CN1203120C - In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material - Google Patents
In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material Download PDFInfo
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- CN1203120C CN1203120C CN 02136031 CN02136031A CN1203120C CN 1203120 C CN1203120 C CN 1203120C CN 02136031 CN02136031 CN 02136031 CN 02136031 A CN02136031 A CN 02136031A CN 1203120 C CN1203120 C CN 1203120C
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Abstract
The present invention provides a new method for preparing chitosan/hydroxyapatite nanocomposite material under the conditions of normal temperature and ordinary pressure (namely mild conditions). In the method, calcium ionic fluid and phosphorus ionic fluid are prepared, uniformly mixed and prepared into solution after ethanoic acid is added; chitosan is dissolve in the solution, and then, the solution containing chitosan is formed and baked after injected into a mould. The method of the present invention enables hydroxyapatite particles to be uniformly dispersed, in nanometer from 20 to 100 nm, in the basal body of chitosan. Materials prepared with the method of the present invention is transparent and slightly yellow, the mechanical property is obviously enhanced, calcium ions and phosphorus ions in hydroxyapatite are released out of chitosan substrates continuously, stably and slowly in the process of bone repair, and the phenomenon of explosive release is avoided.
Description
Technical field
The present invention relates to the compound method for preparing chitosan/hydroxyapatite nano matrix material of original position.
Background technology
(Chitosan CS) is a kind of natural biodegradable polysaccharide to chitosan, and its degraded product is for having weakly alkaline glucosamine, to human body and organize nontoxic, harmless.It also has natural pharmaceutical activity, anti-tumor activity, antiinflammation except having excellent biocompatibility, impaired biological physical efficiency is induced special cells, accelerates wound healing.
(Hydroxyapatite, chemical structural formula HA) are (Ca to hydroxyapatite
10(OH)
2(PO
4)
6), be the main component (containing 60～70%) of human body natural's bone, have the guided bone of fabulous biological activity and osseous tissue growth.Proved that the HA kind plants the growth of physical efficiency inducing peripheral osseous tissue, and formed firm Chemical bond with host bone.
Hydroxyapatite is joined the synosteosis ability that can improve chitosan/hydroxyapatite composite material in the glycan substrate, promote the damaged reparation of bone; At present, the method for preparing chitosan/hydroxyapatite composite material mainly contains in direct blend, lyophilize and the solidification liquid and solidifies.Generally all be that employing is a matrix with the hydroxyapatite, account for 60%～90% (weight), and chitosan mainly be as excipient, tackiness agent in this system.Add chitosan solution in hydroapatite particles, hydroapatite particles is modulated into mashed prod or paste, hydroxyapatite just can be by any plastotype like this.But final material still shows the biological ceramics performance, and promptly fragility is big, and flexural strength is low.And be that the composite degradation of matrix is very slow with the hydroxyapatite, do not match with the process of union of fracture.The matrix material of this method preparation a little less than the two interface binding power of hydroxyapatite and chitosan, causes material opaque in appearance because the hydroxyapatite dispersion is inhomogeneous, presents white; Aspect mechanical property, descend.Therefore how to guarantee that in hydroxyapatite homodisperse in the glycan substrate matrix that is dispersed in chitosan smaller with guaranteeing hydroapatite particles be emphasis and the difficult point problem for preparing this class material at present.
Summary of the invention
The purpose of this invention is to provide the compound method for preparing chitosan/hydroxyapatite nano matrix material of original position, this method can guarantee that hydroxyapatite is dispersed in the glycan substrate.
The inventive method may further comprise the steps:
1) presses hydroxyapatite Ca
10(OH)
2(PO
4)
6To choose suitable calcium salt and phosphoric acid salt compound concentration respectively be that ionic calcium soln and the concentration of 0.5Kg/L～4.0Kg/L is the phosphate ion solution of 0.35Kg/L～2.0Kg/L to the amount of calcium ion and phosphonium ion in the chemical formula;
2) ionic calcium soln and the phosphate ion solution of respectively getting 50ml～400ml mixes in container, adds a certain amount of acetate, is mixed with acetic acid concentration (by volume) and is 1～8% solution;
3) chitosan is dissolved in step 2) in the gained solution, be mixed with chitosan content (by weight) and be 2.5%～6% chitosan solution;
4) chitosan solution that takes a morsel injects mould and forms one deck inner membrance earlier, then chitosan solution is injected mould, putting it into concentration (by weight) again is in 3～10%NaOH solidification liquid and mold removal, after 2～5 hours the chitosan solution gel stick is put into the distilled water rinsing to neutral, put into 50～80 ℃ of drying in oven.
