CN1148392C - Method for synthesizing crust extract or chitosan grafted lactide polymer - Google Patents
Method for synthesizing crust extract or chitosan grafted lactide polymer Download PDFInfo
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- CN1148392C CN1148392C CNB021111073A CN02111107A CN1148392C CN 1148392 C CN1148392 C CN 1148392C CN B021111073 A CNB021111073 A CN B021111073A CN 02111107 A CN02111107 A CN 02111107A CN 1148392 C CN1148392 C CN 1148392C
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- chitosan
- chitin
- lactide
- grafted polymer
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Abstract
The present invention relates to a method for synthesizing crust extract or chitosan grafted lactide polymer. Crust extract or chitosan whose maximum deacetylation degree is 94% is degassed for 1 hour in vacuum; nitrogen is filled; toluene is used as dispersion solution; triethylaluminum is added as a catalyst; in the solution, lactide has ring opening polymerization, which generates the grafted polymer of the crust extract or the chitosan and polylactic acid. The grafted polymer prepared according to the present invention has the special performance, the solubility of the grafted polymer is greatly improved in water, the grafted polymer is not dissolved in not only general solvent of the polylactic acid but also acid solvent of the chitosan, the grafted polymer can be used as an interface coupling agent of a mixture of the crust extract, the chitosan and the polylactic acid, and the grafted polymer can also be used as other kinds of human implantation biological material, such as, material of medicine slow release agents, etc.
Description
Technical field:
The present invention relates to the synthetic method of a kind of chitin or chitosan grafted lactide polymer, institute's synthetic graftomer can directly be used as medicinal slow release agent, artificial skin, outer wound dressing, the tensio-active agent that also can be used as the human-body biological intermingling material, chitin particularly, the tensio-active agent between chitosan and derivative thereof and the poly(lactic acid) belongs to medical material tech field.
Background technology:
In the last thirty years, poly(lactic acid) and multipolymer have been used to make operating sutures as a kind of polymkeric substance with biological degradation nuclearity biocompatibility, artificial nail, artificial skin, surgical plastic material, with medical materials such as medicinal slow release agents, and obtain clinical application widely.Poly(lactic acid) is degraded to lactic acid in human body, get rid of external by kidney.Because the surface hydrophilicity of poly(lactic acid) is relatively poor, causes its degradation time in human body long, make human body produce unnecessary untoward reaction.As Breitenbach and author thereof, (Polymer, Vol.39, No.14, p3261-3271,1998.) decide driedly with water-soluble poval, synthesized the graft copolymer of polyvinyl alcohol and poly(lactic acid), because the physiological action of polyvinyl alcohol is not clear at present, in clinical use, also have many problems to need to solve.
Chitin is a kind of profuse natural resources, and nearly 1,000,000,000 tons more than of annual biosynthesizing is the natural synthetic materials that is only second to cellulose output.Chitosan be chitin take off the acetyl product.Unique biological effects the such as suitably chitin and the chitosan of molecular weight have anti-inflammatory, and hemostasis promotes cell regeneration, and is anticancer are called the hexa-atomic element of human body by people.Chitin is because intermolecular and molecular memory at a large amount of hydrogen bonds, makes its melt temperature be higher than decomposition temperature, and because under general condition, is difficult for dissolving, limited its exploitation and use.
Human cerium salt such as Keisuke are made grafts (the Journal ofApplied Polymer Science of initiator chitin and methacrylic acid, Vol.42 2885-2891 (1991)), people such as Du Xiuying also use similar initiator on chitosan grafting methacrylic acid (polymer material science and engineering, Vol.12.1996 March).Because polymethyl acrylic acid does not have biological degradability, so this analog copolymer can not be can be regarded as biodegradable material.
Summary of the invention:
The objective of the invention is at the deficiencies in the prior art, the synthetic method of a kind of chitin or chitosan grafted lactide polymer is provided, make the gained composite high-molecular material both have poly(lactic acid) favorable mechanical performance and processibility, chitin and chitosan good biological effect are arranged again, have higher using value.
For realizing such purpose, in the technical scheme of the present invention, the natural polymer copolymerization that this synthetic polymer with good biological degradability and biocompatibility of poly(lactic acid) and chitin and this class of chitosan is had unique biological effect, utilizing chitin or the most high deacetylized 94% the chitosan of reaching is catalyzer with the triethyl aluminum with chitin or chitosan 1-3 times molar weight, in solution, make rac-Lactide generation ring-opening polymerization, generate the graft copolymer of chitin or chitosan and poly(lactic acid).
Concrete implementation method is as follows:
Through in the exsiccant reactor repeatedly, add chitosan through strict exsiccant chitin or different deacetylations, vacuum outgas 1 hour charges into nitrogen.Add an amount of toluene and make dispersion liquid.At ambient temperature, the toluene solution of the triethyl aluminum of adding and chitin or chitosan 1-3 times molar weight dropwise.When gas not had is emitted, make it continue reaction 1 hour.Add then and the proportional rac-Lactide through vacuum outgas of chitosan, put in the oil bath that is heated to 70 ℃ in advance, react after 24 hours, reaction solution is poured in the ethanol, filter, drying obtains required product.
This reaction can be in 2: 1 to 40: 1 the scope, all can carry out smoothly from the mol ratio of chitin or chitosan and rac-Lactide.
