阅读说明：本技术 一种耐久型石墨烯杀毒抗菌液及其制备方法 (Durable graphene sterilizing and antibacterial liquid and preparation method thereof ) 是由 孙雪迎 王亚亭 马越 于 2021-10-13 设计创作，主要内容包括：本发明公开了一种耐久型石墨烯杀毒抗菌液及其制备方法,该抗菌液包括如下重量份原料：氧化石墨烯3-8份、抗菌增效剂10-15份、十二烷基苯磺酸钠3.5-5份、乳化剂3-5份、甘油1-3份、丙二醇1-3份、水80-100份；并在制备抗菌液的过程中制备了抗菌增效剂,该抗菌增效剂能够与细菌细胞膜内酸性磷脂的头基作用,导致细胞膜的渗透能力下降,细菌细胞液发生泄漏,造成细菌细胞死亡,同时该增效剂能够与细菌线粒体中细胞色素b的Q0位点结合,阻断细胞色素b与细胞色素c1之间的电子传递,进而抑制线粒体呼吸作用,使得线粒体无法供给细胞正常代谢所需要的能量,使得杀菌更彻底。(The invention discloses a durable graphene sterilizing and antibacterial liquid and a preparation method thereof, wherein the antibacterial liquid comprises the following raw materials in parts by weight: 3-8 parts of graphene oxide, 10-15 parts of an antibacterial synergist, 3.5-5 parts of sodium dodecyl benzene sulfonate, 3-5 parts of an emulsifier, 1-3 parts of glycerol, 1-3 parts of propylene glycol and 80-100 parts of water; and the antibacterial synergist is prepared in the process of preparing the antibacterial liquid, can act with the head group of acidic phospholipid in the bacterial cell membrane to reduce the permeability of the cell membrane and cause the leakage of the bacterial cell liquid to cause the death of the bacterial cell, and can be combined with the Q0 site of cytochrome b in bacterial mitochondria to block the electron transfer between the cytochrome b and cytochrome c1 so as to inhibit the respiration of the mitochondria, so that the mitochondria can not supply energy required by the normal metabolism of the cell, and the sterilization is more thorough.)

1. A durable graphene sterilizing and antibacterial liquid is characterized in that: the feed comprises the following raw materials in parts by weight: 3-8 parts of graphene oxide, 10-15 parts of an antibacterial synergist, 3.5-5 parts of sodium dodecyl benzene sulfonate, 3-5 parts of an emulsifier, 1-3 parts of glycerol, 1-3 parts of propylene glycol and 80-100 parts of water;

the antibacterial synergist is prepared by the following steps:

step A1: adding 2-amino-4-nitrotoluene, deionized water and concentrated hydrochloric acid into a reaction kettle, stirring, cooling, adding a sodium nitrite solution, reacting, adjusting the pH value of a reaction solution to be 5 to obtain an intermediate 1, adding deionized water, copper sulfate pentahydrate and acetic acid into the reaction kettle, stirring, adding acetaldoxime and sodium sulfite, adjusting the pH value of the reaction solution to be 7, cooling, adding the intermediate 1, and reacting to obtain an intermediate 2;

step A2: adding the intermediate 2, deionized water and concentrated hydrochloric acid into a reaction kettle, refluxing to obtain an intermediate 3, adding the intermediate 3, potassium hydroxide and deionized water into the reaction kettle, stirring and adding potassium permanganate, reacting to obtain an intermediate 4, adding the intermediate 4, concentrated sulfuric acid and methanol into the reaction kettle, performing reflux reaction for 3-5h to obtain an intermediate 5, adding the intermediate 5, methoxylamine hydrochloride and ethanol into the reaction kettle, performing reflux reaction to obtain an intermediate 6, adding the intermediate 6, carbon tetrachloride, benzoyl peroxide and N-bromosuccinimide into the reaction kettle, and performing reflux reaction to obtain an intermediate 7;

