阅读说明：本技术 一种石墨烯复合体系水性杀菌消毒剂及其制备方法 (Graphene composite system water-based bactericidal disinfectant and preparation method thereof ) 是由 李艳红 黄永强 王雨婷 于 2021-07-26 设计创作，主要内容包括：本发明公开了一种石墨烯复合体系水性杀菌消毒剂及其制备方法,属于消毒剂生产技术领域。且该种石墨烯复合体系水性杀菌消毒剂包括以下重量百分比的组分：8-35％改性包覆银离子分散液、20-60％氧化石墨烯分散液、3.5-8.5％分散剂、1.5-3.5％乳化剂、0.5-1.5％消泡剂、余量为水。其制备方法包括：步骤一、改性包覆银离子分散液和氧化石墨烯分散液的混合,获得混合液；步骤二、步骤一获得的混合液与剩余物料的混合。且本发明以氧化石墨烯为负载材料,与高分子季铵盐包覆的溴化银复合物进一步复合,形成具有多重抗菌功效的复合材料,且该复合材料水溶性好,用其制成的抗菌剂抗菌高效,毒性低,无腐蚀性。(The invention discloses a graphene composite system aqueous sterilization disinfectant and a preparation method thereof, and belongs to the technical field of disinfectant production. The graphene composite system aqueous sterilization disinfectant comprises the following components in percentage by weight: 8-35% of modified coated silver ion dispersion liquid, 20-60% of graphene oxide dispersion liquid, 3.5-8.5% of dispersing agent, 1.5-3.5% of emulsifying agent, 0.5-1.5% of defoaming agent and the balance of water. The preparation method comprises the following steps: mixing modified coated silver ion dispersion liquid and graphene oxide dispersion liquid to obtain mixed liquid; and step two, mixing the mixed liquid obtained in the step one with the rest materials. The composite material with multiple antibacterial effects is formed by further compounding the graphene oxide serving as a load material and a silver bromide compound coated by the high-molecular quaternary ammonium salt, and the composite material is good in water solubility, and the antibacterial agent prepared from the composite material is high in antibacterial efficiency, low in toxicity and free of corrosiveness.)

1. The graphene composite system aqueous sterilization disinfectant is characterized by comprising the following components in percentage by weight: 8-35% of modified coated silver ion dispersion liquid, 20-60% of graphene oxide dispersion liquid, 3.5-8.5% of dispersing agent, 1.5-3.5% of emulsifying agent, 0.5-1.5% of defoaming agent and the balance of water;

the modified coated silver ion dispersion is prepared by the following steps:

a, introducing nitrogen into absolute ethyl alcohol for 5min, sequentially adding 4-vinylpyridine, (3-acrylamidopropyl) trimethyl ammonium chloride and an initiator azobisisobutyronitrile under the conditions of nitrogen and stirring, heating a reaction system to 62 ℃, stirring for reacting for 30h, precipitating with deionized water after the reaction is finished, filtering, washing, and drying in vacuum to obtain an intermediate product 1;

step B, uniformly stirring the intermediate product 1 and nitromethane, then adding 1-bromohydrocarbon under the conditions of nitrogen and stirring, heating the reaction system to 68 ℃, stirring and reacting for 18 hours, and after the reaction is finished, precipitating with diethyl ether, filtering, washing and drying in vacuum to obtain an intermediate product 2;

step C, uniformly mixing nitromethane and dimethyl sulfoxide, then adding silver p-toluenesulfonate, and carrying out ultrasonic dispersion for 5min to obtain a solution a; uniformly mixing the intermediate product 2 and nitromethane to obtain a solution b; dropping the solution a into the solution b at the speed of 1 drop/second under 200-300r/min in an ice bath, heating the system to room temperature after the dropping is finished, continuing stirring for reaction for 20-60min, then precipitating with diethyl ether, filtering, washing, and drying in vacuum to obtain an intermediate product 2-coated silver bromide compound;

and D, completely dissolving the compound obtained in the step C in absolute ethyl alcohol to obtain the modified coated silver ion dispersion liquid.

2. The graphene composite system aqueous disinfectant and sterilization agent as claimed in claim 1, wherein the amount ratio of the absolute ethyl alcohol, the 4-vinylpyridine, (3-acrylamidopropyl) trimethyl ammonium chloride and the azobisisobutyronitrile in the step A is 200-500 mL: 1-1.5 mol: 1 mol: 3-5 g.

