DEGRADABLE REGENERATIVE MEDICAL MATERIAL FOR PROMOTING TISSUE IN-SITU REGENERATION AND PREPARATION METHOD THEREFOR

Abstract

A degradable regenerative medical material for promoting tissue in-situ regeneration and a preparation method therefor. The degradable regenerative medicine material is formed by means of chemically bonding Si, P, O and metallic elements containing calcium, and is a regular three-dimensional net structure the material of which having a nano-scale mesoporous structure is framework, and pores and micron-scale macropores that communicate with the pores are uniformly distributed in the regular three-dimensional net structure. The preparation method for the degradable regenerative medical material comprises the steps of mixing a sol, foaming, curing and calcining. The degradable regenerative medicine material has a huge specific surface area, powerful biological activity and high biological safety, has the effect of promoting cell proliferation, may induce the rapid regeneration of its own damaged tissue cells, and achieve an in-situ tissue repair function.

Claims

1. A degradable regenerative medical material for promoting tissue in-situ regeneration, characterized in that, the degradable regenerative medical material is formed by means of chemically bonding Si, P, O and metallic elements containing calcium, and is a regular three-dimensional net structure, a material of which having a nano-scale mesoporous structure is framework, and pores and micron-scale macropores that communicate with the pores are uniformly distributed in the regular three-dimensional net structure.

2. The degradable regenerative medical material according to claim 1, characterized in that, in terms of mole portions, raw materials for preparing the degradable regenerative medical material include: 40-78 portions of silicate ester 1-17 portions of phosphate ester 110-200 portions of water 20-40 portions of soluble metal salt 0.01-5 portions of catalyst 1-5 portions of alcohol solvent 0.1-5 portions of thickener 1-5 portions of foam stabilizer 5-10 portions of foam fixative 1-10 portions of foaming agent.

3. The degradable regenerative medical material according to claim 2, characterized in that, the silicate ester is selected at least one from the group consisting of methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate, the phosphate ester is selected at least one from the group consisting of phosphate monoester, phosphodiester, phosphotriester, glycerophosphate and inositol hexaphosphate, the soluble metal salt is selected at least one from the group consisting of inorganic salts of calcium, strontium, cuprum and zincum and alkoxides.

4. The degradable regenerative medical material according to claim 2, characterized in that, the catalyst is an acid or a base; wherein the acid is an inorganic acid or an organic acid, the inorganic acid is nitric acid, hydrochloric acid or sulfuric acid, and the organic acid is selected at least one from the group consisting of acetic acid, oxalic acid, maleic acid and citric acid; the base is an inorganic base or an organic amine, wherein the inorganic base is selected at least one from the group consisting of sodium hydroxide, aqueous ammonia and sodium bicarbonate, and the organic amine is at least one of ethylenediamine and n-propylamine.

5. The degradable regenerative medical material according to claim 2, characterized in that, the alcohol solvent is at least one of methanol, ethanol, ethylene glycol, diethylene glycol and glycerol; the thickener is at least one of water-soluble polyvinyl alcohol, hydroxymethyl cellulose and polyethylene glycol 6000.

6. The degradable regenerative medical material according to claim 2, characterized in that, the foam stabilizer is at least one of a silicon-carbon type surfactant, sodium dodecyl sulfonate, polyoxyethylene fatty acid ether, glyceryl stearate, PEG-75 stearate, ceteth-20, ceteareth-6, ceteareth-25, PEG-100 stearate, cetearyl glucoside, and sodium C20-22 alcohol phosphate; the foam fixative is at least one of corn protein powder, whey protein powder, starch and methyl cellulose; the foaming agent is a physical foaming agent.

7. The degradable regenerative medical material according to claim 1, characterized in that, the mesopores have a pore size of 3-10 nm, and the micron-scale macropores have a pore size of 20-100 μm.

