KR20200012496A - Preparation method of whitrockite using solvothermal synthesis and solid-liquid-solution method - Google Patents

Abstract

The present invention relates to a method for producing whitlockite using a solvent heat synthesis method and a solid-liquid-solution method. The whitlockite manufactured by the method according to the present invention: is able to synthesize pure whitlockite even in a wide range of precursor molar ratio changes compared to conventional methods which could obtain whitlockite only under limited conditions of the ratio of calcium, magnesium, and phosphorus; and has an effect of controlling the shape of crystal particles of whitlockite in various forms by adjusting a mixing ratio of oleic acid, ethanol, and water and a mixing ratio of magnesium (Mg), calcium (Ca), and phosphoric acid (PO_4) precursors. The method comprises: a step (1) of preparing a mixed solvent containing oleic acid, ethanol, and water; a step (2) of preparing a precursor mixed solution; a step (3) of producing a whitlockite precipitate; and a step (4) of separating and purifying the precipitate produced in the step (3).

Description

Preparation method of whitrockite using solvothermal synthesis and solid-liquid-solution method

The present invention relates to a whitlockite production method and a shape control method using a solvent thermal synthesis method and a solid-liquid-solution method.

In addition to physical functions such as body structure maintenance and organ protection, our bones are also responsible for biological and chemical functions in the human body such as blood cell formation, storage of calcium and magnesium ions. Bone is composed of about 30% organic matter and 70% inorganic matter, and hydroxyapatite (HA; Hydroxyapatite; Ca ₁₀ (PO ₄ ) ₆ (OH) ₂ ) is a representative material of the minerals constituting bone and biocompatible It has been studied as a ceramic material and has been used as a material for bone restoration and bone supplement in orthopedic and dental care.

Beta-phase tricalcium phosphate (β-TCP; β-Tricalcium phosphate; Ca ₃ (PO ₄ ) ₂ ), which is not a constituent of bone, is also used as a bone material as a bone material due to its fast decomposition rate and biocompatibility. Much has been studied as biphasic mixed with HA.

Recently, in addition to HA among bone inorganic components, phosphate-based substances called whitlockite (WH; Whitlockite; Ca ₁₈ Mg ₂ (HPO ₄ ) ₂ (PO ₄ ) ₁₂ ) have attracted attention. This substance is a type of calcium phosphate containing magnesium, which is the second largest component of bone minerals after HA. More than 50% of the magnesium in the body is stored in the human bone. WH is thermodynamically unstable than HA and is also present in the tooth, which is contained more in the dentin than the enamel, which is the tooth surface. In addition, it is reported that the ratio of WH in the bones of adolescents is higher than that of adults. In conclusion, it can be predicted that WH is an important intermediate material in the early stage of mineralization process in which the bone is formed in the body. WH is similar to β-TCP in terms of crystal structure, which has been confusing in the past. However, in the XRD graph, WH shows a different pattern from Mg-substituted HA or β-TCP. WH, like HA, is a bone component that has excellent biocompatibility and fast biodegradation, which can be said to have both HA and β-TCP advantages.

However, these WH nanoparticles (WHNPs; Whitlockite nanoparticles) are very demanding in terms of synthesis conditions and require very precise precursor concentration and rate control to make pure WHNPs only.

Therefore, the present inventors have developed a method for easily synthesizing WH using a solvent thermal synthesis method and a solid-liquid-solution (SLS) method, and a wide precursor (calcium, magnesium, phosphorus) mixing ratio and a solvent (oleic acid, ethanol, Development of synthetic method for manufacturing phytoproxite of various shapes such as plate, sphere, grain, etc. as WH nanoparticles (WHNPs) of diameter nanometer in the range of mixing ratio of water) The present invention was completed.

Korea Patent Registration No. 10-1423982

An object of the present invention is to provide a method for producing whitlockite using a solvent thermal synthesis method and a solid-liquid-solution method.

Another object of the present invention is to provide a whiplockite prepared by the above production method.

Another object of the present invention is to provide a method for controlling the shape of whitlockite crystal grains using solvent thermal synthesis and a solid-liquid-solution method.

Another object of the present invention is to provide a whiplockite in which the crystal grain shape produced by the above method is controlled.

In order to achieve the above object,

The present invention comprises the steps of preparing a mixed solvent comprising oleic acid, ethanol and water (step 1); Preparing a precursor mixture solution by adding a magnesium ion feed material, a calcium ion feed material and a phosphate ion feed material to the mixed solvent prepared in step 1 (step 2); Putting the precursor mixture solution prepared in step 2 into a sealed container and heating to 150 to 250 ° C. to produce a phytoproxite precipitate (step 3); And separating and purifying the precipitate produced in step 3 (step 4); It provides a method for producing whitlockite using a solvent-thermal synthesis method and a solid-liquid-solution (Solid-liquid-solution) method comprising a.

In addition, the present invention provides a whiplock kit prepared by the above production method.

Furthermore, the present invention comprises the steps of preparing a mixed solvent comprising oleic acid, ethanol and water (step 1); Preparing a precursor mixed solution by adding a magnesium (Mg) ion feed material, a calcium (Ca) ion feed material and a phosphoric acid (PO ₄ ) ion feed material to the mixed solvent prepared in step 1 (step 2); Putting the precursor mixture solution prepared in step 2 into a sealed container and heating to 150 to 250 ° C. to produce a phytoproxite precipitate (step 3); And separating and purifying the precipitate produced in step 3 (step 4); wherein the mixing ratio of oleic acid, ethanol and water of step 1; And the concentration of magnesium (Mg) ion feed material, calcium (Ca) ion feed material and phosphoric acid (PO ₄ ) ion feed material added in step 2; Shape control of whitlockite crystals using a solvent thermal synthesis method and a solid-liquid-solution method, characterized in that by controlling any one or more of the whiprocketite crystal grain shape Provide a method.

Furthermore, the present invention provides a phytoplockite in which the crystal grain shape produced by the above method is controlled.

Whitlockite prepared by the method using a solvent-thermal synthesis method and a solid-liquid-solution method according to the present invention is whitlockite only under conditions where the ratio of calcium, magnesium and phosphorus is limited in the conventional art. Pure fluorokite synthesis is possible even in a wide range of precursor molar ratio changes compared to the method where kite can be obtained, and the mixing ratio of oleic acid, ethanol and water and the mixing of magnesium (Mg), calcium (Ca) and phosphoric acid (PO ₄ ) precursors By adjusting the ratio, there is an effect that can control the shape of the crystal grains of whitkite in various forms.

