An oral antibacterial composite polymer material and its preparation method

Abstract

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. The oral antibacterial composite polymer material comprises the following raw materials in parts 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 glycerol, 0.03-0.05 parts of menthol and 0.01 part of potassium sorbate; the present invention improves hydrophilicity and complexes Fe by modifying polyimide with sodium diester alginate. 3+ , constructing a S-H / S-S dynamic redox system to realize Fe 3+ / Fe 2+ Self-circulation with enhanced mechanical properties and the introduction of glutathione to chelate Fe via a thiophosphonate intermediate 3+ It produces active oxygen, forming a synergistic mechanism of "bacteria adsorption-continuous killing-material durability", breaking through the limitations of traditional Fenton reaction and providing an efficient and adaptive integrated solution for oral antibacterial materials.

Description

Technical Field

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

[0002] The oral environment is complex, microorganisms are easily bred, and traditional antibacterial materials have defects such as drug resistance, poor biocompatibility and short duration of action. New and efficient antibacterial strategies are urgently needed. Although the Fenton reaction can effectively kill bacteria by producing reactive oxygen species (ROS), its strong acid dependence and Fe 2+ The problem of continuous supply and the risk of metal ion leakage limit its application in the neutral environment of the oral cavity; hydrogels as potential carriers are difficult to meet the needs due to insufficient mechanical strength and lack of dynamic antibacterial ability. Summary of the Invention

[0003] In view of the defects of the prior art, the present invention discloses an oral antibacterial composite polymer material, which improves the hydrophilicity and complexes Fe by modifying polyimide with sodium diester alginate. 3+ SH groups were grafted onto the hydrogel, and glutathione was introduced to construct the SH / SS dynamic redox system to achieve Fe 3+ / Fe 2+ It self-circulates and produces active oxygen, forming a synergistic mechanism of "bacteria adsorption-continuous killing-material durability", breaking through the limitations of traditional Fenton reaction and providing an efficient and adaptive integrated solution for oral antibacterial materials.

[0004] To achieve the above objectives, the technical solution adopted by the present invention is an oral antibacterial composite polymer material, comprising the following raw materials in parts 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 glycerol, 0.03-0.05 parts of menthol and 0.01 part of potassium sorbate.

[0005] Furthermore, the preparation method of the modified hydrogel comprises the following steps:

[0006] A. Weigh 15-25 parts of hydrogel, 0.2 parts of dimethylaminoethyl methacrylate, and 0.1 parts of camphorquinone and add them to 30 parts of deionized water. Stir at a speed of 500 r / min for 30 minutes to obtain a mixture. Inject the mixture into a cross-linking mold and irradiate it with light at a wavelength of 470 nm for 5 minutes, with a light intensity of 30 mW / cm 2 , the distance between the light source and the material in the cross-linking mold was 10 cm, and a cross-linked hydrogel was obtained;

[0007] 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 add 0.1 parts of EDC (1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride), and stir at 500 r / min for 30 minutes to obtain a reaction solution. Weigh 8-12 parts of vinyl thioglycolate, 0.7 parts of ammonium persulfate, 5-8 parts of N-hydroxysuccinimide, and 0.05 parts of dodecyl mercaptan to the reaction solution, and stir at 500 r / min for 30 minutes to obtain a mixed grafting solution.

[0008] C. Immerse the cross-linked hydrogel obtained in step A in the mixed grafting solution obtained in step B, add 0.1 parts of initiator thereto, heat at a temperature of 50-70°C for 4 hours, and stir at a speed of 500 r / min for 30 minutes. Irradiate with visible light with a wavelength of 360 nm for 10 minutes, wherein the distance between the light source and the solution is 15 cm. Then wash five times with a mixed solution of ascorbic acid and sodium dihydrogen phosphate to obtain a modified hydrogel.

[0009] Furthermore, 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 parts of ascorbic acid and 1 part of sodium dihydrogen phosphate to 100 parts of deionized water.

