Injectable fast-curing biological nanofiber root canal sealing material and preparation method thereof

Abstract

The invention relates to an injectable fast-curing biological nanofiber root canal sealing material and a preparation method thereof, and belongs to the technical field of root canal sealing materials. The composite material is prepared from the following raw materials in parts by weight: 20 to 30 parts of modified chitosan nanofiber, 35 to 45 parts of zinc oxide, 10 to 15 parts of aluminum silicate, 10 to 15 parts of hydrophosphate, 2 to 4 parts of alkaline silica sol, 1 to 3 parts of an antioxidant, 1 to 3 parts of a dispersing agent, 30 parts of capric triglyceride and 3 to 5 parts of a hydrophilic auxiliary agent, the root canal sealing material prepared by the invention has good flowability and injectability.

Description

Technical Field

[0001] The invention belongs to the technical field of root canal sealing materials, and relates to an injectable and fast-curing biological nanofiber root canal sealing material and a preparation method thereof. Background Art

[0002] Root canal treatment is an important treatment in dentistry, which aims to remove inflammation and necrotic tissue in the root canal and seal it with appropriate materials to prevent bacteria from invading and infecting again.

[0003] Bio-nanofibers have the advantages of small particle size, large specific surface area and high biocompatibility, which can fill the small gaps in the root canal and effectively prevent bacterial invasion and re-infection. At the same time, they can also promote the regeneration and repair of tissues around the root canal and reduce pain and discomfort during treatment.

[0004] Therefore, the injectability and rapid curing properties of bio-nanofiber root canal sealing materials can make the operation simple and quick, reduce the operation time and the patient's pain, and can quickly cure to form a stable sealing layer, effectively preventing bacterial invasion. Summary of the invention

[0005] The object of the present invention is to provide an injectable and fast-curing biological nanofiber root canal sealing material and a preparation method thereof. The prepared root canal sealing material has good fluidity and injectability.

[0006] The purpose of the present invention can be achieved through the following technical solutions: An injectable fast-curing biological nanofiber root canal sealing material comprises the following raw materials, measured by weight: 20-30 parts of modified chitosan nanofibers, 35-45 parts of zinc oxide, 10-15 parts of aluminum silicate, 10-15 parts of hydrogen phosphate, 2-4 parts of alkaline silica sol, 1-3 parts of antioxidant, 1-3 parts of dispersant, 30 parts of capric triglyceride and 3-5 parts of hydrophilic additive; Wherein, the preparation process of the modified chitosan nanofiber is as follows: S1.1, chitosan was mixed with an acetic acid solution having a concentration of 0.04 g / mL to obtain a solution A having a concentration of 0.05 g / mL, and then freeze-dried at -5°C to obtain a solid A; S1.2. Dissolve dopamine in Tris-HCl buffer solution with a molar concentration of 10 mM to prepare solution B with a mass concentration of 2 - 3 mg / L. Stir solid A and solution B at a speed of 400 r / min for 40 - 60 min, then add ammonia water with a mass fraction of 30% to adjust the pH of the mixture to 8.5, stir and react at room temperature with an open mouth for 24 h. Then place the obtained product in calcium chloride solution with a concentration of 0.02 g / mL, stir at 20 °C for 20 min, and after the stirring ends, conduct freeze-drying at -30 °C to obtain solid B, where the mass ratio of solid A to dopamine is 2.5:1, and the volume ratio of solution A to calcium chloride solution is 5:12; S1.3. Mix keratin, solid B, modified hydroxyapatite, and formic acid with a mass ratio of 1:(0.5 - 0.7):1:20 to obtain a spinning solution, and obtain modified chitosan nanofibers through electrospinning.

[0007] As a preferred technical solution of the present invention, the preparation process of the modified hydroxyapatite is as follows: S2.1. Mix nano-hydroxyapatite with deionized water, stir at a speed of 200 r / min for 35 min to obtain a dispersion with a mass fraction of 10 - 15%, and then mix the mussel protein acetic acid solution with a concentration of 0.5 - 1 mg / mL and the dispersion in a volume ratio of 1:1, and keep stirring for 1 h to obtain a mixed solution; S2.2. After filtering the mixed solution, conduct freeze-drying on the obtained product for 20 - 24 h to obtain modified nano-hydroxyapatite.

[0008] As a preferred technical solution of the present invention, the hydrogen phosphate is one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate.

