Nanoscale calcium sodium phosphosilicate material composition and preparation method thereof

Abstract

The invention relates to the technical field of oral biomedical materials, and particularly discloses a nanoscale calcium sodium phosphosilicate material composition and a preparation method thereof. The nanoscale calcium sodium phosphosilicate material composition is prepared from bioactive glass, glass silica gel, calcium salt and phosphate, and the oxide composition of the bioactive glass is limited. The nano-scale sodium calcium phosphate silicate material composition has high biological activity and can fully play a mineralization role in a saliva environment, and hydroxyapatite newly formed in the mineralization process can fully fill defects and holes in the tooth surface, so that the microhardness of the tooth surface is effectively improved within a short time, and the tooth quality is improved. The repair of damaged teeth is effectively realized.

Description

Technical Field

[0001] This application relates to the technical field of oral biomedical materials, and more specifically, to a nano-calcium sodium phosphate silicate material composition and a preparation method thereof. Background Art

[0002] In oral clinical treatment, tooth defect restoration is an important treatment method to maintain the integrity of oral function. According to statistics from the World Health Organization, about 3.5 billion people worldwide are troubled by dental caries, and the tooth defect restoration rate in developed countries has exceeded 75%. As a direct restorative, traditional oral filling materials not only have to withstand the dynamic biting force of 200 - 500 N during chewing, but also need to be in long-term contact with the oral environment where the pH value fluctuates. With the improvement of patients' requirements for the aesthetic effect and service life of restorations, the existing material system gradually shows technical bottlenecks in terms of functional compounding.

[0003] Since the last century, the mainstream tooth restoration material system has undergone three generations of technological iterations: the first-generation silver amalgam has been strictly restricted in clinical applications by the EU RoHS directive due to mercury toxicity and color difference problems; the second-generation composite resin has achieved a breakthrough in aesthetics by compounding dimethacrylate matrix with inorganic fillers, but the poor dispersion effect of the fillers limits its flexural strength (typical products such as 3M Z350XT); although the third-generation glass ionomer cement has the property of fluoride ion release, its brittleness restricts its application in the posterior tooth area. To overcome the above problems, the industry usually adopts the following strategies: one is to improve the mechanical properties of the material by changing the chemical composition; the second is to introduce new processing technologies to improve the forming efficiency and accuracy; the third is to add specific functional additives to enhance the antibacterial and anti-inflammatory properties. However, in recent years, although new tooth restoration materials have been developed successively based on traditional products in various countries around the world, the comprehensive performance of the new materials is still unsatisfactory.

[0004] Regarding the above-related technologies, the inventor believes that the current commercially available tooth restoration materials have limited mineralization ability and cannot fully fill the defects and micropores on the tooth surface during tooth restoration, resulting in insufficient improvement of the microhardness of the tooth surface. Summary of the Invention

[0005] In the related technology, the commercially available tooth restoration materials cannot fully improve the microhardness of the tooth surface. To improve this defect, this application provides a nano-calcium sodium phosphate silicate material composition and a preparation method thereof.

[0006] In a first aspect, the present application provides a nano-calcium sodium phosphosilicate material composition, adopting the following technical solution: A nano-calcium sodium phosphosilicate material composition includes the following raw material components by weight percentage: bioactive glass 40-45%, calcium salt 0.8-1.2%, phosphate 0.05-0.10%, and the balance is made up to 100% by glass silica gel; the oxide composition of the bioactive glass includes silicon dioxide, phosphorus pentoxide, calcium oxide, sodium oxide, and magnesium oxide, and the percentage of magnesium oxide in the bioactive glass is 1.8-2.6 wt%; the glass silica gel includes the hydrolysis product of the bioactive glass.

