CN1569255A - Poly alpha-alcohol acid ester/chitosan ultrafine fiber hybridization film material and its preparation - Google Patents
Poly alpha-alcohol acid ester/chitosan ultrafine fiber hybridization film material and its preparation Download PDFInfo
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- CN1569255A CN1569255A CN 200410019231 CN200410019231A CN1569255A CN 1569255 A CN1569255 A CN 1569255A CN 200410019231 CN200410019231 CN 200410019231 CN 200410019231 A CN200410019231 A CN 200410019231A CN 1569255 A CN1569255 A CN 1569255A
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Abstract
A poly alpha alcohol acid ester/chitosan superfine fiber hybridization material and the preparation process thereof are disclosed. It belongs to tissue repairing material technology. The film having thickness of 10 mu m-50 mu m is formed by poly alpha alcohol acid ester fiber, the diameter of which being 50nm-500nm, chitosan, the mass percent of which is 10-90%, polyvinyl alcohol or polyoxyethylene, the diameter thereof being 50nm-500nm. The preparation process is as follows: dissolving PLA or PLGA into N,N- dimethytoluamide to prepare poly alpha alcohol acid ester spinning solution with concentration being 20%-25%, dissolving chitosan to acetic acid aqueous solution, adding polyvinyl alcohol or polyoxyethylene to solution to prepare for chitosan spinning solution with concentration 4%-8%, injecting said spinning solutions separately to the multi-channel electrostatic spinning device, conduct simultaneously electrostatic spinning and film converging in separate channels to prepare for film, with the voltage being 5kV-30kV, liquid inventory being 0.1mL/h-0.5mL/h, receiving range being 5cm-25cm. The film has advantages of large water absorption, regulatable degrading rate and favorable cellular affinity.
Description
Technical field
The present invention relates to a kind of poly-Alpha-hydroxy acid esters/chitosan superfine fibre hybridized film material and preparation method thereof, belong to the tissue renovation material technology.
Background technology
The raw material of tissue renovation material comprises natural material and synthesising biological degradable polymer material two big classes.Compare with natural macromolecular, biodegradable fatty gathers the good mechanical performance of Alpha-hydroxy acid esters as poly-Acetic acid, hydroxy-, bimol. cyclic ester (PGA), polylactide (PLA) and copolymer (PLGA) thereof, but lacks cellular affinity; And chitosan is a natural polysaccharide, and cellular affinity is good.With the method for electrostatic spinning, can prepare the superfine fibre that diameter is 50nm～500nm by these polymer, and can be formed directly in superfine fibre nonwoven film, suitable with the yardstick of collagen in the extracellular matrix and glycosaminoglycans, be suitable for the reconstruction of tissues such as skin and cartilage.
Be different from traditional spinning, electrostatic spinning is by means of the spinning process under the extra electric field effect.Under the high voltage electric field effect, be subjected to electrostatic repulsion forces, Coulomb force and capillary combined effect itself, the polymer thread that ejects from the capillary tube top is along unsettled helical trajectory curvilinear motion, drafted thousands of times in a few tens of milliseconds, thereby form superfine fibre (Reneker DH, Yarin AL, Fong H, et al.Bending instability of electrically charged liquid jets ofpolymer solutions in electrospinning.J Appl Phys 2000,87 (9): 4531).Superfine fibre directly is collected on the receiving screen, forms the nonwoven superfine fibre film.Utilize the method can prepare the superfine fibrous membrane materials of diameter for 50nm～500nm.
