Oral antibacterial composite high polymer material and preparation method thereof

Abstract

The invention belongs to the technical field of antibacterial materials, and particularly relates to an oral antibacterial composite high polymer material and a preparation method thereof.The oral antibacterial composite high polymer material is prepared from, by weight, 5.5-7.5 parts of lignin, 10 parts of hydrogel modifier, 3-5 parts of polyimide modifier, 1 part of glutathione, 0.1 part of PAA, 0.2 part of glycerin, 0.03-0.05 part of menthol and 0.01 part of potassium sorbate; the hydrophilicity is improved and Fe < 3 + > is complexed through polysaccharide sulfate modified polyimide, an S-H / S-S dynamic oxidation-reduction system is constructed to realize Fe < 3 + > / Fe < 2 + > self-circulation and mechanical property enhancement, glutathione is introduced to chelate Fe < 3 + > through a thiophosphonate intermediate to generate active oxygen, a synergistic mechanism of bacterial adsorption, continuous killing and material durability is formed, and the antibacterial property of the material is improved. The limitation of the traditional Fenton reaction is broken through, and an efficient and self-adaptive integrated solution is provided for the oral antibacterial material.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial materials, and specifically refers to an oral antibacterial composite polymer material and a preparation method thereof. Background Art

[0002] The oral cavity has a complex environment where microorganisms are prone to grow, and traditional antibacterial materials have defects such as drug resistance, poor biocompatibility, and short action time. There is an urgent need for new and efficient antibacterial strategies. Although the Fenton reaction can efficiently kill bacteria by generating reactive oxygen species (ROS), its strong acid dependence, the problem of continuous supply of Fe 2+ and the risk of metal ion leakage limit its application in the neutral oral environment; as a potential carrier, hydrogels are difficult to meet the requirements due to problems such as insufficient mechanical strength and lack of dynamic antibacterial ability. Summary of the Invention

[0003] Aiming at the defects of the existing technology, the present invention discloses an oral antibacterial composite polymer material. By modifying polyimide with sodium alginate bisulfate to improve hydrophilicity and complex Fe 3+ , grafting S-H groups on the hydrogel, and introducing glutathione to construct an S-H / S-S dynamic redox system to achieve the self-circulation of Fe 3+ / Fe 2+ to generate reactive oxygen species, forming a "bacteria adsorption - continuous killing - material durability" synergistic mechanism, breaking through the limitations of the traditional Fenton reaction, and providing an efficient and adaptive integrated solution for oral antibacterial materials.

[0004] To achieve the above object, the technical solution adopted by the present invention is an oral antibacterial composite polymer material, which includes the following raw materials in parts by mass: 5.5 - 7.5 parts of lignin, 10 parts of hydrogel modifier, 3 - 5 parts of polyimide modifier, 1 part of glutathione, 0.1 part of PAA, 0.2 part of glycerol, 0.03 - 0.05 part of menthol, and 0.01 part of potassium sorbate.

[0005] Further, the preparation method of the hydrogel modifier includes the following steps: A. Weigh 15 - 25 parts of hydrogel, 0.2 part of dimethylaminoethyl methacrylate, and 0.1 part of camphorquinone, add them to 30 parts of deionized water, stir for 30 min under the condition of a rotation speed of 500 r / min to obtain a mixture, inject the mixture into a crosslinking mold, and irradiate it for 5 min under the condition of a light wave wavelength of 470 nm, where the light intensity is 30 mW / cm 2 , and the distance between the light source and the material in the crosslinking mold is 10 cm to obtain a crosslinked hydrogel; B. Weigh 0.5 parts of PBS (polybutylene succinate) and add it to 30 parts of deionized water. Adjust the pH to 7.4, then continue to add 0.1 part of EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride). Stir for 30 min under the condition of a rotation speed of 500 r / min to obtain a reaction solution. Weigh 8 - 12 parts of vinyl mercaptoacetate, 0.7 part of ammonium persulfate, 5 - 8 parts of N-hydroxysuccinimide, and 0.05 part of dodecyl mercaptan and add them to the reaction solution. Stir for 30 min under the condition of a rotation speed of 500 r / min to obtain a mixed grafting solution; C. Immerse the crosslinked hydrogel obtained in step A into the mixed grafting solution obtained in step B. Add 0.1 part of an initiator to it, heat at a temperature of 50 - 70 °C for 4 h, and stir for 30 min under the condition of a rotation speed of 500 r / min. Carry out a visible light irradiation reaction for 10 min with a light wave wavelength of 360 nm, where the distance between the light source and the solution is 15 cm. Then wash it 5 times with a washing solution of ascorbic acid - sodium dihydrogen phosphate to obtain a modified hydrogel.

[0006] Further, the hydrogel in step A is polyethylene glycol diacrylate, and the ascorbic acid - sodium dihydrogen phosphate mixed solution in step C is a solution obtained by adding 0.5 part of ascorbic acid and 1 part of sodium dihydrogen phosphate to 100 parts of deionized water.

