Preparation method of breathable antibacterial super-amphiphobic fabric

Abstract

The application discloses a preparation method of a breathable antibacterial super-amphiphilic fabric. The method comprises the following steps: firstly, adhering polydopamine on the fabric; secondly, fully loading PTFE nanoparticles on the surface of the fabric; thirdly, grafting bPEI on the surface of the fabric through in-situ Schiff base and Michael addition reaction; fourthly, depositing SiO2 / ODA aggregates on the surface of the fabric; and finally, immersing the fabric in a fluorination solution to reduce the surface energy, taking out the fabric, and preliminarily forming a film at room temperature, and finally forming a film at 100-150 DEG C to obtain the breathable antibacterial super-amphiphilic fabric. Through in-situ growth and low surface energy treatment on the fabric, a layered micro-nano structure is constructed, the fabric is endowed with super-amphiphilic properties, and the fabric has excellent breathability, antibacterial property, self-cleaning property and antifouling property, and the problem that the breathability of the fabric is seriously reduced due to the modification of the super-amphiphilic fabric in the traditional sense is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of super-biphobic materials, and particularly relates to a preparation method of a breathable and antibacterial super-biphobic fabric. BACKGROUND

[0002] Fabric is an important decoration and protection material in daily life, and is widely used due to its breathability and softness. However, the fabric surface contains a large number of active groups, which is easy to be contaminated and corroded. More importantly, the breathability and moisture absorption of the fabric create good conditions for the growth of bacteria, which poses a potential threat to human health. In addition, the large amount of washing of cotton fabric not only wastes water resources, but also causes environmental pollution due to the use of chemical detergents. Therefore, it is of great practical and application significance to develop multifunctional cotton fabric with self-cleaning properties.

[0003] There are lotus leaves with self-cleaning properties in nature, and super-hydrophobic materials with "lotus effect" have attracted extensive attention of researchers. However, the lipophilicity of such materials in air seriously limits their practicality in oil-polluted environments. In recent years, inspired by the super-hydrophobic and oleophobic surface of the popillia japonica, the design of super-biphobic materials has attracted the attention of researchers. Super-biphobic surface refers to a surface with a contact angle of more than 150° to aqueous and oily liquids and a rolling angle of less than 10°, which has great potential applications in self-cleaning, anti-fouling, enhanced buoyancy, anti-icing, personal protection, drag reduction, corrosion protection and liquid transportation. In view of this, the combination of super-biphobic surface and fabric is considered as a promising method for manufacturing self-cleaning textiles.

[0004] So far, the preparation process of super-biphobic fabric mostly needs expensive and toxic reagents, and the preparation process is complicated, which is not conducive to environmental friendliness and large-area preparation. For example, the document with the application number 201811399357.6 discloses a multifunctional super-biphobic fabric and its preparation method and application: the fabric is reacted with mercaptosiloxane and tetraethyl orthosilicate in an ammonia atmosphere, and then a click chemistry reaction is carried out with a fluorine-containing double bond compound under the catalysis of a photoinitiator to prepare a super-biphobic fabric. However, this method uses toxic ammonia and tetrahydrofuran, and the use of expensive reagents and harsh reaction conditions limit its large-scale application. On the other hand, the modification of fabric to super-biphobicity usually significantly reduces the breathability. From the perspective of wearing comfort, the loss of fabric breathability should be minimized during the modification of super-biphobicity. In addition, from the perspective of health, the antibacterial activity of super-biphobic fabric during the modification process can effectively offset the harm of bacteria to human body. Therefore, it is of great application value to prepare multifunctional super-biphobic fabric with breathability, antibacterial activity and self-cleaning properties. However, it is still a great challenge to use low-cost materials and simple methods to realize these properties of fabric at the same time. SUMMARY

[0005] In view of the deficiencies of the prior art, the technical problem to be solved by the present application is to provide a preparation method of a breathable antibacterial super-amphiphobic fabric.

[0006] The technical scheme for solving the technical problem of the present application is to provide a preparation method of a breathable antibacterial super-amphiphobic fabric, characterized in that the method comprises the following steps:

[0007] Step 1: Dissolve dopamine hydrochloride in an alkaline solution to obtain a dopamine solution; then immerse the original fabric in the dopamine solution, so that the dopamine performs a self-polymerization grafting reaction on the surface of the original fabric to generate polydopamine; after the immersion is completed, the fabric is taken out and washed to remove the polydopamine that is not firmly combined on the surface of the fabric;

[0008] Step 2: Disperse PTFE nanoparticles in anhydrous ethanol to obtain a uniformly dispersed PTFE dispersion liquid; then immerse the fabric obtained in step 1 in the PTFE dispersion liquid, so that the fabric surface is fully loaded with PTFE nanoparticles;