[0007] By adopting the above technical solution, the present application formulates a nano-calcium sodium phosphosilicate material composition using bioactive glass, glass silica gel, calcium salt, and phosphate, and defines the oxide composition of the bioactive glass. When the nano-calcium sodium phosphosilicate material composition of the present application contacts saliva, the silanol groups on the surface of the glass silica gel can provide favorable nucleation sites for the formation of hydroxyapatite; the calcium salt and phosphate can make calcium ions and phosphate ions in a supersaturated state at the initial stage of the reaction; the bioactive glass can continuously release sodium ions, magnesium ions, calcium ions, and phosphate ions, among which calcium ions and phosphate ions can maintain the ion concentration required for the formation of hydroxyapatite, while sodium ions and magnesium ions can synergistically induce the deposition of hydroxyapatite. While releasing ions, the bioactive glass can also combine with hydrogen ions in saliva to increase the local pH near the teeth, and cooperate with the glass silica gel to provide nucleation sites for hydroxyapatite, which is beneficial to the continuous progress of the mineralization reaction. Under the synergistic effect of the above components, the nano-calcium sodium phosphosilicate material composition of the present application has high biological activity, can fully exert the mineralization effect in a saliva environment, and the newly formed hydroxyapatite during the mineralization process can fully fill the defects and holes on the tooth surface, thereby effectively improving the microhardness of the tooth surface in a short time, and effectively realizing the repair of damaged teeth.

[0008] Preferably, the oxide composition of the bioactive glass further includes strontium oxide.

[0009] By adopting the above technical solution, the present application defines that the oxide composition of the bioactive glass includes strontium oxide and introduces strontium ions. The electronic structure of strontium ions is very close to that of calcium ions, and can replace some calcium ions in the lattice during the preparation of bioactive glass, and improve the solubility of the crystallized phase, which can provide more nucleation sites for hydroxyapatite, thereby promoting the deposition of hydroxyapatite and helping to improve the microhardness of the tooth surface.

[0010] Preferably, the percentage of strontium oxide in the bioactive glass is 3.2-3.9 wt%.

[0011] By adopting the above technical solution, the present application optimizes the proportion of strontium oxide in the bioactive glass, improves the nucleation effect of hydroxyapatite, and helps to fully increase the microhardness of the tooth surface.

[0012] Preferably, the oxide composition of the bioactive glass further includes zinc oxide.

[0013] By adopting the above technical solution, the present application defines that the oxide composition of the bioactive glass includes zinc oxide. In addition to providing a certain antibacterial property, the zinc ions introduced by zinc oxide can also cooperate with sodium ions and magnesium ions to induce the deposition of hydroxyapatite, which helps to fully increase the microhardness of the tooth surface.

[0014] Preferably, the percentage of zinc oxide in the bioactive glass is 2.7 - 5.5 wt%.

[0015] By adopting the above technical solution, the present application optimizes the proportion of zinc oxide in the bioactive glass, enabling zinc oxide to fully exert its synergistic effect with sodium ions and magnesium ions, effectively promoting the deposition of hydroxyapatite, and helping to fully increase the microhardness of the tooth surface.

[0016] Preferably, the bioactive glass is prepared according to the following method: (1) Using tetraethyl orthosilicate as the silicon source and triethyl phosphate as the phosphorus source, dissolve the silicon source, phosphorus source, calcium nitrate, sodium nitrate, magnesium nitrate, strontium nitrate, and zinc nitrate into nitric acid solution, and stir and mix to obtain a sol. (2) Seal and let the sol stand still to obtain a wet gel, heat and age the wet gel, then dry it to obtain a dehydrated gel, calcine the dehydrated gel, and then naturally cool and grind and sieve it to obtain the bioactive glass.

[0017] By adopting the above technical solution, the present application optimizes the preparation method of the bioactive glass. The above method first mixes the raw materials and converts the mixture sol into a wet gel under the catalytic action of nitric acid. After the wet gel is heated and aged and dehydrated, the residue is the dehydrated gel. Thereafter, by calcining the dehydrated gel, sodium ions, magnesium ions, strontium ions, zinc ions and other ions enter the lattice composed of calcium phosphosilicate to replace calcium ions, and finally grind the calcined product to obtain the powdery bioactive glass.