[0007] Further, the preparation method of the polyimide modifier includes the following steps: I. Weigh 10 - 15 parts of polyimide and add it to 50 parts of deionized water. Stir for 30 min under the condition of a rotation speed of 500 r / min. Add 0.5 part of sodium hydroxide alkali solution with a concentration of 1 mol / L to it. Heat at a temperature of 65 - 85 °C for 2 h and stir under the condition of a rotation speed of 500 r / min to obtain an oxidized polyimide product; II. Weigh 2.5 - 4.5 parts of polysaccharide sulfate and add it to the oxidized polyimide product obtained in step I. Add hydrochloric acid to adjust the pH to 4 - 5 with a hydrochloric acid concentration of 1.5 mol / L. Then add 0.1 part of EDC. Heat at a temperature of 55 - 65 °C for 2 h and stir under the condition of a rotation speed of 500 r / min. Naturally cool to room temperature to obtain an activated polyimide; III. Weigh 0.5 - 1.5 parts of iron nitrate and add it to 50 parts of deionized water. Add hydrochloric acid solution to adjust the pH to 2 - 3, with the hydrochloric acid concentration being 2 mol / L. Stir for 30 min under the condition of a rotation speed of 500 r / min. Weigh 0.5 part of citric acid and add it thereto to obtain solution A. Add the activated polyimide obtained in step II into solution A, stir at 500 r / min at room temperature for 1 h, centrifuge for 10 min under the condition of a rotation speed of 8000 r / min, and place the centrifuged product in an oven at 55 °C to dry for 24 h to obtain the polyimide modified product.

[0008] The following is the specific reaction process of the polyimide modified product: PI-(C=O) 2 N+H 2 O PI-(COOH)-NH-(COOH) (Reaction process 1) ; Fe 3+ +3(-SO 3 - / COO - ) Fe(-SO 3 - / COO - ) 3 (Reaction process 3) The present invention also provides a preparation method of an oral antibacterial composite polymer material, including the following steps: Step 1. Weigh 5.5 - 7.5 parts of lignin and add it to 25 parts of an alcohol solution, where the alcohol solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 7:3. Add 0.5 part of sodium hydroxide alkali solution with a concentration of 1.5 mol / L, heat at 70 °C for 5 h, and stir under the condition of a rotation speed of 500 r / min. Then add 1.5 parts of epichlorohydrin and 0.1 part of tetrabutylammonium bromide, continue to heat at 65 °C for 4 h, and stir under the condition of a rotation speed of 500 r / min. Ultrasonic for 15 min under the condition of an ultrasonic power of 80 kHz to obtain activated lignin; Step 2. Weigh 10 parts of the hydrogel modified product and 3 - 5 parts of the polyimide modified product and add them to 30 parts of deionized water. Add 0.5 part of polyethylene glycol, stir under the condition of a rotation speed of 500 r / min, and then continue to add 1 part of glutathione, and heat-treat at 45 °C for 60 min to obtain a homogeneous solution; Step 3. Add the activated lignin obtained in Step 1 to the homogenate obtained in Step 2. Add 0.1 part of glutaraldehyde and 0.05 part of sodium cyanoborohydride thereto. Add a citric acid solution to adjust the pH to 6.5. The concentration of the citric acid solution is 3 mol / L. Pass argon with a flow rate of 500 mL / min and stir and react for 1.5 h under the condition of a rotation speed of 500 r / min to obtain a precursor of the oral antibacterial composite polymer material; Step 4. Weigh 0.1 part of PAA (polyacrylic acid), 0.2 part of glycerol, 0.03 - 0.05 part of menthol and 0.01 part of potassium sorbate and add them to 30 parts of deionized water. Stir for 1.5 h under the condition of a rotation speed of 500 r / min to obtain an improving solution. Slowly add the obtained improving solution to the precursor of the oral antibacterial composite polymer material. The ultrasonic time is 30 min under the condition of an ultrasonic power of 20 kHz, and stir for 30 min under the condition of a rotation speed of 500 r / min. Filter with a 0.22 - μm filter membrane, and seal the liquid in a can to obtain the oral antibacterial composite polymer material.

[0009] The beneficial effects obtained by the present invention are as follows: For the oral antibacterial composite polymer material prepared by the present invention, sodium alginate is used to modify polyimide. On the one hand, the hydrophilicity of the material is effectively improved, which helps the material to better interact with the tissues and liquids in the oral cavity; on the other hand, the introduction of sulfonic acid groups creates abundant active sites for the complexation of ferric ions. Using ferric nitrate as the metal ion source for the Fenton reaction, it is grafted onto polyimide through complexation to construct the basis of an efficient Fenton reaction system.

