CN102757626A - Preparation method of chitosan and polylactic acid composite material - Google Patents
Preparation method of chitosan and polylactic acid composite material Download PDFInfo
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- CN102757626A CN102757626A CN2011101135197A CN201110113519A CN102757626A CN 102757626 A CN102757626 A CN 102757626A CN 2011101135197 A CN2011101135197 A CN 2011101135197A CN 201110113519 A CN201110113519 A CN 201110113519A CN 102757626 A CN102757626 A CN 102757626A
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Abstract
The invention belongs to the technical field of bioengineering, and relates to a preparation method of a chitosan and polylactic acid composite material. The method comprises the following steps of: adding lactic acid into chitosan, mixing and stirring, heating to 120 DEG C and drying to prepare chitosan powder with surface modified by the lactic acid; adding high-molecular-weight polylactic acid into a micro internal mixer; heating to melting temperature of 165 DEG C; adding the chitosan powder into the polylactic acid; mixing; and performing internal mixing for 0.5-2 hours to prepare the chitosan and polylactic acid composite material. As tested, the result shows that the chitosan is fibrously and uniformly distributed in a polylactic acid system in the prepared chitosan and polylactic acid composite material, the tensile strength of the polylactic acid can be obviously improved when the amount of the added chitosan is less than 5 percent, the biocompatibility of the polylactic acid is improved in the synthesized composite material, the inflammatory reaction of the composite material is reduced, and the composite material has wide application values in the aspects of tissue engineering scaffolds and drug carriers.
Description
Technical field
The invention belongs to technical field of bioengineering, relate to the preparation method of lactic acid composite material, be specifically related to a kind of preparation method of chitosan lactic acid composite material.
Background technology
In the modern biotechnology field, tissue engineering bracket material be meant can with organize active somatic cell combine and can implantable bioartificial the material of body, be the basic boom of engineered tissue.The polyester biodegradable material that with the POLYACTIC ACID is representative is in the present Tissue Engineering Study; One of timbering material of the most frequently used transplanted cells; Compare with protein-polysaccharide etc. like collagen with natural extracellular matrix (ECM); The PLA material not only has good physical and mechanical properties, can be through the adjusting of molecular weight and MWD, to adapt to different needs; And have abundant processing means, can adopt to comprise: the tissue engineering bracket that the preparation of serial of methods such as salting-out process, gas foaming method, emulsion lyophilization, phase separation method has suitable three dimensional structure; But poly-lactic acid material do not possess cell epimatrix material good cellular affinity can, its low cellular affinity become restriction its as one of major obstacle of desirable tissue engineering bracket material.
Chitosan is natural alkaline polysaccharide, takes off the chitin product of second phthalein wholly or in part, has excellent biological compatibility, biodegradability, nontoxicity.Chitosan and verivate thereof are used very extensive in technical field of biological material; For example, at wound dressings, can absorb that operating suture, slow releasing pharmaceutical carrier, enzyme are fixed, the application in field such as coagulant and anti-coagulant, diet pill, anticarcinogen, ophthalmology material all has research; But chitosan has shortcomings such as being prone to crisp, difficult processing, shortage lipotropy, has limited the application of chitosan at biomedicine field; And improve its mechanical property and other physicochemical property through chitosan being carried out modification, will expand the Application of Chitosan scope.
There is document (ZL200610116073.2) to disclose a kind of preparation method and application of nano fibrous tissue recovery support of chitosan-containing, wherein, chitosan is dissolved in the mixing solutions of hexafluoroisopropanol/trifluoroacetic acid or hexafluoroisopropanol/formic acid; The blend of POLYACTIC ACID-polycaprolactone is dissolved in hexafluoroisopropanol; With solution mixing and stirring in two; The method of spinning with static; Obtain needed support; Nanofiber silk of preparing and timbering material tool be than high-biocompatibility, mechanical property, higher porosity preferably, but and vivo degradation and the rehabilitation that promotes wounded tissue, be expected to as tissue recovery supports such as skin, cartilage, blood vessel, nerves.But there is the not high defective of mechanical strength in the chitosan/POLYACTIC ACID conjugated fibre support of the method preparation of employing electrostatic spinning.Document ZL200810070606.7 discloses the preparation method that a kind of chitosan strengthens bar; Wherein, The chitosan powder is added in the acetic acid soln that is dispersed with polylactic acid short-fiber in advance, stirs and be made into chitosan/acetic acid soln, smear one deck chitosan/acetic acid soln at mould inner wall; In sodium hydroxide solution, soak deposition then, form the template of chitosan film as the original position precipitating; Chitosan/acetic acid soln is filled with mould; In sodium hydroxide solution, slough mould, be dipped to and form chitosan gel rubber rod completely, the chitosan gel rubber rod is dipped to neutrality in zero(ppm) water; Oven dry promptly obtains polylactic acid short-fiber enhanced chitosan transparent, little Huang and strengthens bar.The chitosan that above-mentioned materials can be used as bone fracture internal fixation material strengthens bar, but there is following defective in this method: adopt solution method to prepare acid fiber by polylactic enhanced chitosan material, chitosan solution viscosity is big, and solid content is low, is difficult to prepare high-intensity bar.