[0009] Step 3: Dissolve bPEI in an alkaline solution to obtain a bPEI solution; then immerse the fabric obtained in step 2 in the bPEI solution to perform in-situ Schiff base and Michael addition reaction grafting bPEI on the surface of the fabric; after the immersion is completed, the fabric is taken out and washed to remove the bPEI that is not firmly combined on the surface of the fabric;

[0010] Step 4: Disperse SiO2 nanoparticles and ODA in anhydrous ethanol to obtain a uniformly dispersed SiO2 / ODA dispersion liquid; then stand the dispersion liquid to perform self-assembly of ODA on the surface of the SiO2 nanoparticles to generate SiO2 / ODA aggregates; then immerse the fabric obtained in step 3 in the standing dispersion liquid, so that the SiO2 / ODA aggregates are deposited on the surface of the fabric;

[0011] Step 5: Dissolve PVDF-HFP and FAS in an organic solvent to obtain a homogeneous fluorinated liquid; then immerse the fabric obtained in step 4 in the fluorinated liquid to reduce the surface energy of the fabric surface; after the immersion is completed, the fabric is taken out and placed at room temperature for 5-30 min to preliminarily volatilize the organic solvent, thereby preliminarily forming a film on the surface of the fabric; then place the fabric at 100-150 DEG C for 0.5-2 h to volatilize the remaining organic solvent, thereby completing the film formation on the surface of the fabric to obtain a breathable antibacterial super-amphiphobic fabric.

[0012] Compared with the prior art, the present application has the following beneficial effects:

[0013] (1) The present application constructs a layered micro-nano structure by in-situ growth and low surface energy treatment on the fabric, endows the fabric with super-amphiphobic property while making it have excellent air permeability, antibacterial, self-cleaning and anti-fouling multifunction, solves the problem that the traditional super-amphiphobic modification will cause the air permeability of the fabric to decrease seriously.

[0014] (2) The present application has simple preparation method, low material cost and green and environment-friendly process, and the process flow is conducive to scale-up production and has potential industrial application prospect.

[0015] (3) The super-amphiphobic fabric of the present application has a surface tension as low as 27.5 mN / n for maintaining the super-amphiphobicity of liquid, and has excellent super-amphiphobic property.

[0016] (4) The fabric super-amphiphobic modification method of the present application makes the air permeability of the fabric have little loss before and after modification, and solves the problem that the traditional super-amphiphobic modification will cause the air permeability of the fabric to decrease greatly.

[0017] (5) The super-amphiphobic fabric of the present application has excellent self-cleaning performance, and water and oil droplets can easily take away the fine sand on the surface of the super-amphiphobic fabric.

[0018] (6) The super-amphiphobic fabric of the present application has excellent anti-fouling performance, and the surface of the super-amphiphobic fabric is not contaminated after being contaminated by various surface tension water-based or oil-based liquids.

[0019] (7) The super-amphiphobic fabric of the present application has excellent antibacterial performance, and the antibacterial rate for E. coli is 99.1%, and the antibacterial rate for S. aureus is 99.9%. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 SEM image of the super-amphiphobic fabric of Example 1 of the present application;

[0021] Figure 2 SEM image of the super-amphiphobic fabric of Example 1 of the present application;

[0022] Figure 3 Optical image of liquid droplets with different surface tensions on the surface of the super-amphiphobic fabric of Example 1 of the present application;

[0023] Figure 4 SEM image and EDS spectrum image of the super-amphiphobic fabric of Example 1 of the present application;

[0024] Figure 5 Air permeability result graph of the original fabric and the super-amphiphobic fabric of Example 1 of the present application;

[0025] Figure 6 The self-cleaning effect diagram of the super-amphiphobic fabric of Example 1 of the present application on water and soybean oil;

[0026] Figure 7 The anti-fouling effect diagram of the super-amphiphobic fabric of Example 1 of the present application;

[0027] Figure 8 The antibacterial effect diagram of the original fabric and the super-amphiphobic fabric of Example 1 of the present application on Escherichia coli;

[0028] Figure 9 The antibacterial effect diagram of the original fabric and the super-amphiphobic fabric of Example 1 of the present application on Staphylococcus aureus. DETAILED DESCRIPTION

[0029] The specific embodiments of the present application are given below. The specific embodiments are only used to further illustrate the present application and do not limit the protection scope of the claims of the present application.

[0030] The present application provides a preparation method of a breathable antibacterial super-amphiphobic fabric (referred to as the method), characterized in that the method comprises the following steps:

[0031] Step 1, dopamine hydrochloride is dissolved in an alkaline solution to obtain a dopamine solution; then the original fabric is immersed in the dopamine solution, so that the dopamine performs self-polymerization grafting reaction on the surface of the original fabric to generate polydopamine; after immersion, the fabric is taken out and washed to remove the polydopamine not firmly combined on the surface of the fabric;

[0032] Preferably, step 1 is carried out at room temperature, and the temperature is 20-30°C.

[0033] Preferably, in step 1, the alkaline solution is NaOH solution (sodium hydroxide solution) or Tris-HCl solution (trihydroxy amino methane-hydrochloric acid solution), and the pH is 8-10.

