Self-repairing type multifunctional super-hydrophobic fabric and preparation method thereof

Abstract

The invention discloses a self-repairing type multifunctional super-hydrophobic fabric and a preparation method thereof, and belongs to the technical field of functional textile materials. Graphene oxide dispersion liquid, hydrophobic long-chain silane with the carbon atom number n larger than or equal to 6, waterborne polyurethane and disperse dye are mixed to form a composite coating solution, fabric is finished through a one-step dispersion dyeing method, the surface of the fabric is covered with the self-repairing multifunctional super-hydrophobic composite coating, and in the composite coating forming process, the self-repairing multifunctional super-hydrophobic composite coating is formed. Graphene oxide is subjected to in-situ reduction, waterborne polyurethane serves as an adhesive, a hydrophobic long-chain silane agent and the reduced graphene oxide are combined, a coarse structure is constructed, surface free energy is reduced, the self-repairing type multifunctional super-hydrophobic fabric is obtained, and meanwhile fabric dyeing is achieved. An efficient and clean strategy is provided, and the firm and colorful fluoride-free super-hydrophobic fabric coating with antibacterial and antistatic properties is prepared through a simple one-step disperse dyeing process.

Description

Technical Field

[0001] The invention belongs to the technical field of functional textile materials, and specifically relates to a self-repairing multifunctional super-hydrophobic fabric and a preparation method thereof. Background Art

[0002] Superhydrophobic fabrics have a wide range of applications in self-cleaning, antifouling, antifreeze / fogging / corrosion, drag reduction, antibacterial growth, and liquid manipulation. Their preparation methods can be divided into physical methods (such as immersion plating, vapor deposition, spraying, self-assembly, and photolithography), chemical methods (such as grafting reaction, in situ polymerization, electrochemical deposition, cross-linking), or both. In general, most superwetting coatings are not durable to chemical and mechanical damage, for example, chemical / solvent attack, UV irradiation, extreme conditions, prolonged washing, and wear. People have invested a lot of effort to improve the durability of coatings, for example, by joining functional layers and substrates through cross-linking or chemical grafting, constructing hierarchical structures on the substrate surface, utilizing strong elastic nanocomposite coatings, and designing self-healing coatings. Fluorosurfactant materials have been widely used to reduce surface free energy and enhance the superhydrophobicity of surfaces, but they have been found to have potential health and environmental hazards. Therefore, people have made great efforts to develop fluorine-free superhydrophobic coatings.

[0003] In recent years, fabrics with different colors and super-hydrophobicity have begun to attract great attention due to their perfect combination of function and aesthetics. Using natural tannin as dyeing dye, trimethoxysilane, alkoxy-silane precursor phenyltriethoxysilane and n-octyltrimethoxysilane as coating materials, a colored super-hydrophobic cotton fabric was prepared by a two-step coating method. The super-hydrophobic colored polyester fabric disclosed in the prior art is formed by pre-treating the fabric under alkaline reduction to form a rough surface, and then dyeing and heat aging at 130 ° C for 24h. However, due to the high temperature and pressure of the disperse dyeing system, it is difficult to accurately control the physical / chemical reactions involved, and high-durability one-step multifunctional dyeing is highly expected, but it is usually difficult to achieve. In addition, the processing of multifunctional fabric surface processing undoubtedly involves multiple processing steps, the application of different equipment and the use of multiple materials, which inevitably produces additional wastewater discharge and consumes more power. Based on this, the present invention provides a green one-step strategy to prepare a strong, colorful, non-fluorinated, antibacterial, antistatic and self-healing super-hydrophobic fabric through a simple one-step disperse dyeing process. Summary of the invention

[0004] The purpose of the present invention is to solve the problems that existing super-hydrophobic fabrics still have poor durability, complicated coating process and toxicity caused by additional chemical treatment. The present invention provides a self-repairing multifunctional super-hydrophobic fabric and a preparation method thereof. The fabric is reduced and finished by a one-step disperse dyeing method, and a self-repairing antibacterial and antistatic super-hydrophobic composite coating is formed on the surface of the fabric. The composite coating comprises a waterborne polyurethane (WPU) resin such as silicone-modified waterborne polyurethane, a hydrophobic long-chain silane such as hexadecyltrimethoxysilane (HDTMS), graphene oxide (GO) and disperse dyes.

