CN101565178A - Method for preparing bone-like apatite controlled by thermodynamics - Google Patents
Method for preparing bone-like apatite controlled by thermodynamics Download PDFInfo
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- CN101565178A CN101565178A CNA2009100595393A CN200910059539A CN101565178A CN 101565178 A CN101565178 A CN 101565178A CN A2009100595393 A CNA2009100595393 A CN A2009100595393A CN 200910059539 A CN200910059539 A CN 200910059539A CN 101565178 A CN101565178 A CN 101565178A
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Abstract
The invention relates to a method for preparing bone-like apatite controlled by thermodynamics. Water micro-soluble calcium salts with a Ksp value larger than that of bone-like apatite, such as calcium sulphate or hydrate thereof and the like, are taken as raw materials and react in a water solution of a water-soluble phosphate, thus obtaining the bone-like apatite; the yield of the product is above 95 percent, and the molar ratio of Ca/P is consistent with the theoretical computation of the raw materials. The method is characterized in that the reaction process is thermodynamic spontaneous reaction controlled by thermodynamics instead of dynamics; therefore, reaction condition does not affect the final composition and property of the product, and the product is stable and has less impurities; the prepared nano bone-like apatite sizing material can be directly applied to preparing corresponding nano biomimetic composite bone repairing and substituting materials and the like or used for obtaining corresponding bone-like apatite powder after being dried.
Description
Technical field
The present invention relates to a kind of preparation method of osteoid apatite, particularly a kind of preparation method of the nanometer osteoid apatite by thermodynamic control reaction.
Background technology
The sclerous tissues of human body is become to be grouped into inorganic mineral by organic collagen, and wherein the inorganic mineral composition mainly is the nano level phosphorite crystal, accounts for 65%～90% of the total composition of bone.In addition, also contain small amount of carbon acid ion, sodium ion etc.Said as " preparation method of crystallinity controllable nano hydroxyapatite powder " Chinese patent literature at publication number CN101143718A, osteoid apatite (HA) has good biological activity and biocompatibility, its particle is tiny more, the torsion modulus of corresponding implant, tensile modulus and tensile strength are just high more, the also corresponding raising of fatigue resistance.The nano-apatite powder that crystallization degree is low can have better degradation property, can directly be used as bone filling renovation material, disperse phase, pharmaceutical carrier or as the starting material of biological ceramics and glass.Can form with body bone tissue at short notice behind the implant into body and combine closely, therefore become the bone grafting surrogate of widespread use.
The preparation method of osteoid apatite is a lot, mainly (Feng Jie such as solid phase method, liquid-phase precipitation method, microemulsion method, mechanochemical reaction, sol-gel method and hydrothermal method can be arranged, Cao Jieming etc.: " two kinds of novel methods of nanometer hydroxyapatite synthetic " " New Chemical Materials " 33,1,2005).Wherein, traditional solid phase method reaction is slow owing to speed, long reaction time, it is big to generate the product particle diameter, and raw material powder needs long-time mix grinding, and its lytic activity is poor, Fan Ying temperature height particularly, reason such as it is big to consume energy, wet chemistry method is the main method of present synthesis of nano phosphatic rock.Wet chemistry method mainly comprises the precipitator method, hydro-thermal reaction method and sol-gel method etc.Compare little, the narrow diameter distribution of granularity of the purity height of wet chemistry method synthetic phosphatic rock, product powder with other method.(Feng Jie, Cao Jieming etc.: " two kinds of novel methods of nanometer hydroxyapatite synthetic " " New Chemical Materials " 33,1,2005)
The preparation feedback of the synthetic osteoid apatite of at present traditional wet chemistry method generally all is to adopt water-soluble Ca salt and phosphoric acid salt (PO
4 3-) reaction obtain, therefore the reactions of carrying out with water-soluble Ca salt such as nitrocalcite and water-soluble phosphate that for example provide among the publication number CN1784975A etc. are reacted and can be had following a plurality of reaction product that is in equilibrium state in the molten objects system simultaneously (each Ksp data is drawn from Central-South China Institute of Mining and Metallurgy and analyzed the Beijing of teaching and research room " Chemistry Hand Book "; SciencePreas, 1991):
Phosphatic rock (HA): Ca
5(PO
4)
3OH===5Ca
2++ 3PO
4 3-+ OH
-(Ksp=1.6 * 10
-58),
Calcium phosphate (TCP): Ca
3(PO
4)
2The 3Ca of===
2++ 2PO
4 3-(Ksp=2.0 * 10
-29),
Secondary calcium phosphate (DCP): CaHPO
4The Ca of===
2++ HPO
4 -(Ksp=2.7 * 10
-7),
Hypophosphite monohydrate hydrogen calcium (DCPD): CaHPO
42H
2O===Ca
2++ HPO
4 -+ 2H
2O (Ksp=10
-6.58)
Obviously, the variation of environment in reaction conditions or the reaction system, the inevitable composition situation that all can influence different products in the reaction system, therefore above-mentioned reaction process and product is subjected to kinetic control.For to obtain for the preparation feedback that osteoid apatite (HA) is a purpose, when carrying out above-mentioned reaction to the requirement height of reaction conditions, the difficult control of processing parameter, the instability that the change of reaction conditions can influence and cause product to form, and simultaneous multiple multi-form equilibrated product in the reaction system makes the impurity in the product also be difficult to remove.