[0034] Preferably, in step 1, the concentration of the dopamine solution is 0.5-2.5 g / L.

[0035] Preferably, in step 1, the original fabric is a cotton fabric, a polyester fabric, a polyamide fabric, a spandex fabric or an acrylic fabric; the original fabric is first subjected to ultrasonic cleaning in deionized water to remove impurities on the surface of the fabric.

[0036] Preferably, in step 1, the immersion time is 16-32 h; stirring or shaking is carried out at the same time, and the stirring speed is 100-500 rpm.

[0037] Preferably, in step 1, deionized water is used for washing.

[0038] Preferably, in step 1, the fabric is dried at room temperature after washing.

[0039] Step 2, disperse PTFE (polytetrafluoroethylene) nanoparticles in anhydrous ethanol to obtain a uniformly dispersed PTFE dispersion; then immerse the fabric obtained in step 1 in the PTFE dispersion to allow the fabric surface to be fully loaded with PTFE nanoparticles;

[0040] Preferably, step 2 is carried out at room temperature, with a temperature of 20-30°C.

[0041] Preferably, in step 2, the average particle size of the PTFE nanoparticles is 100-600 nm.

[0042] Preferably, in step 2, ultrasonic dispersion is used; the power of the ultrasonic dispersion is 400-600 W, and the time is 20-40 min.

[0043] Preferably, in step 2, the concentration of the PTFE dispersion is 1-5 g / L.

[0044] Preferably, in step 2, the immersion time is 0.5-3 h.

[0045] Preferably, in step 2, after immersion, the fabric is dried at room temperature.

[0046] Step 3, dissolve bPEI (branched polyethyleneimine) in an alkaline solution to obtain a bPEI solution; then immerse the fabric obtained in step 2 in the bPEI solution to graft bPEI on the fabric surface in situ through Schiff base and Michael addition reactions; after immersion, remove the fabric and wash it to remove bPEI that is not firmly bound to the fabric surface;

[0047] Preferably, step 3 is carried out at room temperature, with a temperature of 20-30°C.

[0048] Preferably, in step 3, the relative molecular mass of bPEI is 200-30000.

[0049] Preferably, in step 3, the alkaline solution is a NaOH solution or a Tris-HCl solution, with a pH of 8-10.

[0050] Preferably, in step 3, the volume ratio of bPEI to alkaline solution is (0.5-1.5):(50-450).

[0051] Preferably, in step 3, the immersion time is 0.5-2 h.

[0052] Preferably, in step 3, deionized water is used for washing.

[0053] Preferably, in step 3, after washing, drying is carried out at room temperature.

[0054] Step 4, disperse SiO2 (silicon dioxide) nanoparticles and ODA (octadecylamine) in anhydrous ethanol to obtain a uniformly dispersed SiO2 / ODA dispersion; then, let the dispersion stand to allow ODA to self-assemble on the surface of the SiO2 nanoparticles to form SiO2 / ODA aggregates; then, immerse the fabric obtained in step 3 in the standing dispersion to allow the SiO2 / ODA aggregates to deposit on the surface of the fabric;

[0055] Preferably, step 4 is performed at room temperature, at a temperature of 20-30°C.

[0056] Preferably, in step 4, the average particle size of the SiO2 nanoparticles is 10-200 nm.

[0057] Preferably, in step 4, ultrasonic dispersion is used for the dispersion; the power of the ultrasonic dispersion is 400-600 W, and the time is 20-40 min.

[0058] Preferably, in step 4, the mass ratio of SiO2 nanoparticles, ODA, and anhydrous ethanol is (0.5-2):(3-5):(200-400).

[0059] Preferably, in step 4, the standing time of the SiO2 / ODA dispersion is 15-45 min.

[0060] Preferably, in step 4, the immersion time is 1-3 h.

[0061] Preferably, in step 4, after immersion, the fabric is removed and dried at room temperature.

[0062] Step 5, dissolve PVDF-HFP (polyvinylidene fluoride-hexafluoropropylene) and FAS (perfluoroalkylsilane) in an organic solvent to obtain a homogeneous fluorinated liquid; then, immerse the fabric obtained in step 4 in the fluorinated liquid to reduce the surface energy of the fabric surface; after immersion is complete, remove the fabric and remove the liquid (in this embodiment, drop dry) on the surface of the fabric, and then place the fabric at room temperature for 5-30 min to preliminarily volatilize the organic solvent, thereby preliminarily forming a film on the surface of the fabric; then, place the fabric at 100-150°C for 0.5-2 h to completely volatilize the remaining organic solvent and orient the perfluoroalkylsilane, thereby completing the film formation on the surface of the fabric, and obtaining a breathable and antibacterial super-amphiphobic fabric (referred to as a super-amphiphobic fabric).

