Preparation method and application of super-hydrophobic antifouling coating with antibacterial function

Abstract

The application discloses a preparation method of an antibacterial super-hydrophobic antifouling coating, and belongs to the technical field of multifunctional composite antibacterial super-hydrophobic coating modification. The method comprises the following steps: S1, uniformly mixing n-octadecyl triethoxysilane, water and octadecyl trichlorosilane, and then standing and reacting to obtain a super-hydrophobic reaction product; and S2, diluting and dispersing the super-hydrophobic reaction product obtained in the step S1 with n-hexane to obtain a super-hydrophobic coating mixture. Further, silver nitrate can be added into water or silicone quaternary ammonium salt can be added into n-hexane to obtain a super-hydrophobic coating mixture with antibacterial effect. The method is based on improving the reaction rate of organosiloxane with alkyl oxygen or hydroxyl as a functional group, avoids the influence of organosiloxane modification with halogen as a functional group on the surface of a material, is simple and fast in operation, low in cost, environment-friendly, and can be produced on a large scale. Moreover, the method does not involve the use of adhesive and has little influence on the air permeability and hand feeling of fabric materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of multifunctional composite antibacterial super-hydrophobic coating modification, and particularly relates to a preparation method of a super-hydrophobic antifouling coating with antibacterial function and specific application of the coating prepared by the method. BACKGROUND

[0002] Super-hydrophobic coatings can be prepared by surface treatment technology, and can endow the coating surface with excellent antifouling and self-cleaning characteristics. Such coatings have broad market demand. At present, super-hydrophobic coatings have been successfully prepared on solid substrates by various methods, but the application of super-hydrophobic coatings is still limited by single surface function, complicated preparation steps, dangerous chemical materials selected, and inconvenience in large-area manufacturing.

[0003] Fang et al. (J. Adv. Eng. Mater., 2021, 23(12), 2102502) prepared hydrophobic silicone nanofilaments by base-catalyzed reaction of polymethylhydrosiloxane, and prepared flexible fabrics with excellent superhydrophobicity by thermal curing at 120℃. Ye et al. (J. Chem. Eng. J., 2021, 420, 127680) prepared a double-nanocomposite coated fabric by spraying method, and successfully prepared a durable antibacterial and antifouling textile with high efficiency of preventing bacterial adhesion by using polydimethylsiloxane as an adhesive to adhere fluorinated mesoporous silica. However, the current antifouling finishing usually uses an adhesive as a bonding layer, and the low surface energy nanoparticles are modified to the surface of the substrate by simple methods such as scraping and dipping, which has the fatal defect of easy damage of the surface structure and poor durability, and also has a great influence on the air permeability of some object surfaces. Tasixiang et al. (Prog. Org. Coat., 2019, 135, 41-50) obtained a strong, super-amphiphobic self-cleaning fabric on aramid fabric by using a two-step coating method of polytetrafluoroethylene microparticles and fluorinated alkylsilane. However, the flexibility of the fabric decreases and the air permeability decreases from 313mm / s to 10mm / s. The self-assembly of organosiloxane on the surface of the fabric can endow the substrate surface with durable antifouling performance without affecting the air permeability. There are two categories: organosiloxane with alkyl oxygen or hydroxyl as functional group has very slow reaction rate, usually needs to undergo long time heating reaction under strong acid catalysis, and consumes a large amount of water during the reaction process; organosiloxane with halogen as functional group is very sensitive to the humidity of the environment, and has very fast reaction rate (several tens of seconds to several minutes), the reaction process is difficult to control and releases a large amount of strong acid gas, which has a great influence on the mechanical properties. Zhang et al. (Nat. Commun., 2021, 12(1), 982.) prepared a superhydrophobic surface coating by the reaction of chlorosilane with water, which is simple and rapid, but a large amount of hydrogen chloride gas is generated during the reaction process. At present, it is of great practical significance to develop a multifunctional superhydrophobic coating with simple and rapid operation, low cost and environmental protection. SUMMARY

[0004] Based on the above technical problems, the present application provides a preparation method and application of a superhydrophobic antifouling coating with antibacterial function.