[0005] In order to achieve the above purpose, the technical solution adopted in this application is:

[0006] The first object of the present invention is to provide a method for preparing a self-repairing multifunctional super-hydrophobic fabric, comprising the following steps:

[0007] A graphene oxide dispersion, a hydrophobic long-chain silane with a carbon atom number n≥6, an aqueous polyurethane and a disperse dye are mixed to form a composite coating solution, and the fabric is reduced and finished by a one-step disperse dyeing method. A self-repairing antibacterial and antistatic super-hydrophobic composite coating is formed on the surface of the fabric. During the formation of the composite coating, the graphene oxide is reduced in situ, and the aqueous polyurethane is used as an adhesive to combine the hydrophobic long-chain silane and the reduced graphene oxide to construct a rough structure and reduce the surface free energy, thereby obtaining a self-repairing multifunctional super-hydrophobic fabric.

[0008] Furthermore, the usage ratio of graphene oxide dispersion, hydrophobic long-chain silane and aqueous polyurethane is 30 mL: 0.1-1.0 g: 0.5-1.0 g.

[0009] Furthermore, the hydrophobic long-chain silane is a silane coupling agent with a carbon atom number n≥6, and the waterborne polyurethane is a silicone-modified waterborne polyurethane.

[0010] Furthermore, the mass ratio of the disperse dye to the waterborne polyurethane is 1-5:20.

[0011] Furthermore, the concentration of the graphene oxide dispersion is 2-3 g / L.

[0012] Furthermore, the fabric is a fiber fabric that can be dyed with disperse dyes.

[0013] Furthermore, during the reduction finishing process, the fabric is immersed in the composite coating solution, first heated to 50-70°C, then heated to 120-150°C and kept warm for 60 minutes, and then rotated at 60 r / min to cool to room temperature and dried to obtain a self-repairing multifunctional super-hydrophobic fabric.

[0014] Furthermore, the heating rate to 50-70°C is 5-10°C / min, the heating rate to 120-150°C is 2-3°C / min, the pressure is 280-295KPa, and the cooling rate to room temperature is 5°C / min.

[0015] The second object of the present invention is to provide the above-mentioned preparation method to prepare a self-repairing multifunctional super-hydrophobic fabric.

[0016] Furthermore, the hydrophobicity of the super hydrophobic fabric has a self-repairing property under thermal induction.

[0017] Compared with the prior art, the present invention has the following beneficial effects:

[0018] (1) The present invention uses a graphene oxide dispersion, a hydrophobic long-chain silane such as hexadecyltrimethoxysilane (HDTMS), a waterborne polyurethane (WPU) resin such as silicone-modified waterborne polyurethane and a disperse dye to form a composite coating (reduced graphene oxide / HDTMS / WPU / composite coating) solution, and adopts a one-step disperse dyeing method to reduce and finish the fabric. The disperse dyeing treatment under high temperature / high pressure can not only form a multifunctional coating firmly bonded to the fabric surface, but also realize the in-situ reduction of graphene oxide and fabric dyeing, and form a self-repairing antibacterial and antistatic super-hydrophobic composite coating on the fabric surface. In the process of forming the composite coating, WPU is stably attached to the fabric surface as a solid hydrophobic coating matrix and fixed as an adhesive to reduce graphene oxide / HDTMS; the micro-reduced graphene oxide and the hydrophobic long-chain silane such as HDTMS further increase the surface roughness, reduce the surface free energy, and improve the surface super-hydrophobicity, thereby obtaining a self-repairing multifunctional super-hydrophobic fabric.

[0019] (2) The present invention provides an efficient and clean strategy for preparing a strong, colorful, non-fluorinated, antibacterial and antistatic super-hydrophobic fabric coating through a simple one-step disperse dyeing process. The method is simple to operate, highly controllable and widely applicable. The preparation process does not involve any toxic or harmful reagents and gases, is green and environmentally friendly, and has good product uniformity and reproducibility. It has high application potential in realizing the green production of functional fabrics.

[0020] (3) After the self-repairing antibacterial and antistatic super-hydrophobic composite coating is formed on the surface of the fabric, the (water contact angle) WCA of the super-hydrophobic fabric is greater than 155°, and it also has good liquid repellency to various aqueous solutions, giving the fabric the characteristic of self-cleaning, and has significant high stability against washing, abrasion, acid and alkali attack, high temperature and extremely low temperature (i.e., liquid nitrogen) treatment. In addition, the super-hydrophobic composite coating also exhibits the self-healing ability of chemical damage, and the reduced graphene oxide in the coating matrix makes the fabric have antistatic and antibacterial capabilities against Staphylococcus aureus (the antibacterial rate exceeds 98%). BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the dye coating mechanism of the self-repairing multifunctional super-hydrophobic fabric of the present invention.

