Antibacterial high polymer material for toothbrush bristles and preparation method of antibacterial high polymer material

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses an antibacterial high polymer material for toothbrush bristles and a preparation method thereof.The antibacterial high polymer material is prepared from, by weight, 46-62 parts of nylon, 3-5 parts of a modified toughening agent, 8-10 parts of a functional antibacterial agent, 2-3 parts of maleic anhydride grafted POE, 0.3-0.5 part of an antioxidant and 0.4-0.8 part of a lubricating agent; the functional antibacterial agent and the modified toughening agent are added, the functional antibacterial agent is composed of a core-shell structure, a shell of the functional antibacterial agent is of a porous titanium dioxide structure modified by a modifier, an inner core of the functional antibacterial agent is methyl cinnamate, the surface of the modified toughening agent is grafted with sodium alginate and a flexible long-chain alkane structure, and through the synergistic effect of the structures, the antibacterial effect of the functional antibacterial agent is improved. The antibacterial property and the mechanical property of the material are improved.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and more specifically, to an antibacterial polymer material for toothbrush bristles and a preparation method thereof. Background Art

[0002] Oral hygiene is a major problem for people nowadays. Bad oral hygiene habits can lead to various oral inflammations. For this reason, people have developed various types of toothbrushes. Among them, nylon 6 is used as one of the main raw materials for toothbrush bristles because of its superior properties such as high hardness and wear resistance.

[0003] However, nylon 6 has a certain degree of water absorption. During use, it is difficult to completely remove the water. As the use time increases, a large number of bacteria will breed in the toothbrush bristles. After repeated use, it is easy to induce oral infection and affect health. In order to improve the antibacterial properties of toothbrush bristles, inorganic antibacterial agents are often added to the bristle raw materials in the prior art. However, the compatibility between inorganic antibacterial agents and nylon is poor, so that the inorganic antibacterial agents will continue to dissolve during the use of the toothbrush, which not only reduces the antibacterial properties of the material, but also reduces the mechanical properties of the prepared material.

[0004] Based on the above statements, the present application provides an antibacterial polymer material for toothbrush bristles and a preparation method thereof. Summary of the invention

[0005] In order to solve the problem in the prior art that inorganic antibacterial agents and nylon have poor compatibility, resulting in low antibacterial properties and poor mechanical properties of the prepared polymer material, the present application provides an antibacterial polymer material for toothbrush bristles and a preparation method thereof.

[0006] An antibacterial polymer material for toothbrush bristles, comprising the following raw materials in parts by weight: 46-62 parts of nylon, 3-5 parts of a modified toughening agent, 8-10 parts of a functionalized antibacterial agent, 2-3 parts of maleic anhydride grafted POE, 0.3-0.5 parts of an antioxidant, and 0.4-0.8 parts of a lubricant; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: mixing nylon, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant and lubricant in a high-speed mixer to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles.

[0007] Preferably, the antioxidant is antioxidant 1076 or antioxidant 1010.

[0008] Preferably, the lubricant is pentaerythritol stearate, oleamide or erucamide.

[0009] Preferably, in step S1, the stirring speed is 2500-3000 rpm, the stirring temperature is 210-220° C., and the stirring time is 15-20 min.

[0010] Preferably, in step S2, the extrusion process of the twin-screw extruder is: zone one 235-245°C, zone two 245-250°C, zone three 250-255°C, zone four 255-260°C, zone five 260-265°C, head temperature 265°C; screw speed 50-60rpm.

[0011] Preferably, the functionalized antibacterial agent is prepared by the following steps: Step A1, adding methyl cinnamate to anhydrous ethanol, adjusting the pH to 10-11, heating to 56-62°C and uniformly dispersing under ultrasonication, dripping a mixture of tetrabutyl titanate, urea and deionized water, controlling the dripping to be completed within 20 minutes, stirring for 18-22 minutes, adding sodium hydroxide aqueous solution, keeping warm and stirring for 1.2-1.6 hours, filtering, washing and drying after the reaction to obtain modified titanium dioxide; The mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 3-5:36-42:14-18:6-10, the mass ratio of tetrabutyl titanate, urea and deionized water in the mixed solution a is 10-12:1:60-70, and the concentration of the sodium hydroxide aqueous solution is 2-3M. In the above reaction process, anhydrous ethanol is used as a solvent and urea is used as a pore-forming agent to prepare a modified titanium dioxide with a core of methyl cinnamate and a shell of titanium dioxide and a porous structure; Step A2, adding modified titanium dioxide to anhydrous DMF, ultrasonically dispersing it uniformly, then adding a modifier and isocyanate propyl triethoxy silane, heating to 66-72°C, stirring and reacting for 8-10 hours, centrifuging, washing, and drying to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanate propyl triethoxy silane is 2.2-2.6:45-55:3.4-4.2:6-9. During the above reaction process, the active hydroxyl groups on the shell of the modified titanium dioxide can produce hydrogen bonds with the active hydroxyl groups on the modifier, and at the same time, the isocyanate groups on the isocyanate propyl triethoxy silane can chemically bond with the active hydroxyl groups on the modified titanium dioxide and the modifier. Through the above reaction, not only the compatibility of the modified titanium dioxide and the modifier is improved.

[0012] Preferably, the modifier is prepared by the following steps: Borax is added to dichloromethane, dopamine hydrochloride is added under nitrogen protection, stirred evenly, triethylamine is added, and a mixed solution b of dichloromethane, 4-dimethylaminopyridine and nicotinyl chloride hydrochloride is added dropwise under ice bath, and the dripping is controlled to be completed within 15 minutes. After the dripping is completed, the reaction is continued for 0.4-0.6 hours. After the reaction is completed, the mixture is kept at room temperature overnight, the pH is adjusted to 1-2, extracted, filtered, rotary evaporated, and dried to obtain a modifier, wherein borax, dichloromethane, dopamine hydrochloride, triethylamine and The mass ratio of the mixed liquid b is 3-4:80-100:1.6-2.4:0.3-0.5:36-44. In the mixed liquid b, the mass ratio of dichloromethane, 4-dimethylaminopyridine and nicotinyl chloride hydrochloride is 24-28:1.1-1.5:1.5-2.1. In the above reaction process, dichloromethane is used as a solvent and 4-dimethylaminopyridine is used as a catalyst. The active amino group on dopamine hydrochloride undergoes an amidation reaction with nicotinyl chloride hydrochloride to obtain a modifier.