[0010] For the oral antibacterial composite polymer material prepared by the present invention, S - H bonds are introduced into the hydrogel structure to reduce the ferric ions generated during the Fenton reaction, so that the Fenton reaction can proceed continuously in a cycle; at the same time, as a metal cation, ferric ions utilize their adsorption characteristics with anions on the bacterial surface to promote the efficient adsorption of bacteria on the surface of the antibacterial material, greatly enhancing the pertinence and effectiveness of the antibacterial process, and realizing the synergistic effect of the capture and continuous killing of bacteria by the material.

[0011] 2R - SH + 2Fe 3+ →R - S - S - R + 2Fe 2+ + 2H + ; The oral antibacterial composite polymer material prepared by the present invention has S-H bonds converted into S-S bonds after reducing ferric ions, providing additional cross-linking points for the hydrogel, significantly enhancing the mechanical strength and durability of the hydrogel material, and improving the service life of the material in the complex oral environment. By introducing glutathione as a reducing agent for S-S bonds, the antibacterial mechanism of the material is further improved. The thiophosphonate intermediate generated during the process of glutathione reducing some S-S bonds contains phosphoryl groups that can chelate with some free ferric ions, thereby generating reactive oxygen species (ROS), achieving another efficient way to kill bacteria, and maintaining the concentration of ferric ions in the system to ensure the efficient and continuous progress of the Fenton reaction.

[0012] R-S-S-R + 2GSH → 2R-SH + GSSG ; The oral antibacterial composite polymer material prepared by the present invention modifies the traditional Fenton reaction conditions by introducing specific functional groups, enabling the Fenton reaction to occur more conveniently in the oral environment, significantly improving the antibacterial efficiency, and providing a new and efficient antibacterial strategy for the field of oral antibacterial materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 is a diagram of the preparation method of the oral antibacterial composite polymer material proposed by the present invention; Figure 2 is an antibacterial effect diagram of the oral antibacterial composite polymer materials prepared in the examples and comparative examples of the present invention.

[0014] The drawings are used to provide a further understanding of the present invention, and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention, and do not constitute a limitation to the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0015] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0016] Unless otherwise defined, all professional and scientific terms used herein have the same meaning as those familiar to those skilled in the art. In addition, any methods and materials similar or equivalent to the described content can be applied to the present invention. The preferred methods and materials described herein are only for illustrative purposes and do not limit the content of this application.

[0017] The preparation methods in the following embodiments refer to Figure 1, unless otherwise specified, all are conventional methods; for the materials used in the following examples, unless otherwise specified, the parts in the present invention are all parts by mass, wherein the size of lignin is 5-10 μm, the standard of the materials used is medical standard, the material purity is 99.99%, the molecular weight of polyethylene glycol is -4000, and the amounts of parts not mentioned in the technical solution are calculated according to the corresponding ratio.

[0018] Example 1: An oral antibacterial composite polymer material is composed of the following raw materials in parts by mass: 5.5 parts of lignin, 10 parts of hydrogel modifier, 3 parts of polyimide modifier, 1 part of glutathione, 0.1 part of PAA, 0.2 part of glycerol, 0.03 part of menthol, and 0.01 part of potassium sorbate.

[0019] The preparation method of the hydrogel modifier includes the following steps: A. Weigh 15 parts of polyethylene glycol diacrylate, 0.2 part of dimethylaminoethyl methacrylate, and 0.1 part of camphorquinone, add them to 30 parts of deionized water, stir for 30 min under the condition of a rotation speed of 500 r / min to obtain a mixture, inject the mixture into a crosslinking mold, and irradiate it with light for 5 min under the condition of a light wave wavelength of 470 nm, where the light intensity is 30 mW / cm 2 , the distance between the light source and the material in the crosslinking mold is 10 cm, to obtain a crosslinked hydrogel; B. Weigh 0.5 part of PBS, add it to 30 parts of deionized water, adjust the pH to 7.4, continue to add 0.1 part of EDC, stir for 30 min under the condition of a rotation speed of 500 r / min to obtain a reaction solution, weigh 8 parts of vinyl mercaptoacetate, 0.7 part of ammonium persulfate, and 5 parts of N-hydroxysuccinimide, add them to the reaction solution, and stir for 30 min under the condition of a rotation speed of 500 r / min to obtain a mixed grafting solution; C. Immerse the crosslinked hydrogel obtained in step A into the mixed grafting solution obtained in step B, add 0.1 part of Irgacure 2959 to it, heat it at 50 °C for 4 h, and stir it for 30 min under the condition of a rotation speed of 500 r / min. Irradiate it with visible light with a light wave wavelength of 360 nm for 10 min, where the distance between the light source and the solution is 15 cm, and then wash it 5 times with a washing solution of ascorbic acid-sodium dihydrogen phosphate to obtain a hydrogel modifier.