1 is a schematic diagram showing a solid-liquid-solution (SLS) system in whitlockite (WH) synthesis according to the present invention.
FIG. 2 is an X-ray diffraction analysis (XRD) graph and WH and HA reference XRD graphs of phytoproxite (WH) and hydroxyapatite (HAP) prepared according to the present invention. Here, (a) is Example 14, (b) is Example 1, (c) is Example 3, (d) is Example 8, (e) is Example 15, (f) is Example 9, (g) is the comparative example 1.
3 is a three-dimensional diagram showing the Whitokite (WH) product according to the molar ratio conditions of the precursor magnesium (Mg ^{2 +} ), calcium (Ca ^{2 +} ) and phosphoric acid (PO ₄ ^3- ) ions of the present invention.
Figure 4 is a transmission electron microscope (TEM) analysis image of the wheat chlorite prepared in accordance with the present invention (WH). Wherein (a) is Example 8, (b) is Example 7, (c) is Example 6, (d) is Example 3, (e) is Example 1, and (f) is Example 9 The scale bar of the TEM image is 100 nm.
5 is a graph showing changes in precursor ion concentration with reaction time; Where (a) is Mg ^{2 +} : Ca ^{2 +} : PO ₄ ^3- = 2.0: 8.0: 6.0, (b) is Mg ^{2 +} : Ca ^{2 +} : PO ₄ ^3- = 1.0: 9.0: 6.0, (c ) Is Mg ²⁺ : Ca ²⁺ : PO ₄ ^3- = 0.5: 9.5: 6.0, and the area A in the graph represents the WH synthesis region and the area B represents the HAP synthesis region.
FIG. 6 is a high resolution transmission electron microscope (HRTEM) analysis image of wheat chlorite (WH) prepared according to the present invention. Here, (a) is Example 6, (b) is Example 1, and a scale bar is 10 nm.
FIG. 7 is a transmission electron microscope (TEM) analysis image of wheat chlorite (WH) prepared according to the present invention. Here, (a) is Example 1, (b) is Example 12, (c) is Example 14, the scale bar is 100 nm, and the images inserted at the bottom right of each TEM image are hexane (a) and ethanol ( b) and the result of testing the solubility in water (c) is an image taken.
8 is an X-ray diffraction analysis (XRD) graph of Wheatockite (WH) prepared according to the present invention. Here, (a) is Example 1, (b) is Example 12, and (c) is Example 14.
Figure 9 is a graph showing the thermogravimetric (TGA) pattern of whitlockkite (WH) prepared according to the present invention. Here, (a) is Example 1, (b) is Example 12, and (c) is Example 14.
FIG. 10 is a transmission electron microscope (TEM) analysis image and X-ray diffraction analysis (XRD) graph of Wheatock kite (WH) prepared according to the present invention. Here, (a) and (c) are Comparative Example 3, (b) and (d) are Example 16, and the scale bar of a TEM image is 100 nm.
FIG. 11 is a three-dimensional diagram showing the mixed volume ratio conditions of solvent oleic acid (OA), ethanol (EtOH) and water for preparing the whitokite (WH) product of the present invention.
FIG. 12 is a graph obtained by X-ray diffraction analysis (XRD) of phytoproxite (WH) prepared according to the present invention. Here, (a) is Comparative Example 2, (b) is Example 17, (c) is Comparative Example 3, (d) is Example 18, (e) is Example 19, (f) is Example 20, (g) is Example 21, (h) is Example 22, (i) is Example 23, and (j) is Example 24.
FIG. 13 is a transmission electron microscope (TEM) analysis image of wheat chlorite (WH) prepared according to the present invention. Here, (a) is Comparative Example 2, (b) is Example 17, (c) is Comparative Example 3, (d) is Example 18, (e) is Example 19, (f) is Example 20, (g) is Example 21, (h) is Example 22, (i) is Example 23, and (j) is Example 24. Here, the scale bars of (a), (c) to (g), (i) and (j) are 100 nm, and the scale bars of (b) and (h) are 200 nm.
FIG. 14 is an infrared spectroscopy (FTIR) spectrum of Wheatockite (WH) of Example 1 according to the present invention. FIG.
FIG. 15 is a Raman spectrum obtained by 532 nm laser irradiation with respect to Wheat Rock kit (WH) of Example 1 according to the present invention. FIG.
16 is an analysis result using the energy dispersive spectroscopy device (EDS) of the wheat chlorite (WH) of Example 1 according to the present invention. Where (a) is an EDS mapping image of calcium (Ca), (b) is an EDS mapping image of magnesium (Mg), (c) is an EDS mapping image of phosphorus (P), and (d) is an EDS spectrum to be.

Hereinafter, the present invention will be described in detail.

Solvent heat  Synthesis and SLS  Method Whitlockkite ( WH ) Manufacturing method

The present invention comprises the steps of preparing a mixed solvent comprising oleic acid, ethanol and water (step 1);

Preparing a precursor mixture solution by adding a magnesium ion feed material, a calcium ion feed material and a phosphate ion feed material to the mixed solvent prepared in step 1 (step 2);

Putting the precursor mixture solution prepared in step 2 into a sealed container and heating to 150 to 250 ° C. to produce a phytoproxite precipitate (step 3); And

Separating and purifying the precipitate produced in step 3 (step 4);

It provides a method for producing whitlockite using a solvent-thermal synthesis method and a solid-liquid-solution (Solid-liquid-solution) method comprising a.

In the production method according to the present invention, the oleic acid, ethanol and water based on the total volume 1 of the mixed solvent of step 1 may be mixed at a volume ratio of 0.05 to 0.35: 0.05 to 0.60: 0.20 to 0.80. Preferably, oleic acid, ethanol and water may be mixed at a volume ratio of 0.08 to 0.34: 0.06 to 0.58: 0.22 to 0.97, and more preferably at a volume ratio of 0.1 to 0.334: 0.08 to 0.58: 0.22 to 0.78. The mixing may be performed, and more preferably 0.15 to 0.25: 0.54 to 0.58: 0.22 to 0.26 or 0.15 to 0.25: 0.08 to 0.12: 0.65 to 0.75.

In the manufacturing method according to the present invention, the magnesium ion feed material, calcium ion feed material and phosphate ion feed material of step 2 are magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ) and disodium hydrogen phosphate (Na ₂ HPO _{4), respectively.} May be).

In the manufacturing method according to the present invention, the concentration of the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material in step 2 is (Mg ²⁺ + Ca ²⁺ ): PO ₄ ^3- is 10: 2.0 ~ The molar ratio of 11.0 and Mg ²⁺ : Ca ²⁺ may be a molar ratio of 0.1 to 3.5: 6.5 to 9.9. Preferably, (Mg + Ca): PO ₄ may be a molar ratio of 10: 2.4 to 10.5, and Mg: Ca may be a molar ratio of 0.40 to 3.05: 6.95 to 9.90, more preferably (Mg + Ca): PO ₄ may be a molar ratio of 10: 2.5 to 10.1, Mg: Ca may be a molar ratio of 0.5 to 3.0: 7.0 to 9.5, and more preferably, (Mg + Ca): PO ₄ is 10: 4.5 to 10.0. Molar ratio, Mg: Ca may be a molar ratio of 0.6 to 3.0: 7.0 to 9.4, (Mg + Ca): PO ₄ is a molar ratio of 10: 4.7 to 10.0, and Mg: Ca is 0.7 to 3.0: 7.0 to 9.3 It is especially preferable that it is molar ratio of.

According to one embodiment of the present invention, in the preparation of the mixed solvent of step 1, oleic acid, ethanol, and water are mixed in a volume ratio of 0.2: 0.1: 0.7, Mg: Ca: PO ₄ = Volumetric ratios of 0.20: 0.56: 0.24 with fluoroacid, ethanol, and water were prepared by mixing choplockite (Examples 5 to 8 and 10 to 14) and oleic acid, ethanol, and water prepared in a molar ratio of 0.8 to 3.0: 7.0 to 9.2: 5.0 to 10.0. It was confirmed that the highest purity and yield of phytoproxite (Example 16) prepared by mixing with a mixture of Mg: Ca: PO ₄ = 1.0: 9.0: 6.0 in a molar ratio.

In the manufacturing method according to the present invention, the shape of the phytoproxite crystal grains can be controlled by controlling the molar ratio of mixing the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material in step 2. have. In addition, in the mixed solvent of step 1, it is possible to control the shape of the phytoproxite crystal grains by adjusting the volume ratio of oleic acid, ethanol and water. The shape of the fluorokite grains may be one or more shapes selected from the group consisting of spheres, rods, plates, polygons, rice grains, and cubic particles. , Preferably, may be one or more shapes selected from the group consisting of spheres, plates and granules. In this case, the plate may be a polygonal plate.

Whitlockkite ( whitlockite )

In addition, the present invention provides a whiplock kit prepared by the above production method.

Wheatockite according to the present invention may have one or more shapes selected from the group consisting of sphere, rod, plate, polygon, rice grain and cubic. And, preferably, may have one or more shapes selected from the group consisting of spheres, plates, and granules. In this case, the plate may be a polygonal plate.

In the wheatockite according to the present invention, the shape of the wheatockite grains may include a mixing ratio of oleic acid, ethanol, and water in Step 1; And a concentration of adding the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material of step 2; Any one or more of the can be adjusted by controlling.

Method for Control of Whitokite (WH) Shape Using Solvent Thermal Synthesis and SLS Method

The present invention comprises the steps of preparing a mixed solvent comprising oleic acid, ethanol and water (step 1);

Preparing a precursor mixed solution by adding a magnesium (Mg) ion feed material, a calcium (Ca) ion feed material and a phosphoric acid (PO ₄ ) ion feed material to the mixed solvent prepared in step 1 (step 2);

Putting the precursor mixture solution prepared in step 2 into a sealed container and heating to 150 to 250 ° C. to produce a phytoproxite precipitate (step 3); And

And separating and purifying the precipitate produced in step 3 (step 4); and

Mixing ratio of oleic acid, ethanol and water of step 1; And the concentration of magnesium (Mg) ion feed material, calcium (Ca) ion feed material and phosphoric acid (PO ₄ ) ion feed material added in step 2; Whitockite crystal grains using a solvent-thermal synthesis method and a solid-liquid-solution (SLS) method, characterized in that by controlling any one or more of the phytoproxite crystal grain shape Provide a shape control method.

