Preparation method of bone repair raw material, bone repair raw material and application thereof

Abstract

The present invention discloses a preparation method of a bone repair raw material, a bone repair raw material and its application. A preparation method of a bone repair raw material comprises the following steps: (i) preparing a mixed solution of calcium salt and magnesium salt as a first solution; preparing a phosphate solution and adjusting the pH to 9.5-10.5 with an alkali solution as a second solution; (ii) heating and mixing the first solution and the second solution, and reacting at 60-95°C and stirring; (iii) centrifuging the suspension obtained after the reaction in step (ii) to obtain a precipitate, washing, and spray-drying the washed precipitate to obtain a powdered porous bone repair raw material. The reaction conditions of the preparation method of the present invention are relatively mild, which reduces the production cost; the obtained bone repair raw material is a low-density porous powder material, which has a high binding property with polymer materials such as collagen.

Description

Technical Field

[0001] The invention relates to a method for preparing a bone repair raw material, in particular to a method for preparing a magnesium-containing tricalcium phosphate bone repair powder raw material. The bone repair raw material can be used to prepare a bone repair body. Background Art

[0002] As the aging of the population further deepens, the incidence of bone injuries due to various chronic diseases, traffic accidents, work injuries and sports injuries has increased year by year, and it is urgent to develop new artificial bone materials for bone defect repair. Existing bone repair materials are mainly hydroxyapatite, which shows a certain biocompatibility after implantation in the body, but it is almost not degraded and metabolized in the body. Studies have shown that hydroxyapatite has no obvious change after being implanted in the bone defect position in the body for several years, which hinders the growth of new bone, see reference 1: Dorozhkin SV, Epple M. Biological and medical significance of calcium phosphates. Angew. Chem. Int. Ed. 2002, 41: 3130-3146.

[0003] Compared with hydroxyapatite, tricalcium phosphate material has better degradation performance and can form chemical bonds with bones after implantation. However, hydroxyapatite is easy to crystallize in liquid phase synthesis, while tricalcium phosphate is difficult to form. For this reason, tricalcium phosphate raw materials usually need to be prepared by high-temperature calcination or solid-phase reaction at more than 1000 degrees, which consumes a lot of energy and the product particles are dense micron-sized powders with high density and irregular surface. It is difficult to meet the application of 3D printing and some new bone repair composite materials, see document 2: Yadav MK, Pandey V. and et al. A low-cost approach to develop silica doped Tricalcium Phosphate (TCP) scaffold by valorizing animal bone waste and rice husk for tissue engineering applications. Ceram. Int. 2022, 48: 25335-25345.

[0004] Patent ZL201610290891.8 discloses a method for preparing β-phase tricalcium phosphate crystal materials under low temperature conditions. The method first mixes Ca (Mg, Sr) and P sources at room temperature to prepare amorphous calcium phosphate materials, and then places them in a hydrothermal reactor at high temperature and high pressure (160-250°C, 1.5MPa) to crystallize to form tricalcium phosphate crystal materials with grains of 30-100nm. Compared with the traditional process of preparing tricalcium phosphate materials by high-temperature calcination, this method converts amorphous calcium phosphate into tricalcium phosphate crystals under hydrothermal conditions of 160-250°C and 1.5MPa, which can effectively reduce production costs and obtain nano-scale tricalcium phosphate powder. However, the high-temperature and high-pressure hydrothermal conditions of this method make this preparation method difficult to be applied on a large scale; at the same time, the obtained nano-scale tricalcium phosphate powder often causes the powder to fall off and induce inflammatory reactions due to weak binding force when applied to new bone repair composite materials.

[0005] Therefore, it is necessary to develop a tricalcium phosphate bone repair material that is suitable for preparing bone repair bodies and has milder preparation conditions and stronger composite material bonding. Summary of the invention

[0006] The purpose of the present invention is to provide a method for preparing a bone repair raw material, wherein the reaction conditions are relatively mild and the production cost is reduced; the prepared bone repair raw material is a low-density porous powder material, and has good binding properties with polymer materials such as collagen. The bone repair raw material is suitable for preparing a bone repair body, wherein the bone repair raw material has better binding properties and dispersibility in polymer materials such as collagen, and solves the problems of shedding and inflammation of nano tricalcium phosphate powder during application.

