomes transparence 8 liters of formaldehyde, keep the temperature stirring reaction 1 hour, and added 0.3 kilogram of NH
4Cl continues to stir 10 minutes.(this film can replace existing plastic sheeting for the decompression degassing, casting film-forming.)
Claims (2)
1, a kind of biodegradable chitosan sustained-release material is characterized in that, the primary raw material and the content of described slow-release material are as follows:
Chitosan 0.97%
Starch 19.38%
Polyvinyl alcohol 2.42%
Glycerol 0.61%
Tween 80 0.13%
Formaldehyde 1.98%
Ammonium chloride 0.05%
Or
Chitosan 1.70%
Starch 48.70%
Polyvinyl alcohol 6.09%
Glycerol 1.22%
Biformyl 1.39%
Or
Chitosan 1.03%
Starch 12.00%
Polyvinyl alcohol 1.88%
Glycerol 0.43%
Glutaraldehyde 0.18%
Or
Chitosan 0.33%
Starch 33.00%
Polyvinyl alcohol 6.28%
Glycerol 1.01%
Tween 80 0.27%
Formaldehyde 2.10%
Ammonium chloride 0.10%
In reactor, be 2～5 with above-mentioned raw materials at pH, temperature is under 75～100 ℃, keeps reaction 1～2 hour, promptly gets product;
Wherein: described deacetylating degree of chitosan is greater than 75%; The alcoholysis degree of described polyvinyl alcohol is 85～100%, the degree of polymerization is 1000～1700.
2, slow-release material as claimed in claim 1 is characterized in that, chitosan is dissolved in 50 ℃ 2% aqueous acetic acid, is mixed with 2～4% chitosan solution; With starch and water with the ratio of volume ratio 10/90 at 85 ℃ of following gelatinizing 30min, make starch gelatinization liquid; Chitosan solution, starch gelatinization liquid, polyvinyl alcohol, glycerol, Tween 80 are mixed by the described content of claim 1, at pH is 2～5, stirring is warming up to 90～100 ℃, make transparent glue, add formaldehyde, Biformyl or glutaraldehyde, keep reaction 1～1.5h, add a spot of ammonium chloride again, keep reaction 10～20min, make slow-release material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107977 CN1290582C (en) | 2003-10-16 | 2003-10-16 | Biodegradable chitosan slow-release material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310107977 CN1290582C (en) | 2003-10-16 | 2003-10-16 | Biodegradable chitosan slow-release material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1528463A CN1528463A (en) | 2004-09-15 |
| CN1290582C true CN1290582C (en) | 2006-12-20 |
Family
ID=34304580
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310107977 Expired - Fee Related CN1290582C (en) | 2003-10-16 | 2003-10-16 | Biodegradable chitosan slow-release material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1290582C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381181C (en) * | 2005-10-21 | 2008-04-16 | 四川大学 | Step-degrdeable bioactive implanting material comprising growth promotion factor |
| CN101584876B (en) * | 2009-06-19 | 2012-10-24 | 山东赛克赛斯药业科技有限公司 | Medical compound micropore polysaccharide and application thereof |
| CN101953823B (en) * | 2010-09-29 | 2012-05-09 | 宁波大学 | Processing method of antibacterial fishing medicament |
| CN103918655B (en) * | 2014-04-16 | 2015-09-09 | 青海绿原生物工程有限公司 | Recompounded Langdu preventing and killing herbicide and production technology thereof |
| CN103977412B (en) * | 2014-04-23 | 2015-08-26 | 湖南尔康正阳药用胶囊有限公司 | A kind of enteric capsulation material compositions |
| CN108192426A (en) * | 2017-12-01 | 2018-06-22 | 俞小峰 | A kind of preparation method of low-temperature type seed coat agent material |
| CN108285603A (en) * | 2018-03-07 | 2018-07-17 | 常德金德新材料科技股份有限公司 | A kind of degradable high-barrier composite material and preparation method thereof |
| CN111675574A (en) * | 2020-06-28 | 2020-09-18 | 北部湾海洋新材料研究院 | Slow-release selenium-rich ecological fertilizer for golden camellia and preparation method thereof |
-
2003
- 2003-10-16 CN CN 200310107977 patent/CN1290582C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1528463A (en) | 2004-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wahid et al. | Bacterial cellulose and its potential for biomedical applications | |
| Qureshi et al. | Polysaccharide based superabsorbent hydrogels and their methods of synthesis: A review | |
| Barikani et al. | Preparation and application of chitin and its derivatives: a review | |
| da Silva et al. | Alginate and sericin: environmental and pharmaceutical applications | |
| Elçin | Encapsulation of urease enzyme in xanthan-alginate spheres | |
| Qi et al. | Biocompatible hydrogels based on food gums with tunable physicochemical properties as scaffolds for cell culture | |
| CN1290582C (en) | Biodegradable chitosan slow-release material | |
| EP1113827A1 (en) | Polymer immobilized living cells and applications thereof | |
| Yan et al. | Modification on sodium alginate for food preservation: A review | |
| Zhang et al. | Preparation and characterization of tamarind gum/sodium alginate composite gel beads | |
| JP2014187901A (en) | Temperature-sensitive complex containing bacterial cellulose and production method thereof | |
| Yi et al. | Bioinspired adhesive and self-healing bacterial cellulose hydrogels formed by a multiple dynamic crosslinking strategy for sealing hemostasis | |
| Ul-Islam et al. | Synthesis, chemistry, and medical application of bacterial cellulose nanocomposites | |
| Firmanda et al. | Factors influencing the biodegradability of agro-biopolymer based slow or controlled release fertilizer | |
| CN1593385A (en) | Gel capable of injecting temperature sensitive complex and its preparation method | |
| CN1830420A (en) | Injection type pH sepsitive chitin quarternary ammonium salt aquagel and its preparation method | |
| CN1844215A (en) | Process for preparing hyaluronic acid-chitosan crosslinked biocompatible materials | |
| Chen et al. | Natural polysaccharide: Modification and application | |
| Estevam et al. | A review of the strategies used to produce different networks in cellulose-based hydrogels | |
| Singha et al. | Applications of alginate-based bionanocomposites in drug delivery | |
| CN101054575A (en) | Preparation method for modified polyacrylamide immobilization cell | |
| Esparza-Flores et al. | Genipin crosslinked porous chitosan beads as robust supports for β-galactosidase immobilization: Characterization, stability, and bioprocessing potential | |
| CN1268670C (en) | Glucomannan hydrogel of konnjaku and preparation method | |
| CN101157914B (en) | Bentonite, biological polysaccharide plural gel immobilized cell carrier and preparation method thereof | |
| CN114891239B (en) | Boron-nitrogen internal coordination borate hydrogel and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061220 Termination date: 20111016 |