[0009] As a preferred technical solution of the present invention, the antioxidant is one or more of butylated hydroxyanisole, dibutylhydroxytoluene, and tert-butylhydroquinone.

[0010] As a preferred technical solution of the present invention, the hydrophilic auxiliary agent is one of polyvinyl alcohol, polyacrylic acid, and polyamide.

[0011] As a preferred technical solution of the present invention, the dispersant is one of octadecyl phosphate, cetyl phosphate, tetradecyl phosphate, and dodecyl phosphate.

[0012] As a preferred technical solution of the present invention, the purity of the basic silica sol is 40%.

[0013] As a preferred technical solution of the present invention, in step S1.3, the conditions for electrospinning are that the spinning voltage is 30 - 40 kV and the spinning distance is 15 - 25 cm.

[0014] As a preferred technical solution of the present invention, in step S2.1, the acetic acid solution is an aqueous acetic acid solution with a mass fraction of 20%.

[0015] A preparation method of an injectable and rapidly curable bio - nanofiber root canal sealer, comprising the following steps: S1. According to parts by weight, mix modified chitosan nanofibers and zinc oxide, and ball - mill them at a speed of 300 r / min for 1 - 2 h to obtain mixture A; S2. Mix aluminosilicate, hydrogen phosphate, and alkaline silica sol uniformly to obtain mixture B; S3. Mix an antioxidant, a dispersant, tricaprylin, and a hydrophilic auxiliary agent, stir at a speed of 300 r / min for 1 - 2 h, then add mixture A, continue stirring while maintaining the speed for 1 - 2 h, then add mixture B, and ball - mill at a speed of 300 r / min for 1 - 2 h to obtain the injectable and rapidly curable bio - nanofiber root canal sealer.

[0016] In the present invention, chitosan bio - nanofibers are used as the matrix material of the root canal sealer. The main purpose of treating chitosan with acetic acid first is to improve its solubility. Dopamine self - polymerizes under alkaline conditions and is mixed with chitosan. Calcium chloride, as a cross - linker, can form ionic bonds or hydrogen bonds with the hydroxyl and amino groups in chitosan molecules, thereby increasing the cross - linking degree between chitosan molecular chains, helping to improve the mechanical strength and stability of the material, making the chitosan nanofibers have better durability and anti - aging properties. At the same time, the introduction of polydopamine can also interact with chitosan molecules, further enhancing the cross - linked structure of the material. And the functional groups in polydopamine molecules can interact with molecules in the organism, thereby enhancing the compatibility between the material and biological tissues.

[0017] Mussel protein has excellent biocompatibility and can be well integrated with human tissues. Mussel - protein - modified hydroxyapatite can closely adhere to the root canal wall, form an effective sealing layer, and prevent bacteria from invading and infecting again. At the same time, its good biocompatibility and bone - binding ability contribute to promoting the healing of the root canal and the regeneration of bone tissue.

[0018] When preparing chitosan nanofibers, modified hydroxyapatite is added. As an inorganic reinforcing phase, the modified hydroxyapatite can significantly improve the mechanical strength of chitosan nanofibers. The modified chitosan nanofibers prepared by mixing with keratin have a smaller diameter and a higher specific surface area, can closely adhere to the root canal wall, and form an effective sealing layer. This helps prevent bacteria from invading and infecting again, and improves the success rate of root canal treatment.

[0019] Moreover, as one of the main components of bones and teeth, the modified hydroxyapatite has good bone-bonding ability and biological activity. It can chemically bond with the bone tissue around the root canal wall, promoting the regeneration and repair of bone tissue. And through the synergistic effect among various components, it can inhibit the growth and reproduction of bacteria in the oral cavity, reducing the risk of infection.

[0020] The present invention uses alkaline silica sol with a purity of 40%. The alkalinity of the alkaline silica sol can improve the activity of the reaction system, help accelerate the curing of the material, and the alkaline silica sol has a small particle size and high transparency, which can maintain the gloss of the material. Mix the alkaline silica sol with aluminum silicate and hydrogen phosphate. In the root canal sealer, the hydrogen phosphate can form compounds such as calcium phosphate through chemical reactions with calcium ions or other metal ions in the root canal wall. This chemical reaction can generate stable inorganic salt compounds, thereby enhancing the curing effect of the material. The hydrogen phosphate has good solubility and dispersibility and can be evenly distributed in the root canal sealer. Aluminum silicate itself may have certain adhesiveness and fluidity, and can fill the micro-gaps on the root canal wall to form a tight sealing layer.

