METHOD FOR PREPARING WHITLOCKITE, AND WHITLOCKITE PREPARED THEREBY

Abstract

The present invention relates to a method for producing whitlockite, and whitlockite produced thereby. A method for producing whitlockite according to one embodiment of the present invention comprises: a step of preparing a precursor solution by mixing a first solution containing a calcium (Ca) ion source material, a second solution containing a magnesium (Mg) ion source material, and a third solution containing a phosphate (PO4) source material; a heat-treatment step of heat-treating the precursor solution; and a step of separating and purifying the precipitate formed in the solution, after the heat-treatment step.

Claims

1. A method for producing whitlockite comprising: a step of preparing a precursor solution by mixing a first solution containing a calcium (Ca) ion source material, a second solution containing a magnesium (Mg) ion source material, and a third solution containing a phosphate (PO.sub.4) source material; a heat-treatment step of heat-treating the precursor solution; and a step of separating and purifying a precipitate formed in the solution, after the heat-treatment step.

2. The method of claim 1, wherein the calcium ion source material is any one selected from the group consisting of calcium hypochlorite, calcium perchlorate, calcium bromide, calcium iodide, calcium nitrate, calcium chloride, calcium acetate, and mixtures thereof.

3. The method of claim 2, wherein the magnesium ion source material is any one selected from the group consisting of magnesium perchlorate, magnesium bromide, magnesium chloride, magnesium sulfide, magnesium nitrate, magnesium acetate, and mixtures thereof.

4. The method of claim 3, wherein the phosphate source material further comprises any one selected from the group consisting of calcium phosphate, calcium metaphosphate, potassium phosphate, potassium dihydrogen phosphate, sodium phosphate, sodium hydrogen phosphate, magnesium phosphate, magnesium hydrogen phosphate, and mixtures thereof.

5. The method of claim 4, wherein the step of preparing the precursor solution comprises preparing a mixed solution by mixing the first solution with the second solution, and then mixing the third solution with the mixed solution.

6. The method of claim 4, wherein the step of preparing the precursor solution comprises mixing the first solution, the second solution and the third solution together simultaneously.

7. The method of claim 4, wherein the calcium ion source material and the magnesium ion source material are mixed together such that a molar ratio between Ca.sup.2+ and Mg.sup.2+ is 10: 1 to 1: 4.

8. A method for producing a mixture of whitlockite and hydroxyapatite comprising: a step of preparing a precursor solution by mixing a first solution containing a calcium (Ca) ion source material, a second solution containing a magnesium (Mg) ion source material, and a third solution containing a phosphate (PO.sub.4) source material; a step of mixing a fourth solution containing a phosphoric acid (PO.sub.4) source material other than the third solution with the precursor solution; a heat-treatment step of heat-treating the precursor solution; and a step of separating and purifying a precipitate formed in the solution, after the heat-treatment step.

9. Whitlockite produced by the method according to claim 1.

10. A mixture of whitlockite and hydroxyapatite produced by the method for producing a mixture of whitlockite and hydroxyapatite according to claim 8.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0084] FIG. 1 relates to whitlockite produced according to one embodiment of the present invention.

[0085] FIG. 2 relates to a method for producing whitlockite according to one embodiment of the present invention.

[0086] FIG. 3 relates to a method for producing whitlockite according to one embodiment of the present invention, and shows the time and the degree of crystal formation depending on time in the heat treatment step.

[0087] FIG. 4 relates to a flowchart showing a method for producing whitlockite according to one embodiment of the present invention.

[0088] FIG. 5 relates to a flowchart showing a method for producing a mixture of whitlockite and hydroxyapatite according to one embodiment of the present invention.

BEST MODE

[0089] The present invention relates to a method for producing whitlockite and whitlockite produced thereby. More particularly, the present invention provides a method for producing whitlockite, which is capable of producing the whitlockite in large amounts by increasing the production efficiency of whitlockite, and whitlockite produced according to the production method.

Mode for Invention

[0090] Hereinafter, examples of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in a variety of different forms and is not limited to the examples described herein.