8. A method for preparing the degradable regenerative medical material for promoting tissue in-situ regeneration according to claim 2, characterized by comprising the steps of: mixing a sol: add catalyst to water and stir uniformly, then add silicate ester and phosphate ester for pre-hydrolysis reaction, hydrolyze until the mixture solution becomes transparent, then add soluble metal salt, and stir until completely dissolved to obtain a mixed sol; foaming and curing: disperse the thickener with alcohol solvent, and then add to the mixed sol, stir until completely swollen and dissolved, add foam stabilizer and foam fixative, stir uniformly, then age, then add foaming agent and stir uniformly to obtain a mixture material, and then heat the mixture material for foaming and curing, and then dry cured foam to obtain a foam body; calcining: calcine the foam body until completely removing organics to obtain the degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration.

9. The method for preparing the degradable regenerative medical material according to claim 8, characterized in that, in the step of foaming and curing, aging is room temperature aging, the aging refers to aging until a viscosity reaches 6000-20000 cp, and then cooling down to below 25° C.; a stirring speed is 120-300 r/min after adding the foaming agent; in the step of foaming and curing, the heating temperature for foaming and curing is 60-100° C., and the time is 0.5-1 h.

10. The method for preparing the degradable regenerative medical material according to claim 8, characterized in that, in the step of calcinating, calcinating temperature is 500-1000° C., and the time is 1-3 h.

11. The degradable regenerative medical material according to claim 5, characterized in that, the alcohol solvent is a mixture of at least one of methanol, ethanol, ethylene glycol and diethylene glycol with glycerol.

12. The degradable regenerative medical material according to claim 6, characterized in that, the foaming agent is one or more of pentane, hexane, heptane, petroleum ether, chlorofluoromethane, dichlorodiflulromethane, and dichlorotetrafluoroethane.

13. The degradable regenerative medical material according to claim 1, characterized in that, the specific surface area of the degradable regenerative medical material is 740-1500 m.sup.2/g.

14. The degradable regenerative medical material according to claim 1, characterized in that, as shown by molar contents of SiO.sub.2, P.sub.2O.sub.5 and metal oxide, in the degradable regenerative medical material, SiO.sub.2 content is 46.4-75.4%, P.sub.2O.sub.5 content is 3.4-9.4%, metal oxide content is 21.2-44.2%.

15. The method for preparing the degradable regenerative medical material according to claim 8, characterized in that, the silicate ester is selected at least one from the group consisting of methyl orthosilicate, ethyl orthosilicate, and propyl orthosilicate; the phosphate ester is selected at least one from the group consisting of phosphate monoester, phosphodiester, phosphotriester, glycerophosphate and inositol hexaphosphate; the soluble metal salt is selected at least one from the group consisting of inorganic salts of calcium, strontium, cuprum and zincum and alkoxides.

16. The method for preparing the degradable regenerative medical material according to claim 8, characterized in that, the catalyst is an acid or a base; wherein the acid is an inorganic acid or an organic acid, the inorganic acid is nitric acid, hydrochloric acid or sulfuric acid, and the organic acid is selected at least one from the group consisting of acetic acid, oxalic acid, maleic acid and citric acid; the base is an inorganic base or an organic amine, wherein the inorganic base is selected at least one from the group consisting of sodium hydroxide, aqueous ammonia and sodium bicarbonate, and the organic amine is at least one of ethylenediamine and n-propylamine.

17. The method for preparing the degradable regenerative medical material according to claim 8, characterized in that, the alcohol solvent is at least one of methanol, ethanol, ethylene glycol, diethylene glycol and glycerol; the thickener is at least one of water-soluble polyvinyl alcohol, hydroxymethyl cellulose and polyethylene glycol 6000.

