阅读说明：本技术 一种基于石墨烯的复合抗菌材料及其制备方法 (Graphene-based composite antibacterial material and preparation method thereof ) 是由 刘雪琴 刘平莉 于 2021-08-27 设计创作，主要内容包括：本发明公开了一种基于石墨烯的复合抗菌材料及其制备方法,该复合抗菌材料通过改性石墨烯与抗菌增强剂反应,使得改性石墨烯表面包覆一层网格状抗菌增强剂分子,再进行氯化处理,使得抗菌增强剂分子上的仲胺氯化,制得复合抗菌材料,该复合抗菌材料具有多层杀菌层,能够有效的破坏细菌细胞膜,使细菌蛋白质变性,阻碍细菌代谢,进而杀死细菌,且该复合抗菌材料的杀菌层,均以化学键连接,使得复合抗菌材料中的抗菌成分不会出现析出、挥发、颗粒物脱落的现象,大大增长了复合抗菌材料的使用寿命,同时不需要使用纳米银材料,大大降低了复合抗菌材料的制备成本。(The invention discloses a graphene-based composite antibacterial material and a preparation method thereof, the composite antibacterial material is prepared by reacting modified graphene with an antibacterial reinforcing agent, coating a layer of latticed antibacterial reinforcing agent molecules on the surface of the modified graphene, and then performing chlorination treatment to chlorinate secondary amine on the antibacterial reinforcing agent molecules to prepare the composite antibacterial material, the composite antibacterial material has multiple sterilization layers, can effectively destroy bacterial cell membranes, denatures bacterial proteins, hinders bacterial metabolism, further killing bacteria, and the sterilization layer of the composite antibacterial material is connected by chemical bonds, so that the phenomena of precipitation, volatilization and particle shedding of antibacterial components in the composite antibacterial material can be avoided, the service life of the composite antibacterial material is greatly prolonged, meanwhile, a nano silver material is not needed, so that the preparation cost of the composite antibacterial material is greatly reduced.)

1. The composite antibacterial material based on graphene is characterized in that: prepared by reacting modified graphene with an antibacterial reinforcing agent;

the modified graphene is prepared by the following steps:

step A1: uniformly mixing graphite, sodium nitrate and concentrated sulfuric acid, adding potassium permanganate, heating and stirring, heating and preserving heat after stirring, adding deionized water, continuing heating and preserving heat, adding hydrogen peroxide after heat preservation is finished, and stirring to prepare graphene oxide;

step A2: dispersing graphene oxide in deionized water, dropwise adding a chitosan solution and 1-hydroxybenzotriazole, reacting, filtering, drying a filter cake to obtain pre-modified graphene, dispersing the pre-modified graphene in an acetic acid solution, stirring, adding epichlorohydrin, adjusting the pH value of a reaction solution, and reacting to obtain the modified graphene.

2. The graphene-based composite antibacterial material and the preparation method thereof according to claim 1, wherein the graphene-based composite antibacterial material is characterized in that: the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 1g to 0.5g to 25mL to 3g to 120mL to 2.5 mL.

3. The graphene-based composite antibacterial material and the preparation method thereof according to claim 1, wherein the graphene-based composite antibacterial material is characterized in that: the dosage ratio of the graphene oxide, the chitosan solution and the 1-hydroxybenzotriazole in the step A2 is 0.01g to 100mL to 0.02g, and the dosage mass ratio of the pre-modified graphene to the propylene oxide is 0.5 to 1.2.

