CN101293113A - Method for preparing fluorapatite/hydroxyapatite sosoloid nano-powder - Google Patents
Method for preparing fluorapatite/hydroxyapatite sosoloid nano-powder Download PDFInfo
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- CN101293113A CN101293113A CNA2008100624870A CN200810062487A CN101293113A CN 101293113 A CN101293113 A CN 101293113A CN A2008100624870 A CNA2008100624870 A CN A2008100624870A CN 200810062487 A CN200810062487 A CN 200810062487A CN 101293113 A CN101293113 A CN 101293113A
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- hydroxyapatite
- sosoloid
- fluor
- nanometer powder
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Abstract
The present invention discloses a preparation method of fluorapatite/hydroxylapatite solid solution nanometer powder. The method takes calcium compound and part esterification phosphate or organic phosphate alcohol solution as the base and then adds fluoride compounds and organic amine so as to synthesize the fluorapatite/hydroxylapatite solid solution nanometer powder by the method of sol combustion self-spreading. The present invention solves the problems that the fluorapatite/hydroxylapatite solid solution nanometer powder is hard to prepare, and the fluorine content and the existence state of the fluorine are difficult to control, etc. The preparation method provided by the present invention has the advantages of simple operation, low cost and being easy for industrialization.
Description
Technical field
The present invention relates to the preparation method of fluor-apatite/hydroxyapatite sosoloid nanometer powder, belong to biomaterial for medical purpose.
Background technology
Calcium phosphate material is the pottery that hard tissue substituting material is made in a kind of extensive use.It has multiple crystal formation, wherein hydroxyapatite (Ca
10(PO
4)
6(OH)
2, HA) the most frequently used a kind of.Have been found that hydroxyapatite has superior bioactive, can form chemical bonding with osseous tissue.And hydroxyapatite is generally acknowledged to have bone conductibility.Yet, because the difference of applied environment, in the application of ask for something calcium phosphate long-time stability, as when being applied to metal base surface coating under the carrying condition or ceramic artificial eye etc., its dissolubility is excessive, causes the calcium phosphate dissolving easily, makes implant that the possibility of inefficacy be arranged.Therefore, it is very necessary in these are used its dissolubility being controlled.In hydroxyapatite structure, introduce all or part of replacement of F OH formation fluor-apatite/hydroxyapatite sosoloid and can reduce its dissolubility effectively, and it is suitable with hydroxyapatite with the interactional performance of organism.Therefore be a kind of very promising substitution material.
In a lot of practical applications, prepare coating as plasma spraying, porous or compact massive pottery etc. all need be with calcium phosphate powder as raw materials, and the particle diameter of calcium phosphate powder has played important effect in these preparation process, may influence the reactivity, sinterability, gained coating of powder or mechanical property of pottery or the like.Adopt nano-calcium phosphate powder can improve the performance of plasma spraying coating or agglomerating pottery effectively from these aspects.Chinese patent 00127421.X and 200310105951.7 discloses the nanometer hydroxyapatite powder preparation method based on coprecipitation respectively.And for fluor-apatite, CN1475436 discloses a kind of high temperature solid phase synthesis, but this method is difficult to prepare the fluoridated hydroxyapatite of nanoscale.
Summary of the invention
The preparation method that the purpose of this invention is to provide a kind of fluor-apatite/hydroxyapatite sosoloid nanometer powder of excellent performance.
The method for preparing fluor-apatite/hydroxyapatite sosoloid nanometer powder that the present invention proposes, be to adopt the alcoholic solution of phosphoric acid of the calcium salt dissolve in liquid alcohol and phosphate ester or partial esterification as precursor, add organic amine therein, form flammable colloidal sol, make it burning and obtain the dry glue powder end from spreading mode, obtain fluor-apatite/hydroxyapatite sosoloid nanometer powder by heat treatment again with colloidal sol.Concrete steps are as follows:
1) to be dissolved in and to form concentration in the liquid alcohol be the calcium precursor of 0.5mol/L～3.5mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) phosphoric acid of phosphate ester or partial esterification is dissolved in is made into the phosphorus precursor that concentration is 0.5mol/L～6.0mol/L in the liquid alcohol;
3), form mixed liquor A with calcium precursor, phosphorus precursor Ca/P=1.55～1.67 mixed in molar ratio;
4) fluorochemical is added in the mixed liquor A F/Ca=0.01～0.20 in molar ratio, and refluxed 12 hours～48 hours, form mixed liquid B;
5) in mixed liquid B in molar ratio N/F=1～2 add organic amines;
6) heating makes the mixed liquid B spontaneous combustion or directly lights mixed liquid B, becomes the dry glue powder end to the solution bone dry;
7) with 500 ℃～700 ℃ heat treatment dry glue powders end 20 minutes～5 hours, obtain fluor-apatite/hydroxyapatite sosoloid nanometer powder.
Among the present invention, said liquid alcohol can be methanol, ethanol, propanol or butanols.Said calcium compounds can be lime nitrate or calcium acetate.