[0020] The preparation method of the polyimide modifier includes the following steps: I. Weigh 10 parts of polyimide, add it to 50 parts of deionized water, stir for 30 min under the condition of a rotation speed of 500 r / min, add 0.5 part of sodium hydroxide alkali solution to it, the concentration of the sodium hydroxide alkali solution is 1 mol / L, heat it at 65 °C for 2 h, and stir it under the condition of a rotation speed of 500 r / min to obtain an oxidized polyimide product; II. Weigh 2.5 parts of polysaccharide sulfate and add it to the oxidized polyimide obtained in step I. Add hydrochloric acid to adjust the pH to 4, then add 0.1 part of EDC. Heat at 55 °C for 2 h and stir at a speed of 500 r / min, and then cool naturally to room temperature to obtain activated polyimide. III. Weigh 0.5 part of ferric nitrate and add it to 50 parts of deionized water. Add hydrochloric acid solution to adjust the pH to 2, and the concentration of hydrochloric acid is 2 mol / L. Stir at a speed of 500 r / min for 30 min. Weigh 0.5 part of citric acid and add it thereto to obtain solution A. Add the activated polyimide obtained in step II to solution A, stir at 500 r / min at room temperature for 1 h, centrifuge at a speed of 8000 r / min for 10 min, and place the centrifuged product in an oven at 55 °C for drying for 24 h to obtain polyimide modified product.

[0021] The following is the specific reaction process of the polyimide modified product: PI-(C=O) 2 N+H 2 O PI-(COOH)-NH-(COOH) (Reaction process 1) ; Fe 3+ +3(-SO 3 - / COO - ) Fe(-SO 3 - / COO - ) 3 (Reaction process 3) This example also provides a preparation method of an oral antibacterial composite polymer material, including the following steps: Step 1. Weigh 5.5 parts of lignin and add it to 25 parts of alcohol solution, where the alcohol solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 7:3. Add 0.5 part of sodium hydroxide alkali solution, and the concentration of sodium hydroxide alkali solution is 1.5 mol / L. Heat at 70 °C for 5 h and stir at a speed of 500 r / min, then add 1.5 parts of epichlorohydrin and 0.1 part of tetrabutylammonium bromide, continue to heat at 65 °C for 4 h and stir at a speed of 500 r / min, and ultrasonicate at an ultrasonic power of 80 kHz for 15 min to obtain activated lignin. Step 2. Weigh 10 parts of the hydrogel modifier and 3 parts of the polyimide modifier, add them to 30 parts of deionized water, add 0.5 part of polyethylene glycol, stir under the condition of a rotation speed of 500 r / min, continue to add 1 part of glutathione thereto, and perform heat treatment at a temperature of 45 °C for 60 min to obtain a homogeneous liquid; Step 3. Add the activated lignin obtained in Step 1 to the homogeneous liquid obtained in Step 2, add 0.1 part of glutaraldehyde and 0.05 part of sodium cyanoborohydride thereto, add a citric acid solution to adjust the pH to 6.5, the concentration of the citric acid solution is 3 mol / L, introduce argon with a flow rate of 500 mL / min and stir and react under the condition of a rotation speed of 500 r / min for 1.5 h to obtain a precursor of the oral antibacterial composite polymer material; Step 4. Weigh 0.1 part of PAA, 0.2 part of glycerol, 0.03 part of menthol and 0.01 part of potassium sorbate, add them to 30 parts of deionized water, stir under the condition of a rotation speed of 500 r / min for 1.5 h to obtain an improvement liquid, slowly add the obtained improvement liquid to the precursor of the oral antibacterial composite polymer material, perform ultrasonic treatment for 30 min under the condition of an ultrasonic power of 20 kHz, and stir under the condition of a rotation speed of 500 r / min for 30 min, filter with a 0.22-μm filter membrane, and seal the liquid in a can to obtain the oral antibacterial composite polymer material.

[0022] Example 2: An oral antibacterial composite polymer material is composed of the following raw materials in parts by mass: 6.5 parts of lignin, 10 parts of hydrogel modifier, 4 parts of polyimide modifier, 1 part of glutathione, 0.1 part of PAA, 0.2 part of glycerol, 0.04 part of menthol and 0.01 part of potassium sorbate.