In the method for controlling the shape of the whitkite crystal grains according to the present invention, the shape of the whitkite crystal grains may be a sphere, a rod, a plate, a polygon, a grain and a cubic. It may be at least one shape selected from the group consisting of (cubic), preferably, may be at least one shape selected from the group consisting of sphere (plate), plate (plate) and grain (grain). In this case, the plate may be a polygonal plate.

In the method for controlling the shape of phytoprokite crystal grains according to the present invention, the magnesium ion feed material, the calcium ion feed material and the phosphate ion feed material in step 2 are magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ) and disodium hydrogen phosphate. (Na ₂ HPO ₄ ).

In the method for controlling morphology of phytoprokite crystal grains according to the present invention, the mixing ratio of oleic acid, ethanol, and water is 0.05 to 0.35: 0.05 to 0.60: 0.20 to 0.80 based on the total volume 1 of the mixed solvent in step 1. It may be to adjust.

Preferably, the mixture of oleic acid, ethanol and water is adjusted to a volume ratio of 0.15 to 0.25: 0.05 to 0.15: 0.65 to 0.75 based on the total volume 1 of the mixed solvent of step 1 to plate the phytoproxite grains. Or a sphere shape, and the volume ratio of 0.15 to 0.35: 0.10 to 0.60: 0.20 to 0.64 is adjusted to form the spheres of grains of wheat or grains It may be to control.

In the method for controlling morphology of phytoprokite crystal grains according to the present invention, the concentration of magnesium (Mg) ion feed material, calcium (Ca) ion feed material and phosphoric acid (PO ₄ ) ion feed material added in step ² is (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- may be adjusted to a molar ratio of 10.0: 2.0 to 11.0 and Mg ²⁺ : Ca ²⁺ to a molar ratio of 0.1 to 3.5: 6.5 to 9.9. .

Preferably, (Mg + Ca ^{+ 2 + 2):} the PO ₄ ^3- 10.0: 8.6 ~ 11.0 mole ratio and the Mg ^{+ 2:} the Ca ^{2 +} 0.5 ~ 3.0: 7.0 ~ 9.5 by adjusting the molar ratio of Whitman lock kite can be to control so that the two (sphere) shape of the crystal grains, ^{(2 +} Mg + Ca ^{+ 2):} PO ₄ ^3- to 10.0: 6.6 ~ 8.5 and a molar ratio Mg ^{2 +:} 0.5 ~ 3.0 for Ca ^{2 +} By controlling the molar ratio of: 7.0 ~ 9.5 may be to control the fluorokite crystal grains to a plate shape, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- in a molar ratio of 10.0: 5.1 ~ 6.5 And Mg ²⁺ : Ca ²⁺ by adjusting the molar ratio of 0.4 to 2.9: 7.1 to 9.6 to form phytoprocite crystal grains in the form of a plate, sphere and grain. It may be to control to be.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is a volume ratio of 0.15 ~ 0.25: 0.05 ~ 0.15: 0.65 ~ 0.75, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- 10.0 : 8.6 ~ 11.0 mole ratio and Mg ^{2 +:} the Ca ^{2 +} 0.5 ~ 3.0: adjusted to a molar ratio of 7.0 ~ 9.5 may be to control so that the two (sphere) geometry for Whitman lock kite crystal grains, preferably oleic acid volume ratio of ^{0.65 ~ 0.75, (Mg 2+ +} Ca 2+)::, ethanol, and the mixing ratio of water 0.18 ~ 0.22: 0.05 ~ 0.15 PO 4 3- to 10.0: 8.6 ~ 10.5 mole ratio and the Mg ^{2 +:} Ca ^{2 +} may be adjusted to a molar ratio of 0.7 to 0.9: 9.1 to 9.3 to control the fluorokite crystal grains into a sphere shape, and more preferably, the mixing ratio of oleic acid, ethanol and water is 0.18 to 0.22: Volume ratio of 0.08 to 0.12: 0.68 to 0.72, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- to molar ratio of 10.0: 8.6 to 10.5 and Mg ^{2 +} : Ca ^{2 +} to 0.75 to 0.85: 9.15 to 9.25 By controlling the molar ratio, the phytoproxite crystal grains It may be controlled to.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is a volume ratio of 0.15 ~ 0.25: 0.05 ~ 0.15: 0.65 ~ 0.75, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- 10.0 molar ratio, and Mg of 6.6 ~ 8.5 ^{2 +:} the Ca ^{2 +} 0.5 ~ 3.0: adjusted to a molar ratio of 7.0 ~ 9.5 may be to control so that the plate (plate) shape the Whitman lock kite crystal grains, preferably oleic acid , The mixing ratio of ethanol and water, the volume ratio of 0.18 ~ 0.22: 0.05 ~ 0.15: 0.65 ~ 0.75, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- molar ratio of 10.0: 6.6 ~ 8.5 and Mg ^{2 +} : Ca ^{2 +} may be adjusted to a molar ratio of 0.7 to 0.9: 9.1 to 9.3 to control the phytoprockite crystal grains into a plate shape, and more preferably, the mixing ratio of oleic acid, ethanol and water is 0.18 to 0.22: Volume ratio of 0.08 to 0.12: 0.68 to 0.72, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- to molar ratio of 10.0: 6.6 to 8.5 and Mg ^{2 +} : Ca ^{2 +} to 0.75 to 0.85: 9.15 to 9.25 The molar ratio is used to make the phytoproxite grains into a plate shape. It can be to control the lock. In this case, the plate may be a polygonal plate.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is a volume ratio of 0.15 ~ 0.25: 0.05 ~ 0.15: 0.65 ~ 0.75, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- 10.0 : 5.1 to the molar ratio and the Mg ^{2 +} of 6.5: Ca ^{2 +} 0.85 ~ 1.75: can be controlled such that 8.25 ~ by adjusting a molar ratio Whitman lock kite crystal grains plate (plate) shape of 9.15, preferably oleic acid , The mixing ratio of ethanol and water in a volume ratio of 0.18 to 0.22: 0.05 to 0.15: 0.65 to 0.75, (Mg ²⁺ + Ca ²⁺ ): PO ₄ ^3- molar ratio of 10.0: 5.5 to 6.5 and Mg ^{2 +} : Ca ^{2 +} is controlled to a molar ratio of 0.86 to 1.70: 8.30 to 9.14 to control the phytoprockite crystal grains into a plate shape, and more preferably, the mixing ratio of oleic acid, ethanol and water is 0.18 to 0.22: Volume ratio of 0.08 to 0.12: 0.68 to 0.72, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- to molar ratio of 10.0: 5.5 to 6.5 and Mg ^{2 +} : Ca ^{2 +} to 0.88 to 1.60: 8.40 to 9.12 By adjusting the molar ratio, the phytoprockite crystal grains It may be to control to. In this case, the plate may be a polygonal plate.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is a volume ratio of 0.15 ~ 0.25: 0.05 ~ 0.15: 0.65 ~ 0.75, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- 10.0 : 5.1 ~ may be to control so that the molar ratio and the Mg ^{2 +} 0.40 or more 0.85 or less than 1.75 greater than 2.90 molar ratio adjusted to obtain the Whitman lock kite crystal grain (sphere) shape of less than 6.5, preferably oleic acid, ethanol And the mixing ratio of water to a volume ratio of 0.18 to 0.22: 0.05 to 0.15: 0.65 to 0.75, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- to a molar ratio of 10.0: 5.5 to 6.5 and Mg ^{2 +} : Ca ^{2 +} It may be to control the phytoproxite crystal grains to sphere shape by adjusting the molar ratio of 0.45 to 0.84: 9.16 to 9.95 or 1.80 to 2.50: 8.20 to 7.50, more preferably a mixture of oleic acid, ethanol and water volume ratio of ^{0.68 ~ 0.72, (Mg 2+ +} Ca 2+):: the ratio 0.18 ~ 0.22: 0.08 ~ 0.12 PO 4 3- to 10.0: 6.5 molar ratio of 5.5 ~ ^{2 +} and Mg: Ca ^{2 +} 0.48 ~ 0.82: 9.18 ~ 9.52 or 1.80 ~ 2.20: 8.20 ~ 7.8 By controlling to a molar ratio of 0 may be to control the fluorokite crystal grains (sphere) shape.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is 0.32 to 0.35: 0.32 to 0.35: 0.32 to 0.35 or 0.15 to 0.35: 0.10 to 0.35: 0.45 to 0.64, the volume ratio of the (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- is adjusted to a molar ratio of 10.0: 5.1 to 6.5 and Mg ^{2 +} : Ca ^{2 +} to a molar ratio of 0.40 to 0.60: 9.40 to 9.90 to form the phyticokite grains in the sphere shape. It may be to control so that, preferably the mixing ratio of oleic acid, ethanol and water 0.33 ~ 0.34: 0.33 ~ 0.34: 0.33 ~ 0.34 or 0.18 ~ 0.32: 0.15 ~ 0.32: 0.45 ~ 0.62, volume ratio, (Mg ^{2 +} + Ca ²⁺ ): PO ₄ ^3- is adjusted to a molar ratio of 10.0: 5.5 to 6.5 and Mg ^{2 +} : Ca ^{2 +} to a molar ratio of 0.45 to 0.55: 9.45 to 9.95 to form phytoproxite grains in the shape of a sphere. It may be controlled so that, more preferably the mixing ratio of oleic acid, ethanol and water 0.33-0.34: 0.33-0.34: 0.33-0.34, 0.28-0.32: 0.15-0.25: 0.45-0.55, or 0.18-0.22: 0.18 ~ 0.32: 0.48 ~ 0.62 volume ratio, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- to 10 7.0: 5.5 ~ 6.5 mole ratio, and Mg ^{+ 2:} the Ca ^{2 +} 0.48 ~ 0.52: by adjusting a molar ratio of 9.48 ~ 9.52 may be to control so that the two (sphere) geometry for rock Whitman kite crystal grains.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is a volume ratio of 0.15 ~ 0.35: 0.26 ~ 0.50: 0.20 ~ 0.44, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- 10.0 By controlling the molar ratio of: 5.1 to 6.5 and the Mg ^{2 +} : Ca ^{2 +} to a molar ratio of 0.40 to 0.60: 9.40 to 9.90, the fluorokite crystal grains may be controlled to have a grain shape, preferably oleic acid. volume ratio of ^{0.25 ~ 0.44, (Mg 2+ +} Ca 2+)::, ethanol, and the mixing ratio of water 0.18 ~ 0.32: 0.28 ~ 0.45 PO 4 3- to 10.0: 5.5 ~ 6.5 mole ratio, and Mg ^{+ 2:} Ca ^{2 +} may be controlled to a molar ratio of 0.45 to 0.55: 9.45 to 9.95 to control the fluorokite crystal grains to form granules, and more preferably, the mixing ratio of oleic acid, ethanol and water is 0.28 to 0.32: 0.28 ~ 0.42: 0.28 ~ 0.42, or 0.18 ~ 0.22: 0.38 ~ 0.42: volume ratio of ^{0.38 ~ 0.42, (Mg 2+ +} Ca 2+): PO 4 3- to 10.0: 5.5 ~ 6.5 and the molar ratio of Mg ^{2 +} : the Ca ^{2 +} 0.48 ~ 0.52: adjusting a molar ratio of 9.48 ~ 9.52 by Whitman lock The kite crystal grains may be controlled to be in the form of rice grains.