[0007] The first aspect of the present invention provides a method for preparing a bone repair raw material, comprising the following steps:

[0008] (i) preparing a mixed solution of calcium salt and magnesium salt as a first solution; preparing a phosphate solution and adjusting the pH to 9.5 to 10.5 with an alkali solution as a second solution;

[0009] (ii) heating and mixing the first solution and the second solution, and reacting them at 60 to 95° C. with stirring;

[0010] (iii) The suspension obtained after the reaction in step (ii) is centrifuged to obtain a precipitate, which is then washed and spray-dried to obtain a porous bone repair material in powder form.

[0011] In a preferred embodiment, the molar concentration ratio of calcium ions to magnesium ions in the first solution is 6-10.

[0012] In a more preferred embodiment, the molar concentration of calcium ions in the first solution is 0.01-0.9 mol / L, more preferably 0.1-0.8 mol / L, and further preferably 0.2-0.6 mol / L. For example, the molar concentration of calcium ions is 0.01 mol / L, 0.05 mol / L, 0.08 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L or 0.8 mol / L.

[0013] In a more preferred embodiment, the molar concentration of magnesium ions in the first solution is 0.001-0.15 mol / L; more preferably 0.01-0.15 mol / L; further preferably 0.01-0.1 mol / L; more preferably 0.01-0.1 mol / L; especially 0.05-0.08 mol / L. For example, the molar concentration of magnesium ions is 0.001 mol / L, 0.005 mol / L, 0.008 mol / L, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, 0.12 mol / L or 0.15 mol / L.

[0014] Optionally, the concentration of the calcium salt is 1-100 g / L, more preferably 30-100 g / L, further 50-100 g / L, further 60-90 g / L, especially 80-90 g / L, for example 80 g / L, 82 g / L, 84 g / L, 86 g / L, 88 g / L or 90 g / L by weight. Optionally, the concentration of the magnesium salt is 0.4-40 g / L, more preferably 0.4-30 g / L, further 5-30 g / L, further 15-30 g / L, especially 20-30 g / L, for example 20 g / L, 22 g / L, 24 g / L, 25 g / L, 27 g / L or 29 g / L.

[0015] In a preferred embodiment, after the first solution and the second solution are mixed, the molar ratio of calcium ions to phosphate ions is 1.1 to 1.5.

[0016] In a more preferred embodiment, the molar concentration of phosphate in the second solution is 0.008-0.8 mol / L; more preferably 0.01-0.8 mol / L; further preferably 0.05-0.8 mol / L; especially 0.1-0.5 mol / L. For example, the molar concentration of phosphate is 0.008 mol / L, 0.009 mol / L, 0.01 mol / L, 0.02 mol / L, 0.03 mol / L, 0.04 mol / L, 0.05 mol / L, 0.06 mol / L, 0.07 mol / L, 0.08 mol / L, 0.09 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L or 0.8 mol / L.

[0017] Optionally, the concentration of phosphate in the second solution is 1-100 g / L by weight, more preferably 30-100 g / L, further 50-90 g / L, further 70-90 g / L, especially 80-90 g / L; for example, 81 g / L, 83 g / L, 84 g / L, 85 g / L, 87 g / L or 88 g / L.

[0018] Further, the first solution and the second solution are mixed in equal volumes.

[0019] In a preferred embodiment, the solvent of the first solution is water, and the solvent of the second solution is water. Optionally, the solvent of the first solution is selected from a combination of one or more of methanol, ethanol and water, and the solvent of the second solution is selected from a combination of one or more of methanol, ethanol and water.

[0020] In a preferred embodiment, the calcium salt is selected from a combination of one or more of anhydrous calcium chloride, calcium chloride dihydrate and calcium nitrate tetrahydrate, the magnesium salt is selected from magnesium chloride hexahydrate and / or magnesium nitrate hexahydrate, and the phosphate is selected from a combination of one or more of disodium hydrogen phosphate, diammonium hydrogen phosphate and sodium hydrogen phosphate. In a preferred embodiment, the alkali solution is ammonia water or sodium hydroxide.

[0021] In a preferred embodiment, in step (i), the pH of the second solution is adjusted to 9.8-10.2 using aqueous ammonia. More preferably, the pH of the second solution is 9.8-10.0.

[0022] In a preferred embodiment, in step (ii), the first solution and the second solution are heated to 60-95° C. and then mixed.

[0023] In a preferred embodiment, in step (ii), the stirring rate is 100-500 rpm.

[0024] In a preferred embodiment, in step (ii), the reaction is carried out under normal pressure.

[0025] In a preferred embodiment, in step (iii), the cleaned precipitate is spray dried using a spray dryer, the inlet air temperature of the spray dryer is 240-300°C, the outlet air temperature is 120-150°C, and the feed rate is 30-200 mL / min.

