Biological ceramic gutta-percha point and preparation method thereof

By using the formulation of esterified chitosan-loaded nano zinc oxide and allylated gallic acid-modified ceramic powder in the teether tip, the problems of existing teether tips in terms of biocompatibility, antibacteriality and sealing are solved, and better therapeutic effects and contrast effects are achieved.

CN120037134AActive Publication Date: 2025-05-27SHANDONG ORODKA MEDICAL EQUIP CO LTD
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Patent Information

Application Number
CN202510190023.1
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-02-20
Publication Date
2025-05-27
Estimated Expiration
2045-02-20

AI Technical Summary

Technical Problem

The existing bioceramic tooth glue tips have problems with pigment irritating gums in improving biocompatibility and antibacteriality, and the sealing and therapeutic effects are not ideal.

Method used

The dispersion and biocompatibility of the teeth glue tip are improved by esterified chitosan-loaded nano zinc oxide and allylated gallic acid-modified ceramic powder.

Benefits of technology

It achieves good biocompatibility and antibacterial properties of the teether tip, appropriate bending strength, high sealing and comfort, significantly improving the therapeutic effect and contrast effect.

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Abstract

The invention relates to the technical field of gutta-percha tips, in particular to a biological ceramic gutta-percha tip and a preparation method thereof.The biological ceramic gutta-percha tip is prepared from, by weight, 10-20 parts of natural rubber, 30-40 parts of antibacterial agent, 8-12 parts of barium sulfate, 8-15 parts of modified ceramic powder and 2-3 parts of plasticizer. The gutta-percha tip manufactured by the method is good in biocompatibility, has good antibacterial property and proper bending property, and has a radiography effect.
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Description

Technical Field

[0001] The invention relates to the technical field of gutta-percha points, and in particular to a bioceramic gutta-percha point and a preparation method thereof. Background Art

[0002] With the improvement of economic level and living conditions, people's awareness of oral health care has also increased. Oral health not only determines our quality of life, but is also regarded as the first barrier to human health and an important guarantee for healthy life. Because of some bad habits, dental problems such as tooth damage, caries, periodontitis, etc. have received people's attention. In order to remove the infection inside the teeth and prevent the infection from spreading further, thereby protecting the structure of the teeth and avoiding tooth extraction, root canal treatment is one of the commonly used methods. Gutta-percha points are commonly used medical devices for root canal treatment. When filling the root canal, the gap between the gutta-percha point and the root canal wall is filled with paste to improve the sealing effect of the root canal. Therefore, the research and development of gutta-percha point materials has become a key research direction for people in this field.

[0003] Patent CN114099351A discloses a bioceramic gutta-percha tip, which includes components: natural rubber, zinc oxide, barium sulfate, zirconium oxide, silicon dioxide, antioxidant, bioactive material, and pigment. This bioceramic gutta-percha tip has good biocompatibility, solves the microgap and microleakage between the gutta-percha tip and the filling paste, improves the development effect, and increases the brightness by 20%. It has the function of inducing bone regeneration and has no toxic side effects, but the addition of pigment may irritate the gums and affect the treatment effect.

[0004] Patent CN118078641A discloses a hydrophilic root canal filling tip material and a preparation method thereof. The hydrophilic root canal filling tip material is made of thermoplastic polymer materials and a hydrophilic additive is introduced, so that the prepared hydrophilic root canal filling tip material has good swelling properties and biocompatibility, and can completely eliminate the microgaps and microleakage of traditional root canal materials. A modified antibacterial agent is added, and halloysite nanotubes are mixed with thymol, sodium alginate and trehalose respectively. The four can form a carrier system with a synergistic effect. The halloysite nanotubes can effectively load thymol as a carrier, and increase its stability and bioavailability through the synergistic effect of sodium alginate and trehalose, thereby improving the antibacterial and antioxidant properties of the prepared hydrophilic root canal filling tip material. However, the microleakage of the prepared material of the invention has not been studied, and microleakage is one of the important indicators for judging the performance of filling materials.

[0005] Therefore, there is an urgent need in the market for a bioceramic gutta-percha tip with good therapeutic effect and good sealing performance. Summary of the invention

[0006] In view of the problems existing in the prior art, the object of the present invention is to obtain a bioceramic gutta-percha tip with good biocompatibility and antibacterial properties, suitable bending strength, easy treatment and imaging effect.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0008] On the one hand, the present invention provides a bioceramic gutta-percha tip, which comprises the following raw materials, by weight: 10-20 parts of natural rubber, 30-40 parts of antibacterial agent, 8-12 parts of barium sulfate, 8-15 parts of modified ceramic powder, and 2-3 parts of plasticizer.

