A textile antibacterial agent containing graphene and quaternary ammonium salt and its preparation method

Abstract

The present invention discloses a textile antibacterial agent containing graphene and quaternary ammonium salt and a preparation method thereof. The preparation method of the antibacterial agent includes the following steps: modifying graphene with a silane coupling agent containing a double bond to obtain active graphene; providing reaction raw materials; and using water as a solvent, and carrying out a polymerization reaction of active graphene, dimethyldiallylammonium chloride, carboxyl acrylic monomers and allyl glycidyl ether under the initiation of an initiator to generate a composite antibacterial finishing agent. The composite antibacterial finishing agent prepared by the above preparation method of the composite antibacterial finishing agent is a composite of a quaternary ammonium salt copolymer and graphene. Through the synergistic effect of quaternary ammonium cations and graphene, the antibacterial properties of organic and inorganic materials can be fully exerted, endowing the fabric with good antibacterial properties. At the same time, the antibacterial finishing agent contains active groups that can act on cotton fibers, so as to achieve a lasting antibacterial effect.

Description

Technical Field

[0001] The present invention belongs to the technical field of textile antibacterial agents, and particularly relates to a textile antibacterial agent containing graphene and quaternary ammonium salt and a preparation method thereof. Background Art

[0002] People's daily life is closely related to microorganisms. It can be said that human clothing, food, housing and transportation are all inseparable from microorganisms. However, at present, microbial contamination has become a hot issue of common concern around the world. Among the many bacterial transmission routes, textiles are a very important carrier. Because of their porous and loose structure, they are easy to adsorb various impurities and become an ideal place for bacteria to breed and parasitize. The existence of these bacteria not only contaminates and damages the fabric, but more importantly, it increases the cross-infection rate in the public environment and affects human health. In order to reduce the harm of harmful microorganisms to humans and prevent the spread between people, between humans and animals, and between animals, we can artificially control the growth and reproduction of microorganisms in textiles. The main component of antibacterial textiles is antibacterial agents, which are chemical substances that can keep the growth or reproduction of certain microorganisms below a certain level within a certain period of time. The antibacterial process is that the antibacterial agent contacts or enters the bacteria to kill them. However, the antibacterial agents used in antibacterial textiles are different, their antibacterial mechanisms are also different, and their killing effects on different types of bacteria are also different. At present, among the developed textile antibacterial finishing agents, various types of antibacterial agents have many advantages, but they all have some obvious deficiencies.

[0003] Quaternary ammonium salt-based polymer antibacterial agents and graphene are two types of commonly used antibacterial agents, each with its own characteristics, but also having some fatal defects. For example, the deficiencies of quaternary ammonium salt-based polymer antibacterial agents are that they are not wash-resistant, easy to elute, cannot provide long-term antibacterial effect, and are toxic to the human body after elution. Graphene belongs to nano-antibacterial agents and has excellent properties such as non-toxicity, large specific surface area, and antibacterial properties. However, it also has the problem of not being wash-resistant, and there are problems commonly existing in the application of nanomaterials. Therefore, many people have tried to compound the two to prepare a composite antibacterial agent of quaternary ammonium copolymer and graphene and apply it to the post-finishing of textiles. However, the defect of the existing method is that the binding force between graphene particles and quaternary ammonium copolymer is not strong, resulting in the rapid loss of graphene in the textile during use and unable to exert the antibacterial effect of graphene for a long time; the composite antibacterial agent of graphene and quaternary ammonium copolymer is extremely easy to fall off from the textile and loses its antibacterial performance after several washes. Summary of the Invention

[0004] In view of the above technical problems, the present invention provides a textile antibacterial agent containing graphene and quaternary ammonium salt and a preparation method thereof. After the obtained composite antibacterial agent of graphene and quaternary ammonium salt is used to finish the textile, it has a good binding force with the textile and is not easy to lose after washing.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] A preparation method of a textile antibacterial agent containing graphene and quaternary ammonium salt, comprising the following steps:

[0007] The reaction raw materials, by mass percentage, include: 0.2-1.0% of active graphene, 25-35% of dimethyldiallylammonium chloride, 1-3% of carboxyl acrylic acid monomers; 0.5-1% of allyl glycidyl ether; 3-6% of initiator and the balance of deionized water;

[0008] The active graphene, dimethyldiallylammonium chloride, carboxyl acrylic acid monomers and allyl glycidyl ether generate a composite antibacterial finishing agent through a polymerization reaction initiated by an initiator in solvent water;

[0009] Wherein the active graphene is active graphene modified by a silane coupling agent containing double bonds.

