CN102874781A - Method for preparing calcium phosphate microspheres with high specific surface area - Google Patents
Method for preparing calcium phosphate microspheres with high specific surface area Download PDFInfo
- Publication number
- CN102874781A CN102874781A CN2012103721563A CN201210372156A CN102874781A CN 102874781 A CN102874781 A CN 102874781A CN 2012103721563 A CN2012103721563 A CN 2012103721563A CN 201210372156 A CN201210372156 A CN 201210372156A CN 102874781 A CN102874781 A CN 102874781A
- Authority
- CN
- China
- Prior art keywords
- calcium phosphate
- solution
- calcium carbonate
- calcium
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Abstract
The invention discloses a method for preparing calcium phosphate microspheres and a product obtained by the method, and particularly provides a method for quickly preparing calcium phosphate microspheres with high specific surface area. The method includes that solid calcium phosphate microsphere powder is added into phosphate solution for reaction and is characterized in that no surfactant is added during reaction. The calcium phosphate microspheres obtained by the method avoids surfactant pollution and is high in adsorbability to positive charge macromolecules and high in biological safety, and the application area of the calcium phosphate microspheres can be widened. Further, the method is simple and feasible in process and suitable for massive preparation of calcium phosphate microspheres with high specific surface area.
Description
Technical field
The invention belongs to field of porous materials, the preparation method who relates more specifically to calcium phosphate microsphere reaches the product that passes through its acquisition.
Background technology
Calcium phosphate is similar to character, the structure of people's bone and natural teeth, and good biocompatibility is arranged, and realizes mortise artificial bone, artificial joint, artificial nose's cartilage, wears bearing leather joint, artificial blood vessel, artificial tracheae etc.
At present, can see following report about the research of calcium base microballoon:
The U.S. (Biotechnology Progress (biotechnology progress), the 918th page to 925 pages of 21 phases in 2005) reported and utilized calcium carbonate microspheres to adsorb biomacromolecule, but this material only has 20 μ g/mg calcium carbonate by physical adsorption to the adsorptive capacity of bovine serum albumin, such adsorptive power is too little, can not satisfy the application needs in a lot of fields, and vaterite phase calcium carbonate is very unstable in the aqueous solution, is easy to change into calcite phase calcium carbonate and causes adsorptive power greatly to reduce.
The U.S. (Biomacromolecules (biomacromolecule), the 1962nd page to 1972 pages of the 5th phases in 2004) introduced the adsorptive power of calcium carbonate microspheres, and then it is changed into micro-capsule as template, but the calcium carbonate microspheres of this method is very unstable in the aqueous solution, and cost is higher, preparation process is complicated, is difficult to realize large-scale industrial production.
Holland (Microporous and Mesoporous Materials (microporous mesoporous material), the 118th volume was the 480th page to 488 pages in 2009) reported a kind of method that changes into calcium phosphate with calcium carbonate microspheres, calcium chloride is to get by add hydrochloric acid extraction from natural black lip in the method, then add sodium carbonate solution, add fast the calcium carbonate shape matching that sodium carbonate solution obtains regular.Vaterite content is low in the calcium carbonate that but obtains in this method, therefore it is very low to be converted into the ratio of calcium phosphate; Drip at a slow speed the calcium carbonate shape that sodium carbonate solution obtains very irregular in calcium chloride solution, this causes the last calcium phosphate shape that obtains also irregular, can cause the different batches product performance unstable therefore be used for suitability for industrialized production, and the shortcoming such as differ greatly; The 245th page of this magazine the 127th volume in 2010 reported again a kind of method that changes into calcium phosphate with calcium carbonate microspheres, but need to add Surfactant CTAB (cetyl trimethylammonium bromide) among this preparation method, and hexanaphthene, butanols, these additives assist calcium carbonate to the conversion of calcium phosphate as microreactor.Yet synthetic calcium phosphate can be reduced its biological activity by surface active agent pollution like this, also can reduce its reference area simultaneously.In addition, in this magazine also not about the report of the absorption property of calcium phosphate microsphere.
Summary of the invention
Given this, the purpose of this invention is to provide the method that a kind of Simple fast prepares calcium phosphate microsphere in a large number, do not use any tensio-active agent in the preparation process of the calcium phosphate microsphere of the inventive method, and make thus the calcium phosphate microsphere with high-specific surface area, it has high absorption property to positively charged biomacromolecule.