4. The graphene-based composite antibacterial material and the preparation method thereof according to claim 1, wherein the graphene-based composite antibacterial material is characterized in that: the antibacterial reinforcing agent is prepared by the following steps:

step B1: adding dimethylaminoethanol, methyl methacrylate, hydroquinone and tetrabutyl titanate into a reaction kettle for reaction to prepare an intermediate 1, and adding the intermediate 1, acetonitrile, hydroquinone and bromohexadecane into the reaction kettle for reaction to prepare an intermediate 2;

step B2: adding chloropropene and acetone into a reaction kettle, stirring, adding 2,2,6, 6-tetramethyl piperidinol, adjusting the pH value of a reaction solution, reacting to obtain an intermediate 3, adding the intermediate 2, the intermediate 3, vinyl acetate and deionized water into the reaction kettle, stirring, adding an ammonium persulfate solution, and reacting to obtain an intermediate 4;

step B3: dissolving the intermediate 4 in N, N-dimethylformamide, adding sodium hydroxide and ethanol for reaction to obtain an intermediate 5, adding toluene-3, 5-diisocyanate, deionized water and potassium permanganate into a reaction kettle, performing reflux reaction to obtain an intermediate 6, adding the intermediate 5, the intermediate 6, toluene and potassium carbonate into the reaction kettle, and performing reaction to obtain the antibacterial reinforcing agent.

5. The graphene-based composite antibacterial material and the preparation method thereof according to claim 4, wherein the graphene-based composite antibacterial material is characterized in that: the dosage ratio of the dimethylaminoethanol, the methyl methacrylate, the hydroquinone and the tetrabutyl titanate in the step B1 is 0.5mol:1.5mol:4mmol:0.03mol, and the dosage ratio of the intermediate 1, the acetonitrile, the hydroquinone and the bromohexadecane is 0.05mol:30mL:4mmol:0.05 mol.

6. The graphene-based composite antibacterial material and the preparation method thereof according to claim 4, wherein the graphene-based composite antibacterial material is characterized in that: the using amount molar ratio of the chloropropene and the 2,2,6, 6-tetramethyl piperidinol in the step B2 is 1:1, and the using amount ratio of the intermediate 2, the intermediate 3, the vinyl acetate, the deionized water and the ammonium sulfate solution is 0.01:0.01:0.01:50mL:10 mL.

7. The graphene-based composite antibacterial material and the preparation method thereof according to claim 4, wherein the graphene-based composite antibacterial material is characterized in that: the dosage ratio of the intermediate 4, the sodium hydroxide and the ethanol in the step B3 is 3g:0.04g:2mL, the dosage ratio of the toluene-3, 5-diisocyanate, the deionized water and the potassium permanganate is 3g:100mL:5g, and the dosage molar ratio of the intermediate 5, the intermediate 6 and the potassium carbonate is 3:1: 1.

8. The preparation method of the graphene-based composite antibacterial material according to claim 1, characterized by comprising the following steps: the method specifically comprises the following steps:

step S1: dispersing modified graphene in N, N-dimethylformamide, adding an antibacterial reinforcing agent and 4-dimethylaminopyridine, reacting, filtering to remove filtrate, and drying a filter cake;

step S2: and soaking the filter cake in a sodium hypochlorite solution, adjusting the pH value to 7, soaking, filtering and drying to obtain the composite antibacterial material.

Technical Field

The invention relates to the technical field of preparation of antibacterial materials, and particularly relates to a graphene-based composite antibacterial material and a preparation method thereof.

Background

The antibacterial agent can be divided into an organic antibacterial agent, a natural antibacterial agent and an inorganic antibacterial agent according to different structures, the three antibacterial agents have the characteristics of good sterilization effect, low price, poor safety and serious environmental pollution, the natural antibacterial agent has high safety and small environmental pollution, but poor heat resistance and durability, the inorganic antibacterial agent has the excellent characteristics of high durability, good heat resistance, difficult generation of drug resistance, high safety and the like, and the antibacterial agent has wide development space and application potential in the fields of biological medicine, air purification, building coatings, clothes, ceramics, sanitary kitchenware and the like;

graphene is a single-layer sheet-shaped two-dimensional material composed of carbon atoms, the carbon atoms of the graphene form a hexagonal honeycomb-shaped planar structure by sp2 hybrid orbitals, and the graphene has the excellent characteristics of high specific surface area, outstanding mechanical property, heat conductivity, high-efficiency electron transfer property and the like, and recent researches show that: the layered structure of the graphene can directly pierce the cell membrane of bacteria to cause the leakage of bacteria content and cause the death of the bacteria content, and the graphene has small cytotoxicity to mammals, so that the graphene composite antibacterial material gradually enters the visual field of people, the existing composite antibacterial material has poor durability and high production cost, and the market popularization of the composite antibacterial material is greatly hindered.