[0022] Figure 2 It is a process diagram for preparing the super hydrophobic fabric of the present invention.

[0023] Figure 3 The following are scanning electron microscope images and hydrophobic performance images of the super hydrophobic fabric of the present invention. Figure 3 a is a scanning electron microscope image, b is a water drop image on the treated fabric, c is a picture of various aqueous phase drop images, d is a physical picture of Example 1, e is a physical picture of Example 2, f is a physical picture of Example 3, g is a physical picture of Example 4, h is a physical picture of Example 5, and i is a physical picture of Example 6.

[0024] Figure 4 This is the XRD diagram of the graphene oxide flakes before and after the dispersion dyeing treatment of the present invention.

[0025] Figure 5 This is the X-ray photoelectron spectrum of the super-hydrophobic fabric dyeing treatment in Example 1 of the present invention, Figure 5 a is the XPS full spectrum, b is the C1s spectrum, c is the Si2p spectrum, d is the N1s spectrum, e is the EDX dispersion diagram of C, f is the EDX dispersion diagram of O, g is the EDX dispersion diagram of N, and h is the EDX dispersion diagram of Si.

[0026] Figure 6 The super-hydrophobicity of the super-hydrophobic fabric of Example 1 of the present invention after repeated washing cycles and the scanning electron microscope image after the cycles are shown. Figure 6 a is the superhydrophobicity after repeated washing cycles, b is the scanning electron microscopy after 100 washing cycles, and c is the color fastness after washing cycles.

[0027] Figure 7 This is a graph showing the wear resistance of the super hydrophobic fabric of Example 1 of the present invention. Figure 7 a is the effect of wear cycles on superhydrophobicity, b is the scanning electron microscopy after 2000 wear cycles, and c is the color fastness after wear.

[0028] Figure 8 This is a diagram showing the hydrophobic properties of the super-hydrophobic fabric of Example 1 of the present invention after being immersed in an organic solvent.

[0029] Fig. 9 This is a graph showing the hydrophobic performance of the super-hydrophobic fabric of Example 5 of the present invention under ultraviolet irradiation.

[0030] Fig.10 The hydrophobic properties and color fastness of the super hydrophobic fabric of Example 5 of the present invention under ultrasonic treatment are shown in FIG. Fig.10In the figure, a is the hydrophobic property under ultrasonic treatment, and b is the color fastness of the fabric after 30 min ultrasonic treatment.

[0031] Fig.11 This is a diagram showing the hydrophobic performance of the super hydrophobic fabric of Example 5 of the present invention at high and low temperatures. Fig.11 In a, heating was performed at 180°C for 30 min, and in b, freezing was performed with liquid nitrogen for 3 min.

[0032] Fig.12 The electrostatic voltage and half-life performance diagram of the super-hydrophobic fabric before and after treatment in Example 1 of the present invention are shown in FIG. Fig.12 Where a is the static voltage and b is the half-life.

[0033] Fig.13 This is a graph showing the antibacterial performance of the super-hydrophobic fabric of Example 1 of the present invention.

[0034] Fig.14 This is a self-repairing characteristic diagram of the super-hydrophobic fabric of Example 1 of the present invention, Fig.14 a in the figure is after vacuum plasma treatment, b is after plasma treatment and heating at 150°C for 10 min, and c is repeated plasma heating treatment cycle. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the present invention will be described clearly and completely below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0036] It should be noted that the professional terms used in the present invention are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention. Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the following embodiments of the present invention can be purchased from the market or prepared by existing methods. In the present invention, polyester fabric (PET, pure grain, 160g / m 2 ) was provided by the National Dyeing and Finishing Innovation Center. Hexadecyltrimethoxysilane (HTDMS, H3C(CH2) 15 Si(OCH3)3, 85%) and anhydrous ethanol (≥99.7%) were provided by Shanghai Mscklin Biochemical Technology Co., Ltd. Silicone-modified waterborne polyurethane (WPU) was purchased from Tianjin Qisheng Trading Co., Ltd. Graphene oxide (graphene oxide, 6.0 g / L water-borne dispersant) was provided by the National Dyeing and Finishing Innovation Center. Disperse dyes, such as black SE-2R, navy blue S-2R, red S-BR, blue SE-2R, brown S-2RFLN, and purple S-FRL, were provided by Yorkshire Chemical Holdings Co., Ltd.