On the one hand, the invention provides a kind of quick method for preparing the high-ratio surface calcium phosphate microsphere, described method comprises that the pressed powder with calcium carbonate microspheres joins in the phosphate solution to react, and it is characterized in that, does not add any tensio-active agent in the described reaction process.
In a preferred implementation, the pressed powder of the described calcium carbonate microspheres of adding and described phosphate solution react with the amount of Ca/P=1.67 in molar ratio.
In a preferred implementation, the temperature of reaction of described reaction is 10 ℃-160 ℃, and the reaction times is 0.5h-72h.
In a preferred implementation, described calcium carbonate microspheres is by mixing the isocyatic calcium salt soln of equal-volume and carbonate solution and vigorous stirring obtains.
In a preferred implementation, described calcium salt soln is CaCl
2Solution, described carbonate solution is Na
2CO
3Solution, and their concentration is in the scope of 0.1M-1M.
In a preferred implementation, described calcium carbonate microspheres water and/or the washing with alcohol of acquisition obtain the pressed powder of described calcium carbonate microspheres after the drying.
In a preferred implementation, described phosphate solution is to be selected from (NH
4)
2HPO
4, Na
2HPO
4, NH
4H
2PO
4, NaH
2PO
4, K
2HPO
4And KH
2PO
4In one or more the aqueous solution.
In a preferred implementation, the concentration of described phosphate solution is 0.9M-4.5M.
In a preferred implementation, the concentration of described phosphate solution is 1.51M.
On the other hand, the invention provides a kind of high-ratio surface calcium phosphate microsphere that obtains by aforesaid method.
In the method for preparing the high-ratio surface calcium phosphate microsphere of the present invention, owing in reaction process, not adding any tensio-active agent, therefore have good biological safety, harmless, and the inventive method is simple, cost is low, be easy to extension and realize suitability for industrialized production, prepared high-ratio surface calcium phosphate microsphere can be used for the fields such as food, makeup.
Description of drawings
Fig. 1 is the calcium carbonate (CaCO that obtains according in the embodiment of the invention 1
3) scanning electron microscopy of microballoon.
Fig. 2 passes through CaCO according to the embodiment of the invention 1
3Microsphere solid powder and (NH
4)
2HPO
4Solution reacts the X-ray diffraction analysis figure of the different calcium phosphate microsphere products that obtained in 48 hours under differing temps.
Fig. 3 is the scanning electron microscopy according to the calcium phosphate microsphere of the embodiment of the invention 1 (temperature of reaction is 65 ℃) preparation.
Fig. 4 is the scanning electron microscopy according to the calcium phosphate microsphere of the embodiment of the invention 2 (temperature of reaction is 80 ℃) preparation.
Fig. 5 is the transmission electron microscopy figure of calcium phosphate microsphere after ultrasonication according to the embodiment of the invention 2 (temperature of reaction is 80 ℃) preparation.
Fig. 6 is according to the X-ray diffraction analysis figure of the embodiment of the invention 2 by prepared calcium phosphate microsphere of the differential responses time of calcium carbonate microspheres pressed powder in phosphate solution (temperature of reaction is 80 ℃).
Fig. 7 is the scanning electron microscopy according to the calcium phosphate microsphere of the embodiment of the invention 3 (temperature of reaction is 160 ℃) preparation.
Fig. 8 is the transmission electron microscopy figure of calcium phosphate microsphere after ultrasonication according to the embodiment of the invention 3 (temperature of reaction is 160 ℃) preparation.
Fig. 9 is the X-ray diffraction analysis figure according to the stability of calcium phosphate microsphere different time in water of the embodiment of the invention 3 preparations.
Figure 10 (a)～(c) is respectively according to the fluorescence microscopy figure behind the calcium phosphate microsphere absorption FITC-CMC (fluorescein isothiocyanate-cm-chitosan) of the embodiment of the invention 1～3 preparation.
Embodiment
The present invention relates to a kind of Simple fast and prepare in a large number the method for calcium phosphate microsphere, do not use any tensio-active agent in the preparation process of the calcium phosphate microsphere of the inventive method, and make thus the calcium phosphate microsphere with high-specific surface area, it has high absorption property to positively charged biomacromolecule.