[0063] Preferably, in step 5, in the fluorinated liquid, the mass concentration of PVDF-HFP is 10-40 g / L, and the volume ratio of FAS to organic solvent is (1-2):(50-150).

[0064] Preferably, in step 5, the configuration temperature of the fluorinated liquid is 50-70°C.

[0065] Preferably, in step 5, FAS is 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane or 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane; the organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide.

[0066] Preferably, in step 5, the dipping temperature is room temperature, and the dipping time is 1-10 min.

[0067] Example 1

[0068] (1) At room temperature, 40 mg of dopamine hydrochloride was dissolved in 40 ml of NaOH solution with pH of 8.5 to obtain a dopamine solution; then a 4x4 cm original fabric was immersed in the dopamine solution and stirred at a stirring speed of 300 rpm for 24 h, so that the dopamine on the surface of the original fabric was subjected to a self-polymerization grafting reaction to generate polydopamine; after the completion of the immersion, the fabric was taken out and washed with deionized water to remove the polydopamine which was not firmly combined on the surface, and then dried at room temperature;

[0069] (2) At room temperature, 80 mg of PTFE nanoparticles with an average particle size of 200 nm were ultrasonically dispersed in 40 ml of anhydrous ethanol at a power of 600 W for 30 min to obtain a uniformly dispersed PTFE dispersion liquid; then the fabric obtained in step 1 was immersed in the PTFE dispersion liquid for 2 h, so that the fabric surface was fully loaded with PTFE nanoparticles;

[0070] (3) At room temperature, 40 μL of bPEI with a relative molecular mass of 20000 was dissolved in 10 ml of NaOH solution with pH of 8.5 to obtain a bPEI solution; then the fabric obtained in step 2 was immersed in the bPEI solution for 1 h, so that the bPEI was grafted on the fabric surface in situ through Schiff base and Michael addition reactions; after the completion of the immersion, the fabric was taken out and washed to remove the bPEI which was not firmly combined on the surface of the fabric;

[0071] (4) At room temperature, 125 mg of SiO2 nanoparticles with an average particle size of 20 nm and 500 mg of ODA were dispersed in 50 ml of anhydrous ethanol and ultrasonically dispersed at a power of 600 W for 30 min to obtain a uniformly dispersed SiO2 / ODA dispersion liquid; then the dispersion liquid was allowed to stand for 10 min to allow the ODA to self-assemble on the surface of the SiO2 nanoparticles to generate SiO2 / ODA aggregates; subsequently, the fabric obtained in step 3 was immersed in the standing dispersion liquid for 2 h, so that the SiO2 / ODA aggregates were deposited on the surface of the fabric;

[0072] (5) 250 mg of PVDF-HFP and 150 μL of 1H,1H,2H,2H-Perfluorodecyltriethoxysilane were dissolved in 10 ml of N,N dimethylformamide at 50 °C to obtain a homogeneous fluorinated solution; then the fabric obtained in step 4 was immersed in the fluorinated solution at room temperature for 5 min to reduce the surface energy of the fabric surface; after immersion, the fabric was taken out, the surface liquid drops were dropped dry, and then placed at room temperature for 10 min for preliminary volatilization of the organic solvent, thereby preliminarily forming a film on the fabric surface; then placed at 130 °C for 30 min for volatilization of the remaining N,N dimethylformamide, thereby completing the film formation on the fabric surface, to obtain a breathable and antibacterial super-amphiphobic fabric.

[0073] From Figure 1 and Figure 2 It can be seen that the SEM image of the super-amphiphobic fabric shows a layered micro-nano structure.

[0074] Figure 3 Images of 5 μL of liquid with different surface tensions on the surface of the super-amphiphobic fabric are shown, from Figure 3 It can be seen that all the liquid drops on the fabric surface are spherical and have a contact angle > 150°.

[0075] Figure 4 In the EDS scanning of the SEM image of the super-amphiphobic fabric, the EDS image obtained shows that carbon, oxygen, silicon, fluorine and nitrogen elements are uniformly distributed on the fabric, thereby proving the uniformity of the modification process.

[0076] From Figure 5 It can be seen that the air permeability of the original fabric and the super-amphiphobic fabric (i.e. before and after super-amphiphobic modification) in step 1 does not change much, solving the problem that the air permeability of the fabric is greatly reduced by the current super-amphiphobic modification. The air permeability of the super-amphiphobic fabric is only reduced from 74.2 mm / s of the original fabric to 72.4 mm / s.

[0077] From Figure 6 It can be seen that the water and oil drops can easily take away the fine sand on the surface of the super-amphiphobic fabric, thereby confirming the excellent self-cleaning performance of the super-amphiphobic fabric.

[0078] From Figure 7 It can be seen that the surface of the super-amphiphobic fabric is not contaminated after being immersed in various surface tension liquids, proving its excellent anti-fouling performance.

