CN111943157A - Method for preparing alpha-tricalcium phosphate based on inositol molecules and application thereof - Google Patents

Method for preparing alpha-tricalcium phosphate based on inositol molecules and application thereof Download PDF

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CN111943157A
CN111943157A CN202010818794.8A CN202010818794A CN111943157A CN 111943157 A CN111943157 A CN 111943157A CN 202010818794 A CN202010818794 A CN 202010818794A CN 111943157 A CN111943157 A CN 111943157A
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solution
phosphate
tricalcium phosphate
inositol
alpha
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CN111943157B (en
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毕见强
王璐
孙康宁
李爱民
袁震
毛俊杰
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Shandong University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
    • C04B12/02—Phosphate cements
    • C04B12/025—Phosphates of ammonium or of the alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram

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Abstract

The invention provides a method for preparing alpha-tricalcium phosphate based on inositol molecules and application thereof, belonging to the technical field of material science and biomedicine. The present invention promotes the directional conversion of amorphous calcium phosphate to α -tricalcium phosphate below the phase transition temperature by precipitation reaction of inositol-containing calcium salt solutions and phosphate solution at a specific pH followed by low temperature calcination. Compared with the traditional preparation process of high-temperature solid-phase reaction followed by rapid cooling, the method has the advantages of simple equipment and low energy consumption, effectively avoids the coarsening of crystal grains caused by high-temperature calcination, and realizes the rapid mass preparation of the nano-grade alpha-tricalcium phosphate powder under the low-temperature calcination. The prepared powder has good crystallinity and uniform particle size, is an ideal raw material of calcium phosphate cement, and therefore has good practical application prospect.

Description

Method for preparing alpha-tricalcium phosphate based on inositol molecules and application thereof
Technical Field
The invention belongs to the technical field of material science and biomedicine, and particularly relates to a method for preparing alpha-tricalcium phosphate based on inositol molecules and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The calcium phosphate cement has good biocompatibility, bone conduction and bone induction performance which are widely concerned by researchers, and has wide application prospect in the fields of bone replacement, drug delivery and the like. Compared with brushite bone cement, the brushite bone cement can be hardened under an acidic condition, the apatite bone cement shows excellent solidification performance under a body fluid environment, and the final product of hydration reaction is calcium-deficient hydroxyapatite which is similar to the bone component of a human body. Despite the wide variety of apatite formulations, the core curing reaction is still based on the hydration of α -tricalcium phosphate (α -TCP). Therefore, the exploration of an efficient preparation method of the alpha-tricalcium phosphate is a precondition for realizing the wide application of the apatite bone cement.
The tricalcium phosphate mainly has three crystal forms of low-temperature phase beta-TCP and high-temperature phase alpha-TCP and alpha '-TCP, wherein the alpha' -TCP exists only at the temperature higher than 1430 ℃, the low-temperature phase beta-TCP can be rebuilt and converted into the alpha-TCP at about 1125 ℃, but the alpha-TCP can be stored to the room temperature by quenching. The traditional preparation method of the alpha-TCP is based on solid-phase reaction at the temperature of more than 1200 ℃, and the alpha-TCP is obtained by heat preservation and then quenching. The method consumes time and energy, and the high-temperature heat preservation often causes grain growth, so that the grain diameter of the obtained powder is larger, and meanwhile, the beta-TCP is inevitably generated in the cooling process, and the beta phase has no self-curing effect, thereby influencing the mechanical strength of the bone cement. Therefore, most of the medical grade α -TCP powders currently on the market are expensive.
The use of amorphous calcium phosphates with specific structures followed by the production of tricalcium phosphate at low temperatures provides a new synthetic route to the low temperature production of alpha-tricalcium phosphate. The document reports that the alpha/beta phase mixture is obtained by low-temperature calcination of amorphous calcium phosphate with the calcium-phosphorus ratio of 1.5, but how to stably obtain the pure alpha phase is not known, and the inventor finds that the state of the precursor amorphous calcium phosphate greatly influences the effect of a subsequent product in long-term experiments. Amorphous calcium phosphate precipitates out of supersaturated solutions as a transition phase, the composition and state of which depends largely on the pH of the solution, the concentration of the mixed solution, and the additive organic molecules. Therefore, it is difficult to find a preparation process of amorphous calcium phosphate which can stably convert alpha-tricalcium phosphate.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing alpha-tricalcium phosphate based on inositol molecules and application thereof.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided the use of inositol in the preparation of α -tricalcium phosphate. According to the invention, researches show that inositol molecules can stabilize amorphous calcium phosphate and promote the amorphous calcium phosphate to be directionally converted into alpha-tricalcium phosphate, so that a large amount of alpha-TCP can be efficiently synthesized at a temperature far lower than the phase transition temperature.