More specifically, the quick method for preparing the high-ratio surface calcium phosphate microsphere of the present invention comprises that the pressed powder with calcium carbonate microspheres joins in the phosphate solution to react, do not add any tensio-active agent in described reaction process, the tensio-active agent here can be mentioned for example CTAB (cetyl trimethylammonium bromide), MDP (list-n-dodecylphosphoric acid), multipolymer EO
106PO
70EO
106(EO is poly(propylene oxide) for poly-ethylene oxide,1,2-epoxyethane, PO) etc.
Have in the method for the calcium phosphate microsphere that well carries attached macromole characteristic in rapid, high volume preparation of the present invention, utilize pressed powder existing or by synthetic calcium carbonate microspheres, it is joined in the phosphate solution, wherein in order not form defective type calcium phosphate, the add-on of the two is preferably calculated with Ca/P=1.67 in molar ratio, for example react more than the 0.5h for 10 ℃-160 ℃ times in differing temps, thereby obtained calcium phosphate microsphere.For the not restriction of the upper limit in reaction times of the present invention, but from economical and practical angle, the preferred reaction time is not long, for example below 72h.The calcium phosphate microsphere that the inventive method obtains has high-specific surface area, and than calcium carbonate microspheres of the prior art or calcium phosphate microsphere, the calcium phosphate microsphere that the present invention obtains has higher absorption property to positively charged macromole.
Preferably, the calcium carbonate microspheres that uses in the inventive method is by being prepared as follows acquisition: for example with the isocyatic calcium salt soln of equal-volume CaCl for example
2Solution, Ca (NO
3)
2Solution etc. and carbonate solution be Na for example
2CO
3Solution, K
2CO
3The short mix such as solution, their concentration be for example in the scope of 0.1M-1M, vigorous stirring simultaneously, and the calcium carbonate that obtains can obtain can be used for calcium carbonate microspheres of the present invention through washing, drying.For example, the preferred water of the calcium carbonate microspheres of acquisition and/or washing with alcohol, and dry and obtain the pressed powder of calcium carbonate microspheres.
Preferably, the phosphate solution that uses in the inventive method can be to be selected from (NH
4)
2HPO
4, Na
2HPO
4, NH
4H
2PO
4, NaH
2PO
4, K
2HPO
4And KH
2PO
4In one or more phosphate solutions.Preferably, the concentration of described phosphate solution for example is about 1.5M between 0.9M-4.5M.
In the methods of the invention, the reaction times of described reaction all can obtain to expect product more than 0.5 hour; Usually the reaction times is longer, calcium carbonate transforms more complete to calcium phosphate, in order to make reaction more complete, preferred low temperature (below 100 ℃) the lower reaction times of situation is approximately 48 hours, can suitably shorten the time in high temperature (more than 100 ℃) situation, this helps to keep the complete of calcium phosphate microsphere structure.
In the method for the invention, temperature of reaction all can obtain to expect product between 10 ℃ to 160 ℃; Usually temperature of reaction is higher, and calcium carbonate transforms more complete to calcium phosphate, be not subject to particular theory, in general, is the dissolution precipitation reaction under the low temperature, for example is higher than 140 ℃ of ion exchange reactions at high temperature.
As previously mentioned, more specifically, the preparation method of calcium phosphate microsphere of the present invention can comprise two key steps, at first is the synthetic of calcium carbonate microspheres, then calcium carbonate microspheres is changed into calcium phosphate microsphere.Here need to prove, the calcium carbonate microspheres that uses in the inventive method can be by commercially available or obtain by method known to those skilled in the art, and need not be confined to obtain by synthetic method of the present invention.Preferably, calcium carbonate microspheres synthetic is with the equal-volume isoconcentration calcium salt soln CaCl for example of 0.1M-1M for example
2Solution and carbonate solution be Na for example
2CO
3The solution short mix, vigorous stirring, the calcium carbonate water and the washing with alcohol that obtain, and place for example interior room temperature oven dry of loft drier for example to obtain the pressed powder of calcium carbonate microspheres after 24 hours.Follow the phosphate solution of formulation example such as 0.9M-4.5M, calcium carbonate powders is added (Ca/P=1.67 adds quantitative calcium carbonate in molar ratio), react more than 0.5 hour the calcium phosphate microsphere that obtains expecting in differing temps (10 ℃-160 ℃) is lower.The calcium phosphate microsphere that this method obtains has higher absorption property to the macromole of positive charge, namely, the present invention has adopted the method for the synthetic a large amount of high-ratio surface calcium phosphate microspheres of a kind of Simple fast, and the calcium phosphate microsphere that obtains simultaneously has higher absorption property to positively charged biomacromolecule.