[0037] Multifunctional super-hydrophobic fabrics have great application potential in daily life. In recent years, super-wetting coatings have been formed on the surface of fabrics by physical methods (such as immersion plating, vapor deposition, spraying, etc.), chemical methods (such as grafting reaction, in-situ polymerization, electrochemical deposition, etc.) or both. However, their chemical and mechanical damage is not persistent, and they also have poor durability and cumbersome coating processes. Although the use of fluorosurfactant materials can reduce surface free energy and enhance the super-hydrophobicity of the surface, some solvents that are harmful to the human body and the environment will be used additionally, or toxic and harmful gases will be produced. Therefore, it is particularly important to study and develop a fast, environmentally friendly and durable super-hydrophobic fabric finishing method.

[0038] In recent years, graphene materials have attracted widespread attention due to their excellent low density, high conductivity, flexibility, excellent thermal stability and chemical stability. Some man-made fibers have the problem of surface static electricity accumulation, which has an adverse effect on their wearing comfort. The adhesion and proliferation of microorganisms on fabrics can cause bad odors, stains, discoloration, and can cause pathogen infection, affecting human health. Therefore, it is of great significance to give fabrics antibacterial properties. The application of graphene materials in coatings gives them antistatic and bactericidal functions. However, directly dispersing graphene in the coating solution is uneven and unstable, and because graphene itself is also black, it is impossible to dye the fabric into different colors to make the fabric present different colors, and its use is limited.

[0039] Based on this, the present invention provides a green one-step strategy to easily prepare colorful, multifunctional fluorine-free super-hydrophobic coatings on fabrics using traditional disperse dyeing methods. This one-step multifunctional coating strategy is ideal for the simple manufacture of fabric coatings by showing the advantages of energy saving, emission reduction, carbon footprint reduction and environmental protection. It provides an application for preparing durable multifunctional colored fabrics through traditional disperse dyeing processes, and has high application potential in achieving green production of functional fabrics.

[0040] In one aspect, the present invention provides a method for preparing a self-repairing multifunctional super-hydrophobic fabric, comprising the following steps:

[0041] A graphene oxide dispersion, a hydrophobic long-chain silane with a carbon atom number n≥6, an aqueous polyurethane and a disperse dye are mixed to form a composite coating solution, and the fabric is reduced and finished by a one-step disperse dyeing method. A self-repairing antibacterial and antistatic super-hydrophobic composite coating is formed on the surface of the fabric. During the formation of the composite coating, the graphene oxide is reduced in situ, and the aqueous polyurethane is used as an adhesive to combine the hydrophobic long-chain silane and the reduced graphene oxide to construct a rough structure and reduce the surface free energy, thereby obtaining a self-repairing multifunctional super-hydrophobic fabric.

[0042] The present invention forms a composite coating solution by mixing graphene oxide dispersion, hexadecyltrimethoxysilane, waterborne polyurethane and disperse dyes, and performs reduction finishing on the fabric by a one-step disperse dyeing method. The disperse dyeing treatment under high temperature / high pressure can not only form a multifunctional coating firmly bonded to the fabric surface, but also realize in-situ reduction of graphene oxide and fabric dyeing, and form a self-repairing antibacterial and antistatic super-hydrophobic composite coating on the fabric surface. In the process of forming the composite coating, WPU is stably attached to the fabric surface as a solid hydrophobic coating matrix, and is used as an adhesive to fix the reduced graphene oxide / HDTMS; the micro-reduced graphene oxide and the long carbon chain HDTMS further increase the surface roughness, reduce the surface free energy, and improve the surface super-hydrophobicity, thereby obtaining a self-repairing multifunctional super-hydrophobic fabric.