[0023] The preparation method of the hydrogel modifier includes the following steps: A. Weigh 20 parts of polyethylene glycol diacrylate, 0.2 part of dimethylaminoethyl methacrylate and 0.1 part of camphorquinone, add them to 30 parts of deionized water, stir under the condition of a rotation speed of 500 r / min for 30 min to obtain a mixture, inject the mixture into a crosslinking mold and irradiate with light at a light wave wavelength of 470 nm for 5 min, wherein the light intensity is 30 mW / cm 2 , and the distance between the light source and the material in the crosslinking mold is 10 cm to obtain a crosslinked hydrogel; B. Weigh 0.5 part of PBS, add it to 30 parts of deionized water, adjust the pH to 7.4, continue to add 0.1 part of EDC, stir under the condition of a rotation speed of 500 r / min for 30 min to obtain a reaction solution, weigh 10 parts of vinyl mercaptoacetate, 0.7 part of ammonium persulfate and 6.5 parts of N-hydroxysuccinimide, add them to the reaction solution, and stir under the condition of a rotation speed of 500 r / min for 30 min to obtain a mixed grafting solution; C. Immerse the crosslinked hydrogel obtained in step A into the mixed grafting solution obtained in step B, add 0.1 part of Irgacure 2959 thereto, heat at a temperature of 60 °C for 4 h, stir at a rotation speed of 500 r / min for 30 min, carry out a visible light irradiation reaction for 10 min with a light wave wavelength of 360 nm, wherein the distance between the light source and the solution is 15 cm, and then wash 5 times with a washing solution of ascorbic acid-sodium dihydrogen phosphate to obtain a modified hydrogel.

[0024] A preparation method of a polyimide modified product, comprising the following steps: I. Weigh 13 parts of polyimide, add it to 50 parts of water, stir at a rotation speed of 500 r / min for 30 min, add 0.5 part of sodium hydroxide alkali solution with a concentration of 1 mol / L, heat at a temperature of 75 °C for 2 h, and stir at a rotation speed of 500 r / min to obtain an oxidized polyimide product; II. Weigh 3.5 parts of sodium alginate, add it to the oxidized polyimide product obtained in step I, adjust the pH to 4.5 with hydrochloric acid, add 0.1 part of EDC, heat at a temperature of 60 °C for 2 h and stir at a rotation speed of 500 r / min, and naturally cool to room temperature to obtain an activated polyimide; III. Weigh 1 part of ferric nitrate, add it to 50 parts of deionized water, adjust the pH to 2.5 with a hydrochloric acid solution with a concentration of 2 mol / L, stir at a rotation speed of 500 r / min for 30 min, weigh 0.5 part of citric acid and add it thereto to obtain solution A, add the activated polyimide obtained in step II to solution A, stir at 500 r / min at room temperature for 1 h, centrifuge at a rotation speed of 8000 r / min for 10 min, and place the centrifuged product in an oven at 55 °C to dry for 24 h to obtain a polyimide modified product.

[0025] This embodiment also provides a preparation method of an oral antibacterial composite polymer material, comprising the following steps: Step 1. Weigh 6.5 parts of lignin, add it to 25 parts of an alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water with a mass ratio of ethanol to water of 7:3, add 0.5 part of sodium hydroxide alkali solution with a concentration of 1.5 mol / L, heat at a temperature of 70 °C for 5 h, and stir at a rotation speed of 500 r / min, then add 1.5 parts of epichlorohydrin and 0.1 part of tetrabutylammonium bromide, continue to heat at a temperature of 65 °C for 4 h, and stir at a rotation speed of 500 r / min, and carry out ultrasonic treatment at an ultrasonic power of 80 kHz for 15 min to obtain activated lignin; Step 2. Weigh 10 parts of the hydrogel modifier and 4 parts of the polyimide modifier, add them to 30 parts of deionized water, add 0.5 part of polyethylene glycol, stir under the condition of a rotation speed of 500 r / min, continue to add 1 part of glutathione thereto, and perform heat treatment at a temperature of 45 °C for 60 min to obtain a homogeneous liquid; Step 3. Add the activated lignin obtained in Step 1 to the homogeneous liquid obtained in Step 2, add 0.1 part of glutaraldehyde and 0.05 part of sodium cyanoborohydride thereto, add a citric acid solution to adjust the pH to 6.5, the concentration of the citric acid solution is 3 mol / L, pass argon with a flow rate of 500 mL / min and stir and react at a rotation speed of 500 r / min for 1.5 h to obtain a precursor of the oral antibacterial composite polymer material; Step 4. Weigh 0.1 part of PAA, 0.2 part of glycerol, 0.04 part of menthol and 0.01 part of potassium sorbate, add them to 30 parts of deionized water, stir under the condition of a rotation speed of 500 r / min for 1.5 h to obtain an improvement liquid, slowly add the obtained improvement liquid to the precursor of the oral antibacterial composite polymer material, perform ultrasonic treatment for 30 min under the condition of an ultrasonic power of 20 kHz, and stir under the condition of a rotation speed of 500 r / min for 30 min, filter with a 0.22 μm filter membrane, and seal the liquid in a can to obtain the oral antibacterial composite polymer material.

[0026] Example 3: An oral antibacterial composite polymer material is composed of the following raw materials in parts by mass: 7.5 parts of lignin, 10 parts of hydrogel modifier, 5 parts of polyimide modifier, 1 part of glutathione, 0.1 part of PAA, 0.2 part of glycerol, 0.05 part of menthol and 0.01 part of potassium sorbate.