In a specific embodiment of the present invention, for example, above-mentioned calcium phosphate microsphere preparation method comprises: with the equal-volume isoconcentration, and 0.33M CaCl for example
2Solution and for example 0.33M Na
2CO
3The solution short mix, vigorous stirring, water and ethanol are washed the calcium carbonate that obtains three times again, are placed on oven dry in the thermostatic drying chamber approximately obtains calcium carbonate microspheres after 24 hours pressed powder.Then (the NH of formulation example such as 1.51M in the 10ml deionized water
4)
2HPO
4, the ratio of Ca/P=1.67 adds 2.5g calcium carbonate pressed powder in molar ratio again, is to react under the differing temps for example 48 hours in 10 ℃-160 ℃, the calcium phosphate microsphere that obtains expecting, and this calcium phosphate microsphere has high absorption property to positively charged macromole.
Below in conjunction with embodiment the environment-friendly preparation method thereof of calcium phosphate microsphere of the present invention is done specific description.
Embodiment 1:
With isopyknic 0.33M CaCl
2With 0.33M Na
2CO
3Short mix in the reaction vessel of whipping appts, and vigorous stirring obtains the calcium carbonate microspheres solid precipitation about half a minute, water and ethanol will precipitate centrifugal (3000r/min again, 2min) washing is three times, be placed on the interior room temperature of vacuum drying oven and dry the pressed powder that approximately obtains calcium carbonate microspheres after 24 hours, sampling is analyzed its shape, and the result as shown in Figure 1.Then in the 10ml deionized water, prepare (the NH of 1.51M
4)
2HPO
4Solution, the ratio of Ca/P=1.67 adds the before pressed powder of the calcium carbonate microspheres of acquisition of 2.5g in molar ratio again, in 65 ℃ of lower reactions 48 hours, carry out centrifugal (3000r/min, 2min) obtain the calcium phosphate microsphere solid precipitation after the removal supernatant liquor, water and ethanol will wash three times again, be placed in the vacuum drying oven room temperature and dry approximately after 24 hours, obtain the pressed powder of calcium phosphate microsphere.X-ray diffraction analysis by powder shows, the calcium phosphate that obtains is hydroxyl carbapatite (HCAP) (it is a kind of calcium carbonate).The HCAP calcium carbonate microspheres surface shape that obtains is analyzed, and the result as shown in Figure 3.It is 67.47m that the full-automatic specific surface area of this oven dry pressed powder warp and pore analysis instrument (the Tristar II3020M of U.S. Micromeritics company) record specific surface area
2g
-1, this value is far above the 15.3678m of the calcium carbonate pressed powder that obtains before
2g
-1, above chemical reagent all can be available from for example Chemical Reagent Co., Ltd., Sinopharm Group.
Adsorptive power to the calcium phosphate microsphere that obtains detects, particularly, itself and FITC-CMC are compared blend with 1: 1 quality, 37 ℃ of lower shaking table 12h, centrifugal (8000r/min, 5min), record the fluorescent value (FITC-CMC in the supernatant liquor is the FITC-CMC that is not adsorbed) of supernatant liquor.The FITC-CMC of preparation different concns records its fluorescent value through spectrophotofluorometer, and obtains typical curve.By the fluorescent value of aforementioned supernatant liquor, can in typical curve, draw the concentration that is not adsorbed FITC-CMC accordingly, thereby can instead release the FITC-CMC amount of being adsorbed by calcium phosphate microsphere.Calculate afterwards after tested, the adsorptive capacity of the calcium phosphate microsphere that the present invention obtains is 402 μ g/mg HCAP.