[0010] Furthermore, the preparation method of the modified polyimide comprises the following steps:

[0011] I. Weigh 10-15 parts of polyimide and add them to 50 parts of deionized water, stir at a speed of 500 r / min for 30 min, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1 mol / L, heat at a temperature of 65-85 ° C for 2 h, and stir at a speed of 500 r / min to obtain an oxidized polyimide;

[0012] II. Weigh 2.5-4.5 parts of sodium diester alginate and add the oxidized polyimide obtained in step I, add hydrochloric acid to adjust the pH to 4-5, the hydrochloric acid concentration is 1.5 mol / L, then add 0.1 parts of EDC, heat at a temperature of 55-65 ℃ for 2h and stir at a speed of 500r / min, and cool naturally to room temperature to obtain an activated polyimide;

[0013] III. Weigh 0.5-1.5 parts of ferric nitrate and add them to 50 parts of deionized water, add hydrochloric acid solution to adjust the pH to 2-3, the hydrochloric acid concentration is 2 mol / L, and stir at a speed of 500r / min for 30min. Weigh 0.5 parts of citric acid and add them thereto to obtain a solution A. The activated polyimide obtained in step II was added to solution A, stirred at room temperature at 500r / min for 1h, centrifuged at a speed of 8000r / min for 10min, and the centrifuge was placed in an oven at 55 ° C and dried for 24h to obtain a modified polyimide.

[0014] The following is the specific reaction process of polyimide modification:

[0015] PI-(C=O)2N+H2O PI-(COOH)-NH-(COOH) (Reaction Process 1)

[0016] ;

[0017] Fe 3+ +3(-SO3 - / COO - ) Fe(-SO3 - / COO - )3 (Reaction process three)

[0018] The present invention also provides a method for preparing an oral antibacterial composite polymer material, comprising the following steps:

[0019] Step 1. Weigh 5.5-7.5 parts of lignin and add 25 parts of alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water, the mass ratio of ethanol and water is 7:3, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1.5 mol / L, heat at a temperature of 70 ° C for 5h, and stir at a speed of 500r / min, then add 1.5 parts of epichlorohydrin and 0.1 parts of tetrabutylammonium bromide, continue heating at a temperature of 65 ° C for 4h, and stir at a speed of 500r / min, and ultrasonic time is 15min under the conditions of an ultrasonic power of 80kHz to obtain activated lignin;

[0020] Step 2. Weigh 10 parts of the hydrogel modifier and 3-5 parts of the polyimide modifier, add 30 parts of deionized water, add 0.5 parts of polyethylene glycol, stir at a speed of 500 r / min, continue to add 1 part of glutathione, heat treatment at a temperature of 45 ° C for 60 min to obtain a homogeneous solution;

[0021] Step 3. The activated lignin obtained in step 1 was added to the homogenized solution obtained in step 2, 0.1 parts of glutaraldehyde and 0.05 parts of sodium cyanoborohydride were added thereto, citric acid solution was added to adjust the pH to 6.5, the concentration of the citric acid solution was 3 mol / L, argon was introduced at a flow rate of 500 mL / min and the reaction was stirred at a speed of 500 r / min for 1.5 h to obtain an oral antibacterial composite polymer material precursor;

[0022] Step 4. Weigh 0.1 parts of PAA (polyacrylic acid), 0.2 parts of glycerol, 0.03-0.05 parts of menthol and 0.01 parts of potassium sorbate, add them to 30 parts of deionized water, stir at a speed of 500 r / min for 1.5 hours to obtain an improvement liquid, and slowly add the obtained improvement liquid to the oral antibacterial composite polymer material precursor. Ultrasonic time is 30 minutes under the condition of ultrasonic power of 20 kHz, and stirring is carried out at a speed of 500 r / min for 30 minutes. Filter with a 0.22 μm filter membrane, can and seal the liquid to obtain the oral antibacterial composite polymer material.

[0023] The beneficial effects achieved by the present invention are as follows:

[0024] The oral antibacterial composite polymer material prepared by the present invention uses sodium diester alginate to modify polyimide. On the one hand, this effectively improves the hydrophilicity of the material, helping the material to better interact with oral tissues and fluids; on the other hand, the introduction of sulfonic acid groups creates abundant active sites for the complexation of trivalent iron ions; iron nitrate is used as the metal ion source for the Fenton reaction and is grafted onto polyimide through complexation, thus constructing the basis for an efficient Fenton reaction system.