[0026] In a preferred embodiment, in step (iii), the precipitate is added to water and centrifuged and washed multiple times, the washed precipitate is added to 5 to 20 times the mass of water, stirred evenly to form a slurry, and then spray-dried.

[0027] In a specific and preferred embodiment, the preparation method is implemented as follows:

[0028] Dissolving a calcium salt and a magnesium salt in water to obtain a first solution, wherein the concentration of the calcium salt is 1 to 100 g / L, and the concentration of the magnesium salt is 0.4 to 40 g / L;

[0029] Dissolving phosphate in water, and adjusting the pH to 9.5 to 10.5 using aqueous ammonia to obtain a second solution, wherein the concentration of phosphate is 1 to 100 g / L;

[0030] The first solution and the second solution of equal volume are heated to 60-95° C. and then mixed, and reacted under normal pressure under stirring conditions to generate a suspension, wherein the stirring rate is 100-500 rpm;

[0031] The suspension obtained after the reaction is centrifuged to separate the precipitate, which is centrifugally washed with water for 4 to 8 times, and the washed precipitate is added into water of 5 to 20 times its mass, and stirred evenly to form a slurry. The slurry is processed into a micron-sized porous tricalcium phosphate powder using a spray dryer to obtain the bone repair raw material, wherein the inlet air temperature of the spray dryer is 240 to 300° C., the outlet air temperature is 120 to 150° C., and the feed rate is 30 to 200 mL / min.

[0032] The second aspect of the present invention provides a bone repair raw material, which is prepared by the above-mentioned method for preparing bone repair raw materials. The bone repair raw material is in powder form and has a porous structure, and the particle size is 1-20 μm.

[0033] The third aspect of the present invention provides the use of the bone repair raw material in preparing a bone repair body.

[0034] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0035] The preparation method of the present invention is that the calcium / magnesium mixed solution and the phosphate solution are directly wet chemically reacted under 60-95°C normal pressure to generate a magnesium-containing tricalcium phosphate suspension, which is shaped by spray drying to obtain a low-density porous magnesium-containing tricalcium phosphate powder with a particle size of 1-20 μm. The reaction conditions are mild and the preparation process is simple, avoiding the use of a high-temperature calcination process or preparation by solid-phase reaction, and the porous structure can provide better binding force and dispersibility in the process of preparing a bone repair body. The obtained powder material effectively promotes the osteogenic differentiation of bone tissue cells and promotes new bone formation. In the process of preparing a bone repair body from the powder material of the present invention, the special porous structure can enable tricalcium phosphate to form an interlocking structure with a polymer (such as collagen), significantly improving the binding property of the body, and solving the problems of shedding and inflammation that may occur in the application of nano tricalcium phosphate powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] In order to more clearly illustrate the technical solution of the present invention, the accompanying drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0037] Figure 1 This is the XRD spectrum of the powder material prepared in Example 1 of the present invention.

[0038] Figure 2 This is a SEM microscopic morphology of the powder material prepared in Example 1 of the present invention.

[0039] Figure 3 This is a diagram of the interpenetrating microstructure of the powder material prepared in Example 1 of the present invention and the composite of collagen.

[0040] Figure 4 This is the XRD spectrum of the powder material prepared in Example 2 of the present invention.

[0041] Figure 5 This is the XRD spectrum of the powder material prepared in Comparative Example 1.

[0042] Figure 6 This is the XRD spectrum of the powder material prepared in Comparative Example 2. DETAILED DESCRIPTION

[0043] The preferred embodiments of the present invention are described in detail below in conjunction with the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art. It should be noted that the description of these embodiments is used to help understand the present invention, but does not constitute a limitation of the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0044] Compared with hydroxyapatite, tricalcium phosphate materials have better degradation performance, and therefore have significant advantages in the application of bone repair materials. However, since the solubility product of hydroxyapatite (10-57.8) is much lower than that of tricalcium phosphate materials (10-28.7), hydroxyapatite is easy to crystallize in liquid phase synthesis, while tricalcium phosphate is difficult to form. Tricalcium phosphate raw materials usually need to be prepared by high-temperature calcination or solid-phase reaction at more than 1000 degrees, which consumes a lot of energy and the product particles are micron-level, with high density and irregular surface. At present, although some manufacturers can stably produce tricalcium phosphate powder raw materials, most of them calcine the raw materials through solid-phase reaction method and crush the powder through mechanical grinding, which is expensive, the grains are larger after sintering, and the shape is irregular geometry, and the fluidity is poor in the preparation process of liquid composite materials. The present application proposes a new method for preparing magnesium-containing tricalcium phosphate powder based on wet chemical reaction, which directly generates a magnesium-containing tricalcium phosphate suspension by wet chemical reaction under normal pressure at 60-95°C, and obtains a low-density porous magnesium-containing tricalcium phosphate powder of 1-20 μm through a special molding method of spray drying. The porous structure can provide better bonding strength and dispersibility in the process of preparing bone repair bodies.

