CN103466580A - Preparation method of hydroxyapatite microspheres - Google Patents
Preparation method of hydroxyapatite microspheres Download PDFInfo
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- CN103466580A CN103466580A CN2013103493523A CN201310349352A CN103466580A CN 103466580 A CN103466580 A CN 103466580A CN 2013103493523 A CN2013103493523 A CN 2013103493523A CN 201310349352 A CN201310349352 A CN 201310349352A CN 103466580 A CN103466580 A CN 103466580A
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Abstract
The invention discloses a preparation method of hydroxyapatite microspheres. Methods for synthesizing spherical hydroxyapatite at present mainly comprise a secondary granulation molding method and a direct synthesis method, and the secondary granulation molding method has a high cost because of high apparatus requirements, strict reaction conditions and large energy consumption. Particles prepared through the direct synthesis method have a wide particle size distribution and have an irregular morphology. The method disclosed in the invention comprises the following steps: placing spherical calcium carbonate in an aqueous solution of phosphate as a precursor template, carrying out a hydrothermal method and a microwave radiation method, and carrying out an anion exchange reaction to prepare the hydroxyapatite microspheres. The method disclosed in the invention has the characteristics of rapid reaction, simple operation process, no need of template removal and the like. The obtained hydroxyapatite microspheres can be widely used in the biomedical field as an ideal carrier material for drug sustained release.
Description
Technical field
The invention belongs to the lithotroph field of medical materials, be specifically related to a kind of preparation method of hydroxyapatite micro-sphere.
Background technology
In organizational engineering, Microspheres Technique is an important technology.Microballoon can be used as the carrier of seed cell and medicine etc., also can be used in the tissue engineering bracket preparation.The microballoon medicine carrying with respect to the support medicine carrying have the controlled release ability strong, can realize the advantages (Cui Daichao, model rural area, 2010) such as multi-medicament sequentially discharges.Aspect cell cultures, it can provide three-dimensional environment, has simulated the phenotype that cell growing environment in vivo is conducive to cell; In addition, traditional nano material is because very easily reunite, and simple, while relying under physisorption medicine carrying, drug loading is limited; And that the micron-size spherical inorganic materials has tap density is large, good fluidity, the characteristics such as workability is good.
Hydroxyapatite is a kind of important inorganic composition part in skeleton and tooth, because it has good biocompatibility, osteoconductive, mobility and adsorptivity, and is widely used in the aspects such as bone tissue engineer technology.The hydroxyapatite material of the variforms such as in recent years,, for meeting different application demands, that investigators have prepared is spherical, bar-shaped, sheet, crystal whisker-shaped.In these forms, spherical hydroxyapatite has the advantages such as good fluidity, specific surface area is high, affinity good, compactedness is high, minimum tumor promotion rate and receives great concern.At present, the main secondary granulation method of forming of the method for synthesizing spherical hydroxyapatite and direct synthesis technique, wherein post forming method comprises plasma fusion, spray-drying process.These class methods are higher to equipment requirements because of it, severe reaction conditions, and energy consumption causes cost high greatly, is unfavorable for practical application in industry production.Direct synthesis technique mainly is divided into two kinds: a kind of is to utilize calcium salt and phosphoric acid salt as raw material, by the parameters such as stoichiometric ratio, pH value, ionic strength, temperature in the furnishing reaction process, directly controls the synthetic particle with certain special appearance, specific dimensions and microstructure.Usually, the prepared particle diameter of this kind of method is distributed more widely, and pattern is rule not.Another kind is to using the large flexible organic molecule of structurally variable as the soft template method of template and using to have the hard template method of the material of rigid structure as template, by ion exchange reaction, synthesizes the particle of preparing desired structure and pattern.Calcium carbonate, as a kind of important inorganic materials, because it has good biocompatibility and pattern highly variable, and becomes the desirable template material for preparing hydroxyapatite, existing Patents file.Prepared the hydroxyapatite active material as Chinese patent (patent No. 97103827.9) utilizes natural coral calcium carbonate under hydrothermal condition, Chinese patent (number of patent application 200310107928.1) discloses a kind of hydrothermal method of utilizing and coral calcium carbonate has been converted into to the preparation method of porous hydroxyapatite.It is worthy of note, the two is simple utilizes hydrothermal method, and the reaction times, reaction process was slow all more than a couple of days, is unfavorable for that industry produces fast.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of hydroxyapatite micro-sphere is provided, has usingd spherical calcium carbonate as pioneer's template, be placed in aqueous phosphatic, be aided with microwave irradiation on the basis of hydrothermal method, by anion exchange reaction, prepare hydroxyapatite micro-sphere.