18. The method for preparing the degradable regenerative medical material according to claim 8, characterized in that, the foam stabilizer is at least one of a silicon-carbon type surfactant, sodium dodecyl sulfonate, polyoxyethylene fatty acid ether, glyceryl stearate, PEG-75 stearate, ceteth-20, ceteareth-6, ceteareth-25, PEG-100 stearate, cetearyl glucoside, and sodium C20-22 alcohol phosphate; the foam fixative is at least one of corn protein powder, whey protein powder, starch and methyl cellulose; the foaming agent is a physical foaming agent.

19. The method for preparing the degradable regenerative medical material according to claim 17, characterized in that, the alcohol solvent is a mixture of at least one of methanol, ethanol, ethylene glycol and diethylene glycol with glycerol.

20. The method for preparing the degradable regenerative medical material according to claim 18, characterized in that, the foaming agent is one or more of pentane, hexane, heptane, petroleum ether, chlorofluoromethane, dichlorodiflulromethane, and dichlorotetrafluoroethane.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0052] FIG. 1 is a surface topography diagram of the sample of Example 2.

[0053] FIG. 2 is a comparison diagram of samples of Examples 1-4 before and after mineralization in the SBF simulated body fluid.

[0054] FIG. 3 is a morphology diagram of carbonated hydroxyapatite formed after the sample of Example 2 is mineralized.

[0055] FIG. 4 is an animal experimental model and process record diagram of sample efficacy verification in Example 2 of the present invention.

[0056] FIG. 5 is an analysis diagram of pathological slices of animal experiments of sample efficacy verification in Example 2 of the present invention.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0057] In order to make the contents of the present invention easier to be understood clearly, the present invention will be further described in detail below according to the specific embodiments of the present invention. The implementation process and beneficial effects of the present invention are illustrated in detail below according to specific examples, which aims to help readers better understand the essence and characteristics of the present invention, and is not intended to limit the scope of implementation of this case.

Example 1

[0058] A degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration, in terms of mole portions, raw materials include:

[0059] 78 portions of silicate ester

[0060] 7 portions of phosphate esters

[0061] 110 portions of deionized water

[0062] 22 portions of soluble metal salt

[0063] 0.2 portions of catalyst

[0064] 2 portions of alcohol solvent

[0065] 0.5 portions of thickener

[0066] 1 portion of foam stabilizer

[0067] 5 portions of foam fixative

[0068] 4 portions of foaming agent

[0069] A method for preparing the degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration in this example is as follows.

[0070] Firstly, prepare a mixed sol: add 110 portions of water to the reactor, add 0.2 portions of catalysts and stir uniformly, and then add 78 portions of silicate ester and 7 portions of phosphate ester for pre-hydrolysis reaction, hydrolyze until the mixture solution becomes transparent and clear, add 22 portions of soluble metal salt and stir until completely dissolved to obtain a mixed sol;

[0071] Then, disperse 0.5 portions of thickener with 2 portions of alcohol solvent and add it to the mixed sol, stir until it is completely swollen and dissolved, then add 1 portion of foam stabilizer and 5 portions of foam fixative, stir uniformly and then age at room temperature;

[0072] continue aging until the viscosity of the system reaches 10000 cp and then cool to below 25° C., then add 4 portions of foaming agent and stir uniformly with high speed, then pour the mixture material into a vessel with a volume five times larger than the volume of the mixture material, and place it in a oven of 70° C. to heat for foaming and curing for 0.5 h;

[0073] then, move the cured and molded foam body to an oven of 120° C. and continue to dry until the system moisture volatilizes to no more than 5%;

[0074] place the dried foam body in a muffle furnace and calcinate at 800° C. for 1 hour to completely remove organics, the resulting material is the final product.