For the present embodiment 1, Fig. 1 is the calcium carbonate (CaCO for preparing according in the present embodiment 1 process
3) scanning electron microscopy of microsphere solid powder, as can be seen from the figure, the calcium carbonate (CaCO that makes according to the present embodiment 1
3) microballoon is that particle diameter ratio is than the CaCO of homogeneous
3Microballoon.Because the calcium carbonate nucleation rate is very fast, therefore make fast the isopyknic CaCl of isoconcentration in present method
2With Na
2CO
3Solution mixes, and can form the relatively calcium carbonate microspheres of homogeneous of pattern.
Fig. 2 passes through CaCO according to the present embodiment 1
3Microsphere solid powder and (NH
4)
2HPO
4Solution reacts the X-ray diffraction analysis figure of the different calcium phosphate microsphere products that obtained in 48 hours under differing temps, wherein this calcium carbonate microspheres is placed (NH
4)
2HPO
4(10 ℃, room temperature (approximately 25 ℃), 37 ℃, 50 ℃, 65 ℃, 80 ℃, 160 ℃) reaction 48 hours under differing temps in the solution obtains the X-ray diffraction analysis figure of synthetic calcium phosphate under the differing temps.As shown in Figure 2, along with the rising of temperature, the content of calcium phosphate increases gradually, CaCO
3Content reduce gradually.In the time of 10 ℃ because CaCO
3Unstable in the aqueous solution, be converted into more the C phase, there is a small amount of calcium phosphate to generate; After temperature rose to room temperature, the calcium phosphate formation volume slightly had increase; In the time of 37 ℃, this temperature also is not enough to allow CaCO
3Be converted into rapidly calcium phosphate; In the time of 50 ℃, CaCO
3Can promptly be converted into calcium phosphate, therefore almost there is not the C phase, be the pure phase of HCAP substantially; In the time of 65 ℃, without C phase peak, be the pure phase of HCAP; In the time of 80 ℃, high temperature is CO
3 2-Removed, therefore HCAP is converted into hydroxyapatite (HAP) (for another kind of calcium phosphate) fully, be the pure phase of HAP, these can be referring to following examples 2; The same during with 80 ℃ on the phase in the time of 160 ℃, without any variation.
Fig. 3 obtains the scanning electron microscopy of HCAP microballoon (wherein for clearer when temperature of reaction is 65 ℃ in the present embodiment 1, in the upper right portion of this figure, shown the view that partly amplifies), as can be seen from Figure 3, the surface of the HCAP microballoon that obtains is queen of flowers's shape structure, such structure can increase the specific surface area of this calcium phosphate microsphere than smooth calcium phosphate microsphere, be conducive to increase its adsorptive power.
Embodiment 2:
Reaction process is similar to embodiment 1, by isopyknic 0.33M CaCl
2Solution and 0.33MNa
2CO
3Solution obtains the pressed powder of calcium carbonate microspheres.Then in the 10ml deionized water, prepare (the NH of 1.51M
4)
2HPO
4Ca/P=1.67 adds the resulting calcium carbonate pressed powder of 2.5g in molar ratio again, reaction obtained calcium phosphate in 48 hours under 80 ℃ of conditions, water and ethanol will precipitate centrifugal (3000r/min again, 2min) washing obtains the calcium phosphate solid precipitation for three times, be placed on the interior room temperature of vacuum drying oven and dry the pressed powder that approximately obtains calcium phosphate microsphere after 24 hours, the X-ray diffraction analysis figure of powder shows, the calcium phosphate that obtains is hydroxyapatite (HAP) (for another kind of calcium phosphate).The specific surface area that this oven dry pressed powder records is 53.35m
2g
-1, with itself and FITC-CMC with 1: 1 quality than blend, the amount of absorption FITC-CMC is 376 μ g/1mg HAP.
Fig. 4 be the present embodiment 2 when temperature of reaction is 80 ℃, obtain the HAP microballoon scanning electron microscopy (wherein for clearer, in the upper right portion of this figure, shown the view that partly amplifies), as can be seen from Figure 4, the surface of the HAP microballoon that obtains is fine hair shape structure, such surface tissue can increase the specific surface area of this calcium phosphate microsphere than smooth calcium phosphate microsphere, be conducive to increase its adsorptive power.
Fig. 5 is the transmission electron microscopy figure after the HAP ultrasonication that obtains in the present embodiment 2, as can be seen from Figure 5, this HAP microballoon that obtains than low reaction temperatures (80 ℃) is that flaky material forms, such structure is because than under the low reaction temperatures, and it is that dissolving-precipitator method by the surface form that calcium carbonate transforms to calcium phosphate.