[0013] Preferably, the modified toughening agent is prepared by the following steps: Step B1, add sodium alginate to deionized water, stir evenly, adjust the pH value to 8-9, then add a mixed solution c of epichlorohydrin and isopropanol, control the dripping within 10 minutes, after the dripping is completed, heat to 64-72 ° C, continue to stir for 4.2-5.4 hours, filter, then add 2-(dimethylamino)ethyl acetate, heat to 78-82 ° C, continue to react for 5.8-6.4 hours, after the reaction is completed, filter, wash, and dry to obtain functionalized sodium alginate, wherein the mass ratio of sodium alginate, deionized water, mixed solution c and 2-(dimethylamino)ethyl acetate is 5-7:100-120:26-30:3.2 -4.0, in the mixed solution c, the mass ratio of epichlorohydrin to isopropanol is 2-4:8-10, in the above steps, under alkaline conditions, the active hydroxyl groups on the sodium alginate undergo a ring-opening esterification reaction with epichlorohydrin, and the obtained substance then undergoes a nucleophilic substitution reaction with 2-(dimethylamino)ethyl acetate to obtain functionalized sodium alginate, in the process of preparing functionalized sodium alginate, 2-(dimethylamino)ethyl acetate is selected as a raw material, an ester group is introduced, and the hydrophobicity of sodium alginate is improved, and in the above reaction process, the amount of epichlorohydrin is controlled so that after the reaction is completed, there are still remaining hydroxyl groups on the sodium alginate that can participate in the subsequent process; Step B2, add functionalized sodium alginate to anhydrous DMF, stir evenly, adjust the pH value to 8-9, then drop a mixed solution d of octenyl succinic anhydride and isopropanol, control the dripping within 30 minutes, heat to 56-62 ° C, continue stirring and reacting for 5-6 hours, then add ethylene and azobisisobutyronitrile, heat to 72-76 ° C, continue stirring and reacting for 4-6 hours, adjust the pH value to 6.4-6.8, filter, wash, and dry to obtain a modified toughening agent, wherein the functionalized sodium alginate and anhydrous D The mass ratio of MF, mixed liquid d, ethylene and azobisisobutyronitrile is 4-6:55-65:24-30:2.4-2.8:0.06-0.1. In the mixed liquid d, the mass ratio of octenyl succinic anhydride and isopropanol is 2.8-3.2:20. In the above reaction process, the active hydroxyl groups on the functionalized sodium alginate can undergo a ring-opening esterification reaction with octenyl succinic anhydride, and the obtained substance continues to undergo a free radical polymerization reaction with ethylene under the initiator of azobisisobutyronitrile to obtain a modified toughening agent.

[0014] In summary, the present application has the following beneficial effects: in order to improve the antibacterial properties and mechanical properties of antibacterial polymer materials for toothbrush bristles, the present application starts from two aspects. First, a functionalized antibacterial agent is added. The functionalized antibacterial agent contains a porous titanium dioxide structure with an outer shell modified by a modifier, and the inner core is methyl cinnamate. The modifier contains a pyridine group, a dopamine-like structure and an isocyanate group with good antibacterial properties. The pyridine group and the dopamine-like structure have excellent antibacterial properties, which improve the antibacterial properties of the antibacterial polymer materials for toothbrush bristles. The isocyanate group can produce chemical bonds with the nylon substrate, which improves the compatibility of the functionalized antibacterial agent with the nylon substrate and improves the mechanical properties of the antibacterial polymer materials for toothbrush bristles. The porous titanium dioxide structure in the outer shell has a good antibacterial property. The titanium dioxide structure has excellent antibacterial properties, and the benzene ring on the methyl cinnamate on its core can produce π-π interaction with the benzene ring on the modifier, thereby improving the compatibility of porous titanium dioxide and further exerting its own good antibacterial properties, thereby improving the antibacterial properties and mechanical properties of the antibacterial polymer material for toothbrush bristles; secondly, a modified toughening agent is added, which, on the one hand, exerts the quaternary ammonium salt structure to further improve the antibacterial properties of the antibacterial polymer material for toothbrush bristles, and on the other hand, the surface of the modified toughening agent is grafted with sodium alginate and flexible long-chain alkane structures, which have high flexibility and good toughness. Introducing it into the modified toughening agent can synergize with the functional antibacterial agent to jointly improve the antibacterial properties and mechanical properties of the antibacterial polymer material for toothbrush bristles. DETAILED DESCRIPTION

[0015] In order to make the implementation methods of the present application easier to understand, the present application will be described in detail below in conjunction with specific examples. These examples are only for illustration and are not limited to the scope of application of the present application.

[0016] The contents of the main raw materials and their components used in the examples and comparative examples are as follows: The nylon used is food grade nylon 6 with brand number 1030B sold on behalf of Jiuju International Trading (Shanghai) Co., Ltd.

[0017] Preparation Examples 1-3 and Comparative Preparation Examples 1-2 provide a modified toughening agent.

