Preparation process of a new liquid mildew and antibacterial agent

Abstract

The present invention relates to a new material, in particular to the technical field of coatings, and more particularly to a preparation process for a novel liquid mildew and antibacterial agent. The preparation process comprises the following steps: preparing an ionic liquid, preparing a microcapsule mildew-proof material, preparing a molecular sieve MCM-41-NH2, preparing a modified molecular sieve Ag / MCM-41-NH2, preparing a nanocomposite material, preparing a liquid antibacterial agent containing nanosilver, and the like. The novel liquid mildew and antibacterial agent prepared by the present invention, which creatively combines a solvent purification technology and other preparation methods, has the advantages of a simple preparation process, being environmentally friendly, having excellent mildew-proof performance, and having a long antibacterial effect, can be used in multiple fields such as the textile industry, the construction industry, and the medical protection industry.

Description

Technical Field

[0001] The present invention relates to the technical field of new materials, in particular to coatings, and in particular to a preparation process of a novel liquid mildew and antibacterial agent. Background Art

[0002] With the rapid development of society and the significant improvement in people's living standards, the public's attention to personal health and environmental protection has been increasing. In recent years, there have been many outbreaks of infectious diseases caused by pathogenic microorganisms around the world. These incidents not only threaten global public health security, but also have brought major impacts on the economy and society.

[0003] Especially in the field of textiles and leather products, since the production process is often in a relatively humid environment, leather and other materials are rich in fat and protein, which are very susceptible to microbial invasion, resulting in frequent mildew. Mildew not only forms spots of various colors on the leather surface, but also is difficult to completely remove even after subsequent treatment. This not only reduces the aesthetics and market value of the product, but also further erodes the leather structure and affects performance. In addition, some molds can produce toxins that are harmful to the human body. Long-term exposure may cause serious health problems. Therefore, the development of disinfection and antibacterial products that are both environmentally friendly and efficient has become a social consensus. Summary of the Invention

[0004] In view of the above problems, the present invention provides a preparation process of a novel liquid mildew and antibacterial agent.

[0005] The invention relates to a preparation process of a novel liquid mildew and antibacterial agent, comprising the following steps: preparing an ionic liquid, preparing a microcapsule mildew-proof material, preparing a molecular sieve MCM-41-NH2, preparing a modified molecular sieve Ag / MCM-41-NH2, preparing a nanocomposite material, and preparing a liquid antibacterial agent containing nanosilver.

[0006] Preferably, in step (1), the preparation of the ionic liquid

[0007] An appropriate amount of trilaurylamine and an appropriate amount of hexadecane bromide are added to a three-necked flask, and a certain amount of acetonitrile is added as a solvent. Under nitrogen protection, the mixture is stirred for reaction, and the solvent is removed by distillation under reduced pressure. Ethanol is then added to dissolve the mixture, and then an appropriate amount of sodium bis(2-ethylhexyl) phosphate is added. After the reaction, the mixture is distilled under reduced pressure. N-hexane is added to the residue, and the mixture is allowed to stand for a period of time, and then filtered. The filtrate is collected to obtain an ionic liquid.

[0008] Step (2) Preparation of microcapsule anti-mildew material

[0009] Weigh an appropriate amount of gelatin and an appropriate amount of gum arabic, soak and swell them with an appropriate amount of the ionic liquid in step (1), heat and dissolve them, weigh an appropriate amount of isothiazolinone (OIT, BBIT, BIT), and use an emulsifier to make a mixed emulsion of the three, then mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir, continue stirring, add warm water, and then add glutaraldehyde to solidify, continue stirring, and let it stand overnight. Centrifuge the prepared microcapsule suspension for a period of time, wash the precipitate with isopropyl alcohol, then wash with anhydrous ethanol, and vacuum dry to obtain a microcapsule anti-mildew material;

[0010] Step (3) Preparation of molecular sieve MCM-41-NH2

[0011] MCM-41 (ordered mesoporous silica material) was dissolved in anhydrous ethanol, APTES (3-aminopropyltriethoxysilane) was added dropwise, and the microcapsule mildew-proof material of step (2) was added together, stirred and refluxed, and the resulting mixed solution was filtered and washed with ethanol and water respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain a surface amino-modified molecular sieve MCM-41-NH2;

[0012] Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0013] Add nanosilver (Ag) to the molecular sieve MCM-41-NH2 in step (3) and dissolve them together in anhydrous ethanol, then gradually add ascorbic acid solution dropwise, seal and stir in a dark place, then add an appropriate amount of sodium citrate solution dropwise, filter the resulting mixed solution, and wash with ethanol and water respectively to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs;

[0014] Step (5) Preparation of nanocomposite materials

[0015] First, water, OP-10 (dodecylphenol polyoxyethylene ether) and SDS (sodium dodecyl sulfate) are added to a three-necked flask, and then the modified molecular sieve Ag / MCM-41-NH2 of step (4) is added, the temperature is raised, emulsified for a period of time, and the reaction is performed to obtain a seed emulsion, and then a shell monomer mixture (including KH570) is added to the seed emulsion and reacted. After the reaction is completed, the mixture is allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion, and MCZ (mixed copper-zinc oxide) is mixed with the acrylate emulsion in a certain proportion, and the mixed solution is stirred evenly with a magnetic stirrer, and ultrasonically dispersed for a period of time to obtain a nanocomposite material;

[0016] Step (6) Preparation of liquid antibacterial agent containing nanosilver

[0017] Take an appropriate amount of the nanocomposite material of step (5) and add it to the ionic liquid, then add PVP (polyvinyl pyrrolidone), stir and mix evenly to obtain an antibacterial liquid containing nanosilver, then put the pre-prepared aluminum spray into an automated filling device, fill and seal the device, and finally obtain a liquid antibacterial agent containing nanosilver.