[0005] The technical solution adopted by the present application is:

[0006] A preparation method of a superhydrophobic antifouling coating with antibacterial function, comprising the following steps:

[0007] S1, uniformly mixing n-octadecyl triethoxysilane, water and octadecyl trichlorosilane, and then standing and reacting to obtain a superhydrophobic reaction product;

[0008] S2, diluting and dispersing the super-hydrophobic reaction product obtained in step S1 with n-hexane to obtain a super-hydrophobic coating mixture.

[0009] Preferably, in step S1, the amount ratio of n-octadecyl triethoxysilane to water is 1ml:20-80μL; the amount ratio of octadecyltrichlorosilane to n-octadecyl triethoxysilane is 1-6μL:1ml.

[0010] Preferably, in step S1, after mixing n-octadecyl triethoxysilane, water and octadecyltrichlorosilane, the mixture is first mixed uniformly on a vortex mixer and then treated by ultrasonic oscillation in an ultrasonic cleaner.

[0011] Preferably, in step S1, the standing reaction time is 1-5h.

[0012] Preferably, in step S1, silver nitrate is added when preparing the super-hydrophobic reaction product; the silver nitrate is first added to water to prepare a silver nitrate solution; then n-octadecyl triethoxysilane, octadecyltrichlorosilane and the silver nitrate solution are mixed uniformly.

[0013] Preferably, the concentration of the silver nitrate solution is 0.5-5wt%.

[0014] Preferably, in step S2, n-hexane is added to the super-hydrophobic reaction product; the volume fraction of the super-hydrophobic reaction product in the obtained super-hydrophobic coating mixture is 1-10%.

[0015] Preferably, in step S2, organosilicon quaternary ammonium salt is added when preparing the super-hydrophobic coating mixture.

[0016] Preferably, the organosilicon quaternary ammonium salt is first added to n-hexane to obtain an organosilicon quaternary ammonium salt / n-hexane solution, and then the organosilicon quaternary ammonium salt / n-hexane solution is added to the super-hydrophobic reaction product for mixing; the mass / volume ratio of the added amount of organosilicon quaternary ammonium salt to the amount of n-hexane is 0.01-0.04g / ml.

[0017] The application of the super-hydrophobic coating mixture prepared as above in the modification of the surface of solid materials is as follows:

[0018] The solid material is immersed in the obtained super-hydrophobic coating mixture, taken out after 12-24h, washed with n-hexane and then dried in air; or the obtained super-hydrophobic coating mixture is transferred to a spray bottle and sprayed on the solid material to obtain a super-hydrophobic antifouling coating with antibacterial function.

[0019] The beneficial technical effects of the present application are as follows:

[0020] a. Take alkyl siloxane as self-assembly prepolymer, trigger the reaction of the prepolymer by trace water and halogen siloxane, form a water-in-oil emulsion system, then dilute the emulsion system with organic solvent as medium, and complement the disadvantages of the two types of organic alkyl oxygen to the advantages of the whole reaction system.

[0021] b. Add water-soluble antibacterial agent silver nitrate in the reaction initiator water, and graft the antibacterial agent on the material surface in the copolymerization self-assembly process through the water initiator, so as to simultaneously give the material good antibacterial performance in the antifouling finishing process.

[0022] c. Add antibacterial agent organic silicon quaternary ammonium salt in the dilution dispersion solvent n-hexane, which is attached to the material surface without affecting the copolymerization self-assembly of the super-hydrophobic coating, so as to simultaneously give the material good antibacterial performance in the antifouling finishing process.

[0023] d. The antibacterial super-hydrophobic coating prepared by the application shows good dynamic hydrophobic effect and good antifouling and antibacterial performance.

[0024] e. The antibacterial super-hydrophobic coating prepared by the application shows good hydrophobic and antibacterial performance on the surface of the textile, and has little effect on the air permeability and mechanical properties of the fabric.

[0025] f. The preparation method of the antibacterial super-hydrophobic antifouling coating also has the advantages of simple and rapid operation, low cost, environmental friendliness, and large-scale production.