Disclosure of Invention

The composite antibacterial material is prepared by reacting modified graphene with an antibacterial reinforcing agent, so that the problems that an organic antibacterial agent is volatile and easy to separate out at the present stage are solved, the use of a nano-silver material is avoided, and the preparation cost of the composite antibacterial material is reduced.

The purpose of the invention can be realized by the following technical scheme:

a composite antibacterial material based on graphene is prepared by reacting modified graphene with an antibacterial reinforcing agent;

the modified graphene is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring for 20-30min at the rotation speed of 150-;

step A2: dispersing graphene oxide in deionized water, dropwise adding a chitosan solution and 1-hydroxybenzotriazole, reacting for 3-5h at the rotation speed of 300-50 ℃ for 3-5h, filtering, drying a filter cake to obtain pre-modified graphene, dispersing the pre-modified graphene in an acetic acid solution, stirring and adding epoxy chloropropane at the rotation speed of 150-200r/min and the temperature of 35-45 ℃, adjusting the pH value of a reaction solution to 9-10, and reacting for 1-3h to obtain the modified graphene.

Further, the using amount ratio of the graphite, the sodium nitrate, the concentrated sulfuric acid, the potassium permanganate, the deionized water and the hydrogen peroxide in the step A1 is 1g to 0.5g to 25mL to 3g to 120mL to 2.5mL, the mass fraction of the concentrated sulfuric acid is 98%, and the mass fraction of the hydrogen peroxide is 30%.

Further, the dosage ratio of the graphene oxide, the chitosan solution and the 1-hydroxybenzotriazole in the step A2 is 0.01g:100mL:0.02g, the mass fraction of the chitosan solution is 0.5%, the dosage mass ratio of the pre-modified graphene and the propylene oxide is 0.5:1.2, and the mass fraction of the acetic acid solution is 2%.

Further, the antibacterial reinforcing agent is prepared by the following steps:

step B1: adding dimethylaminoethanol, methyl methacrylate, hydroquinone and tetrabutyl titanate into a reaction kettle, reacting for 4-6h at the rotation speed of 150-200r/min and the temperature of 60-65 ℃ to obtain an intermediate 1, adding the intermediate 1, acetonitrile, hydroquinone and bromohexadecane into the reaction kettle, and reacting for 10-15h at the rotation speed of 150-200r/min and the temperature of 45-50 ℃ to obtain an intermediate 2;

the reaction process is as follows:

step B2: adding chloropropene and acetone into a reaction kettle, stirring and adding 2,2,6, 6-tetramethylpiperidinol under the conditions of a rotation speed of 120-5 ℃ and a temperature of 0-5 ℃, adjusting the pH value of a reaction solution to 7-8, reacting for 3-5h to prepare an intermediate 3, adding the intermediate 2, the intermediate 3, vinyl acetate and deionized water into the reaction kettle, stirring for 20-30min under the conditions of a rotation speed of 200-300r/min, adding an ammonium persulfate solution, and reacting for 1-1.5h under the conditions of 80-90 ℃ to prepare an intermediate 4;

the reaction process is as follows:

step B3: dissolving the intermediate 4 in N, N-dimethylformamide, adding sodium hydroxide and ethanol, reacting for 1-1.5h at the rotation speed of 150-200r/min and the temperature of 30-35 ℃ to obtain an intermediate 5, adding toluene-3, 5-diisocyanate, deionized water and potassium permanganate into a reaction kettle, refluxing for 2-3h at the temperature of 110-120 ℃ to obtain an intermediate 6, adding the intermediate 5, the intermediate 6, toluene and potassium carbonate into the reaction kettle, and reacting for 3-5h at the rotation speed of 120-150r/min and the temperature of 50-60 ℃ to obtain the antibacterial enhancer.