3. The graphene composite system aqueous disinfectant according to claim 1, wherein the amount ratio of the intermediate product 1, nitromethane and 1-bromohydrocarbon in the step B is 8-12 g: 80-200 mL: 0.5-1.5g, 1-bromohydrocarbon is one of linear alkyl bromides with 6-16 carbon atoms.

4. The graphene composite system aqueous disinfectant according to claim 1, wherein the mass ratio of the solution a to the solution b in the step C is 1: 1-1.5, wherein the dosage ratio of nitromethane, dimethyl sulfoxide and silver p-toluenesulfonate in the solution a is 1 mL: 1mL of: 0.05-0.1g, the dosage ratio of the intermediate product 2 to the nitromethane in the solution b is 0.05-0.1 g: 2 mL.

5. The graphene composite system aqueous disinfectant according to claim 1, wherein the mass ratio of the composite to the absolute ethyl alcohol in the step D is 0.005-0.01: 1.

6. the preparation method of the graphene composite system aqueous disinfectant according to claim 1, characterized by comprising the following steps:

step one, dropwise adding the modified coated silver ion dispersion liquid into the graphene oxide dispersion liquid under a stirring state, wherein the dropwise adding speed is 3 drops/second, after the dropwise adding is completed, heating the temperature of a reaction system to 68 ℃, continuously stirring for reacting for 36 hours, stopping stirring, and cooling to room temperature to obtain a mixed liquid c;

step two, uniformly stirring the dispersing agent, the emulsifying agent, the defoaming agent and water at room temperature and 300r/min, then adding the mixed solution c obtained in the step one at room temperature and 1200r/min, and stirring for 4-8h to obtain the graphene composite system aqueous sterilization disinfectant.

Technical Field

The invention belongs to the technical field of disinfectant production, and particularly relates to a graphene composite system aqueous disinfectant and a preparation method thereof.

Background

The disinfectant is widely applied to crowd concentrated areas to reduce the infection and the flow of germs in the crowd, such as hospitals, schools and subway stations. In particular, in hospitals, there are more patients and more concentrated germs. Currently, there are several major types of disinfectants on the market, namely acids, alcohols, halogens, oxidants, and gas-volatile alkanes. The above disinfectants have some common disadvantages, namely poor stability, high corrosiveness and strong irritation to human body, some of them have certain toxicity and harm to human body, for example, phenols have large influence on respiratory tract and lung of human body, and even have carcinogenic effect.

For example, chinese patent CN1102050A provides a quaternary ammonium salt compound disinfectant, and the main components of the quaternary ammonium salt compound disinfectant are composed of a double-long-chain quaternary ammonium salt containing 8-12 carbon atoms, a single-long-chain quaternary ammonium salt containing 8-16 carbon atoms, penta-carbon diacetal and formaldehyde, and the quaternary ammonium salt compound disinfectant is formed by diluting with an organic or inorganic solution, and is applied to various disinfection places. However, the quaternary ammonium salt compound disinfectant has the defects of low disinfection effect and incomplete disinfection.

Therefore, the invention provides a graphene composite system aqueous disinfectant and a preparation method thereof.

Disclosure of Invention

The invention aims to provide a graphene composite system aqueous disinfectant and a preparation method thereof, and aims to solve the technical problems of low efficiency, strong corrosivity and strong toxicity of the existing disinfectant.

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

a graphene composite system aqueous sterilization disinfectant comprises the following components in percentage by weight: 8-35% of modified coated silver ion dispersion liquid, 20-60% of graphene oxide dispersion liquid, 3.5-8.5% of dispersing agent, 1.5-3.5% of emulsifying agent, 0.5-1.5% of defoaming agent and the balance of water.

Further, the dispersing agent is one or a mixture of several of sodium dodecyl sulfate, methyl amyl alcohol and fatty acid polyglycol ester in any ratio.

Further, the emulsifier is one or a mixture of several of polyoxyethylene ether, polyoxypropylene ether, polyol fatty acid ester and polyvinyl alcohol in any ratio.

Further, the defoaming agent is organic silicone oil.