step A3: adding benzyl chloride, sodium cyanide, ethanol and dimethylamine into a reaction kettle, performing reflux reaction to obtain an intermediate 8, adding the intermediate 8, phosphorus pentasulfide and anhydrous sodium sulfite into the reaction kettle, stirring, adding deionized water, continuously stirring to obtain an intermediate 9, adding the intermediate 9, acetonitrile, 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate into the reaction kettle, stirring, adding triethylamine for reflux to obtain an intermediate 10, mixing the intermediate 10 with a sodium hydroxide solution, performing reflux reaction, and adjusting the pH value of a reaction solution to obtain an intermediate 11;

step A4: adding the intermediate 7, tin powder and concentrated hydrochloric acid into a reaction kettle for reaction, adjusting the pH value of reaction liquid to obtain an intermediate 12, adding the intermediate 11, thionyl chloride and N, N-dimethylformamide into the reaction kettle, refluxing, removing a solvent, adding xylene and the intermediate 12, performing reflux reaction to obtain an intermediate 13, adding the intermediate 13, dimethylaminoethanol and sodium acetate into the reaction kettle for reaction to obtain an intermediate 14, adding the intermediate 14, acetonitrile and hydroquinone into the reaction kettle, stirring, adding bromohexadecane, and reacting to obtain the antibacterial synergist.

2. The durable graphene bactericidal/antibacterial solution of claim 1, wherein: the emulsifier is one or two of sorbitan monooleate and sorbitan monooleate which are mixed in any proportion.

3. The durable graphene bactericidal/antibacterial solution of claim 1, wherein: the dosage ratio of the 2-amino-4-nitrotoluene, the deionized water, the concentrated hydrochloric acid and the sodium nitrite solution in the step A1 is 0.5mol:120mL:43g:70mL, the mass fraction of the concentrated hydrochloric acid is 36%, the mass fraction of the sodium nitrite solution is 45%, and the dosage ratio of the deionized water, the copper sulfate pentahydrate, the acetic acid, the acetaldoxime, the sodium sulfite and the intermediate 1 is 200mL:15g:42g:28.2g:1.8g:15 g.

4. The durable graphene bactericidal/antibacterial solution of claim 1, wherein: the dosage ratio of the intermediate 2, the deionized water and the concentrated hydrochloric acid in the step A2 is 15g:200mL:300mL, the dosage ratio of the intermediate 3, the potassium hydroxide, the deionized water and the potassium permanganate is 3.8g:1.2g:200mL:4.5g, the dosage ratio of the intermediate 4, the concentrated sulfuric acid and the methanol is 0.01mol:20mL:0.01mol, the mass fraction of the concentrated sulfuric acid is 95%, the dosage ratio of the intermediate 5, the methoxylamine hydrochloride and the ethanol is 0.02mol:0.09mol:40mL, and the dosage ratio of the intermediate 6, the carbon tetrachloride, the benzoyl peroxide and the N-bromosuccinimide is 0.012mol:30mL:0.2g:0.015 mol.

5. The durable graphene bactericidal/antibacterial solution of claim 1, wherein: the dosage mass ratio of the p-methyl benzyl chloride, the sodium cyanide, the ethanol and the dimethylamine described in the step A3 is 125:50:55:2, the dosage mass ratio of the intermediate 8, the phosphorus pentasulfide, the anhydrous sodium sulfite and the deionized water is 0.015mol:0.02mol:0.02mol:40mL, the dosage mass ratio of the intermediate 9, the acetonitrile, the 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate and the triethylamine is 0.5mol:300mL:0.4mol:1.05mol, the dosage mass ratio of the intermediate 10 and the sodium hydroxide solution is 1g:10mL, and the mass fraction of the sodium hydroxide solution is 40%.

6. The durable graphene bactericidal/antibacterial solution of claim 1, wherein: the dosage ratio of the intermediate 7, the tin powder and the concentrated hydrochloric acid in the step A4 is 3.5g:8g:80mL, the dosage ratio of the intermediate 11, the thionyl chloride, the N, N-dimethylformamide, the xylene and the intermediate 12 is 0.2mol:0.25mol:3mL:140mL:0.19mol, the dosage ratio of the intermediate 13, the dimethylaminoethanol and the sodium acetate is 1:1:1, and the dosage ratio of the intermediate 14, the acetonitrile, the hydroquinone and the bromohexadecane is 0.1mol:20mL:0.1mol:0.1 mol.