The research work of Zong etc. shows, utilize the poly-Alpha-hydroxy acid esters superfine fibre film of biological degradability of electrostatic spinning preparation, carrier (the Zong XH that can be used as the cell storage and discharge, Chu B, Fang DF, et al.Cell storage anddelivery system.US Patent 2,003 054035).Luu etc. integrate with PLGA solution with DNA and carry out electrostatic spinning, the DNA that has formed nanofibrous structures reprints support (Luu YK, Kim K, Hsiao BS el al.Development ofa nanostructured DNA delivery scaffold via electrospinning of PLGA and PLA-PEG blockcopolymer.J Control Release 2003,89 (2): 341).Li etc. have prepared the PLGA nonwoven web with electrostatic spinning, point out that from the aspects such as adhesion of porosity, mechanical property and pair cell it can satisfy the basic demand of tissue engineering bracket (Li WJ, Laurencin CT, Caterson EJ et al.Electrospun nanofirous structure:a novel scaffoldfor tissue engineering.J Biomed Mater Res 2002,60 (4): 613).
Existing superfine fibre repair membrane material is not seen research report or patent of invention natural and the hydridization superfine fibre film that the common electrostatic spinning of synthetic polymer forms.
Summary of the invention
The object of the present invention is to provide a kind of poly-Alpha-hydroxy acid esters/chitosan superfine fibre hybridized film material and preparation method thereof, this membrane material has the advantage that tensile strength is better, degradation speed is adjustable, cellular affinity is good as artificial skin and artificial cartilage material, and its preparation method process is simple.
For achieving the above object, the present invention is realized by following technical proposals: a kind of poly-Alpha-hydroxy acid esters/chitosan superfine fibre hybridized film material, it is characterized in that, this film is that the diameter by the poly-Alpha-hydroxy acid esters of PLA or PLGA is 50nm～500nm fiber, with mass percent be that the diameter of 10～90% chitosans and polyvinyl alcohol or polyethylene glycol oxide is that the fiber of 50nm～500nm compiles that to form thickness be the thin film of 10 μ m～50 μ m, poly-Alpha-hydroxy acid esters mass percent in the film is 50～98%, chitosan mass percentage ratio is 1～40%, and polyvinyl alcohol or polyethylene glycol oxide mass percent are 1～40%.
Above-mentioned hybridized film preparation methods is characterized in that comprising following process: will glue all molecular mass (M relatively
η) be that 50,000～200,000 PLA or PLGA are dissolved in N, be made into concentration in the dinethylformamide (DMF) and be 20～25% poly-Alpha-hydroxy acid esters spinning solution; To glue M
ηBe that 50,000～1,000,000 chitosan is dissolved in 1%～5% the acetic acid aqueous solution, and be 10/90～90/10 in solution, to add polyvinyl alcohol (PVA) or polyethylene glycol oxide (PEO), be made into 4～8% chitosan spinning solution by chitosan/second constituent mass ratio.Above-mentioned two kinds of spinning solutions are injected into respectively in the multiple tracks electrostatic spinning apparatus, are that 5kV～30kV, liquid inventory are that 0.1mL/h～0.5mL/h, receiving range are to make their shuntings electrostatic spinning and compile film forming simultaneously under the condition of 5cm～25cm at voltage.
The invention has the advantages that superfine fibre hybridized film material has the advantage that tensile strength is good, degradation speed is adjustable, cellular affinity is good, its preparation method process is simple.
The specific embodiment:
Embodiment 1:
Get M
ηBe 50,000 d, l-PLA 2.2g is dissolved under the room temperature among the 10mL DMF, and adds 1% triethylbenzene ammonium chloride and be made into spinning solution.Get M
ηBe 200,000 chitosan 0.6g, and get that the degree of polymerization is 1750 ± 50, alcoholysis degree is 98% PVA 0.6g, is dissolved in 10mL 2% acetic acid,diluted in room temperature under magnetic agitation respectively, both mix and form the another kind of spinning solution of 20mL then.In having two 50mL syringes that internal diameter is the flat lancet head of 0.8mm, inject above two kinds of spinning solutions respectively, syringe is fixed on the two pass micro-injection pump, the vertical metal receiving screen of placing ground connection at distance syringe needle 10cm place.Syringe needle is linked to each other with the 10kV high-voltage DC power supply, and the setting liquid inventory is 0.1mL/h and carries out electrostatic spinning, and through collect the superfine fibre hybridized film that diameter is 100nm～300nm behind the 72h on receiving screen, wherein chitosan content is 10%～20%.
