CN101015712B - Process for preparation of polycaprolactone-chitosan network/hydroxyapatite porous compound support frame material - Google Patents
Process for preparation of polycaprolactone-chitosan network/hydroxyapatite porous compound support frame material Download PDFInfo
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- CN101015712B CN101015712B CN200710085930A CN200710085930A CN101015712B CN 101015712 B CN101015712 B CN 101015712B CN 200710085930 A CN200710085930 A CN 200710085930A CN 200710085930 A CN200710085930 A CN 200710085930A CN 101015712 B CN101015712 B CN 101015712B
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Abstract
The invention discloses a method for preparing polycaprolacton-chitosan/hydroxyapatite nanoparticles porous composite scaffold. The method comprises mixing polycaprolactone with glacial acetic acid to obtain a mixed solution, adding chitosan powder, pouring into NaOH solution, solidifying and oven-drying to obtain polycaprolactone-chitosan porous material; mixing hydroxyapatite nanoparticles to polyvinyl alcohol aqueous solution to obtain a slurry; placing the polycaprolactone-chitosan porous material in a centrifuge tube, and performing grout-filling with the slurry for 3-5 times. The produced composite scaffold has the advantages of good biological and mechanical properties and controllable porosity, and can be widely used as tissue-engineering scaffold for repairing various bone defects.
Description
Technical field
The present invention relates to the preparation method of a kind of polycaprolactone-chitosan network/hydroxyapatite porous compound timbering material, belong to biomedical engineering field.
Background technology
Tissue engineering provides new method and thinking for the reparation of bone defective, three-dimensional stent material, and promptly the extracellular matrix substitute is one of key of bone tissue engineer research.Bone holder material both can the inducing peripheral tissue to the transformation of bone, can be used as the carrier of bone graft cell again, should have excellent biological compatibility, bone conductibility, osteoinductive and favorable mechanical performance.And existing homogenous material is difficult to satisfy the requirement of bone tissue engineer to timbering material, based on bionical notion---natural bone is the inorganic/organic composite material that is made of nano-apatite and macromolecule glue fibril, and nano-apatite and the macromolecule compound support frame material of making that combines has caused that people pay close attention to widely.People (Biomaterials, 22 (2003): 1705-1711) under bionical condition, prepared the hydroxyapatite/collagen composite such as Kikuchi M by self-organizing mechanism; People such as Li Yubao have prepared nano-apatite/polyamide compound support frame material (ZL 03135262.6); People such as Yao Kangde have prepared chitosan-gelatin/calcium phosphate composite stent material (ZL 00136757.9); The polylactic acid/nano-hydroxyapatite porous support materials is also adopted (Acta Biomaterials, 1 (2005): 653-662 by most scholars; Biomaterials, 25 (2004): 4749-4757).But these composites all also have its weak point, and improving and controlling the dispersion situation of hydroxyapatite in support is the emphasis of studying.
Porous is very important for timbering material, because it can make cell migration or propagation.The method that is used at present to prepare porous support materials both at home and abroad mainly contains solvent cast/particle leaching method, gas foaming method, is separated/emulsion process, freeze-drying etc.Solvent cast/particle leaching method (CN 1316464) generally adopts the NaCl granule of certain size, and remove the NaCl granule behind the forming materials again and obtain loose structure, but this method complex procedures, the NaCl granule can not be removed totally.The aperture that thermic induces phase separation method to obtain is generally less, can not satisfy the needs of organizational project.Regulate coarsening time, hole diameter enlargement (CN1272383) to a certain extent.The gas foaming method adopts continuous extrusion equipment to prepare the porous polymer compound rest, but the material surface hole of this method preparation easily seals.Be separated/emulsion process will be with an organic solvent, and difficulty is all compared in the removing of solvent usually, thereby makes material some toxicity of meeting pair cell when tissue culture, influences histiocyte and forms neoblastic ability in vivo.Though freeze-drying has been avoided the use of organic solvent, it is the preparation of suitable water-soluble material only.Therefore, seek a kind of new method for preparing porous support materials, avoid the use of poisonous organic solvent, the preparation that can be used for water-insoluble tissue engineering bracket material again is one of vital task of present Tissue Engineering Study.