[0026] In summary, the application first takes alkyl siloxane as self-assembly prepolymer, triggers the reaction of the prepolymer by trace water (initiator) and halogen siloxane (catalyst), forms a water-in-oil emulsion system, and then dilutes the emulsion system with organic solvent as medium to finish the textile. On the basis of improving the reaction rate of organosiloxane with alkyl oxygen or hydroxyl as functional group, the influence of organosiloxane modification with halogen as functional group on the material surface is avoided. By adding water-soluble antibacterial agent silver nitrate in the above reaction initiator water or adding organic silicon quaternary ammonium salt in n-hexane, a super-hydrophobic coating mixture with antibacterial effect is obtained, and the textile is simultaneously given good antibacterial performance. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 The change curve of the contact angle of the coating obtained by the application example 1 and the comparative example 1 before and after adding catalyst with the change of the reaction time of the super-hydrophobic reaction product is shown in the following figure;

[0028] Figure 2SEM images of the super-hydrophobic coating mixture obtained by the present application using Example 1 and Comparative Example 1 impregnated on the surface of polyester fabric to form a coating layer, wherein (a) is the SEM image corresponding to the formation of a super-hydrophobic anti-fouling coating layer of Example 1, (b) is the SEM image corresponding to the formation of a super-hydrophobic anti-fouling coating layer of Comparative Example 1;

[0029] Figure 3 Effect of the antibacterial super-hydrophobic anti-fouling coating prepared by the present application on the contact angle of the coating layer under different conditions; wherein (a) shows the effect of different reaction times on the contact angle of the coating layer, (b) shows the effect of different water and reaction reagent dosage ratios on the contact angle of the coating layer, (c) shows the effect of different catalyst usage amounts on the contact angle of the coating layer, (d) shows the effect of different reaction reagents on the contact angle of the coating layer;

[0030] Figure 4 Application of the coating layer prepared by Example 3 of the present application on different material surfaces, wherein (a) shows application on the surface of fabric, (b) shows application on the surface of filter paper, (c) shows application on the surface of wood board, (d) shows application on the surface of sponge; water droplets are used in (b), (c), and (d);

[0031] Figure 5 Antibacterial effect of the coating layer prepared by Example 3 of the present application on the surface of cotton fabric; wherein (a1) shows the antibacterial performance of raw cotton fabric against Escherichia coli, (a2) shows the antibacterial performance of coated cotton fabric against Escherichia coli, (b1) shows the antibacterial performance of raw cotton fabric against Staphylococcus aureus, (b2) shows the antibacterial performance of coated cotton fabric against Staphylococcus aureus;

[0032] Figure 6 Effect of the coating layer prepared by Example 3 of the present application by changing the amount of OTS, etc. on the air permeability and mechanical properties of fabric; wherein (a) shows the effect of different amounts of water added in the coating layer reaction on the air permeability of cotton fabric, (b) shows the effect of the amount of catalyst added in the coating layer reaction on the air permeability of cotton fabric, (c) shows the effect of the coating layer on the mechanical properties of polyester fabric, (d) shows the effect of the coating layer on the mechanical properties of cotton fabric;

[0033] Figure 7 Change in the contact angle and antibacterial effect of the coating layer prepared by Example 3 of the present application after the experiment, wherein (a) shows the change in the contact angle after the water droplet experiment, (b) shows the change in the antibacterial effect after the washing experiment. DETAILED DESCRIPTION

[0034] The application discloses a preparation method and application of an antibacterial super-hydrophobic antifouling coating. The method comprises the following steps: (1) adding a small amount of water and octadecyltrichlorosilane into n-octadecyltriethoxysilane, ultrasonically oscillating to uniformly mix the n-octadecyltriethoxysilane, and then standing and reacting to obtain micron-to-nanometer hierarchical siloxane aggregates; (2) dispersing the aggregates in n-hexane to obtain a super-hydrophobic coating mixture; (3) adding silver nitrate into the initiator water or adding a silicone quaternary ammonium salt into n-hexane to obtain a super-hydrophobic coating mixture with antibacterial effect; and (4) forming the super-hydrophobic coating with antibacterial effect on the surface of a solid material by immersing or spraying the coating mixture. The application triggers the prepolymer reaction of octadecyltrichlorosilane and water on octadecyltriethoxysilane, forms a water-in-oil emulsion system, disperses the emulsion system in an organic solvent as a medium, and complements the disadvantages of the two types of organic alkyl oxygen into the advantages of the whole reaction system, so that the reaction speed is high, no gas is generated, and the reaction condition is simple. Further, the antibacterial agent is added into the reaction system to obtain the super-hydrophobic coating with antibacterial effect. On the basis of improving the reaction rate of the organic siloxane with alkyl oxygen or hydroxyl as a functional group, the method avoids the influence of the modification of the organic siloxane with halogen as a functional group on the surface of a material, and has the advantages of simple and rapid operation, low cost, environmental protection and large-scale production. Moreover, the method does not involve the use of adhesive, and has little influence on the air permeability and hand feeling of fabric materials.