Summary of the invention
The objective of the invention is to overcome the defective that prior art exists, a kind of method for preparing lactic acid composite material is provided, be specifically related to a kind of preparation method of chitosan lactic acid composite material.
Particularly, the preparation method of chitosan lactic acid composite material of the present invention is characterized in that, it comprises step:
(1) in chitosan, add lactic acid and mix stirring, be heated to 120 ℃ of dryings, make the chitosan powder of lactic acid surface-treated,
Wherein, described chitosan molecule amount is 300,000-500,000 KDa, deacetylation 90%, and powder size is 200 orders, the lactic acid add-on is 5% of a chitosan mass;
(2) poly-lactic acid in high molecular weight (PLLA) joins in the miniature internal mixer, is heated to 165 ℃ of melt temperatures,
Wherein, described poly-lactic acid in high molecular weight, its molecular weight is greater than 200,000 KDa;
In one embodiment of the present of invention, add the 100g poly-lactic acid in high molecular weight in miniature internal mixer, be heated to 165 ℃ of melt temperatures;
(3) the chitosan powder 1-20g with the lactic acid surface-treated of step (1) joins in the POLYACTIC ACID, under the melt temperature of POLYACTIC ACID, and blend, banburying 0.5-2h makes the chitosan lactic acid composite material then.
Among the present invention, described chitosan is the product by de-acetyl chitin, and it is a kind of natural linear alkaline polysaccharide; Chitin is that the occurring in nature reserves are only second to cellulosic second largest natural organic-compound, but because the crystallinity of the compactness of molecular structure and height be insoluble to soda acid and general organic solvent, so its application receives great restriction; Chitosan of the present invention is because a large amount of free amine group of deacetylated existence; Have not shared electron pair on these amino nitrogen-atoms, make amino present weakly alkaline, can from solution, combine a hydrogen ion; Thereby make chitosan become positively charged polyelectrolyte; Destroyed between chitosan molecule and intramolecular hydrogen bond, make it to be dissolved in the acid, so the present invention has been in order to improve consistency and the dispersiveness of chitosan in POLYACTIC ACID; Adopt lactic acid that pulverous chitosan is carried out surface-treated; Make the carboxyl of amino and lactic acid in the chitosan surface molecular form the lactic acid salt of chitosan, chitosan molecule is to present the molecular conformation that highly curls under general state, in good solvent, can present the molecular chain conformation of stretching, extension; In fused POLYACTIC ACID system, can present the fiber condition distribution of stretching, extension through the high molecular weight chitosan of finishing, thereby strengthen the mechanical property of POLYACTIC ACID.
Among the present invention; Described poly-lactic acid in high molecular weight is meant the PLLA PLLA of high-molecular weight spinning level; Its molecular weight >=200,000 KDa, this high molecular weight polylactic acid have higher mechanical strength and long degradation time, are suitable for preparing tissue engineering bracket material.
Among the present invention, adopt polymer processing equipment Banbury mixer, POLYACTIC ACID and chitosan modified are carried out melt blending, realize the distribution of the uniform nanofiber state of chitosan in POLYACTIC ACID, its advantage is:
(1) effectively raises the mechanical strength of POLYACTIC ACID;
(2) through chitosan the degradation time of POLYACTIC ACID is regulated and control;
(3) the alkaline bleach liquor degradation product of chitosan can with the acid degradation product generation neutralization reaction of POLYACTIC ACID, pH value reduction in avoiding organizing is avoided the Inflammatory response of tardy property foreign matter, thereby has been improved the biocompatibility of POLYACTIC ACID.