[0043] Figure 1 This is the dye coating mechanism of the self-repairing multifunctional super-hydrophobic fabric of the present invention. Figure 1 As shown, due to the high temperature and pressure in the disperse dyeing process, the hydrophobic disperse dye is easily separated from the bath solution, migrates to the surface of the hydrophobic polyester fiber and deposits, and finally diffuses into the fiber, showing bright colors. At the same time, the graphene oxide flakes are successfully reduced to reduced graphene oxide and evenly dispersed in the solution. When the dyed fabric is removed from the solution, a thin layer of reduced graphene oxide / HDTMS / WPU / composite coating solution remains on the surface, forming a durable multifunctional coating; after the heating process at 150 ° C, WPU plays a vital role in the matrix to fix the reduced graphene oxide / HDTMS / dye molecules and firmly adhere to the coating surface. Reduced graphene oxide improves the surface roughness of the coating, while giving the coating antistatic and antibacterial properties. The low surface energy HDTMS in the coating and the hierarchical surface of the coating make it superhydrophobic. In addition, the HDTMS molecules make the coating exhibit self-healing properties because they can migrate to the surface under thermal treatment and replace the hydrophilic groups caused by chemical damage, reducing the surface energy again.

[0044] The present invention provides an efficient and clean strategy to prepare a strong, colorful, non-fluorinated, antibacterial and antistatic super-hydrophobic fabric coating through a simple one-step disperse dyeing process. The method is simple to operate, highly controllable and widely applicable. The preparation process does not involve any toxic or harmful reagents and gases, is green and environmentally friendly, and has good product uniformity and reproducibility, and has high application potential in realizing the green production of functional fabrics.

[0045] In a specific embodiment, the amount ratio of the graphene oxide dispersion, the hydrophobic long-chain silane and the aqueous polyurethane is 30mL: 0.1-1.0g: 0.5-1.0g. In the present invention, within a certain range, a high amount of graphene oxide will improve the conductivity and antibacterial properties. Since the graphene oxide is reduced to form reduced graphene oxide, it has color. When the amount of graphene oxide increases, the dyeing effect of the fabric increases, and in the process of disperse dyeing under high temperature / high pressure, partial reduction is caused, the dispersion is uneven, and it is unstable, and the fabric cannot be dyed into different colors, so that the fabric presents different colors, and the use is limited.

[0046] In a specific embodiment, the hydrophobic long-chain silane is a silane coupling agent with a carbon atom number n≥6, and the waterborne polyurethane is a silicone-modified waterborne polyurethane. In the present invention, the silane coupling agent can be one or two of hexadecyltrimethoxysilane (HDTMS), polydimethylsiloxane (PDMS), octadecyltrichlorosilane (OTS), octadecylamine (ODA), silicone oil, etc., the purpose is to increase the surface roughness, reduce the surface free energy, and improve the surface super-hydrophobicity. Preferably, the silane coupling agent is HDTMS, and the HDTMS molecules make the coating exhibit self-healing properties, because they can migrate to the surface under heat treatment, replace the hydrophilic groups caused by chemical damage, and reduce the surface energy again; the waterborne polyurethane can also be other hydrophobic fluorine-free waterborne polyurethanes, which are stably attached to the fabric surface as a solid hydrophobic coating matrix, and fixed as an adhesive to reduce graphene oxide / HDTMS.

[0047] In a specific embodiment, the mass ratio of the disperse dye to the aqueous polyurethane is 1-5:20. In the present invention, a one-step disperse dyeing process is used to reduce and finish the fabric to prepare a colorful, multifunctional fluorine-free super-hydrophobic coating, and the amount of the disperse dye can be determined and optimized according to the actual needs of the dyeing degree of the fabric. The mass ratio of the disperse dye to the aqueous polyurethane can be any ratio between 1-5:20, such as 1:20, 2:20, 3:20, 4:20 or 5:20, etc.

[0048] In a specific embodiment, the concentration of the graphene oxide dispersion is 2-3 g / L. In the present invention, the graphene oxide dispersion is successfully reduced to reduced graphene oxide during the dispersion dyeing process under high temperature / high pressure, and is evenly dispersed in the solution, and has a certain dyeing effect on the fabric. The multifunctional coating is formed by WPU fixation, and the reduced graphene oxide improves the surface roughness of the coating, while making the coating have antistatic and antibacterial properties. Preferably, the preparation method of the graphene oxide dispersion comprises the following steps: adding water to the graphene oxide dispersion, adding ethanol after mixing evenly, and obtaining the graphene oxide dispersion after mixing evenly; the graphene oxide is a graphene oxide aqueous dispersion with a graphene oxide content of 6.0 g / L; the volume ratio of the graphene oxide dispersion, water and ethanol is 9:18:3.

[0049] In a specific embodiment, the fabric is a fiber fabric that can be dyed with disperse dyes. In the present invention, the fiber fabric is not specifically limited, as long as it is a fiber fabric that can be dyed with disperse dyes and a stable coating is formed on the surface of the fiber fabric. Preferably, the fiber fabric is polyester.