[0091] [Production method: Production of whitlockite]

[0092] 1. S1 small-scale precipitation (S1CP)

[0093] The reactor was configured to have such a size that the final product was obtained in mg scale. A solution containing a calcium ion source material was mixed with a solution containing a magnesium ion source material, and a solution containing a phosphate source material was added dropwi se to the mixed solution for a predetermined period of time at predetermined intervals. Next, the resulting mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

[0094] 2. S2 large-scale precipitation (S2CP)

[0095] The reactor was configured to have such a size that the final product was obtained in mg scale. A solution containing a calcium ion source material was mixed with a solution containing a magnesium ion source material, and the mixed solution was added dropwise to a solution containing a phosphate source material for a predetermined period of time at predetermined intervals. Next, the resulting mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

[0096] 3. S3 large-scale precipitation (S3CP)

[0097] The reactor was configured to have such a size that the final product was obtained in kg scale. A solution containing a calcium ion source material, a solution containing a magnesium ion source material, and a solution containing a phosphate source material were mixed together. The mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

[0098] 4. L1 large-scale precipitation (L1CP)

[0099] The reactor was configured to have such a size that the final product was obtained in kg scale. A solution containing a calcium ion source material was mixed with a solution containing a magnesium ion source material, and a solution containing a phosphate source material was added dropwise to the mixed solution for a predetermined period of time at predetermined intervals. Next, the resulting mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

[0100] 5. L2 large-scale precipitation (L2CP)

[0101] The reactor was configured to have such a size that the final product was obtained in kg scale. A solution containing a calcium ion source material was mixed with a solution containing a magnesium ion source material, and the mixed solution was added dropwise to a solution containing a phosphate source material for a predetermined period of time at predetermined intervals. Next, the resulting mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

[0102] 6. L3 large-scale precipitation (L3CP)

[0103] The reactor was configured to have such a size that the final product was obtained in kg scale. A solution containing a calcium ion source material, a solution containing a magnesium ion source material, and a solution containing a phosphate source material are mixed together. Next, the mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

PRODUCTION EXAMPLE 1

Small-Scale Precipitation

[0104] 1. S1CP-1

[0105] The materials shown in Table 1 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00001 TABLE 1 Raw material and molar Material concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material H.sub.3PO.sub.4 0.5M

[0106] 2. S1CP-2

[0107] The materials shown in Table 2 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00002 TABLE 2 Raw material and molar Material concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material CaHPO.sub.4 0.5M

[0108] 3. S1CP-3

[0109] The materials shown in Table 3 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00003 TABLE 3 Raw material and molar Material concentration used Calcium ion source material CaCl.sub.2 0.4M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.1M

[0110] 4. S1CP-4

[0111] The materials shown in Table 4 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00004 TABLE 4 Raw material and molar Material concentration used Calcium ion source material Ca(NO.sub.3).sub.2 0.4M Magnesium ion source Mg(NO.sub.3).sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.5M

[0112] 5. S1CP-5

[0113] The materials shown in Table 5 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00005 TABLE 5 Raw material and molar Material concentration used Calcium ion source material CaCl.sub.2 0.4M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material NaH.sub.2PO.sub.4 0.5M

[0114] 6. S1CP-6

[0115] The materials shown in Table 6 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00006 TABLE 6 Raw material and molar Material concentration used Calcium ion source material CaCl.sub.2 0.4M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.3PO.sub.4 0.5M

[0116] 7. S1CP-7

[0117] The materials shown in Table 7 below were used according to S1CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00007 TABLE 7 Raw material and molar Material concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material Mg.sub.3(PO.sub.4).sub.2 0.5M

[0118] 8. S2CP-1

[0119] The materials shown in Table 8 below were used according to S2CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00008 TABLE 8 Raw material and molar Material concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material H.sub.3PO.sub.4 0.5M

[0120] 9. S2CP-2

[0121] The materials shown in Table 9 below were used according to S2CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00009 TABLE 9 Material Raw material and molar concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material CaHPO.sub.4 0.5M

[0122] 10. S2CP-3

[0123] The materials shown in Table 10 below were used according to S2CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

[0124] [Table 10]

TABLE-US-00010 TABLE 10 Raw material and molar Material concentration used Calcium ion source material CaCl.sub.2 0.1M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.1M

[0125] 11. S2CP-4

[0126] The materials shown in Table 11 below were used according to S2CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00011 TABLE 11 Material Raw material and molar concentration used Calcium ion source material CaCl.sub.2 0.4M Magnesium ion source MgCl.sub.2 0.12M material Phosphate source material NaH.sub.2PO.sub.4 0.5M

[0127] 12. S3CP-1

[0128] The materials shown in Table 12 below were used according to S3CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00012 TABLE 12 Material Raw material and molar concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material H.sub.3PO.sub.4 0.5M

[0129] 13. S3CP-2

[0130] The materials shown in Table 13 below were used according to S3CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00013 TABLE 13 Material Raw material and molar concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material CaHPO.sub.4 0.5M

[0131] 14. S3CP-3

[0132] The materials shown in Table 14 below were used according to S3CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00014 TABLE 14 Material Raw material and molar concentration used Calcium ion source material CaCl.sub.2 0.1M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.1M

[0133] 15. S3CP-4

[0134] The materials shown in Table 15 below were used according to S3CP. Heat treatment was performed at a temperature of 80° C. for 12 hours.