[0025] The oral antibacterial composite polymer material prepared by the present invention introduces SH bonds in the hydrogel structure to reduce the trivalent iron produced during the Fenton reaction, allowing the Fenton reaction to continue in a cycle; at the same time, the trivalent iron, as a metal cation, utilizes its adsorption properties with the anions on the bacterial surface to promote the efficient adsorption of bacteria on the surface of the antibacterial material, greatly enhancing the specificity and effectiveness of the antibacterial process and achieving a synergistic effect of the material in capturing and continuously killing bacteria.

[0026] 2R-SH+2Fe 3+ →RSS-R+2Fe 2+ +2H +

[0027] ;

[0028] In the oral antibacterial composite polymer material prepared by the present invention, SH bonds are converted into SS bonds after reducing trivalent iron, providing additional cross-linking points for the hydrogel, significantly enhancing the mechanical strength and durability of the hydrogel material, and increasing the service life of the material in the complex environment of the oral cavity. By introducing glutathione as a reducing agent for the SS bonds, the antibacterial mechanism of the material is further improved. The thiophosphonate intermediate generated during the reduction of some SS bonds by glutathione contains a phosphoryl group that can undergo a chelation reaction with some free trivalent iron to generate reactive oxygen species (ROS), thereby achieving another efficient way to kill bacteria. At the same time, the concentration of trivalent iron in the system is maintained, ensuring the efficient and continuous progress of the Fenton reaction.

[0029] RSS-R+2GSH→2R-SH+GSSG

[0030] ;

[0031] The oral antibacterial composite polymer material prepared by the present invention improves the traditional Fenton reaction conditions by introducing specific functional groups, allowing 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

[0032] Figure 1 This is a diagram showing the preparation method of the oral antibacterial composite polymer material proposed by the present invention;

[0033] Figure 2 These are diagrams showing the antibacterial effects of oral antibacterial composite polymer materials prepared in the examples and comparative examples of the present invention.

[0034] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described herein can be applied to the present invention. The preferred embodiments and materials described herein are for illustrative purposes only and are not intended to limit the scope of this application.

[0037] The preparation methods in the following examples are described in detail in Figure 1 Unless otherwise specified, conventional methods are used; the materials used in the following embodiments, unless otherwise specified, are all parts by mass in the present invention, wherein the size of lignin is 5-10 μm, the standard of the materials used is medical standard, the purity of the material is 99.99%, the molecular weight of polyethylene glycol is -4000, and the quantities not mentioned in the technical solution are calculated according to the ratio of the corresponding amounts.

[0038] 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.

[0039] The preparation method of the modified hydrogel comprises the following steps:

[0040] A. Weigh 15 parts of polyethylene glycol diacrylate, 0.2 parts of dimethylaminoethyl methacrylate, and 0.1 parts of camphorquinone and add them to 30 parts of deionized water. Stir at a speed of 500 r / min for 30 minutes to obtain a mixture. Inject the mixture into a cross-linking mold and irradiate it with light at a wavelength of 470 nm for 5 minutes, with a light intensity of 30 mW / cm 2 , the distance between the light source and the material in the cross-linking mold was 10 cm, and a cross-linked hydrogel was obtained;

[0041] B. Weigh 0.5 parts of PBS and add it to 30 parts of deionized water, adjust the pH to 7.4, continue to add 0.1 parts of EDC, and stir at a speed of 500 r / min for 30 minutes to obtain a reaction solution. Weigh 8 parts of vinyl thioglycolate, 0.7 parts of ammonium persulfate, and 5 parts of N-hydroxysuccinimide and add them to the reaction solution, and stir at a speed of 500 r / min for 30 minutes to obtain a mixed grafting solution;

[0042] C. The cross-linked hydrogel obtained in step A was immersed in the mixed grafting solution obtained in step B, 0.1 parts of Irgacure 2959 was added thereto, and the mixture was heated at 50° C. for 4 hours and stirred at 500 r / min for 30 minutes. The mixture was then illuminated with visible light of 360 nm for 10 minutes, with the light source being 15 cm away from the solution. The mixture was then washed five times with a mixed solution of ascorbic acid and sodium dihydrogen phosphate to obtain a modified hydrogel.

[0043] The preparation method of the modified polyimide comprises the following steps:

[0044] I. Weigh 10 parts of polyimide and add them to 50 parts of deionized water. Stir the mixture at a speed of 500 r / min for 30 min. Then, add 0.5 parts of sodium hydroxide solution with a concentration of 1 mol / L. Heat the mixture at 65°C for 2 h and stir the mixture at a speed of 500 r / min to obtain an oxidized polyimide.