Summary of the invention
At above-mentioned situation, the purpose of this invention is to provide the preparation method of a kind of polycaprolactone-chitosan network/hydroxyapatite porous compound timbering material.Feature of the present invention is: (1) polycaprolactone and glacial acetic acid are mixed and made into the polycaprolactone glacial acetic acid solution, add the chitosan powder, pour in the NaOH solution, dry behind the curing molding, make polycaprolactone-chitosan porous rack materials for later use; (2) nano-grade hydroxy apatite joins in the polyvinyl alcohol water solution, makes hydroxyapatite/polyvinyl alcohol pulp; (3) standby polycaprolactone-chitosan porous rack material is put into centrifuge tube, pour hydroxyapatite/polyvinyl alcohol pulp into and carry out the slip casting filling.
Concrete feature comprises the steps:
1) polycaprolactone is dissolved in glacial acetic acid, stirring and dissolving is made mass fraction and is 5～10% polycaprolactone glacial acetic acid solution.
2) take by weighing the certain amount of chitosan powder, add in the polycaprolactone glacial acetic acid solution, add low amounts of water, the consumption of water is 0.5～2% of a polycaprolactone glacial acetic acid solution quality, magnetic agitation is made the glacial acetic acid solution of polycaprolactone-chitosan until obtaining homogeneous solution.The mass fraction of chitosan is controlled at 5～20% in polycaprolactone-chitosan glacial acetic acid solution.
3) glacial acetic acid solution of polycaprolactone-chitosan is poured into filled in the beaker that mass fraction is 40% NaOH solution, left standstill 24 hours, allow its curing molding.Use the distilled water rinsing then 10 times, and soaked 24 hours, 40 ℃ of oven dry make polycaprolactone-chitosan porous rack material.
4) take by weighing certain amount of nano level hydroxyapatite (can directly buy or adopt currently reported method to prepare), join mass fraction and be in 10% the polyvinyl alcohol water solution, sonic oscillation is made mass fraction and is hydroxyapatite/polyvinyl alcohol pulp of 5～10%.
5) polycaprolactone-chitosan porous rack material for preparing is put into the centrifuge tube of the about 4cm of diameter, pour hydroxyapatite/polyvinyl alcohol pulp into porous support materials is carried out the slip casting filling.With the speed centrifugalize of 4000～10000rpm 3～10 minutes, take out in 40 ℃ of constant temperature air dry ovens dry.Fill so repeatedly 3～5 times, obtain polycaprolactone-chitosan/hydroxyapatite composite porous bracket material.
The used primary raw material source of the present invention is: polycaprolactone, molecular weight 80000: Japan big plug the Lushui River (Daicel) chemical company; Polyvinyl alcohol (PVA-1750), Chemical Reagent Co., Ltd., Sinopharm Group; Chitosan (food stage), sea, Jinan Derby marine biotechnology company limited is produced, and deacetylation is 85%.
The present invention is simple to operate, and prior art is compared, has following advantage:
When 1) glacial acetic acid solution of polycaprolactone-chitosan added in the NaOH solution, polycaprolactone was separated out rapidly, promptly is polymer in water---and stingy.Comparatively speaking, the chitosan in aqueous solution is a polymer---rich phase, so being separated appears in two polymer.Therefore but chitosan is the existence of rich phase is very of short duration (chitosan is separated out greater than 6 o'clock at pH value), separates out from NaOH solution just very soon after being separated, and presents swollen gel state, has occupied certain volume.After the material drying, swollen chitosan syneresis, its volume that occupied has originally formed hole, and is interconnected between the hole, is equivalent to the polycaprolactone fiber chitosan swelling system has been carried out " cutting ".Hole is interweaved by the fiber of many polycaprolactones and chitosan and forms, fiber not only is intertwined to form macropore, the aperture is at 300～800 μ m, as shown in Figure 1, and include more complicated secondary microcellular structure at fibrous inside, micro-pore diameter is 10～40 μ m on the fiber, as shown in Figure 2.Composite has higher porosity, reaches 60-85%, and porosity can be by the regulation and control of chitosan components contents.