Thus, in particular, said applications comprise the following 1) and/or 2):
1) stabilizing amorphous calcium phosphate;
2) promoting the directional conversion of amorphous calcium phosphate to alpha-tricalcium phosphate.
In a second aspect of the present invention, there is provided a method for preparing α -tricalcium phosphate, the method comprising:
s1, adding inositol into the calcium salt solution to obtain a solution A, and adjusting the pH to be alkaline;
s2, preparing a phosphate solution, setting the phosphate solution as a solution B, adding the solution B into the solution A, stirring and continuously adding alkali liquor in the process to keep the pH value stable until the reaction is completed to obtain emulsion;
s3, purifying the obtained emulsion to obtain a precursor;
and S4, calcining the precursor, and cooling to obtain the alpha-tricalcium phosphate.
Amorphous calcium phosphate is an intermediate metastable phase of variable chemical composition, high activation energy, and many researchers believe that either calcium phosphate salt undergoes either a long or short amorphous calcium phosphate process when precipitated in aqueous solution. Its intrinsic metastable state determines that it will crystallize and convert into stable crystalline phase, but since amorphous calcium phosphate has a local ordered structure, a tiny structural unit called a Person cluster, it shows high reactivity at low temperature, and prepares pure phase α -tricalcium phosphate at a temperature far below the phase transition temperature.
Firstly, the concentration of calcium ions and phosphate ions in a solution is adjusted, amorphous calcium phosphate is directly prepared under an alkaline condition, inositol is used as a space stabilizer, the migration of phosphate ions and calcium ions in the preparation process is reduced, and the amorphous calcium phosphate is stabilized; by designing a proper drying system, the phase change is avoided while physically bound water is removed, and the amorphous state is better ensured; finally, the alpha-tricalcium phosphate is prepared in a reasonable calcining mode as shown in the formula (1).
Ca9(PO4)6∙nH2O(s)→α-Ca3(PO4)2(S)+nH2O(g)(1)
In a third aspect of the present invention, there is provided α -tricalcium phosphate prepared by the above process. The method optimizes the process flow, and the prepared alpha-tricalcium phosphate has extremely high purity, good crystallinity and uniform particle size, and is favorable for practical production and application.
In a fourth aspect of the present invention, there is provided the use of α -tricalcium phosphate as defined above in the preparation of an apatite bone cement.
The beneficial technical effects of one or more technical schemes are as follows:
1) the technical scheme has the advantages of simple process flow, wide raw material source and low energy consumption, and is suitable for batch production;
2) compared with the traditional solid phase reaction method, the ball milling mixing and subsequent high-temperature quenching processes are avoided, so that the energy consumption is reduced while the introduction of impurities is avoided; compared with other thermal conversion methods of crystalline phases (calcium-deficient hydroxyapatite, beta-tricalcium phosphate and the like), amorphous calcium phosphate needs lower reaction energy as a metastable phase, and the phase change of an alpha phase is reduced while the reaction temperature is reduced; compared with other thermal conversion methods based on amorphous calcium phosphate, the method utilizes common inositol molecules to stabilize the amorphous calcium phosphate in the solution, shortens the preparation period and simultaneously reduces the phase change of the amorphous calcium phosphate before the calcination process, thereby preparing the pure-phase alpha-tricalcium phosphate by calcination;
3) the technical scheme researches and researches the stable preparation process and the heat treatment of the amorphous calcium phosphate, and other calcium phosphate biomaterials such as the amorphous calcium phosphate, the beta-tricalcium phosphate and the like can be prepared by changing the reaction conditions, so that the actual application range and the field are widened.