[0009] In some embodiments, the method for preparing the antibacterial agent comprises the following steps:

[0010] 1) adding glutathione and chitosan into DMSO, and then adding sulfuric acid solution, reacting at 70-80°C for 7-8h, filtering, washing and drying to obtain esterified chitosan;

[0011] 2) Stirring a 0.05-0.06 mol / L zinc acetate anhydrous ethanol solution at 40-50° C. for 50-70 min, then adding a 0.08-0.09 mol / L sodium hydroxide solution while stirring, and simultaneously adding the esterified chitosan obtained in step 1), stirring at 40-50° C. for 1-2 h, standing, filtering, washing, and drying to obtain an antibacterial agent.

[0012] The present invention firstly utilizes glutathione and chitosan to react to obtain esterified chitosan, and prepares nano zinc oxide by a hydrothermal synthesis method, and adds esterified chitosan in the preparation process, and loads chitosan on the nano zinc oxide to obtain an antibacterial agent with good antibacterial and sealing properties. The possible reason is that the hydroxyl groups on the surface of the nano zinc oxide loaded with chitosan are consumed, and the esterified chitosan with a certain steric hindrance effect is loaded at the same time, the surface energy is reduced, it is not easy to agglomerate itself, and it is easier to mix evenly with natural rubber. In addition, the esterified chitosan has certain softness and biocompatibility, which can avoid the problem of gaps caused by loose connection between the tooth glue tip and the paste. In addition, the amino group of the esterified chitosan can be combined with zinc oxide, and the two synergistically enhance the antibacterial effect.

[0013] In some embodiments, the mass ratio of glutathione to chitosan in step 1) is (0.2-0.5):1.

[0014] In some embodiments, the mass ratio of the anhydrous ethanol solution of zinc acetate to the esterified chitosan in step 2) is 1:(0.1-0.5).

[0015] The present invention limits the mass ratio of glutathione to chitosan so that glutathione is grafted on the surface of chitosan, which not only improves the dispersibility of the antibacterial agent but also avoids the problem of sensitive filling parts and reduced sealing due to excessive glutathione and excessive hardness of the gutta-percha tip. In addition, the mass ratio of the anhydrous ethanol solution of zinc acetate to the esterified chitosan is limited so that the antibacterial property is improved without affecting the mechanical properties of the gutta-percha tip.

[0016] In some embodiments, the method for preparing the modified ceramic powder comprises the following steps:

[0017] (1) Gallic acid and acrylic acid are added to dichloromethane, and then a phosphoric acid solution is added, and the mixture is stirred at 70-80° C. for 7-8 hours, extracted, concentrated, and dried to obtain allylated gallic acid;

[0018] (2) adding the ceramic powder and KH570 into ethanol, reacting at 70-80° C. for 5-6 h, then adding the allylated gallic acid and azobisisobutyronitrile obtained in step (1), and continuing the reaction for 1-2 h to obtain a modified ceramic powder.

[0019] Adding ceramic powder and zirconium oxide to the gutta-percha tip can improve the toughness of the gutta-percha tip, making it less likely to break during use, and better adapting to the shape of the tooth root canal, thereby achieving the effect of tightly filling the root canal, and at the same time improving the imaging effect of the gutta-percha tip. However, the dispersibility of the ceramic powder in the system is poor, and it may be mixed unevenly, affecting the toughness. The present invention improves the dispersibility and biocompatibility of the ceramic powder by modifying the ceramic powder with allylated gallic acid, and can reduce the microgap and microleakage between the gutta-percha tip and the filling paste, while improving the imaging effect, which may The reason is that the hydroxyl and ester groups on the surface of allylated gallic acid increase the interaction and biocompatibility with antibacterial agents. In addition, a π-π effect is produced between the benzene ring structure and the double bonds of natural rubber, which makes it easier to mix evenly and has a higher compatibility with the filling paste, which not only synergistically improves the filling properties, but also improves the imaging effect. During root canal treatment, doctors can adjust the filling strategy according to the position of the gutta-percha tip on the X-ray to reduce patient discomfort. In addition, the alkane chain segment increases the fluidity of the gutta-percha tip, making it easier to enter the root canal, further improving the filling effect.