[0045] First, the present application overcomes the problem that tricalcium phosphate cannot be prepared at low temperature. By regulating the ion binding path in the liquid phase reaction, a low-temperature chemical synthesis process of tricalcium phosphate is developed. The reaction temperature is as low as 60-95°C, which greatly reduces the production cost by more than 90%; it avoids the harsh reaction conditions of high-temperature calcination (above 1000°C) and hydrothermal synthesis (160-250°C, 1.5MPa). Secondly, the powder material prepared by the present application is doped with active magnesium elements, which can effectively promote the osteogenic differentiation of bone tissue cells and promote new bone formation. In view of the problems of weak binding force and poor dispersibility of tricalcium phosphate materials in the application process, the active tricalcium phosphate material synthesized by the low-temperature wet chemical method of the present application is formed into a micron-level low-density porous powder through a spray drying process. This special porous structure can make the tricalcium phosphate powder form an interlocking structure with polymers such as collagen in the process of preparing bone repair bodies, and has good dispersibility and binding properties, which solves the problems of shedding and inflammation that may occur in the application process of nano tricalcium phosphate powder, and has important practical application value.

[0046] The preparation method of bone repair raw material specifically comprises the following steps:

[0047] (1) Dissolving a calcium salt and a magnesium salt in water to obtain a first solution, wherein the concentration of the calcium salt is 1 to 100 g / L, and the concentration of the magnesium salt is 0.4 to 40 g / L. Further, the molar ratio of calcium ions to magnesium ions is 6 to 10; more preferably 7 to 10, and further preferably 7 to 9; for example, 6.0, 7.0, 8.0, 9.0, 10.0.

[0048] (2) Dissolving phosphate in water, and adjusting the pH to 9.5 to 10.5 with aqueous ammonia to obtain a second solution, wherein the concentration of phosphate is 1 to 100 g / L.

[0049] (3) The first solution and the second solution of equal volume are heated to 60-95° C. and then mixed, and a wet chemical reaction is carried out under stirring at normal pressure, wherein the stirring rate is 100-500 rpm. The molar ratio of calcium ion to phosphate ion is 1.1-1.5; preferably 1.1-1.4; more preferably 1.2-1.4; for example, 1.1, 1.2, 1.3, 1.4, 1.5.

[0050] (4) The suspension after the wet chemical reaction is centrifuged to obtain a precipitate, which is centrifugally washed with water for 4 to 8 times, and the washed precipitate is added to 5 to 20 times the mass of water, stirred evenly to form a slurry, and the slurry is processed into a micron-sized porous tricalcium phosphate powder using a spray dryer to obtain the bone repair raw material, wherein the inlet temperature of the spray dryer is 240 to 300° C., the outlet temperature is 120 to 150° C., and the feed rate is 30 to 200 mL / min.

[0051] The micron-scale porous tricalcium phosphate powder has a particle size of 1 to 20 μm and a porous structure. The magnesium content thereof is 1 to 2 wt%, preferably 1.3% to 1.9 wt%, showing excellent biological activity and effectively promoting new bone formation.

[0052] The micron-sized porous tricalcium phosphate powder and a polymer material (such as collagen) are mixed to obtain a slurry, which is dried and molded to obtain a molded bone repair body.

[0053] Example 1

[0054] Weighing and dissolving: weigh 900 g of anhydrous calcium chloride and 270 g of magnesium chloride hexahydrate, dissolve in 10 L of water to obtain solution A; weigh 830 g of diammonium hydrogen phosphate, dissolve in 10 L of water, and use ammonia water to adjust the pH value of the solution to 10.0 to obtain solution B.

[0055] Heating and mixing: Heat solution A and solution B to 70°C and mix them, and continue stirring at 100 rpm to form a suspension.

[0056] Wet chemical reaction: The mixed suspension was heated and stirred at 70°C and 100 rpm for 12 hours.

[0057] Centrifugal washing: The suspension after the wet chemical reaction was centrifuged at 2000 rpm for 3 minutes to obtain the precipitate, and water was added and centrifuged for washing 5 times.