[0027] The preparation method of the hydrogel modifier includes the following steps: A. Weigh 25 parts of polyethylene glycol diacrylate, 0.2 part of dimethylaminoethyl methacrylate and 0.1 part of camphorquinone, add them to 30 parts of deionized water, stir under the condition of a rotation speed of 500 r / min for 30 min to obtain a mixture, inject the mixture into a crosslinking mold and irradiate with light at a light wave wavelength of 470 nm for 5 min, wherein the light intensity is 30 mW / cm 2 , the distance between the light source and the material in the crosslinking mold is 10 cm, to obtain a crosslinked hydrogel; B. Weigh 0.5 part of PBS, add it to 30 parts of deionized water, adjust the pH to 7.4, continue to add 0.1 part of EDC, stir under the condition of a rotation speed of 500 r / min for 30 min to obtain a reaction solution, weigh 12 parts of vinyl mercaptoacetate, 0.7 part of ammonium persulfate and 8 parts of N-hydroxysuccinimide, add them to the reaction solution, and stir under the condition of a rotation speed of 500 r / min for 30 min to obtain a mixed grafting solution; C. Immerse the crosslinked hydrogel obtained in step A into the mixed grafting solution obtained in step B, add 0.1 part of Irgacure 2959 thereto, heat it at a temperature of 70 °C for 4 h, stir it at a rotation speed of 500 r / min for 30 min, carry out a visible light irradiation reaction for 10 min with a light wave wavelength of 360 nm, wherein the distance between the light source and the solution is 15 cm, and then wash it 5 times with a washing solution of ascorbic acid - sodium dihydrogen phosphate to obtain a modified hydrogel.

[0028] A preparation method of a polyimide modified product, comprising the following steps: I. Weigh 15 parts of polyimide and add it to 50 parts of deionized water, stir it at a rotation speed of 500 r / min for 30 min, add 0.5 part of sodium hydroxide alkali solution with a concentration of 1 mol / L thereto, heat it at a temperature of 85 °C for 2 h, and stir it at a rotation speed of 500 r / min to obtain an oxidized polyimide product; II. Weigh 4.5 parts of sodium alginate and add it to the oxidized polyimide product obtained in step I, adjust the pH to 5 with hydrochloric acid, then add 0.1 part of EDC, heat it at a temperature of 65 °C for 2 h and stir it at a rotation speed of 500 r / min, and naturally cool it to room temperature to obtain an activated polyimide; III. Weigh 1.5 parts of ferric nitrate and add it to 50 parts of deionized water, adjust the pH to 3 with a hydrochloric acid solution with a concentration of 2 mol / L, stir it at a rotation speed of 500 r / min for 30 min, weigh 0.5 part of citric acid and add it thereto to obtain solution A, add the activated polyimide obtained in step II to solution A, stir it at 500 r / min at room temperature for 1 h, centrifuge it at a rotation speed of 8000 r / min for 10 min, and place the centrifuged product in an oven at 55 °C to dry for 24 h to obtain a polyimide modified product.

[0029] This example also provides a preparation method of an oral antibacterial composite polymer material, comprising the following steps: Step 1. Weigh 7.5 parts of lignin and add it to 25 parts of an alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 7:3, add 0.5 part of sodium hydroxide alkali solution with a concentration of 1.5 mol / L thereto, heat it at a temperature of 70 °C for 5 h, and stir it at a rotation speed of 500 r / min, then add 1.5 parts of epichlorohydrin and 0.1 part of tetrabutylammonium bromide, continue to heat it at a temperature of 65 °C for 4 h, and stir it at a rotation speed of 500 r / min, and carry out ultrasonic treatment at an ultrasonic power of 80 kHz for 15 min to obtain an activated lignin; Step 2. Weigh 10 parts of the hydrogel modifier and 5 parts of the polyimide modifier, add them to 30 parts of deionized water, add 0.5 part of polyethylene glycol, stir under the condition of a rotation speed of 500 r / min, continue to add 1 part of glutathione thereto, and perform heat treatment at a temperature of 45 °C for 60 min to obtain a homogeneous solution; Step 3. Add the activated lignin obtained in Step 1 to the homogeneous solution obtained in Step 2, add 0.1 part of glutaraldehyde and 0.05 part of sodium cyanoborohydride thereto, add a citric acid solution to adjust the pH to 6.5, the concentration of the citric acid solution is 3 mol / L, introduce argon with a flow rate of 500 mL / min, and stir and react under the condition of a rotation speed of 500 r / min for 1.5 h to obtain a precursor of the oral antibacterial composite polymer material; Step 4. Weigh 0.1 part of PAA, 0.2 part of glycerol, 0.05 part of menthol and 0.01 part of potassium sorbate, add them to 30 parts of deionized water, stir under the condition of a rotation speed of 500 r / min for 1.5 h to obtain an improvement solution, slowly add the obtained improvement solution to the precursor of the oral antibacterial composite polymer material, perform ultrasonic treatment for 30 min under the condition of an ultrasonic power of 20 kHz, and stir under the condition of a rotation speed of 500 r / min for 30 min, filter with a 0.22-μm filter membrane, and seal the liquid in a can to obtain the oral antibacterial composite polymer material.