Summary of the invention
At above-mentioned situation, the present invention will provide a kind of preparation method of the osteoid apatite by thermodynamic control reaction, make product stable, impurity is few, and the nano level osteoid apatite slurry for preparing can be directly used in the preparation of compound bone reparation of corresponding nano bionic and equivalent material etc.
The preparation method of the osteoid apatite of thermodynamic control of the present invention is with the calcium salt of Ksp value greater than the water microsolubility of osteoid apatite.The notion of said water microsolubility among the application, generalized case are meant that the solubleness of compound is solubilized 0.01～0.1g in the 100g water.For example and particularly preferred this class calcium salt be that (as anhydrous calciumsulphate, calcium sulphate hemihydrate and terra alba etc., wherein calcium sulfate Ksp is 2.4 * 10 for calcium sulfate or its hydrate
-5) be raw material, at water-soluble phosphate, PO particularly
4 3-With salt that basic metal became such as potassium, sodium, or corresponding ammonium salt, or obtain after the reaction in the aqueous solution of these compositions, particularly said alkali metal phosphate hydrate.
Because used calcium source is the calcium salt of water microsolubility in the aforesaid method of the present invention, so under its equilibrium state in reaction system, the calcium ion of the participation that dissociates reaction is micro-, with a large amount of phosphate radical (PO that exist around it
4 3-) can react rapidly after the contact and generate HA and the TCP Thermodynamically stable product with littler Ksp value.The balance of (as calcium sulfate etc.) is constantly broken because this solid phase water microsolubility calcium salt in the reaction system, and calcium wherein also just will constantly dissolve in the reaction system medium (water), and carry out above-mentioned reaction generation HA and TCP rapidly.Thereby make the product of the some irrelevant dissociation equilibrium state that is difficult to avoid in the above-mentioned conventional wet chemistry method building-up reactions, in preparation feedback process of the present invention, can greatly reduce and avoid.The thermodynamic data of related associated products (thermodynamic data is drawn from inorganic chemistry teaching and research room of Dalian University of Technology volume " inorganic chemistry ") as shown in table 1.
The thermodynamic data of table 1 associated products (KJ/mol, 298.15k)
| Ca 10(PO 4) 6(OH) 2 | Ca 3(PO 4) 2 | CaHPO 4 | CaHPO 4·2H 2O | CaSO 4·2H 2O | |
| ΔfG Θm | -12677 | -3884.7 | -1681.18 | -2154.58 | -1797.28 |
By the thermodynamic data of table 1 as can be seen, during as the calcium source, continue the Ca that trace dissolves in the calcium sulphate dihydrate of microsolubility in the reaction system
2+Obviously be to generate the more stable HA of thermodynamics easily, TCP, thereby above-mentioned reaction process and the product of the present invention belongs to thermodynamic control, unlikely generally speaking final component and the performance that influences product of reaction conditions, the condition of reaction is more easy to control, the product that generates is more stable, and the composition of reaction system is also more simple.