[0021] Advantages of the present invention: The present invention prepares a root canal sealer of bio-nanofibers. The modified chitosan nanofibers, zinc oxide, antioxidant, aluminum silicate, hydrogen phosphate, and alkaline silica sol are used as solid-phase components, and a dispersant, glyceryl tricaprylate, and a hydrophilic auxiliary agent are used as liquid-phase components, and they are mixed to obtain an injectable sealer. Detailed implementation manners

[0022] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following examples are used to describe in detail the specific implementation manners, structures, features, and their effects according to the present invention.

[0023] In the following examples and comparative examples: The acetic acid solution is an aqueous acetic acid solution with a mass fraction of 20%.

[0024] In the present invention, the alkaline silica sol with a purity of 40% was purchased from Jinan Feiyue Chemical Co., Ltd.; zinc oxide was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number: R049551; aluminum silicate was purchased from Tianjin Sino-US Biochemical Technology Co., Ltd., product number: A-0445618; potassium dihydrogen phosphate was purchased from Shanghai Kemi Chemical Technology Co., Ltd., product number: C066993; butylated hydroxyanisole was purchased from Shandong Yatu Biotechnology Co., Ltd.; octadecyl phosphate was purchased from Wuhan Jiyesheng Chemical Co., Ltd.; capric triglyceride was purchased from Wuhan Camike Technology Co., Ltd.; polyvinyl alcohol was purchased from Shanghai Macklin Biochemical Co., Ltd., product number: P909857; dopamine was purchased from Shanghai Macklin Biochemical Co., Ltd., product number: A902400; keratin was purchased from Shanghai Macklin Biochemical Co., Ltd., product number: 768435.

[0025] Example 1 The root canal sealer comprises the following raw materials in parts by weight: 20 parts of modified chitosan nanofibers, 35 parts of zinc oxide, 10 parts of aluminum silicate, 10 parts of potassium dihydrogen phosphate, 2 parts of alkaline silica sol, 1 part of butylated hydroxyanisole, 1 part of octadecyl phosphate, 30 parts of capric triglyceride, and 3 parts of polyvinyl alcohol; The preparation process of the modified chitosan nanofibers is as follows: S1.1. Mix chitosan with acetic acid solution with a concentration of 0.04 g / mL to obtain solution A with a concentration of 0.05 g / mL, and then freeze-dry at -5 °C to obtain solid A; S1.2. Dissolve dopamine in Tris-HCl buffer solution with a molar concentration of 10 mM to prepare solution B with a mass concentration of 2 mg / L. Stir solid A and solution B at a speed of 400 r / min for 40 min, then add ammonia water with a mass fraction of 30% to adjust the pH of the mixture to 8.5, stir and react at room temperature with an open mouth for 24 h, and then place the obtained product in calcium chloride solution with a concentration of 0.02 g / mL, stir at 20 °C for 20 min, and after stirring, perform freeze-drying at -30 °C to obtain solid B, wherein the mass ratio of solid A to dopamine is 2.5:1, and the volume ratio of solution A to calcium chloride solution is 5:12; S1.3. Mix keratin, solid B, modified hydroxyapatite, and formic acid with a mass ratio of 1:0.5:1:20 to obtain a spinning solution, and obtain modified chitosan nanofibers by electrospinning. The conditions of the electrospinning are: the spinning voltage is 30 kv, and the spinning distance is 15 cm.

[0026] The preparation process of the modified hydroxyapatite is as follows: S2.1. Mix nano-hydroxyapatite with deionized water, stir at a speed of 200 r / min for 35 min to obtain a dispersion with a mass fraction of 10%. Then mix the mussel protein acetic acid solution with a concentration of 0.5 mg / mL and the dispersion in a volume ratio of 1:1, and keep stirring at the same speed for 1 h to obtain a mixed solution; S2.2. After filtering the mixed solution, freeze-dry the obtained product for 20 h to obtain modified nano-hydroxyapatite.

[0027] Preparation of injectable and rapidly curable bio-nanofiber root canal sealer: S1. According to weight parts, mix modified chitosan nanofibers and zinc oxide, and ball-mill at a speed of 300 r / min for 1 h using a ball mill to obtain mixture A; S2. Mix aluminum silicate, hydrogen phosphate, and alkaline silica sol evenly to obtain mixture B; S3. Mix an antioxidant, a dispersant, glyceryl tricaprylate, and a hydrophilic auxiliary agent, stir at a speed of 300 r / min for 1 h, then add mixture A, keep stirring at the same speed for 1 h, then add mixture B, and ball-mill at a speed of 300 r / min for 1 h to obtain the injectable and rapidly curable bio-nanofiber root canal sealer.