[0058] Spray drying: Add the washed precipitate to 10L of water and stir to form a slurry. Set the spray dryer inlet temperature to 250°C and outlet temperature to 120°C, spray dry the slurry at a rate of 50mL / min, and finally obtain micron-level low-density porous tricalcium phosphate powder with a particle size distribution in the range of 1 to 20μm.

[0059] Detection: X-ray diffraction results of micron-sized low-density porous tricalcium phosphate powder are as follows Figure 1 , where the mass percentage of magnesium is 1.9%. The microscopic morphology of micron-scale low-density porous tricalcium phosphate powder is as follows Figure 2 The powder has a porous structure at the microscopic level. This special porous structure can enable the tricalcium phosphate powder to form an interlocking structure with the polymer during the preparation of bone repair materials. Figure 3 The microscopic photograph of the bone repair body prepared by mixing the powder material with collagen and adding a crosslinking agent is shown. Figure 3 It can be seen that the micron-scale low-density porous tricalcium phosphate powder forms an interpenetrating microstructure with collagen. The micron-scale low-density porous tricalcium phosphate powder significantly improves the binding property with collagen and solves the problems of shedding and inflammation that may occur during the application of nano tricalcium phosphate powder.

[0060] Example 2

[0061] Weighing and dissolving: weigh 1800 g of anhydrous calcium chloride and 400 g of magnesium chloride hexahydrate, dissolve in 20 L of water to obtain solution A; weigh 1700 g of diammonium hydrogen phosphate, dissolve in 20 L of water, and use ammonia water to adjust the pH value of the solution to 9.8 to obtain solution B.

[0062] Heating and mixing: Heat solution A and solution B to 90°C and mix them, stirring continuously at 100 rpm to form a suspension.

[0063] Wet chemical reaction: The mixed suspension was heated and stirred at 90°C and 100 rpm for 4 hours.

[0064] Centrifugal washing: The suspension after the wet chemical reaction was centrifuged at 2000 rpm for 3 minutes to obtain the precipitate, and water was added and centrifuged for washing 5 times.

[0065] Spray drying: Add the washed precipitate to 20L of water and stir to form a slurry. Set the spray dryer inlet temperature to 270°C and outlet temperature to 140°C, spray dry the slurry at a rate of 100mL / min, and finally obtain micron-level low-density porous tricalcium phosphate powder with a particle size distribution in the range of 1 to 20μm.

[0066] Detection: X-ray diffraction results of micron-sized low-density porous tricalcium phosphate powder are as follows Figure 4, of which the mass percentage of magnesium is 1.3%.

[0067] Comparative Example 1

[0068] Weighing and dissolving: weigh 1800 g of anhydrous calcium chloride and 300 g of magnesium chloride hexahydrate, dissolve in 20 L of water to obtain solution A; weigh 1700 g of diammonium hydrogen phosphate, dissolve in 20 L of water, and use ammonia water to adjust the pH value of the solution to 9.3 to obtain solution B.

[0069] Heating and mixing: Heat solution A and solution B to 90°C and mix them, stirring continuously at 100 rpm to form a suspension.

[0070] Wet chemical reaction: The mixed suspension was heated and stirred at 90°C and 100 rpm for 4 hours.

[0071] Centrifugal washing: The suspension after the wet chemical reaction was centrifuged at 2000 rpm for 3 minutes to obtain the precipitate, and water was added and centrifuged for washing 5 times.

[0072] Spray drying: Add the washed precipitate into 20L of water and stir to form a slurry. Set the spray dryer inlet air temperature to 270°C and outlet air temperature to 140°C, spray dry the slurry at a rate of 100mL / min, and finally obtain micron-level low-density porous tricalcium phosphate powder.

[0073] Test: X-ray diffraction results of tricalcium phosphate powder are as follows Figure 5 .like Figure 5 As shown, the porous tricalcium phosphate powder contains impurity phases, mainly calcium hydrogen phosphate impurity phases.

[0074] Comparative Example 2

[0075] The preparation process of Comparative Example 2 is different from that of Example 2 in that after diammonium hydrogen phosphate is dissolved in water, the pH value of the solution is adjusted to 10.8 with aqueous ammonia, and the other steps are the same.

[0076] The obtained powder material was subjected to XRD test. Figure 6 The X-ray diffraction results shown in FIG. 2 show that the powder material prepared in Comparative Example 2 contains more hydroxyapatite.