Further, the modified coated silver ion dispersion is prepared by the following steps:

step A, adding absolute ethyl alcohol into a three-neck flask, introducing nitrogen for 5min, discharging air in a solvent, sequentially adding 4-vinylpyridine, (3-acrylamidopropyl) trimethyl ammonium chloride and an initiator azobisisobutyronitrile under the conditions of nitrogen and stirring, heating a reaction system to 62 ℃ in a water bath kettle, stirring for reaction for 30h, precipitating with deionized water after the reaction is finished, filtering, washing with deionized water for 3 times, and drying in a vacuum drying oven for 12h to obtain an intermediate product 1, wherein the reaction formula is shown as follows;

step B, sequentially adding the intermediate product 1 and nitromethane into a three-neck flask, stirring until the intermediate product 1 is completely dissolved, then adding 1-bromohydrocarbon under the conditions of nitrogen and stirring, heating a reaction system to 68 ℃ by using a water bath kettle, stirring for reacting for 18 hours, after the reaction is finished, precipitating by using diethyl ether, filtering, washing for 3 times by using deionized water, placing the obtained solid precipitate in a vacuum drying oven for drying for 12 hours to obtain an intermediate product 2, wherein the reaction formula is shown as follows;

step C, mixing the nitromethane and the dimethyl sulfoxide uniformly to form a mixed solution, then adding the silver p-toluenesulfonate, and carrying out ultrasonic dispersion for 5min to obtain a solution a; adding the intermediate product 2 into a flask, then adding 10mL of nitromethane, and performing ultrasonic treatment until the nitromethane is completely dissolved to obtain a solution b; dropwise adding the solution a into the solution b by using a constant-pressure dropping funnel under the conditions of ice bath and 300r/min, wherein the dropping speed is 1 drop/second, raising the temperature of the system to room temperature after dropping, continuously stirring for reaction for 20-60min, then precipitating by using ether, filtering, washing for 3 times by using deionized water, and drying the obtained solid precipitate in a vacuum drying box for 12 hours to obtain an intermediate product 2-coated silver bromide compound;

and D, dissolving the compound obtained in the step C in absolute ethyl alcohol, and performing ultrasonic treatment until the compound is completely dissolved to obtain the modified coated silver ion dispersion liquid.

Further, the dosage ratio of the absolute ethyl alcohol, the 4-vinylpyridine, (3-acrylamidopropyl) trimethyl ammonium chloride and the azobisisobutyronitrile in the step A is 200-500 mL: 1-1.5 mol: 1 mol: 3-5 g.

Further, the using amount ratio of the intermediate product 1, the nitromethane and the 1-bromohydrocarbon in the step B is 8-12 g: 80-200 mL: 0.5-1.5g of 1-bromohydrocarbon is one of linear brominated alkanes with 6-16 carbon atoms, namely R in the reaction formula of the step B is C₆H₁₃、C₇H_15、C₈H_17、C₉H_19、C₁₀H_21、C₁₁H_23、C₁₂H_23、C₁₃H_25、C₁₄H_27、C₁₅H_31、C₁₆H₃₃One kind of (1).

Further, the mass ratio of the solution a to the solution b in the step C is 1: 1-1.5, wherein the dosage ratio of nitromethane, dimethyl sulfoxide and silver p-toluenesulfonate in the solution a is 1 mL: 1mL of: 0.05-0.1g, the dosage ratio of the intermediate product 2 to the nitromethane in the solution b is 0.05-0.1 g: 2 mL.

Further, the mass ratio of the compound in the step D to the absolute ethyl alcohol is 0.005-0.01: 1.

further, the graphene oxide dispersion liquid is prepared by the following steps: dissolving graphene oxide in absolute ethyl alcohol, performing ultrasonic dispersion until the solution is uniform, adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to be between 8 and 9, and obtaining the graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the absolute ethyl alcohol is 0.005-0.01: 4.

a preparation method of a graphene composite system aqueous disinfectant comprises the following steps:

step one, dropwise adding the modified coated silver ion dispersion liquid into the graphene oxide dispersion liquid by using a constant-pressure dropping funnel under a stirring state, wherein the dropping speed is 3 drops/second, heating the temperature of a reaction system to 68 ℃ after complete dropwise addition, continuously stirring for reacting for 36 hours, stopping stirring, and cooling to room temperature to obtain a mixed liquid c;

step two, uniformly stirring the dispersing agent, the emulsifying agent, the defoaming agent and water at room temperature and 300r/min, then adding the mixed solution c obtained in the step one at room temperature and 1200r/min, and stirring for 4-8h to obtain the graphene composite system aqueous sterilization disinfectant.