[0075] The silicate ester is ethyl orthosilicate;

[0076] the phosphate ester is glycerophosphate;

[0077] the soluble metal salt is a mixture of calcium chloride, zinc lactate, and strontium chloride in a molar ratio of 100:5:2, strontium, zincum and other trace elements can promote wound repair and osteoblast proliferation, strontium, zincum and other trace elements are added to improve material performance;

[0078] the catalyst is hydrochloric acid with a mass fraction of 36%;

[0079] the alcohol solvent is a mixture of ethylene glycol and glycerin with a mass ratio of 1:1;

[0080] the compatibility of the materials in the system can be increased according to the difference in the structure of each (ethylene glycol and glycerin);

[0081] the thickener is water-soluble polyvinyl alcohol PVA1788;

[0082] the foam stabilizer is H-203 polysiloxane type surfactant (Zhongshan Dongjun Chemical);

[0083] the foam fixative is a mixture of corn protein powder and starch with a mass ratio of 1:1;

[0084] The foaming agent is a mixture of n-pentane and hexane with a mass ratio of 1:1.

[0085] The material synthesized in this example is a composite structure formed by chemical bonding of each element composed of Si, P, O, and metal elements. As shown by molar contents of SiO2, P2O5 and metal oxide, the material composition is 75.4% SiO2, 3.4% P205, 21.2% metal oxides of calcium, zincum, and strontium, respectively. The final material structure contains 3-20 nm of mesopores and 40-100 μmmicron-scale macropores.

Example 2

[0086] A degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration, in terms of mole portions, includes:

[0087] 60 portions of silicate ester

[0088] 15 portions of phosphate esters

[0089] 150 portions of deionized water

[0090] 30 portions of soluble metal salt

[0091] 0.4 portions of catalyst

[0092] 3.5 portions of alcohol solvent

[0093] 1.5 portions of thickener

[0094] 2 portions of foam stabilizer

[0095] 7.5 portions of foam fixative

[0096] 5 portions of foaming agent

[0097] A method for preparing the degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration in this example is as follows.

[0098] Firstly, prepare a mixed sol: add 150 portions of water to the reactor, add 0.4 portions of catalysts and stir uniformly, and then add 60 portions of silicate ester and 15 portions of phosphate ester for pre-hydrolysis reaction, hydrolyze until the mixture solution becomes transparent and clear, add 30 portions of soluble metal salt and stir until it is completely dissolved to obtain a mixed sol;

[0099] Then, disperse 1.5 portions of thickener with 3.5 portions of alcohol and add it to the mixed sol, stir until it is completely swollen and dissolved, then add 2 portions of foam stabilizer and 7.5 portions of foam fixative, stir uniformly and then age at room temperature;

[0100] continue aging until the viscosity of the system reaches 12000 cp and then cool to below 25° C., then add 5 portions of foaming agent and stir uniformly with high speed, then pour the mixture material into a vessel with a volume five times larger than the volume of the mixture material, and place it in an oven of 60° C. to heat for foaming and curing for 1 h;

[0101] then, move the cured and molded foam body to a oven of 120° C. and continue to dry until the system moisture volatilizes to no more than 5%;

[0102] place the dried foam body in a muffle furnace and calcinate at 700° C. for 1.5 hours to completely remove organics, the resulting material is the final product.

[0103] The silicate ester is ethyl orthosilicate;

[0104] the phosphate ester is glycerophosphate;

[0105] the soluble metal salt is a mixture of calcium acetate, zinc lactate, strontium nitrate in a molar ratio of 100:5:2,

[0106] the catalyst is nitric acid with a mass fraction of 50%;

[0107] the alcohol solvent is a mixture of ethylene glycol and glycerin with a mass ratio of 1:1;

[0108] the thickener is water-soluble polyvinyl alcohol PVA1788;

[0109] the foam stabilizer is a mixture of PEG-75 stearate and H-203 polysiloxane type surfactant with a mass ratio of 1:1;

[0110] the foam fixative is a mixture of whey protein powder and methyl cellulose with a mass ratio of 1:1;

[0111] The foaming agent is a mixture of n-pentane and hexane with a mass ratio of 1:1.