Test result shows; In the chitosan lactic acid composite material that the present invention makes; Described chitosan becomes fibrous and is evenly distributed in the POLYACTIC ACID system, the chitosan addition be lower than 5% can obviously improve POLYACTIC ACID when following tensile strength, and the synthetic matrix material has improved the biocompatibility of POLYACTIC ACID; Reduce its Inflammatory response, be with a wide range of applications aspect tissue engineering bracket and the pharmaceutical carrier.
For the ease of understanding, through specific embodiment the preparation method of lactic acid composite material of the present invention is carried out detailed description below.What need particularly point out is, specific embodiment only is in order to explain that obviously those skilled in the art can explain according to this paper, and the present invention is carried out various corrections or change, and these corrections and changing also will be included within the scope.
Embodiment
Embodiment 1
In reaction flask, add chitosan 100g (molecular weight is 300,000, deacetylation 90%), add lactic acid 5g and mix stirring 3h, reaction product is heated to 120 ℃ of dry 2h; 100g poly-lactic acid in high molecular weight (PLLA) (molecular weight 200,000 KDa) joins in the miniature internal mixer; Be heated to 165 ℃ of melt temperatures, the chitosan powder 1g of extracting lactic acid surface-treated joins in the POLYACTIC ACID, and banburying 0.5 under the melt temperature of POLYACTIC ACID; The chitosan lactic acid composite material that obtains; Preparation standard batten in mould is tested its mechanical property, and the mensuration tensile strength is 66N/mm
2
Embodiment 2-5
Concrete preparation process is identical with embodiment 1, only changes lactic modified chitosan add-on and is: 5g, and 10g, 15g, 20g, the result is as shown in table 1 in its Mechanics Performance Testing.
Table 1
Embodiment 6
In reaction flask, add high molecular weight chitosan 100g (molecular weight is 500,000, deacetylation 90%), add lactic acid 5g and mix stirring 3h, reaction product is heated to 120 ℃ of dry 2h; 100g poly-lactic acid in high molecular weight (PLLA) (molecular weight 200,000 KDa) joins in the miniature internal mixer; Be heated to 165 ℃ of melt temperatures, the chitosan powder 1g of extracting lactic acid surface-treated joins in the POLYACTIC ACID, banburying 0.5h under the melt temperature of POLYACTIC ACID; The chitosan lactic acid composite material that obtains; Preparation standard batten in mould is tested its mechanical property, and the mensuration tensile strength is 69N/mm
2
Embodiment 7-10
Concrete preparation process is identical with embodiment 6, and only changing lactic modified chitosan add-on is 5g, 10g, and 15g, 20g, the result is as shown in table 2 in its Mechanics Performance Testing.
Table 2
The result of the foregoing description shows; In the chitosan lactic acid composite material that the present invention makes; Described chitosan becomes fibrous and is evenly distributed in the POLYACTIC ACID system, the chitosan addition be lower than 5% can obviously improve POLYACTIC ACID when following tensile strength, and the synthetic matrix material has improved the biocompatibility of POLYACTIC ACID; Reduce its Inflammatory response, be with a wide range of applications aspect tissue engineering bracket and the pharmaceutical carrier.
Claims (5)
1. the preparation method of a chitosan lactic acid composite material is characterized in that, it comprises step:
(1) in chitosan, add lactic acid and mix stirring, be heated to 120 ℃ of dryings, make the chitosan powder of lactic acid surface-treated,
(2) poly-lactic acid in high molecular weight joins in the miniature internal mixer, is heated to 165 ℃ of melt temperatures,
(3) the chitosan powder 1-20g with the lactic acid surface-treated of step (1) joins in the POLYACTIC ACID, under the melt temperature of POLYACTIC ACID, and blend, banburying 0.5-2h makes the chitosan lactic acid composite material then.
2. the preparation method of chitosan lactic acid composite material according to claim 1 is characterized in that, described chitosan molecule amount is 300,000-500,000 KDa, deacetylation 90%, and powder size is 200 orders.
3. the preparation method of chitosan lactic acid composite material according to claim 1 is characterized in that, described lactic acid add-on is 5% of a chitosan mass.
4. the preparation method of chitosan lactic acid composite material according to claim 1 is characterized in that, described poly-lactic acid in high molecular weight is that poly-lactic acid in high molecular weight is used in spinning, and its molecular weight is greater than >=20 ten thousand KDa.