7. The method for preparing the durable graphene bactericidal and antibacterial liquid according to claim 1, wherein the method comprises the following steps: the method specifically comprises the following steps:

step S1: adding graphene oxide, sodium dodecyl benzene sulfonate and water into a reaction kettle, and stirring for 20-30min under the condition that the rotating speed is 600-800r/min to prepare a dispersion liquid;

step S2: and (3) adding the dispersion, the antibacterial synergist, the emulsifier, the glycerol and the propylene glycol into a reaction kettle, and stirring for 1-1.5 hours under the condition that the rotating speed is 1000-1200r/min to obtain the sterilizing and antibacterial liquid.

Technical Field

The invention relates to the technical field of bactericide preparation, and particularly relates to a durable graphene sterilizing and antibacterial liquid and a preparation method thereof.

Background

Along with social progress and economic development, people pay more attention to self health. Two thirds of the time every day is spent at home, and a clean and sterile home environment is particularly important, so that the antibacterial liquid is used in thousands of households. The main component of the antibacterial liquid in the market is parachlorometaxylenol or quaternary ammonium salt, and the two reagents have toxicity and are not beneficial to the environment and human bodies after being used for a long time. Therefore, the antibacterial liquid which is safe and environment-friendly and has broad-spectrum antibacterial efficacy is the demand of consumers.

Graphene is a honeycomb-shaped planar thin film formed by carbon atoms in an Sp2 hybridization mode, is a quasi-two-dimensional material with the thickness of only one atomic layer, is called monoatomic layer graphite, and can cause the damage of a bacterial structure and the functional disorder by damaging the integrity of cell membranes; however, graphene is poor in antibacterial effect, cell membranes of part of bacteria are damaged, but the cells can still work normally, so that after antibacterial liquid is used, bacterial breeding occurs, and the use of the antibacterial liquid is further influenced.

Disclosure of Invention

The invention aims to provide a durable graphene sterilizing and antibacterial liquid and a preparation method thereof.

The technical problems to be solved by the invention are as follows:

the existing graphene sterilizing and antibacterial liquid has a common antibacterial effect, and bacterial breeding still occurs in the use process.

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

the durable graphene sterilizing and antibacterial liquid comprises the following raw materials in parts by weight: 3-8 parts of graphene oxide, 10-15 parts of an antibacterial synergist, 3.5-5 parts of sodium dodecyl benzene sulfonate, 3-5 parts of an emulsifier, 1-3 parts of glycerol, 1-3 parts of propylene glycol and 80-100 parts of water;

the sterilizing and antibacterial liquid is prepared by the following steps:

step S1: adding graphene oxide, sodium dodecyl benzene sulfonate and water into a reaction kettle, and stirring for 20-30min under the condition that the rotating speed is 600-800r/min to prepare a dispersion liquid;

step S2: and (3) adding the dispersion, the antibacterial synergist, the emulsifier, the glycerol and the propylene glycol into a reaction kettle, and stirring for 1-1.5 hours under the condition that the rotating speed is 1000-1200r/min to obtain the sterilizing and antibacterial liquid.

Further, the emulsifier is one or two of sorbitan monooleate and sorbitan monooleate which are mixed in any proportion.

Further, the antibacterial synergist is prepared by the following steps:

step A1: adding 2-amino-4-nitrotoluene, deionized water and concentrated hydrochloric acid into a reaction kettle, stirring at the rotation speed of 150-;

the reaction process is as follows:

step A2: adding the intermediate 2, deionized water and concentrated hydrochloric acid into a reaction kettle, refluxing for 3-4h at 90-95 ℃ to obtain an intermediate 3, adding the intermediate 3, potassium hydroxide and deionized water into the reaction kettle, stirring at a rotation speed of 150-, Adding carbon tetrachloride, benzoyl peroxide and N-bromosuccinimide into a reaction kettle, and performing reflux reaction for 3-5h at the temperature of 80-90 ℃ to prepare an intermediate 7;

the reaction process is as follows:

step A3: adding benzyl chloride, sodium cyanide, ethanol and dimethylamine into a reaction kettle, carrying out reflux reaction for 3-5h at the temperature of 80-100 ℃ to obtain an intermediate 8, adding the intermediate 8, phosphorus pentasulfide and anhydrous sodium sulfite into the reaction kettle, stirring for 20-30min at the rotation speed of 200r/min, adding deionized water, continuing stirring for 10-15min to obtain an intermediate 9, adding the intermediate 9, acetonitrile and 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate into the reaction kettle, stirring for 2-3h at the rotation speed of 200r/min and the temperature of 30-35 ℃ to obtain an intermediate 10, adding triethylamine, refluxing for 1-1.5h to obtain an intermediate 10, mixing the intermediate 10 with a sodium hydroxide solution, carrying out reflux reaction for 4-6h, and adjusting the pH value of the reaction solution to 1-2 to prepare an intermediate 11;

the reaction process is as follows:

step A4: adding the intermediate 7, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 30-40min under the conditions that the rotation speed is 120-150r/min and the temperature is 30-35 ℃, adjusting the pH value of a reaction solution to be 11-12 to prepare an intermediate 12, adding the intermediate 11, thionyl chloride and N, N-dimethylformamide into the reaction kettle, refluxing for 7-9h under the conditions that the rotation speed is 150-200r/min and the temperature is 60-70 ℃, removing the solvent, adding xylene and the intermediate 12, performing reflux reaction for 13-15h to prepare an intermediate 13, adding the intermediate 13, dimethylaminoethanol and sodium acetate into the reaction kettle, reacting for 2-3h under the condition that the temperature is 30-35 ℃ to prepare an intermediate 14, adding the intermediate 14, acetonitrile and hydroquinone into the reaction kettle, stirring and adding bromohexadecane for reaction for 10-15h under the conditions that the rotating speed is 150 plus one 200r/min and the temperature is 45-50 ℃, thus obtaining the antibacterial synergist.

The reaction process is as follows:

further, the dosage ratio of the 2-amino-4-nitrotoluene, the deionized water, the concentrated hydrochloric acid and the sodium nitrite solution in the step A1 is 0.5mol:120mL:43g:70mL, the mass fraction of the concentrated hydrochloric acid is 36%, the mass fraction of the sodium nitrite solution is 45%, and the dosage ratio of the deionized water, the copper sulfate pentahydrate, the acetic acid, the acetaldoxime, the sodium sulfite and the intermediate 1 is 200mL:15g:42g:28.2g:1.8g:15 g.

Further, the dosage ratio of the intermediate 2, deionized water and concentrated hydrochloric acid in the step A2 is 15g:200mL:300mL, the dosage ratio of the intermediate 3, potassium hydroxide, deionized water and potassium permanganate is 3.8g:1.2g:200mL:4.5g, the dosage ratio of the intermediate 4, concentrated sulfuric acid and methanol is 0.01mol:20mL:0.01mol, the mass fraction of concentrated sulfuric acid is 95%, the dosage ratio of the intermediate 5, methoxylamine hydrochloride and ethanol is 0.02mol:0.09mol:40mL, and the dosage ratio of the intermediate 6, carbon tetrachloride, benzoyl peroxide and N-bromosuccinimide is 0.012mol:30mL:0.2g:0.015 mol.

Further, the dosage mass ratio of the p-methyl benzyl chloride, the sodium cyanide, the ethanol and the dimethylamine described in the step A3 is 125:50:55:2, the dosage mass ratio of the intermediate 8, the phosphorus pentasulfide, the anhydrous sodium sulfite and the deionized water is 0.015mol:0.02mol:0.02mol:40mL, the dosage mass ratio of the intermediate 9, the acetonitrile, the 2-chloro-4, 4,4, -ethyl trifluoroacetoacetate and the triethylamine is 0.5mol:300mL:0.4mol:1.05mol, the dosage ratio of the intermediate 10 and the sodium hydroxide solution is 1g:10mL, and the mass fraction of the sodium hydroxide solution is 40%.

Further, the dosage ratio of the intermediate 7, the tin powder and the concentrated hydrochloric acid in the step A4 is 3.5g:8g:80mL, the dosage ratio of the intermediate 11, the thionyl chloride, the N, N-dimethylformamide, the xylene and the intermediate 12 is 0.2mol:0.25mol:3mL:140mL:0.19mol, the dosage ratio of the intermediate 13, the dimethylaminoethanol and the sodium acetate is 1:1:1, and the dosage ratio of the intermediate 14, the acetonitrile, the hydroquinone and the bromohexadecane is 0.1mol:20mL:0.1mol:0.1 mol.