Concrete grammar of the present invention comprises the following steps:
Step (1). regulate with alkaline solution the aqueous phosphatic that concentration is 2.17～27.6g/L, until the pH value is 10;
Described alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and its concentration is 0.1～1mol/L.
Described phosphoric acid salt is Sodium phosphate dibasic, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
Step (2). add calcium carbonate powders in the aqueous phosphatic after regulating the pH value, and stir at normal temperatures the formation suspension liquid; The calcium carbonate added and phosphatic mol ratio are 1:0.6～7.5.
The granule-morphology of described calcium carbonate powders is spherical.
Step (3). the suspension liquid of gained is placed in to the microwave oven reacting by heating, and the microwave firepower is 60～100W, and the reaction times is 5～15min.
Described microwave oven is commercially available common microwave stove.
Step (4). by the solution filter after step (3) heating, and replace flush cake respectively more than 3 times with deionized water, dehydrated alcohol.
The millipore filtration suction filtration that described filtration is is 0.1～0.22 μ m by filtrate with aperture.
Step (5). the filter cake of rinsing well in step (4) is put into to thermostatic drying chamber dry, then solid matter is ground to form to dry powder, obtain hydroxyapatite micro-sphere.
Described drying conditions is dry 24～48h under 40～60 ℃.
The present invention can recently prepare the single dispersion hydroxyapatite micro-sphere that size distribution is even, sphericity is high by control reaction times, microwave firepower, calcium phosphorus mole.The ball shaped hydroxy-apatite median size that the present invention prepares is 6.0～7.0 μ m, and particle surface is open microvoid structure by fine hair shape nanoparticle weave in, is a kind of ideal material as pharmaceutical carrier.In addition, by changing reaction parameter, can prepare the residual hydroxyapatite micro-sphere that a certain amount of calcium carbonate is arranged.
The invention has the beneficial effects as follows:
The present invention be take hydrothermal method as basis, is aided with microwave irradiation Reaction time shorten greatly, prepares hydroxyapatite micro-sphere in short several minutes, thereby has improved production efficiency.
The present invention utilizes calcium carbonate structure, pattern, characteristics easy to control in size, by microwave hydrothermal, reacts and is translated into hydroxyapatite, and the particle of gained has retained pattern and the size of calcium carbonate.
Calcium carbonate is the inorganic materials of a class good biocompatibility, utilizes calcium carbonate to prepare hydroxyapatite without removing template as template, thereby has avoided the problems such as pollution of template to final sample.On the contrary, the difference due to calcium carbonate and calcium phosphate degradation rate, can realize the control to the hydroxyapatite degradation rate.
Reaction conditions gentleness of the present invention, operating process is simple, is swift in response.
The accompanying drawing explanation
The field emission scanning electron microscope figure that Fig. 1～4 are hydroxyapatite micro-sphere in the embodiment of the present invention; Wherein (a) is the low power scanning electron microscope (SEM) photograph; (b) be the high power scanning electron microscope (SEM) photograph;
The x-ray diffraction pattern that Fig. 5～7 are hydroxyapatite micro-sphere in the embodiment of the present invention;
Fourier's infrared spectrogram that Fig. 8 is hydroxyapatite micro-sphere in the embodiment of the present invention.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) by 0.434g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide that concentration is 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 80W, and the reaction times is 15min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.1 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse each 3 times, then put into 40
oobtain hydroxyapatite micro-sphere in the thermostatic drying chamber of C after dry 24h.
After testing: the prepared microballoon principal phase of embodiment 1 is hydroxyapatite, particle diameter is about 6.8 μ m, the microsphere surface thin layer is comprised of the rod-like nano particle, and these nanoparticle weave ins present fine and close microvoid structure (as Fig. 1), and residual calcium carbonate diffraction peak more (as Fig. 5).
withanalytical pure calcium carbonate and analytical pure hydroxyapatite are formulated typical curve as standard specimen, utilize the external standard method in the X-ray diffraction quantitative analysis method to analyze phase content in the gained particle.In the known particle of analytical results, the transformation efficiency of calcium carbonate is 12.3 ﹪.
Embodiment 2
(1) by 1.808g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 100W, and the reaction times is 5min, carries out the microwave heating reaction.