Test shows that the change of temperature of reaction is also not obvious to the influence of the above-mentioned reaction process of the present invention generally speaking.But do not avoid that to spend the low or too high activity of relevant ions in the reaction system that makes too low or too high because of reaction temperature, may cause reacting not exclusively and the product foreign matter content higher, or generate more thermodynamic instability by product, generally under 4 ℃～95 ℃ and pH 6.5-10 condition, can carry out smoothly and finish.
The pH of reaction system can adopt generally speaking as yellow soda ash, sodium bicarbonate, bicarbonate of ammonia etc. have weaken alkalescence carbonate regulate, its carbanion can also be entrained in the end product phosphorite crystal simultaneously, for the product type osteolith provides needed carbanion.
For the composition that makes resulting osteoid apatite product more near the natural composition form of people's bone, used calcium salt and the Ca/P mol ratio in the phosphoric acid salt preferably are adopted as (1～1.7)/1 during preparation.Test-results shows, the Ca/P mol ratio in the osteoid apatite product for preparing by the inventive method is consistent substantially with calculated value by reaction raw materials.
Adopt the reaction times of aforesaid method of the present invention, decided by the charging capacity of reactant, reacting weight is big, and required time prolongs.Generally speaking, this is reflected in 2～8 hours and can finishes, and for example, generally need 4～8 hours with industrial tun equipment reaction, and bench-scale small-sized reaction (hundreds of grams for example feed intake) then can be finished reaction in 2～4 hours.For making the calcium phosphate (TCP) that generates in the reaction can fully be converted into said osteoid apatite (HA), after above-mentioned reaction is finished, generally with still aging at least 24 hours for well, for example can be still aging 24～72 hours, obtain the slurry of corresponding nano level osteoid apatite then after water (as the hot deionized water) washing.This slurry can directly be used for currently reported and/or the compound bone reparation of nano bionic of use and the preparation of equivalent material as raw material, also can be dry under 80 ℃～100 ℃, obtain corresponding osteoid apatite powder.
Below in conjunction with the embodiment of accompanying drawing illustrated embodiment, foregoing of the present invention is described in further detail again.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following example.Do not breaking away under the above-mentioned technological thought situation of the present invention, various replacements or change according to ordinary skill knowledge and customary means are made all should comprise within the scope of the invention.
Description of drawings
Fig. 1 is the IR collection of illustrative plates that adopts behind the nano-apatite slurry drying of the inventive method preparation.
Fig. 2 is the XRD figure spectrum that adopts behind the nano-apatite slurry drying of the inventive method preparation.
Embodiment
Embodiment 1
Get 456g 12 hypophosphite monohydrate trisodiums and join wiring solution-forming in 3000 ml deionized water, under agitation condition, add the 345g terra alba, constantly stir and make it reaction.Add 0.2g sodium bicarbonate conditioned reaction system pH～7 simultaneously, stop after 8 hours stirring in reaction under 20 ℃ of conditions, still aging at ambient temperature, ageing 48 hours.Remove supernatant liquor after the ageing, with 60 ℃ of deionized water wash at least 6 times.Be prepared into the slurry of water content 70% after the washing.Get prepared slurry after oven dry under 80 ℃～100 ℃, do the detection of the analysis of infrared absorption spectrum (IR) and X-ray diffraction (XRD) and calcium/phosphorus ratio.
Test result is as follows:
1. calcium in the prepared nano-apatite/phosphorus ratio is 1.64, meets calcium phosphorus content ratio in the natural bone.
2. in this crystal IR collection of illustrative plates shown in Figure 1,3570cm
-1And 628cm
-1The peak is the characteristic peak of hydroxyl, 871cm
-1Be HPO
4 2-The peak, 1400cm
-1And 1500cm
-1Be CO
3 2-The peak, 1038cm
-1And 564cm
-1It is the characteristic peak of phosphate radical.The IR spectrogram that this IR spectrogram and human body natural's bone high temperature are burnt behind the organism is very close, illustrates that the phosphorite crystal of the present invention's preparation and natural bone phosphorite crystal are very approaching on forming.