[0018] The first technical purpose of the present invention is achieved through the following technical solutions:

[0019] Preferably, in step (1), the preparation of the ionic liquid

[0020] 0.1-0.5 mol of trilaurylamine and 0.1-0.5 mol of hexadecane bromide were added to a three-necked flask, and 150-200 mL of acetonitrile was added as a solvent. After stirring and reacting for 70-80 hours under N2 protection, the solvent was removed by distillation under reduced pressure. 10-20 g of ethanol was added to dissolve it, and then 0.1-0.5 mol of sodium bis(2-ethylhexyl) phosphate was added. After reacting for 24-48 hours, distillation was carried out under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 12-24 hours before filtering. The filtrate was collected to obtain an ionic liquid.

[0021] The present invention has the advantages that the preparation process is carried out under nitrogen protection, which effectively avoids the occurrence of oxidative side reactions, ensures the high purity of the product, and at the same time can ensure the stability and antibacterial effect of the product. The use of solvents such as acetonitrile and n-hexane not only helps to improve the product yield, but also the prepared ionic liquid has good antibacterial properties.

[0022] As a preferred method, step (2) preparation of microcapsule anti-mildew material

[0023] Weigh 10-20 g of gelatin and 15-20 g of gum arabic, take 10-20 mL of the ionic liquid of step (1) to soak and swell, heat and dissolve, then weigh 10-20 g of isothiazolinone (OIT, BBIT, BIT), use an emulsifier to make a mixed emulsion, then mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir for 1-5 hours to adjust the pH value to 3-5, continue stirring for 30-60 minutes, add 20-50 mL of 50-100 ° C warm water, then add 25-50% glutaraldehyde to solidify for 30-60 minutes, adjust the pH value to 10-20, continue stirring for 20-40 minutes, let it stand overnight, centrifuge the prepared microcapsule suspension for 30-60 minutes, wash the precipitate with isopropyl alcohol 1-5 times, wash with anhydrous ethanol 2-6 times, and vacuum dry to obtain a microcapsule anti-mildew material.

[0024] The advantage of the present invention is that the prepared material forms a stable microcapsule structure, which not only improves the sustained release performance of the mildew inhibitor, but also reduces decomposition and volatilization caused by direct exposure.

[0025] Moreover, adjusting the pH value enhances the stability and mildew-proof effect of the microcapsules, and utilizing preparation processes such as emulsification and solidification ensures the purity and uniformity of the microcapsules.

[0026] The second technical purpose of the present invention is achieved through the following technical solutions:

[0027] As a preference, step (3) preparation of molecular sieve MCM-41-NH2

[0028] Dissolve 3-10 g of MCM-41 (ordered mesoporous silica material) in 10-20 mL of anhydrous ethanol, add 10-20 mL of APTES (3-aminopropyltriethoxysilane) dropwise, and add 10-20 g of the microcapsule anti-mildew material from step (2) at the same time. Stir and reflux for 12-24 h. Filter the resulting mixed solution and wash it with ethanol and water for 3-10 times respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain the surface amino-modified molecular sieve MCM-41-NH2.

[0029] The advantage of the present invention is that by combining the microcapsule mildew-proof material of the previous step with MCM-41, the antibacterial component can be continuously released on the surface of the material, ensuring long-term effective protection, ensuring the high purity of the product, and ensuring the stability and antibacterial effect of the product. APTES (3-aminopropyltriethoxysilane) is used for surface amino modification, which improves the surface activity of the molecular sieve MCM-41 and enhances its adsorption capacity and ability to load antibacterial agents.

[0030] As a preference, step (4) preparation of modified molecular sieve Ag / MCM-41-NH2

[0031] 10-20 g of nanosilver (Ag) was added to 10-20 mL of the molecular sieve MCM-41-NH2 prepared in step (3), and the mixture was dissolved in 15-30 mL of anhydrous ethanol. 0.01-0.05 mol / L of ascorbic acid solution was gradually added dropwise. The mixture was sealed and stirred at 40-60 ° C in a dark place for 30-60 min, and then an appropriate amount of 0.05-0.1 mol / L of sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed with ethanol and water for 3-10 times, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0032] The invention has the advantage of combining the high-efficiency antibacterial performance of nanosilver with the excellent adsorption performance of the surface amino-modified molecular sieve MCM-41-NH2, thereby ensuring the stability and antibacterial effect of the product and enhancing the adsorption capacity of the molecular sieve Ag / MCM-41-NH2.

[0033] Preferably, step (5) preparation of nanocomposite materials

[0034] First, 30-60 mL of water, 1.5-5 g of OP-10 (dodecylphenol polyoxyethylene ether) and 0.5-1 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 10-20 g of the modified molecular sieve Ag / MCM-41-NH2 of step (4) was added. The temperature was raised to 80-100 ° C., emulsified for 30-60 min, and reacted for 2-6 h to obtain a seed emulsion. Then, 10-20 g of a shell monomer mixture (containing 5-10 g of KH570) was added to the seed emulsion and reacted for 2-10 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 1-5:2-5, and the mixed solution was stirred evenly with a magnetic stirrer for 5-10 min at a speed of 500-1000 r / min and ultrasonically dispersed for 10-20 min to obtain a nanocomposite material.

[0035] The advantage of the present invention is that, by optimizing the emulsification and polymerization conditions, the modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs is successfully combined with the shell monomer mixture to form a stable silicon-containing acrylate emulsion, and then MCZ (mixed copper-zinc oxide) is introduced and subjected to magnetic stirring and ultrasonic dispersion treatment, thereby ensuring the uniformity and stability of the nanocomposite material, improving the heat resistance and corrosion resistance of the nanocomposite material, and also having excellent antibacterial and mildew-proof properties, improving the surface activity of the molecular sieve MCM-41, and enhancing its adsorption capacity and ability to load antibacterial agents.

[0036] Preferably, step (6) is the preparation of a liquid antibacterial agent containing nanosilver

[0037] Take 2-5g of the nanocomposite material prepared in step (5) and add it to 50-100mL of ionic liquid. Then add 0.01-0.05g of PVP (polyvinyl pyrrolidone) and stir for 20-50min to mix evenly to obtain an antibacterial liquid containing nanosilver. Then put the pre-prepared aluminum spray into an automated filling device, which fills and seals the device to finally obtain a liquid antibacterial agent containing nanosilver.