Among the present invention, said phosphate ester can adopt tributyl phosphate or triethyl phosphate.The phosphoric acid of said partial esterification is that molecular formula is PO (OH)
X(OR)
3-XPhosphoric acid, R is an alcohol radical in the formula, X equals 1 or 2.
Among the present invention, said fluorochemical can be trifluoroacetic acid (CF
3COOH), hexafluorophosphoric acid (HPF
6), ammonium hexafluorophosphate (NH
4PF
6), single fluorophosphoric acid (H
2PO
3F) or ammonium fluoride (NH
4F).
Among the present invention, said organic amine can be ethanolamine, diethanolamine, triethanolamine, diethylenetriamine or hexamethylenetetramine.
The present invention introduces fluorine in calcium phosphate, according to the difference that adds fluorochemical content, can obtain fluorine and replace the different fluor-apatite/hydroxyapatite sosoloid nanometer powder of degree, because the existence of fluorine has reduced dissolubility effectively, and its biological activity and biocompatibility are uninfluenced, when its during as coating or block ceramic applications, the variation on this composition will very help taking into account the long-lasting and biological activity of material.The present invention has generated fluor-apatite/hydroxyapatite sosoloid with colloidal sol from the method that spreads, the nanometer powder phase purity height of gained, and impurity phases such as oxygen-free calcium, calcium pyrophosphate, and fluorine content controllability is good, and crystallite dimension is controlled in 20nm～100nm scope.Preparation method of the present invention is simple, and is simple to operate, and cost is low, is easy to industrialization.
The specific embodiment
Further specify the present invention below in conjunction with example.
Example 1
Lime nitrate is dissolved in the ethanol forms concentration in 2mol/L calcium precursor; With molecular formula is PO (OH)
1(OR)
2Phosphoric acid be dissolved in the ethanol that to form concentration be the phosphorus precursor of 2mol/L; With calcium precursor, phosphorus precursor Ca/P=1.67 mixed in molar ratio, form mixed liquor A;
In trifluoroacetic acid F/Ca=0.20 adding in molar ratio mixed liquor A, and refluxed 12 hours, form mixed liquid B; N: F=1 in molar ratio in mixed liquid B: 1 adds triethanolamine, and the heating mixed liquid B makes it spontaneous combustion until forming the dry glue powder end on hot platform, and the 700 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 20 minutes, and nominal molecular formula is Ca
10(PO
4)
6(OH)
0.01F
1.99, the crystal grain mean size is 92nm.
Example 2
Lime nitrate is dissolved in the ethanol forms concentration in 0.5mol/L calcium precursor; With molecular formula such as PO (OH)
2(OR)
1Phosphoric acid be dissolved in the ethanol that to form concentration be the phosphorus precursor of 6.0mol/L; With calcium precursor, phosphorus precursor Ca/P=1.67 mixed in molar ratio, form mixed liquor A;
In trifluoroacetic acid F/Ca=0.133 adding in molar ratio mixed liquor A, and refluxed 12 hours, form mixed liquid B; N: F=1.5 in molar ratio in mixed liquid B: 1 adds diethanolamine, lights colloidal sol until forming the dry glue powder end, and the 650 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 4 hours, and nominal molecular formula is Ca
10(PO
4)
6(OH)
0.69F
1.31, the crystal grain mean size is 78nm.
Example 3
Lime nitrate is dissolved in the ethanol forms concentration in 3.5mol/L calcium precursor; With molecular formula such as PO (OH)
2(OR)
1Phosphoric acid be dissolved in the ethanol that to form concentration be the phosphorus precursor of 2.0mol/L; With calcium precursor, phosphorus precursor Ca/P=1.55 mixed in molar ratio, form mixed liquor A;
In single fluorophosphoric acid F/Ca=0.01 adding in molar ratio mixed liquor A, and refluxed 48 hours, form mixed liquid B; N: F=2 in molar ratio in mixed liquid B: 1 adds diethanolamine, lights colloidal sol until forming the dry glue powder end, and the 500 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 5 hours, and nominal molecular formula is Ca
9.3(PO
4)
6(OH)
1.907F
0.093, the crystal grain mean size is 45nm.
Example 4
Calcium acetate is dissolved in the ethanol forms concentration in 1.0mol/L calcium precursor; Triethyl phosphate is dissolved in the ethanol to form concentration be the phosphorus precursor of 0.5mol/L; With calcium precursor, phosphorus precursor Ca/P=1.65 mixed in molar ratio, form mixed liquor A;
In hexafluorophosphoric acid F/Ca=0.067 adding in molar ratio mixed liquor A, and refluxed 36 hours, form mixed liquid B; N: F=2 in molar ratio in mixed liquid B: 1 adds diethylenetriamine, lights colloidal sol until forming the dry glue powder end, and the 650 ℃ of heat treatments in dry glue powder end promptly became the fluoridated hydroxyapatite nano powder in 4 hours, and nominal molecular formula is Ca
9.9(PO
4)
6(OH)
1.337F
0.663, the crystal grain mean size is 68nm.