[0112] The material synthesized in this example is a composite structure formed by chemical bonding of each element composed of Si, P, O, and metal elements. As shown by molar contents of SiO.sub.2, P.sub.2O.sub.5 and metal oxide, the material composition is 61.5% SiO.sub.2, 7.7% P.sub.2O.sub.5, 30.8% metal oxides of calcium, zincum and strontium, respectively. The final material structure contains 3-7 nm of mesopores and 30-100 μm micron-scale macropores.

Example 3

[0113] A degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration, in terms of mole portions, includes:

[0114] 60 portions of silicate ester

[0115] 15 portions of phosphate esters

[0116] 150 portions of deionized water

[0117] 30 portions of soluble metal salt

[0118] 0.4 portions of catalyst

[0119] 5 portions of alcohol solvent

[0120] 2.5 portions of thickener

[0121] 3 portions of foam stabilizer

[0122] 10 portions of foam fixative

[0123] 6 portions of foaming agent

[0124] A method for preparing the degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration in this example is as follows.

[0125] Firstly, prepare a mixed sol: add 150 portions of water to the reactor, add 0.4 portions of catalysts and stir uniformly, and then add 60 portions of silicate ester and 15 portions of phosphate ester for pre-hydrolysis reaction, hydrolyze until the mixture solution becomes transparent and clear, add 30 portions of soluble metal salt and stir until it is completely dissolved to obtain a mixed sol;

[0126] Then, disperse 2.5 portions of thickener with 5 portions of alcohol and add it to the mixed sol, stir until it is completely swollen and dissolved, then add 3 portions of foam stabilizer and 10 portions of foam fixative, stir uniformly and then age at room temperature;

[0127] continue aging until the viscosity of the system reaches 14000 cp and then cool to below 25° C., then add 6 portions of foaming agent and stir uniformly with high speed, then pour the mixture material into a vessel with a volume five times larger than the volume of the mixture material, and place it in a oven of 70° C. to heat for foaming and curing for 45 min;

[0128] then, move the cured and molded foam body to a oven of 120° C. and continue to dry until the system moisture volatilizes to no more than 5%;

[0129] place the dried foam body in a muffle furnace and calcinate at 700° C. for 1.5 hours to completely remove organics, the resulting material is the final product.

[0130] The silicate ester is ethyl orthosilicate;

[0131] the phosphate ester is glycerophosphate;

[0132] the soluble metal salt is a mixture of calcium nitrate, zinc nitrate, and strontium acetate in a molar ratio of 100:5:2;

[0133] the catalyst is nitric acid with a mass fraction of 50%;

[0134] the alcohol solvent is a mixture of ethylene glycol and glycerin with a mass ratio of 1:1;

[0135] the thickener is water-soluble polyvinyl alcohol PVA1788;

[0136] the foam stabilizer is a mixture of PEG-75 stearate and H-203 polysiloxane type surfactant with a mass ratio of 1:1;

[0137] the foam fixative is a mixture of whey protein powder and starch with a mass ratio of 1:1;

[0138] The foaming agent is a mixture of n-pentane and hexane with a mass ratio of 1:1.

[0139] The material synthesized in this example is a composite structure formed by chemical bonding of each element composed of Si, P, O, and metal elements. As shown by molar contents of SiO2, P2O5 and metal oxide, the material composition is 61.5% SiO2, 7.7% P.sub.2O.sub.5, 30.8% metal oxides of calcium, zincum and strontium, respectively. The finanl material structure contains 3-7 nm of mesopores and 20-80 μm micron-scale macropores.

Example 4

[0140] A degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration, in terms of mole portions, includes:

[0141] 42 portions of silicate ester

[0142] 17 portions of phosphate esters

[0143] 200 portions of deionized water

[0144] 40 portions of soluble metal salt

[0145] 0.6 portions of catalyst

[0146] 5 portions of alcohol solvent

[0147] 2.5 portions of thickener

[0148] 3 portions of foam stabilizer

[0149] 10 portions of foam fixative

[0150] 6 portions of foaming agent

[0151] A method for preparing the degradable regenerative medical material with a three-dimensional network structure for promoting tissue in-situ regeneration in this example is as follows.