Embodiment 2:
Get M
ηBe 50,000 d, l-PLA 2.2g is dissolved under the room temperature among the 10mL DMF and is made into spinning solution.Get M
ηBe 650,000 chitosan 0.6g, and get M
ηBe 2,300,000 PEO 0.6g, under magnetic agitation, be dissolved in 20mL 2% acetic acid,diluted, obtain another kind of spinning solution in room temperature.The same two pass electrostatic spinning apparatus that uses, in having two 50mL syringes that internal diameter is the flat lancet head of 0.8mm, inject above two kinds of spinning solutions respectively, at receiving range is that 15cm, voltage are that 15kV, liquid inventory are to carry out electrostatic spinning under the 0.1mL/h condition, collecting diameter behind the 72h on receiving screen is the superfine fibre hybridized film of 100nm～500nm, and wherein chitosan content is 1%～20%.
Embodiment 3:
Get M
ηBe 50,000 PLGA75/25 2.2g, be dissolved under the room temperature among the 10mL DMF, and add 1% triethylbenzene ammonium chloride and be made into spinning solution.Get M
ηBe 200,000 chitosan 0.6g, and get that the degree of polymerization is 1750 ± 50, alcoholysis degree is 98% PVA 0.6g, is dissolved in 10mL 2% acetic acid,diluted in room temperature under magnetic agitation respectively, both mix and form the another kind of spinning solution of 20mL then.In having two 50mL syringes that internal diameter is the flat lancet head of 0.8mm, inject above two kinds of spinning solutions respectively, syringe is fixed on the two pass micro-injection pump, the vertical metal receiving screen of placing ground connection at distance syringe needle 10cm place.Syringe needle is linked to each other with the 10kV high-voltage DC power supply, and the setting liquid inventory is 0.1mL/h and carries out electrostatic spinning, and through collect the superfine fibre hybridized film that diameter is 100nm～300nm behind the 72h on receiving screen, wherein chitosan content is 10%～20%.
Embodiment 4:
Get M
ηBe 50,000 PLGA75/25 2.2g, be dissolved under the room temperature among the 10mL DMF and be made into spinning solution.Get M
ηBe 650,000 chitosan 0.6g, and get M
ηBe 2,300,000 PEO 0.6g, under magnetic agitation, be dissolved in the 20mL2% acetic acid,diluted, obtain another kind of spinning solution in room temperature.The same two pass electrostatic spinning apparatus that uses, in having two 50mL syringes that internal diameter is the flat lancet head of 0.8mm, inject above two kinds of spinning solutions respectively, at receiving range is that 15cm, voltage are that 15kV, liquid inventory are to carry out electrostatic spinning under the 0.1mL/h condition, collecting diameter behind the 72h on receiving screen is the superfine fibre hybridized film of 100nm～500nm, and wherein chitosan content is 1%～20%.
Claims (2)
1, a kind of poly-Alpha-hydroxy acid esters/chitosan superfine fibre hybridized film material, it is characterized in that: this film is that the diameter by the poly-Alpha-hydroxy acid esters of PLA or PLGA is 50nm～500nm fiber, with mass percent be that the diameter of 10～90% chitosans and polyvinyl alcohol or polyethylene glycol oxide is that the fiber of 50nm～500nm compiles that to form thickness be the thin film of 10 μ m～50 μ m, poly-Alpha-hydroxy acid esters mass percent is 50～98% in the film, chitosan mass percentage ratio is 1～40%, and polyvinyl alcohol or polyethylene glycol oxide mass percent are 1～10%.