The invention has the beneficial effects that: the invention discloses a process for preparing durable graphene sterilizing and antibacterial liquid, which comprises the steps of preparing an antibacterial synergist by taking 2-amino-4-nitrotoluene as a raw material to react to prepare an intermediate 1, further reacting the intermediate 1 to prepare an intermediate 2, treating the intermediate 2 with concentrated hydrochloric acid to prepare an intermediate 3, further treating the intermediate 3 to prepare an intermediate 4, carrying out esterification reaction on the intermediate 4 and methanol to prepare an intermediate 5, reacting the intermediate 5 with methoxylamine hydrochloride to prepare an intermediate 6, treating the intermediate 6 with N-bromosuccinimide to prepare an intermediate 7, reacting p-methyl benzyl chloride with sodium cyanide to prepare an intermediate 8, reacting the intermediate 8 with phosphorus pentasulfide to prepare an intermediate 9, reacting the intermediate 9 with 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate to react to obtain an intermediate 10, further processing the intermediate 10 to obtain an intermediate 11, reducing the intermediate 7 by tin powder to reduce nitro groups on the intermediate 7 into amino groups to obtain an intermediate 12, processing the intermediate 11 and thionyl chloride to react with the intermediate 12 to obtain an intermediate 13, reacting the intermediate 13 with dimethylaminoethanol to obtain an intermediate 14, reacting the intermediate 14 with bromohexadecane to obtain an antibacterial synergist, wherein the antibacterial synergist can act with a head group of acidic phospholipid in bacterial cell membranes to reduce the permeability of the cell membranes and leak bacterial cell sap to cause bacterial cell death, and can be combined with a Q0 site of cytochrome b in bacterial mitochondria to block the electron transfer between the cytochrome b and the cytochrome c1, and then the respiratory action of mitochondria is inhibited, so that the mitochondria can not supply energy required by normal metabolism of cells, the sterilization is more thorough, and the antibacterial synergist has high relative molecular weight and is not easy to volatilize, so that the antibacterial effect of the antibacterial liquid is longer.

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

The durable graphene sterilizing and antibacterial liquid comprises the following raw materials in parts by weight: 3 parts of graphene oxide, 10 parts of antibacterial synergist, 3.5 parts of sodium dodecyl benzene sulfonate, 3 parts of sorbitan monooleate, 1 part of glycerol, 1 part of propylene glycol and 80 parts of water;

the sterilizing and antibacterial liquid is prepared by the following steps:

step S1: adding graphene oxide, sodium dodecyl benzene sulfonate and water into a reaction kettle, and stirring for 20min under the condition that the rotating speed is 600r/min to prepare a dispersion liquid;

step S2: and (3) adding the dispersion, the antibacterial synergist, the sorbitan monooleate, the glycerol and the propylene glycol into a reaction kettle, and stirring for 1h at the rotating speed of 1000r/min to obtain the sterilizing and antibacterial liquid.

The antibacterial synergist is prepared by the following steps:

step A1: adding 2-amino-4-nitrotoluene, deionized water and concentrated hydrochloric acid into a reaction kettle, stirring for 1h at the rotation speed of 150r/min and the temperature of 50 ℃, cooling to the temperature of 0 ℃, adding a sodium nitrite solution, continuing to react for 1h, adjusting the pH value of the reaction solution to 5 to prepare an intermediate 1, adding deionized water, copper sulfate pentahydrate and acetic acid into the reaction kettle, stirring and adding acetaldehyde oxime and sodium sulfite at the rotation speed of 200r/min and the temperature of 15 ℃, stirring for 10min, adjusting the pH value of the reaction solution to 7, cooling to the temperature of 5 ℃, adding the intermediate 1, and reacting for 1h to prepare an intermediate 2;