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The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a graph showing the effect of different temperatures on the calcined product when inositol molecules are added in examples 1 to 3 of the present invention;
FIG. 2 is a graph showing the effect of different temperatures on the calcined product without the addition of inositol molecules in examples 1-3 of the present invention;
FIG. 3 is a graph showing the effect of different reaction conditions on the calcined product in examples 4 to 5 of the present invention;
fig. 4 is a scanned image of α -tricalcium phosphate at different magnifications according to example 3 of the present invention.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
As previously described, the use of amorphous calcium phosphates with specific structures followed by the production of tricalcium phosphate at low temperatures provides a new synthetic route to the low temperature production of alpha-tricalcium phosphate. However, it is difficult to find a preparation process of amorphous calcium phosphate which can stably convert α -tricalcium phosphate.
In view of this, in one exemplary embodiment of the present invention, there is provided the use of inositol in the preparation of α -tricalcium phosphate. According to the invention, researches show that inositol molecules can stabilize amorphous calcium phosphate and promote the amorphous calcium phosphate to be directionally converted into alpha-tricalcium phosphate, so that a large amount of alpha-TCP can be efficiently synthesized at a temperature far lower than the phase transition temperature.
Thus, in particular, said applications comprise the following 1) and/or 2):
1) stabilizing amorphous calcium phosphate;
2) promoting the directional conversion of amorphous calcium phosphate to alpha-tricalcium phosphate.
In another embodiment of the present invention, there is provided a method for preparing α -tricalcium phosphate, the method comprising:
s1, adding inositol into the calcium salt solution to obtain a solution A, and adjusting the pH to be alkaline;
s2, preparing a phosphate solution, setting the phosphate solution as a solution B, adding the solution B into the solution A, stirring and continuously adding alkali liquor in the process to keep the pH value stable until the reaction is completed to obtain emulsion;
s3, purifying the obtained emulsion to obtain a precursor;
and S4, calcining the precursor, and cooling to obtain the alpha-tricalcium phosphate.
In still another embodiment of the present invention, in the steps S1 and S2,
the calcium salt is calcium nitrate, and the phosphate is ammonium dihydrogen phosphate; the dissolution processes of the two are not released by heat, and the price is low, so the product is a good industrial raw material;
the calcium-phosphorus ratio (molar ratio) is controlled to be 1.5:1, and the volumes of the calcium salt solution and the phosphate solution are kept consistent; when the concentration of the calcium nitrate solution is too low, the amorphous phase in the emulsion has a better hydration environment, and the mesostability is difficult to maintain, so that beta-tricalcium phosphate and the like appear in a final product; when the concentration of calcium nitrate is too high, the mixed solution is in a pseudo-gel state, the diffusion of calcium ions and phosphate ions is limited, a large number of ion clusters appear in a system, the mixing reaction is incomplete, and other impurities with the calcium-phosphorus ratio higher than 1.5 or lower than 1.5 appear; therefore, the concentration of the calcium nitrate solution is controlled to be 0.3-0.5 mol/L (preferably 0.4mol/L), and correspondingly, the concentration of the diammonium phosphate solution is controlled to be 0.2-0.333 mol/L (preferably 0.2667 mol/L).
The mass fraction of inositol in the solution is 1-2%, preferably 1%; inositol is an organic molecule which is easy to dissolve in water, can be widely existed in a solution with a lower mass fraction, and is easy to introduce carbon impurities after calcination when the mass fraction is higher.
Controlling the pH to 10.0-10.5, further 10.2-10.5; experiments have shown that when the system is weakly basic (e.g. pH less than 10), the resulting calcined product contains a large proportion of β -tricalcium phosphate (fig. 3), whereas when the system is strongly basic (e.g. pH greater than 11), amorphous calcium phosphate is not formed and the solution directly forms more dense Hydroxyapatite (HA).
In yet another embodiment of the invention, the pH of the solution is adjusted and controlled by adding lye; preferably, the alkali liquor is ammonia water, so that the pH value of the solution can be adjusted, and the introduction of other impurity elements can be reduced.
Particularly, the inventor finds that the pH value is suddenly reduced at the beginning of the reaction, excessive ammonia water is dripped to compensate the pH change, and preferably, the mixing reaction condition is low-temperature water bath and magnetic stirring, the water bath temperature is 25-30 ℃, and the stirring speed is 600-700 rad/min.