[0030] Comparative examples: The difference between Comparative Example 1 and Example 2 is that no hydrogel modifier is added, and the rest is the same as Example 2; The difference between Comparative Example 2 and Example 2 is that no polyimide modifier is added, and the rest is the same as Example 2; The difference between Comparative Example 3 and Example 2 is that no glutathione is added, and the rest is the same as Example 2; The difference between Comparative Example 4 and Comparative Example 5 is that no light is added, and the rest is the same as Comparative Example 5; Comparative Example 5 is a photocatalytic Fenton antibacterial test with light. The preparation raw materials include 6.5 parts of lignin, 10 parts of hydrogel, 4 parts of polyimide, 1 part of iron nitrate, 0.5 part of sodium borate, 0.1 part of PAA, 0.2 part of glycerol, 0.04 part of menthol and 0.01 part of potassium sorbate.

[0031] A preparation method of an oral antibacterial composite polymer material comprises the following steps: Step 1. Weigh 6.5 parts of lignin and add it to 25 parts of alcohol solution. The alcohol solution is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 7:3. Add 0.5 part of sodium hydroxide alkali solution with a concentration of 1.5 mol / L. Heat it at 70 °C for 5 h and stir it at a rotation speed of 500 r / min. Then add 1.5 parts of epichlorohydrin and 0.1 part of tetrabutylammonium bromide, continue to heat it at 65 °C for 4 h and stir it at a rotation speed of 500 r / min. Ultrasonic for 15 min under the condition of an ultrasonic power of 80 kHz to obtain activated lignin; Step 2. Weigh 10 parts of hydrogel modifier and 4 parts of polyimide modifier and add them to 30 parts of deionized water. Add 0.5 part of polyethylene glycol and stir it at a rotation speed of 500 r / min. Then continue to add 1 part of glutathione and heat-treat it at 45 °C for 60 min to obtain a homogeneous liquid; Step 3. Add the activated lignin obtained in Step 1 to the homogeneous liquid obtained in Step 2. Add 0.1 part of glutaraldehyde and 0.05 part of sodium cyanoborohydride, add citric acid solution to adjust the pH to 6.5, and the concentration of the citric acid solution is 3 mol / L. Pass argon with a flow rate of 500 mL / min and stir and react at a rotation speed of 500 r / min for 1.5 h to obtain a precursor of oral antibacterial composite polymer material; Step 4. Weigh 0.1 part of PAA, 0.2 part of glycerol, 0.04 part of menthol, and 0.01 part of potassium sorbate and add them to 30 parts of deionized water. Stir it at a rotation speed of 500 r / min for 1.5 h to obtain an improvement liquid. Slowly add the obtained improvement liquid to the precursor of the oral antibacterial composite polymer material, ultrasonic for 30 min under the condition of an ultrasonic power of 20 kHz, and stir it at a rotation speed of 500 r / min for 30 min. Filter it with a 0.22 μm filter membrane, and seal the liquid in a can to obtain the oral antibacterial composite polymer material.

[0032] Take a medical cotton sheet, cut it into a uniform cotton sheet of 1 cm·1 cm, evenly spray 3 mL of nutrients required for bacterial reproduction, drop 2 drops of bacterial liquid containing bacteria on the cotton sheet, and then take the prepared oral antibacterial composite polymer material and evenly spray 3 mL on the surface of the cotton sheet. Place it under suitable temperature conditions to grow for 24 h, and calculate the antibacterial rate by the plate counting method. Among them, the light condition is irradiated with light waves with a wavelength of 420 nm and a light intensity of 2 mW / cm 2 For the second test, on the basis of the first test, spray 2 mL of deionized water to ensure the wetness of the cotton sheet surface, and additionally supplement 3 mL of nutrients. Then drop 2 drops of bacterial liquid containing bacteria on the cotton sheet, and keep other conditions such as the environment unchanged, and continue to grow for 24 h.Figure 2 For the antibacterial test and secondary antibacterial test of the prepared oral antibacterial composite polymer material against bacteria, the statistical results show that the oral antibacterial composite polymer material prepared in the examples exhibits good antibacterial properties in single antibacterial, and the effect is better than that in the comparative examples. In addition, for the Fenton reaction, under the condition of adding light, the antibacterial property is better than that of the comparative example without adding light. For the statistical results of the performance test of secondary antibacterial, it is found that the oral antibacterial composite polymer material prepared in the examples still exhibits high antibacterial properties, and there is no obvious change compared with the first antibacterial effect, indicating that the prepared oral antibacterial composite polymer material shows persistence in antibacterial performance.