[0018] Preparation Example 1 This preparation example provides a modified toughening agent, which is prepared by the following steps: Step B1, adding sodium alginate to deionized water, stirring at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH value to 8 with a 0.6M sodium hydroxide aqueous solution, and then adding a mixed solution c of epichlorohydrin and isopropanol, controlling the dripping within 10 minutes, and after the dripping, maintaining the speed unchanged, heating to 64°C, continuing to stir for 4.2 hours, filtering, and then adding 2-(dimethylamino)ethyl acetate, heating to 78°C, and continuing to react for 5.8 hours. After the reaction is completed, filtering, washing with anhydrous ethanol and deionized water for 3 times in sequence, and drying at 55°C to constant weight to obtain functionalized sodium alginate, wherein the mass ratio of sodium alginate, deionized water, mixed solution c and 2-(dimethylamino)ethyl acetate is 2:100:26:3.2, and the mass ratio of epichlorohydrin and isopropanol in the mixed solution c is 2:8; Step B2, add functionalized sodium alginate to anhydrous DMF, stir at a speed of 500 rpm for 12 minutes until uniform, adjust the pH value to 8 with 0.8M sodium hydroxide aqueous solution, and then add a mixed solution d of octenyl succinic anhydride and isopropanol, control the dripping within 30 minutes, heat to 56 ° C, maintain the speed unchanged, continue to stir and react for 5 hours, then add ethylene and azobisisobutyronitrile, heat to 72 ° C, continue to stir and react for 4 hours, adjust the pH value to 6.4, filter, wash with anhydrous ethanol and deionized water 3 times in sequence, and dry at 60 ° C to constant weight to obtain a modified toughening agent, wherein the mass ratio of functionalized sodium alginate, anhydrous DMF, mixed solution d, ethylene and azobisisobutyronitrile is 4:55:24:2.4:0.06, and the mass ratio of octenyl succinic anhydride and isopropanol in the mixed solution d is 2.8:20.

[0019] Preparation Example 2 This preparation example provides a modified toughening agent, which is prepared by the following steps: Step B1, add sodium alginate to deionized water, stir at a speed of 550rpm for 20min until uniform, adjust the pH value to 8.5 with 0.8M sodium hydroxide aqueous solution, then add a mixed solution c of epichlorohydrin and isopropanol, control the dripping within 10min, after the dripping is completed, heat to 68°C, maintain the speed unchanged, continue to stir for 4.8h, filter, then add 2-(dimethylamino)ethyl acetate, heat to 80°C, continue to react for 6.1h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 4 times in sequence, dry at 60°C to constant weight, and obtain functionalized sodium alginate, wherein the mass ratio of sodium alginate, deionized water, mixed solution c and 2-(dimethylamino)ethyl acetate is 6:110:28:3.6, and the mass ratio of epichlorohydrin and isopropanol in the mixed solution c is 3:9; Step B2, add functionalized sodium alginate to anhydrous DMF, stir at a speed of 600 rpm for 16 minutes until uniform, adjust the pH value to 8.5 with 1.0M sodium hydroxide aqueous solution, and then add a mixed solution d of octenyl succinic anhydride and isopropanol, control the dripping within 30 minutes, heat to 59 ° C, maintain the speed unchanged, continue to stir and react for 5.5 hours, then add ethylene and azobisisobutyronitrile, heat to 74 ° C, continue to stir and react for 5 hours, adjust the pH value to 6.6, filter, wash with anhydrous ethanol and deionized water 4 times in turn, and dry at 65 ° C to constant weight to obtain a modified toughening agent, wherein the mass ratio of functionalized sodium alginate, anhydrous DMF, mixed solution d, ethylene and azobisisobutyronitrile is 5:60:27:2.6:0.08, and the mass ratio of octenyl succinic anhydride and isopropanol in the mixed solution d is 3.0:20.

[0020] Preparation Example 3 This preparation example provides a modified toughening agent, which is prepared by the following steps: Step B1, adding sodium alginate to deionized water, stirring at a speed of 600 rpm for 24 minutes until uniform, adjusting the pH value to 9 with a 1M sodium hydroxide aqueous solution, and then adding a mixed solution c of epichlorohydrin and isopropanol, controlling the dripping to be completed within 10 minutes, heating to 72°C, maintaining the speed unchanged, continuing to stir for 5.4 hours, filtering, and then adding diethyl iminodiacetate, heating to 82°C, and continuing to react for 6.4 hours. After the reaction is completed, filtering, washing with anhydrous ethanol and deionized water for 5 times in sequence, and drying at 65°C to constant weight to obtain functionalized sodium alginate, wherein the mass ratio of sodium alginate, deionized water, mixed solution c and diethyl iminodiacetate is 4:120:30:4.0, and the mass ratio of epichlorohydrin and isopropanol in the mixed solution c is 4:10; Step B2, add functionalized sodium alginate to anhydrous DMF, stir at a speed of 700 rpm for 20 min until uniform, adjust the pH value to 9 with 1.2M sodium hydroxide aqueous solution, and then add a mixed solution d of octenyl succinic anhydride and isopropanol, control the dripping within 30 min, heat to 62 ° C, maintain the speed unchanged, continue stirring to react for 6 h, then add ethylene and azobisisobutyronitrile, heat to 76 ° C, continue stirring to react for 6 h, adjust the pH value to 6.8, filter, wash with anhydrous ethanol and deionized water 5 times in sequence, dry to constant weight at 70 ° C, and dry to obtain a modified toughening agent, wherein the mass ratio of functionalized sodium alginate, anhydrous DMF, mixed solution d, ethylene and azobisisobutyronitrile is 6:65:30:2.8:0.1, and the mass ratio of octenyl succinic anhydride and isopropanol in the mixed solution d is 3.2:20.

[0021] Comparative Preparation Example 1 This comparative preparation example provides a modified toughening agent, which is prepared by the following steps: Step B1, adding sodium alginate to deionized water, stirring at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH value to 8 with a 0.6M sodium hydroxide aqueous solution, and then adding a mixed solution c of epichlorohydrin and isopropanol, controlling the dripping within 10 minutes, maintaining the speed unchanged, heating to 64°C, continuing to stir for 4.2 hours, filtering, and then adding N, N-dimethylethanolamine, heating to 78°C, and continuing to react for 5.8 hours. After the reaction is completed, filtering, washing with anhydrous ethanol and deionized water for 3 times in sequence, and drying at 55°C to constant weight to obtain functionalized sodium alginate, wherein the mass ratio of sodium alginate, deionized water, mixed solution c and N, N-dimethylethanolamine is 5:100:26:3.2, and the mass ratio of epichlorohydrin and isopropanol in the mixed solution c is 2:8; Step B2, add functionalized sodium alginate to anhydrous DMF, stir at a speed of 500 rpm for 12 minutes until uniform, adjust the pH value to 8 with 0.8M sodium hydroxide aqueous solution, and then add a mixed solution d of octenyl succinic anhydride and isopropanol, control the dripping within 30 minutes, heat to 56 ° C, maintain the speed unchanged, continue to stir and react for 5 hours, then add ethylene and azobisisobutyronitrile, heat to 72 ° C, continue to stir and react for 4 hours, adjust the pH value to 6.4, filter, wash with anhydrous ethanol and deionized water 3 times in sequence, and dry at 60 ° C to constant weight to obtain a modified toughening agent, wherein the mass ratio of functionalized sodium alginate, anhydrous DMF, mixed solution d, ethylene and azobisisobutyronitrile is 4:55:24:2.4:0.06, and the mass ratio of octenyl succinic anhydride and isopropanol in the mixed solution d is 2.8:20.