In another embodiment of the invention, the step of adding the solution B into the solution a is preferably performed by a dropping method, and the dropping speed is controlled to be 4-5 ml/min, preferably 4 ml/min; after the dropwise adding is finished, continuously stirring for 30-40 minutes, preferably for 30 minutes; in general, too long a titration time and mixing time will prolong the experimental procedure, and the ACP produced will be easily converted under long-term aqueous conditions, while too short a reaction time will result in insufficient reaction, thereby introducing impurities into the final product.
In another embodiment of the present invention, in step S3, the purification process includes suction filtration, washing the precipitate, and drying; the washing step may be carried out with water and/or a non-aqueous solvent (e.g., alcohol, etc.), preferably a non-aqueous solvent, to reduce the contact of the amorphous calcium phosphate with the aqueous solution; meanwhile, in order to save cost, the water can be washed firstly and then the alcohol is used for washing. Since hydration is an important driving force for spontaneous crystallization of amorphous calcium phosphate, once ACP is obtained by suction filtration, contact with moisture should be minimized to reduce phase transition (FIG. 3). Meanwhile, the alcohol is adopted for washing, the subsequent drying is facilitated due to the fact that the alcohol is volatilized more quickly, and when the precipitate is not washed by the alcohol, the final product is beta-tricalcium phosphate. The drying process aims at removing the physically adsorbed moisture, the process is as short as possible, the phase change process of the material before calcination is reduced, and the invention adopts the flowing air drying for 6-8 hours.
In another embodiment of the present invention, the purification process employs vacuum filtration, washing with water and alcohol sequentially, and then drying by flowing air; preferably, for 500ml of solution to be subjected to suction filtration, the suction filtration pressure is 0.06-0.08 MPa, the volume of washing water is 100-200 ml, and the volume of washing pure alcohol is 300-400 ml; and drying for 6-8 hours by flowing air.
In another embodiment of the present invention, in the step S4, the calcination conditions are as follows: heating to 600-700 ℃ at a heating rate of 5-10 ℃/min (preferably 10 ℃), and preserving heat for 3-5 hours. By adopting a higher temperature rise speed, the phase change caused by long-time heating can be effectively reduced, so that the product is further purified.
In another embodiment of the present invention, the air-dried precursor (amorphous calcium phosphate) is subjected to coarse grinding (e.g. grinding) before calcination, and the coarse grinding can increase the heat treatment area of the reactant and promote the reaction to be complete. Therefore, the method comprises the steps of grinding the fluffy particle mortar before calcination, then adopting a temperature rise speed of 5-10 ℃, and then adopting a furnace cooling mode for calcination, so as to improve the purity of the alpha-tricalcium phosphate.
In another embodiment of the present invention, there is provided α -tricalcium phosphate prepared by the above process. The method optimizes the process flow, and the prepared alpha-tricalcium phosphate has extremely high purity, good crystallinity and uniform particle size, and is favorable for practical production and application.
In another embodiment of the present invention, there is provided the use of the above α -tricalcium phosphate for the preparation of an apatite bone cement.
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) Under the hydrothermal and magnetic stirring at 28 ℃, 2g of inositol is added into the solution A, the solution A is stirred for 30 minutes to obtain a uniform solution, then ammonia water is dripped to increase the pH value to 10.2-10.5, and then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2-10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 600 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 1 (inositol 600).
Example 2
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) Under the hydrothermal and magnetic stirring at 28 ℃, 2g of inositol is added into the solution A, the solution A is stirred for 30 minutes to obtain a uniform solution, then ammonia water is dripped to increase the pH value to 10.2-10.5, and then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2-10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 650 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 1 (inositol 650).
Example 3
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution N).
2) Under the hydrothermal and magnetic stirring at 28 ℃, 2g of inositol is added into the solution A, the solution A is stirred for 30 minutes to obtain a uniform solution, then ammonia water is dripped to increase the pH value to 10.2-10.5, and then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2-10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 700 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction patterns are shown in figure 1 (inositol 700) and figure 3 (inositol 700). Its SEM scanning pattern is shown in figure 4.