[0020] In some embodiments, the mass ratio of gallic acid to acrylic acid in step (1) is 1:(0.5-0.9).

[0021] In some embodiments, the mass ratio of the ceramic powder to the allylated gallic acid is 1:(0.2-0.6).

[0022] In some embodiments, the ceramic powder is nano-scale zirconia ceramic powder with a particle size of 30-50 nm.

[0023] The present invention limits the double bonds of the grafted part of gallic acid by limiting the relationship between gallic acid and acrylic acid, and then limits the mass ratio of ceramic powder to allylated gallic acid, thereby enhancing the dispersibility of ceramic powder and the fluidity of the gutta-percha tip. In addition, the type and particle size of the ceramic powder are limited to make it easier to fill and have a good imaging effect.

[0024] In some embodiments, the plasticizer is one or more of rosin, beeswax or palm wax.

[0025] The second aspect of the present invention provides a method for preparing a bioceramic gutta-percha tip, comprising the following steps: refining natural rubber at 80-100°C for 1-2h, then adding an antibacterial agent, barium sulfate, modified ceramic powder and a plasticizer, heating to 100-110°C and stirring for 55-65min, then adding it to a mold, cooling it at room temperature, and obtaining a bioceramic gutta-percha tip.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The gutta-percha tip prepared by the present invention has good biocompatibility and antibacterial properties, suitable bending strength, high comfort and high sealing performance.

[0028] (2) The present invention first utilizes glutathione and chitosan to react to obtain esterified chitosan, and prepares nano zinc oxide by a hydrothermal synthesis method. In the preparation process, esterified chitosan is added to load chitosan on the nano zinc oxide. The hydroxyl groups on the surface of the nano zinc oxide loaded with chitosan are consumed, and at the same time, the esterified chitosan with a certain steric hindrance effect is loaded, so the surface energy is reduced, the nano zinc oxide is not easy to agglomerate, and the nano zinc oxide is easier to mix evenly with natural rubber. In addition, the esterified chitosan has certain softness and biocompatibility, which can avoid the problem of loose connection between the tip of the gutta-percha and the paste and the formation of gaps. In addition, the amino group of the esterified chitosan can combine with zinc oxide, and the two synergistically enhance the antibacterial effect.

[0029] (3) The present invention modifies the ceramic powder by using allylated gallic acid. The hydroxyl group and ester group on the surface of allylated gallic acid increase the interaction force and biocompatibility with the antibacterial agent. In addition, the benzene ring structure and the double bond of natural rubber produce a π-π effect, which makes it easier to mix evenly and has higher compatibility with the filling paste. It not only synergistically improves the filling property, but also enhances the imaging effect. During root canal treatment, the doctor can adjust the filling strategy according to the position of the gutta-percha tip on the X-ray film to reduce the patient's discomfort. In addition, the alkane chain segment increases the fluidity of the gutta-percha tip, making it easier to enter the root canal, further improving the filling effect. DETAILED DESCRIPTION

[0030] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0031] In the following embodiments and comparative examples, the compounds and related reagents used can be purchased from the market. Among them, the model of natural rubber is 3L rubber, purchased from Guangzhou Housheng New Materials Co., Ltd.; the ceramic powder is nano-grade zirconia ceramic powder with a particle size of 40 nm, purchased from Hangzhou Jikang New Materials Co., Ltd.; the beeswax is medicinal grade yellow beeswax purchased from Xi'an Jinxiang Pharmaceutical Excipients Co., Ltd., and ZOE paste is purchased from Shanghai Jinghua Chemical Plant.

[0032] Preparation Example 1

[0033] The preparation method of antibacterial agent-1 comprises the following steps:

[0034] 1) Add 4 g glutathione and 10 g chitosan to 100 ml DMSO, then add 85 wt % sulfuric acid solution, react at 75° C. for 7.5 h, filter, wash and dry to obtain esterified chitosan;

[0035] 2) 10 g of 0.05 mol / L zinc acetate in anhydrous ethanol solution was stirred at 45° C. for 60 min, and then 0.08 mol / L sodium hydroxide solution was added while stirring, and 3 g of the esterified chitosan obtained in step 1) was added at the same time, and the mixture was stirred at 45° C. for 1.5 h, allowed to stand, filtered, washed, and dried to obtain antibacterial agent-1.