[0010] In one embodiment, the steps of preparing the composite antibacterial finishing agent are specifically as follows:

[0011] S1: Mix the active graphene, the dimethyldiallylammonium chloride, the deionized water, an initiator aqueous solution containing one-third of the initiator, one-third of the allyl glycidyl ether and one-third of the carboxyl acrylic acid monomers to obtain a mixed solution;

[0012] Heat the mixed solution to 70-85 °C and stir and react for 8-15 minutes to obtain a first reaction solution;

[0013] S2: Dropwise add an initiator aqueous solution containing one-third of the initiator, one-third of the allyl glycidyl ether and one-third of the carboxyl acrylic acid monomers to the first reaction solution, and stir and react at 70-85 °C for 10-20 minutes to obtain a second reaction solution;

[0014] S3: Dropwise add an initiator aqueous solution containing one-third of the initiator, one-third of the allyl glycidyl ether and one-third of the carboxyl acrylic acid monomers to the second reaction solution, and stir and react at 70-85 °C for 3-5 hours to obtain the composite antibacterial finishing agent.

[0015] In one embodiment, the preparation method of the active graphene is specifically as follows:

[0016] Graphene, a silane coupling agent containing double bonds, and a solvent are mixed and then ultrasonically dispersed to obtain a dispersion liquid. The dispersion liquid is refluxed for 10 - 20 hours to obtain active graphene, where the graphene is prepared by a conventional oxidation-reduction reaction method and is graphene that is not fully reduced and contains some oxygen-containing functional groups.

[0017] In one embodiment, the solvent includes ethanol and water.

[0018] In one embodiment, the mass ratio of the graphene, the ethanol, the water, and the silane coupling agent containing double bonds is 1:10 - 20:30 - 60:1 - 5.

[0019] In one embodiment, the silane coupling agent containing double bonds is γ-methacryloxypropyltrimethoxysilane.

[0020] In one embodiment, the initiator is selected from at least one of sodium persulfate, potassium persulfate, and ammonium persulfate; or the initiator includes at least one of sodium persulfate, potassium persulfate, and ammonium persulfate and sodium bisulfite.

[0021] In one embodiment, the carboxyl acrylic monomer is selected from at least one of acrylic acid and methacrylic acid.

[0022] A textile antibacterial agent containing graphene and quaternary ammonium salt, and the textile antibacterial agent containing graphene and quaternary ammonium salt is obtained by the above preparation method.

[0023] Due to the adoption of the above technical solutions, the present invention has the following advantages and positive effects compared with the prior art:

[0024] The graphene of the present invention obtains reactive groups after being modified by a silane coupling agent containing double bonds. The modified graphene copolymerizes with dimethyldiallylammonium chloride, carboxyl acrylic monomers, and allyl glycidyl ether. In the obtained antibacterial agent, the graphene and the quaternary ammonium salt are bonded by chemical bonds, enhancing the binding force between the graphene and the quaternary ammonium salt, making the antibacterial agent not easily lost during washing and use. At the same time, the structure also contains a large number of carboxyl and epoxy groups. When performing functional finishing on cotton fabrics, it can chemically react with the hydroxyl groups on the cotton fabrics to graft the antibacterial agent onto the cotton fibers, thereby maintaining the long-term functionality. Among them, since the graphene in the product is modified by a silane coupling agent containing double bonds, the aggregation of graphene is avoided, so that the antibacterial effect of graphene can be fully exerted. Further, the quaternary ammonium salt cations in the product synergize with the graphene, and can fully exert the antibacterial properties of inorganic materials and organic materials. After synergistic effect, the effect is improved, thereby endowing the fabric with good antibacterial properties. Specific embodiments

[0025] The following further elaborates in detail on a textile antibacterial agent containing graphene and quaternary ammonium salt and its preparation method proposed by the present invention in combination with specific embodiments. According to the following description, the advantages and features of the present invention will be clearer.