The reaction process is as follows:

furthermore, the dosage ratio of the dimethylaminoethanol, the methyl methacrylate, the hydroquinone and the tetrabutyl titanate in the step B1 is 0.5mol:1.5mol:4mmol:0.03mol, and the dosage ratio of the intermediate 1, the acetonitrile, the hydroquinone and the bromohexadecane is 0.05mol:30mL:4mmol:0.05 mol.

Further, the dosage molar ratio of the chloropropene and the 2,2,6, 6-tetramethylpiperidinol in the step B2 is 1:1, and the dosage ratio of the intermediate 2, the intermediate 3, the vinyl acetate, the deionized water and the ammonium sulfate solution is 0.01:0.01:0.01:50mL:10 mL.

Further, the dosage ratio of the intermediate 4, sodium hydroxide and ethanol in the step B3 is 3g:0.04g:2mL, the dosage ratio of the toluene-3, 5-diisocyanate, the deionized water and the potassium permanganate is 3g:100mL:5g, and the dosage molar ratio of the intermediate 5, the intermediate 6 and the potassium carbonate is 3:1: 1.

The preparation method of the graphene-based composite antibacterial material specifically comprises the following steps:

step S1: dispersing modified graphene in N, N-dimethylformamide, adding an antibacterial reinforcing agent and 4-dimethylaminopyridine, reacting for 5-8h at the rotation speed of 200-300r/min and the temperature of 100-120 ℃, filtering to remove filtrate, and drying a filter cake;

step S2: and soaking the filter cake in a sodium hypochlorite solution, adjusting the pH value to 7, soaking for 1-1.5h, filtering and drying to obtain the composite antibacterial material.

Further, the using amount ratio of the modified graphene, the N, N-dimethylformamide, the antibacterial reinforcing agent and the 4-dimethylaminopyridine in the step S1 is 1g:80mL:3g:6g, and the mass fraction of the sodium hypochlorite solution in the step S2 is 5%.

The invention has the following beneficial effects:

the composite antibacterial material based on graphene is prepared by reacting modified graphene with an antibacterial reinforcing agent, wherein the modified graphene is prepared by oxidizing graphite serving as a raw material to convert active hydroxyl on the surface of the graphene into carboxyl to prepare graphene oxide, then the graphene oxide is reacted with chitosan to perform dehydration condensation on the carboxyl on the surface of the graphene oxide and amino on the chitosan to prepare the modified graphene, the pre-modified graphene is treated by epichlorohydrin, the epoxy group of one epichlorohydrin molecule is subjected to ring opening reaction with the hydroxyl on one chitosan molecule on the surface of the modified graphene, the chlorine atom site of the epichlorohydrin is subjected to reaction with the hydroxyl on the other chitosan molecule to perform crosslinking reaction on the chitosan on the surface of the modified graphene to coat a layer of chitosan film on the surface of the modified graphene, and the antibacterial reinforcing agent is prepared by reacting dimethylaminoethanol and methyl methacrylate serving as raw materials, preparing an intermediate 1, reacting the intermediate 1 with bromohexadecane to prepare an intermediate 2, reacting chloropropene with 2,2,6, 6-tetramethylpiperidinol to prepare an intermediate 3, polymerizing the intermediate 2, the intermediate 3 and vinyl acetate to prepare an intermediate 4, carrying out alcoholysis on the intermediate 4 to prepare an intermediate 5, oxidizing toluene-3, 5-diisocyanate by potassium permanganate to oxidize methyl into carboxyl, reacting the intermediate 5 with the intermediate 6 to react isocyanate ester on the intermediate 6 with hydroxyl on the intermediate 5 to prepare an antibacterial reinforcing agent, reacting the modified graphene with the antibacterial reinforcing agent to carry out esterification reaction on the carboxyl on the antibacterial reinforcing agent and the hydroxyl on the surface of the modified graphene so as to coat a layer of latticed antibacterial reinforcing agent molecules on the surface of the modified graphene, chlorination is carried out again, secondary amine on the molecules of the antibacterial reinforcing agent is chlorinated, a composite antibacterial material is prepared, the composite antibacterial material is provided with a plurality of sterilization layers, the bacterial cell membranes can be effectively damaged, bacterial protein is denatured, bacterial metabolism is hindered, bacteria are killed, the sterilization layers of the composite antibacterial material are connected by chemical bonds, the antibacterial ingredients in the composite antibacterial material can not be separated out, volatilized, and the particles fall off, the service life of the composite antibacterial material is greatly prolonged, meanwhile, a nano-silver material is not needed to be used, and the preparation cost of the composite antibacterial material is greatly reduced.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A graphene-based composite antibacterial material comprises the following steps:

step S1: dispersing modified graphene in N, N-dimethylformamide, adding an antibacterial reinforcing agent and 4-dimethylaminopyridine, reacting for 5 hours at the rotation speed of 200r/min and the temperature of 100 ℃, filtering to remove filtrate, and drying a filter cake;

step S2: and soaking the filter cake in a sodium hypochlorite solution, adjusting the pH value to 7, soaking for 1h, filtering and drying to obtain the composite antibacterial material.

The modified graphene is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring for 20min at the rotation speed of 150r/min and the temperature of 0 ℃, adding potassium permanganate, heating to 10 ℃, continuing stirring for 1h, heating to 35 ℃, keeping the temperature for 20min, adding deionized water, heating to 95 ℃, keeping the temperature for 10min, adding hydrogen peroxide, and stirring for 3min to obtain graphene oxide;

step A2: dispersing graphene oxide in deionized water, dropwise adding a chitosan solution and 1-hydroxybenzotriazole, reacting for 3 hours at the rotation speed of 300r/min and the temperature of 40 ℃, filtering, drying a filter cake to obtain pre-modified graphene, dispersing the pre-modified graphene in an acetic acid solution, stirring and adding epoxy chloropropane at the rotation speed of 150r/min and the temperature of 35 ℃, adjusting the pH value of a reaction solution to 9, and reacting for 1 hour to obtain the modified graphene.

The antibacterial reinforcing agent is prepared by the following steps:

step B1: adding dimethylaminoethanol, methyl methacrylate, hydroquinone and tetrabutyl titanate into a reaction kettle, reacting for 4 hours at the rotating speed of 150r/min and the temperature of 60 ℃ to obtain an intermediate 1, adding the intermediate 1, acetonitrile, hydroquinone and bromohexadecane into the reaction kettle, and reacting for 10 hours at the rotating speed of 150r/min and the temperature of 45 ℃ to obtain an intermediate 2;

step B2: adding chloropropene and acetone into a reaction kettle, stirring and adding 2,2,6, 6-tetramethyl piperidinol under the conditions of the rotating speed of 120r/min and the temperature of 0 ℃, adjusting the pH value of a reaction solution to 7, reacting for 3 hours to prepare an intermediate 3, adding the intermediate 2, the intermediate 3, vinyl acetate and deionized water into the reaction kettle, stirring for 20 minutes under the condition of the rotating speed of 200r/min, adding an ammonium persulfate solution, and reacting for 1 hour under the condition of 80 ℃ to prepare an intermediate 4;

step B3: dissolving the intermediate 4 in N, N-dimethylformamide, adding sodium hydroxide and ethanol, reacting for 1h at the rotation speed of 150r/min and the temperature of 30 ℃ to obtain an intermediate 5, adding toluene-3, 5-diisocyanate, deionized water and potassium permanganate into a reaction kettle, performing reflux reaction for 2h at the temperature of 110 ℃ to obtain an intermediate 6, adding the intermediate 5, the intermediate 6, toluene and potassium carbonate into the reaction kettle, and reacting for 3h at the rotation speed of 120r/min and the temperature of 50 ℃ to obtain the antibacterial reinforcing agent.