[0038] The advantage of the present invention is that by mixing the nanocomposite material containing nanosilver with the ionic liquid, antibacterial components can be continuously released on the liquid surface of the nanosilver, thereby ensuring long-term effective protection.

[0039] In summary, the present invention has the following beneficial effects:

[0040] 1. The advantages of the present invention are that the preparation process is carried out under nitrogen protection, which effectively avoids the occurrence of oxidative side reactions, ensures the high purity of the product, and at the same time can ensure the stability and antibacterial effect of the product. The use of solvents such as acetonitrile and n-hexane not only helps to improve the product yield, but also the prepared ionic liquid has good antibacterial properties;

[0041] 2. The advantages of the present invention are that the prepared material forms a stable microcapsule structure, which not only improves the sustained release performance of the mildew inhibitor and reduces the decomposition and volatilization caused by direct exposure, but also adjusts the pH value to enhance the stability and mildew prevention effect of the microcapsules. The preparation process of emulsification and solidification ensures the purity and uniformity of the microcapsules.

[0042] 3. The advantage of the present invention is that by combining the microcapsule mildew-proof material of the previous step with MCM-41, the antibacterial component can be continuously released on the surface of the material, ensuring long-term effective protection and high purity of the product. In addition, in order to ensure the stability and antibacterial effect of the product, APTES (3-aminopropyltriethoxysilane) is used for surface amino modification, which improves the surface activity of the molecular sieve MCM-41 and enhances its adsorption capacity and ability to load antibacterial agents;

[0043] 4. The advantage of the present invention is that it combines the high-efficiency antibacterial properties of nanosilver with the excellent adsorption properties of the surface amino-modified molecular sieve MCM-41-NH2, ensuring the stability and antibacterial effect of the product while enhancing the adsorption capacity of the molecular sieve Ag / MCM-41-NH2;

[0044] 5. The advantages of the present invention are that, by optimizing the emulsification and polymerization conditions, the modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs is successfully combined with the shell monomer mixture to form a stable silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) is then introduced and subjected to magnetic stirring and ultrasonic dispersion treatments to ensure the uniformity and stability of the nanocomposite material, improve the heat resistance and corrosion resistance of the nanocomposite material, and also have excellent antibacterial and mildew-proof properties. The surface activity of the molecular sieve MCM-41 is increased, and its adsorption capacity and ability to load antibacterial agents are enhanced.

[0045] 6. The advantage of the present invention is that by mixing the nanocomposite material containing nanosilver with the ionic liquid, the antibacterial component can be continuously released on the liquid surface of the nanosilver, ensuring long-term effective protection. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 This is a process flow chart for the preparation of a new liquid mildew and antibacterial agent. DETAILED DESCRIPTION

[0047] The following examples are provided to illustrate the present invention but are not intended to limit the scope of the present invention. Without departing from the spirit and substance of the present invention, modifications or substitutions made to the methods, steps or conditions of the present invention are within the scope of the present invention.

[0048] Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. In addition, all the components and raw materials used in the examples are known commercial products. Example 1

[0049] like Figure 1 The preparation process of a new liquid mildew and antibacterial agent is shown in Figure 1 , specifically including:

[0050] Step (1) Preparation of ionic liquid

[0051] 0.1 mol of trilaurylamine and 0.1 mol of hexadecane bromide were added to a three-necked flask, and 150 mL of acetonitrile was added as a solvent. After stirring and reacting for 70 hours under N2 protection, the solvent was distilled off under reduced pressure, and 10 g of ethanol was added to dissolve it. Then, 0.1 mol of sodium bis(2-ethylhexyl) phosphate was added, and after reacting for 24 hours, distillation was carried out under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 12 hours, and then filtered. The filtrate was collected to obtain an ionic liquid;

[0052] Step (2) Preparation of microcapsule anti-mildew material

[0053] Weigh 10 g of gelatin and 15 g of gum arabic, soak and swell 10 mL of the ionic liquid of step (1), heat and dissolve, weigh 10 g of isothiazolinone (OIT, BBIT, BIT), and use an emulsifier to make a mixed emulsion. Then, mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir for 1 hour to adjust the pH value to 3, continue stirring for 30 minutes, add 20 mL of 50 ° C warm water, and then add 25% glutaraldehyde to solidify for 35 minutes, adjust the pH value to 10, continue stirring for 20 minutes, let it stand overnight, centrifuge the obtained microcapsule suspension for 30 minutes, wash the precipitate with isopropyl alcohol once, wash it with anhydrous ethanol twice, and vacuum dry it to obtain a microcapsule anti-mildew material;

[0054] Step (3) Preparation of molecular sieve MCM-41-NH2

[0055] 3 g of MCM-41 (ordered mesoporous silica material) was dissolved in 10 mL of anhydrous ethanol, and 10 mL of APTES (3-aminopropyltriethoxysilane) was added dropwise. At the same time, 10 g of the microcapsule mildew-proof material from step (2) was added together. The mixture was stirred and refluxed for 12 h. The resulting mixed solution was filtered and washed with ethanol and water three times respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain a surface amino-modified molecular sieve MCM-41-NH2.

[0056] Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0057] 10 g of nanosilver (Ag) was added to 10 mL of the molecular sieve MCM-41-NH2 prepared in step (3), and the mixture was dissolved in 15 mL of anhydrous ethanol. 0.01 mol / L ascorbic acid solution was then gradually added dropwise. The mixture was sealed and stirred at 40°C in the dark for 30 min, and then an appropriate amount of 0.05 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed three times with ethanol and water, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0058] Step (5) Preparation of nanocomposite materials

[0059] First, 30 mL of water, 1.5 g of OP-10 (dodecylphenol polyoxyethylene ether) and 0.5 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 10 g of the modified molecular sieve Ag / MCM-41-NH2 in step (4) was added. The temperature was raised to 80 ° C., emulsified for 30 min, and reacted for 2 h to obtain a seed emulsion. Then, 10 g of a shell monomer mixture (including 5 g of KH570) was added to the seed emulsion and reacted for 2 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 1:2, and the mixed solution was stirred evenly with a magnetic stirrer for 5 min at a speed of 500 r / min and ultrasonically dispersed for 10 min to obtain a nanocomposite material.