[0028] Example 2 The root canal sealer comprises the following raw materials in weight parts: 25 parts of modified chitosan nanofibers, 40 parts of zinc oxide, 13 parts of aluminum silicate, 13 parts of potassium dihydrogen phosphate, 3 parts of alkaline silica sol, 2 parts of butylated hydroxyanisole, 2 parts of octadecyl phosphate, 30 parts of glyceryl tricaprylate, and 4 parts of polyvinyl alcohol; The preparation process of the modified chitosan nanofibers is as follows: S1.1. Mix chitosan with an acetic acid solution with a concentration of 0.04 g / mL to obtain solution A with a concentration of 0.05 g / mL, and then freeze-dry at -5°C to obtain solid A; S1.2. Dissolve dopamine in a Tris-HCl buffer solution with a molar concentration of 10 mM to prepare solution B with a mass concentration of 2.5 mg / L. Stir solid A and solution B at a speed of 400 r / min for 50 min, then add an ammonia water solution with a mass fraction of 30% to adjust the pH of the mixed solution to 8.5, stir and react at room temperature with the container open for 24 h, then place the obtained product in a calcium chloride solution with a concentration of 0.02 g / mL, stir at 20°C for 20 min, and after the stirring ends, perform freeze-drying at -30°C to obtain solid B, wherein the mass ratio of solid A to dopamine is 2.5:1, and the volume ratio of solution A to the calcium chloride solution is 5:12; S1.3. Mix keratin, solid B, modified hydroxyapatite, and formic acid with a mass ratio of 1:0.6:1:20 to obtain a spinning solution, and obtain modified chitosan nanofibers by electrospinning. The conditions for electrospinning are a spinning voltage of 35 kv and a spinning distance of 20 cm.

[0029] The preparation process of the modified hydroxyapatite is as follows: S2.1. Mix nano-hydroxyapatite with deionized water, stir at a speed of 200 r / min for 35 min to obtain a dispersion with a mass fraction of 13%, and then mix the mussel protein acetic acid solution with a concentration of 0.8 mg / mL and the dispersion in a volume ratio of 1:1, and keep stirring at the speed for 1 h to obtain a mixed solution; S2.2. After filtering the mixed solution, freeze-dry the obtained product for 22 h to obtain the modified nano-hydroxyapatite.

[0030] Preparation of an injectable and rapidly curable bio-nanofiber root canal sealer: S1. According to weight parts, mix modified chitosan nanofibers and zinc oxide, and ball-mill at a speed of 300 r / min for 1.5 h to obtain mixture A; S2. Mix aluminum silicate, hydrogen phosphate, and alkaline silica sol evenly to obtain mixture B; S3. Mix an antioxidant, a dispersant, glyceryl tricaprylate, and a hydrophilic auxiliary agent, stir at a speed of 300 r / min for 1.5 h, then add mixture A, keep stirring at the speed for 1.5 h, then add mixture B, and ball-mill at a speed of 300 r / min for 1.5 h to obtain the injectable and rapidly curable bio-nanofiber root canal sealer.

[0031] Example 3 The root canal sealer includes the following raw materials in weight parts: 30 parts of modified chitosan nanofibers, 45 parts of zinc oxide, 15 parts of aluminum silicate, 15 parts of potassium dihydrogen phosphate, 4 parts of alkaline silica sol, 3 parts of butylated hydroxyanisole, 3 parts of octadecyl phosphate, 30 parts of glyceryl tricaprylate, and 5 parts of polyvinyl alcohol; The preparation process of the modified chitosan nanofibers is as follows: S1.1. Mix chitosan with an acetic acid solution with a concentration of 0.04 g / mL to obtain solution A with a concentration of 0.05 g / mL, and then freeze-dry at -5 °C to obtain solid A; S1.2. Dissolve dopamine in Tris-HCl buffer with a molar concentration of 10 mM to prepare solution B with a mass concentration of 3 mg / L. Stir solid A and solution B at a speed of 400 r / min for 60 min, then add ammonia water with a mass fraction of 30% to adjust the pH of the mixture to 8.5. Stir and react the mixture open to the air at room temperature for 24 h, and then place the obtained product in calcium chloride solution with a concentration of 0.02 g / mL and stir at 20 °C for 20 min. After stirring, perform freeze-drying at -30 °C to obtain solid B, where the mass ratio of solid A to dopamine is 2.5:1, and the volume ratio of solution A to calcium chloride solution is 5:12; S1.3. Mix keratin, solid B, modified hydroxyapatite, and formic acid with a mass ratio of 1:0.7:1:20 to obtain a spinning solution, and obtain modified chitosan nanofibers by electrospinning. The conditions for electrospinning are a spinning voltage of 40 kv and a spinning distance of 25 cm.