[0045] II. Weigh 2.5 parts of sodium diester alginate and add the oxidized polyimide obtained in step I, add hydrochloric acid to adjust the pH to 4, then add 0.1 parts of EDC, heat at 55 ° C for 2h and stir at a speed of 500r / min, and cool naturally to room temperature to obtain an activated polyimide;

[0046] III. Weigh 0.5 parts of ferric nitrate and add them to 50 parts of deionized water, add hydrochloric acid solution to adjust the pH to 2, the hydrochloric acid concentration is 2 mol / L, and stir at a speed of 500r / min for 30min. Weigh 0.5 parts of citric acid and add them to obtain solution A. The activated polyimide obtained in step II was added to solution A, stirred at room temperature at 500r / min for 1h, centrifuged at a speed of 8000r / min for 10min, and the centrifuged material was placed in an oven at 55°C and dried for 24h to obtain a modified polyimide.

[0047] The following is the specific reaction process of polyimide modification:

[0048] PI-(C=O)2N+H2O PI-(COOH)-NH-(COOH) (Reaction Process 1)

[0049] ;

[0050] Fe 3+ +3(-SO3 - / COO - ) Fe(-SO3 - / COO - )3 (Reaction process three)

[0051] This embodiment also provides a method for preparing an oral antibacterial composite polymer material, comprising the following steps:

[0052] Step 1. Weigh 5.5 parts of lignin and add 25 parts of alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water, the mass ratio of ethanol and water is 7:3, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1.5 mol / L, heat at a temperature of 70 ° C for 5h, and stir at a speed of 500r / min, then add 1.5 parts of epichlorohydrin and 0.1 parts of tetrabutylammonium bromide, continue heating at a temperature of 65 ° C for 4h, and stir at a speed of 500r / min, and ultrasonic time is 15min under the conditions of an ultrasonic power of 80kHz to obtain activated lignin;

[0053] Step 2. Weigh 10 parts of the hydrogel modification and 3 parts of the polyimide modification into 30 parts of deionized water, add 0.5 parts of polyethylene glycol, stir at a speed of 500 r / min, continue to add 1 part of glutathione, heat treat at a temperature of 45 ° C for 60 min to obtain a homogeneous solution;

[0054] Step 3. The activated lignin obtained in step 1 was added to the homogenized solution obtained in step 2, 0.1 parts of glutaraldehyde and 0.05 parts of sodium cyanoborohydride were added thereto, citric acid solution was added to adjust the pH to 6.5, the concentration of the citric acid solution was 3 mol / L, argon was introduced at a flow rate of 500 mL / min and the reaction was stirred at a speed of 500 r / min for 1.5 h to obtain an oral antibacterial composite polymer material precursor;

[0055] Step 4. Weigh 0.1 parts of PAA, 0.2 parts of glycerol, 0.03 parts of menthol and 0.01 parts of potassium sorbate, add them to 30 parts of deionized water, stir at a speed of 500 r / min for 1.5 hours to obtain an improvement liquid, and slowly add the obtained improvement liquid to the oral antibacterial composite polymer material precursor. The ultrasonic time is 30 minutes under the condition of ultrasonic power of 20 kHz, and stirred at a speed of 500 r / min for 30 minutes. Filter using a 0.22 μm filter membrane, can and seal the liquid to obtain an oral antibacterial composite polymer material.

[0056] 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.

[0057] The preparation method of the modified hydrogel comprises the following steps:

[0058] A. Weigh 20 parts of polyethylene glycol diacrylate, 0.2 parts of dimethylaminoethyl methacrylate, and 0.1 parts of camphorquinone and add them to 30 parts of deionized water. Stir at a speed of 500 r / min for 30 minutes to obtain a mixture. Inject the mixture into a cross-linking mold and irradiate it with light at a wavelength of 470 nm for 5 minutes, with a light intensity of 30 mW / cm 2 , the distance between the light source and the material in the cross-linking mold was 10 cm, and a cross-linked hydrogel was obtained;