[0036] Preparation Example 2

[0037] The preparation method of antibacterial agent-2 is the same as that of Preparation Example 1, except that the amount of glutathione added is 7 g.

[0038] Preparation Example 3

[0039] The preparation method of antibacterial agent-3 is the same as that of Preparation Example 1, except that the amount of esterified chitosan added is 7 g.

[0040] Preparation Example 4

[0041] The preparation method of antibacterial agent-4 comprises the following steps: stirring 10 g of 0.05 mol / L zinc acetate anhydrous ethanol solution at 45° C. for 60 min, then adding 0.08 mol / L sodium hydroxide solution while stirring, stirring at 45° C. for 1.5 h, standing, filtering, washing, and drying to obtain antibacterial agent-4.

[0042] Preparation Example 5

[0043] The preparation method of antibacterial agent-5 comprises the following steps: stirring 10 g of 0.05 mol / L zinc acetate anhydrous ethanol solution at 45° C. for 60 min, then adding 0.08 mol / L sodium hydroxide solution while stirring, and adding 3 g of chitosan at the same time, stirring at 45° C. for 1.5 h, standing, filtering, washing, and drying to obtain antibacterial agent-5.

[0044] Preparation Example 6

[0045] The preparation method of modified ceramic powder-1 comprises the following steps:

[0046] (1) 10 g of gallic acid and 7 g of acrylic acid were added to 100 ml of dichloromethane, and then a 75 wt % phosphoric acid solution was added, and the mixture was stirred at 75° C. for 7.5 h, extracted, concentrated, and dried to obtain allylated gallic acid;

[0047] (2) 10 g of zirconium oxide ceramic powder and 5 g of KH570 were added to 100 ml of anhydrous ethanol, and the mixture was reacted at 75° C. for 5.5 h. Then, 4 g of allylated gallic acid obtained in step (1) and 0.1 g of azobisisobutyronitrile were added, and the reaction was continued for 1.5 h to obtain modified ceramic powder-1.

[0048] Preparation Example 7

[0049] The preparation method of modified ceramic powder-2 is the same as that of Preparation Example 5, except that the amount of acrylic acid added is 11 g.

[0050] Preparation Example 8

[0051] The preparation method of modified ceramic powder-3 is the same as that of Preparation Example 5, except that the amount of allylated gallic acid added is 8 g.

[0052] Example 1

[0053] A bioceramic gutta-percha tip, comprising the following raw materials, measured by weight: 15 parts of natural rubber, 35 parts of antibacterial agent-1, 10 parts of barium sulfate, 112 parts of modified ceramic powder-1, and 2.5 parts of beeswax;

[0054] The preparation method of the bioceramic gutta-percha tip of the present embodiment comprises the following steps: refining natural rubber at 90° C. for 1.5 h, then adding antibacterial agent-1, barium sulfate, modified ceramic powder-1 and beeswax, heating to 105° C. and stirring for 60 min, then adding into a mold, cooling at room temperature, and obtaining a bioceramic gutta-percha tip.

[0055] Example 2

[0056] A bioceramic gutta-percha tip, comprising the following raw materials, measured by weight: 10 parts of natural rubber, 30 parts of antibacterial agent-1, 8 parts of barium sulfate, 8 parts of modified ceramic powder-1, and 2 parts of beeswax;

[0057] The preparation method of the bioceramic gutta-percha tip of the present embodiment comprises the following steps: refining natural rubber at 80°C for 2h, then adding antibacterial agent-1, barium sulfate, modified ceramic powder-1 and beeswax, heating to 100°C and stirring for 65min, then adding into a mold, cooling at room temperature, and obtaining a bioceramic gutta-percha tip.

[0058] Example 3

[0059] A bioceramic gutta-percha tip, comprising the following raw materials, measured by weight: 20 parts of natural rubber, 40 parts of antibacterial agent-1, 12 parts of barium sulfate, 15 parts of modified ceramic powder-1, and 3 parts of beeswax;

[0060] The preparation method of the bioceramic gutta-percha tip of this embodiment comprises the following steps: refining natural rubber at 100° C. for 1 hour, then adding antibacterial agent-1, barium sulfate, modified ceramic powder-1 and beeswax, heating to 110° C. and stirring for 55 minutes, then adding into a mold, cooling at room temperature, and obtaining a bioceramic gutta-percha tip.