[0032] The preparation process of modified hydroxyapatite is as follows: S2.1. Mix nano-hydroxyapatite with deionized water and stir at a speed of 200 r / min for 35 min to obtain a dispersion with a mass fraction of 15%. Then mix the mussel protein acetic acid solution with a concentration of 1 mg / mL and the dispersion in a volume ratio of 1:1, and keep stirring for 1 h to obtain a mixed solution; S2.2. After filtering the mixed solution, perform freeze-drying on the obtained product for 24 h to obtain modified nano-hydroxyapatite.

[0033] Preparation of injectable and rapidly curable bio-nanofiber root canal sealer: S1. According to weight parts, mix modified chitosan nanofibers and zinc oxide, and ball-mill them at a speed of 300 r / min for 2 h to obtain mixture A; S2. Mix aluminosilicate, hydrogen phosphate, and basic silica sol evenly to obtain mixture B; S3. Mix antioxidant, dispersant, tricaprylin, and hydrophilic auxiliary agent, stir at a speed of 300 r / min for 2 h, then add mixture A, keep stirring at the same speed for 2 h, and then add mixture B, and ball-mill at a speed of 300 r / min for 2 h to obtain the injectable and rapidly curable bio-nanofiber root canal sealer.

[0034] Comparative Example 1 The difference between the comparative example and Example 1 is that in Comparative Example 1, hydroxyapatite was not modified, and the rest of the operations were the same.

[0035] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 did not go through Step S1.2, and the rest of the operations were the same.

[0036] Comparative Example 3 The difference between Comparative Example 3 and Example 1 is that keratin was not added in Comparative Example 3, and the rest of the operations were the same.

[0037] Comparative Example 4 The difference between Comparative Example 4 and Example 1 is that in Step S2 of Comparative Example 4, alkaline silica sol was not added, and the rest of the operations were the same.

[0038] Performance Test: 1. Curing Time Test: According to the test method specified in the industry standard YY 0717-2009, the obturating materials prepared in Examples 1-3 and Comparative Examples 1-4 were filled into the hydrated gypsum mold, placed in a constant temperature and humidity chamber at a temperature of 37°C and a relative humidity of 95%, and the curing state was evaluated with a penetrometer, and the curing time was observed and recorded; 2. Injectability: 1 mL of the obturating materials of Examples 1-3 and Comparative Examples 1-4 was loaded into a plastic syringe container, a 21-gauge blunt needle was installed at the tip of the plastic syringe container, and using a small bench-top precision universal tester, the syringe was displaced to 10 mm at a crosshead speed of 20 mm / min, and it was observed whether the paste was easily discharged from the syringe container. A resistance value below 40 N was evaluated as qualified, and a resistance value exceeding 40 N was evaluated as unqualified. The test results are shown in Table 1 below: Table 1

[0039] The root canal obturating materials prepared in Examples 1 and 2 and Comparative Examples 1 and 4 were prepared. The fluidity test method referred to the international standard ISO 6876 / 2012. Two square glass slides (40×40×5 mm), each weighing about 20 g, were prepared. 0.05 mL of the prepared premixed root canal obturating material was extruded in the center of one glass slide through a syringe, and the other glass plate was placed on top of the dental root canal filling material, and then a 100-g weight was placed on top. After 10 min, the weight was removed, and the diameter of the flattened dental root canal filling material was measured. Each sample was measured 3 times, and the average value was taken as the fluidity of the dental root canal filling material. The results showed that the fluidity of all root canal obturating materials was higher than 17 mm, meeting the requirements of ISO 6876 / 2012. Therefore, the root canal obturating material prepared by the present invention has good fluidity and can ensure complete filling of the root canal. From the above data, it can be seen that the present invention has good injectability and curability.