3. in the XRD figure spectrum of Fig. 2, its reflection angle 2 θ have corresponding characteristic peak near 26 °, 32 °, 34 °, 40 °, 47 ° and 50 °, quite similar with people's spongy bone phosphorite crystal collection of illustrative plates.According to the Scherrer formula:
(λ is the X ray wavelength to D=K λ/β cos θ; K is the Scherrer constant, and its value is 0.89; D is grain-size (nm); β is an integration halfwidth degree; θ is a diffraction angle) calculating prepared phosphorite crystal particle diameter D=(10.7 ± 1) nm.Therefore, the prepared phosphorite crystal of the present invention is of a size of nano level.
By above-mentioned analysis, contain CO in the nano level phosphatic rock that adopts the present invention to prepare
3 2-, HPO
4 2-Plasma.In addition, the IR of the prepared nano-apatite crystals of the present invention and XRD spectra are quite similar with the spectrogram of nature bone phosphatic rock, illustrate that the The Nomenclature Composition and Structure of Complexes of prepared nano-apatite crystals and nature bone phosphorite crystal is very approaching, can have good biological activity.
Embodiment 2
Get 380g 12 hypophosphite monohydrate trisodiums and join wiring solution-forming in 3000 ml deionized water, under agitation condition, add the 258g calcium sulphate dihydrate, constantly stir and make it reaction.Add the 0.16g sodium bicarbonate simultaneously with conditioned reaction system pH～7, after 8 hours, stop to stir still aging at ambient temperature 48～72 hours in reaction under 20 ℃ of conditions.Remove supernatant liquor after the ageing, get final product at least 6 times with 60 ℃ of deionized water wash.Yield reaches 98.5%.The test ratio of calcium and phosphorus is 1.53 behind the slurry drying.
Embodiment 3～12
According to the form below is got the different phosphate hydrochlorate and is joined wiring solution-forming in 3000 ml deionized water, adds calcium salt under agitation condition, constantly stirs to make it reaction.Add sodium bicarbonate conditioned reaction system pH simultaneously.After finishing, reaction stops to stir still aging at ambient temperature 48 hours.Remove supernatant liquor after the ageing, with 60 ℃ of deionized water wash at least 6 roads.Yield and ratio of calcium and phosphorus such as table 2.
The correlation parameter of table 2 embodiment 3～12
Claims (8)
1. the preparation method of the osteoid apatite of thermodynamic control is characterized in that be raw material with the Ksp value greater than the calcium salt of the water microsolubility of osteoid apatite, obtains after the reaction in the aqueous solution of water-soluble phosphate.
2. preparation method as claimed in claim 1 is characterized in that said calcium salt is calcium sulfate or its hydrate, and said water-soluble phosphate is PO
4 3-The salt that is become with basic metal, corresponding ammonium salt, or the hydrate of these compositions.
3. preparation method as claimed in claim 1 is characterized in that said temperature of reaction is 4 ℃～95 ℃.
4. preparation method as claimed in claim 1 is characterized in that carrying out under the condition of the said pH of being reflected at value 6.5-10.
5. preparation method as claimed in claim 4 is characterized in that said pH value in reaction regulates with sodium bicarbonate.
6. preparation method as claimed in claim 1 is characterized in that the Ca/P mol ratio in said calcium salt and the phosphoric acid salt is (1～1.7)/1.
7. as the described preparation method of one of claim 1 to 6, it is characterized in that said reaction is finished after, still aging at least 24 hours.
8. preparation method as claimed in claim 7 is characterized in that the still aging time after said reaction is finished is 24～72 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN112938917A (en) * | 2021-01-28 | 2021-06-11 | 北京大学 | Preparation method of efficient nano-phosphate fertilizer and nano-phosphate fertilizer |
-
2009
- 2009-06-09 CN CNA2009100595393A patent/CN101565178A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102616762A (en) * | 2011-02-01 | 2012-08-01 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN102616762B (en) * | 2011-02-01 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Method for hydro-thermal preparation of hydroxyapatite powder by calcium silicate precursor |
| CN112938917A (en) * | 2021-01-28 | 2021-06-11 | 北京大学 | Preparation method of efficient nano-phosphate fertilizer and nano-phosphate fertilizer |
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Open date: 20091028 |