Among the present invention, said calcium salt can be calcium chloride, lime carbonate, nitrocalcite, and phosphoric acid salt can be SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, dipotassium hydrogen phosphate.
The invention provides a kind of in (both under mild conditions) preparation chitosan/hydroxyapatite nano matrix material novel method under normal temperature, the normal pressure.This method can guarantee hydroapatite particles, and (20～100nm) are dispersed in the chitosan basal body with nano-scale, the transparent little Huang of material that makes with the inventive method, mechanical property obviously improves, can remain in the bone repair process in the hydroxyapatite calcium ion and phosphonium ion continues, steadily, from glycan substrate, discharge lentamente, avoided the burst release phenomenon.
Embodiment
Further specify the present invention below in conjunction with specific examples.
The compound method for preparing chitosan/hydroxyapatite nano matrix material of original position of the present invention may further comprise the steps:
1) presses hydroxyapatite Ca
10(OH)
2(PO
4)
6To choose suitable calcium salt and phosphoric acid salt compound concentration respectively be that ionic calcium soln and the concentration of 1.6Kg/L is the phosphate ion solution of 0.8Kg/L to the amount of calcium ion and phosphonium ion in the chemical formula;
2) ionic calcium soln and the phosphate ion solution of respectively getting 200ml mixes in container, adds a certain amount of acetate, is mixed with acetic acid concentration (by volume) and is 2% solution;
3) chitosan is dissolved in step 2) in the gained solution, be mixed with chitosan content (by weight) and be 4% chitosan solution;
4) chitosan solution that takes a morsel injects mould and forms one deck inner membrance earlier, then chitosan solution is injected mould, putting it into concentration again is in the 5%NaOH solidification liquid and mold removal, after 4 hours the chitosan solution gel stick is put into the distilled water rinsing to neutral, put into 70 ℃ of drying in oven.Make chitosan of the present invention/hydroxyapatite nano material, its color and luster: little Huang is transparent, flexural strength: 89 ± 4MPa, modulus in flexure: 3.5 ± 0.1Gpa.
The mechanical property that table 1 has provided several samples compares.
Table 1
| Sample | Flexural strength (MPa) | Modulus in flexure (GPa) |
| Natural bone | 22±0.8 | ?1.4±0.4 |
| Pure chitosan | 94±12 | ?3.5±0.5 |
| Direct blend CS/HA=100/5 | 68±2 | ?3.2±0.2 |
| The compound CS/HA=100/5 of original position | 86±7 | ?3.4±0.1 |
By table 1 as seen, prepare the mechanical property height of the mechanical property of material with in-situ compounding process, and be higher than the mechanical property of natural bone far away than the preparation sample of blend.
Claims (2)
1. the compound method for preparing chitosan/hydroxyapatite nano matrix material of original position is characterized in that may further comprise the steps:
1) presses hydroxyapatite Ca
10(OH)
2(PO
4)
6To choose calcium salt and phosphoric acid salt compound concentration respectively be that ionic calcium soln and the concentration of 0.5Kg/L～4.0Kg/L is the phosphate ion solution of 0.35Kg/L～2.0Kg/L to the amount of calcium ion and phosphonium ion in the chemical formula;
2) ionic calcium soln and the phosphate ion solution of respectively getting 50ml～400ml mixes in container, adds a certain amount of acetate, is mixed with acetic acid concentration (by volume) and is 1～8% solution;
3) chitosan is dissolved in step 2) in the gained solution, be mixed with chitosan content (by weight) and be 2.5%～6% chitosan solution;
4) chitosan solution that takes a morsel injects mould and forms one deck inner membrance earlier, then chitosan solution is injected mould, it is 3～10%NaOH solidification liquid and mold removal that the mould that will be marked with chitosan solution is again put into concentration (by weight), after 2～5 hours the chitosan solution gel stick is put into the distilled water rinsing to neutral, put into 50～80 ℃ of drying in oven.