[0060] Step (6) Preparation of liquid antibacterial agent containing nanosilver

[0061] Take 2 g of the nanocomposite material prepared in step (5) and add it to 50 mL of the ionic liquid. Then add 0.01 g of PVP (polyvinyl pyrrolidone) and stir for 20 min to mix evenly to obtain an antibacterial liquid containing nanosilver. Then put the pre-prepared aluminum spray into an automated filling device, which fills and seals the device to finally obtain a liquid antibacterial agent containing nanosilver. Example 2

[0062] Step (1) Preparation of ionic liquid

[0063] 0.2 mol of trilaurylamine and 0.2 mol of hexadecane bromide were added to a three-necked flask, and 160 mL of acetonitrile was added as a solvent. The mixture was stirred under N2 protection for 73 h, and then the solvent was removed by distillation under reduced pressure. 12 g of ethanol was added to dissolve the mixture, and then 0.2 mol of sodium bis(2-ethylhexyl) phosphate was added. The mixture was reacted for 26 h and then distilled under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 14 h, and then filtered. The filtrate was collected to obtain an ionic liquid.

[0064] Step (2) Preparation of microcapsule anti-mildew material

[0065] Weigh 13 g of gelatin and 16 g of gum arabic, take 12 mL of the ionic liquid of step (1) and soak them in the ionic liquid for swelling, then heat and dissolve them, weigh 12 g of isothiazolinone (OIT, BBIT, BIT), and use an emulsifier to make a mixed emulsion. Then, mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir for 2 h to adjust the pH value to 4, continue stirring for 35 min, add 25 mL of 55 ° C warm water, and then add 30% glutaraldehyde to solidify for 40 min, adjust the pH value to 12, continue stirring for 25 min, let it stand overnight, centrifuge the obtained microcapsule suspension for 35 min, wash the precipitate with isopropyl alcohol twice, wash with anhydrous ethanol three times, and vacuum dry to obtain a microcapsule anti-mildew material;

[0066] Step (3) Preparation of molecular sieve MCM-41-NH2

[0067] 5 g of MCM-41 (ordered mesoporous silica material) was dissolved in 13 mL of anhydrous ethanol, and 12 mL of APTES (3-aminopropyltriethoxysilane) was added dropwise. At the same time, 12 g of the microcapsule mildew-proof material from step (2) was added together. The mixture was stirred and refluxed for 14 h. The resulting mixed solution was filtered and washed with ethanol and water four times respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain a surface amino-modified molecular sieve MCM-41-NH2.

[0068] Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0069] 13 g of nanosilver (Ag) was added to 15 mL of the molecular sieve MCM-41-NH2 prepared in step (3), and the mixture was dissolved in 20 mL of anhydrous ethanol. 0.02 mol / L ascorbic acid solution was then gradually added dropwise. The mixture was sealed and stirred at 45°C in the dark for 35 min, and then 0.06 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed four times with ethanol and water, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0070] Step (5) Preparation of nanocomposite materials

[0071] First, 35 mL of water, 2 g of OP-10 (dodecylphenol polyoxyethylene ether) and 0.6 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 12 g of the modified molecular sieve Ag / MCM-41-NH2 in step (4) was added. The temperature was raised to 85 ° C., emulsified for 35 min, and reacted for 3 h to obtain a seed emulsion. Then, 15 g of a shell monomer mixture (including 5 g of KH570) was added to the seed emulsion and reacted for 3 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 2:3, and the mixed solution was stirred evenly with a magnetic stirrer for 7 min at a speed of 600 r / min and ultrasonically dispersed for 13 min to obtain a nanocomposite material.

[0072] Step (6) Preparation of liquid antibacterial agent containing nanosilver

[0073] Take 3 g of the nanocomposite material prepared in step (5) and add it to 60 mL of the ionic liquid. Then add 0.02 g of PVP (polyvinyl pyrrolidone) and stir for 25 min to mix evenly to obtain an antibacterial liquid containing nanosilver. Then put the pre-prepared aluminum spray into an automated filling device, which performs filling and sealing to finally obtain a liquid antibacterial agent containing nanosilver. Example 3

[0074] Step (1) Preparation of ionic liquid

[0075] 0.3 mol of trilaurylamine and 0.3 mol of hexadecane bromide were added to a three-necked flask, and 170 mL of acetonitrile was added as a solvent. The mixture was stirred under N2 protection for 75 h, and then the solvent was removed by distillation under reduced pressure. 15 g of ethanol was added to dissolve the mixture, and then 0.3 mol of sodium bis(2-ethylhexyl) phosphate was added. The mixture was reacted for 30 h and then distilled under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 15 h, and then filtered. The filtrate was collected to obtain an ionic liquid.

[0076] Step (2) Preparation of microcapsule anti-mildew material

[0077] Weigh 15 g of gelatin and 18 g of gum arabic, soak and swell 16 mL of the ionic liquid of step (1), heat and dissolve, weigh 15 g of isothiazolinone (OIT, BBIT, BIT), and use an emulsifier to make a mixed emulsion. Then, mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir for 4 hours to adjust the pH value to 5, continue stirring for 40 minutes, add 30 mL of 70 ° C warm water, and then add 40% glutaraldehyde to solidify for 50 minutes, adjust the pH value to 17, continue stirring for 30 minutes, let it stand overnight, centrifuge the obtained microcapsule suspension for 50 minutes, wash the precipitate with isopropyl alcohol 4 times, wash it with anhydrous ethanol 5 times, and vacuum dry it to obtain a microcapsule anti-mildew material;