[0059] B. Weigh 0.5 parts of PBS and add it to 30 parts of deionized water, adjust the pH to 7.4, continue to add 0.1 parts of EDC, and stir at a speed of 500 r / min for 30 minutes to obtain a reaction solution. Weigh 10 parts of vinyl thioglycolate, 0.7 parts of ammonium persulfate, and 6.5 parts of N-hydroxysuccinimide and add them to the reaction solution, and stir at a speed of 500 r / min for 30 minutes to obtain a mixed grafting solution;

[0060] C. The cross-linked hydrogel obtained in step A was immersed in the mixed grafting solution obtained in step B, 0.1 parts of Irgacure 2959 was added thereto, and the mixture was heated at 60°C for 4 hours and stirred at 500 r / min for 30 minutes. The mixture was then illuminated with visible light of 360 nm for 10 minutes, with the light source being 15 cm away from the solution. The mixture was then washed five times with a mixed solution of ascorbic acid and sodium dihydrogen phosphate to obtain a modified hydrogel.

[0061] The preparation method of the modified polyimide comprises the following steps:

[0062] I. Weigh 13 parts of polyimide and add them to 50 parts of water, stir at a speed of 500 r / min for 30 min, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1 mol / L, heat at a temperature of 75 ° C for 2 h, and stir at a speed of 500 r / min to obtain an oxidized polyimide;

[0063] II. Weigh 3.5 parts of sodium diester alginate and add the oxidized polyimide obtained in step I, add hydrochloric acid to adjust the pH to 4.5, then add 0.1 parts of EDC, heat at 60 ° C for 2h and stir at a speed of 500r / min, and cool naturally to room temperature to obtain an activated polyimide;

[0064] III. Weigh 1 part of ferric nitrate and add it to 50 parts of deionized water, add hydrochloric acid solution to adjust the pH to 2.5, the hydrochloric acid concentration is 2 mol / L, and stir at a speed of 500r / min for 30min. Weigh 0.5 parts of citric acid and add it thereto to obtain a solution A. The activated polyimide obtained in step II was added to solution A, stirred at room temperature at 500r / min for 1h, centrifuged at a speed of 8000r / min for 10min, and the centrifuge was placed in an oven at 55°C and dried for 24h to obtain a modified polyimide.

[0065] This embodiment also provides a method for preparing an oral antibacterial composite polymer material, comprising the following steps:

[0066] Step 1. Weigh 6.5 parts of lignin and add 25 parts of alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water, the mass ratio of ethanol and water is 7:3, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1.5 mol / L, heat at a temperature of 70 ° C for 5h, and stir at a speed of 500r / min, then add 1.5 parts of epichlorohydrin and 0.1 parts of tetrabutylammonium bromide, continue heating at a temperature of 65 ° C for 4h, and stir at a speed of 500r / min, and ultrasonic time is 15min under the conditions of an ultrasonic power of 80kHz to obtain activated lignin;

[0067] Step 2. Weigh 10 parts of the hydrogel modifier and 4 parts of the polyimide modifier into 30 parts of deionized water, add 0.5 parts of polyethylene glycol, stir at a speed of 500 r / min, continue to add 1 part of glutathione, heat treat at a temperature of 45 ° C for 60 min to obtain a homogeneous solution;

[0068] Step 3. The activated lignin obtained in step 1 was added to the homogenized solution obtained in step 2, 0.1 parts of glutaraldehyde and 0.05 parts of sodium cyanoborohydride were added thereto, citric acid solution was added to adjust the pH to 6.5, the concentration of the citric acid solution was 3 mol / L, argon was introduced at a flow rate of 500 mL / min and the reaction was stirred at a speed of 500 r / min for 1.5 h to obtain an oral antibacterial composite polymer material precursor;

[0069] Step 4. Weigh 0.1 parts of PAA, 0.2 parts of glycerol, 0.04 parts of menthol and 0.01 parts of potassium sorbate, add them to 30 parts of deionized water, stir at a speed of 500 r / min for 1.5 hours to obtain an improvement liquid, and slowly add the obtained improvement liquid to the oral antibacterial composite polymer material precursor. The ultrasonic time is 30 minutes under the condition of ultrasonic power of 20 kHz, and stirred at a speed of 500 r / min for 30 minutes. Filter using a 0.22 μm filter membrane, can and seal the liquid to obtain an oral antibacterial composite polymer material.