Claims (7)
1. method for preparing fluor-apatite/hydroxyapatite sosoloid nanometer powder is characterized in that may further comprise the steps:
1) to be dissolved in and to form concentration in the liquid alcohol be the calcium precursor of 0.5mol/L～3.5mol/L to the calcium compounds that will dissolve in liquid alcohol;
2) phosphoric acid of phosphate ester or partial esterification is dissolved in is made into the phosphorus precursor that concentration is 0.5mol/L～6.0mol/L in the liquid alcohol;
3), form mixed liquor A with calcium precursor, phosphorus precursor Ca/P=1.55～1.67 mixed in molar ratio;
4) fluorochemical is added in the mixed liquor A F/Ca=0.01～0.20 in molar ratio, and refluxed 12 hours～48 hours, form mixed liquid B;
5) in mixed liquid B in molar ratio N/F=1～2 add organic amines;
6) heating makes the mixed liquid B spontaneous combustion or directly lights mixed liquid B, becomes the dry glue powder end to the solution bone dry;
7) with 500 ℃～700 ℃ heat treatment dry glue powders end 20 minutes～5 hours, obtain fluor-apatite/hydroxyapatite sosoloid nanometer powder.
2. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said liquid alcohol is methanol, ethanol, propanol or butanols.
3. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said calcium compounds is lime nitrate or calcium acetate.
4. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said phosphate ester is tributyl phosphate or triethyl phosphate.
5. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder, the phosphoric acid that it is characterized in that said partial esterification are that molecular formula is PO (OH)
X(OR)
3-XPhosphoric acid, R is an alcohol radical in the formula, X equals 1 or 2.
6. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said fluorochemical is trifluoroacetic acid, hexafluorophosphoric acid, ammonium hexafluorophosphate, single fluorophosphoric acid or ammonium fluoride.
7. the preparation method of fluor-apatite according to claim 1/hydroxyapatite sosoloid nanometer powder is characterized in that said organic amine is ethanolamine, diethanolamine, triethanolamine, diethylenetriamine or hexamethylenetetramine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293461A (en) * | 2015-11-18 | 2016-02-03 | 湖北工业大学 | Oil-soluble hydroxyapatite nano-sheet preparation method |
| CN106317031A (en) * | 2016-08-19 | 2017-01-11 | 淮阴师范学院 | Method for synthesizing 2-(4,6-di(2,4-xylyl)-1,3,5-triazine-2-base)-5-glycidyl ether phenol |
| CN108609593A (en) * | 2018-04-27 | 2018-10-02 | 武汉亚洲生物材料有限公司 | A kind of hydroxyapatite and its preparation method and application |
| CN114014288A (en) * | 2021-11-09 | 2022-02-08 | 中南大学 | Calcium fluoride modified hydroxyapatite powder and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105678C (en) * | 2000-11-10 | 2003-04-16 | 中国科学院上海硅酸盐研究所 | Preparation of low temperature sinterable hydroxyapatite powder |
| US7572298B2 (en) * | 2003-03-28 | 2009-08-11 | Ethicon, Inc. | Implantable medical devices and methods for making same |
| CN1775309A (en) * | 2005-09-28 | 2006-05-24 | 浙江大学 | Method for preparing calcium phosphate coating on medical transplant by flame heat treatment |
-
2008
- 2008-06-12 CN CN2008100624870A patent/CN101293113B/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105293461A (en) * | 2015-11-18 | 2016-02-03 | 湖北工业大学 | Oil-soluble hydroxyapatite nano-sheet preparation method |
| CN105293461B (en) * | 2015-11-18 | 2017-08-29 | 湖北工业大学 | A kind of preparation method of Oil soluble hydroxy apatite nanometer sheet |
| CN106317031A (en) * | 2016-08-19 | 2017-01-11 | 淮阴师范学院 | Method for synthesizing 2-(4,6-di(2,4-xylyl)-1,3,5-triazine-2-base)-5-glycidyl ether phenol |
| CN106317031B (en) * | 2016-08-19 | 2018-10-02 | 淮阴师范学院 | A method of synthesis 2- (4,6- bis- (2,4- xylyls) -1,3,5- triazine -2- bases) -5- glycidol ether phenol |
| CN108609593A (en) * | 2018-04-27 | 2018-10-02 | 武汉亚洲生物材料有限公司 | A kind of hydroxyapatite and its preparation method and application |
| CN114014288A (en) * | 2021-11-09 | 2022-02-08 | 中南大学 | Calcium fluoride modified hydroxyapatite powder and preparation method thereof |
| CN114014288B (en) * | 2021-11-09 | 2022-12-13 | 中南大学 | Calcium fluoride modified hydroxyapatite powder and preparation method thereof |
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Granted publication date: 20110309 Termination date: 20130612 |