[0078] Step (3) Preparation of molecular sieve MCM-41-NH2

[0079] 7g of MCM-41 (ordered mesoporous silica material) was dissolved in 17mL of anhydrous ethanol, and 17mL of APTES (3-aminopropyltriethoxysilane) was added dropwise. At the same time, 16g of the microcapsule mildew-proof material of step (2) was added together. The mixture was stirred and refluxed for 20h. The obtained mixed solution was filtered and washed with ethanol and water for 7 times respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain the surface amino-modified molecular sieve MCM-41-NH2;

[0080] Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0081] 17 g of nanosilver (Ag) was added to 17 mL of the molecular sieve MCM-41-NH2 prepared in step (3), and the mixture was dissolved in 25 mL of anhydrous ethanol. 0.04 mol / L ascorbic acid solution was gradually added dropwise. The mixture was sealed and stirred at 50°C in a dark place for 40 min, and then 0.07 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed with ethanol and water for 7 times, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0082] Step (5) Preparation of nanocomposite materials

[0083] First, 50 mL of water, 4 g of OP-10 (dodecylphenol polyoxyethylene ether) and 0.7 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 17 g of the modified molecular sieve Ag / MCM-41-NH2 of step (4) was added. The temperature was raised to 90 ° C., emulsified for 50 min, and reacted for 5 h to obtain a seed emulsion. Then, 17 g of a shell monomer mixture (including 8 g of KH570) was added to the seed emulsion and reacted for 7 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 4:4, and the mixed solution was stirred evenly with a magnetic stirrer for 9 min at a speed of 700 r / min and ultrasonically dispersed for 15 min to obtain a nanocomposite material.

[0084] Step (6) Preparation of liquid antibacterial agent containing nanosilver

[0085] 4 g of the nanocomposite material prepared in step (5) was added to 70 mL of the ionic liquid, and then 0.03 g of PVP (polyvinyl pyrrolidone) was added and stirred for 30 min to mix evenly to obtain an antibacterial liquid containing nanosilver. The prepared aluminum spray was then placed in an automated filling device, which was used for filling and sealing to finally obtain a liquid antibacterial agent containing nanosilver. Example 4

[0086] Step (1) Preparation of ionic liquid

[0087] 0.5 mol of trilaurylamine and 0.5 mol of hexadecane bromide were added to a three-necked flask, and 200 mL of acetonitrile was added as a solvent. After stirring and reacting for 80 h under N2 protection, the solvent was distilled off under reduced pressure, and 20 g of ethanol was added to dissolve it. Then, 0.5 mol of sodium bis(2-ethylhexyl) phosphate was added, and the mixture was reacted for 48 h and distilled off under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 24 h, and then filtered. The filtrate was collected to obtain an ionic liquid;

[0088] Step (2) Preparation of microcapsule anti-mildew material

[0089] Weigh 20 g of gelatin and 20 g of gum arabic, soak and swell 20 mL of the ionic liquid of step (1), heat and dissolve, weigh 20 g of isothiazolinone (OIT, BBIT, BIT), and use an emulsifier to make a mixed emulsion. Then, mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir for 5 hours to adjust the pH value to 5, continue stirring for 60 minutes, add 45 mL of 80 ° C warm water, and then add 50% glutaraldehyde to solidify for 60 minutes, adjust the pH value to 20, continue stirring for 35 minutes, let it stand overnight, centrifuge the obtained microcapsule suspension for 60 minutes, wash the precipitate with isopropyl alcohol 5 times, wash it with anhydrous ethanol 6 times, and vacuum dry it to obtain a microcapsule anti-mildew material;

[0090] Step (3) Preparation of molecular sieve MCM-41-NH2

[0091] Dissolve 10g of MCM-41 (ordered mesoporous silica material) in 20mL of anhydrous ethanol, add 20mL of APTES (3-aminopropyltriethoxysilane) dropwise, and add 20g of the microcapsule mildew-proof material in step (2) together, stir and reflux for 24h, filter the resulting mixed solution and wash it with ethanol and water 10 times respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain the surface amino-modified molecular sieve MCM-41-NH2;

[0092] Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0093] 20 g of nanosilver (Ag) was added to 20 mL of the molecular sieve MCM-41-NH2 prepared in step (3), and the mixture was dissolved in 30 mL of anhydrous ethanol. 0.05 mol / L ascorbic acid solution was gradually added dropwise. The mixture was sealed and stirred at 60°C in a dark place for 55 min, and then 0.08 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed 10 times with ethanol and water, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0094] Step (5) Preparation of nanocomposite materials

[0095] First, 60 mL of water, 5 g of OP-10 (dodecylphenol polyoxyethylene ether) and 1 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 20 g of the modified molecular sieve Ag / MCM-41-NH2 of step (4) was added. The temperature was raised to 100 ° C., emulsified for 60 min, and reacted for 6 h to obtain a seed emulsion. Then, 20 g of a shell monomer mixture (including 10 g of KH570) was added to the seed emulsion and reacted for 9 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 5:5, and the mixed solution was stirred evenly with a magnetic stirrer for 10 min at a speed of 900 r / min and ultrasonically dispersed for 17 min to obtain a nanocomposite material.

[0096] Step (6) Preparation of liquid antibacterial agent containing nanosilver

[0097] 5 g of the nanocomposite material prepared in step (5) was added to 100 mL of the ionic liquid, and then 0.04 g of PVP (polyvinyl pyrrolidone) was added and stirred for 45 min to mix evenly to obtain an antibacterial liquid containing nanosilver. The prepared aluminum spray was then placed in an automated filling device, which was used for filling and sealing to finally obtain a liquid antibacterial agent containing nanosilver. Comparative Example 1

[0098] Step (1) Preparation of ionic liquid

[0099] 0.9 mol of trilaurylamine and 0.9 mol of hexadecane bromide were added to a three-necked flask, and 250 mL of acetonitrile was added as a solvent. After stirring and reacting for 90 hours under N2 protection, the solvent was distilled off under reduced pressure, and 25 g of ethanol was added to dissolve it. Then, 0.7 mol of sodium bis(2-ethylhexyl) phosphate was added, and after reacting for 50 hours, distillation was carried out under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 30 hours, and then filtered. The filtrate was collected to obtain an ionic liquid;