[0022] Comparative Preparation Example 2 This comparative preparation example provides a modified toughening agent, which is prepared by the following steps: Step B1, adding sodium alginate to deionized water, stirring at a speed of 500 rpm for 16 minutes until uniform, adjusting the pH value to 8 with a 0.6M sodium hydroxide aqueous solution, and then adding a mixed solution c of epichlorohydrin and isopropanol, controlling the dripping within 10 minutes, and after the dripping, maintaining the speed unchanged, heating to 64°C, continuing to stir for 4.2 hours, filtering, and then adding 2-(dimethylamino)ethyl acetate, heating to 78°C, and continuing to react for 5.8 hours. After the reaction is completed, filtering, washing with anhydrous ethanol and deionized water for 3 times in sequence, and drying at 55°C to constant weight to obtain functionalized sodium alginate, wherein the mass ratio of sodium alginate, deionized water, mixed solution c and 2-(dimethylamino)ethyl acetate is 5:100:26:3.2, and the mass ratio of epichlorohydrin and isopropanol in the mixed solution c is 2:8; Step B2, add functionalized sodium alginate to anhydrous DMF, stir at a speed of 500 rpm for 12 minutes until uniform, adjust the pH value to 8 with 0.8M sodium hydroxide aqueous solution, and then add a mixed solution d of 2-methylsuccinic anhydride and isopropanol, control the dripping within 30 minutes, heat to 56 ° C, maintain the speed unchanged, continue to stir and react for 5 hours, then add ethylene and azobisisobutyronitrile, heat to 72 ° C, continue to stir and react for 4 hours, adjust the pH value to 6.4, filter, wash with anhydrous ethanol and deionized water 3 times in sequence, and dry at 60 ° C to constant weight to obtain a modified toughening agent, wherein the mass ratio of functionalized sodium alginate, anhydrous DMF, mixed solution d, ethylene and azobisisobutyronitrile is 4:55:24:2.4:0.06, and the mass ratio of 2-methylsuccinic anhydride and isopropanol in the mixed solution d is 2.8:20.

[0023] Preparation Examples 4-6 and Comparative Preparation Example 3 provide a modifier.

[0024] Preparation Example 4 This preparation example provides a modifier, which is prepared by the following steps: Borax was added to dichloromethane, and dopamine hydrochloride was added under nitrogen protection. The mixture was stirred at 650 rpm for 18 min until uniform. Triethylamine was added, and a mixture of dichloromethane, 4-dimethylaminopyridine and nicotinyl chloride hydrochloride was added dropwise under ice bath. The dripping was controlled to be completed within 15 min. After the dripping was completed, the speed was maintained unchanged and the reaction was continued for 0.4 h. After the reaction was completed, the mixture was kept at room temperature overnight, and the pH was adjusted to 1.0 with 12.2 M hydrochloric acid. The mixture was extracted three times, and the extracts were combined and dried with magnesium sulfate to remove moisture. The mixture was filtered and the rotary evaporation temperature was controlled to be 36°C. The dichloromethane was removed by rotary evaporation and the mixture was dried at 50°C to constant weight to obtain a modifier, wherein the mass ratio of borax, dichloromethane, dopamine hydrochloride, triethylamine and mixed solution b was 3:80:1.6:0.3:36, and the mass ratio of dichloromethane, 4-dimethylaminopyridine and nicotinoyl chloride hydrochloride in the mixed solution b was 24:1.1:1.5.

[0025] Preparation Example 5 This preparation example provides a modifier, which is prepared by the following steps: Borax was added to dichloromethane, and dopamine hydrochloride was added under nitrogen protection. The mixture was stirred at 700 rpm for 22 min until uniform. Triethylamine was added, and a mixture of dichloromethane, 4-dimethylaminopyridine and nicotinyl chloride hydrochloride was added dropwise under ice bath. The mixture was dripped within 15 min. After the dripping was completed, the rotation speed was maintained unchanged and the reaction was continued for 0.5 h. After the reaction was completed, the mixture was kept at room temperature overnight, and the pH was adjusted to 1.5 with 12.2 M hydrochloric acid. The mixture was extracted with ethyl acetate. Take 4 times, combine the extracts, dry with magnesium sulfate to remove moisture, filter, control the rotary evaporation temperature to 37°C, rotary evaporation to remove dichloromethane, and dry at 55°C to constant weight to obtain a modifier, wherein the mass ratio of borax, dichloromethane, dopamine hydrochloride, triethylamine and mixed solution b is 3.5:90:2.0:0.4:40, and the mass ratio of dichloromethane, 4-dimethylaminopyridine and nicotinoyl chloride hydrochloride in mixed solution b is 26:1.3:1.8.

[0026] Preparation Example 6 This preparation example provides a modifier, which is prepared by the following steps: Borax was added to dichloromethane, and dopamine hydrochloride was added under nitrogen protection. The mixture was stirred at 750 rpm for 26 min until uniform. Triethylamine was added, and a mixed solution b of dichloromethane, 4-dimethylaminopyridine and nicotinyl chloride hydrochloride was added dropwise under ice bath. The dripping was controlled to be completed within 15 min. After the dripping was completed, the speed was maintained unchanged and the reaction was continued for 0.6 h. After the reaction was completed, the mixture was kept at room temperature overnight, and the pH was adjusted to 2.0 with 12.0 M hydrochloric acid. The mixture was extracted with ethyl acetate. Take 5 times, combine the extracts, dry with magnesium sulfate to remove moisture, filter, control the rotary evaporation temperature to 40°C, rotary evaporation to remove dichloromethane, and dry at 60°C to constant weight to obtain a modifier, wherein the mass ratio of borax, dichloromethane, dopamine hydrochloride, triethylamine and mixed solution b is 4:100:2.4:0.5:44, and the mass ratio of dichloromethane, 4-dimethylaminopyridine and nicotinoyl chloride hydrochloride in the mixed solution b is 28:1.5:2.1.