[0026] Example 1

[0027] (1) Preparation of active graphene: Mix 2.0 g of graphene, 80 g of ethanol, 24 g of water, and 8 g of γ-methacryloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 18 h, then cool to room temperature. The dispersion is centrifuged and washed to obtain active graphene;

[0028] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.4 g of ammonium persulfate in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, and divide the ammonium persulfate aqueous solution into three equal parts. Then add 0.45 g of active graphene, 50 g of dimethyldiallylammonium chloride, 117.6 g of deionized water, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution into a three-necked flask, stir evenly, then heat in a water bath to 80 °C and react for 15 min; then add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and react for 15 min in a water bath at 80 °C; add dropwise again 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and keep stirring and reacting at 80 °C in a water bath for 4.0 h, then cool to room temperature. After filtration, the composite antibacterial finishing agent is obtained.

[0029] Example 2

[0030] (1) Preparation of active graphene: Mix 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 8 g of γ-methacryloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 12 h, then cool to room temperature. The dispersion is centrifuged and washed to obtain active graphene;

[0031] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.4 g of ammonium persulfate in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, and divide the ammonium persulfate aqueous solution into three equal parts. Then, add 0.45 g of activated graphene, 50 g of dimethyldiallylammonium chloride, 116.4 g of deionized water, 1.6 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution into a three-necked flask, stir evenly, and then heat in a water bath to 80 °C and react for 15 min; then add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and react for 15 min under a water bath at 80 °C; add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution again, and keep stirring and reacting for 4.0 h under a water bath at 80 °C, then cool to room temperature, and filter to obtain the composite antibacterial finishing agent.

[0032] Example 3

[0033] (1) Preparation of activated graphene: Mix 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 8 g of γ-methacryloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 12 h, then cool to room temperature, and the dispersion is centrifuged and washed to obtain activated graphene;

[0034] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.4 g of ammonium persulfate in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, and divide the ammonium persulfate aqueous solution into three equal parts. Then, add 0.45 g of activated graphene, 70 g of dimethyldiallylammonium chloride, 97.6 g of deionized water, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution into a three-necked flask, stir evenly, and then heat in a water bath to 80 °C and react for 15 min; then add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and react for 15 min under a water bath at 80 °C; add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution again, and keep stirring and reacting for 4.0 h under a water bath at 80 °C, then cool to room temperature, and filter to obtain the composite antibacterial finishing agent.

[0035] Example 4

[0036] (1) Preparation of activated graphene: Mix 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 3 g of γ-methacryloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 16 h, then cool to room temperature, and the dispersion is centrifuged and washed to obtain activated graphene;

[0037] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.4 g of ammonium persulfate in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, and divide the ammonium persulfate aqueous solution into three equal parts. Then, add 0.45 g of activated graphene, 50 g of dimethyldiallylammonium chloride, 117.6 g of deionized water, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution into a three-necked flask, stir evenly, and then heat in a water bath to 80 °C and react for 15 min; then add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and react for 15 min in a water bath at 80 °C; add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution again, and keep stirring and reacting at 80 °C in a water bath for 4.0 h, then cool to room temperature, and obtain the composite antibacterial finishing agent after filtration.

[0038] Example 5

[0039] (1) Preparation of activated graphene: Mix 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 8 g of γ-methacryloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 12 h, then cool to room temperature, and obtain the activated graphene after centrifugal separation and washing of the dispersion.

[0040] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.4 g of ammonium persulfate in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, and divide the ammonium persulfate aqueous solution into three equal parts. Then, add 0.15 g of activated graphene, 50 g of dimethyldiallylammonium chloride, 119 g of deionized water, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution into a three-necked flask, stir evenly, and then heat in a water bath to 80 °C and react for 15 min; then add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and react for 15 min in a water bath at 80 °C; add dropwise 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution again, and keep stirring and reacting at 80 °C in a water bath for 4.0 h, then cool to room temperature, and obtain the composite antibacterial finishing agent after filtration.

[0041] Example 6

[0042] (1) Preparation of activated graphene: Mix 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 8 g of γ-methacryloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 12 h, then cool to room temperature, and obtain the activated graphene after centrifugal separation and washing of the dispersion.

[0043] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.4 g of ammonium persulfate in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, and divide the ammonium persulfate aqueous solution into three equal parts. Then, add 0.45 g of activated graphene, 50 g of dimethyldiallylammonium chloride, 115.8 g of deionized water, 1.8 g of acrylic acid, 0.4 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution into a three-necked flask, stir evenly, and then heat in a water bath to 80 °C and react for 15 min; then dropwise add 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution, and react for 15 min in a water bath at 80 °C; dropwise add 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of the ammonium persulfate aqueous solution again, and keep stirring and reacting at 80 °C in a water bath for 4.0 h, then cool to room temperature, and filter to obtain the composite antibacterial finishing agent.