[0100] Step (2) Preparation of molecular sieve MCM-41-NH2

[0101] 20 g of MCM-41 (ordered mesoporous silica material) was dissolved in 30 mL of anhydrous ethanol, 29 mL of APTES (3-aminopropyltriethoxysilane) was added dropwise, and 10 mL of the ionic liquid of step (1) was added, and the mixture was stirred and refluxed for 30 h. The resulting mixed solution was filtered and washed 15 times with ethanol and water respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain the surface amino-modified molecular sieve MCM-41-NH2;

[0102] Step (3) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0103] 25 g of nanosilver (Ag) was added to 30 mL of the molecular sieve MCM-41-NH2 prepared in step (2), and the mixture was dissolved in 30 mL of anhydrous ethanol. 0.09 mol / L ascorbic acid solution was gradually added dropwise. The mixture was sealed and stirred at 70°C in the dark for 60 min, and then 0.09 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed 15 times with ethanol and water, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0104] Step (4) Preparation of nanocomposite materials

[0105] First, 70 mL of water, 7 g of OP-10 (dodecylphenol polyoxyethylene ether) and 8 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 26 g of the modified molecular sieve Ag / MCM-41-NH2 in step (3) was added. The temperature was raised to 120 ° C., emulsified for 70 min, and reacted for 9 h to obtain a seed emulsion. Then, 40 g of a shell monomer mixture (including 20 g of KH570) was added to the seed emulsion and reacted for 11 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 7:8, and the mixed solution was stirred evenly with a magnetic stirrer for 15 min at a speed of 1000 r / min and ultrasonically dispersed for 20 min to obtain a nanocomposite material.

[0106] Step (5) Preparation of liquid antibacterial agent containing nanosilver

[0107] 8 g of the nanocomposite material prepared in step (4) was added to 120 mL of the ionic liquid, and then 0.05 g of PVP (polyvinyl pyrrolidone) was added and stirred for 50 min to mix evenly to obtain an antibacterial liquid containing nanosilver. The prepared aluminum spray was then placed in an automated filling device, which was used for filling and sealing to finally obtain a liquid antibacterial agent containing nanosilver. Comparative Example 2

[0108] Step (1) Preparation of molecular sieve MCM-41-NH2

[0109] 20g MCM-41 (ordered mesoporous silica material) was dissolved in 30mL of anhydrous ethanol, 29mL APTES (3-aminopropyltriethoxysilane) was added dropwise, 10mL of ionic liquid was added, and the mixture was stirred and refluxed for 30h. The resulting mixed solution was filtered and washed with ethanol and water 15 times respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain the surface amino-modified molecular sieve MCM-41-NH2;

[0110] Step (2) Preparation of modified molecular sieve Ag / MCM-41-NH2

[0111] 25 g of nanosilver (Ag) was added to 30 mL of the molecular sieve MCM-41-NH2 prepared in step (1), and the mixture was dissolved in 30 mL of anhydrous ethanol. 0.09 mol / L ascorbic acid solution was gradually added dropwise. The mixture was sealed and stirred at 70°C in a dark place for 60 min, and then 0.09 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed 15 times with ethanol and water, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

[0112] Step (3) Preparation of nanocomposite materials

[0113] First, 70 mL of water, 7 g of OP-10 (dodecylphenol polyoxyethylene ether) and 8 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 26 g of the modified molecular sieve Ag / MCM-41-NH2 in step (2) was added. The temperature was raised to 120 ° C., emulsified for 70 min, and reacted for 9 h to obtain a seed emulsion. Then, 40 g of a shell monomer mixture (including 20 g of KH570) was added to the seed emulsion and reacted for 11 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. MCZ (mixed copper-zinc oxide) was mixed with the acrylate emulsion in a ratio of 7:8, and the mixed solution was stirred evenly with a magnetic stirrer for 15 min at a speed of 1000 r / min and ultrasonically dispersed for 20 min to obtain a nanocomposite material.

[0114] Step (4) Preparation of liquid antibacterial agent containing nanosilver

[0115] 8 g of the nanocomposite material prepared in step (3) was added to 120 mL of the ionic liquid, and then 0.05 g of PVP (polyvinyl pyrrolidone) was added and stirred for 50 min to mix evenly to obtain an antibacterial liquid containing nanosilver. The prepared aluminum spray was then placed in an automated filling device, which was used for filling and sealing to finally obtain a liquid antibacterial agent containing nanosilver.

[0116] Comparison of detection experiments:

[0117] The liquid antibacterial agents containing nanosilver obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were tested. The specific testing methods are as follows:

[0118] Antibacterial testing method

[0119] The antibacterial rate test method is used to evaluate the antibacterial performance and antibacterial durability of the prepared liquid antifungal and antimicrobial agent. A high initial antibacterial rate indicates that the antibacterial agent has a strong ability to kill bacteria, and also indicates that the antibacterial agent can take effect quickly and can quickly kill bacteria upon initial contact.

[0120] This test uses Staphylococcus aureus, a commonly used microorganism. If the initial antibacterial rate of the test is high, it means that the prepared antibacterial agent has strong antibacterial efficacy and long antibacterial durability. If the initial antibacterial rate of the test is low, the antibacterial efficacy and antibacterial effect are poor.

[0121] Mold Growth Inhibition Test (MIC)

[0122] The mold growth inhibition test method is used to evaluate the mold inhibition effect of liquid antifungal agents. The MIC value refers to the minimum drug concentration that can inhibit mold growth. A circular leather piece that has been treated with mold prevention is placed on a bacterial plate, and then the liquid antifungal agent is sprayed on the bacterial plate. After 14 days of incubation and observation, the MIC value is measured to obtain the mold growth situation. If the MIC value is small, the mold occupies a small area of ​​the bacterial plate and there is a small amount of mold growth, indicating that the prepared liquid antifungal agent has a strong antifungal effect. If the MIC value is large, the opposite is true.