[0027] Comparative Preparation Example 3 This comparative preparation example provides a modifier, which is prepared by the following steps: Borax was added to dichloromethane, and dopamine hydrochloride was added under nitrogen protection. The mixture was stirred at 650 rpm for 18 min until uniform. Triethylamine was added, and a mixed solution b of dichloromethane, 4-dimethylaminopyridine and 3-phenylpropionyl chloride was added dropwise under ice bath. The dripping was controlled to be completed within 15 min. After the dripping was completed, the speed was maintained unchanged and the reaction was continued for 0.4 h. After the reaction was completed, the mixture was kept at room temperature overnight, and the pH was adjusted to 1.0 with 12.2 M hydrochloric acid. The mixture was washed with ethyl acetate. The mixture was extracted three times, and the extracts were combined and dried with magnesium sulfate to remove moisture. The mixture was filtered and the rotary evaporation temperature was controlled to be 36°C. The dichloromethane was removed by rotary evaporation and the mixture was dried at 50°C to constant weight to obtain a modifier, wherein the mass ratio of borax, dichloromethane, dopamine hydrochloride, triethylamine and mixed solution b was 3:80:1.6:0.3:36, and the mass ratio of dichloromethane, 4-dimethylaminopyridine and 3-phenylpropionyl chloride in the mixed solution b was 24:1.1:1.5.

[0028] Preparation Examples 7-9 and Comparative Preparation Examples 4-6 provide a functionalized antibacterial agent.

[0029] Preparation Example 7 This preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: Step A1, add methyl cinnamate to anhydrous ethanol, adjust the pH to 10, heat to 56°C, control the ultrasonic frequency to 30kHz, the ultrasonic power to 450w, ultrasonic for 0.6h until uniform, drip tetrabutyl titanate, urea and deionized water mixed solution a, control the dripping to be completed within 20min, after the dripping is completed, stir at a speed of 650rpm for 18min, add 2M sodium hydroxide aqueous solution, keep warm, maintain the speed unchanged, stir and react for 1.2h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 3 times, and dry at 60°C to constant weight to obtain modified titanium dioxide, wherein the mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 3:36:14:6, and the mass ratio of tetrabutyl titanate, urea and deionized water in the mixed solution a is 10:1:60; Step A2, add modified titanium dioxide to anhydrous DMF, control the ultrasonic frequency to 40kHz, the ultrasonic power to 550w, and ultrasonicate for 1.2h until uniform, then add the modifier and isocyanatepropyltriethoxysilane prepared in Preparation Example 4, raise the temperature to 66°C, stir and react at a speed of 600rpm for 8h, centrifuge, wash with anhydrous ethanol and deionized water 3 times, and dry at 50°C to constant weight to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanatepropyltriethoxysilane is 2.2:45:3.4:6.

[0030] Preparation Example 8 This preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: Step A1, add methyl cinnamate to anhydrous ethanol, adjust the pH to 10.5, heat to 59°C, control the ultrasonic frequency to 35kHz, the ultrasonic power to 500w, ultrasonic for 0.8h until uniform, drip tetrabutyl titanate, urea and deionized water mixed solution a, control the dripping to be completed within 20min, after the dripping, stir at a speed of 700rpm for 20min, add 2.5M sodium hydroxide aqueous solution, keep warm, maintain the speed unchanged, stir and react for 1.4h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 4 times, and dry at 65°C to constant weight to obtain modified titanium dioxide, wherein the mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 4:39:16:8, and the mass ratio of tetrabutyl titanate, urea and deionized water in the mixed solution a is 11:1:65; Step A2, add modified titanium dioxide to anhydrous DMF, control the ultrasonic frequency to 35kHz, the ultrasonic power to 500w, and ultrasonicate for 1.4h until uniform, then add the modifier and isocyanatepropyltriethoxysilane prepared in Preparation Example 5, raise the temperature to 69°C, stir and react at a speed of 700rpm for 9h, centrifuge, wash with anhydrous ethanol and deionized water 4 times, and dry at 55°C to constant weight to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanatepropyltriethoxysilane is 2.4:50:3.8:7.5.

[0031] Preparation Example 9 This preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: Step A1, add methyl cinnamate to anhydrous ethanol, adjust the pH to 11, heat to 62°C, control the ultrasonic frequency to 40kHz, the ultrasonic power to 550w, ultrasonic for 1.0h until uniform, drip tetrabutyl titanate, urea and deionized water mixed solution a, control the dripping to be completed within 20min, after the dripping, stir at a speed of 700rpm for 22min, add 3M sodium hydroxide aqueous solution, keep warm, maintain the speed unchanged, stir and react for 1.6h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 5 times, and dry at 70°C to constant weight to obtain modified titanium dioxide, wherein the mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 5:42:18:10, and the mass ratio of tetrabutyl titanate, urea and deionized water in the mixed solution a is 12:1:0; Step A2, add modified titanium dioxide to anhydrous DMF, control the ultrasonic frequency to 30kHz, the ultrasonic power to 450w, and ultrasonicate for 1.6h until uniform, then add the modifier and isocyanatepropyltriethoxysilane prepared in Preparation Example 6, raise the temperature to 72°C, stir the reaction at a speed of 750rpm for 10h, centrifuge, wash with anhydrous ethanol and deionized water 5 times, and dry at 60°C to constant weight to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanatepropyltriethoxysilane is 2.6:55:4.2:9.