[0152] Firstly, prepare a mixed sol: add 200 portions of water to the reactor, add 0.6 portions of catalysts and stir uniformly, and then add 42 portions of silicate ester and 17 portions of phosphate ester for pre-hydrolysis reaction, and hydrolyze until the mixture solution becomes transparent and clear, add 40 portions of soluble metal salt and stir until it is completely dissolved to obtain a mixed sol;

[0153] Then, disperse 2.5 portions of thickener with 5 portions of alcohol and add it to the mixed sol, stir until completely swollen and dissolved, then add 3 portions of foam stabilizer and 10 portions of foam fixative, stir uniformly and then age at room temperature;

[0154] continue aging until the viscosity of the system reaches 10000 cp and then cool to below 25° C., then add 6 portions of foaming agent and stir uniformly with high speed, then pour the mixture material into a vessel with a volume five times larger than the volume of the mixture material, and place it in an oven of 65° C. to heat for foaming and curing for 45 minutes;

[0155] then, move the cured and molded foam body to a oven of 120° C. and continue to dry until the system moisture volatilizes to no more than 5%;

[0156] place the dried foam body in a muffle furnace and calcinate at 600° C. for 2 hours to completely remove organics, the resulting material is the final product.

[0157] The silicate ester is ethyl orthosilicate;

[0158] the phosphate ester is dimethyl phosphate;

[0159] the soluble metal salt is a mixture of calcium nitrate, zinc acetate, and strontium nitrate in a molar ratio of 100:5:1;

[0160] the catalyst is citric acid aqueous solution with a mass fraction of 50%;

[0161] the alcohol solvent is a mixture of ethylene glycol and glycerin with a mass ratio of 1:1;

[0162] the thickener is water-soluble polyvinyl alcohol PVA1788;

[0163] the foam stabilizer is a mixture of stearate triglyceride and sodium dodecyl sulfonate with a mass ratio of 1:1;

[0164] the foam fixative is a mixture of corn protein powder and starch with a mass ratio of 1:1;

[0165] The foaming agent is a mixture of n-pentane and hexane with a mass ratio of 1:1.

[0166] The material synthesized in this example is a composite structure formed by chemical bonding of each element composed of Si, P, O, and metal elements. As shown by molar contents of SiO.sub.2, P.sub.2O.sub.5 and metal oxide, the material composition is 46.4% SiO.sub.2, 9.4% P.sub.2O.sub.5, 44.2% metal oxides of calcium, zincum and strontium, respectively. The finnal material structure contains 3-7 nm of mesopores and 30-100 μm micron-scale macropores.

[0167] Performance Study:

[0168] The regenerative medical material test: in order to verify whether the present invention achieves the expected effect, the three-dimensional network structure, mesopores and macroporous structure, specific surface area, biological activity, degradation performance, etc. of the samples in each example of the present invention are tested and analyzed, details are as follows:

[0169] Test-Example 1 Test of the Three-Dimensional Network Structure of the Regenerative Medical Materials

[0170] The SEM test was performed on the samples obtained in Examples 1-4, and the results showed that the samples obtained in each of the Examples all formed a regular three-dimensional network structure forms with uniform pore size and pores that communicated with each other. Among them, the SEM test result of the sample obtained in Example 2 is shown in FIG. 1. As can be seen from FIG. 1, the sample obtained in Example 2 formed a regular three-dimensional network structure with uniform pore size and pores that communicated with each other.

[0171] Test-Example 2 Analysis of Mesoporous Structure and Porosity of the Regenerative Medical Materials

[0172] The gas adsorption method was used to test the samples obtained in each example. The test results of the gas adsorption method shows that while the material formed macropores, the material framework constructing macroporous has a mesoporous structure. The pore size of and porosity of mesopores of each example are as follows in Table 1.