The invention has the beneficial effects that:

1. the invention synthesizes the macromolecule quaternary ammonium salt antibacterial agent by using 4-vinylpyridine and (3-acrylamidopropyl) trimethyl ammonium chloride as copolymerization materials, and in order to increase the antibacterial performance of the macromolecule, the nitrogen on the pyridine ring is subjected to quaternary ammonification process, so that the charge density in the macromolecule is increased, and the antibacterial performance of the macromolecule is enhanced; thirdly, a coordination bond is formed between nitrogen on the pyridine ring and metal ions, so that the polymer quaternary ammonium salt can coat the metal ions, and by utilizing the principle, the invention finishes the coating of silver bromide by the polymer quaternary ammonium salt and realizes the compounding of two compounds with different antibacterial mechanisms, wherein the antibacterial mechanism of the polymer quaternary ammonium salt is contact type antibacterial, the silver ions are release type antibacterial agents, the compound application of bactericides with different antibacterial mechanisms is finished, a compound antibacterial material with multiple components is constructed, the advantages of each component are exerted, so that the synergistic antibacterial effect is realized, and the antibacterial activity and the effect of the compound antibacterial agent are enhanced; finally, the graphene oxide is selected as a load material, rich oxygen-containing functional groups on the surface of the graphene oxide are utilized, metal ions can be firmly combined, the surface of the graphene oxide is in a negative charge state, electrostatic attraction can be formed between the graphene oxide and the polymer quaternary ammonium salt with positive charge, and a water-soluble system of the graphene oxide has a certain antibacterial effect on germ cells, so that the composition of three antibacterial materials can be formed, and the antibacterial effect of the composite material is further enhanced;

2. in addition, due to the fact that the graphene oxide is good in water solubility, the use of organic solvents in the antibacterial agent is reduced, on one hand, the shortcoming of flammability of a common antibacterial agent is overcome, on the other hand, the dispersibility of the triple antibacterial effect material in water is promoted, and the stability of the antibacterial agent is improved;

3. finally, because the graphene oxide material utilized by the invention has no toxicity and corrosiveness on cells, and the high-molecular quaternary ammonium salt material is mild, relatively safe and also has no corrosiveness, the effective concentration of silver ions in the antibacterial agent can be greatly reduced and the toxicity and corrosiveness of the antibacterial agent can be reduced by compounding the two materials with the silver ions.

In conclusion, the graphene composite system aqueous sterilization disinfectant provided by the invention has the characteristics of high antibacterial efficiency, no toxicity and no corrosion.

Detailed Description

The technical solutions in the embodiments of the present invention are clearly and completely described, 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 silver ion-coated dispersion liquid is prepared by the following steps:

step A, adding absolute ethyl alcohol into a three-neck flask, introducing nitrogen for 5min, discharging air in a solvent, sequentially adding 4-vinylpyridine, (3-acrylamidopropyl) trimethyl ammonium chloride and an initiator azobisisobutyronitrile under the conditions of nitrogen and stirring, heating a reaction system to 62 ℃ in a water bath kettle, stirring for reaction for 30h, precipitating with deionized water after the reaction is finished, filtering, washing with deionized water for 3 times, and drying in a vacuum drying oven for 12h to obtain an intermediate product 1;

step B, sequentially adding the intermediate product 1 and nitromethane into a three-neck flask, stirring until the intermediate product 1 is completely dissolved, then adding 1-bromohydrocarbon under the conditions of nitrogen and stirring, heating a reaction system to 68 ℃ by using a water bath kettle, stirring for reacting for 18 hours, after the reaction is finished, precipitating by using diethyl ether, filtering, washing a filter cake by using deionized water for 3 times, and placing the obtained solid precipitate in a vacuum drying oven for drying for 12 hours to obtain an intermediate product 2;

step C, mixing the nitromethane and the dimethyl sulfoxide uniformly to form a mixed solution, then adding the silver p-toluenesulfonate, and carrying out ultrasonic dispersion for 5min to obtain a solution a; adding the intermediate product 2 into a flask, then adding 10mL of nitromethane, and performing ultrasonic treatment until the nitromethane is completely dissolved to obtain a solution b; dropwise adding the solution a into the solution b by using a constant-pressure dropping funnel under 200r/min in an ice bath at the dropping speed of 1 drop/second, heating the system to room temperature after the dropping is finished, continuously stirring for reaction for 30min, then precipitating by using diethyl ether, filtering, washing a filter cake by using deionized water for 3 times, and drying the obtained solid precipitate in a vacuum drying oven for 12h to obtain an intermediate product 2-coated silver bromide compound;

and D, dissolving the compound obtained in the step C in absolute ethyl alcohol, and performing ultrasonic treatment until the compound is completely dissolved to obtain the modified coated silver ion dispersion liquid.

The amounts of the raw materials used in the above steps are shown in Table 1.