TABLE-US-00015 TABLE 15 Material Raw material and molar concentration used Calcium ion source material Ca(NO.sub.3).sub.2 0.4M Magnesium ion source Mg(NO.sub.3).sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.5M

EXPERIMENTAL EXAMPLE 1

Results of WH Synthesis

[0135] The purity and particle phase of whitlockite for each product produced in the Production Example above were evaluated. For evaluation of each product produced in the Production

[0136] Example, the case in which high-purity whitlockite that can be used industrially was produced was indicated by WH, and the case in which high-purity whitlockite was not produced due to problems such as purity and particle phase was indicated by X. The results are shown in Tables 16 and 17 below. Meanwhile, FIG. 1 relates to S1CP-3.

TABLE-US-00016 TABLE 16 S1CP-1 S1CP-2 S1CP-3 S2CP-4 S2CP-5 S2CP-6 S2CP-7 Crystal phase WH WH WH WH x x x

TABLE-US-00017 TABLE 17 S2CP-1 S2CP-2 S2CP-3 S2CP-4 S3CP-1 S3CP-2 S3CP-3 S3CP-4 Crystal phase x x WH x x x WH x

[0137] Referring to Table 16 above, it can be seen that, in the case of the small-scale process, more diverse materials could be used. It can be confirmed that, in the case of some compositions, the same whitlockite was not produced. In addition, referring to Table 17 above, it can be seen that, in the case of S2CP and S3CP in which process changes occurred and in the case of some compositions, whitlockite was not generated or problems in purity, shape and the like occurred. Meanwhile, FIG. 2 relates to S2CP-3.

[0138] However, referring to S2CP-3 and S3CP-3, it can be confirmed that the source materials had a relatively small effect on the reaction even when process changes occurred. Therefore, it can be seen that, in the case of the above compositions, not only simplification of the process is easily achieved, unlike in the case of other compositions, but also the possibility of mass production is high.

PRODUCTION EXAMPLE 2

Large-Scale Precipitation

[0139] 1. L1CP-1

[0140] The materials shown in Table 18 below were used according to L1CP. Heat treatment was performed at a temperature of 80° C. for 24 hours.

TABLE-US-00018 TABLE 18 Material Raw material and molar concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material H.sub.3PO.sub.4 0.5M

[0141] 2. L1CP-2

[0142] The materials shown in Table 19 below were used according to L1CP. Heat treatment was performed at a temperature of 80° C. for 24 hours.

TABLE-US-00019 TABLE 19 Material Raw material and molar concentration used Calcium ion source material Ca(OH).sub.2 0.4M Magnesium ion source Mg(OH).sub.2 0.12M material Phosphate source material CaHPO.sub.4 0.5M

[0143] 3. L1CP-3

[0144] The materials shown in Table 20 below were used according to L1CP. Heat treatment was performed at a temperature of 80° C. for 24 hours.

TABLE-US-00020 TABLE 20 Material Raw material and molar concentration used Calcium ion source material CaCl.sub.2 0.1M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.1M

[0145] 4. L1CP-4

[0146] The materials shown in Table 21 below were used according to L1CP. Heat treatment was performed at a temperature of 80° C. for 24 hours.

TABLE-US-00021 TABLE 21 Material Raw material and molar concentration used Calcium ion source material Ca(NO.sub.3).sub.2 0.4M Magnesium ion source Mg(NO.sub.3).sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.5M

[0147] 5. L2CP-3

[0148] The materials shown in Table 22 below were used according to L2CP. Heat treatment was performed at a temperature of 80° C. for 24 hours.

TABLE-US-00022 TABLE 22 Material Raw material and molar concentration used Calcium ion source material CaCl.sub.2 0.1M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.1M

[0149] 6. L3CP-3

[0150] The materials shown in Table 23 below were used according to L3CP. Heat treatment was performed at a temperature of 80° C. for 24 hours.

TABLE-US-00023 TABLE 23 Material Raw material and molar concentration used Calcium ion source material CaCl.sub.2 0.1M Magnesium ion source MgCl.sub.2 0.1M material Phosphate source material Na.sub.2HPO.sub.4 0.1M

EXPERIMENTAL EXAMPLE 2

Results of WH Synthesis

[0151] Evaluation was performed in the same manner as in Experimental Example 1 above, and the results are shown in Table 24 below.