TABLE-US-00001 TABLE 1 Test results of pore size and porosity of samples Test results Number of samples pore size porosity Example 1 3-20 nm  0.52 cc/g Example 2 3-7 nm 0.44 cc/g Example 3 3-7 nm 0.40 cc/g Example 4 3-7 nm 0.33 cc/g

[0173] Test-Example 3 Specific Surface Area Detection of the Regenerative Medical Materials

[0174] Specific surface areas of the samples obtained from Examples 1-4 were tested by nitrogen adsorption method and the results are shown in Table 2.

TABLE-US-00002 TABLE 2 Test results of specific surface areas of samples Number of samples Test result (m.sup.2/g) Example 1 1282 Example 2 932 Example 3 1104 Example 4 742

[0175] Test-Example 4 Tests of pH Value and the Stability of the Regenerative Medical materials:

[0176] Detection method: Scheme 1: take solid samples from Examples 1-4 and add water to prepare a mixture solution with mass fraction of 5%, soak the solid samples (standing) for 2 h, and then filter and measure the pH value of the filtrate, respectively;

[0177] Scheme 2, take three groups of solid samples and prepare the mixture solution according to the method in Scheme 1, soak for different times (1 d, 3 d, 7 d) and then filter, determine the pH value of the filtrate, respectively; Scheme 3: prepare a solution according to the method of Scheme 1, soak for 24 h, filter the solution, wash and dry the filter residue, and determine the pH value again according to the method of Scheme 1.

[0178] The Test results are shown in Table 3.

TABLE-US-00003 TABLE 3 Test results of pH values of samples obtained from Examples 1-4 pH value Number of Scheme 2 samples Scheme 1 1 d 3 d 7 d Scheme 3 Example 1 8.82 8.79 8.81 8.76 8.78 Example 2 8.20 8.23 8.19 8.14 8.16 Example 3 7.48 7.51 7.50 7.48 7.46 Example 4 9.32 9.26 9.33 9.24 9.24

[0179] As can be seen from the results in Table 3, the pH value of the regenerative medical material of the present invention can be adjusted according to demand. The pH value of the single sample is stable during the action process. After soaking, washing, the PH value of the material remains unchanged, indicating that the material has the ability to release ions continuously.

[0180] Test-Example 5 Biological Activity Test of the Regenerative Medical Materials

[0181] The in-vitro mineralization experiments were conducted according to YY/T 0964-2014 “Methods for Determining Deposited Hydroxyapatite” to verify the biological activity of the regenerative medical materials.

[0182] Specific implementation method: Take glass conical flask or polyethylene plastic flask as the reaction vessel. The materials were placed in the reaction vessel, and measure 200.0 mL of SBF simulated body fluid per 0.3 g powder. After mixing, place the vessel in a water bath shaker of 37° C., and oscillated the reaction vessel at an oscillation speed of 175 r/min to conduct mineralization experiment. After soaking the samples for a period of time (no more than 28 d), the soaked and mineralized samples were separated, washed with deionized water and acetone solution respectively, and dried at room temperature. The samples were tested by X-ray diffraction (XRD) and scanning electron microscopy.

[0183] In this experiment, the immersion mineralization time was 4 h, and the test results of the samples after mineralization were as follows: X-ray diffraction pattern was shown in FIG. 2 of the specification, in which obvious characteristic peaks of carbonated hydroxyapatite were formed. The results of scanning electron microscopy (SEM) were shown in FIG. 3. A three-dimensional network structure constructed by a large number of acicular and clustered carbonated hydroxyapatites was formed on the inner surface of the macropore of the material of Example 2. The rapid mineralization and formation of hydroxyapatite phase on the surface of the material indicate that the material has high biological activity and achieves the purpose of the invention.