[0079] From Figure 8 and Figure 9It can be seen that the original fabric has no antibacterial activity against E. coli and S. aureus because the original fabric does not contain antibacterial substances. The presence of amine substances and long-chain alkane antibacterial materials in the super-biphobic fabric exhibits good antibacterial activity, with an antibacterial rate of 99.1% against E. coli and 99.9% against S. aureus.

[0080] Example 2

[0081] (1) At room temperature, 80 mg of dopamine hydrochloride was dissolved in 40 ml of NaOH solution with a pH of 8.5 to obtain a dopamine solution; then a 5x5 cm original fabric was immersed in the dopamine solution and stirred at a stirring speed of 250 rpm for 20 h, so that the dopamine on the surface of the original fabric underwent a self-polymerization grafting reaction to form polydopamine; after the immersion was completed, the fabric was taken out and washed with deionized water to remove the polydopamine that was not firmly combined on the surface, and then dried at room temperature;

[0082] (2) At room temperature, 120 mg of PTFE nanoparticles with an average particle size of 200 nm were ultrasonically dispersed in 60 ml of anhydrous ethanol at a power of 400 W for 40 min to obtain a uniformly dispersed PTFE dispersion liquid; then the fabric obtained in step 1 was immersed in the PTFE dispersion liquid for 2.5 h, so that the fabric surface was fully loaded with PTFE nanoparticles;

[0083] (3) At room temperature, 80 μL of bPEI with a relative molecular mass of 20000 was dissolved in 20 ml of NaOH solution with a pH of 8.0 to obtain a bPEI solution; then the fabric obtained in step 2 was immersed in the bPEI solution for 0.5 h to graft bPEI on the fabric surface in situ through Schiff base and Michael addition reactions; after the immersion was completed, the fabric was taken out and washed to remove the bPEI that was not firmly combined on the surface of the fabric;

[0084] (4) At room temperature, 250 mg of SiO2 nanoparticles with an average particle size of 20 nm and 1.0 g of ODA were dispersed in 100 ml of anhydrous ethanol and ultrasonically dispersed at a power of 400 W for 40 min to obtain a uniformly dispersed SiO2 / ODA dispersion liquid; then the dispersion liquid was allowed to stand for 15 min for self-assembly of ODA on the surface of the SiO2 nanoparticles to form SiO2 / ODA aggregates; then the fabric obtained in step 3 was immersed in the standing dispersion liquid for 2.5 h, so that the SiO2 / ODA aggregates were deposited on the surface of the fabric;

[0085] (5) 500 mg of PVDF-HFP and 300 μL of 1H, 1H, 2H, 2H- perfluorodecyltriethoxysilane were dissolved in 20 ml of N,N dimethylformamide at 60°C to obtain a homogeneous fluorinated solution; then the fabric obtained in step 4 was immersed in the fluorinated solution at room temperature for 5 min to reduce the surface energy of the fabric surface; after immersion, the fabric was taken out, the liquid drops on the fabric surface were dropped dry, and then the fabric was placed at room temperature for 15 min for preliminary volatilization of the organic solvent, thereby preliminarily forming a film on the fabric surface; then the fabric was placed at 125°C for 40 min for volatilization of the remaining N,N dimethylformamide, thereby completing the film formation on the fabric surface, and obtaining the breathable and antibacterial super-amphiphobic fabric.

[0086] The SEM image, anti-fouling performance and antibacterial performance of the super-amphiphobic fabric were consistent with those of Example 1. In the super-amphiphobic performance, the contact angles of soybean oil, pump oil and hexadecane were 153.9°, 153.7° and 150.1°, respectively, and the remaining liquid drop angles were consistent with those of Example 1, and the contact angles of all liquid drops were > 150°. The air permeability was reduced from 74.2 mm / s of the original fabric to 72.2 mm / s.

[0087] Example 3

[0088] (1) 60 mg of dopamine hydrochloride was dissolved in 40 ml of NaOH solution with a pH of 8.5 at room temperature to obtain a dopamine solution; then a 3x3 cm original fabric was immersed in the dopamine solution, and stirred at a stirring speed of 290 rpm for 22 h, so that the dopamine on the surface of the original fabric was subjected to a self-polymerization grafting reaction to generate polydopamine; after immersion, the fabric was taken out, washed with deionized water to remove the polydopamine not firmly combined on the surface, and then dried at room temperature;

[0089] (2) 90 mg of PTFE nanoparticles with an average particle size of 200 nm were ultrasonically dispersed in 45 ml of anhydrous ethanol at a power of 500 W for 35 min at room temperature to obtain a uniformly dispersed PTFE dispersion liquid; then the fabric obtained in step 1 was immersed in the PTFE dispersion liquid for 2 h, so that the fabric surface was fully loaded with PTFE nanoparticles;