Fig. 6 is at the differential responses time (X-ray diffractogram of 0～48h) product that obtains when calcium carbonate transforms to calcium phosphate in the present embodiment 2, as can be seen from Figure 6, along with the prolongation in reaction times, the content of calcium phosphate increases gradually and the amount of calcium carbonate reduces gradually.Particularly, being 0.5h when the reaction times, having had quite a few calcium carbonate to change calcium phosphate into, is 1h when the reaction times, the calcium carbonate of all vaterite phases all is converted into calcium phosphate, phase is calcium phosphate and calcite phase calcium carbonate, is 6h when the reaction times, and all calcium carbonate all is converted into calcium phosphate, the calcium phosphate of this moment is HCAP, be increased to 36h when the reaction times, the conversion of this moment is along with the prolongation of time is more abundant, and the calcium phosphate that obtains is HAP.
Embodiment 3:
Reaction process is similar to embodiment 1, by isopyknic 0.33M CaCl
2Solution and 0.33MNa
2CO
3Solution obtains calcium carbonate microspheres.(the NH of preparation 1.51M in the 10ml deionized water
4)
2HPO
4Ca/P=1.67 adds 2.5g calcium carbonate pressed powder in molar ratio again, and reaction obtained calcium phosphate in 48 hours under 160 ℃ of hydrothermal conditions, and water and ethanol will precipitate centrifugal (3000r/min again, 2min) washing obtains the calcium phosphate solid precipitation for three times, and oven dry obtains the HAP powder.The specific surface area that this oven dry pressed powder records is 35.20m
2g
-1, with itself and FITC-CMC with 1: 1 quality than blend, the amount of absorption FITC-CMC is 367 μ g/1mg HAP.
Fig. 7 is the scanning electron microscopy that obtains the HAP microballoon when temperature of reaction is 160 ℃ in the present embodiment 3, as can be seen from Figure 7, the surface of the HAP microballoon that obtains is fine hair shape structure, such structure can increase the specific surface area of this calcium phosphate microsphere than smooth calcium phosphate microsphere, be conducive to increase its adsorptive power.
Fig. 8 is the transmission electron microscopy figure after the HAP microballoon ultrasonication that obtains in the present embodiment 3, as can be seen from Figure 8, the HAP that this hydrothermal high-temperature (160 ℃) obtains is that needle-like material forms, this is that the calcium phosphate microsphere that obtains is more loose owing to the ion exchange reaction that is converted into of the calcium carbonate under the hot conditions to calcium phosphate.
In addition, for testing by the stability of HAP microballoon in water that obtains in the present embodiment 3, the result as shown in Figure 9.As can be seen from Figure 9, from the time 3h water to year, the HAP calcium phosphate microsphere that the present invention obtains demonstrates good stability, phase transition did not occur in the aqueous solution in 1 year yet, remarkable stability can well be applied to numerous areas so that the calcium phosphate microsphere of the present invention's preparation has broad application prospects like this.
In addition, test for the absorption property of three kinds of calcium phosphate microspheres that obtain in the embodiment of the invention 1～3, its result is shown in Figure 10 (a)～(c).Figure 10 (a)～(c) is respectively the fluorescence microscopy figure behind three kinds of calcium phosphate microsphere absorption FITC-CMC that obtain among the embodiment 1～3, as can be seen from the figure, demonstrate very strong fluorescence behind the calcium phosphate microsphere absorption FITC-CMC that the inventive method obtains, show that the calcium phosphate microsphere that present method obtains has very strong adsorptive power to the macromole with positive charge, this is because the calcium phosphate that this law obtains has loose porous structure, high-ratio surface can increase its adsorptive power, itself is with negative charge in addition, therefore can produce electrostatic adsorption to positively charged macromole, thereby obtain higher adsorption rate.