TABLE 1

Example 2:

the silver ion-coated dispersion liquid is prepared by the following steps: reference is made to the steps in example 1;

the amounts of the raw materials used in the above steps are shown in Table 2.

TABLE 2

Example 3:

the graphene oxide dispersion liquid is prepared by the following steps: dissolving graphene oxide in absolute ethyl alcohol, performing ultrasonic dispersion until the solution is uniform, adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to be 8, and obtaining the graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the absolute ethyl alcohol is 0.005: 4.

example 4:

the graphene oxide dispersion liquid is prepared by the following steps: dissolving graphene oxide in absolute ethyl alcohol, performing ultrasonic dispersion until the solution is uniform, adding ammonia water into the graphene oxide dispersion liquid to adjust the pH value of the solution to be 9, and obtaining the graphene oxide dispersion liquid, wherein the mass ratio of the graphene oxide to the absolute ethyl alcohol is 0.01: 4.

example 5:

the graphene composite system aqueous disinfectant comprises the raw materials and the weight percentage shown in table 3.

TABLE 3

The preparation method comprises the following steps: step one, dropwise adding the modified coated silver ion dispersion liquid into the graphene oxide dispersion liquid by using a constant-pressure dropping funnel under a stirring state of 300r/min, wherein the dropping speed is 3 drops/second, after the dropwise adding is completed, heating the temperature of a reaction system to 68 ℃, continuously stirring for reacting for 36 hours, stopping stirring, and cooling to room temperature to obtain a mixed liquid c;

and step two, uniformly stirring the dispersing agent, the emulsifying agent, the defoaming agent and water at room temperature and 300r/min, then adding the mixed solution c obtained in the step one at room temperature and 1200r/min, and stirring for 4 hours to obtain the graphene composite system water-based bactericidal disinfectant.

Example 6:

the graphene composite system aqueous disinfectant comprises the raw materials and the weight percentage shown in table 4.

TABLE 4

The preparation method comprises the following steps: step one, dropwise adding the modified coated silver ion dispersion liquid into the graphene oxide dispersion liquid by using a constant-pressure dropping funnel under a stirring state of 400r/min, wherein the dropping speed is 3 drops/second, after the dropwise adding is completed, heating the temperature of a reaction system to 68 ℃, continuously stirring for reacting for 36 hours, stopping stirring, and cooling to room temperature to obtain a mixed liquid c;

and step two, uniformly stirring the dispersing agent, the emulsifying agent, the defoaming agent and water at room temperature and 300r/min, then adding the mixed solution c obtained in the step one at room temperature and 1200r/min, and stirring for 8 hours to obtain the graphene composite system water-based bactericidal disinfectant.

Example 7:

the graphene composite system aqueous disinfectant comprises the raw materials in percentage by weight as shown in Table 5.

TABLE 5

Modified coated silver ion dispersion liquid: preparation for example 1	35％
		Graphene oxide dispersion liquid: preparation for example 3	60％
Dispersing agent: fatty acid polyglycol ester	8.5％
		Emulsifier: polyvinyl alcohol	3.5％
Defoaming agent: organic silicone oil	1.5％
		Water (W)	Balance of

The preparation method comprises the following steps: step one, dropwise adding the modified coated silver ion dispersion liquid into the graphene oxide dispersion liquid by using a constant-pressure dropping funnel under a stirring state of 350r/min, wherein the dropping speed is 3 drops/second, after the dropwise adding is completed, heating the temperature of a reaction system to 68 ℃, continuously stirring for reacting for 36 hours, stopping stirring, and cooling to room temperature to obtain a mixed liquid c;

step two, uniformly stirring the dispersing agent, the emulsifying agent, the defoaming agent and water at room temperature and 300r/min, then adding the mixed solution c obtained in the step one at room temperature and 1200r/min, and stirring for 4-8h to obtain the graphene composite system aqueous sterilization disinfectant.