[0090] (3) 60 μL of bPEI with a relative molecular mass of 30000 was dissolved in 15 ml of NaOH solution with a pH of 9.0 at room temperature to obtain a bPEI solution; then the fabric obtained in step 2 was immersed in the bPEI solution for 0.8 h to graft bPEI on the fabric surface in situ through Schiff base and Michael addition reactions; after immersion, the fabric was taken out and washed to remove the bPEI not firmly combined on the surface of the fabric;

[0091] (4) At room temperature, 150 mg of SiO2 nanoparticles with an average particle size of 20 nm and 600 mg of ODA were dispersed in 60 ml of anhydrous ethanol, and ultrasonic dispersion was performed at a power of 500 W for 25 min to obtain a uniformly dispersed SiO2 / ODA dispersion; the dispersion was then allowed to stand for 10 min to perform self-assembly of ODA on the surface of the SiO2 nanoparticles, generating SiO2 / ODA aggregates; subsequently, the fabric obtained in step 3 was immersed in the dispersion after standing for 1.5 h, so that the SiO2 / ODA aggregates were deposited on the surface of the fabric;

[0092] (5) 400 mg of PVDF-HFP and 240 μL of 1H,1H,2H,2H-perfluorodecyltrimethoxysilane were dissolved in 16 ml of N,N-dimethylacetamide at 70°C to obtain a homogeneous fluorinated liquid; the fabric obtained in step 4 was then immersed in the fluorinated liquid at room temperature for 4 min to reduce the surface energy of the fabric surface; after immersion, the fabric was taken out, the liquid droplets on the fabric surface were dropped dry, and the fabric was then placed at room temperature for 12 min to perform preliminary volatilization of the organic solvent, thereby preliminarily forming a film on the fabric surface; then the fabric was placed at 135°C for 25 min to volatilize the remaining N,N-dimethylacetamide, thereby completing the film formation on the fabric surface, and obtaining a breathable and antibacterial super-amphiphobic fabric.

[0093] The SEM image, stain resistance, and antibacterial performance of the super-amphiphobic fabric were consistent with those of Example 1. In the super-amphiphobic performance, the contact angles of soybean oil, pump oil, and hexadecane were 154.0°, 153.5°, and 150.4°, respectively, and the remaining liquid droplet angles were consistent with those of Example 1, with all liquid droplet contact angles being > 150°. The air permeability was reduced from 74.2 mm / s for the original fabric to 71.9 mm / s.

[0094] Example 4

[0095] (1) At room temperature, 40 mg of dopamine hydrochloride was dissolved in 40 ml of a Tris-HCl solution with a pH of 8.5 to obtain a dopamine solution; a 4x4 cm original fabric was then immersed in the dopamine solution, and stirred at a stirring speed of 310 rpm for 28 h, so that the dopamine performed a self-polymerization grafting reaction on the surface of the original fabric to generate polydopamine; after immersion, the fabric was taken out, washed with deionized water to remove polydopamine that was not firmly combined on the surface, and then dried at room temperature;

[0096] (2) At room temperature, 120 mg of PTFE nanoparticles with an average particle size of 200 nm were ultrasonically dispersed in 60 ml of anhydrous ethanol at a power of 600 W for 50 min to obtain a uniformly dispersed PTFE dispersion; the fabric obtained in step 1 was then immersed in the PTFE dispersion for 1.5 h, so that the fabric surface was fully loaded with PTFE nanoparticles;

[0097] (3) At room temperature, 80 μΐ of bPEI with a relative molecular mass of 20000 was dissolved in 20 ml of Tris-HCl solution with a pH of 8.5 to obtain a bPEI solution; then the fabric obtained in step 2 was immersed in the bPEI solution for 1.5 h to perform in-situ Schiff base and Michael addition reaction to graft bPEI on the fabric surface; after the immersion was completed, the fabric was taken out and washed to remove the bPEI not firmly combined on the fabric surface;

[0098] (4) At room temperature, 200 mg of SiO2 nanoparticles with an average particle size of 20 nm and 800 mg of ODA were dispersed in 80 ml of anhydrous ethanol, and ultrasonic dispersion was performed at a power of 600 W for 20 min to obtain a uniformly dispersed SiO2 / ODA dispersion; the dispersion was then left to stand for 20 min to perform self-assembly of ODA on the surface of the SiO2 nanoparticles to generate SiO2 / ODA aggregates; then the fabric obtained in step 3 was immersed in the dispersion left to stand for 2 h to deposit the SiO2 / ODA aggregates on the fabric surface;

[0099] (5) 600 mg of PVDF-HFP and 360 μΐ of 1H, 1H, 2H, 2H-perfluorodecyltrimethoxysilane were dissolved in 24 ml of N,N-dimethylacetamide at 50°C to obtain a homogeneous fluorinated liquid; then the fabric obtained in step 4 was immersed in the fluorinated liquid at room temperature for 3 min to reduce the surface energy of the fabric surface; after the immersion was completed, the fabric was taken out, and liquid drops on the fabric surface were dropped dry, and then the fabric was left to stand at room temperature for 8 min to perform preliminary volatilization of the organic solvent, thereby preliminarily forming a film on the fabric surface; then the fabric was left to stand at 130°C for 30 min to perform volatilization of the remaining N,N-dimethylacetamide, thereby completing the film formation on the fabric surface, and obtaining the air-permeable and antibacterial super-amphiphobic fabric.