Embodiment 4:
Reaction process is similar to embodiment 1, by isopyknic 0.1M CaCl
2Solution and 0.1MNa
2CO
3Solution obtains the calcium carbonate microspheres pressed powder.(the NH of preparation 1.51M in the 10ml deionized water
4)
2HPO
4Solution, Ca/P=1.67 adds 2.5g calcium carbonate microspheres pressed powder in molar ratio again, reaction is 48 hours under 110 ℃ of hydrothermal conditions, throw out is washed 3 times with deionized water and ethanol, oven dry obtains calcium phosphate powder, this powder is shown as HAP through X ray diffracting spectrum, and is similar to Example 2 to the result of its analysis.
Embodiment 5:
Reaction process is similar to embodiment 1, by isopyknic 1M CaCl
2Solution and 1M Na
2CO
3Solution obtains the calcium carbonate microspheres pressed powder, and the Fig. 1 among the scanning electron microscopy of this microballoon powder and the embodiment 1 is similar, just smaller than embodiment 1 of microspherulite diameter.(the NH of preparation 1.51M in the 10ml deionized water
4)
2HPO
4Solution, Ca/P=1.67 adds 2.5g calcium carbonate microspheres pressed powder in molar ratio again, reaction is 24 hours under 150 ℃ of hydrothermal conditions, wash three times with deionized water and ethanol, oven dry obtains calcium phosphate powder, and oven dry obtains calcium phosphate powder, this powder is shown as HAP through X ray diffracting spectrum, result to its analysis is similar to Example 3, wherein because the method before the calcium carbonate particle diameter ratio is little, therefore synthetic HAP microspherulite diameter is also less before.
Therefore, the characteristics that the synthetic calcium phosphate of present method has simply, quick, cost is low, output is large, and the adding without any other tensio-active agent, therefore without any side effects, the calcium phosphate that obtains has good biocompatibility, and highly stable, the macromole with positive charge is had very strong adsorptive power, therefore can be widely used in the numerous areas such as food, makeup, chemical industry.
Below the present invention is described in detail, but the present invention is not limited to embodiment described herein.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, can make other changes and distortion.Scope of the present invention is defined by the following claims.
Claims (10)
1. method for preparing fast the high-ratio surface calcium phosphate microsphere, described method comprise that the pressed powder with calcium carbonate microspheres joins in the phosphate solution to react, and it is characterized in that, do not add any tensio-active agent in the described reaction process.
2. method according to claim 1 is characterized in that, the pressed powder of the described calcium carbonate microspheres of adding and described phosphate solution react with the amount of Ca/P=1.67 in molar ratio.
3. method according to claim 1 is characterized in that, the temperature of reaction of described reaction is 10 ℃-160 ℃, and the reaction times is 0.5h-72h.
4. method according to claim 1 is characterized in that, described calcium carbonate microspheres is by mixing the isocyatic calcium salt soln of equal-volume and carbonate solution and vigorous stirring obtains.
5. method according to claim 4 is characterized in that, described calcium salt soln is CaCl
2Solution, described carbonate solution is Na
2CO
3Solution, and their concentration is in the scope of 0.1M-1M.
6. method according to claim 4 is characterized in that, described calcium carbonate microspheres water and/or the washing with alcohol of acquisition obtain the pressed powder of described calcium carbonate microspheres after the drying.
7. method according to claim 1 is characterized in that, described phosphate solution is to be selected from (NH
4)
2HPO
4, Na
2HPO
4, NH
4H
2PO
4, NaH
2PO
4, K
2HPO
4And KH
2PO
4In one or more the aqueous solution.
8. method according to claim 7 is characterized in that, the concentration of described phosphate solution is 0.9M-4.5M.
9. method according to claim 7 is characterized in that, the concentration of described phosphate solution is 1.5M.