5. according to the preparation method of claim 1 or 4 described chitosan lactic acid composite materials, it is characterized in that the amount that described poly-lactic acid in high molecular weight joins in the miniature internal mixer is 100g.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818543A (en) * | 2015-04-16 | 2015-08-05 | 长兴永鑫纺织印染有限公司 | Modified polylactic acid fiber excellent in performance |
| CN107217485A (en) * | 2017-07-25 | 2017-09-29 | 魏科峰 | A kind of Biofibre facial mask base fabric and Biofibre facial mask |
| CN108338828A (en) * | 2018-03-05 | 2018-07-31 | 新疆大学 | A kind of design and manufacturing method of the customization Degradable bone fracture plate of composite construction |
| CN112274705A (en) * | 2020-10-26 | 2021-01-29 | 杭州电子科技大学 | 3D printing porous support material and preparation method thereof |
| CN112779671A (en) * | 2020-12-28 | 2021-05-11 | 浙江大学台州研究院 | Preparation method of polylactic acid and chitin composite melt-blown filter material |
| CN113174702A (en) * | 2021-04-28 | 2021-07-27 | 临沂大学 | Preparation method and application of polylactic acid/chitosan/honeysuckle chlorogenic acid nanofiber membrane |
| CN114163793A (en) * | 2021-11-29 | 2022-03-11 | 浙江大学台州研究院 | Chitosan antibacterial outer surface modified polylactic acid extrusion wire and preparation method thereof |
| CN116392639A (en) * | 2023-02-17 | 2023-07-07 | 无锡市中医医院 | Full-layer repair double-layer bracket and preparation method and application thereof |
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| CN101139404A (en) * | 2007-10-26 | 2008-03-12 | 大连利健生物技术开发股份有限公司 | Method for preparing chitosan lactate |
| CN101284883A (en) * | 2008-05-14 | 2008-10-15 | 西北大学 | Preparation method of polylactic acid-chitose graft copolymer |
| CN101792580A (en) * | 2010-03-26 | 2010-08-04 | 暨南大学 | Modified chitosan fiber and polylactic acid composite material and preparation method thereof |
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- 2011-04-29 CN CN201110113519.7A patent/CN102757626B/en not_active Expired - Fee Related
Patent Citations (3)
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| CN101139404A (en) * | 2007-10-26 | 2008-03-12 | 大连利健生物技术开发股份有限公司 | Method for preparing chitosan lactate |
| CN101284883A (en) * | 2008-05-14 | 2008-10-15 | 西北大学 | Preparation method of polylactic acid-chitose graft copolymer |
| CN101792580A (en) * | 2010-03-26 | 2010-08-04 | 暨南大学 | Modified chitosan fiber and polylactic acid composite material and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818543A (en) * | 2015-04-16 | 2015-08-05 | 长兴永鑫纺织印染有限公司 | Modified polylactic acid fiber excellent in performance |
| CN107217485A (en) * | 2017-07-25 | 2017-09-29 | 魏科峰 | A kind of Biofibre facial mask base fabric and Biofibre facial mask |
| CN108338828A (en) * | 2018-03-05 | 2018-07-31 | 新疆大学 | A kind of design and manufacturing method of the customization Degradable bone fracture plate of composite construction |
| CN108338828B (en) * | 2018-03-05 | 2021-03-16 | 新疆大学 | Design and manufacturing method of customized degradable bone fracture plate with composite structure |
| CN112274705A (en) * | 2020-10-26 | 2021-01-29 | 杭州电子科技大学 | 3D printing porous support material and preparation method thereof |
| CN112779671A (en) * | 2020-12-28 | 2021-05-11 | 浙江大学台州研究院 | Preparation method of polylactic acid and chitin composite melt-blown filter material |
| CN113174702A (en) * | 2021-04-28 | 2021-07-27 | 临沂大学 | Preparation method and application of polylactic acid/chitosan/honeysuckle chlorogenic acid nanofiber membrane |
| CN114163793A (en) * | 2021-11-29 | 2022-03-11 | 浙江大学台州研究院 | Chitosan antibacterial outer surface modified polylactic acid extrusion wire and preparation method thereof |
| CN116392639A (en) * | 2023-02-17 | 2023-07-07 | 无锡市中医医院 | Full-layer repair double-layer bracket and preparation method and application thereof |
| CN116392639B (en) * | 2023-02-17 | 2024-02-13 | 无锡市中医医院 | Full-layer repair double-layer bracket and preparation method and application thereof |
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| CN102757626B (en) | 2014-05-14 |
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