(5) by the solution after heating, with aperture, being 0.1 μ m, millipore filtration carries out suction filtration, and deionized water, the dehydrated alcohol filter cake for that obtain alternately rinse respectively 4 times, obtains hydroxyapatite micro-sphere after then putting into the dry 48h of thermostatic drying chamber of 40 ℃.
After testing: the prepared microballoon principal phase of embodiment 2 is hydroxyapatite, and particle diameter is about 6.5 μ m, and the microsphere surface thin layer is comprised of shuttle shape nanoparticle, and these nanoparticle weave ins present fine and close microvoid structure (as Fig. 2).The material phase analysis that these particles are carried out shows: in particle, the residual quantity of calcium carbonate is still higher (as figure
6), utilize as known as calcium carbonate content in the analysis of the X-ray diffraction external standard method in embodiment 1 gained particle: in the particle prepared under this condition, the calcium carbonate transformation efficiency is 50.1 ﹪.
Embodiment 3
(1) by 3.616g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 0.1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 60W, and the reaction times is 15min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.15 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse each 3 times, then put into 60
oobtain hydroxyapatite micro-sphere in the thermostatic drying chamber of C after dry 24h.
After testing: the prepared microballoon principal phase of embodiment 3 is hydroxyapatite, and particle diameter is about 6.0 μ m, and microsphere surface is comprised of acicular nanoparticles, and these nanoparticle weave ins present comparatively open microvoid structure.Utilize as known as calcium carbonate content in the analysis of the X-ray diffraction external standard method in embodiment 1 gained particle: in the particle prepared under this condition, the calcium carbonate transformation efficiency is 71.7 ﹪.
Embodiment 4
(1) by 5.52g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 80W, and the reaction times is 10min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.2 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse each 3 times, then put into 60
oobtain hydroxyapatite micro-sphere in the thermostatic drying chamber of C after dry 48h.
After testing: the prepared microballoon principal phase of embodiment 4 is hydroxyapatite (as Fig. 3), and particle diameter is about 6.5 μ m, and microsphere surface presents open microvoid structure (as Fig. 3) by fine hair shape nanoparticle weave in.The material phase analysis that these particles are carried out shows: in particle, the residual quantity of calcium carbonate is higher (as figure
7), utilize as known as calcium carbonate content in the analysis of the X-ray diffraction external standard method in embodiment 1 gained particle: in the particle prepared under this condition, the calcium carbonate transformation efficiency is 94.5 ﹪.
Embodiment 5
(1) by 5.52g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 80W, and the reaction times is 5min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.22 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse each 3 times, then put into 60
oobtain hydroxyapatite micro-sphere in the thermostatic drying chamber of C after dry 48h.
After testing: the prepared microballoon principal phase of embodiment 5 is hydroxyapatite, and particle diameter is about 6.3 μ m, and the microsphere surface thin layer presents fine and close microvoid structure (as Fig. 4) by the acicular nanoparticles weave in.Utilize as known as calcium carbonate content in the analysis of the X-ray diffraction external standard method in embodiment 1 gained particle: in the particle prepared under this condition, the calcium carbonate transformation efficiency is 76 ﹪.
Embodiment 6
(1) by 5.52g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 80W, and the reaction times is 10min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.22 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse each 3 times, then put into 60
oobtain hydroxyapatite micro-sphere in the thermostatic drying chamber of C after dry 48h.
After testing: the prepared microballoon principal phase of embodiment 6 is hydroxyapatite, and particle diameter is about 7 μ m, and the microsphere surface thin layer presents open microvoid structure by fine hair shape nanoparticle weave in.Utilize as the X-ray diffraction external standard method in embodiment 1 and analyze calcium carbonate content in the gained particle, in the particle prepared under known this condition, the calcium carbonate transformation efficiency is 79.8 ﹪.
Embodiment 7
(1) by 5.52g Sodium phosphate dibasic (Na
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 60W, and the reaction times is 15min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.22 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse each 3 times, then put into 60
oobtain hydroxyapatite micro-sphere in the thermostatic drying chamber of C after dry 48h.
After testing: the prepared microballoon principal phase of embodiment 7 is hydroxyapatite, and particle diameter is about 6.3 μ m, and microsphere surface presents fine and close microvoid structure by rod-like nano particle weave in.Utilize as the X-ray diffraction external standard method in embodiment 1 and analyze calcium carbonate content in the gained particle, in the particle prepared under known this condition, the calcium carbonate transformation efficiency is 40.4 ﹪.