[0044] Example 7

[0045] (1) Preparation of activated graphene: Mix 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 8 g of γ-methacryloyloxypropyltrimethoxysilane evenly, ultrasonically disperse for 1 h to obtain a dispersion, reflux and react in a water bath at 60 °C for 12 h, then cool to room temperature, and the dispersion is centrifuged and washed to obtain activated graphene;

[0046] (2) Synthesis of the composite antibacterial finishing agent: First, dissolve 8.2 g of potassium persulfate in 16.4 g of deionized water to obtain a potassium persulfate aqueous solution, dissolve 2.2 g of sodium bisulfite in 9.8 g of deionized water to obtain a sodium bisulfite aqueous solution, and divide the potassium persulfate aqueous solution and the sodium bisulfite aqueous solution into three equal parts. Then, add 0.45 g of activated graphene, 50 g of dimethyldiallylammonium chloride, 117.6 g of deionized water, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, 8.2 g of the potassium persulfate aqueous solution, and 4 g of the sodium bisulfite aqueous solution into a three-necked flask, stir evenly, and then heat in a water bath to 80 °C and react for 15 min; then dropwise add 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, 8.2 g of the potassium persulfate aqueous solution, and 4 g of the sodium bisulfite aqueous solution, and react for 15 min in a water bath at 80 °C; dropwise add 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, 8.2 g of the potassium persulfate aqueous solution, and 4 g of the sodium bisulfite aqueous solution again, and keep stirring and reacting at 80 °C in a water bath for 4.0 h, then cool to room temperature, and filter to obtain the composite antibacterial finishing agent.

[0047] Example 8

[0048] (1) Preparation of active graphene: 2.0 g of graphene, 80 g of ethanol, 36 g of water, and 8 g of γ-methacryloyloxypropyltrimethoxysilane were mixed evenly and ultrasonically dispersed for 1 h to obtain a dispersion. The dispersion was refluxed in a water bath at 60 °C for 12 h, and then cooled to room temperature. The dispersion was centrifuged and washed to obtain active graphene;

[0049] (2) Synthesis of composite antibacterial finishing agent: First, 8.4 g of ammonium persulfate was dissolved in 16.8 g of deionized water to obtain an ammonium persulfate aqueous solution, which was equally divided into three portions. Then, 0.45 g of active graphene, 50 g of dimethyldiallylammonium chloride, 117.6 g of deionized water, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of ammonium persulfate aqueous solution were added to a three-necked flask, stirred evenly, and then heated in a water bath to 80 °C and reacted for 15 min; then 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of ammonium persulfate aqueous solution were added dropwise, and the reaction was carried out in a water bath at 80 °C for 15 min; again, 1.2 g of acrylic acid, 0.6 g of allyl glycidyl ether, and 8.4 g of ammonium persulfate aqueous solution were added dropwise, and the reaction was carried out under stirring in a water bath at 80 °C for 4.0 h, and then cooled to room temperature. After filtration, the composite antibacterial finishing agent was obtained.

[0050] The composite antibacterial finishing agents prepared in Examples 1-8 were respectively formulated with water into antibacterial agents with a concentration of 100 g / L. Eight identical pure cotton knitted fabrics with a weight of 110 g / m 2 (each weighing 120 g) were respectively immersed in the antibacterial agents prepared from the composite antibacterial finishing agents prepared in Examples 1-8 for padding, and the liquor pickup rate was 75%. After drying and setting, 1#-8# antibacterial fabrics were obtained.

[0051] According to the regulations of the National Standard of the People's Republic of China GB8629-2001 "Domestic Washing and Drying Procedures for Textile Testing", a Type B agitator washing machine and washing program 8B were selected to perform washing treatments on the 1#-8# antibacterial fabrics, commercially available antibacterial fabrics, and untreated pure cotton knitted fabrics respectively. Each sample was washed 10 times, 20 times, and 50 times, and the antibacterial properties of the washed samples were measured.