[0033] To further verify the biocompatibility of the prepared oral antibacterial composite polymer material, 8 rats (4 - 6 months old, 180 - 200 g, with an equal number of males and females) were selected. In 3 groups of examples, one male and one female were included in each group. 0.1 mL of the oral antibacterial composite polymer material was injected into each rat once a day for a total of 7 times. The body weight was statistically recorded every five days. A blank control group was also set up, and physiological saline was injected according to the injection cycle of the above materials. After 15 days, the rats were sacrificed and the organ lesions were observed. Table 1 shows the statistical results of the body weight, respiratory rate, and activity of the rats after injecting the oral antibacterial composite polymer material. It can be seen that injecting the oral antibacterial composite polymer material prepared in the examples does not have an obvious impact on the body weight of the rats, and the respiratory rate and activity are normal, indicating that the prepared oral antibacterial composite polymer material does not cause toxic effects.

[0034] Table 1 shows the results of the test rats:

[0035] Obviously, the above - mentioned comparative examples and examples are only a part of the comparative examples and examples of the present invention, and the scope protected by the present invention includes all the comparative examples and examples based on such references.

[0036] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

[0037] The above describes the present invention and its embodiments. This description is not restrictive. What is shown in the drawings is only one of the embodiments of the present invention, and the actual application is not limited to this. Generally speaking, if those of ordinary skill in the art are inspired by it and design similar methods and embodiments without creative efforts without departing from the purpose of the present invention, they should all fall within the protection scope of the present invention.

Claims

1. An oral antibacterial composite polymer material, characterized in that: The invention comprises the following raw materials in parts by weight: 5.5-7.5 parts of lignin, 10 parts of hydrogel modification, 3-5 parts of polyimide modification, 1 part of glutathione, 0.1 part of PAA, 0.2 part of glycerol, 0.03-0.05 part of menthol and 0.01 part of potassium sorbate; The raw materials for preparing the polyimide modification include the following raw materials in the following weight ratios: polyimide: sodium alginate diester: ferric nitrate: citric acid = 10-15: 2.5-4.5: 0.5-1.5: 0.5; The preparation method of the modified polyimide comprises the following steps: I. Weigh polyimide and add it to water, stir, add alkali solution, heat and stir to obtain oxidized polyimide; II. Weigh sodium alginate diester and add it to the oxidized polyimide, add acid, add EDC, heat and stir to obtain an activated polyimide; III. Weigh ferric nitrate and add it to water, add acid, stir, add citric acid to obtain solution A, add activated polyimide to solution A, stir, and dry to obtain a modified polyimide.

2. The oral antibacterial composite polymer material according to claim 1, characterized in that: The raw materials for preparing the hydrogel modification include the following raw materials in the following weight ratios: hydrogel: N-hydroxysuccinimide: ammonium persulfate: vinyl thioglycolate: dimethylaminoethyl methacrylate = 15-25: 5-8: 0.7: 8-12: 0.

2.

3. The oral antibacterial composite polymer material according to claim 2, characterized in that: The preparation method of the modified hydrogel comprises the following steps: A. weighing a hydrogel, dimethylaminoethyl methacrylate and camphorquinone, adding them into water, stirring to obtain a mixture, and irradiating the mixture with light to obtain a cross-linked hydrogel; B. Weigh PBS and add it to water, adjust the pH, add EDC, stir to obtain a reaction solution, weigh vinyl thioglycolate, ammonium persulfate, N-hydroxysuccinimide and dodecyl mercaptan and add them to the reaction solution, stir to obtain a mixed grafting solution; C. Immerse the cross-linked hydrogel in the mixed grafting solution, add an initiator, heat and stir, photoreact, and wash to obtain a modified hydrogel.

4. A method for preparing an oral antibacterial composite polymer material according to any one of claims 1 to 3, characterized in that: The steps include: Step 1. Weigh lignin and add it to alcohol solution, add alkali solution, heat and stir, add epichlorohydrin and tetrabutylammonium bromide, heat and sonicate to obtain activated lignin; Step 2. Weigh the hydrogel modification and the polyimide modification, add them to water, add polyethylene glycol, stir, add glutathione, heat treat, and obtain a homogenous solution; Step 3. Add activated lignin to the homogenized liquid, add glutaraldehyde and sodium cyanoborohydride, add acid solution, and ventilate to react to obtain an oral antibacterial composite polymer material precursor; Step 4. Weigh PAA, glycerol, menthol and potassium sorbate, add them into water, stir to obtain an improved solution, add the improved solution into the oral antibacterial composite polymer material precursor, ultrasonicate and stir, filter, seal, and obtain the oral antibacterial composite polymer material.

5. The method for preparing an oral antibacterial composite polymer material according to claim 4, characterized in that: The alcohol solution in step one is a mixed solution of ethanol and water, and the mass ratio of ethanol to water is 7:

3. The ventilation gas in step three is argon.

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