[0040] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments by using the disclosed technical content within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. An injectable and rapidly curable bio-nanofiber root canal sealer, characterized in that, By weight parts, it includes the following raw materials: 20 - 30 parts of modified chitosan nanofibers, 35 - 45 parts of zinc oxide, 10 - 15 parts of aluminum silicate, 10 - 15 parts of hydrogen phosphate, 2 - 4 parts of basic silica sol, 1 - 3 parts of antioxidant, 1 - 3 parts of dispersant, 30 parts of glyceryl tricaprylate, and 3 - 5 parts of hydrophilic aid; Among them, the preparation process of the modified chitosan nanofibers is as follows: S1.

1. Mix chitosan with acetic acid solution with a concentration of 0.04 g / mL to obtain solution A with a concentration of 0.05 g / mL, and then freeze-dry at -5 °C to obtain solid A; S1.

2. Dissolve dopamine in Tris-HCl buffer solution with a molar concentration of 10 mM to prepare solution B with a mass concentration of 2 - 3 mg / L. Stir solid A and solution B at a speed of 400 r / min for 40 - 60 min, then add ammonia water with a mass fraction of 30% to adjust the pH of the mixed solution to 8.5, stir and react at room temperature with an open mouth for 24 h, and then place the obtained product in calcium chloride solution with a concentration of 0.02 g / mL, stir at 20 °C for 20 min, and after stirring, perform freeze-drying at -30 °C to obtain solid B. Among them, the mass ratio of solid A to dopamine is 2.5:1, and the volume ratio of solution A to calcium chloride solution is 5:12; S1.

3. Mix keratin, solid B, modified hydroxyapatite, and formic acid with a mass ratio of 1:(0.5 - 0.7):1:20 to obtain a spinning solution, and obtain modified chitosan nanofibers through electrospinning.

2. The injectable and rapidly curable bio-nanofiber root canal sealer according to claim 1, wherein The preparation process of the modified hydroxyapatite is as follows: S2.

1. Mix nano-hydroxyapatite with deionized water, stir at a speed of 200 r / min for 35 min to obtain a dispersion with a mass fraction of 10 - 15%, and then mix the mussel protein acetic acid solution with a concentration of 0.5 - 1 mg / mL and the dispersion in a volume ratio of 1:1, and keep stirring for 1 h to obtain a mixed solution; S2.

2. After filtering the mixed solution, freeze-dry the obtained product for 20 - 24 h to obtain modified nano-hydroxyapatite.

3. The injectable and rapidly curable bio-nanofiber root canal sealer material according to claim 1, wherein The hydrogen phosphate is one of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, and disodium hydrogen phosphate.

4. The injectable and rapidly curable bio-nanofiber root canal sealer according to claim 1, characterized in that, The antioxidant is one or more of butylated hydroxyanisole, dibutylhydroxytoluene, and tert-butylhydroquinone.

5. The injectable and rapidly curable bio-nanofiber root canal sealer according to claim 1, wherein The hydrophilic aid is one of polyvinyl alcohol, polyacrylic acid, and polyamide.

6. The injectable and rapidly curable bio-nanofiber root canal sealer according to claim 1, wherein The dispersant is one of octadecyl phosphate, cetyl phosphate, tetradecyl phosphate, and dodecyl phosphate.

7. The injectable and rapidly curable bio-nanofiber root canal sealer according to claim 1, wherein The purity of the basic silica sol is 40%.

8. The injectable and rapidly curable bio-nanofiber root canal sealer according to claim 1, wherein In step S1.3, the conditions of the electrospinning are that the spinning voltage is 30 - 40 kv and the spinning distance is 15 - 25 cm.

9. The injectable and rapidly curable bio-nanofiber root canal sealing material according to claim 2, wherein In step S2.1, the acetic acid solution is acetic acid aqueous solution with a mass fraction of 20%.

10. A preparation method of an injectable and rapidly curable bio-nanofiber root canal sealer as described in any one of claims 1-9, characterized in that, It includes the following steps: S1. According to weight parts, mix the modified chitosan nanofibers and zinc oxide, and ball-mill at a speed of 300 r / min for 1 - 2 h with a ball mill to obtain mixture A; S2. Mix aluminum silicate, hydrogen phosphate, and alkaline silica sol evenly to obtain mixture B; S3. Mix an antioxidant, a dispersant, tricaprylin, and a hydrophilic auxiliary agent, stir at a speed of 300 r / min for 1 - 2 h, then add mixture A, continue stirring while maintaining the speed for 1 - 2 h, then add mixture B, and ball mill at a speed of 300 r / min for 1 - 2 h to obtain the injectable and rapidly curable bio-nanofiber root canal sealer.

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