[0052] According to the test method for the antibacterial properties of products in the National Standard of the People's Republic of China GB1759-2002 "Hygienic Standard for Disposable Sanitary Products", the antibacterial properties of the washed samples were measured. The test strains were bacteria: Staphylococcus aureus (ATCC6538), Escherichia coli (ATCC 25922), and fungi: Candida albicans (ATCC 10231). The test results are shown in the following table:

[0053]

[0054]

[0055] Note: Bacteriostasis rate "***": ≥99%, "**": ≥90%, "*": ≥50%, "--": <50%.

[0056] It can be seen from the measurement results that the cotton fabrics treated with the antibacterial agents prepared from the composite antibacterial finishing agents prepared in Examples 1-8 all have good antibacterial properties and good wash resistance, and can also maintain good antibacterial properties after multiple washings, indicating that the cotton fabrics finished with the composite antibacterial finishing agents have good wash resistance and long-term good antibacterial effects.

[0057] The embodiments of the present invention have been described in detail above in conjunction with specific embodiments, but the present invention is not limited to the above embodiments. Even if various changes are made to the present invention, provided that these changes fall within the scope of the claims of the present invention and their equivalent technologies, they still fall within the protection scope of the present invention.

Claims

1. A preparation method of a textile antibacterial agent containing graphene and quaternary ammonium salt, characterized in that, it includes the following steps: The reaction raw materials, calculated by mass percentage, include: 0.2 - 1.0% of active graphene, 25 - 35% of dimethyldiallylammonium chloride, 1 - 3% of carboxyl acrylic acid monomers; 0.5 - 1% of allyl glycidyl ether; 3 - 6% of initiator and the balance of deionized water; The active graphene, dimethyldiallylammonium chloride, carboxyl acrylic acid monomers and allyl glycidyl ether generate a composite antibacterial finishing agent through a polymerization reaction initiated by an initiator in solvent water; Wherein the active graphene is active graphene modified by a silane coupling agent containing double bonds, and the preparation method of the active graphene is specifically: After mixing graphene, a silane coupling agent containing double bonds and a solvent, ultrasonic dispersion is carried out to obtain a dispersion liquid, and the dispersion liquid is refluxed for reaction for 10 - 20 hours to obtain active graphene; The solvent includes ethanol and water; the mass ratio of graphene, ethanol, water and the silane coupling agent containing double bonds is 1:10 - 20:30 - 60:1 - 5.

2. The preparation method of the textile antibacterial agent containing graphene and quaternary ammonium salt according to claim 1, characterized in that, the steps of preparing the composite antibacterial finishing agent are specifically: S1: Mix the active graphene, the dimethyldiallylammonium chloride, the deionized water, an initiator aqueous solution containing one-third of the initiator, one-third of the allyl glycidyl ether and one-third of the carboxyl acrylic acid monomers to obtain a mixed liquid; Heat the mixed liquid to 70 - 85 °C and stir and react for 8 - 15 minutes to obtain a first reaction liquid; S2: Dropwise add an initiator aqueous solution containing one-third of the initiator, one-third of the allyl glycidyl ether and one-third of the carboxyl acrylic acid monomers to the first reaction liquid, and stir and react at 70 - 85 °C for 10 - 20 minutes to obtain a second reaction liquid; S3: Dropwise add an initiator aqueous solution containing one-third of the initiator, one-third of the allyl glycidyl ether and one-third of the carboxyl acrylic acid monomers to the second reaction liquid, and stir and react at 70 - 85 °C for 3 - 5 hours to obtain the composite antibacterial finishing agent.

3. The preparation method of the textile antibacterial agent containing graphene and quaternary ammonium salt according to claim 1, characterized in that, the silane coupling agent containing double bonds is γ-methacryloxypropyltrimethoxysilane.

4. The preparation method of the textile antibacterial agent containing graphene and quaternary ammonium salt according to claim 1, characterized in that, the initiator is selected from at least one of sodium persulfate, potassium persulfate and ammonium persulfate; or the initiator includes at least one of sodium persulfate, potassium persulfate and ammonium persulfate and sodium bisulfite.

5. The preparation method of the textile antibacterial agent containing graphene and quaternary ammonium salt according to claim 1, characterized in that, the carboxyl acrylic acid monomers are selected from at least one of acrylic acid and methacrylic acid.

6. A textile antibacterial agent containing graphene and quaternary ammonium salt, characterized in that, The textile antibacterial agent containing graphene and quaternary ammonium salt is obtained by the preparation method described in any one of claims 1-5.

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