Example 2

A graphene-based composite antibacterial material comprises the following steps:

step S1: dispersing modified graphene in N, N-dimethylformamide, adding an antibacterial reinforcing agent and 4-dimethylaminopyridine, reacting for 6 hours at the rotation speed of 200r/min and the temperature of 110 ℃, filtering to remove filtrate, and drying a filter cake;

step S2: and soaking the filter cake in a sodium hypochlorite solution, adjusting the pH value to 7, soaking for 1.3h, filtering and drying to obtain the composite antibacterial material.

The modified graphene is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring for 25min at the rotation speed of 180r/min and the temperature of 0 ℃, adding potassium permanganate, heating to the temperature of 13 ℃, continuing stirring for 1.3h, heating to the temperature of 38 ℃, keeping the temperature for 25min, adding deionized water, heating to the temperature of 96 ℃, keeping the temperature for 13min, adding hydrogen peroxide, and stirring for 4min to obtain graphene oxide;

step A2: dispersing graphene oxide in deionized water, dropwise adding a chitosan solution and 1-hydroxybenzotriazole, reacting for 4 hours at the rotation speed of 400r/min and the temperature of 45 ℃, filtering, drying a filter cake to obtain pre-modified graphene, dispersing the pre-modified graphene in an acetic acid solution, stirring and adding epoxy chloropropane at the rotation speed of 180r/min and the temperature of 40 ℃, adjusting the pH value of a reaction solution to be 9, and reacting for 2 hours to obtain the modified graphene.

The antibacterial reinforcing agent is prepared by the following steps:

step B1: adding dimethylaminoethanol, methyl methacrylate, hydroquinone and tetrabutyl titanate into a reaction kettle, reacting for 5 hours at the rotating speed of 180r/min and the temperature of 63 ℃ to obtain an intermediate 1, adding the intermediate 1, acetonitrile, hydroquinone and bromohexadecane into the reaction kettle, and reacting for 13 hours at the rotating speed of 180r/min and the temperature of 480 ℃ to obtain an intermediate 2;

step B2: adding chloropropene and acetone into a reaction kettle, stirring and adding 2,2,6, 6-tetramethyl piperidinol under the conditions of the rotating speed of 120r/min and the temperature of 3 ℃, adjusting the pH value of a reaction solution to 8, reacting for 4 hours to prepare an intermediate 3, adding the intermediate 2, the intermediate 3, vinyl acetate and deionized water into the reaction kettle, stirring for 25 minutes under the condition of the rotating speed of 300r/min, adding an ammonium persulfate solution, and reacting for 1.3 hours under the condition of 85 ℃ to prepare an intermediate 4;

step B3: dissolving the intermediate 4 in N, N-dimethylformamide, adding sodium hydroxide and ethanol, reacting for 1.3h at the rotation speed of 180r/min and the temperature of 33 ℃ to obtain an intermediate 5, adding toluene-3, 5-diisocyanate, deionized water and potassium permanganate into a reaction kettle, performing reflux reaction for 2.5h at the temperature of 115 ℃ to obtain an intermediate 6, adding the intermediate 5, the intermediate 6, toluene and potassium carbonate into the reaction kettle, and reacting for 4h at the rotation speed of 120r/min and the temperature of 55 ℃ to obtain the antibacterial reinforcing agent.

Example 3

A graphene-based composite antibacterial material comprises the following steps:

step S1: dispersing modified graphene in N, N-dimethylformamide, adding an antibacterial reinforcing agent and 4-dimethylaminopyridine, reacting for 8 hours at the rotation speed of 300r/min and the temperature of 120 ℃, filtering to remove filtrate, and drying a filter cake;

step S2: and soaking the filter cake in a sodium hypochlorite solution, adjusting the pH value to 7, soaking for 1.5h, filtering and drying to obtain the composite antibacterial material.