In one embodiment of the present invention, the mixing ratio of the oleic acid, ethanol and water is a volume ratio of 0.15 ~ 0.25: 0.40 ~ 0.70: 0.10 ~ 0.40, the (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- 10.0 By controlling the molar ratio of: 5.1 to 6.5 and the Mg ^{2 +} : Ca ^{2 +} to a molar ratio of 0.8 to 1.5: 8.5 to 9.2, it is possible to control the phytoprocite crystal grains into a grain shape, preferably oleic acid. volume ratio of ^{0.15 ~ 0.35, (Mg 2+ +} Ca 2+)::, ethanol, and the mixing ratio of water 0.18 ~ 0.22: 0.45 ~ 0.65 PO 4 3- to 10.0: 5.5 ~ 6.5 mole ratio, and Mg ^{+ 2:} Ca ^{2 +} may be adjusted to a molar ratio of 0.8 to 1.2: 8.8 to 9.2 to control the fluorokite crystal grains to form grains of rice, and more preferably, the mixing ratio of oleic acid, ethanol and water is 0.18 to 0.22: Volume ratio of 0.50 to 0.60: 0.20 to 0.30, (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- to molar ratio of 10.0: 5.5 to 6.5 and Mg ^{2 +} : Ca ^{2 +} to 0.9 to 1.1: 8.9 to 9.1 Wheatrokite grains are grain shaped by adjusting the molar ratio It may be to control so that, more preferably, the mixing ratio of oleic acid, ethanol and water is the volume ratio of 0.18 to 0.22: 0.54 to 0.58: 0.22 to 0.26, (Mg ²⁺ + Ca ²⁺ ): PO ₄ ^3- To adjust the molar ratio of 10.0: 5.8 ~ 6.2 and Mg ^{2 +} : Ca ^{2 +} in a molar ratio of 0.9 ~ 1.1: 8.9 ~ 9.1 may be to control the fluorokite crystal grains to form a grain (grain).

Whitlockite with controlled shape

The present invention also provides a whiplockite in which the crystal grain shape produced by the above method is controlled. Wheatockite according to the present invention may have one or more shapes selected from the group consisting of sphere, rod, plate, polygon, rice grain and cubic. And, preferably, may have one or more shapes selected from the group consisting of spheres, plates, and granules. In this case, the plate may be a polygonal plate.

In the wheatockite according to the present invention, the shape of the wheatockite crystal grains may include a mixing ratio of oleic acid, ethanol and water in Step 1; And a concentration of adding the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material of step 2; Any one or more of the can be adjusted by controlling.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are merely to illustrate the present invention, the contents of the present invention is not limited by the following examples.

< Example  1> Solvent heat  Synthesis and solid-liquid-solution ( SLS ) Method Of Whitlockite (WH)  Produce

Step 1: Preparation of Mixed Solvent

The mixed solvent for the precursor reaction was prepared by mixing oleic acid, ethanol and water in a volume ratio of 0.2: 0.1: 0.7 based on the total volume of the mixed solvent 1.

Specifically, 10 mL of oleic acid, 5 mL of ethanol (ethyl alcohol), and 30 mL of water were mixed in a 150 mL beaker to prepare a mixed solvent by stirring at 900 rpm for 5 minutes.

Step 2: Preparation of Precursor Mixed Solution

9 mL (299.646 mg / 9 mL) aqueous solution of 0.3 M calcium chloride (CaCl ₂ ), 0.3 M magnesium chloride (MgCl ₂ ) solution (28.563), which is a precursor for the manufacture of phytoproxite (WH), in the mixed solvent prepared in step 1 mg / 1 mL) and 0.18M disodium hydrogen phosphate (Na ₂ HPO ₄ ) 10 mL (255.528 mg / 10 mL) of the aqueous solution was added sequentially and stirred for 30 minutes to prepare a precursor mixed solution of a solid-liquid-solution (SLS) system. At this time, the final molar ratio of Mg ^{2 +} : Ca ^{2 +} : PO ₄ ^3- (hereinafter, described as 'Mg: Ca: PO ₄ ') added for preparing the precursor mixed solution is shown in Table 1 below.

Or less, Mg: Ca: PO ₄ mole ratio of the precursor to a mixed solution containing within the Mg ^{2 +,} Ca ^{2 +,} and PO ₄ ^3- ions the molar ratio of Mg ^{2 + +} Ca ^{2 +} (hereinafter, 'Mg + Ca' It means the ratio converted to the value of 10).

Example 1 Mg 0.8 Ca 9.2 PO ₄ 6.0

Here, a schematic diagram of the solid-liquid-solution (SLS) system for fluorokite synthesis is shown in FIG. 1. Specifically, in the solid region of the SLS system, calcium ions (Ca ²⁺ ) and magnesium ions (Mg ^{2 +} ) combine with oleic acid to form a solid phase of calcium oleate and magnesium oleate, and the liquid region. In the mixture of oleic acid and ethanol, in the final solution section, ethanol and water are mixed and phosphate ion (PO ₄ ^3- ) is present.