[0018] Preferably, the calcination temperature is 580 - 610 °C.

[0019] By adopting the above technical solution, the present application optimizes the calcination temperature of the bioactive glass, which helps to fully remove the residual nitrate, organic matter and crystal water, can obtain a bioactive glass with higher purity, and helps to improve the deposition effect of hydroxyapatite.

[0020] Preferably, the glass silica gel further comprises a TEOS-modified gel, and the TEOS-modified gel is prepared according to the following method: (1) Soak the bioactive glass with hydrochloric acid, then wash and dry it to obtain a hydrolysis product; (2) Mix the hydrolysis product with tetraethyl orthosilicate and add it to a solvent to obtain an intermediate dispersion. Preheat the intermediate dispersion, then add hydrochloric acid under the heat preservation state, continue the heat preservation reaction and then cool naturally. Finally, filter and dry it to obtain the TEOS-modified gel; the solvent includes water and an alcohol solvent.

[0021] By adopting the above technical solution, on the basis of preparing the glass silica gel in this application, TEOS is used to further modify the hydrolysis product of the bioactive glass. The hydrolysis product of TEOS can undergo dehydration condensation with the silanol groups on the surface of the hydrolysis product of the bioactive glass, and introduce more silanol groups on the surface of the hydrolysis product of the bioactive glass, thereby increasing the nucleation sites of hydroxyapatite, helping to promote the deposition of hydroxyapatite, and improving the repair effect of hydroxyapatite on teeth.

[0022] Preferably, the alcohol solvent is selected from one of ethanol, isopropanol, and n-butanol.

[0023] By adopting the above technical solution, among the above three alcohol solvents, isopropanol and n-butanol can more effectively promote the hydrolysis of TEOS, can effectively reduce the particle size of the hydrolysis product, enable the hydrolysis product of TEOS to more fully combine with the hydrolysis product of the bioactive glass, increase the nucleation sites of hydroxyapatite, and improve the repair effect of hydroxyapatite on teeth.

[0024] In the second aspect, this application provides a preparation method of a nano calcium sodium phosphate silicate material composition, adopting the following technical solution.

[0025] A preparation method of a nano calcium sodium phosphate silicate material composition includes the following steps: (1) Mix the bioactive glass and the glass silica gel and then grind them to obtain a base material for standby; (2) Mix the base material with a calcium salt and a phosphate, and grind them again to obtain the nano calcium sodium phosphate silicate material composition.

[0026] By adopting the above technical solution, this application mixes components such as bioactive glass, glass silica gel, calcium salt, and phosphate, and makes each component uniformly dispersed through grinding, thereby obtaining the nano calcium sodium phosphate silicate material composition.

[0027] In summary, this application has the following beneficial effects: 1. The present application prepared a nano-calcium sodium phosphate silicate material composition using bioactive glass, glass silica gel, calcium salts, and phosphates, and defined the oxide composition of the bioactive glass. The nano-calcium sodium phosphate silicate material composition of the present application has high bioactivity and can fully exert its mineralization effect in a saliva environment. The newly formed hydroxyapatite during the mineralization process can fully fill the defects and pores on the tooth surface, thereby effectively improving the microhardness of the tooth surface in a short time and effectively achieving the repair of damaged teeth.

[0028] 2. Strontium ions were introduced into the bioactive glass in the present application. The electronic structure of strontium ions is very close to that of calcium ions. During the preparation of bioactive glass, part of the calcium ions in the lattice can be replaced, and the solubility of the crystallized phase is increased, which can provide more nucleation sites for hydroxyapatite, thereby promoting the deposition of hydroxyapatite and contributing to the improvement of the microhardness of the tooth surface.

[0029] 3. TEOS was used in the present application to further modify the hydrolysis product of bioactive glass, introducing more silanol groups on the surface of the hydrolysis product of bioactive glass, thereby increasing the nucleation sites of hydroxyapatite, contributing to the promotion of the deposition of hydroxyapatite, and improving the repair effect of hydroxyapatite on teeth. Detailed Embodiments

[0030] The present application will be further described in detail below with reference to examples, preparation examples, and comparative examples. All raw materials involved in the present application are commercially available.