[0070] 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.

[0071] The preparation method of the modified hydrogel comprises the following steps:

[0072] A. Weigh 25 parts of polyethylene glycol diacrylate, 0.2 parts of dimethylaminoethyl methacrylate, and 0.1 parts of camphorquinone and add them to 30 parts of deionized water. Stir at a speed of 500 r / min for 30 minutes to obtain a mixture. Inject the mixture into a cross-linking mold and irradiate it with light at a wavelength of 470 nm for 5 minutes, with a light intensity of 30 mW / cm 2 , the distance between the light source and the material in the cross-linking mold was 10 cm, and a cross-linked hydrogel was obtained;

[0073] B. Weigh 0.5 parts of PBS and add it to 30 parts of deionized water, adjust the pH to 7.4, continue to add 0.1 parts of EDC, and stir at a speed of 500 r / min for 30 minutes to obtain a reaction solution. Weigh 12 parts of vinyl thioglycolate, 0.7 parts of ammonium persulfate, and 8 parts of N-hydroxysuccinimide and add them to the reaction solution, and stir at a speed of 500 r / min for 30 minutes to obtain a mixed grafting solution;

[0074] C. The cross-linked hydrogel obtained in step A was immersed in the mixed grafting solution obtained in step B, 0.1 parts of Irgacure 2959 was added thereto, and the mixture was heated at 70°C for 4 hours and stirred at 500 r / min for 30 minutes. The mixture was then illuminated with visible light of 360 nm for 10 minutes, with the light source being 15 cm away from the solution. The mixture was then washed five times with a mixed solution of ascorbic acid and sodium dihydrogen phosphate to obtain a modified hydrogel.

[0075] The preparation method of the modified polyimide comprises the following steps:

[0076] I. Weigh 15 parts of polyimide and add them to 50 parts of deionized water. Stir the mixture at a speed of 500 r / min for 30 min. Then, add 0.5 parts of sodium hydroxide solution with a concentration of 1 mol / L. Heat the mixture at 85°C for 2 h and stir the mixture at a speed of 500 r / min to obtain an oxidized polyimide.

[0077] II. Weigh 4.5 parts of sodium diester alginate and add the oxidized polyimide obtained in step I, add hydrochloric acid to adjust the pH to 5, then add 0.1 parts of EDC, heat at 65 ° C for 2h and stir at a speed of 500r / min, and cool naturally to room temperature to obtain an activated polyimide;

[0078] III. Weigh 1.5 parts of ferric nitrate and add them to 50 parts of deionized water, add hydrochloric acid solution to adjust the pH to 3, the hydrochloric acid concentration is 2 mol / L, and stir at a speed of 500r / min for 30min. Weigh 0.5 parts of citric acid and add them to obtain solution A. The activated polyimide obtained in step II was added to solution A, stirred at room temperature at 500r / min for 1h, centrifuged at a speed of 8000r / min for 10min, and the centrifuged material was placed in an oven at 55 ° C and dried for 24h to obtain a modified polyimide.

[0079] This embodiment also provides a method for preparing an oral antibacterial composite polymer material, comprising the following steps:

[0080] Step 1. Weigh 7.5 parts of lignin and add 25 parts of alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water, the mass ratio of ethanol and water is 7:3, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1.5 mol / L, heat at a temperature of 70 ° C for 5h, and stir at a speed of 500r / min, then add 1.5 parts of epichlorohydrin and 0.1 parts of tetrabutylammonium bromide, continue heating at a temperature of 65 ° C for 4h, and stir at a speed of 500r / min, and ultrasonic time is 15min under the condition of an ultrasonic power of 80kHz to obtain activated lignin;

[0081] Step 2. Weigh 10 parts of the hydrogel modification and 5 parts of the polyimide modification into 30 parts of deionized water, add 0.5 parts of polyethylene glycol, stir at a speed of 500 r / min, continue to add 1 part of glutathione, heat treat at a temperature of 45 ° C for 60 min to obtain a homogeneous solution;

[0082] Step 3. The activated lignin obtained in step 1 was added to the homogenized solution obtained in step 2, 0.1 parts of glutaraldehyde and 0.05 parts of sodium cyanoborohydride were added thereto, citric acid solution was added to adjust the pH to 6.5, the concentration of the citric acid solution was 3 mol / L, argon was introduced at a flow rate of 500 mL / min and the reaction was stirred at a speed of 500 r / min for 1.5 h to obtain an oral antibacterial composite polymer material precursor;