Comparative example 1:

the silver ion dispersion liquid is prepared by the following steps:

dissolving silver bromide in water, and ultrasonically dispersing until the silver bromide is uniform to obtain a silver ion dispersion liquid, wherein the mass ratio of the silver bromide to the water is 0.005: 1.

comparative example 2:

the polymer quaternary ammonium salt dispersion liquid is prepared by the following steps:

step A, adding absolute ethyl alcohol into a three-neck flask, introducing nitrogen for 5min, discharging air in a solvent, sequentially adding 4-vinylpyridine, (3-acrylamidopropyl) trimethyl ammonium chloride and an initiator azobisisobutyronitrile under the conditions of nitrogen and stirring, heating a reaction system to 62 ℃ in a water bath kettle, stirring for reaction for 30h, precipitating with deionized water after the reaction is finished, filtering, and drying in a vacuum drying oven for 12h to obtain an intermediate product 1;

step B, sequentially adding the intermediate product 1 and nitromethane into a three-neck flask, stirring until the intermediate product 1 is completely dissolved, then adding 1-bromohydrocarbon under the conditions of nitrogen and stirring, heating a reaction system to 68 ℃ by using a water bath kettle, stirring for reacting for 18 hours, after the reaction is finished, precipitating by using diethyl ether, filtering, washing by using deionized water for 3 times, and placing the obtained solid precipitate in a vacuum drying oven for drying for 12 hours to obtain a high-molecular quaternary ammonium salt, namely the intermediate product 2;

and C, dissolving the high molecular quaternary ammonium salt obtained in the step B in absolute ethyl alcohol, and performing ultrasonic treatment until the high molecular quaternary ammonium salt is completely dissolved to obtain a high molecular quaternary ammonium salt dispersion liquid.

The amounts of the raw materials used in the above steps are shown in Table 6.

TABLE 6

Comparative example 3:

the graphene composite system aqueous disinfectant comprises the raw materials and the weight percentage shown in table 7.

TABLE 7

The preparation method comprises the following steps: refer to the steps of example 5.

Comparative example 4:

the graphene composite system aqueous disinfectant comprises the raw materials and the weight percentage shown in table 8.

TABLE 8

The preparation method comprises the following steps: refer to the steps of example 6.

Comparative example 5:

the graphene composite system aqueous disinfectant comprises the raw materials and the weight percentage shown in table 8.

TABLE 8

Modified coated silver ion dispersion liquid: preparation for example 1	35％
		Dispersing agent: fatty acid polyglycol ester	8.5％
Emulsifier: polyvinyl alcohol	3.5％
		Defoaming agent: organic silicone oil	1.5％
Water (W)	Balance of

The preparation method comprises the following steps: refer to the steps in example 7.

Example 8:

examples 5 to 7 and comparative examples 3 to 5 were subjected to an antibacterial test by the following test methods:

an antibacterial ring: first, the area is 2cm²The sterile filter paper sheets are put into 5mL of ethanol solution containing samples (the concentration of a bacteriostatic agent is 1mg/mL) to be soaked for 30min, then the sterile filter paper sheets are taken out to be dried, meanwhile, 100 mu L of escherichia coli bacterial liquid (107 plus 108CFU/mL) is transferred to a culture dish containing a solid culture medium by a liquid transfer gun, the bacterial liquid is uniformly coated and dispersed by a glass coater, then four filter paper sheets containing the samples are clamped by tweezers and placed into the culture dish containing the bacterial liquid, the culture dish is inverted in a constant temperature and humidity culture box and is cultured for 24h at 37 ℃, the filter paper sheets are taken out to observe the growth condition of bacteria around the filter paper sheets, each group is provided with three parallel samples, and staphylococcus aureus is tested according to the same method.

The sterilization rate is as follows: firstly, adding 100 mu L of triple distilled water into each hole of a 96-hole plate; secondly, respectively adding 500 mug/mL samples in the row 1, and sequentially diluting the samples to the next row by adopting a 2-time dilution method; then, adding 100 mu L of escherichia coli suspension or staphylococcus aureus suspension into each hole, uniformly mixing, putting into a constant-temperature incubator at 37 ℃ for culturing for 24h, and using a non-sample group as a control; and finally, measuring the OD value at 600nm by using a microplate reader, simultaneously dyeing the OD value by using a bacterial dyeing kit, marking live bacteria by using green light and dead bacteria by using red light, and calculating the sterilization rate, wherein the calculation formula is as follows:

wherein d (OD) is the optical density value of the control sample; d' (OD) is the optical density value of the sample.

The data obtained from the above tests are shown in table 9.

TABLE 9

From the data in Table 9, it can be seen that the antibacterial rings obtained in examples 5 to 7 and comparative examples 3 and 5 have the characteristics of the releasing type antibacterial agent and the data difference therebetween is not large, and the antibacterial agents obtained in the illustrated examples 5 to 7 and comparative examples 3 and 5 can release silver ions excessively; as can be seen from the antibacterial ratio data, the antibacterial efficacies of the antibacterial agents obtained in examples 5 to 7 are better than the corresponding performances of the antibacterial agents obtained in comparative examples 3 to 5.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

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.