[0035] The application will be further described in combination with specific examples.

[0036] Example 1

[0037] (1) 2 μL of octadecyltrichlorosilane and 20 μL of water are added into 1 ml of octadecyltriethoxysilane, and then the mixture is immediately placed on a vortex mixer at 3000 rpm for 10 s, ultrasonically treated in an ultrasonic cleaner for 10 s, and subjected to another round of vortex mixing for 10 s to obtain an emulsion.

[0038] (2) 500 μL of the obtained emulsion is transferred into a 20 mL vial. After standing and reacting for 2 hours, 10 mL of n-hexane is added into the vial to obtain a super-hydrophobic coating mixture.

[0039] Example 2

[0040] (1) 2 μL of octadecyltrichlorosilane and 45 μL of a 2wt% silver nitrate solution are added into 1 ml of octadecyltriethoxysilane, and then the mixture is immediately placed on a vortex mixer at 3000 rpm for 10 s, ultrasonically treated in an ultrasonic cleaner for 10 s, and subjected to another round of vortex mixing for 10 s.

[0041] (2) 500 μL of the obtained emulsion is transferred into a 20 mL vial. After 2 hours, 10 mL of n-hexane is added into the vial to obtain a super-hydrophobic coating mixture with antibacterial effect.

[0042] Example 3

[0043] (1) To 1 ml of octadecyltriethoxysilane was added 2 μL of octadecyltrichlorosilane and 20 μL of water, which was immediately placed on a vortex mixer at 3000 rpm for 10 s, followed by sonication in an ultrasonic cleaner for 10 s, and another round of vortex mixing for 10 s.

[0044] (2) 500 μL of the resulting emulsion was transferred to a 20 mL vial. After 2 hours, 10 mL of n-hexane containing 0.3 g of a silicone quaternary ammonium salt was added to the vial.

[0045] Example 4

[0046] (1) To 1 ml of octadecyltriethoxysilane was added 4 μL of octadecyltrichlorosilane and 65 μL of a 5 wt% silver nitrate solution, which was immediately placed on a vortex mixer at 3000 rpm for 10 s, followed by sonication in an ultrasonic cleaner for 10 s, and another round of vortex mixing for 10 s.

[0047] (2) 500 μL of the resulting emulsion was transferred to a 20 mL vial. After 1 hour, 15 mL of n-hexane was added to the vial.

[0048] Example 5

[0049] (1) To 1 ml of octadecyltriethoxysilane was added 2 μL of octadecyltrichlorosilane and 80 μL of water, which was immediately placed on a vortex mixer at 3000 rpm for 10 s, followed by sonication in an ultrasonic cleaner for 10 s, and another round of vortex mixing for 10 s.

[0050] (2) 500 μL of the resulting emulsion was transferred to a 20 mL vial. After 4 hours, 10 mL of n-hexane containing 0.1 g of a silicone quaternary ammonium salt was added to the vial.

[0051] Example 6

[0052] (1) To 1 ml of octadecyltriethoxysilane was added 6 μL of octadecyltrichlorosilane and 30 μL of water, which was immediately placed on a vortex mixer at 3000 rpm for 10 s, followed by sonication in an ultrasonic cleaner for 10 s, to give an emulsion.

[0053] (2) 500 μL of the resulting emulsion was transferred to a 20 mL vial. After 5 hours of standing reaction, 10 mL of n-hexane containing 0.2 g of a silicone quaternary ammonium salt was added to the vial.

[0054] Example 7

[0055] (1) Add 3 μL octadecyltrichlorosilane and 15 μL water to 1 ml of octadecyltriethoxysilane, immediately place it on a vortex mixer at 3000 rpm for 10 s, then ultrasonic treatment in an ultrasonic cleaner for 10 s to obtain an emulsion.

[0056] (2) Transfer 500 μL of the obtained emulsion into a 20 mL vial. After standing for 3 hours, add 20 mL of n-hexane containing 0.3 g of silicone quaternary ammonium salt into the vial.