10. one kind is passed through the high-ratio surface calcium phosphate microsphere that each described method obtains in the claim 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103721563A CN102874781A (en) | 2012-09-28 | 2012-09-28 | Method for preparing calcium phosphate microspheres with high specific surface area |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103721563A CN102874781A (en) | 2012-09-28 | 2012-09-28 | Method for preparing calcium phosphate microspheres with high specific surface area |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102874781A true CN102874781A (en) | 2013-01-16 |
Family
ID=47476346
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103721563A Pending CN102874781A (en) | 2012-09-28 | 2012-09-28 | Method for preparing calcium phosphate microspheres with high specific surface area |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102874781A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776164A (en) * | 2016-02-03 | 2016-07-20 | 中国科学技术大学 | Inorganic hollow particle and preparation method thereof |
| CN114516766A (en) * | 2022-01-26 | 2022-05-20 | 华南农业大学 | Method for recovering phosphate in sewage by in-situ generation of calcium carbonate microsphere phosphate fertilizer and application of method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126211A1 (en) * | 2006-05-03 | 2007-11-08 | Megagen Co., Ltd. | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| CN101622196A (en) * | 2007-02-09 | 2010-01-06 | 索尔维公司 | Handle the method for contaminated by heavy metals material |
| CN102649995A (en) * | 2012-05-24 | 2012-08-29 | 崇义章源钨业股份有限公司 | Method for transforming wolframite into scheelite |
-
2012
- 2012-09-28 CN CN2012103721563A patent/CN102874781A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007126211A1 (en) * | 2006-05-03 | 2007-11-08 | Megagen Co., Ltd. | Method for fabricating calcium phosphate and calcium phosphate fabricated by using the same |
| CN101622196A (en) * | 2007-02-09 | 2010-01-06 | 索尔维公司 | Handle the method for contaminated by heavy metals material |
| CN102649995A (en) * | 2012-05-24 | 2012-08-29 | 崇义章源钨业股份有限公司 | Method for transforming wolframite into scheelite |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105776164A (en) * | 2016-02-03 | 2016-07-20 | 中国科学技术大学 | Inorganic hollow particle and preparation method thereof |
| CN105776164B (en) * | 2016-02-03 | 2018-07-03 | 中国科学技术大学 | A kind of inorganic hollow particle and preparation method thereof |
| CN114516766A (en) * | 2022-01-26 | 2022-05-20 | 华南农业大学 | Method for recovering phosphate in sewage by in-situ generation of calcium carbonate microsphere phosphate fertilizer and application of method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102701172B (en) | Method for preparing hydroxyapatite nanocrystals or microcrystals by using plant as template | |
| CN101787101B (en) | Preparation method of nanometer resin with high hygroscopy | |
| CN102716723B (en) | Method for preparing environment-friendly starch/bentonite composite material | |
| CN100564258C (en) | A kind of method of utilizing the hard mould agent synthesizing high specific surface area meso-porous carbon molecular sieve | |
| CN106010601A (en) | Biochar prepared from banana peel, preparation method and application thereof | |
| CN102569749B (en) | Graphene/hydroxyapatite nano composite and preparation method thereof | |
| CN101786615B (en) | Hydroxyapatite nanotube and preparation and application thereof in bone repair | |
| CN103708551A (en) | Preparation method of bismuth oxycarbonate flower-like microsphere thermally synthesized by ethylene glycol-water mixed solvent | |
| CN103112898B (en) | Method for preparing flowerlike bismuth tungstate by hydrothermal process | |
| CN101428779A (en) | Hollow nanostructured hydroxyapatite and method for producing the same | |
| CN102703977B (en) | Hydroxyapatite mono-crystal nano-rod and preparation method thereof | |
| CN109574507A (en) | A kind of nano-level sphere bioactivity glass and preparation method thereof | |
| CN101716370B (en) | Method for preparing nano doped hydroxylapatite powder | |
| CN103030159A (en) | Porous magnesium oxide, and preparation method and use thereof | |
| CN109928406A (en) | A kind of analcime and its synthetic method | |
| CN103466580A (en) | Preparation method of hydroxyapatite microspheres | |
| CN104445130A (en) | Preparation method of mesoporous beta-TCP (tricalcium phosphate) powder | |
| CN102874781A (en) | Method for preparing calcium phosphate microspheres with high specific surface area | |
| CN103058159A (en) | Hollow hierarchical hydroxyapatite microspheres and preparation method and application thereof | |
| CN107308499A (en) | Nanometer biological glass/polymer three-dimensional porous material and its preparation method and application | |
| CN101306806B (en) | Process for synthesizing hydroxylapatite | |
| CN104495922A (en) | Bismuth yttrate nanorod as well as preparation method and application thereof | |
| CN101585523A (en) | The preparation method of the nanometer hydroxyapatite that grain orientation is arranged | |
| CN106564923A (en) | Calcite phase spherical porous calcium carbonate granule and preparation method thereof | |
| CN110745804B (en) | Preparation method of length-controllable rod-shaped hydroxyapatite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130116 |