2, a kind of by the described poly-Alpha-hydroxy acid esters of claim 1/chitosan superfine fibre hybridized film preparation methods, it is characterized in that comprising following process: will glue all molecular mass M η relatively and be 50,000～200,000 PLA or PLGA and be dissolved in N, and be made into concentration among the dinethylformamide DMF and be 20～25% poly-Alpha-hydroxy acid esters spinning solution; With sticking M η is that 50,000～1,000,000 chitosan is dissolved in 1%～5% the acetic acid aqueous solution, and be 10/90～90/10 in solution, to add PVAC polyvinylalcohol or polyethylene glycol oxide PEO by chitosan/second constituent mass ratio, it is molten to be made into 4～8% chitosan spinning, above-mentioned two kinds of spinning solutions are injected into respectively in the multiple tracks electrostatic spinning apparatus, are that 5kV～30kV, liquid inventory are that 0.1mL/h～0.5mL/h, receiving range are shunting electrostatic spinning and compile film forming simultaneously under the condition of 5cm～25cm at voltage.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376623C (en) * | 2006-08-15 | 2008-03-26 | 浙江大学 | Process for preparing chitosan nano fiber film with stable state |
| CN100548456C (en) * | 2007-08-29 | 2009-10-14 | 浙江大学 | A kind of preparation method of affinity vinyl cyanide base co-polymer superfine fibre film and application |
| CN101235155B (en) * | 2007-10-31 | 2010-06-16 | 江南大学 | Method for preparing polylactic acid, polyvinyl alcohol and brazilwood mixed nano or micron fibrous membrane |
| CN101892529A (en) * | 2010-07-07 | 2010-11-24 | 天津大学 | Emulsion core coaxial electrically spun ultrafine fibrous membrane with clad proteins and preparation method thereof |
| CN101413183B (en) * | 2007-10-16 | 2011-02-09 | 国家纳米科学中心 | Polymer electrostatic spinning film, preparation and use in biological detection |
| CN103924383A (en) * | 2014-03-20 | 2014-07-16 | 北京化工大学常州先进材料研究院 | Production method of polylactic acid/chitosan hybrid nano-fiber membrane |
| CN105079883A (en) * | 2015-08-12 | 2015-11-25 | 华南理工大学 | Multistage nanofiber composite drug-loaded periodontal tissue material and preparation method thereof |
| CN109468748A (en) * | 2019-01-15 | 2019-03-15 | 山东蓝色时光新材料有限公司 | A kind of preparation method of high efficiency filter and intelligent antibacterial porous nanofiber membrane |
-
2004
- 2004-05-12 CN CN 200410019231 patent/CN1291760C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376623C (en) * | 2006-08-15 | 2008-03-26 | 浙江大学 | Process for preparing chitosan nano fiber film with stable state |
| CN100548456C (en) * | 2007-08-29 | 2009-10-14 | 浙江大学 | A kind of preparation method of affinity vinyl cyanide base co-polymer superfine fibre film and application |
| CN101413183B (en) * | 2007-10-16 | 2011-02-09 | 国家纳米科学中心 | Polymer electrostatic spinning film, preparation and use in biological detection |
| CN101235155B (en) * | 2007-10-31 | 2010-06-16 | 江南大学 | Method for preparing polylactic acid, polyvinyl alcohol and brazilwood mixed nano or micron fibrous membrane |
| CN101892529A (en) * | 2010-07-07 | 2010-11-24 | 天津大学 | Emulsion core coaxial electrically spun ultrafine fibrous membrane with clad proteins and preparation method thereof |
| CN103924383A (en) * | 2014-03-20 | 2014-07-16 | 北京化工大学常州先进材料研究院 | Production method of polylactic acid/chitosan hybrid nano-fiber membrane |
| CN105079883A (en) * | 2015-08-12 | 2015-11-25 | 华南理工大学 | Multistage nanofiber composite drug-loaded periodontal tissue material and preparation method thereof |
| CN105079883B (en) * | 2015-08-12 | 2018-02-27 | 华南理工大学 | A kind of multi-stage nano fiber composite medicine-carried periodontium material and preparation method thereof |
| CN109468748A (en) * | 2019-01-15 | 2019-03-15 | 山东蓝色时光新材料有限公司 | A kind of preparation method of high efficiency filter and intelligent antibacterial porous nanofiber membrane |
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| CN1291760C (en) | 2006-12-27 |
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