[0057] Soak the solid material in the super-hydrophobic coating mixture finally prepared in the above examples, take it out of the solution after overnight, wash it with n-hexane for three times, and then dry it in air. Or, transfer the super-hydrophobic coating mixture prepared in the above examples into a spray bottle, spray it to the sample to be treated at an angle of 30° above the sample, to obtain a super-hydrophobic and anti-fouling coating with antibacterial function. The coating has good antibacterial effect and super-hydrophobic effect.

[0058] Comparative Example 1

[0059] (1) Add 20 μL water to 1 ml of octadecyltriethoxysilane, immediately place it on a vortex mixer at 3000 rpm for 10 s, then ultrasonic treatment in an ultrasonic cleaner for 10 s, and another round of vortex mixing for 10 s.

[0060] (2) Transfer 500 μL of the obtained emulsion into a 20 mL vial. After 2 hours, add 10 mL of n-hexane into the vial.

[0061] Take the coating mixture prepared in the examples and comparative examples, dip the polyester and cotton fabrics, observe the apparent morphology of the treated polyester and cotton fabrics, analyze the element composition, test the water contact angle, test the antibacterial property, test the air permeability and mechanical property, and evaluate the super-hydrophobic property, antibacterial property, air permeability, durability, etc. of the coating, the method and results are as follows:

[0062] (1) Super-hydrophobic property characterization:

[0063] Test the hydrophobic property of the polyester fabric soaked in the super-hydrophobic coating mixture prepared in Example 1 and Comparative Example 1 overnight, take it out of the solution, wash it with n-hexane for three times, and then dry it in air. Figure 1 The contact angle change of the super-hydrophobic coating mixture at different reaction times before and after adding octadecyltrichlorosilane (control step as in Example 1 and Comparative Example 1, change the standing reaction time). From Figure 1The test result analysis in Table 1 shows that the reaction speed is obviously accelerated and the contact angle is increased after catalysis by octadecyltrichlorosilane. When the reaction time is 2h, the contact angle of the coating catalyzed by octadecyltrichlorosilane is close to 160°, which is increased by more than 15° compared with the coating without catalysis. In addition, it can be seen from the SEM images in Table 1 that the micro-nano particles between the fibers of Comparative Example 1 without catalysis increase the surface roughness, so that the fabric has a hydrophobic effect, but the reaction is not complete and the particle distribution is not dense and uniform. The micro-nano particles generated by the reaction of Example 1 after catalysis self-assemble on the fibers to form a compact and highly oriented rough surface, which gives the fabric good hydrophobic effect. Figure 2

[0064] In order to obtain the best hydrophobic effect of the hydrophobic coating, the changes of the contact angle of the coating with different amounts of water and catalysts, the reaction time of the coating, and the hydrophobic effect of different reaction reagents are tested, as shown in Table 2. OTES is octadecyltriethoxysilane, OTS is octadecyltrichlorosilane, MTMS is methyltrimethoxysilane, and VTMS is vinyltrimethoxysilane. Figure 3

[0065] In order to characterize the super-hydrophobic and anti-fouling properties of the fabric, the anti-fouling properties of the modified fabric to soy sauce, cola, rose b dye solution and other liquids are tested, as shown in Table 3. Figure 4 Figure 4 It can be seen from Table 3 that the modified cotton fabric has excellent anti-fouling properties to the above liquids.

[0066] (2) Antibacterial property characterization:

[0067] Silver ions have strong oxidation and reduction properties, can destroy the structure of bacterial cell membrane, cause the rupture and dissolution of cell membrane, and thus affect the normal metabolism of cells. At the same time, silver ions can also combine with the DNA of bacteria, thereby inhibiting the replication and transcription of DNA and destroying the biological function of bacteria, so as to achieve the effect of antibiosis. Silver ion antibacterial agent has high efficiency and stability, and has wide application. In Example 3, silver nitrate is added to the reaction initiator water, and silver ions are encapsulated in the coating with octadecyltriethoxysilane and water during the reaction, and adhere to the surface of the fabric. The fabric has super-hydrophobic modification and antibacterial effect, and has excellent bactericidal effect on Escherichia coli and Staphylococcus aureus.