Embodiment 8
(1) by 5.52g dipotassium hydrogen phosphate (K
2hPO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the potassium hydroxide of 0.1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 60W, and the reaction times is 15min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.22 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse 4 times, then put into 60
oin the thermostatic drying chamber of C, dry 48h, obtain hydroxyapatite micro-sphere.
Embodiment 9
(1) by 5.04g SODIUM PHOSPHATE, MONOBASIC (NaH
2pO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the sodium hydroxide of 0.1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 100W, and the reaction times is 5min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.22 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse 5 times, then put into 60
oin the thermostatic drying chamber of C, dry 48h, obtain hydroxyapatite micro-sphere.
(1) by 5.04g SODIUM PHOSPHATE, MONOBASIC (KH
2pO
412H
2o) be dissolved in the 200ml deionized water, be made into phosphate solution.
(2) slowly drip while stirring the potassium hydroxide of 1mol/L in above-mentioned solution, until the pH value reaches 10.
(3) add the 0.2g calcium carbonate granule in the phosphate solution of step (2), and constantly stir the formation suspension liquid.
(4) suspension liquid of gained is put into to microwave oven, regulating the microwave firepower is 80W, and the reaction times is 10min, carries out the microwave heating reaction.
(5) millipore filtration that is 0.22 μ m by reacted solution with aperture carries out suction filtration, and deionized water, the dehydrated alcohol for filter cake that obtain alternately rinse 3 times, then put into 60
oin the thermostatic drying chamber of C, dry 48h, obtain hydroxyapatite micro-sphere.
The granule-morphology of the calcium carbonate powders that embodiment 1～10 is used is spherical.
Embodiment is in conjunction with Fig. 3: prepared hydroxyapatite micro-sphere detects through scanning electron microscope, and grain diameter is even, good dispersity, and the sphericity ideal, particle surface forms open microvoid structure by fine hair shape crystal weave in.
Embodiment is in conjunction with Fig. 7: illustrating that prepared particle principal phase is hydroxyapatite, also contain a small amount of calcite, is the complete calcium carbonate of microballoon inside unreacted.
Embodiment is in conjunction with Fig. 8: conclusion is consistent with Fig. 7.
Finally, it should be noted that above lifted be only the specific embodiment of the invention case.
Obviously, the present invention is not limited only to above examples of implementation, and many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (5)
1. the preparation method of a hydroxyapatite micro-sphere is characterized in that the method comprises the following steps:
Step (1). regulate with alkaline solution the aqueous phosphatic that concentration is 2.17～27.6g/L, until the pH value is 10;
Step (2). add calcium carbonate powders in the aqueous phosphatic after regulating the pH value, and stir at normal temperatures the formation suspension liquid; The calcium carbonate added and phosphatic mol ratio are 1:0.6～7.5;
Step (3). the suspension liquid of gained is placed in to the microwave oven reacting by heating, and the microwave firepower is 60～100W, and the reaction times is 5～15min;
Step (4). by the solution filter after step (3) heating, and replace flush cake respectively more than 3 times with deionized water, dehydrated alcohol;
Step (5). the filter cake of rinsing well in step (4) is put into to thermostatic drying chamber, and under 40～60 ℃, dry 24～48h, then grind to form dry powder by solid matter, obtains hydroxyapatite micro-sphere.
2. the preparation method of a kind of hydroxyapatite micro-sphere as claimed in claim, is characterized in that described alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and its concentration is 0.1～1mol/L.
3. the preparation method of a kind of hydroxyapatite micro-sphere as claimed in claim, is characterized in that the described phosphoric acid salt of step (2) is Sodium phosphate dibasic, dipotassium hydrogen phosphate, SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate.
4. the preparation method of a kind of hydroxyapatite micro-sphere as claimed in claim, is characterized in that the granule-morphology of the described calcium carbonate powders of step (2) is spherical.
5. the preparation method of a kind of hydroxyapatite micro-sphere as claimed in claim, is characterized in that the described filtration of step (4) is the millipore filtration suction filtration that is 0.1～0.22 μ m by filtrate with aperture.
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| CN105347322A (en) * | 2015-12-08 | 2016-02-24 | 浙江理工大学 | Spherical nano-porous hydroxylapatite prepared through shells and preparation method thereof |
| CN110182778A (en) * | 2019-04-22 | 2019-08-30 | 武汉理工大学 | A kind of nano-grade hydroxy apatite raw powder's production technology |
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