[0083] Step 4. Weigh 0.1 parts of PAA, 0.2 parts of glycerol, 0.05 parts of menthol and 0.01 parts of potassium sorbate, add them to 30 parts of deionized water, stir at a speed of 500 r / min for 1.5 hours to obtain an improvement liquid, and slowly add the obtained improvement liquid to the oral antibacterial composite polymer material precursor. The ultrasonic time is 30 minutes under the condition of ultrasonic power of 20 kHz, and stirred at a speed of 500 r / min for 30 minutes. Filter using a 0.22 μm filter membrane, can and seal the liquid to obtain an oral antibacterial composite polymer material.

[0084] Comparative Example:

[0085] The difference between Comparative Example 1 and Example 2 is that no hydrogel modifier is added, and the rest of the process is the same as Example 2;

[0086] The difference between Comparative Example 2 and Example 2 is that no polyimide modification was added, and the rest of the components were the same as in Example 2.

[0087] The difference between Comparative Example 3 and Example 2 is that glutathione is not added, and the rest is the same as Example 2;

[0088] The difference between Comparative Example 4 and Comparative Example 5 is that no light is applied, which is the same as Part and Comparative Example 5;

[0089] Comparative Example 5 is a light-Fenton antibacterial test, and the raw materials for the preparation include 6.5 parts of lignin, 10 parts of hydrogel, 4 parts of polyimide, 1 part of ferric nitrate, 0.5 parts of sodium borate, 0.1 parts of PAA, 0.2 parts of glycerol, 0.04 parts of menthol and 0.01 parts of potassium sorbate.

[0090] The preparation method of oral antibacterial composite polymer material comprises the following steps:

[0091] Step 1. Weigh 6.5 parts of lignin and add 25 parts of alcohol solution, wherein the alcohol solution is a mixed solution of ethanol and water, the mass ratio of ethanol and water is 7:3, add 0.5 parts of sodium hydroxide lye, the concentration of sodium hydroxide lye is 1.5 mol / L, heat at a temperature of 70 ° C for 5h, and stir at a speed of 500r / min, then add 1.5 parts of epichlorohydrin and 0.1 parts of tetrabutylammonium bromide, continue heating at a temperature of 65 ° C for 4h, and stir at a speed of 500r / min, and ultrasonic time is 15min under the conditions of an ultrasonic power of 80kHz to obtain activated lignin;

[0092] Step 2. Weigh 10 parts of the hydrogel modifier and 4 parts of the polyimide modifier into 30 parts of deionized water, add 0.5 parts of polyethylene glycol, stir at a speed of 500 r / min, continue to add 1 part of glutathione, heat treat at a temperature of 45 ° C for 60 min to obtain a homogeneous solution;

[0093] Step 3. The activated lignin obtained in step 1 was added to the homogenized solution obtained in step 2, 0.1 parts of glutaraldehyde and 0.05 parts of sodium cyanoborohydride were added thereto, citric acid solution was added to adjust the pH to 6.5, the concentration of the citric acid solution was 3 mol / L, argon was introduced at a flow rate of 500 mL / min and the reaction was stirred at a speed of 500 r / min for 1.5 h to obtain an oral antibacterial composite polymer material precursor;

[0094] Step 4. Weigh 0.1 parts of PAA, 0.2 parts of glycerol, 0.04 parts of menthol and 0.01 parts of potassium sorbate, add them to 30 parts of deionized water, stir at a speed of 500 r / min for 1.5 hours to obtain an improvement liquid, and slowly add the obtained improvement liquid to the oral antibacterial composite polymer material precursor. The ultrasonic time is 30 minutes under the condition of ultrasonic power of 20 kHz, and stirred at a speed of 500 r / min for 30 minutes. Filter using a 0.22 μm filter membrane, can and seal the liquid to obtain an oral antibacterial composite polymer material.