2. the compound method for preparing chitosan/hydroxyapatite nano matrix material of original position according to claim 1 is characterized in that said calcium salt is calcium chloride, lime carbonate or nitrocalcite, and phosphoric acid salt is SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate or dipotassium hydrogen phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136031 CN1203120C (en) | 2002-07-15 | 2002-07-15 | In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136031 CN1203120C (en) | 2002-07-15 | 2002-07-15 | In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1389503A CN1389503A (en) | 2003-01-08 |
| CN1203120C true CN1203120C (en) | 2005-05-25 |
Family
ID=4748473
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02136031 Expired - Fee Related CN1203120C (en) | 2002-07-15 | 2002-07-15 | In-situ compounding process of synthesizing nano composite chitosan/hydroxyapatite material |
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Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307253C (en) * | 2005-02-03 | 2007-03-28 | 徐放 | Chitosan water-retaining gel adhesive substrate materials and method for preparing same |
| CN100381181C (en) * | 2005-10-21 | 2008-04-16 | 四川大学 | Step-degrdeable bioactive implanting material comprising growth promotion factor |
| CN1326574C (en) * | 2005-12-13 | 2007-07-18 | 天津大学 | Nanometer hydroxyapatite/chitosan/gelatin porous scaffold material and preparation method thereof |
| CN100551451C (en) * | 2007-04-26 | 2009-10-21 | 山东大学 | Composite of a kind of repairing bone defect and preparation method thereof |
| CN101301495B (en) * | 2008-06-03 | 2012-07-25 | 陕西科技大学 | Method for preparing bone screw biological compound material |
| CN101352585B (en) * | 2008-07-31 | 2012-02-01 | 华南理工大学 | Method for preparing directionally arranged nano hydroxylapatite granule/chitosan stent |
| CN101648036B (en) * | 2009-08-26 | 2012-10-03 | 天津大学 | Lamellar hydroxylapatite and chitosan nano composite material as well as preparation method and application thereof |
| CN101693774B (en) * | 2009-09-28 | 2011-05-25 | 暨南大学 | Nanometer hydroxyapatite/natural polymer composite, preparation method and application thereof |
| CN101822961B (en) * | 2010-03-10 | 2012-06-27 | 武汉理工大学 | In situ preparation method of hydroxyapatite /chitosan core-shell nanospheres |
| CN102276879A (en) * | 2010-06-11 | 2011-12-14 | 中国科学院合肥物质科学研究院 | Fibrous nano-hydroxyapatite/chitosan composite material and preparation method thereof |
| CN102397581A (en) * | 2011-11-21 | 2012-04-04 | 浙江大学 | Method for generating chitosan/calcium phosphate hybrid material by electrochemical method biomimetic mineralization |
| CN103463680A (en) * | 2013-08-21 | 2013-12-25 | 吴江市英力达塑料包装有限公司 | Preparation process of medical implant material |
| CN105086319B (en) * | 2015-08-18 | 2018-05-08 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite/polymer composite material with bionical construction and preparation method and application |
| CN106512099B (en) * | 2016-11-24 | 2019-07-23 | 上海大学 | Chitosan-based biotic bone tissue engineering stent and preparation method thereof |
| CN109549928A (en) * | 2017-09-26 | 2019-04-02 | 清华大学深圳研究生院 | A kind of compound microballoon of Chitosan-Thiolated Polymers/calcium carbonate and preparation method thereof |
| CN108714251A (en) * | 2018-06-06 | 2018-10-30 | 浙江大学 | The method that two-step method prepares the chitosan-based synthetism plate material of high hydroxyapatite content |
| CN110172199B (en) * | 2019-06-25 | 2022-03-01 | 扬州大学 | Preparation method of hydroxyapatite/ultra-high molecular weight polyethylene nano composite |
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