[0068] ​​​The silicone quaternary ammonium salt antibacterial agent is prepared by introducing siloxane into the chemical structure of quaternary ammonium salt antibacterial agent, and is a new type of antibacterial agent. It has no obvious irritation to human skin and extremely low toxicity, acts on the surface of bacteria, can destroy the cell wall and cell membrane of bacteria, has obvious inhibition or killing effect on pathogenic bacteria, has high and broad-spectrum antibacterial function, is resistant to washing and heat, and also has strong antibacterial durability. In addition, the fabric treated by the silicone quaternary ammonium salt antibacterial agent also has excellent softness and antistatic property.

[0069] Example 3 The hydrophobic modified fabric has antibacterial property after adding silicone quaternary ammonium salt in n-hexane. As shown in Figure 5 , the modified cotton fabric has obvious bactericidal efficiency on Escherichia coli and Staphylococcus aureus, and no bacterial colony grows on the agar medium after 24 hours of culture, and the bactericidal efficiency on Escherichia coli and Staphylococcus aureus reaches 99.99%.

[0070] (3) Air permeability and mechanical property characterization:

[0071] The tensile breaking strength of the antibacterial and hydrophobic modified polyester and cotton fabrics was tested by using a universal material testing machine, the sample holding distance was 40 mm, and the tensile speed was 20 mm / min. The stress-strain curves of the fabrics before and after antibacterial super-hydrophobic modification (using the super-hydrophobic coating mixture obtained in Example 3) are shown in (c) and (d) of Figure 6 . It can be seen from (c) and (d) of Figure 6 that after antibacterial super-hydrophobic modification, the tensile stress and strain of the cotton fabric decrease by 2.1% and 1.2%, respectively, and the tensile stress and strain of the polyester fabric decrease by 5.5% and 2.1%, respectively. This is because the addition of a small amount of octadecyltrichlorosilane produces acid gas during the catalytic reaction process, which causes certain damage to the mechanical properties of the fabric.

[0072] The air permeability of the cotton fabric under different experimental parameters was evaluated by using a full-automatic air permeability tester, the measurement pressure was 100 Pa, the measurement area was 20 cm 2 , and the results are shown in (a) and (b) of Figure 6 . It can be seen from (a) and (b) of Figure 6 that the air permeability of the original cotton fabric is 270 mm / s, and the air permeability of the cotton fabric after antibacterial hydrophobic modification in Example 3 is 221.7 mm / s. Compared with the original cotton fabric, the air permeability of the fabric after antibacterial hydrophobic modification treatment decreases slightly, because the air permeability of the fabric is mainly determined by the porosity, and the antibacterial hydrophobic coating self-assembled on the surface of the fabric reduces the porosity of the fabric, thereby causing the air permeability of the modified fabric to decrease.

[0073] (4) Coating durability characterization:

[0074] To test the durability of the surface structure and performance of the coating, the fabric after the antibacterial and hydrophobic treatment was subjected to a water drop experiment, a washing experiment and an antibacterial test after washing. After the antibacterial and hydrophobic treatment (using the super-hydrophobic coating mixture obtained in Example 3), continuous water drops were provided by a disposable syringe and dropped on the cotton fabric placed at an inclination of 30° to further characterize the hydrophobicity and durability of the coating. As shown in Fig. 2(a), the contact angle of the coated fabric was 156.3° before water dropping, and the contact angle of the fabric was still 146.4° after 24 h of water dropping. Figure 7

[0075] The antibacterial and hydrophobic stability test was performed using the household double-barrel washing machine washing method in the test standard of GB / T 20944.3-2008. The cotton fabric after the antibacterial and hydrophobic treatment was subjected to water washing treatment using a household drum washing machine. During the experiment, 20 g of the sample, 180 g of the accompanying fabric, 12 g of the detergent (AATCC 1993 WOB non-phosphorus standard detergent) and 6 L of water (40 ± 3°C) were washed for 25 min using the household drum washing machine, and then 6 L of tap water was injected for 2 min, the fabric was taken out and centrifuged for 1 min, and then 6 L of tap water was injected for 2 min, the fabric was taken out and centrifuged for 1 min. The procedure was repeated for multiple water washing treatments, and the change in the contact angle of the fabric and the antibacterial performance of the fabric were measured by the shaking method. As shown in Fig. 2(b), the contact angle of the fabric was still 140.9° after 30 times of water washing, and the bactericidal efficiency on E. coli and S. aureus reached 99.98%. Figure 7