step A2: adding the intermediate 2, deionized water and concentrated hydrochloric acid into a reaction kettle, refluxing for 3h at 90 ℃ to obtain an intermediate 3, adding the intermediate 3, potassium hydroxide and deionized water into the reaction kettle, stirring at a rotation speed of 150r/min and at 0 ℃ and adding potassium permanganate to react for 1h to obtain an intermediate 4, adding the intermediate 4, concentrated sulfuric acid and methanol into the reaction kettle, refluxing for 3h at 80 ℃ to obtain an intermediate 5, adding the intermediate 5, methoxylamine hydrochloride and ethanol into the reaction kettle, refluxing for 3h at 80 ℃ and a pH value of 8 to obtain an intermediate 6, adding the intermediate 6, carbon tetrachloride, benzoyl peroxide and N-bromosuccinimide into the reaction kettle, refluxing at 80 ℃, carrying out reflux reaction for 3h to prepare an intermediate 7;

step A3: adding p-methyl benzyl chloride, sodium cyanide, ethanol and dimethylamine into a reaction kettle, carrying out reflux reaction for 3 hours at the temperature of 80 ℃ to obtain an intermediate 8, adding the intermediate 8, phosphorus pentasulfide and anhydrous sodium sulfite into the reaction kettle, stirring for 20 minutes at the rotation speed of 150r/min, adding deionized water, continuing stirring for 10 minutes to obtain an intermediate 9, adding the intermediate 9, acetonitrile, 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate into the reaction kettle, stirring for 2 hours at the rotation speed of 200r/min and the temperature of 30 ℃, adding triethylamine, refluxing for 1 hour to obtain an intermediate 10, mixing the intermediate 10 with a sodium hydroxide solution, carrying out reflux reaction for 4 hours, and adjusting the pH value of a reaction solution to be 1 to obtain an intermediate 11;

step A4: adding the intermediate 7, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 30min at the rotation speed of 120r/min and the temperature of 30 ℃, adjusting the pH value of a reaction solution to be 11 to prepare an intermediate 12, adding the intermediate 11, thionyl chloride and N, N-dimethylformamide into the reaction kettle, refluxing for 7h at the rotation speed of 150r/min and the temperature of 60 ℃, removing a solvent, adding xylene and the intermediate 12, performing reflux reaction for 13h to prepare an intermediate 13, adding the intermediate 13, dimethylaminoethanol and sodium acetate into the reaction kettle, reacting for 2h at the temperature of 30 ℃ to prepare an intermediate 14, adding the intermediate 14, acetonitrile and hydroquinone into the reaction kettle, stirring and adding bromohexadecane at the rotation speed of 150r/min and the temperature of 45 ℃, and reacting for 10 hours to obtain the antibacterial synergist.

Example 2

The durable graphene sterilizing and antibacterial liquid comprises the following raw materials in parts by weight: 5 parts of graphene oxide, 13 parts of an antibacterial synergist, 4.2 parts of sodium dodecyl benzene sulfonate, 4 parts of sorbitan monooleate, 2 parts of glycerol, 2 parts of propylene glycol and 90 parts of water;

the sterilizing and antibacterial liquid is prepared by the following steps:

step S1: adding graphene oxide, sodium dodecyl benzene sulfonate and water into a reaction kettle, and stirring for 30min under the condition that the rotating speed is 600r/min to prepare a dispersion liquid;

step S2: and (3) adding the dispersion, the antibacterial synergist, the sorbitan monooleate, the glycerol and the propylene glycol into a reaction kettle, and stirring for 1.5 hours at the rotating speed of 1000r/min to obtain the sterilizing and antibacterial liquid.

The antibacterial synergist is prepared by the following steps:

step A1: adding 2-amino-4-nitrotoluene, deionized water and concentrated hydrochloric acid into a reaction kettle, stirring for 1h at the rotation speed of 150r/min and the temperature of 60 ℃, cooling to the temperature of 3 ℃, adding a sodium nitrite solution, continuing to react for 1h, adjusting the pH value of a reaction solution to 5 to prepare an intermediate 1, adding deionized water, copper sulfate pentahydrate and acetic acid into the reaction kettle, stirring and adding acetaldehyde oxime and sodium sulfite at the rotation speed of 300r/min and the temperature of 15 ℃, stirring for 15min, adjusting the pH value of the reaction solution to 7, cooling to the temperature of 5 ℃, adding the intermediate 1, and reacting for 1.5h to prepare an intermediate 2;