Step 3: Heat the Precursor Mix Solution and Generate Precipitate

The precursor mixture solution prepared in step 2 was placed in a Teflon tube, and the temperature was raised to 200 ° C. for 30 minutes at a rate of 6 to 6.3 ° C. per minute from a temperature of 10 to 20 ° C., which is a laboratory itself, and then maintained at a high temperature of 200 ° C. The reaction was carried out for 12 hours to perform solvent thermal synthesis and SLS synthesis. After the reaction was completed, it was left to cool to room temperature.

Step 4: WH  Separation and Purification

After the reaction of step 3, the supernatant was discarded and the precipitated whitchite (WH) precipitate was separated by a centrifuge (4000 rpm, 5 minutes). WH separated for purification was washed three times with isopropanol (isopropanol), and centrifuged again to remove the unreacted residue, and dried in a vacuum oven at 60 ℃ for 12 hours to prepare the Wheat of Example 1 Rockite (WH) was prepared.

< Example  2-9> Adjusting Magnesium and Calcium Ion Mixing Ratio Of Whitlockkite (WH)  Produce

When mixing the precursor of step 2, the mixing ratio of the precursor is fixed at a molar ratio of (Mg + Ca): PO ₄ at 10: 6, and the final molar ratio of Mg: Ca: PO ₄ is changed only by the Mg: Ca ratio. Except that the molar ratio is adjusted to be as shown in Table 2, was carried out in the same manner as in Example 1 to prepare a Wheatrocket kit (WH) of Examples 2 to 9.

Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Mg 0.9 1.0 1.1 1.2 1.5 2.0 3.0 0.5 Ca 9.1 9.0 8.9 8.8 8.5 8.0 7.0 9.5 PO ₄ 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0

< Example  10-14> Adjusting the phosphate ion mixing ratio Of Whitlockkite (WH)  Produce

The ratio of Mg and Ca in the precursor mixing of step 2 was fixed at 0.8: 9.2, and the mixing ratio of (Mg + Ca): PO ₄ was adjusted to 10: 5 to 10:10 to obtain a final Mg: Ca: PO ₄ ratio. Except that the molar ratio was as shown in Table 3, was carried out in the same manner as in Example 1 to prepare a whiplockite (WH) of Examples 10 to 14.

Example 10 Example 11 Example 12 Example 13 Example 14 Mg 0.8 0.8 0.8 0.8 0.8 Ca 9.2 9.2 9.2 9.2 9.2 PO ₄ 5.0 7.0 8.0 9.0 10.0

< Example  15> Adjusting the precursor mixing ratio Of Whitlockkite (WH)  Produce

Wheatockite (WH) of Example 15 was prepared in the same manner as in Example 1, except that the final molar ratio of Mg: Ca: PO ₄ when the precursor was mixed in Step 2 was changed as shown in Table 4 below. .

Example 15 Mg 0.625 Ca 9.375 PO ₄ 2.5

< Comparative example  1> Of hydroxyapatite (HAP)  Produce

Except for magnesium (Mg) when mixing the precursor of step 2 except that the final molar ratio of Mg: Ca: PO ₄ as shown in Table 5, the same procedure as in Example 1 to the hydroxy of Comparative Example 1 Apatite (HAP) was prepared.

Comparative Example 1 Mg 0 Ca 10.0 PO ₄ 6.0

< Example  16-25> Adjusting the mixed solvent ratio Of Whitlockkite (WH)  Produce

The mixing ratio of the mixed solvent (oleic acid, ethanol, water) of step 1 was changed to the volume ratio of Table 6 below, and the total mixture of 45 mL of the mixed solvent and the precursor mixing ratio of the precursor of step 2 (final molar ratio of Mg: Ca: PO ₄ ) were used. Except as shown in Table 6, was carried out in the same manner as in Example 1 to prepare a whiplockite (WH) of Examples 16 to 24.

Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Example 23 Example 24 Mg: Ca: PO ₄ 1.0: 9.0: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 0.5: 9.5: 6.0 Oleic acid 0.2 0.2 0.2 0.3 0.2 0.3 0.333 0.2 0.3 ethanol 0.56 0.1 0.2 0.2 0.3 0.3 0.333 0.4 0.4 Water (DI) 0.24 0.7 0.6 0.5 0.5 0.4 0.333 0.4 0.3

< Comparative example  2-3> Adjust the mixed solvent ratio Of hydroxyapatite (HAP)  Produce

The mixing ratio of the mixed solvent (oleic acid, ethanol, water) of step 1 was changed to the volume ratio of Table 7 below, and the total mixture of 45 mL of the mixed solvent and the precursor mixing ratio of the precursor of step 2 (final molar ratio of Mg: Ca: PO ₄ ) were used. A hydroxyapatite (HAP) of Comparative Examples 2 to 3 was prepared in the same manner as in Example 1, except that it was different from Table 7 below.

Comparative Example 2 Comparative Example 3 Mg: Ca: PO ₄ 0.5: 9.5: 6.0 0.5: 9.5: 6.0 Oleic acid 0.14 0.1 ethanol 0.08 0.2 Water (DI) 0.78 0.7

< Experimental Example  1> precursor On molar ratio  According Whitlockkite  X-ray diffraction analysis XRD )

X-ray diffraction analysis (XRD) was performed on the wheat chlorite (WH) and hydroxyapatite (HAP) prepared by the methods of Examples 1 to 15 and Comparative Example 1, and magnesium (Mg) and calcium (Ca). XRD graph according to precursor molar ratio (Mg: Ca: PO ₄ ) of phosphoric acid (PO ₄ ) and WH (JCPDS 70-2064) and HAP (JCPDS 09-0432) reference XRD peaks were compared.

FIG. 2 is an XRD graph of whitockite (WH) and hydroxyapatite (HAP) prepared according to the present invention, wherein (a) is Example 14, (b) is Example 1, and (c) is Example 3, (d) shows Example 8, (e) shows Example 15, (f) shows Example 9, and (g) shows Comparative Example 1. FIG.

First, (Mg + Ca): PO ₄ is fixed at a molar ratio of 10: 6, and only the Mg (x): Ca (10-x) ratio is changed, so as to change the XRD graph according to the change of Mg and Ca ratio. As a result of confirming the change, in the case of Comparative Example 1 (Mg: Ca: PO ₄ = 0: 10.0: 6.0), which is a composite prepared by setting the ratio of Mg precursor to 0, as shown in FIG. 2G, CaCl ₂ and Na ₂ HPO ₄ Hydroxyapatite (HAP), not Whitockite (WH), was prepared under a binary system, confirming that an XRD graph consistent with the hydroxyapatite (HAP) reference XRD peak (JCPDS 09-0432) appeared. It was.

For Example 9 (Mg: Ca: PO ₄ = 0.5: 9.5: 6.0), a composite prepared by increasing the Mg precursor molar ratio to 0.5, HAP and WH were shown to be mixed (FIG. 2F).

As the Mg precursor molar ratio was continuously increased, as shown in FIGS. 2B (Example 1) and 2C (Example 3), the yield of WH was increased so that the Wheatockite (WH) reference XRD peak (JCPDS 70-2064). It was confirmed that a graph similar to) appeared, and the XRD graph of the Wheatockite (WH) according to Examples 1 to 8 of the present invention including the same also appeared in a similar aspect. In particular, it was confirmed that the Wheatockite (WH) according to Examples 5 to 8 almost coincided with the Wheatockite reference XRD peak (JCPDS 70-2064), thereby confirming that a very high purity of Wheatockite was prepared.

On the other hand, when the Mg precursor molar ratio was continuously increased to 3.0 (Example 8), the peak appeared slightly broad (FIG. 2D), and it was confirmed that the state of the product was amorphous, and the Mg precursor The peak was broadened broadly as the amount added increased, confirming that Mg content plays an important role in pure WH synthesis.

In addition, Wheatockite (WH) according to Examples 1, 10 to 15, prepared by maintaining the molar ratio of Mg and Ca at 0.8: 9.2 and varying the molar ratio of PO _{4 to} the molar ratio of 'Mg + Ca'. Analysis of the XRD graph showed that most of the graphs were similar to those of the Wheatockite (WH) reference XRD peak (JCPDS 70-2064), and in particular, the Wheatockite (WH) XRD peaks different from Examples 10-14. Was found to be in close agreement with the Wheatockite reference XRD peak (JCPDS 70-2064), confirming that very high purity Wheatockite was produced. At this time, as shown in Figure 2a (Example 14) and Figure 2b (Example 1), it was confirmed that the crystallinity (crystallinity) is improved as the ratio of PO ₄ increases, the more distinct peak appears.