[0061] Example 4

[0062] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of antibacterial agent-1 is replaced by antibacterial agent-2.

[0063] Example 5

[0064] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of antibacterial agent-1 is replaced by antibacterial agent-3.

[0065] Example 6

[0066] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of antibacterial agent-1 is replaced by antibacterial agent-4.

[0067] Example 7

[0068] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of antibacterial agent-1 is replaced by antibacterial agent-5.

[0069] Example 8

[0070] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of modified ceramic powder-1 is replaced by modified ceramic powder-2.

[0071] Example 9

[0072] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of modified ceramic powder-1 is replaced by modified ceramic powder-3.

[0073] Comparative Example 1

[0074] A bioceramic gutta-percha tip and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of modified ceramic powder-1 is replaced by ceramic powder.

[0075] Performance Testing

[0076] 1. Bending strength

[0077] The bioceramic gutta-percha tips prepared in the above embodiments and comparative examples were tested with reference to GB / T 9341-2021.

[0078] 2. Antibacterial

[0079] The bioceramic gutta-percha tips prepared in the above embodiments and comparative examples were subjected to antibacterial experiments with reference to GB / T 31402-2023.

[0080] 3. Cytotoxicity Assay

[0081] The gutta-percha tips obtained in the examples and comparative examples were tested with reference to GB / T 16886.5-2017 “Biological evaluation of medical devices - Part 5: In vitro cytotoxicity test” and showed no cytotoxicity.

[0082] 4. Microleakage test

[0083] 4.1 Sample collection and preparation

[0084] Single-rooted anterior teeth without caries were collected from patients with periodontal disease who were freshly extracted from the maxillofacial surgery clinic of a dental hospital. The teeth were placed in 5.25% sodium hypochlorite for 1 hour, and the calculus and periodontal membrane were scraped off. After cleaning, the teeth were soaked in normal saline for later use. The pulp was opened and the material in the root canal was removed. The apical foramen was opened with a No. 15 K file and the working length was determined. The root canal was prepared by the step-back method, and 3wt% H 2 O 2 Alternately rinse with saline, and finally rinse with 5.25wt% sodium hypochlorite. Dry the root canal with a paper tip, divide the prepared teeth into groups, 30 teeth in each group, and fill the root canal with ZOE paste and gutta-percha tip lateral pressure. When filling with paste, use a No. 35 root canal file to rotate the paste counterclockwise and evenly apply it to the inner wall of the root canal. Root filling requires no overfilling or underfilling. After root filling, the crown is padded with zinc phosphate cement and filled with amalgam.

[0085] 4.2 Experimental Procedure

[0086] All samples were placed in a sealed glass container with sterile cotton balls and placed in a 37°C thermostat for 7 days. After the root filling material solidified, it was taken out and blown dry. Two layers of nail polish were evenly applied on the root surface 2 mm above the apical foramen. After standing for 24 hours, the samples were immersed in a 2wt% methyl blue solution and placed in a 37°C thermostat for 7 days. The samples were taken out, rinsed with running water, dried, and the nail polish was scraped off.

[0087] The teeth were made into transparent specimens using Robertson's technique. After the dye was rinsed off, they were placed in 5wt% nitric acid (just enough to submerge the specimen) for 72 hours, and the nitric acid solution was changed every 24 hours. After being rinsed with running water, they were placed in 80wt% alcohol solution for 12 hours, 90%wt alcohol solution for 24 hours, and finally placed in anhydrous ethanol for 24 hours to dehydrate the specimens. Wintergreen oil was applied overnight to increase the transparency of the specimens. The specimens were observed under a root canal microscope at a magnification of 40 times, and the length of the dye penetrating into the root canal wall of each specimen was measured with a vernier caliper, and the average value of each group of specimens was recorded.