[0031] Preparation Examples of Bioactive Glass and Glass Silica Gel Taking Preparation Example 1 as an example for illustration below.

[0032] Preparation Example 1 In this preparation example, the oxide composition of the bioactive glass includes phosphorus pentoxide (4 wt%), calcium oxide (23 wt%), sodium oxide (22 wt%), magnesium oxide (1.8 wt%), and silicon dioxide (made up to 100 wt%). When preparing, tetraethyl orthosilicate was used as the silicon source, triethyl phosphate was used as the phosphorus source, and the metal oxides corresponded to the corresponding metal nitrates.

[0033] In this preparation example, the bioactive glass was prepared according to the following method: (1) Weigh each raw material according to the oxide composition. Dissolve the silicon source, phosphorus source, calcium nitrate, sodium nitrate, magnesium nitrate, strontium nitrate, and zinc nitrate into a 0.2 mol / L nitric acid solution in sequence, keeping the addition interval between two raw materials at 45 minutes. Continuously stir during the addition process, and continue to stir for 1 hour after the addition is completed to obtain a sol; in this step, the total weight of the silicon source, phosphorus source, calcium nitrate, sodium nitrate, magnesium nitrate, strontium nitrate, and zinc nitrate and the weight of the nitric acid solution are in a ratio of 1:3; (2) Seal the sol at 37 °C and let it stand still for 3 days to obtain a wet gel. Heat-aging the wet gel at 70 °C for 3 days, then drying it at 120 °C for 2 days to obtain a dehydrated gel. Calcinate the dehydrated gel at 570 °C for 3 hours, then cool it naturally and grind and sieve it to obtain bioactive glass.

[0034] In this preparation example, the glass silica gel is a hydrolysis product of bioactive glass and is prepared according to the following method: Soak the bioactive glass in 2 mol / L hydrochloric acid for 5 hours for pickling, then wash and dry the bioactive glass after pickling to obtain the bioactive glass hydrolysis product.

[0035] Preparation Example 2 The difference between this preparation example and Preparation Example 1 is that in the oxide composition of the bioactive glass, the proportion of magnesium oxide is 2.2 wt%.

[0036] Preparation Example 3 The difference between this preparation example and Preparation Example 1 is that in the oxide composition of the bioactive glass, the proportion of magnesium oxide is 2.6 wt%.

[0037] Preparation Example 4 The difference between this preparation example and Preparation Example 3 is that the oxide composition of the bioactive glass further includes strontium oxide, and the proportion of strontium oxide is 2.8 wt%. The strontium source is added to the preparation system of the sol in the form of strontium nitrate.

[0038] Preparation Example 5 The difference between this preparation example and Preparation Example 4 is that in the oxide composition of the bioactive glass, the proportion of strontium oxide is 3.2 wt%.

[0039] Preparation Example 6 The difference between this preparation example and Preparation Example 4 is that in the oxide composition of the bioactive glass, the proportion of strontium oxide is 3.5 wt%.

[0040] Preparation Example 7 The difference between this preparation example and Preparation Example 4 is that in the oxide composition of the bioactive glass, the proportion of strontium oxide is 3.9 wt%.

[0041] Preparation Example 8 The difference between this preparation example and Preparation Example 7 is that the oxide composition of the bioactive glass further includes zinc oxide, and the proportion of zinc oxide is 2.4 wt%. The zinc source is added to the nitric acid solution in the form of zinc nitrate.

[0042] Preparation Example 9 The difference between this preparation example and Preparation Example 8 is that in the oxide composition of the bioactive glass, the proportion of zinc oxide is 2.7 wt%.

[0043] Preparation Example 10 The difference between this preparation example and Preparation Example 8 is that in the oxide composition of the bioactive glass, the proportion of zinc oxide is 4.1 wt%.