When the molar ratio of PO ₄ to the molar ratio 10 of 'Mg + Ca' is extremely small at 2.5, as shown in FIG. 2E (Example 15), the XRD peak of calcium oleate (CAO) at around 20 degree (JCPDS) No. 18-0297), a broad peak appeared, indicating that the peak of the fluorokite composite was obscured.

Therefore, through the above results, it was confirmed that under a wide range of precursor mixing conditions as shown in Figure 3, it is possible to obtain a high yield and purity of Whitokite (WH).

Here, Mg ^{+ 2} appears on the three won chart of Figure 3, Ca ^{+ 2,} and the value of the PO ₄ ^3- is the mole fraction (mole fraction) values for each precursor ion represented by calculated by the following equation.

[Equation 1]

Figure three won the Mg ^{2 +} ion molar fraction value (Mf _Mg) = Mg ^{2 +} ion mole number / (Mg ^{+ 2} ions Ca ²⁺ ion molar number + number of moles + number of moles of PO ₄ ^3- ions in a) of the

[Equation 2]

Figure three won the Ca ^{2 +} molar fraction value of the ion _(Ca Mf) = Ca ^{2 +} ion mole number / (Mg ^{+ 2} ions Ca ²⁺ ion molar number + number of moles + number of moles of PO ₄ ^3- ions in) of

[Equation 3]

Molar fraction value (Mf _P ) of PO ₄ ^3- ions on the ternary diagram = number of moles of PO ₄ ^3- ions / (number of moles of Mg ^{2 +} ions ^{+ number} of moles of Ca ²⁺ ions + number of moles of PO ₄ ³ ions)

On the other hand, although the full width half maxium (FWHM) of the XRD peak is different depending on the size of the synthesized particles, it can be confirmed that the half width is large, because the size or thickness of the particles is several nanometers and the crystal unit is small. It can be seen as. This small crystal unit has the advantage of fast biodegradation in the body, and also can increase the crystallinity through the sintering process, it is possible to control the rate of biodegradation by adjusting the sintering temperature and time.

< Experimental Example  2> precursor On molar ratio  According Whitlockkite  Shape analysis

Mg ^{2 +} ions, (Mg + Ca) In order to examine the effects on nucleation (nucleation) and growth of calcium phosphate (growth): the molar ratio of PO ₄ 10: maintained at 6, and the Mg and Ca The shapes of the Wheatock kites (WH) were compared through transmission electron microscope (TEM) analysis images for Examples 1 to 9 and Comparative Example 1 with varying molar ratios.

Figure 4 is a TEM analysis image of the Wheatockite (WH) prepared according to the present invention, where (a) is Example 8, (b) is Example 7, (c) is Example 6, (d) is Example 3, (e) shows Example 1, (f) shows Example 9. At this time, all of the scale bars are 100 nm.

As a result, as the molar ratio of Ca to Mg increases, the shape was changed from a nanosphere (nanosphere, nanospheres) (FIG. 4B) to a polygonal plate (FIG. 4C and 4D).

Specifically, in Example 8 prepared with an Mg ratio of 3.0, an amorphous state was shown (FIG. 4A), and in Example 7, in which the Mg ratio was slightly reduced to 2.0, nucleation occurred. It appeared to be isotropic to lead to nuclear growth, which induced growth into nanospheres (FIG. 4B), and the size of the nanospheres was found to be about 4.5 ± 1.0 nm.

Crystallization and anisotropic growth in Examples 2-6 (Mg: Ca = 1.0: 9.0-1.5: 8.5) with lower Mg ratios led to growth on polygonal plates (FIG. 4C and 4d), due to the interaction between alkyl chains of oleic acid adsorbed on the surface as surfactants and soft templates, most of the polygonal plates are self-assembled side by side on the TEM grid. assembly) tended to form (FIGS. 4C-4D). The spontaneous evaporation of the solvent can easily produce a close-packed pattern of two-dimensional regions, which can be an ideal building block for the formation of two-dimensional arrays.

Meanwhile, in Examples 1 (Mg: Ca = 0.8: 9.2) and Example 9 (Mg: Ca = 0.5: 9.5), where the Mg concentration was further lowered, wheatockite (WH) and b in the form of nanospheres It was shown that hydroxyapatite (HAP) in the form of nanowires consisted of a mixed mixture (FIGS. 4E and 4F).

From these results, magnesium has a significant inhibitory effect on the nucleation and growth of calcium phosphate, and it is confirmed that hydroxyapatite (HAP) nanowires are synthesized after magnesium is exhausted in the synthesis of fluorokite (WH). . Specifically, when fluorokite (WH) is synthesized, Mg, Ca, and PO ₄ are synthesized in the composition ratio (1: 9: 7) in the chemical formula, and the ratio of Mg in the chemical formula of fluorophyte (WH) When higher than the composition ratio of, as shown in FIG. 5A (Mg ²⁺ : Ca ²⁺ : PO ₄ ^3- = 2.0: 8.0: 6.0), Mg ions inhibit the formation of hydroxyapatite (HAP) and thus Ca ions. Wheatockite (WH) is synthesized until all of the and PO ₄ ions are exhausted (area A), and since only Mg ions remain, no further synthesis proceeds. In addition, when the Ma: Ca ratio is equal to the composition ratio in the chemical formula, as shown in FIG. 5B (Mg ²⁺ : Ca ²⁺ : PO ₄ ^3- = 1.0: 9.0: 6.0), all of the PO ₄ ions are exhausted. The synthesis of WH proceeds until it is (A region), and when the ratio of Mg is lower than the composition ratio in the chemical formula of fluorokite (WH), FIG. 5C (Mg ^{2 +} : Ca ^{2 +} : PO ₄ ^3- 0.5: 9.5: 6.0), phytoprokite (WH) is synthesized until all of the Mg ions are exhausted (area A), after which only Ca and PO ₄ ions remain and crystallization by Mg ions Since the growth is not hindered, hydroxyapatite (HAP) is synthesized until all of the PO ₄ ions are exhausted (B region).

In addition, it was confirmed that various forms of WH could be formed by changing the Mg ratio. In other words, the shape of phytoprock can be easily controlled by adjusting the precursor molar ratios of calcium and magnesium, and the shape of the fluorokite is various, such as ceramic quantum dots (nanospheres) having a diameter of 6 nm, and thick rod-shaped particles (polygonal plates). appear.

< Experimental Example  3> Whitlockkite  High resolution transmission electron microscope HRTEM ) analysis

Wheatockite (WH) prepared in Example 1 and Example 6 was analyzed using a high resolution transmission electron microscope (HRTEM).

FIG. 6 is a high resolution transmission electron microscope (HRTEM) analysis image of wheat chlorite (WH) prepared according to the present invention. Here, (a) is Example 6, (b) is Example 1, and a scale bar is 10 nm.

FIG. 6A is an HRTEM analysis image of each of the polygonal plates (Example 6) and FIG. 6B of the nanospheres (Example 1) of Whitlockkite (WH), wherein the scale bars of FIGS. 6A and 6B are shown. ) Are 10 nm and 5 nm, respectively.

Specifically, as shown in FIG. 6A, the interplanar distance of the WH polygonal plate of Example 6 was measured to be 0.5091 nm (5.091 kV) and 0.5104 nm (5.104 kV), which is the surface of the WH 110 plane. d-spacing corresponds to 0.5175 nm.

As shown in FIG. 6B, in Example 1, the spherical WH was not measured, and the crystal lattice of the HAP nanowire was measured to be about 0.344 nm (3.44 GHz) corresponding to the HAP (002) plane. It became.