step A2: adding the intermediate 2, deionized water and concentrated hydrochloric acid into a reaction kettle, refluxing for 4h at 90 ℃ to obtain an intermediate 3, adding the intermediate 3, potassium hydroxide and deionized water into the reaction kettle, stirring at a rotation speed of 150r/min and at 0 ℃ and adding potassium permanganate to react for 2h to obtain an intermediate 4, adding the intermediate 4, concentrated sulfuric acid and methanol into the reaction kettle, refluxing for 5h at 80 ℃ to obtain an intermediate 5, adding the intermediate 5, methoxylamine hydrochloride and ethanol into the reaction kettle, refluxing for 3h at 80 ℃ and a pH value of 9 to obtain an intermediate 6, adding the intermediate 6, carbon tetrachloride, benzoyl peroxide and N-bromosuccinimide into the reaction kettle, refluxing at 90 ℃, carrying out reflux reaction for 3h to prepare an intermediate 7;

step A3: adding p-methyl benzyl chloride, sodium cyanide, ethanol and dimethylamine into a reaction kettle, carrying out reflux reaction for 3 hours at the temperature of 100 ℃ to obtain an intermediate 8, adding the intermediate 8, phosphorus pentasulfide and anhydrous sodium sulfite into the reaction kettle, stirring for 20 minutes at the rotation speed of 200r/min, adding deionized water, continuing stirring for 15 minutes to obtain an intermediate 9, adding the intermediate 9, acetonitrile, 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate into the reaction kettle, stirring for 2 hours at the rotation speed of 200r/min and the temperature of 35 ℃, adding triethylamine, refluxing for 1.5 hours to obtain an intermediate 10, mixing the intermediate 10 with a sodium hydroxide solution, carrying out reflux reaction for 4 hours, and adjusting the pH value of a reaction solution to be 2 to obtain an intermediate 11;

step A4: adding the intermediate 7, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 30min at the rotation speed of 120r/min and the temperature of 35 ℃, adjusting the pH value of a reaction solution to be 12 to prepare an intermediate 12, adding the intermediate 11, thionyl chloride and N, N-dimethylformamide into the reaction kettle, refluxing for 7h at the rotation speed of 150r/min and the temperature of 70 ℃, removing a solvent, adding xylene and the intermediate 12, performing reflux reaction for 15h to prepare an intermediate 13, adding the intermediate 13, dimethylaminoethanol and sodium acetate into the reaction kettle, reacting for 3h at the temperature of 30 ℃ to prepare an intermediate 14, adding the intermediate 14, acetonitrile and hydroquinone into the reaction kettle, stirring and adding bromohexadecane at the rotation speed of 150r/min and the temperature of 50 ℃, and reacting for 10 hours to obtain the antibacterial synergist.

Example 3

The durable graphene sterilizing and antibacterial liquid comprises the following raw materials in parts by weight: 8 parts of graphene oxide, 15 parts of antibacterial synergist, 5 parts of sodium dodecyl benzene sulfonate, 5 parts of sorbitan monooleate, 1-3 parts of glycerol, 3 parts of propylene glycol and 100 parts of water;

the sterilizing and antibacterial liquid is prepared by the following steps:

step S1: adding graphene oxide, sodium dodecyl benzene sulfonate and water into a reaction kettle, and stirring for 30min under the condition that the rotating speed is 800r/min to prepare a dispersion liquid;

step S2: and (3) adding the dispersion, the antibacterial synergist, the sorbitan monooleate, the glycerol and the propylene glycol into a reaction kettle, and stirring for 1.5 hours at the rotating speed of 1200r/min to obtain the sterilizing and antibacterial liquid.