The chitin of wood invention preparation or the copolymerized grafting thing of chitosan and rac-Lactide, at normal temperatures, the solvability in water improves greatly, and it can not be dissolved in the common solvent of poly(lactic acid), also is not dissolved in the acid solvent of chitosan.Under the contrast general condition, the surface hydrophilicity of poly(lactic acid) is relatively poor, chitosan can only be dissolved in the acidic medium, products therefrom of the present invention has its property, because the structure of its grafts can be used as chitin, the interface coupling agent of chitosan and polylactic acid blend, also can be used as other human body implantable bioartificial materials such as medicament slow release agent material, have higher using value.
Embodiment:
Be further described below in conjunction with the technical scheme of specific embodiment the wood invention.
Embodiment 1:
Chitin and 1: 2 enforcement of rac-Lactide mol ratio.
With chitin in vacuum drying oven dry 48 hours, remove its surperficial planar water.Take by weighing the 0.05mol chitin and join in the reactor, the degassing is 1 hour under vacuum, adds 40 milliliters of process exsiccant toluene as dispersion agent.Take by weighing the triethyl aluminum of 0.05mol, be mixed with 15% toluene solution.At room temperature triethyl aluminium solution is dropwise joined in the dispersion liquid of chitin toluene, when waiting not have the gas generation, reacted again 1 hour.Add 0.1mol through 1 hour rac-Lactide of vacuum outgas, then reactor is placed the oil bath that is heated to 70 ℃ in advance, react after 24 hours, reaction solution is poured in the ethanol, it is fully precipitated, obtain product behind the filtration drying.
Embodiment 2:
1: 2 enforcement of the chitosan of deacetylation 94% and rac-Lactide.
With the chitosan of deacetylation 94% in vacuum drying oven dry 48 hours, remove its surperficial planar water.Take by weighing the 0.05mol chitosan and join in the reactor, the degassing is 1 hour under vacuum.Add 40 milliliters of process exsiccant toluene and make dispersion agent.Take by weighing the triethyl aluminum of 0.05mol, be mixed with 15% toluene solution.At room temperature triethyl aluminium solution is dropwise joined in the dispersion liquid of chitosan toluene, when waiting not have the gas generation, reacted again 1 hour.Add 0.1mol through 1 hour rac-Lactide of vacuum outgas, then reactor is placed the oil bath that is heated to 70 ℃ in advance, react after 24 hours, reaction solution is poured in the ethanol, it is fully precipitated, obtain product behind the filtration drying.
Embodiment 3:
1: 40 enforcement of the chitosan of acetyl degree 94% and rac-Lactide.
With the chitosan of deacetylation 94% in vacuum drying oven dry 48 hours, remove its surperficial planar water.Take by weighing the 0.005mol chitosan and join in the reactor, the degassing is 1 hour under vacuum.Add 40 milliliters of process exsiccant toluene and make dispersion agent.Take by weighing the triethyl aluminum of 0.005mol, be mixed with 15% toluene solution.At room temperature triethyl aluminium solution is dropwise joined in the dispersion liquid of chitosan toluene, when waiting not have the gas generation, reacted again 1 hour.Add 0.2mol through 1 hour rac-Lactide of vacuum outgas, then reactor is placed the oil bath that is heated to 70 ℃ in advance, react after 24 hours, reaction solution is poured in the ethanol, it is fully precipitated, obtain product behind the filtration drying.
Claims (1)
1, the synthetic method of a kind of chitin or chitosan grafted lactide polymer, it is characterized in that chitin or the most high deacetylizedly reached 94% chitosan vacuum outgas 1 hour, charge into nitrogen, add toluene and make dispersion liquid, at ambient temperature, dropwise the toluene solution of the triethyl aluminum of adding and chitin or chitosan equal molar quantities is made catalyzer, when gas not had is emitted, make it continue reaction 1 hour, add the rac-Lactide through vacuum outgas then, rac-Lactide and chitin or chitosan mol ratio are 2: 1 to 40: 1, reaction is after 24 hours in 70 ℃ oil bath, reaction solution is poured in the ethanol, filters, drying obtains required product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021111073A CN1148392C (en) | 2002-03-21 | 2002-03-21 | Method for synthesizing crust extract or chitosan grafted lactide polymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021111073A CN1148392C (en) | 2002-03-21 | 2002-03-21 | Method for synthesizing crust extract or chitosan grafted lactide polymer |
Publications (2)
| Publication Number | Publication Date |
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| CN1371921A CN1371921A (en) | 2002-10-02 |
| CN1148392C true CN1148392C (en) | 2004-05-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB021111073A Expired - Fee Related CN1148392C (en) | 2002-03-21 | 2002-03-21 | Method for synthesizing crust extract or chitosan grafted lactide polymer |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318464C (en) * | 2005-01-14 | 2007-05-30 | 华南理工大学 | Chitosan graft ternary polymerization polymeric flocculant and its preparation method and use |
| CN101284896B (en) * | 2007-12-28 | 2010-06-02 | 北京航空航天大学 | Chitosan oligosaccharide-poly L-beta-indole alanine graft copolymer homogeneous phase synthetic method |
| CN101284883B (en) * | 2008-05-14 | 2011-02-16 | 西北大学 | Preparation method of polylactic acid-chitose graft copolymer |
| CN102329422B (en) * | 2011-08-24 | 2013-06-12 | 华南理工大学 | Method for preparing chitosan grafted polylactic acid in ionic liquid |
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2002
- 2002-03-21 CN CNB021111073A patent/CN1148392C/en not_active Expired - Fee Related
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