[0076] The above description of the embodiments is to facilitate the understanding and use of the present application by those of ordinary skill in the art. Of course, the above description is not a limitation of the present application, and the present application is not limited to the above examples. Changes, modifications, additions or substitutions made by those of ordinary skill in the art within the spirit and scope of the present application should also be included in the protection scope of the present application.​​

Claims

1. A method for preparing a superhydrophobic and antifouling coating with antibacterial function, characterized in that... Includes the following steps: S1. First, add silver nitrate to water to prepare a silver nitrate solution; then mix n-octadecyltriethoxysilane, octadecyltrichlorosilane, and the silver nitrate solution evenly, and then let the reaction stand to obtain a superhydrophobic reaction product; the ratio of n-octadecyltriethoxysilane to water is 1 mL: 20-80 μL; the ratio of octadecyltrichlorosilane to n-octadecyltriethoxysilane is 1-6 μL: 1 mL; the reaction time is 1-5 h; S2. Dilute and disperse the superhydrophobic reaction product obtained in step S1 with n-hexane to obtain a superhydrophobic coating mixture; S3. By impregnating or spraying a superhydrophobic coating mixture, a superhydrophobic and antifouling coating with antibacterial function is formed on the surface of a solid material.

2. The method for preparing a superhydrophobic and antifouling coating with antibacterial function according to claim 1, characterized in that, In step S1: after mixing octadecyltriethoxysilane, silver nitrate solution and octadecyltrichlorosilane, the mixture is first placed on a vortex mixer to mix evenly, and then placed in an ultrasonic cleaner for ultrasonic vibration treatment.

3. The method for preparing a superhydrophobic and antifouling coating with antibacterial function according to claim 1, characterized in that: The concentration of the silver nitrate solution is 0.5-5 wt%.

4. The method for preparing a superhydrophobic and antifouling coating with antibacterial function according to claim 1, characterized in that, In step S2: hexane is added to the superhydrophobic reaction product; the volume fraction of the superhydrophobic reaction product in the resulting superhydrophobic coating mixture is 1-10%.

5. A method for preparing a superhydrophobic and antifouling coating with antibacterial function, characterized in that... Includes the following steps: S1. Mix n-octadecyltriethoxysilane, water, and octadecyltrichlorosilane thoroughly, then allow the mixture to stand and react to obtain a superhydrophobic reaction product; the ratio of n-octadecyltriethoxysilane to water is 1 mL: 20-80 μL; the ratio of octadecyltrichlorosilane to n-octadecyltriethoxysilane is 1-6 μL: 1 mL; the reaction time is 1-5 h. S2. First, add the organosilicon quaternary ammonium salt to n-hexane to obtain an organosilicon quaternary ammonium salt / n-hexane solution. Then, add the organosilicon quaternary ammonium salt / n-hexane solution to the superhydrophobic reaction product for mixing to obtain a superhydrophobic coating mixture. S3. By impregnating or spraying a superhydrophobic coating mixture, a superhydrophobic and antifouling coating with antibacterial function is formed on the surface of a solid material.

6. The method for preparing a superhydrophobic and antifouling coating with antibacterial function according to claim 5, characterized in that, In step S1: after mixing octadecyltriethoxysilane, water and octadecyltrichlorosilane, the mixture is first placed on a vortex mixer to mix evenly, and then placed in an ultrasonic cleaner for ultrasonic vibration treatment.

7. The method for preparing a superhydrophobic and antifouling coating with antibacterial function according to claim 5, characterized in that: The mass-to-volume ratio of the amount of organosilicon quaternary ammonium salt added to the amount of n-hexane used is 0.01-0.04 g / mL.

8. A method for preparing a superhydrophobic and antifouling coating with antibacterial function according to any one of claims 1-7, characterized in that, Step S3 is: The solid material is immersed in the obtained superhydrophobic coating mixture, removed after 12-24 hours, washed with n-hexane, and then dried in air to obtain a superhydrophobic and antifouling coating with antibacterial function; or, the obtained superhydrophobic coating mixture is transferred to a spray bottle and sprayed on top of the solid material to obtain a superhydrophobic and antifouling coating with antibacterial function.

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