[0100] The SEM image, stain resistance and antibacterial performance of the super-amphiphobic fabric were consistent with those of Example 1. In the super-amphiphobic performance, the contact angles of soybean oil, pump oil and hexadecane were 153.9°, 153.6° and 150.2°, respectively, and the remaining drop angles were consistent with those of Example 1, and the contact angles of all the drops were > 150°. The air permeability was reduced from 74.2 mm / s of the original fabric to 72.1 mm / s.

[0101] Example 5

[0102] (1) At room temperature, 45 mg of dopamine hydrochloride was dissolved in 30 ml of Tris-HCl solution with a pH of 9.0 to obtain a dopamine solution; then a 2x2 cm original fabric was immersed in the dopamine solution, and stirring was performed at a stirring speed of 320 rpm for 24 h to perform a self-polymerization grafting reaction of dopamine on the surface of the original fabric to generate polydopamine; after the immersion was completed, the fabric was taken out, washed with deionized water to remove the polydopamine not firmly combined on the surface, and then dried at room temperature;

[0103] (2) At room temperature, 60 mg of PTFE nanoparticles with an average particle size of 200 nm were ultrasonically dispersed in 30 ml of anhydrous ethanol at a power of 600 W for 35 min to obtain a uniformly dispersed PTFE dispersion; then the fabric obtained in step 1 was immersed in the PTFE dispersion for 1.5 h to allow the fabric surface to be fully loaded with PTFE nanoparticles;

[0104] (3) At room temperature, 40 μL of bPEI with a relative molecular mass of 20000 was dissolved in 10 ml of a NaOH solution with a pH of 9.0 to obtain a bPEI solution; then the fabric obtained in step 2 was immersed in the bPEI solution for 1 h to graft bPEI on the fabric surface in situ through Schiff base and Michael addition reactions; after immersion, the fabric was removed and washed to remove bPEI that was not firmly bound to the fabric surface;

[0105] (4) At room temperature, 100 mg of SiO2 nanoparticles with an average particle size of 20 nm and 400 mg of ODA were dispersed in 40 ml of anhydrous ethanol and ultrasonically dispersed at a power of 600 W for 35 min to obtain a uniformly dispersed SiO2 / ODA dispersion; then the dispersion was allowed to stand for 15 min to allow ODA to self-assemble on the surface of the SiO2 nanoparticles to form SiO2 / ODA aggregates; then the fabric obtained in step 3 was immersed in the standing dispersion for 2 h to allow the SiO2 / ODA aggregates to deposit on the fabric surface;

[0106] (5) 200 mg of PVDF-HFP and 120 μL of 1H,1H,2H,2H-perfluorodecyltriethoxysilane were dissolved in 8 ml of N,N dimethylformamide at 70°C to obtain a homogeneous fluorinated liquid; then the fabric obtained in step 4 was immersed in the fluorinated liquid at room temperature for 5 min to reduce the surface energy of the fabric surface; after immersion, the fabric was removed, the liquid droplets on the fabric surface were dropped off, and the fabric was left to stand at room temperature for 10 min to allow the organic solvent to be preliminarily volatilized, thereby preliminarily forming a film on the fabric surface; then the fabric was left to stand at 130°C for 30 min to allow the remaining N,N dimethylformamide to be volatilized, thereby completing the film formation on the fabric surface to obtain a breathable and antibacterial super-amphiphobic fabric.

[0107] The SEM image, stain resistance and antibacterial properties of the super-amphiphobic fabric were the same as those of Example 1. In the super-amphiphobic properties, the contact angles of soybean oil, pump oil and hexadecane were 153.6°, 153.2° and 150.1°, respectively, and the remaining droplet angles were the same as those of Example 1, all of which were > 150°. The air permeability was reduced from 74.2 mm / s for the original fabric to 71.8 mm / s.

[0108] Comparative Example 1

[0109] The comparative example is identical to example 1, except that in step 5, no PVDF-HFP is added to the fluorination solution, resulting in a dual-repellent fabric.

[0110] Compared to the super-amphiphobic fabric of example 1, the dual-repellent fabric of the comparative example has a significantly reduced performance, exhibiting super-amphiphobicity only for ethylene glycol having a surface tension of 46.7 mN / m and for liquids having a surface tension greater than 46.7 mN / m.

[0111] The present application is applicable to the prior art where not specified.