2) the polyvinyl alcohol molecular structure contains hydrophilic group and two kinds of groups of hydrophobic group, with nano-hydroapatite particles the fabulous compatibility is arranged, Ca in the hydroxyapatite
2+Produce firm bonding with the polyvinyl alcohol molecule, can effectively improve the dispersion situation of nanometer hydroxyapatite.Hydroxyapatite forms strong bonded by polyvinyl alcohol and polycaprolactone, hydroapatite particles and polycaprolactone compound, and the decline that can replenish the pH value that poly-caprolactone degradation causes helps to prevent the generation of aseptic inflammation.
3) behind filling hydroxyapatite/polyvinyl alcohol pulp, compressive property significantly improves, and can delay the depolymerization time, improves the mechanical property of polymer, can obtain having good biological and learn performance, can satisfy the porous support materials of mechanical property requirements again.
Accompanying drawing and description of drawings
Fig. 1 is the photo figure of the specific embodiment of the invention 1 obtained polycaprolactone-chitosan/hydroxyapatite composite porous bracket material.
Fig. 2 is the microscopic appearance figure of the specific embodiment of the invention 1 obtained polycaprolactone-chitosan/hydroxyapatite composite porous bracket material.
The specific embodiment
Embodiment 1
The preparation mass fraction is 10% polycaprolactone glacial acetic acid solution, gets this solution 30g, adds 0.75g chitosan powder, splashes into 0.6ml water, and magnetic agitation is until obtaining homogeneous solution.Then this solution is under agitation slowly poured in the 100ml beaker that fills 30g 40%NaOH solution, left standstill molding in 24 hours.Take out after the molding with distilled water rinsing 10 times, and soaked 24 hours, 40 ℃ of oven dry make polycaprolactone-chitosan porous rack material.
Preparation 50ml mass fraction is 10% polyvinyl alcohol water solution, adds nanometer hydroxyapatite powder 5g, and sonic oscillation is made hydroxyapatite/polyvinyl alcohol pulp.
Polycaprolactone-chitosan porous rack material is put into the centrifuge tube of the about 4cm of diameter, poured hydroxyapatite/polyvinyl alcohol pulp into.With 4000rpm centrifugalize 4 minutes, take out in 40 ℃ of constant temperature air dry ovens dry.Fill so repeatedly 3 times, obtain polycaprolactone-chitosan/hydroxyapatite composite porous bracket material.Its aperture is at 300～800 μ m after measured, and porosity is 80.25%, and comprcssive strength is 25.7MPa.
Embodiment 2
The preparation mass fraction is 5% polycaprolactone glacial acetic acid solution, gets this solution 30g, adds 0.16g chitosan powder, splashes into 0.15ml water, and magnetic agitation is until obtaining homogeneous solution.Then this solution is under agitation slowly poured in the 100ml beaker that fills 30g 40%NaOH solution, left standstill molding in 24 hours.Take out after the molding with distilled water rinsing 10 times, and soaked 24 hours, 40 ℃ of oven dry make polycaprolactone-chitosan porous rack material.
Preparation 50ml mass fraction is 10% polyvinyl alcohol water solution, adds nanometer hydroxyapatite powder 2.5g, and sonic oscillation is made hydroxyapatite/polyvinyl alcohol pulp.
Polycaprolactone-chitosan porous rack material is put into the centrifuge tube of the about 4cm of diameter, poured hydroxyapatite/polyvinyl alcohol pulp into.With 10000rpm centrifugalize 5 minutes, take out in 40 ℃ of constant temperature air dry ovens dry.Fill so repeatedly 5 times, obtain polycaprolactone-chitosan/hydroxyapatite composite porous bracket material.Its aperture is at 300～500 μ m after measured, and porosity is 65.13%, and comprcssive strength is 12.5MPa.
Claims (7)
1. the preparation method of polycaprolactone-chitosan network/hydroxyapatite porous compound timbering material, it is characterized in that: (1) polycaprolactone and glacial acetic acid are mixed and made into the polycaprolactone glacial acetic acid solution, add the chitosan powder, add water, polycaprolactone after stirring-chitosan glacial acetic acid solution is poured in the NaOH solution, dry behind the curing molding, make polycaprolactone-chitosan porous rack materials for later use; (2) nano-grade hydroxy apatite joins in the polyvinyl alcohol water solution, makes hydroxyapatite/polyvinyl alcohol pulp; (3) standby polycaprolactone-chitosan porous rack material is put into centrifuge tube, pour hydroxyapatite/polyvinyl alcohol pulp into and carry out the slip casting filling.