Experimental example 1
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) Under the hydrothermal and magnetic stirring conditions at 28 ℃, ammonia water is dripped into the solution A, the pH value of the solution A is increased to 10.2-10.5, then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2-10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 600 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 2 (blank 600).
Experimental example 2
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) Under the hydrothermal and magnetic stirring conditions at 28 ℃, ammonia water is dripped into the solution A, the pH value of the solution A is increased to 10.2-10.5, then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2-10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 650 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 2 (blank 650).
Experimental example 3
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) Under the hydrothermal and magnetic stirring conditions at 28 ℃, ammonia water is dripped into the solution A, the pH value of the solution A is increased to 10.2-10.5, then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2-10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the heating speed is 10 ℃/min, the calcining temperature is 700 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 2 (blank 700).
Experimental example 4
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) To solution a, 2g of inositol was added under hydrothermal and magnetic stirring at 28 ℃, stirred for 30 minutes to obtain a homogeneous solution, and then solution B was dropwise added to solution a through a separatory funnel, and after 40 minutes, the dropwise addition was completed, and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration of the original solution is finished, the original solution is washed by water and absolute ethyl alcohol for three times, then the solution is air-dried for 6 to 8 hours under the condition of room temperature (28 ℃), and then the dried particles are roughly ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 700 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 3 (without alkalinity).
Experimental example 5
1) Accurately preparing 0.4mol/L Ca (NO) by using a precise balance and a volumetric flask3)2200ml of solution (solution A), and 0.266mol/L of (NH)4)2HPO4200ml of solution (solution B).
2) Under the hydrothermal and magnetic stirring at 28 ℃, 2g of inositol is added into the solution A, the solution A is stirred for 30 minutes to obtain a uniform solution, then ammonia water is dripped to increase the pH value to 10.2-10.5, then the solution B is dripped into the solution A through a separating funnel, and the pH value of the mixed solution is kept between 10.2 and 10.5 all the time in the process. After 40 minutes the dropwise addition was complete and stirring was continued for 30 minutes.
3) The solution is filtered by suction, after the filtration, the original solution is washed with water for three times, then dried in air at room temperature (28 ℃) for 6 to 8 hours, and then the dried particles are coarsely ground in a mortar and then calcined, wherein the calcination treatment conditions are as follows: the temperature rising speed is 10 ℃/min, the calcining temperature is 700 ℃, the calcining time is 180min, and the furnace cooling is carried out naturally.
4) After cooling to room temperature, the resulting powder was finely ground through a 200 mesh sieve to test its composition, morphology, and the like. The XRD diffraction pattern is shown in figure 3 (no alcohol rinse).
Analysis of results
Examples 1-3 and examples 1-3, respectively, compare the effect of calcination temperature on the purity of the resulting product when inositol molecules are present, indicating that the presence of inositol plays an important role in the pure phase α -tricalcium phosphate, and based on this, examples 4 and 5 indicate the necessity of alkaline environment and alcohol rinse, respectively, for the reaction process.
The preparation method provided by the invention comprehensively utilizes the structural characteristics of the amorphous calcium phosphate and the stabilizing effect of inositol molecules on the amorphous phase in the solution, promotes the directional conversion from the amorphous phase to the alpha phase under a mild condition, shortens the reaction period on the premise of ensuring the purity of the product, improves the production efficiency, and provides possibility for the mass application of the alpha-tricalcium phosphate-based apatite bone cement.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (10)

1. The application of inositol in preparing alpha-tricalcium phosphate.
2. The use according to claim 1, wherein the use comprises 1) and/or 2) as follows:
1) stabilizing amorphous calcium phosphate;
2) promoting the directional conversion of amorphous calcium phosphate to alpha-tricalcium phosphate.
3. A method for producing α -tricalcium phosphate, said method comprising:
s1, adding inositol into the calcium salt solution to obtain a solution A, and adjusting the pH to be alkaline;
s2, preparing a phosphate solution, setting the phosphate solution as a solution B, adding the solution B into the solution A, stirring and continuously adding alkali liquor in the process to keep the pH value stable until the reaction is completed to obtain emulsion;
s3, purifying the obtained emulsion to obtain a precursor;
and S4, calcining the precursor, and cooling to obtain the alpha-tricalcium phosphate.