Claims

1. A method for preparing a breathable, antibacterial, superhydrophobic fabric, characterized in that, The method includes the following steps: Step 1: Dissolve dopamine hydrochloride in an alkaline solution to obtain a dopamine solution; then immerse the original fabric in the dopamine solution to allow the dopamine to undergo a self-polymerization grafting reaction on the surface of the original fabric to generate polydopamine; after immersion, remove the fabric and wash it to remove the loosely bonded polydopamine from the fabric surface. Step 2: Disperse PTFE nanoparticles in anhydrous ethanol to obtain a uniformly dispersed PTFE dispersion; then immerse the fabric obtained in Step 1 in the PTFE dispersion to ensure that the fabric surface is fully loaded with PTFE nanoparticles. Step 3: Dissolve bPEI in an alkaline solution to obtain a bPEI solution; then immerse the fabric obtained in Step 2 in the bPEI solution and perform Schiff base and Michael addition reaction on the fabric surface in situ to graft bPEI; after immersion, remove the fabric and wash it to remove the bPEI that is not firmly bonded to the fabric surface. Step 4: Disperse SiO2 nanoparticles and ODA in anhydrous ethanol to obtain a uniformly dispersed SiO2 / ODA dispersion; allow the dispersion to stand to allow ODA to self-assemble on the surface of SiO2 nanoparticles, generating SiO2 / ODA aggregates; then immerse the fabric obtained in Step 3 in the standing dispersion to allow the SiO2 / ODA aggregates to deposit on the fabric surface. Step 5: Dissolve PVDF-HFP and FAS in an organic solvent to obtain a homogeneous fluorinated solution; then immerse the fabric obtained in Step 4 in the fluorinated solution to reduce the surface energy of the fabric surface; after immersion, remove the fabric and place it at room temperature for 5-30 minutes to allow the organic solvent to evaporate initially, thereby forming a preliminary film on the fabric surface; then place it at 100-150℃ for 0.5-2 hours to allow the remaining organic solvent to evaporate, thereby completing the film formation on the fabric surface and obtaining a breathable and antibacterial superhydrophobic fabric.

2. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, Step 1 is carried out at room temperature, specifically 20–30°C. In step 1, the alkaline solution is either NaOH solution or Tris-HCl solution with a pH of 8 to 10; In step 1, the concentration of the dopamine solution is 0.5–2.5 g / L; In step 1, the original fabric is cotton, polyester, nylon, spandex, or acrylic fabric; the original fabric is first ultrasonically cleaned in deionized water to remove impurities from the fabric surface. In step 1, the soaking time is 16 to 32 hours; during soaking, stirring or shaking is performed at a speed of 100 to 500 rpm. In step 1, deionized water is used for cleaning; In step 1, the fabric is dried at room temperature after washing.

3. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, In step 2, the average particle size of the PTFE nanoparticles is 100–600 nm; In step 2, the concentration of the PTFE dispersion is 1–5 g / L; In step 2, the soaking time is 0.5 to 3 hours.

4. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, Step 2 is carried out at room temperature, specifically 20–30°C. In step 2, ultrasonic dispersion is used; the power of ultrasonic dispersion is 400-600W, and the time is 20-40min. In step 2, after soaking, the fabric is removed and dried at room temperature.

5. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, In step 3, the relative molecular mass of bPEI is 200–30,000; In step 3, the volume ratio of bPEI to alkaline solution is (0.5-1.5):(50-450); In step 3, the soaking time is 0.5 to 2 hours.

6. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, Step 3 is carried out at room temperature, specifically 20–30°C. In step 3, the alkaline solution is either NaOH solution or Tris-HCl solution, with a pH of 8 to 10; In step 3, deionized water is used for cleaning; In step 3, the product is dried at room temperature after cleaning.

7. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, In step 4, the average particle size of the SiO2 nanoparticles is 10–200 nm; In step 4, the mass ratio of SiO2 nanoparticles, ODA and anhydrous ethanol is (0.5-2):(3-5):(200-400); In step 4, the standing time of the SiO2 / ODA dispersion is 15–45 min; In step 4, the soaking time is 1 to 3 hours.

8. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, Step 4 is performed at room temperature, specifically 20–30°C. In step 4, ultrasonic dispersion is used; the power of ultrasonic dispersion is 400-600W, and the time is 20-40min. In step 4, after soaking, the fabric is removed and dried at room temperature.

9. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, In step 5, the mass concentration of PVDF-HFP in the fluorinated solution is 10-40 g / L, and the volume ratio of FAS to organic solvent is (1-2):(50-150). In step 5, the preparation temperature of the fluorinated liquid is 50–70°C; In step 5, the FAS is 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, or 1H,1H,2H,2H-perfluorodecyltriethoxysilane; the organic solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, or dimethyl sulfoxide. In step 5, the immersion temperature is room temperature and the immersion time is 1 to 10 minutes.

10. The method for preparing the breathable and antibacterial superhydrophobic fabric according to claim 1, characterized in that, In step 5, after the impregnation is completed, remove the fabric, first remove the liquid from the surface of the fabric, and then place it at room temperature for 5 to 30 minutes to allow the organic solvent to evaporate initially.

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