[0044] Preparation Example 11 The difference between this preparation example and Preparation Example 8 is that in the oxide composition of the bioactive glass, the proportion of zinc oxide is 5.5 wt%.

[0045] Preparation Example 12 The difference between this preparation example and Preparation Example 11 is that the calcination temperature of the dehydrated gel is 580 °C.

[0046] Preparation Example 13 The difference between this preparation example and Preparation Example 11 is that the calcination temperature of the dehydrated gel is 595 °C.

[0047] Preparation Example 14 The difference between this preparation example and Preparation Example 11 is that the calcination temperature of the dehydrated gel is 610 °C.

[0048] Preparation Example 15 The difference between this preparation example and Preparation Example 14 is that the glass silica gel is formed by mixing the hydrolysis product of the bioactive glass and the TEOS modified gel in a weight ratio of 1:1. The TEOS modified gel is prepared according to the following method: (1) Use 2 mol / L hydrochloric acid to pickle and soak the bioactive glass for 5 h, then wash and dry the pickled bioactive glass to obtain the bioactive glass hydrolysis product; (2) After mixing the hydrolysis product and tetraethyl orthosilicate in a weight ratio of 10:1, add the mixture to 1.5 times the weight of the solvent to obtain an intermediate dispersion. Preheat the intermediate dispersion at 60 °C for 30 min, then add 1 mol / L hydrochloric acid under the insulation state, continue the insulation reaction and then cool naturally. Finally, filter and dry to obtain the TEOS modified gel. In this step, the solvent is composed of water and an alcohol solvent in a weight ratio of 2:1, and the alcohol solvent is ethanol; the molar ratio between the silicon element in tetraethyl orthosilicate and the hydrogen chloride in hydrochloric acid is 1:50.

[0049] Preparation Example 16 The difference between this preparation example and Preparation Example 15 is that the alcohol solvent is isopropyl alcohol.

[0050] Preparation Example 17 The difference between this preparation example and Preparation Example 15 is that the alcohol solvent is n-butanol. Example

[0051] Examples 1 - 5 Taking Example 1 as an example, the description is as follows.

[0052] Example 1 In this example, calcium chloride is selected as the calcium salt, sodium phosphate is selected as the phosphate salt, and bioactive glass and glass silica gel are prepared according to the method of Preparation Example 1.

[0053] This example provides a nano-calcium sodium phosphate silicate material composition, which includes the following raw material components by weight percentage: 40% bioactive glass, 0.8% calcium salt, 0.05% phosphate salt, and the balance is made up to 100% by glass silica gel.

[0054] This example provides a preparation method of a nano-calcium sodium phosphate silicate material composition, which includes the following steps: (1) Mix bioactive glass and glass silica gel and then grind them to obtain a base material for standby; (2) Mix the base material with calcium salt and phosphate salt and grind them again to obtain a nano-calcium sodium phosphate silicate material composition.

[0055] As shown in Table 1, the main difference between Examples 1 - 3 lies in the different raw material ratios of the nano-calcium sodium phosphate silicate material composition.

[0056] Table 1 Raw material ratios As shown in Table 2, the difference between Examples 3 - 19 lies in the different preparation examples of bioactive glass and glass silica gel.

[0057] Table 2 Preparation examples of bioactive glass and glass silica gel Comparative example Comparative Example 1 The difference between this comparative example and Example 1 is that 45S5 bioactive glass is specifically selected as the bioactive glass, and the glass silica gel is prepared according to the following method: Use 2mol / L hydrochloric acid to pickle and soak 45S5 bioactive glass for 5 hours, then wash and dry the pickled bioactive glass to obtain a bioactive glass hydrolysis product.

[0058] Comparative Example 2 The difference between this comparative example and Example 1 is that the oxide composition of the bioactive glass does not include sodium oxide.

[0059] Comparative Example 3 The difference between this comparative example and Example 1 is that the oxide composition of the bioactive glass does not include magnesium oxide.