< Experimental Example  4> According to the phosphate ion ratio Whitlockkite  X-ray diffraction ( XRD ), Before transmission Microscopic (TEM) and Thermogravimetric (TGA) Analysis

The production was carried out by maintaining the molar ratio of Mg: Ca at 0.8: 9.2 and the molar ratio of (Mg + Ca): PO ₄ at 10: 6 to 10:10 during the production of phytoproxite (WH). The surface characteristics of WH were analyzed by X-ray diffraction (XRD), transmission electron microscope (TEM), and thermogravimetric (TGA) patterns for Examples 1 and 10 to 14. FIGS. 7, 8, and 9 As shown in 7 to 9 show Example 1, (b) shows Example 12, and (c) shows Example 14. The scale bar of FIG. 7 is 100 nm, and the images inserted in the lower right of each drawing test the dispersion degrees of Examples 1, 12, and 14 for hexane (a), ethanol (b), and water (c), respectively. to be.

As shown in FIG. 7 and FIG. 8, as a result of analyzing the surface properties of the WH nanomaterial according to the phosphate ion molar ratio, as the content of PO ₄ ^3- increases, the morphology of the WH is promoted and the hydrophilic WH is formed. and, the particle surface is a PO ₄ ^3- occupied than Ca ^{+ 2.} At this time, the oleic acid molecules on the particle surface fall off, and the particle surface becomes hydrophilic. As a result, the oleic acid molecules did not act as a soft template during the nucleation and growth of the nuclei, and thus the WH was closer to the spherical (nanosphere) type.

These characteristics were also shown in the TGA analysis result (FIG. 9). The weight reduction at 300-400 ° C. was caused by the thermal decomposition of oleic acid, a surfactant of WH. As the molar ratio of phosphate ions increased from 6 (Example 1, a) to 10 (Example 14, c), It was confirmed that the weight change was reduced due to the reduction of the oleic acid present. Meanwhile, the weight loss at 200 ° C. or lower is due to evaporation of water, and in the case of Example 14 (FIG. 9C), which is a hydrophilic sample, Example 1 (FIG. 9A) or Example 12 (FIG. 9B). It can be seen that the weight loss is greater. These results indicate that more water was adsorbed on the surface of Example 14 (c) than Examples 1 and 12 (a, b) due to strong electrostatic attraction with water molecules.

Similarly, in the case of the Wheatockite (WH) of Example 10 having a very small molar ratio of phosphate ions of 5.0, crystal growth did not occur well, and thus it was confirmed that the amorphous form had a very small particle size. It was confirmed in the form of a polygonal plate, it was confirmed that in the case of Examples 13 and 14 in the form of a sphere (nanosphere).

In general, surface properties are an important factor in determining the assembly form of nanostructures, in particular, a great influence on the assembly of organic and inorganic complexes, and also affects cytotoxicity in interaction with cells. From the above results, it was confirmed that the surface properties of the WH nanomaterials can be reasonably controlled by the molar ratio of PO ₄ .

< Experimental Example  5> according to the solvent ratio Of Whitlockkite (WH)  X-ray diffraction ( XRD ) And transmission electron microscope (TEM) analysis

TEM and XRD pattern analysis of WH according to the ratio of Mg: Ca: PO ₄ as precursor material and the ratio of oleic acid, ethanol and water (OA: EtOH: DI) used as solvent in the synthesis of fluorokite using SLS method As shown in FIG. At this time, (a, c) is Comparative Example 3 (Mg: Ca: PO ₄ = 0.5: 9.5: 6.0, OA: EtOH: DI = 0.1: 0.2: 0.7), (b, d) is Example 16 (Mg: Ca: PO ₄ = 1.0: 9.0: 6.0, OA: EtOH: DI = 0.2: 0.56: 0.24), and the scale bar is 100 nm.

As described in Example 1, in the solid region of the SLS system, calcium ions and magnesium ions combine with oleic acid to form a solid phase of calcium oleate and magnesium oleate, and oleic acid and ethanol are mixed in the liquid region. In the section, ethanol and water are mixed and phosphate ions are present (FIG. 1). In other words, the formation of phytoprokite is achieved by the diffusion of phosphate ions in solution to a solid state in which calcium and magnesium ions are present. In this process, phosphate ions must pass through the liquid region. The ratio of oleic acid and ethanol constituting is important. When the ratio of ethanol is large and the ratio of oleic acid is low (Fig. 1a), since the concentration gradient between oleic acid and water is made in a wide area, a wide liquid region is formed so that phosphate ions easily enter the oleic acid layer and the amount of oleic acid is large. Because of this, it is easy to reach the metal phase (marked with M) region of calcium oleate and magnesium oleate, and the mineralization reaction can proceed to synthesize fluorokite. However, when the ratio of ethanol is small and the ratio of oleic acid is high (Fig. 2b), the diffusion of oleic acid and water is made in a thin layer of ethanol and the concentration gradient of oleic acid and water changes rapidly, which causes phosphate ions in water to diffuse through the liquid region. This is not easy, and even though it passes, the thick layer of oleic acid makes it difficult to meet and react with calcium and magnesium.

Accordingly, in Comparative Example 3 and Example 16 of the TEM and XRD analysis results shown in Figure 10, if the comparison is oleic acid content of less Example 3, since Ca ^{2 +} is used as a relatively higher concentration than the Mg ^{2 +} Ca ^{2 +} as to the reaction with oleic acid and primary, Mg ^{+ 2} is failure to effectively participate in the reaction due to the presence of an inorganic state, the end product was made of pure HAP (Figs. 10a and 10c). On the other hand, in the case of Example 16, it was confirmed that WH having high purity and yield in the form of rice grains having a size of 20 nm (FIGS. 10B and 10D).

< Experimental Example  6> according to the solvent ratio Whitlockkite  Shape analysis

Examples 17 to 24 prepared by fixing the molar ratio of the precursor to Mg: Ca: PO ₄ = 9.5: 0.5: 6.0 and varying the mixing ratio of oleic acid, ethanol (EtOH) and water (DI) With respect to the Whitokkite (WH), the volume ratio of oleic acid: ethanol: water is shown in a three-dimensional diagram as shown in FIG.

Here, the values of oleic acid (oleic acid), ethanol (EtOH) and water shown in the three-way diagram of FIG. 11 are the volume ratio values of the solvents calculated through the following equation.

[Equation 4]

Volume ratio value (v / v) of oleic acid on the ternary plot = total volume of mixed solvent for oleic acid addition / precursor reaction

[Equation 5]

Volume ratio value (v / v) of ethanol on the ternary plot = total volume of mixed solvent for ethanol addition volume / precursor reaction

[Equation 6]

Volume fraction value (v / v) of water on ternary plot = total volume of mixed solvent for water addition volume / precursor reaction

X-ray diffraction analysis (XRD) and transmission electron microscopy (TEM) of phytoprokite (WH) prepared by the method of Examples 17 to 24 and hydroxyapatite (HAP) prepared by the method of Comparative Examples 2 to 3 ) Shapes were compared through analytical images.

12 and 13 are XRD graphs and TEM images of Wheatockite (WH) prepared according to the present invention. (A) is Comparative Example 2, (b) is Example 17, (c) is Comparative Example 3, (d) is Example 18, (e) is Example 19, (f) is Example 20, ( g) shows Example 21, (h) shows Example 22, (i) shows Example 23, and (j) shows Example 24.

First, as a result of confirming the change of the XRD graph according to the change of the ratio of oleic acid, ethanol and water, as shown in Figure 12, it was confirmed that the graph of the pattern similar to most of the Wheatockite (WH) reference XRD peak appeared.

On the other hand, as a result of comparing the shape change of the wheat chlorite (WH) according to the change of the ratio of oleic acid, ethanol and water through a transmission electron microscope (TEM) analysis image, as shown in Figure 13, as the ratio of oleic acid increases WH surface As the density of oleic acid molecules bound to increased, precursors did not react easily, and it was confirmed that they exist in the form of small particles. As the ratio of ethanol increases, the concentration gradient between the solid region (WH, oleic acid) and the solution region (water, phosphate ions) is gentle as shown in FIG. Confirmed.

In addition, the Wheatockites of Examples 18 to 20 and 22 were identified in the form of spheres (nanospheres), and the Wheatockites of Examples 21, 23 and 24 were in the form of rice grains.

From these results, not only the proportion of the precursor but also the proportion of the solvent (oleic acid, ethanol and water) also influences the morphology of the fluorokite (WH), and the shape of the fluorokite is determined by the volume ratio of the mixture of oleic acid, ethanol and water. It was confirmed that the control can also be controlled.