[0032] Comparative Preparation Example 4 This comparative preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: Step A1, add methyl cinnamate to anhydrous ethanol, adjust the pH to 10, heat to 56°C, control the ultrasonic frequency to 30kHz, the ultrasonic power to 450w, ultrasonic for 0.6h until uniform, drip tetrabutyl titanate, urea and deionized water mixed solution a, control the dripping to be completed within 20min, after the dripping is completed, stir at a speed of 650rpm for 18min, add 2M sodium hydroxide aqueous solution, keep warm, maintain the speed unchanged, stir and react for 1.2h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 3 times, and dry at 60°C to constant weight to obtain modified titanium dioxide, wherein the mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 3:36:14:6, and the mass ratio of tetrabutyl titanate, urea and deionized water in the mixed solution a is 10:1:60; Step A2, add modified titanium dioxide to anhydrous DMF, control the ultrasonic frequency to 40kHz, the ultrasonic power to 550w, and ultrasonicate for 1.2h until uniform, then add the modifier and isocyanatepropyltriethoxysilane prepared in Comparative Preparation Example 3, raise the temperature to 66°C, stir and react at a speed of 600rpm for 8h, centrifuge, wash with anhydrous ethanol and deionized water 3 times, and dry at 50°C to constant weight to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanatepropyltriethoxysilane is 2.2:45:3.4:6.

[0033] Comparative Preparation Example 5 This comparative preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: Step A1, add methyl benzoate to anhydrous ethanol, adjust the pH to 10, heat to 56°C, control the ultrasonic frequency to 30kHz, the ultrasonic power to 450w, ultrasonic for 0.6h until uniform, drip tetrabutyl titanate, urea and deionized water mixed solution a, control the dripping to be completed within 20min, after the dripping is completed, stir at a speed of 650rpm for 18min, add 2M sodium hydroxide aqueous solution, keep warm, maintain the speed unchanged, stir and react for 1.2h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 3 times, and dry at 60°C to constant weight to obtain modified titanium dioxide, wherein the mass ratio of methyl benzoate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 3:36:14:6, and the mass ratio of tetrabutyl titanate, urea and deionized water in the mixed solution a is 10:1:60; Step A2, add modified titanium dioxide to anhydrous DMF, control the ultrasonic frequency to 40kHz, the ultrasonic power to 550w, and ultrasonicate for 1.2h until uniform, then add the modifier and isocyanatepropyltriethoxysilane prepared in Preparation Example 4, raise the temperature to 66°C, stir and react at a speed of 600rpm for 8h, centrifuge, wash with anhydrous ethanol and deionized water 3 times, and dry at 50°C to constant weight to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanatepropyltriethoxysilane is 2.2:45:3.4:6.

[0034] Comparative Preparation Example 6 This comparative preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: This preparation example provides a functionalized antibacterial agent, which is prepared by the following steps: Step A1, add methyl cinnamate to anhydrous ethanol, adjust the pH to 10, heat to 56°C, control the ultrasonic frequency to 30kHz, the ultrasonic power to 450w, ultrasonic for 0.6h until uniform, drip tetrabutyl titanate, anhydrous ethanol and deionized water mixed solution a, control the dripping to be completed within 20min, after the dripping is completed, stir at a speed of 650rpm for 18min, add 2M sodium hydroxide aqueous solution, keep warm, maintain the speed unchanged, stir and react for 1.2h, after the reaction is completed, filter, wash with anhydrous ethanol and deionized water 3 times, and dry at 60°C to constant weight to obtain modified titanium dioxide, wherein the mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 3:36:14:6, and the mass ratio of tetrabutyl titanate, anhydrous ethanol and deionized water in the mixed solution a is 10:1:60; Step A2, add modified titanium dioxide to anhydrous DMF, control the ultrasonic frequency to 40kHz, the ultrasonic power to 550w, and ultrasonicate for 1.2h until uniform, then add the modifier and isocyanatepropyltriethoxysilane prepared in Preparation Example 4, raise the temperature to 66°C, stir and react at a speed of 600rpm for 8h, centrifuge, wash with anhydrous ethanol and deionized water 3 times, and dry at 50°C to constant weight to obtain a functionalized antibacterial agent, wherein the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanatepropyltriethoxysilane is 2.2:45:3.4:6.

[0035] Examples 1-3 and Comparative Examples 1-5 provide an antibacterial polymer material for toothbrush bristles and a preparation method thereof.

[0036] Example 1 This embodiment provides an antibacterial polymer material for toothbrush bristles, comprising the following raw materials in parts by weight: 46 parts of nylon 6, 3 parts of the modified toughening agent prepared in Preparation Example 1, 8 parts of the functionalized antibacterial agent prepared in Preparation Example 7, 2 parts of maleic anhydride grafted POE, 0.3 parts of antioxidant 1076 and 0.4 parts of pentaerythritol stearate; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and pentaerythritol stearate into a high-speed mixer, stirring at 2500 rpm and 210° C. for 15 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 235°C, zone 245°C, zone 3 250°C, zone 4 255°C, zone 5 260°C, die head temperature 265°C; screw speed 50rpm.

[0037] Example 2 This embodiment provides an antibacterial polymer material for toothbrush bristles, comprising the following raw materials in parts by weight: 54 parts of nylon 6, 4 parts of the modified toughening agent prepared in Preparation Example 2, 9 parts of the functionalized antibacterial agent prepared in Preparation Example 8, 2.5 parts of maleic anhydride grafted POE, 0.4 parts of antioxidant 1010 and 0.6 parts of oleic acid amide; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1010 and oleic acid amide into a high-speed mixer, stirring at 27500 rpm and 215° C. for 17 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 240°C, zone 248°C, zone 3 253°C, zone 4 257°C, zone 5 263°C, die head temperature 265°C; screw speed 55rpm.

[0038] Example 3 This embodiment provides an antibacterial polymer material for toothbrush bristles, comprising the following raw materials in parts by weight: 62 parts of nylon 6, 5 parts of the modified toughening agent prepared in Preparation Example 3, 10 parts of the functionalized antibacterial agent prepared in Preparation Example 9, 3 parts of maleic anhydride grafted POE, 0.5 parts of antioxidant 1076 and 0.8 parts of erucamide; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and erucic acid amide into a high-speed mixer, stirring at 3000 rpm and 220° C. for 20 min to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 245°C, zone 250°C, zone 3 255°C, zone 4 260°C, zone 5 265°C, die head temperature 265°C; screw speed 60rpm.