[0060] Performance Detection Test Method Test Materials: Take a batch of extracted bovine teeth and soak them in sodium azide disinfectant solution for 24 h. Cut the teeth along the cementoenamel junction with a cutting disc, and use the crown part as the specimen. Cut the crown longitudinally along the buccolingual direction to obtain buccolingual enamel slices. Place the enamel slices face down in a mold of 25 mm * 25 mm * 3 mm and embed them with self-curing resin. Place the embedded sample on an automatic grinding machine with the enamel surface facing the grinding disc. After grinding out the enamel surface, polish the enamel surface with alumina slurry with an average particle size of 0.3 μm. Store the treated enamel specimens in artificial saliva at 37 °C and pH 6.5.

[0061] Test Method: Take 1 g of the composition and put it into the enamel specimen. Grind it repeatedly with a soft-bristle toothbrush for ten minutes and then put it into artificial saliva to simulate brushing twice a day for adults in the morning and evening for 13 consecutive days. Measure the surface microhardness values of the enamel surface before and after treatment. When testing, rinse the surface of the enamel specimen with water and then dry it. Use a Vickers hardness tester to test the surface microhardness of the enamel surface. The indenter of the hardness tester applies a load of 0.49 N to the enamel surface and maintains it for 15 s. Each specimen is tested three times repeatedly and the average value is taken.

[0062] Calculate the change rate of the surface microhardness of the enamel specimen before and after surface treatment. The calculation method is: change rate of surface microhardness (%) = (average value of enamel hardness after treatment - average value of enamel hardness before treatment) / (average value of enamel hardness before treatment). The results are shown in Table 3.

[0063] Table 3 Change Rate of Surface Microhardness Combined with Examples 1-5 and Comparative Example 1 and Table 3, it can be seen that the change rates of the surface microhardness measured in Examples 1-5 are all higher than those in Comparative Example 1. This is because under the synergistic effect of each component, the nano-calcium sodium phosphosilicate material composition of the present application has high bioactivity and can fully exert its mineralization effect in the saliva environment. The newly formed hydroxyapatite during the mineralization process can fully fill the defects and pores on the tooth surface, so that the microhardness of the tooth surface can be effectively improved in a short time, effectively realizing the repair of damaged teeth.

[0064] Combined with Example 1 and Comparative Examples 2-3 and Table 3, it can be seen that when any one of sodium oxide and magnesium oxide is missing in the bioactive glass, due to the lack of corresponding synergistic effect, the deposition effect of hydroxyapatite is poor, so the enamel cannot be fully repaired and the microhardness of the tooth surface is not fully improved.

[0065] Combined with Example 5 and Examples 6 - 9 and with reference to Table 3, it can be seen that the microhardness measured in Examples 6 - 9 increased more. This is because the addition of strontium ions can provide more nucleation sites for hydroxyapatite, thus promoting the deposition of hydroxyapatite. When the percentage of strontium oxide in the bioactive glass is 3.2 - 3.9 wt%, the increase in microhardness is more obvious.

[0066] Combined with Example 9, Examples 10 - 13 and with reference to Table 3, it can be seen that the microhardness measured in Examples 10 - 13 increased more. This is because the zinc ions introduced by zinc oxide can synergistically induce the deposition of hydroxyapatite with sodium ions and magnesium ions. When the percentage of zinc oxide in the bioactive glass is 2.7 - 5.5 wt%, the increase in microhardness is more obvious.

[0067] Combined with Example 13, Examples 14 - 16 and with reference to Table 3, it can be seen that the bioactive glass prepared under the condition that the calcination temperature is 580 - 610 °C and the glass silica gel prepared using this bioactive glass are more helpful for improving the deposition effect of hydroxyapatite, resulting in a more obvious increase in microhardness.