< Experimental Example  7> Whitlockkite ( WH ) Infrared spectroscopy ( FTIR ), Raman and Energy dispersion Optical (EDS) Analysis

In order to confirm whether fluorokite was prepared by the method according to the present invention, infrared spectral analysis, Raman analysis, and energy dispersive spectroscopic analysis were performed on the phytoproxite prepared in Example 1.

FIG. 14 is an infrared spectroscopy (FTIR) spectrum of Wheatockite (WH) of Example 1 according to the present invention. FIG.

As shown in Figure 14, 950cm ^{- 1} and 1000 to a peak caused by the vibration of the PO ₄ ^3- group was found at 1100cm ^-1, HPO ₄ ^2, which exists only in Whitman lock kite at 900 cm ^{-1 -} the group P- The peak corresponding to (OH) vibration was confirmed.

FIG. 15 is a Raman spectrum obtained by 532 nm laser irradiation with respect to Wheat Rock kit (WH) of Example 1 according to the present invention. FIG.

As shown in FIG. 15, the Raman spectra of WH were found to have prominent peaks due to vibrations in the phosphate tetrahedra. As the peak associated with the ν 1 symmetry-stretch vibration of the phosphate group, the strongest band at 972 cm ⁻¹ was identified. In addition, other peaks were observed in the 1050-1100 cm ^-1 region (ν3 asymmetric-stretch vibration), the 400-500 cm ^-1 region (ν2 bending mode), and the 550-660 cm ^-1 region (ν4 bending mode). Weak bands in the region below 400 cm ⁻¹ indicate a lattice mode.

FIG. 16 is an energy-dispersive X-ray spectroscopy apparatus of Wheatockite (WH) of Example 1 according to the present invention. Analysis results using EDS). Where (a) is an EDS mapping image of calcium (calcium, Ca), (b) is an EDS mapping image of magnesium (magnesium, Mg), (c) is an EDS mapping image of phosphorous (P), (d) is the EDS spectrum.

As shown in FIG. 16, as measured by using an energy dispersive spectroscopy device (EDS) attached to a transmission electron microscope device, the Wheatockite (WH) of Example 1 was shown to be composed of Ca, Mg, and PO ₄ . And uniformly distributed.

So far I looked at the center of the preferred embodiment for the present invention. Those skilled in the art will appreciate that the present invention can be implemented in a modified form without departing from the essential features of the present invention. Therefore, the disclosed embodiments should be considered in descriptive sense only and not for purposes of limitation. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope will be construed as being included in the present invention.

Claims (17)

Preparing a mixed solvent comprising oleic acid, ethanol and water (step 1);
Preparing a precursor mixed solution by adding a magnesium (Mg) ion feed material, a calcium (Ca) ion feed material and a phosphoric acid (PO ₄ ) ion feed material to the mixed solvent prepared in step 1 (step 2);
Putting the precursor mixture solution prepared in step 2 into a sealed container and heating to 150 to 250 ° C. to produce a phytoproxite precipitate (step 3); And
Separating and purifying the precipitate produced in step 3 (step 4);
Method for producing whitlockite using a solvent-thermal synthesis method and a solid-liquid-solution method comprising a.
The method of claim 1,
Oleic acid, ethanol and water based on the total volume 1 of the mixed solvent of step 1, characterized in that the mixing ratio of 0.05 to 0.35: 0.05 to 0.60: 0.20 to 0.80 by volume ratio.
The method of claim 2,
Based on the total volume 1 of the mixed solvent of step 1, oleic acid, ethanol and water are mixed at a volume ratio of 0.08 to 0.34: 0.06 to 0.58: 0.22 to 0.97.
The method of claim 1,
The magnesium ion feed material, the calcium ion feed material and the phosphate ion feed material of step 2 are magnesium chloride (MgCl ₂ ), calcium chloride (CaCl ₂ ) and disodium hydrogen phosphate (Na ₂ HPO ₄ ), respectively.
The method of claim 1,
The addition concentration of the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material in step 2 is (Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- is a molar ratio of 10: 2.0-11.0, Mg ²⁺ : Ca ²⁺ is a manufacturing method characterized in that the molar ratio (molar ratio) of 0.1 to 3.5: 6.5 to 9.9.
The method of claim 5,
The concentration of the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material in step 2 is (Mg + Ca): PO ₄ is a molar ratio of 10: 2.4 to 10.5, and Mg: Ca is 0.40 to A molar ratio of 3.05: 6.95 to 9.90.
The method of claim 6,
The addition concentration of the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material in step 2 is (Mg + Ca): PO ₄ is a molar ratio of 10: 2.5 to 10.1, and Mg: Ca is 0.5 to Method of producing a molar ratio of 3.0: 7.0 ~ 9.5.
The method of claim 1,
Mixing ratio of oleic acid, ethanol and water of step 1; And a concentration for adding the magnesium ion feed material, the phosphate ion feed material and the calcium ion feed material in step 2; A method for producing a fluorocarbon crystal grain by controlling any one or more of the above.
Wheatockite prepared by the method of claim 1.
The method of claim 9,
Whitockite is a wheat, characterized in that it has at least one shape selected from the group consisting of sphere (rod), rod (rod), plate (polygon), rice grain (granule) and cubic (cubic) Rock Kite.
Preparing a mixed solvent comprising oleic acid, ethanol and water (step 1);
Preparing a precursor mixed solution by adding a magnesium (Mg) ion feed material, a calcium (Ca) ion feed material and a phosphoric acid (PO ₄ ) ion feed material to the mixed solvent prepared in step 1 (step 2);
Putting the precursor mixture solution prepared in step 2 into a sealed container and heating to 150 to 250 ° C. to produce a phytoproxite precipitate (step 3); And
And separating and purifying the precipitate produced in step 3 (step 4); and
Mixing ratio of oleic acid, ethanol and water of step 1; And the concentration of magnesium (Mg) ion feed material, calcium (Ca) ion feed material and phosphoric acid (PO ₄ ) ion feed material added in step 2; Shape control of whitlockite crystals using a solvent thermal synthesis method and a solid-liquid-solution method, characterized in that by controlling any one or more of the whiprocketite crystal grain shape Way.
The method of claim 11,
Based on the total volume 1 of the mixed solvent of step 1, the mixture ratio of oleic acid, ethanol, and water is adjusted to a volume ratio of 0.15 to 0.25: 0.05 to 0.15: 0.65 to 0.75 to form fluorocarbon crystal grains in a plate or sphere ( A method for controlling the shape of a whitkite crystal grain, characterized in that it is controlled to have a sphere shape.
The method of claim 11,
By adjusting the mixing ratio of oleic acid, ethanol and water based on the total volume 1 of the mixed solvent of step 1 to a volume ratio of 0.15 to 0.35: 0.10 to 0.60: 0.20 to 0.64, the phytoproxite crystal grains are formed into spheres or rice grains ( A method for controlling the shape of grains of whiprite, characterized in that it is controlled to have a granule shape.
The method of claim 11,
(Mg + Ca ^{+ 2 + 2):} PO ₄ ^3- to 10.0: 8.6 ~ 11.0 mole ratio and the Mg ^{+ 2:} the Ca ^{2 +} 0.5 ~ 3.0: adjusted to a molar ratio of 7.0 ~ 9.5 to obtain the lock Whitman kite crystal grain A method for controlling the shape of a phytoproxite crystal grain, characterized in that it is controlled to have a (sphere) shape.
The method of claim 11,
(Mg ²⁺ + Ca ^2+): PO ₄ ^3- to 10.0 molar ratio of 6.6 ~ 8.5 and the Mg ^{+ 2:} the Ca ^{2 +} 0.5 ~ 3.0: 7.0 ~ 9.5 by adjusting the molar ratio of the plate lock Whitman kite crystal grain A method for controlling the shape of a whitkite crystal grain, characterized by controlling the plate shape.
The method of claim 11,
(Mg ^{2 +} + Ca ^{2 +} ): PO ₄ ^3- is adjusted to a molar ratio of 10.0: 5.1 to 6.5 and Mg ^{2 +} : Ca ^{2 +} to a molar ratio of 0.4 to 2.9: 7.1 to 9.6 to determine the phytoproxite grains. A method for controlling the shape of a phytoproxite grain, characterized in that it is controlled so as to be a shape of one kind selected from the group consisting of a plate, a sphere and a grain.
Wheatockite having controlled crystal grain shape produced by the method of claim 11.

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