[0088] The test results are shown in Table 1:

[0089] Table 1

[0090] Group Bending strength(MPa) Antibacterial rate (%) Average value(mm) Example 1 53.6 99 0.36 Example 2 48.7 96 0.47 Example 3 50.3 98 0.41 Example 4 58.9 97 0.98 Example 5 41.2 99 0.90 Example 6 46.2 91 0.77 Example 7 48.4 97 0.59 Example 8 49.6 98 0.40 Example 9 55.9 98 0.52 Comparative Example 1 45.6 97 0.81

[0091] By comparing the experimental data of Examples 1-3 in Table 1, it can be seen that the gutta-percha tip prepared by the present invention has good tensile strength and antibacterial properties; by comparing Example 4 with Example 1, it can be seen that the change in the ratio of glutathione and chitosan may cause the bending strength of the gutta-percha tip to be too high and easy to leak; by comparing Example 5 with Example 1, it can be seen that the change in the ratio of anhydrous ethanol solution of zinc acetate and esterified chitosan leads to a decrease in the bending strength and inability to fit tightly in the root canal, resulting in leakage; by comparing Example 6 with Example 1, it can be seen that the use of an antibacterial agent that does not contain chitosan has poor dispersibility and all performances are reduced; by comparing Example 7 with Example 1, it can be seen that the use of an antibacterial agent with unesterified chitosan has a reduced sealing property; by comparing Examples 8 and 9 with Example 1, it can be seen that the change in the ratio of gallic acid to acrylic acid and ceramic powder to allylated gallic acid leads to a decrease in bending performance and causes leakage; by comparing Comparative Example 1 with Example 1, it can be seen that the bending performance and anti-leakage property of the gutta-percha tip are poor when ceramic powder is used directly.

[0092] The above implementation modes are only for illustrating the technical concept and features of the present invention, and their purpose is to enable people familiar with this technology to understand the content of the present invention and implement it, and they cannot be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the protection scope of the present invention.

Claims

1. A bioceramic gutta-percha tip, characterized in that: The invention comprises the following raw materials in parts by weight: 10-20 parts of natural rubber, 30-40 parts of antibacterial agent, 8-12 parts of barium sulfate, 8-15 parts of modified ceramic powder and 0.7-3 parts of plasticizer.

2. The bioceramic gutta-percha tip according to claim 1, characterized in that: The preparation method of the antibacterial agent comprises the following steps: 1) adding glutathione and chitosan into DMSO, and then adding sulfuric acid solution, reacting at 70-80°C for 7-8h, filtering, washing and drying to obtain esterified chitosan; 2) Stirring a 0.05-0.06 mol / L zinc acetate anhydrous ethanol solution at 40-50° C. for 50-70 min, then adding a 0.08-0.09 mol / L sodium hydroxide solution while stirring, and simultaneously adding the esterified chitosan obtained in step 1), stirring at 40-50° C. for 1-2 h, standing, filtering, washing, and drying to obtain an antibacterial agent.

3. The bioceramic gutta-percha tip according to claim 2, characterized in that: The mass ratio of glutathione to chitosan in step 1) is (0.2-0.5):

1.

4. The bioceramic gutta-percha tip according to claim 2, characterized in that: The mass ratio of the anhydrous ethanol solution of zinc acetate to the esterified chitosan in step 2) is 1:(0.1-0.5).

5. The bioceramic gutta-percha tip according to claim 1, characterized in that: The method for preparing the modified ceramic powder comprises the following steps: (1) Gallic acid and acrylic acid are added to dichloromethane, and then a phosphoric acid solution is added, and the mixture is stirred at 70-80° C. for 7-8 hours, extracted, concentrated, and dried to obtain allylated gallic acid; (2) adding the ceramic powder and KH570 into ethanol, reacting at 70-80° C. for 5-6 h, then adding the allylated gallic acid and azobisisobutyronitrile obtained in step (1), and continuing the reaction for 1-2 h to obtain a modified ceramic powder.

6. The bioceramic gutta-percha tip according to claim 5, characterized in that: The mass ratio of gallic acid to acrylic acid in step (1) is 1:(0.5-0.9).

7. The bioceramic gutta-percha tip according to claim 5, characterized in that: The mass ratio of the ceramic powder to the allyl gallic acid is 1:(0.2-0.6).

8. The bioceramic gutta-percha tip according to claim 5, characterized in that: The ceramic powder is nano-scale zirconium dioxide ceramic powder with a particle size of 30-50nm.

9. The bioceramic gutta-percha tip according to claim 1, characterized in that: The plasticizer is one or more of rosin, beeswax or palm wax.

10. A method for preparing the bioceramic gutta-percha tip according to any one of claims 1 to 9, characterized in that: The method comprises the following steps: refining natural rubber at 80-100°C for 1-2h, then adding antibacterial agent, barium sulfate, modified ceramic powder and plasticizer, heating to 100-110°C and stirring for 55-65min, then adding into a mold, cooling at room temperature, and obtaining a bioceramic gutta-percha tip.

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