2. the preparation method of polycaprolactone according to claim 1-chitosan network/hydroxyapatite porous compound timbering material, the mass fraction that it is characterized in that described polycaprolactone glacial acetic acid solution is 5-10%.
3. the preparation method of polycaprolactone according to claim 1-chitosan network/hydroxyapatite porous compound timbering material, it is characterized in that when preparation polycaprolactone-chitosan glacial acetic acid solution, the mass fraction of chitosan is controlled between 5～20%, the mass fraction of the water that is added is controlled at 0.5～2%, adopts magnetic agitation even simultaneously.
4. the preparation method of polycaprolactone according to claim 1-chitosan network/hydroxyapatite porous compound timbering material, the mass fraction that it is characterized in that described sodium hydroxide solution is 40%.
5. the preparation method of polycaprolactone according to claim 1-chitosan network/hydroxyapatite porous compound timbering material, it is characterized in that when preparation polycaprolactone-chitosan porous rack material, after pouring the glacial acetic acid solution of polycaprolactone-chitosan into sodium hydroxide solution, left standstill 24 hours, distilled water rinsing 10 times, soaked 40 ℃ of oven dry 24 hours.
6. the preparation method of polycaprolactone according to claim 1-chitosan network/hydroxyapatite porous compound timbering material, it is characterized in that it is in 10% the polyvinyl alcohol water solution that nano-grade hydroxy apatite joins mass fraction, sonic oscillation is made mass fraction and is hydroxyapatite/polyvinyl alcohol pulp of 5～10%.
7. the preparation method of polycaprolactone according to claim 1-chitosan network/hydroxyapatite porous compound timbering material, when it is characterized in that the slip casting filling polycaprolactone-chitosan porous rack material is put into the centrifuge tube of diameter 4cm, pour hydroxyapatite/polyvinyl alcohol pulp into, with 4000～10000rpm centrifugalize 3～10 minutes, and fill repeatedly 3～5 times.
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| CN101491702B (en) * | 2009-03-03 | 2012-07-25 | 福建师范大学 | Preparation method of nano dahllite/chitosan-polylactic acid bone tissue engineer bracket material |
| CN102585460B (en) * | 2011-01-06 | 2015-10-07 | 合肥杰事杰新材料股份有限公司 | A kind of chitosan-polycaprolactone porous composite and preparation method thereof |
| CN103212761B (en) * | 2012-06-26 | 2015-05-06 | 深圳市堃琦鑫华股份有限公司 | Welding method |
| CN103418028A (en) * | 2013-07-31 | 2013-12-04 | 苏州纳埃净化科技有限公司 | Preparation method of porous scaffold material |
| CN105885366A (en) * | 2014-11-05 | 2016-08-24 | 安徽邦尼新材料有限公司 | Chitosan-polycaprolactone porous composite material and preparation method thereof |
| CN105169477A (en) * | 2015-08-15 | 2015-12-23 | 罗卫华 | Preparation method of nano cellulose/chitosan/polycaprolactone porous scaffold |
| WO2017116355A1 (en) | 2015-12-29 | 2017-07-06 | Atilim Universitesi | Tissue scaffold with enhanced biocompatibility and mechanical properties and a method for producing it |
| CN107596451B (en) * | 2017-08-22 | 2020-11-20 | 东南大学 | HA/CS/P (MVE-alt-MA) -based composite bone repair material and preparation method thereof |
| CN107744604B (en) * | 2017-10-18 | 2019-02-12 | 崔旭 | A kind of polyvinyl alcohol/hydroxyapatite compound rest |
| CN113384746B (en) * | 2021-07-21 | 2022-08-16 | 中国人民解放军总医院 | Bone cement composite material and preparation method thereof |
| CN114712060A (en) * | 2022-03-22 | 2022-07-08 | 和医世德(佛山)科技有限公司 | Chinese fir fiber bionic traditional Chinese medicine bonesetting splint and manufacturing method thereof |
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| CN1272383A (en) * | 2000-05-19 | 2000-11-08 | 清华大学 | Preparation method of nanometer phase calcium-phosphorus salt/collagen/polylactic acid bone composite material |
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