4. The method of claim 3, wherein in the steps S1 and S2,
the calcium salt is calcium nitrate, and the phosphate is ammonium dihydrogen phosphate;
preferably, the calcium-phosphorus ratio (molar ratio) is controlled to be 1.5: 1;
preferably, the volumes of the calcium salt solution and the phosphate solution are kept consistent;
preferably, the concentration of the calcium nitrate solution is 0.3-0.5 mol/L (preferably 0.4 mol/L); the concentration of the diammonium hydrogen phosphate solution is 0.2-0.333 mol/L (preferably 0.2667 mol/L).
5. A process according to claim 3, wherein the inositol is present in the solution at a mass fraction of 1 to 2%, preferably 1%.
6. The method according to claim 3, wherein in steps S1 and S2, the pH is controlled to 10.0 to 10.5, preferably 10.2 to 10.5;
preferably, the pH of the solution is adjusted and controlled by adding lye; further preferably, the alkali liquor is ammonia water;
preferably, the mixing reaction conditions comprise low-temperature water bath and magnetic stirring, wherein the water bath temperature is 25-30 ℃, and the stirring speed is 600-700 rad/min;
the process of adding the solution B into the solution A is preferably carried out in a dropwise manner, and the dropwise adding speed is controlled to be 4-5 ml/min, preferably 4 ml/min; after the completion of the dropwise addition, the stirring treatment is continued for 30 to 40 minutes, preferably 30 minutes.
7. The method of claim 3, wherein in step S3, the purification process comprises suction filtration, washing the precipitate and drying; the washing step may be carried out with water and/or a non-aqueous solvent (e.g., alcohol, etc.), preferably with a non-aqueous solvent;
or, the washing and precipitating process comprises the following steps: washing with water, and then washing with alcohol; drying for 6-8 hours by adopting flowing air blowing;
preferably, the purification process: vacuum filtering, washing with water and alcohol, and drying with flowing air;
preferably, for 500ml of solution to be subjected to suction filtration, the suction filtration pressure is 0.06-0.08 MPa, the volume of washing water is 100-200 ml, and the volume of washing pure alcohol is 300-400 ml; and drying for 6-8 hours by flowing air.
8. The method according to claim 3, wherein in step S4, the calcining conditions are as follows: heating to 600-700 ℃ at a heating rate of 5-10 ℃/min (preferably 10 ℃), and preserving heat for 3-5 hours;
preferably, the dried precursor is subjected to a coarse grinding treatment before calcination.
9.α -tricalcium phosphate produced by the process according to any one of claims 3 to 8.
10. Use of α -tricalcium phosphate according to claim 9 for the preparation of an apatite bone cement.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1072653A (en) * 1991-11-26 1993-06-02 仙居县饲料公司 A kind of method of producing secondary calcium phosphate
CN106976850A (en) * 2017-03-24 2017-07-25 常州大学 A kind of preparation method of mesoporous hydroxyapatite scale
CN107188148A (en) * 2017-06-16 2017-09-22 山东大学 A kind of method that low temperature calcination prepares α tricalcium phosphates
WO2019201710A1 (en) * 2018-04-16 2019-10-24 Croda Denmark A/S Organically modified mineral micro-particles, methods of preparing the same and uses thereof
KR102177267B1 (en) * 2020-04-20 2020-11-11 주식회사 동양케미칼 Method for producing phosphate triclacite for feed using byproducts generated during inositol extraction

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1072653A (en) * 1991-11-26 1993-06-02 仙居县饲料公司 A kind of method of producing secondary calcium phosphate
CN106976850A (en) * 2017-03-24 2017-07-25 常州大学 A kind of preparation method of mesoporous hydroxyapatite scale
CN107188148A (en) * 2017-06-16 2017-09-22 山东大学 A kind of method that low temperature calcination prepares α tricalcium phosphates
WO2019201710A1 (en) * 2018-04-16 2019-10-24 Croda Denmark A/S Organically modified mineral micro-particles, methods of preparing the same and uses thereof
KR102177267B1 (en) * 2020-04-20 2020-11-11 주식회사 동양케미칼 Method for producing phosphate triclacite for feed using byproducts generated during inositol extraction

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