[0123] Inhibition zone test

[0124] The inhibition zone test is a method used to evaluate the inhibitory effect of antimicrobial substances on microbial growth. It uses the diffusion of antimicrobial substances in the culture medium to inhibit the growth of surrounding microorganisms. The size of the inhibition zone reflects the antimicrobial strength of the antimicrobial substance. The larger the inhibition zone, the stronger the antimicrobial effect of the antimicrobial substance, and the smaller the inhibition zone, the stronger the antimicrobial effect.

[0125] Table 1 Antibacterial test method

[0126]

[0127] As can be seen from Table 1, Example 1 is the best and Comparative Example 2 is the worst. In Example 1, its initial antibacterial rate is the highest, indicating that the prepared liquid mildew and antibacterial agent has a strong ability to kill bacteria and can take effect quickly, quickly killing bacteria upon initial contact. This is because the nanoparticles themselves have extremely strong antibacterial properties and can effectively kill a variety of bacteria and fungi. By being loaded on the molecular sieve to achieve sustained release, the antibacterial effect is further improved. The liquid mildew and antibacterial agent prepared by Comparative Example 2 lacks the high-efficiency antibacterial benefit of the microcapsule mildew-proof material, resulting in a low initial antibacterial rate and poor effect.

[0128] Table 2 Mold Growth Inhibition Test (MIC)

[0129]

[0130] As shown in Table 2, Example 1 performed best, while Comparative Example 2 performed poorly. In Example 1, the MIC value was 25%, indicating that the area of ​​mold growth accounted for a relatively small portion of the plate containing the bacteria. This indicates that the liquid mildew and antimicrobial agent prepared by this method has a strong mildew-proofing effect. The liquid mildew and antimicrobial agent can inhibit mildew growth at a relatively low concentration. Nanosilver effectively inhibits mildew growth and reproduction, allowing the mildew-proofing component to more effectively inhibit mildew growth. In Comparative Example 2, the MIC value was 65%, indicating that the area of ​​mold growth accounted for a relatively large portion of the plate containing the bacteria, resulting in a poor mildew-proofing effect.

[0131] Table 3 Inhibition zone test method

[0132]

[0133] As shown in Table 3, Example 1 performed best, while Comparative Example 2 performed poorly. In Example 1, the diameter of the inhibition zone was 18 mm, indicating that the liquid mildew and antimicrobial agent formed a relatively large inhibition zone. This large inhibition zone diameter reflects the liquid mildew and antimicrobial agent's ability to effectively inhibit the growth of surrounding microorganisms, demonstrating its strong antimicrobial effect. The diameter of the inhibition zone in Comparative Example 2 was 8 mm, indicating that the liquid mildew and antimicrobial agent was unable to effectively inhibit the growth of bacteria and other microorganisms, resulting in poor antimicrobial effectiveness.

[0134] This specific embodiment is merely an explanation of the present invention and does not limit the present invention. After reading this specification, those skilled in the art can make non-creative modifications to this embodiment as needed, but as long as they are within the scope of the claims of the present invention, they are protected by patent law.

Claims

1. A preparation process of a novel liquid mildew and antibacterial agent, characterized in that: include: Preparation of ionic liquids, preparation of microcapsule mildew-proof materials, preparation of molecular sieve MCM-41-NH2, preparation of modified molecular sieve Ag / MCM-41-NH2, preparation of nanocomposites, preparation of liquid mildew-proof and antibacterial agents containing nanosilver; specifically including Step (1) Preparation of ionic liquid An appropriate amount of trilaurylamine and an appropriate amount of hexadecane bromide are added to a three-necked flask, and a certain amount of acetonitrile is added as a solvent. Under nitrogen protection, the mixture is stirred for reaction, and the solvent is removed by distillation under reduced pressure. Ethanol is then added to dissolve the mixture, and then an appropriate amount of sodium bis(2-ethylhexyl) phosphate is added. After the reaction, the mixture is distilled under reduced pressure. N-hexane is added to the residue, and the mixture is allowed to stand for a period of time, and then filtered. The filtrate is collected to obtain an ionic liquid. Step (2) Preparation of microcapsule anti-mildew material Weigh an appropriate amount of gelatin and an appropriate amount of gum arabic, soak and swell them with an appropriate amount of the ionic liquid in step (1), heat and dissolve them, weigh an appropriate amount of isothiazolinone OIT, BBIT, and BIT, use an emulsifier to make a mixed emulsion, then mix the mixed emulsion, gelatin solution, and gum arabic solution and add them to a three-necked flask, stir, continue stirring, add warm water, then add glutaraldehyde to solidify, continue stirring, let it stand overnight, centrifuge the obtained microcapsule suspension for a period of time, wash the precipitate with isopropyl alcohol, then wash with anhydrous ethanol, and vacuum dry to obtain a microcapsule anti-mildew material; Step (3) Preparation of molecular sieve MCM-41-NH2 The ordered mesoporous silica material MCM-41 was dissolved in anhydrous ethanol, and APTES (3-aminopropyltriethoxysilane) was added dropwise. At the same time, the microcapsule mildew-proof material of step (2) was added together, and the mixture was stirred and refluxed. The resulting mixed solution was filtered and washed with ethanol and water respectively to remove excess APTES (3-aminopropyltriethoxysilane) to obtain the surface amino-modified molecular sieve MCM-41-NH2; Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2 Add nanosilver to the molecular sieve MCM-41-NH2 in step (3) and dissolve them together in anhydrous ethanol, then gradually add ascorbic acid solution dropwise, seal and stir in a dark place, then add an appropriate amount of sodium citrate solution dropwise, filter the resulting mixed solution, and wash with ethanol and water respectively to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs; Step (5) Preparation of nanocomposite materials First, water, OP-10 (dodecylphenol polyoxyethylene ether) and SDS (sodium dodecyl sulfate) are added to a three-necked flask, and then the modified molecular sieve Ag / MCM-41-NH2 of step (4) is added, the temperature is raised, emulsified for a period of time, and the reaction is performed to obtain a seed emulsion, and then a shell monomer mixture containing KH570 is added to the seed emulsion for reaction. After the reaction is completed, the mixture is allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion, and the mixed copper-zinc oxide MCZ is mixed with the acrylate emulsion in a certain proportion, and the mixed solution is stirred evenly with a magnetic stirrer, and ultrasonically dispersed for a period of time to obtain a nanocomposite material; Step (6) Preparation of liquid antifungal and antibacterial agent containing nanosilver Take an appropriate amount of the nanocomposite material of step (5) and add it to the ionic liquid, then add PVP (polyvinyl pyrrolidone), stir and mix evenly to obtain an antibacterial liquid containing nanosilver, then put the pre-prepared aluminum spray into an automated filling device, fill and seal the device, and finally obtain a liquid antifungal agent containing nanosilver.