[0077] As shown in this specification and claims, the terms "comprises" and "include" only indicate the inclusion of the steps and elements that have been clearly identified, and these steps and elements do not constitute an exclusive list, and the method or device may also include other steps or elements. The term "and / or" as used herein includes any combination of one or more of the relevant listed items.

[0078] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0079] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those commonly understood by those skilled in the art. If there is any conflict or inconsistency between the definitions used herein and the definitions contained in other public documents, the definitions used herein shall prevail.

[0080] The above embodiment is only for illustrating the technical concept and features of the present invention, and is a preferred embodiment. Its purpose is to enable people familiar with the technology to understand the content of the present invention and implement it accordingly, and it cannot be used to limit the protection scope of the present invention. Any equivalent transformation or modification made according to the principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing a porous magnesium-containing tricalcium phosphate bone repair raw material, characterized in that: The steps include: (i) preparing a mixed solution of calcium salt and magnesium salt as a first solution; preparing a phosphate solution and adjusting the pH to 9.8-10.2 with an alkali solution as a second solution; (ii) heating and mixing the first solution and the second solution, and reacting them at 60-95° C. with stirring; wherein the first solution and the second solution are mixed in equal volumes; (iii) The suspension obtained after the reaction in step (ii) is centrifuged to separate the precipitate, which is then washed and spray-dried to obtain a powdery porous magnesium-containing tricalcium phosphate porous bone repair material.

2. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1, characterized in that: The molar ratio of calcium ions to magnesium ions in the first solution is 6-10.

3. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 2, characterized in that: The molar concentration of calcium ions in the first solution is 0.01-0.9 mol / L, and the molar concentration of magnesium ions is 0.001-0.15 mol / L.

4. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to any one of claims 1 to 3, characterized in that: After the first solution and the second solution are mixed, the molar ratio of calcium ions to phosphate ions is 1.1 to 1.

5.

5. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 4, characterized in that: The molar concentration of phosphate in the second solution is 0.008-0.8 mol / L.

6. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to any one of claims 1 to 3, characterized in that: The calcium salt is selected from a combination of one or more of anhydrous calcium chloride, calcium chloride dihydrate and calcium nitrate tetrahydrate, the magnesium salt is selected from magnesium chloride hexahydrate and / or magnesium nitrate hexahydrate, the phosphate is selected from a combination of one or more of disodium hydrogen phosphate, diammonium hydrogen phosphate and sodium hydrogen phosphate, and the alkali solution is ammonia water or sodium hydroxide.

7. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1, characterized in that: In step (i), the pH of the second solution is adjusted to 9.8-10.2 using aqueous ammonia.

8. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1, characterized in that: In step (ii), the first solution and the second solution are heated to 60-95° C. and then mixed.

9. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1 or 8, characterized in that: In step (ii), the stirring rate is 100-500 rpm.

10. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1, characterized in that: In step (iii), the washed precipitate is spray dried using a spray dryer, wherein the inlet air temperature of the spray dryer is 240-300°C, the outlet air temperature is 120-150°C, and the feed rate is 30-200 mL / min.

11. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1 or 10, characterized in that: In step (iii), the precipitate is added to water and centrifuged for multiple washings, the washed precipitate is added to water with a mass of 5 to 20 times, stirred evenly to form a slurry, and then spray dried.

12. The method for preparing the porous magnesium-containing tricalcium phosphate bone repair material according to claim 1, characterized in that: The preparation method is specifically implemented as follows: Dissolving a calcium salt and a magnesium salt in water to obtain a first solution, wherein the concentration of the calcium salt is 1-100 g / L, and the concentration of the magnesium salt is 0.4-40 g / L; Dissolving phosphate in water, and adjusting the pH to 9.8-10.2 with aqueous ammonia to obtain a second solution, wherein the concentration of phosphate is 1-100 g / L; The first solution and the second solution of equal volume are heated to 60-95°C and then mixed, and reacted under normal pressure with stirring, wherein the stirring rate is 100-500 rpm; The suspension after the reaction is centrifuged to obtain a precipitate, which is centrifugally washed with water for 4 to 8 times, and the washed precipitate is added to 5 to 20 times the mass of water, stirred evenly to form a slurry, and the slurry is processed into a micron-sized porous magnesium-containing tricalcium phosphate powder using a spray dryer to obtain the porous magnesium-containing tricalcium phosphate bone repair raw material, wherein the inlet temperature of the spray dryer is 240 to 300 ° C, the outlet temperature is 120 to 150 ° C, and the feed rate is 30 to 200 mL / min.

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