The antibacterial synergist is prepared by the following steps:

step A1: adding 2-amino-4-nitrotoluene, deionized water and concentrated hydrochloric acid into a reaction kettle, stirring for 1.5h at the rotation speed of 200r/min and the temperature of 60 ℃, cooling to the temperature of 3 ℃, adding a sodium nitrite solution, continuing to react for 1.5h, adjusting the pH value of the reaction solution to 5 to prepare an intermediate 1, adding deionized water, copper sulfate pentahydrate and acetic acid into the reaction kettle, stirring and adding acetaldehyde oxime and sodium sulfite at the rotation speed of 300r/min and the temperature of 20 ℃, stirring for 15min, adjusting the pH value of the reaction solution to 7, cooling to the temperature of 10 ℃, adding the intermediate 1, and reacting for 1.5h to prepare an intermediate 2;

step A2: adding the intermediate 2, deionized water and concentrated hydrochloric acid into a reaction kettle, refluxing for 4h at the temperature of 95 ℃ to obtain an intermediate 3, adding the intermediate 3, potassium hydroxide and deionized water into the reaction kettle, stirring and adding potassium permanganate at the rotation speed of 200r/min and the temperature of 0 ℃ to react for 2h to obtain an intermediate 4, adding the intermediate 4, concentrated sulfuric acid and methanol into the reaction kettle, refluxing for 5h at the temperature of 90 ℃ to obtain an intermediate 5, adding the intermediate 5, methoxylamine hydrochloride and ethanol into the reaction kettle, refluxing for 5h at the temperature of 90 ℃ and the pH value of 9 to obtain an intermediate 6, adding the intermediate 6, carbon tetrachloride, benzoyl peroxide and N-bromosuccinimide into the reaction kettle, refluxing at the temperature of 90 ℃, carrying out reflux reaction for 5h to prepare an intermediate 7;

step A3: adding p-methyl benzyl chloride, sodium cyanide, ethanol and dimethylamine into a reaction kettle, carrying out reflux reaction for 5 hours at the temperature of 100 ℃ to obtain an intermediate 8, adding the intermediate 8, phosphorus pentasulfide and anhydrous sodium sulfite into the reaction kettle, stirring for 30 minutes at the rotation speed of 200r/min, adding deionized water, continuing stirring for 15 minutes to obtain an intermediate 9, adding the intermediate 9, acetonitrile, 2-chloro-4, 4, 4-ethyl trifluoroacetoacetate into the reaction kettle, stirring for 3 hours at the rotation speed of 300r/min and the temperature of 35 ℃, adding triethylamine, refluxing for 1.5 hours to obtain an intermediate 10, mixing the intermediate 10 with a sodium hydroxide solution, carrying out reflux reaction for 6 hours, and adjusting the pH value of a reaction solution to be 2 to obtain an intermediate 11;

step A4: adding the intermediate 7, tin powder and concentrated hydrochloric acid into a reaction kettle, reacting for 40min at the rotation speed of 150r/min and the temperature of 35 ℃, adjusting the pH value of a reaction solution to be 12 to prepare an intermediate 12, adding the intermediate 11, thionyl chloride and N, N-dimethylformamide into the reaction kettle, refluxing for 9h at the rotation speed of 200r/min and the temperature of 70 ℃, removing a solvent, adding xylene and the intermediate 12, performing reflux reaction for 15h to prepare an intermediate 13, adding the intermediate 13, dimethylaminoethanol and sodium acetate into the reaction kettle, reacting for 3h at the temperature of 35 ℃ to prepare an intermediate 14, adding the intermediate 14, acetonitrile and hydroquinone into the reaction kettle, stirring and adding bromohexadecane at the rotation speed of 200r/min and the temperature of 50 ℃, and reacting for 15 hours to obtain the antibacterial synergist.

Comparative example 1

Compared with the example 1, the comparative example does not add the antibacterial synergist, and the rest steps are the same.

Comparative example 2

Compared with the example 1, the comparative example uses p-nitrophenol to replace the antibacterial synergist, and the rest steps are the same.

Comparative example 3

The comparative example is the antibacterial liquid disclosed in Chinese patent CN 107006516A.

The antibacterial liquids prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to a performance test according to the method of GB/T2738-2012, and the test results are shown in table 1 below;

TABLE 1

As shown in the above Table 1, the antibacterial ratio of the antibacterial liquid prepared in the examples 1-3 to Escherichia coli is 99.93-99.95%, the antibacterial ratio to Candida albicans is 99.93-99.95%, the antibacterial ratio to Staphylococcus aureus is 99.92-99.93%, and the antibacterial ratio of the antibacterial liquid prepared in the comparative examples 1-3 is lower than that of the examples 1-3, which indicates that the antibacterial liquid has good antibacterial effect and better durable effect.

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.