[0039] Comparative Example 1 This comparative example provides an antibacterial polymer material for toothbrush bristles and a preparation method thereof. The antibacterial polymer material for toothbrush bristles comprises the following raw materials in parts by weight: 46 parts of nylon 6, 3 parts of a modified toughening agent prepared in comparative preparation example 1, 8 parts of a functionalized antibacterial agent prepared in preparation example 7, 2 parts of maleic anhydride grafted POE, 0.3 parts of an antioxidant 1076, and 0.4 parts of pentaerythritol stearate; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and pentaerythritol stearate into a high-speed mixer, stirring at 2500 rpm and 210° C. for 15 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 235°C, zone 245°C, zone 3 250°C, zone 4 255°C, zone 5 260°C, die head temperature 265°C; screw speed 50rpm.

[0040] Comparative Example 2 This comparative example provides an antibacterial polymer material for toothbrush bristles and a preparation method thereof. The antibacterial polymer material for toothbrush bristles comprises the following raw materials in parts by weight: 46 parts of nylon 6, 3 parts of a modified toughening agent prepared in comparative preparation example 2, 8 parts of a functionalized antibacterial agent prepared in preparation example 7, 2 parts of maleic anhydride grafted POE, 0.3 parts of an antioxidant 1076, and 0.4 parts of pentaerythritol stearate; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and pentaerythritol stearate into a high-speed mixer, stirring at 2500 rpm and 210° C. for 15 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 235°C, zone 245°C, zone 3 250°C, zone 4 255°C, zone 5 260°C, die head temperature 265°C; screw speed 50rpm.

[0041] Comparative Example 3 This comparative example provides an antibacterial polymer material for toothbrush bristles and a preparation method thereof. The antibacterial polymer material for toothbrush bristles comprises the following raw materials in parts by weight: 46 parts of nylon 6, 3 parts of a modified toughening agent prepared in Preparation Example 1, 8 parts of a functionalized antibacterial agent prepared in Comparative Preparation Example 4, 2 parts of maleic anhydride grafted POE, 0.3 parts of an antioxidant 1076, and 0.4 parts of pentaerythritol stearate; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and pentaerythritol stearate into a high-speed mixer, stirring at 2500 rpm and 210° C. for 15 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 235°C, zone 245°C, zone 3 250°C, zone 4 255°C, zone 5 260°C, die head temperature 265°C; screw speed 50rpm.

[0042] Comparative Example 4 This comparative example provides an antibacterial polymer material for toothbrush bristles and a preparation method thereof. The antibacterial polymer material for toothbrush bristles comprises the following raw materials in parts by weight: 46 parts of nylon 6, 3 parts of a modified toughening agent prepared in Preparation Example 1, 8 parts of a functionalized antibacterial agent prepared in Comparative Preparation Example 5, 2 parts of maleic anhydride grafted POE, 0.3 parts of an antioxidant 1076, and 0.4 parts of pentaerythritol stearate; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and pentaerythritol stearate into a high-speed mixer, stirring at 2500 rpm and 210° C. for 15 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 235°C, zone 245°C, zone 3 250°C, zone 4 255°C, zone 5 260°C, die head temperature 265°C; screw speed 50rpm.

[0043] Comparative Example 5 This comparative example provides an antibacterial polymer material for toothbrush bristles, comprising the following raw materials in parts by weight: 46 parts of nylon 6, 3 parts of the modified toughening agent prepared in Preparation Example 1, 8 parts of the functionalized antibacterial agent prepared in Comparative Preparation Example 6, 2 parts of maleic anhydride grafted POE, 0.3 parts of antioxidant 1076 and 0.4 parts of pentaerythritol stearate; The method for preparing the antibacterial polymer material for toothbrush bristles comprises the following steps: Step S1, mixing: adding nylon 6, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant 1076 and pentaerythritol stearate into a high-speed mixer, stirring at 2500 rpm and 210° C. for 15 minutes to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles, wherein the extrusion process of the twin-screw extruder is: zone 1 235°C, zone 245°C, zone 3 250°C, zone 4 255°C, zone 5 260°C, die head temperature 265°C; screw speed 50rpm.

[0044] Performance Testing 1. Antibacterial rate: The test was conducted according to the provisions of Appendix B of GB / T 21510-2008 "Test Method for Antibacterial Performance of Nano-inorganic Materials"; 107 cfu / mL bacterial solution was prepared with Escherichia coli and Staphylococcus aureus, 1.00 g of the antibacterial polymer material prepared in Examples 1-3 and Comparative Examples 1-5 and 5 mL of the bacterial solution were added to a shaking flask, and the viable bacteria were counted after curing at 25°C for 10 hours, and the sterilization rate was calculated; in addition, the antibacterial polymer material prepared in Examples 1-3 and Comparative Examples 1-5 was immersed in a 10wt% sucrose solution for 3 minutes every day, and then rinsed with tap water for 1 minute, and the sterilization rate was calculated after 120 days; the test results are shown in Table 1; 2. Mechanical properties: The tensile strength and elongation at break of the antibacterial polymer materials prepared in Examples 1-3 and Comparative Examples 1-5 of the present application were tested according to the GB / T1040.1-2006 test standard, and the bending modulus of the antibacterial polymer materials prepared in Examples 1-3 and Comparative Examples 1-5 of the present application was tested according to the GB / T 9341-2008 test standard. The test results are shown in Table 1; Table 1 Antibacterial and tensile properties test of antibacterial polymer materials

[0045] It can be seen from Table 1 that, compared with Comparative Examples 1-5, the antibacterial polymer materials prepared in Examples 1-3 have more excellent antibacterial properties and mechanical properties.