TABLE-US-00024 TABLE 24 L1CP-1 L1CP-2 L1CP-3 L1CP-4 L2CP-3 L3CP-3 Crystal phase x x WH x WH WH

[0152] Referring to Table 24 above, it can be confirmed that, in the case of the L1 CP-1, L1 CP-2 and L1CP-3 compositions, whitlockite could not be produced. Thereby, it can be confirmed that, in the case of the L1CP-1, L 1 CP-2 and L 1 CP-3 compositions, it was difficult to perform process scale-up for mass production. Accordingly, the L2CP and L3CP processes did not need to be performed. On the other hand, it can be confirmed that, in the case of the L1CP-3 composition, whitlockite was produced in L 1 CP-3, L2CP-3, and L3CP-3. Therefore, it can be seen that, in the case of the above range, whitlockite could be mass-produced through the scale-up of the process.

[0153] In addition, the production yield was the highest in the case of L2CP-3, and L3CP-3 showed a yield similar to that of L1CP-1, but had excellent process efficiency due to process simplification. In particular, higher scale-up level may be more advantageous in terms of the process efficiency.

[0154] Specifically, L3CP-3 and L 1 CP-1 showed a production yield corresponding to about 70 to 80% of the production yield shown by L2CP-3. Meanwhile, L3CP-3 showed very higher process efficiency than L1CP-1. Specifically, for example, in the case of L3CP-3, the number of reactions can be reduced to half or less of that in L 1 CP-1, and the process may be performed using an in-line mixer or the like without a reactor due to the process of mixing the materials together simultaneously, unlike the case of L1CP-1 which necessarily requires a reactor. Thus, in the case of L3CP-3, it is possible to greatly reduce the process equipment, and the greater the size of the process, the greater the advantage.

EXPERIMENTAL EXAMPLE 3

Experiment on WH Synthesis Conditions

[0155] To confirm the production yield of whitlockite depending on reaction conditions, the reactor was configured to have such a size that the final product was obtained in mg scale. According to Table 25 below, a solution containing a calcium ion source material was mixed with a solution containing a magnesium ion source material, and the mixed solution was added dropwise to a solution containing a phosphate source material for a predetermined period of time at predetermined intervals. Then, the resulting mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried. Matters on whether or not whitlockite was produced under each condition are shown in Table 26 below.

[0156] Meanwhile, FIG. 3 relates to the crystal structure of whitlockite particles depending on time.

TABLE-US-00025 TABLE 25 Material Raw material used Calcium ion source material CaCl.sub.2 Magnesium ion source material MgCl.sub.2 Phosphate source material Na.sub.2HPO.sub.4

TABLE-US-00026 TABLE 26 Ca:Mg Temperature Example molar ratio (° C.) Time (hr) Crystal phase M1    9:1 90 24 x M2  7.34:1 90 24 WH M3  5.67:1 90 24 WH M4    4:1 90 24 WH M5    7:1 90 24 WH M6    1:1 90 24 WH M7   2.3:1 90 24 x M8    1:1 40 24 x M9    4:1 50 24 WH M10   4:1 60 24 WH M11   4:1 60 24 WH M12   4:1 70 24 WH M13   4:1 80 24 WH M14   4:1 90 24 WH

PRODUCTION EXAMPLE 3

Production of Mixture of WH and HAP

[0157] In order to produce a mixture of whitlockite and hydroxyapatite mixed together at an artificial ratio according to the control of a fourth solution, according to Table 27 below, a solution containing a calcium ion source material and a solution containing a magnesium ion source material were mixed together, and the mixed solution was added dropwise to a third solution containing a phosphate source material for a predetermined period of time at predetermined intervals. Next, a fourth solution containing a phosphate source material was added dropwise to the mixed solution. The resulting mixture was heat-treated with stirring, and then the precipitate was separated and purified, and then dried.

TABLE-US-00027 TABLE 27 Material Raw material used Calcium ion source material CaCl.sub.2 Magnesium ion source material MgCl.sub.2 Phosphate source material of third solution Na.sub.2HPO.sub.4 Phosphate source material of fourth Na.sub.3PO.sub.4 solution

[0158] From the above-described experimental results, it could be confirmed that a mixture of whitlockite and hydroxyapatite was produced, whitlockite was produced in proportion to the content of sodium hydrogen phosphate contained in the third solution, and hydroxyapatite was produced in proportion to the content of trisodium phosphate contained in the fourth solution. Therefore, it was confirmed that, according to the above-described method, it was possible to produce a mixture of whitlockite and hydroxyapatite in which the contents of the components were artificially designed/controlled/adjusted.

[0159] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art without departing from the basic concept of the present invention as defined in the appended claims also fall within the scope of the present invention.

INDUSTRIAL APPLICABILITY

[0160] The present invention relates to a method for producing whitlockite and whitlockite produced thereby. More particularly, the present invention provides a method for producing whitlockite, which is capable of producing whitlockite in large amounts by increasing the production efficiency of whitlockite, and whitlockite produced according to the production method.