[0184] Test-Example 6 Degradation Performance Test of the Regenerative Medical Material

[0185] According to GB/T 16886.14 “Biological Evaluation of Medical Devices: Part 14”, the degradation performance of the regenerative medical material was tested by the method of implant simulation solution test.

[0186] Specific Implementation Method:

[0187] TRIS buffer solution with pH of 7.4±0.1 was prepared by using tri (hydroxymethyl) aminomethane and hydrochloric acid solution (Preparation of TRIS buffer solution: put 800 ML deionized water in a 2000 ML beaker, and place the beaker on a magnetic stirrer to stir, then add 35 ML of 1 mol/L hydrochloric acid solution, and add tri (hydroxymethyl) aminomethane under the condition of stirring and adjust pH value to 7.25, finally, move the solution to a 1000 mL volumetric flask for constant volume to obtain a TRIS buffer solution); soak the material in it and oscillate for 120±1 h, and then take out the insoluble material for washing and drying, weigh and calculate the weight change before and after the test to obtain the degradation rate.

[0188] Test results are shown in Table 4.

TABLE-US-00004 TABLE 4 Degradation rate of the regenerative medical materials Number of samples Experiment time Degradation percentage (%) Example 1 120 h 19.7 Example 2 120 h 21.6 Example 3 120 h 25.2 Example 4 120 h 30.1

[0189] As can be seen from the results in Table 4, the higher the phosphorus content in the regenerative medical material, the faster the degradation rate of the material will be. When the composition is the same, the larger the specific surface area, the faster the degradation rate of the material will be.

[0190] Test-Example 7 Efficacy Verification of Regenerative Medical Materials in Animal Experiments

[0191] Experimental subjects: female Guizhou miniature pigs, age: 6-10 months, weight: 20-25 kg;

[0192] Experiment period: 7+21 days (7 days for animal adaptation period and 21 days for experiment period)

[0193] Experiment methods: three defects were made on the right side of the spine of the same Guizhou pig (defect size: 5*5 cm, skin removed, fat removed, to the muscle layer, 3-6 cm deep). After adding the repair materials, and each defect was treated with traditional package technology, covering the wound, regularly changing drugs, and replacing gauze.

[0194] Defect 1: the regenerative medical material described in Example 2 of the present invention was used (denoted as Group A).

[0195] Defect 2: 45 S5 biological activity glass was used as a control group (denoted as Group B).

[0196] Defect 3: no product was used as blank control group (denoted as Group C).

[0197] The experimental model and process are shown in FIG. 4 of the specification.

[0198] The pathological section analysis of the experimental results is shown in FIG. 5 of the specification.

[0199] Experiment results: According to the experimental repair process (as shown in FIG. 4), the healing rate of the experimental group using the regenerative medical material of the present application in the repair process of tissue defects was significantly higher than that of the control group and the blank control group; as can be seen from the experimental pathological section analysis (FIG. 5), the experimental group using the regenerative medical material of the present application realizes orderly tissues growth, promotes the growth of capillaries, and promotes the orderly proliferation of fibroblasts, collagen tissues, etc., wherein the new tissue structure was complete, accompanied by the formation of hair follicles.

[0200] It can be seen from the above test results that the regenerative medical material synthesized by the examples of the present invention uses a material with mesoporous structure as the framework to form porous materials with a homogenous pore size and pores that communicate with each other. It has a large specific surface area, high biological activity, controllable degradation rate, and can improve the healing rate in the process of tissue repair, promote the orderly growth of tissues, and achieve in-situ tissue regeneration. It is a new type of the regenerative medical material.

[0201] Finally, it should be noted that the above examples are only used to describe the technical solutions of the present invention and do not limit them. Although the present invention is described by reference to the above-mentioned examples, those skilled in the art should understand that it is still possible to modify the technical solution recorded in the above-mentioned examples or to replace equivalents of some or all of the technical features thereof. Such modifications or replacements do not detract the nature of the corresponding technical solutions from the scope of the technical solutions in all examples of the present invention.