[0046] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. An antibacterial polymer material for toothbrush bristles, characterized in that: The invention comprises the following raw materials in parts by weight: 46-62 parts of nylon, 3-5 parts of modified toughening agent, 8-10 parts of functionalized antibacterial agent, 2-3 parts of maleic anhydride grafted POE, 0.3-0.5 parts of antioxidant and 0.4-0.8 parts of lubricant; The modified toughening agent is firstly prepared by reacting sodium alginate with epichlorohydrin through a ring-opening esterification reaction, then reacting with 2-(dimethylamino)ethyl acetate through a nucleophilic substitution reaction to obtain functionalized sodium alginate, then reacting with octenyl succinic anhydride through a ring-opening esterification reaction, and finally reacting with ethylene through a free radical polymerization reaction to obtain the modified toughening agent; The functional antibacterial agent is prepared by hydrolyzing tetrabutyl titanate under alkaline conditions, coating methyl cinnamate to obtain modified titanium dioxide, and then chemically bonding with a modifier and isocyanate propyl triethoxysilane; The modifier is prepared by amidation reaction of dopamine hydrochloride and nicotinyl hydrochloride chloride.

2. The antibacterial polymer material for toothbrush bristles according to claim 1, characterized in that: The functionalized antibacterial agent is prepared by the following steps: Step A1, adding methyl cinnamate to anhydrous ethanol, adjusting the pH to 10-11, heating to 56-62°C and uniformly dispersing under ultrasonication, dripping a mixture of tetrabutyl titanate, urea and deionized water, controlling the dripping to be completed within 20 minutes, stirring for 18-22 minutes, adding sodium hydroxide aqueous solution, keeping warm and stirring for 1.2-1.6 hours, filtering, washing and drying after the reaction to obtain modified titanium dioxide; Step A2, adding modified titanium dioxide into anhydrous DMF, uniformly dispersing by ultrasonication, then adding modifier and isocyanatepropyltriethoxysilane, heating to 66-72° C., stirring for reaction for 8-10 hours, centrifuging, washing, and drying to obtain a functionalized antibacterial agent.

3. The antibacterial polymer material for toothbrush bristles according to claim 2, characterized in that: In the step A1, the mass ratio of methyl cinnamate, anhydrous ethanol, mixed solution a and sodium hydroxide aqueous solution is 3-5:36-42:14-18:6-10, in the mixed solution a, the mass ratio of tetrabutyl titanate, urea and deionized water is 10-12:1:60-70, and the concentration of the sodium hydroxide aqueous solution is 2-3M.

4. The antibacterial polymer material for toothbrush bristles according to claim 2, characterized in that: In the step A2, the mass ratio of modified titanium dioxide, anhydrous DMF, modifier and isocyanate propyl triethoxysilane is 2.2-2.6:45-55:3.4-4.2:6-9.

5. The antibacterial polymer material for toothbrush bristles according to claim 1, characterized in that: The modifying agent is prepared by the following steps: Add borax to dichloromethane, add dopamine hydrochloride under nitrogen protection, stir evenly, add triethylamine, and under ice bath, dropwise add a mixture B of dichloromethane, 4-dimethylaminopyridine and nicotinyl chloride hydrochloride, and control the dropwise addition within 15 minutes. After the dropwise addition is completed, continue the reaction for 0.4-0.6 hours. After the reaction is completed, keep at room temperature overnight, adjust the pH to 1-2, extract, filter, rotary evaporate, and dry to obtain the modifier.

6. The antibacterial polymer material for toothbrush bristles according to claim 5, characterized in that: The mass ratio of borax, dichloromethane, dopamine hydrochloride, triethylamine and mixed solution b is 3-4:80-100:1.6-2.4:0.3-0.5:36-44. In the mixed solution b, the mass ratio of dichloromethane, 4-dimethylaminopyridine and nicotinoyl chloride hydrochloride is 24-28: 1.1-1.5：1.5-2.1。 7. The antibacterial polymer material for toothbrush bristles according to claim 1, characterized in that: The modified toughening agent is prepared by the following steps: Step B1, adding sodium alginate to deionized water, stirring evenly, adjusting the pH value to 8-9, then adding a mixed solution c of epichlorohydrin and isopropanol, controlling the dripping to be completed within 10 minutes, after the dripping is completed, heating to 64-72° C., continuing to stir for 4.2-5.4 hours, filtering, then adding 2-(dimethylamino)ethyl acetate, heating to 78-82° C., continuing to react for 5.8-6.4 hours, after the reaction is completed, filtering, washing, and drying to obtain functionalized sodium alginate; Step B2, add functionalized sodium alginate to anhydrous DMF, stir evenly, adjust the pH value to 8-9, then add a mixed solution d of octenyl succinic anhydride and isopropanol dropwise, control the dripping within 30 minutes, raise the temperature to 56-62 ° C, continue stirring and reacting for 5-6 hours, then add ethylene and azobisisobutyronitrile, raise the temperature to 72-76 ° C, continue stirring and reacting for 4-6 hours, adjust the pH value to 6.4-6.8, filter, wash, and dry to obtain a modified toughening agent.

8. The antibacterial polymer material for toothbrush bristles according to claim 7, characterized in that: In the step B1, the mass ratio of sodium alginate, deionized water, mixed solution c and 2-(dimethylamino)ethyl acetate is 5-7:100-120:26-30:3.2-4.0, and in the mixed solution c, the mass ratio of epichlorohydrin and isopropanol is 2-4:8-10.

9. The antibacterial polymer material for toothbrush bristles according to claim 7, characterized in that: In the step B2, the mass ratio of functionalized sodium alginate, anhydrous DMF, mixed solution d, ethylene and azobisisobutyronitrile is 4-6:55-65:24-30:2.4-2.8:0.06-0.1, and in the mixed solution d, the mass ratio of octenylsuccinic anhydride and isopropanol is 2.8-3.2:

20.

10. A method for preparing the antibacterial polymer material for toothbrush bristles according to any one of claims 1 to 9, characterized in that: The following steps are involved: Step S1, mixing: mixing nylon, functionalized antibacterial agent, modified toughening agent, maleic anhydride grafted POE, antioxidant and lubricant in a high-speed mixer to obtain a mixture; Step S2, extrusion: feeding the mixed material into a twin-screw extruder and extruding it through a die head to obtain an antibacterial polymer material for toothbrush bristles.

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