[0068] Combined with Example 16, Examples 17 - 19 and with reference to Table 3, it can be seen that the growth rate of microhardness measured in Examples 17 - 19 is higher. This is because the hydrolysis products of TEOS can undergo dehydration condensation with the silanol groups on the surface of the hydrolysis products of the bioactive glass, and introduce more silanol groups on the surface of the hydrolysis products of the bioactive glass, thereby increasing the nucleation sites of hydroxyapatite, helping to promote the deposition of hydroxyapatite, and improving the repair effect of hydroxyapatite on teeth. When preparing the TEOS - modified gel, isopropanol and n - butanol can more effectively promote the hydrolysis of TEOS, can effectively reduce the particle size of the hydrolysis products, enable the hydrolysis products of TEOS to more fully combine with the hydrolysis products of the bioactive glass, increase the nucleation sites of hydroxyapatite, and improve the repair effect of hydroxyapatite on teeth.

[0069] The above - mentioned examples are only explanations of the present application, not limitations of the present application. Those skilled in the art can make modifications to the embodiments of the present application without creative contributions after reading this specification, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A nano-scale calcium sodium phosphosilicate material composition, characterized in that, It comprises the following raw material components by weight percentage: 40-45% of bioactive glass, 0.8-1.2% of calcium salt, 0.05-0.10% of phosphate, and the balance is made up to 100% by glass silica gel; the oxide composition of the bioactive glass includes silicon dioxide, phosphorus pentoxide, calcium oxide, sodium oxide and magnesium oxide, and the percentage of magnesium oxide in the bioactive glass is 1.8-2.6 wt%; the glass silica gel includes the hydrolysis product of bioactive glass.

2. The nano-calcium sodium phosphate silicate material composition according to claim 1, wherein The oxide composition of the bioactive glass further includes strontium oxide.

3. The nano-calcium sodium phosphate silicate material composition according to claim 2, wherein The percentage of strontium oxide in the bioactive glass is 3.2-3.9 wt%.

4. The calcium sodium phosphosilicate material composition according to claim 2, wherein The oxide composition of the bioactive glass further includes zinc oxide.

5. The nano-calcium sodium phosphosilicate material composition according to claim 4, characterized in that, The percentage of zinc oxide in the bioactive glass is 2.7-5.5 wt%.

6. The nano-calcium sodium phosphate silicate material composition according to claim 4, wherein The bioactive glass is prepared by the following method: (1) Using tetraethyl orthosilicate as the silicon source and triethyl phosphate as the phosphorus source, dissolve the silicon source, phosphorus source, calcium nitrate, sodium nitrate, magnesium nitrate, strontium nitrate, zinc nitrate into nitric acid solution, and obtain a sol after stirring and mixing. (2) Seal and stand the sol to obtain a wet gel, heat and age the wet gel, then dry it to obtain a dehydrated gel, calcine the dehydrated gel, then naturally cool and grind and screen it to obtain bioactive glass.

7. The nano calcium sodium phosphate silicate material composition according to claim 6, characterized in that The calcination temperature is 580-610 °C.

8. The nano calcium sodium phosphate silicate material composition according to claim 1, characterized in that, The glass silica gel further includes TEOS modified gel, and the TEOS modified gel is prepared by the following method: (1) Immerse the bioactive glass in hydrochloric acid, then wash and dry it to obtain a hydrolysis product. (2) Mix the hydrolysis product with tetraethyl orthosilicate and add it to a solvent to obtain an intermediate dispersion liquid, preheat the intermediate dispersion liquid, then add hydrochloric acid under the heat preservation state, continue to react under heat preservation and then naturally cool, and finally filter and dry it to obtain TEOS modified gel; the solvent includes water and alcohol solvents.

9. The nano calcium sodium phosphate silicate material composition according to claim 8, characterized in that, The alcohol solvent is selected from one of ethanol, isopropanol, and n-butanol.

10. The preparation method of the nano calcium sodium phosphate silicate material composition according to any one of claims 1-9, characterized in that, It includes the following steps: (1) Mix the bioactive glass and glass silica gel and grind them to obtain a base material for standby. (2) Mix the base material with calcium salt and phosphate, and grind them again to obtain a nano-scale calcium sodium phosphate silicate material composition.

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