The modified graphene is prepared by the following steps:

step A1: adding graphite, sodium nitrate and concentrated sulfuric acid into a reaction kettle, stirring for 30min at the rotation speed of 200r/min and the temperature of 0 ℃, adding potassium permanganate, heating to 15 ℃, continuing stirring for 1.5h, heating to 40 ℃, keeping the temperature for 30min, adding deionized water, heating to 98 ℃, keeping the temperature for 15min, adding hydrogen peroxide, and stirring for 5min to obtain graphene oxide;

step A2: dispersing graphene oxide in deionized water, dropwise adding a chitosan solution and 1-hydroxybenzotriazole, reacting for 5 hours at the rotation speed of 500r/min and the temperature of 50 ℃, filtering, drying a filter cake to obtain pre-modified graphene, dispersing the pre-modified graphene in an acetic acid solution, stirring and adding epoxy chloropropane at the rotation speed of 200r/min and the temperature of 45 ℃, adjusting the pH value of a reaction solution to 10, and reacting for 3 hours to obtain the modified graphene.

The antibacterial reinforcing agent is prepared by the following steps:

step B1: adding dimethylaminoethanol, methyl methacrylate, hydroquinone and tetrabutyl titanate into a reaction kettle, reacting for 6 hours at the rotating speed of 200r/min and the temperature of 65 ℃ to obtain an intermediate 1, adding the intermediate 1, acetonitrile, hydroquinone and bromohexadecane into the reaction kettle, and reacting for 15 hours at the rotating speed of 200r/min and the temperature of 50 ℃ to obtain an intermediate 2;

step B2: adding chloropropene and acetone into a reaction kettle, stirring and adding 2,2,6, 6-tetramethyl piperidinol under the conditions of the rotating speed of 150r/min and the temperature of 5 ℃, adjusting the pH value of a reaction solution to 8, reacting for 5 hours to prepare an intermediate 3, adding the intermediate 2, the intermediate 3, vinyl acetate and deionized water into the reaction kettle, stirring for 30 minutes under the condition of the rotating speed of 300r/min, adding an ammonium persulfate solution, and reacting for 1.5 hours under the condition of 90 ℃ to prepare an intermediate 4;

step B3: dissolving the intermediate 4 in N, N-dimethylformamide, adding sodium hydroxide and ethanol, reacting for 1.5h at the rotation speed of 200r/min and the temperature of 35 ℃ to obtain an intermediate 5, adding toluene-3, 5-diisocyanate, deionized water and potassium permanganate into a reaction kettle, performing reflux reaction for 3h at the temperature of 120 ℃ to obtain an intermediate 6, adding the intermediate 5, the intermediate 6, toluene and potassium carbonate into the reaction kettle, and reacting for 5h at the rotation speed of 150r/min and the temperature of 60 ℃ to obtain the antibacterial reinforcing agent.

Comparative example 1

The composite antibacterial material prepared by the comparative example is subjected to ultrasonic treatment by using graphene oxide and an antibacterial reinforcing agent.

Comparative example 2

The composite antibacterial material prepared by the comparative example is prepared by dehydration condensation of graphene oxide and chitosan.

Comparative example 3

The comparative example is a graphene antibacterial material disclosed in Chinese patent CN 109329304A.

The antibacterial materials obtained in examples 1 to 3 and comparative examples 1 to 3 were put into triangular flasks, respectively, and 20mL10 was added⁵The bacterial suspension with the material concentration of 1.25mg/mL is incubated for 3h at 37 ℃ by using a constant temperature shaker at 200rpm, and 100 mu L of supernatant is taken out to be placed in a culture dish for observing the bacterial growth.

The antibacterial materials prepared in examples 1-3 and comparative examples 1-3 were placed in a ventilated environment for 3, 6, and 9 months, and then observed for the presence of particulate matter falling off the surface of the antibacterial material, and the resistance of the material was examined, with the results shown in the following table;

it can be known from the above table that the composite antibacterial material prepared in the embodiments 1-3 has two bactericidal layers on the surface of the graphene through chemical bond connection, so that the antibacterial component on the surface of the antibacterial material cannot fall off after the antibacterial material is used for a long time, the antibacterial effect cannot be greatly reduced, and the service life of the antibacterial material is greatly prolonged.

The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.