2. The preparation process of a novel liquid mildew and antibacterial agent according to claim 1, characterized in that: Step (1) Preparation of ionic liquid 0.1-0.5 mol of trilaurylamine and 0.1-0.5 mol of hexadecane bromide were added to a three-necked flask, and 150-200 mL of acetonitrile was added as a solvent. After stirring and reacting for 70-80 hours under N2 protection, the solvent was removed by distillation under reduced pressure. 10-20 g of ethanol was added to dissolve it, and then 0.1-0.5 mol of sodium bis(2-ethylhexyl) phosphate was added. After reacting for 24-48 hours, distillation was carried out under reduced pressure. N-hexane was added to the residue, and the mixture was allowed to stand for 12-24 hours before filtering. The filtrate was collected to obtain an ionic liquid.

3. The preparation process of a novel liquid mildew and antibacterial agent according to claim 2, characterized in that: Step (2) Preparation of microcapsule anti-mildew material Weigh 10-20 g of gelatin and 15-20 g of gum arabic, take 10-20 mL of the ionic liquid of step (1) to soak and swell, heat and dissolve, then weigh 10-20 g of isothiazolinone OIT, BBIT, and BIT, use an emulsifier to make a mixed emulsion, then mix the mixed emulsion, gelatin solution and gum arabic solution and add them to a three-necked flask, stir for 1-5 hours to adjust the pH value to 3-5, continue stirring for 30-60 minutes, add 20-50 mL of 50-100 ° C warm water, then add 25-50% glutaraldehyde to solidify for 30-60 minutes, adjust the pH value to 10-20, continue stirring for 20-40 minutes, let it stand overnight, centrifuge the obtained microcapsule suspension for 30-60 minutes, wash the precipitate with isopropyl alcohol 1-5 times, wash with anhydrous ethanol 2-6 times, and vacuum dry to obtain a microcapsule anti-mildew material.

4. The preparation process of a novel liquid mildew and antibacterial agent according to claim 3, characterized in that: Step (3) Preparation of molecular sieve MCM-41-NH2 Dissolve 3-10 g of ordered mesoporous silica material MCM-41 in 10-20 mL of anhydrous ethanol, add 10-20 mL of APTES (3-aminopropyltriethoxysilane) dropwise, and add 10-20 g of the microcapsule anti-mildew material in step (2) at the same time, stir and reflux for 12-24 h, filter the resulting mixed solution and wash it with ethanol and water for 3-10 times respectively to remove excess APTES (3-aminopropyltriethoxysilane), thereby obtaining a surface amino-modified molecular sieve MCM-41-NH2.

5. The preparation process of a novel liquid mildew and antibacterial agent according to claim 4, characterized in that: Step (4) Preparation of modified molecular sieve Ag / MCM-41-NH2 10-20 g of nanosilver was added to 10-20 mL of the molecular sieve MCM-41-NH2 prepared in step (3), and the mixture was dissolved in 15-30 mL of anhydrous ethanol. An appropriate amount of 0.01-0.05 mol / L ascorbic acid solution was gradually added dropwise. The mixture was sealed and stirred at 40-60 ° C in a dark place for 30-60 min, and then 0.05-0.1 mol / L sodium citrate solution was added dropwise. The resulting mixed solution was filtered and washed with ethanol and water for 3-10 times, respectively, to obtain a modified molecular sieve Ag / MCM-41-NH2 loaded with AgNPs.

6. The preparation process of the novel liquid mildew and antibacterial agent according to claim 5, characterized in that: Step (5) Preparation of nanocomposite materials First, 30-60 mL of water, 1.5-5 g of OP-10 (dodecylphenol polyoxyethylene ether) and 0.5-1 g of SDS (sodium dodecyl sulfate) were added to a three-necked flask, and then 10-20 g of the modified molecular sieve Ag / MCM-41-NH2 of step (4) was added. The temperature was raised to 80-100 ° C., emulsified for 30-60 min, and reacted for 2-6 h to obtain a seed emulsion. Then, 10-20 g of a shell monomer mixture (containing 5-10 g of KH570) was added to the seed emulsion and reacted for 2-10 h. After the reaction was completed, the mixture was allowed to cool to room temperature to obtain a silicon-containing acrylate emulsion. The mixed copper-zinc oxide MCZ was mixed with the acrylate emulsion in a ratio of 1-5:2-5, and the mixed solution was stirred evenly with a magnetic stirrer for 5-10 min at a speed of 500-1000 r / min and ultrasonically dispersed for 10-20 min to obtain a nanocomposite material.

7. The preparation process of the novel liquid mildew and antibacterial agent according to claim 6, characterized in that: Step (6) Preparation of liquid antifungal and antibacterial agent containing nanosilver Take 2-5g of the nanocomposite material prepared in step (5) and add it to 50-100mL of ionic liquid. Then add 0.01-0.05g of PVP (polyvinyl pyrrolidone) and stir for 20-50min to mix evenly to obtain an antibacterial liquid containing nanosilver. Then put the pre-prepared aluminum spray into an automated filling device, which performs filling and sealing to finally obtain a liquid antifungal agent containing nanosilver.

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