[0095] Take a medical cotton piece, cut it into a uniform cotton piece of 1cm·1cm, evenly spray 3mL of nutrients required for bacterial reproduction, add 2 drops of bacterial solution on the cotton piece, then take the prepared oral antibacterial composite polymer material and evenly spray 3mL on the surface of the cotton piece, place it under suitable temperature conditions for growth for 24 hours, and calculate the antibacterial rate by plate counting method. The light condition is based on the light intensity of 2mW / cm 2The wavelength of the light wave is 420nm. It should be noted that the corresponding embodiments and comparative examples are all tested in a separate environment. The conditions of the second test are based on the first test, spraying 2mL of deionized water to ensure the wettability of the cotton surface, and adding 3mL of nutrients. Then, 2 drops of bacterial solution containing bacteria are added to the cotton sheet. The environment and conditions remain unchanged and continue to grow for 24h. Figure 2 The prepared oral antibacterial composite polymer material was used for antibacterial tests and secondary antibacterial tests on bacteria. The statistical results showed that the oral antibacterial composite polymer material prepared in the embodiment showed good antibacterial properties in single antibacterial tests, and the effect was better than the antibacterial properties of the comparative example. In addition, for the Fenton reaction, under the condition of adding light, the antibacterial properties were better than the comparative example without adding light. The statistical results of the secondary antibacterial performance test showed that the oral antibacterial composite polymer material prepared in the embodiment still showed high antibacterial properties, and there was no obvious change compared with the first antibacterial effect, indicating that the prepared oral antibacterial composite polymer material showed sustained antibacterial properties.

[0096] In order to further verify the biocompatibility of the prepared oral antibacterial composite polymer material, 8 rats (growth cycle 4-6 months, 180-200g) of half male and half female were selected. In three groups of examples, one male and one female were injected into each group, and 0.1 mL of oral antibacterial composite polymer material was injected once a day for a total of 7 injections. The body weight was recorded every five days. A blank control group was also prepared. According to the injection cycle of the above materials, physiological saline was injected and the rats were killed after 15 days to observe the organ lesions. Table 1 shows the statistical results of the body weight, respiratory rate and activity of the rats after injection of the oral antibacterial composite polymer material. It can be seen that the injection of the oral antibacterial composite polymer material prepared in the example did not significantly affect the body weight of the rats. At the same time, the respiratory rate and activity were normal, indicating that the prepared oral antibacterial composite polymer material did not cause toxic effects.

[0097] Table 1 shows the results of the experimental rats:

[0098]

[0099] Obviously, the above comparative examples and embodiments are only a part of the comparative examples and embodiments of the present invention, and they and the comparative examples and embodiments based on such references are all within the scope of protection of this invention.

[0100] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0101] The present invention and its embodiments are described above. Such description is not restrictive. The drawings show only one embodiment of the present invention, and actual applications are not limited thereto. In short, if a person skilled in the art is inspired by the above, and does not deviate from the purpose of the present invention, any method and embodiment similar to the technical solution without creative design shall fall within the scope of protection 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 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; The raw materials for preparing the polyimide modification include the following raw materials in the following weight ratios: polyimide: sodium diester alginate: 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 weighed sodium diester alginate was added to the oxidized polyimide, acid was added, EDC was added, heated and stirred 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 the 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 preparation method of the modified hydrogel comprises the following steps: A. Weighing a hydrogel, dimethylaminoethyl methacrylate, and camphorquinone, adding the mixture to water, stirring, 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, and 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.

3. A method for preparing an oral antibacterial composite polymer material according to any one of claims 1-2, characterized in that: The steps include: Step 1. Weigh lignin and add it to the 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 polyethylene glycol, stir, add glutathione, heat treat, and obtain a homogeneous solution; Step 3. Adding activated lignin to the homogenized liquid, adding glutaraldehyde and sodium cyanoborohydride, adding acid solution, and aerating the reaction to obtain an oral antibacterial composite polymer material precursor; Step 4. Weigh PAA, glycerol, menthol and potassium sorbate, add them to water, stir to obtain an improvement solution, add the improvement solution to the oral antibacterial composite polymer material precursor, sonicate and stir, filter, and seal to obtain the oral antibacterial composite polymer material.

4. The method for preparing an oral antibacterial composite polymer material according to claim 3, characterized in that: The alcohol solution in step 1 is a mixed solution of ethanol and water, with the mass ratio of ethanol to water being 7:

3. The ventilation gas in step 3 is argon.

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