[0050] In a specific embodiment, the fabric is immersed in a composite coating solution, first heated to 50-70°C, then heated to 120-150°C for 60 minutes, and then rotated at 60r / min to cool to room temperature, and dried to obtain a self-repairing multifunctional super-hydrophobic fabric. The heating rate for heating to 50-70°C is 5-10°C / min, the heating rate for heating to 120-150°C is 2-3°C / min, the pressure is 280-295KPa, and the cooling rate to room temperature is 5°C / min. In the present invention, the disperse dyeing method is conventional disperse dye dyeing, which adopts conventional dyeing temperature and pressure, does not require additional dyeing steps, and adapts to a variety of conventional dyeing equipment, and provides many possibilities for preparing durable multifunctional colored fabrics by traditional disperse dyeing processes, and has high application potential in realizing the green production of functional fabrics.

[0051] On the other hand, the present invention provides a self-repairing multifunctional super-hydrophobic fabric. The (water contact angle) WCA of the super-hydrophobic fabric is greater than 155°, and it also has good liquid repellency to various aqueous solutions, giving the fabric the characteristic of self-cleaning, and having a significantly high stability against washing, abrasion, acid-base attack, high temperature and extremely low temperature (i.e., liquid nitrogen) treatment. In addition, when its super-hydrophobicity is physically and chemically destroyed, its original hydrophobicity can be restored by a simple heating process, that is, the hydrophobicity of the super-hydrophobic fabric has self-repairing properties under heat induction, showing the self-healing ability of chemical damage, and the reduced graphene oxide in the coating matrix makes the fabric antistatic and antibacterial against Staphylococcus aureus (the antibacterial rate exceeds 98%).

[0052] The invention is further described below through specific examples.

[0053] Example 1

[0054] A method for preparing a self-repairing multifunctional super-hydrophobic fabric comprises the following steps:

[0055] S1. 9 mL of graphene oxide dispersion was added to 18 mL of distilled water, followed by stirring for 5 min, and then 3 mL of ethanol was slowly added to the prepared graphene oxide dispersion, followed by stirring for another 5 min, and then magnetically stirred for 10 min to form a graphene oxide dispersion;

[0056] S2. Hexadecyltrimethoxysilane (HDTMS) and silicone waterborne polyurethane (WPU) were sequentially added to 30 mL of graphene oxide dispersion to obtain a functionally uniform graphene oxide / HDTMS / WPU coating solution. To prepare a colored functional coating solution, 0.03 g of disperse dye black SE-2R was added to the obtained GO / HDTMS / WPU / dye composite coating solution.

[0057] S3. A 5cm×5cm polyester fabric (PET) was immersed in a dyeing machine containing 30mL of GO / HDTMS / WPU / dye composite coating solution. To ensure uniform dyeing, the dyeing bath temperature of the dyeing machine was rapidly increased to 70°C (heating rate 5°C / min), then gradually increased to 130°C (heating rate 2°C / min), and finally maintained at 130°C for 60min. The steam pressure in the container was about 280-295kPa. After dyeing, the container temperature was lowered to room temperature at a cooling rate of 5°C / min. During the cooling process, the container rotated at a speed of 60r / min; the treated fabric was thoroughly rinsed with tap water to remove the floating redundant coating, and dried at 150°C for 30min to obtain a self-repairing multifunctional superhydrophobic fabric.

[0058] Example 2

[0059] A method for preparing a self-repairing multifunctional super-hydrophobic fabric comprises the following steps:

[0060] S1. 9 mL of graphene oxide dispersion was added to 18 mL of distilled water, followed by stirring for 5 min, and then 3 mL of ethanol was slowly added to the prepared graphene oxide dispersion, followed by stirring for another 5 min, and then magnetically stirred for 10 min to form a graphene oxide dispersion;

[0061] S2. Hexadecyltrimethoxysilane (HDTMS) and silicone waterborne polyurethane (WPU) were sequentially added to 30 mL of graphene oxide dispersion to obtain a functionally uniform graphene oxide / HDTMS / WPU coating solution. To prepare a colored functional coating solution, 0.03 g of disperse dye navy blue S-2R was added to the obtained GO / HDTMS / WPU / dye composite coating solution.

[0062] S3, a 5cm×5cm polyester fabric (PET) was immersed in a dyeing machine containing 30mL GO / HDTMS / WPU / dye composite coating solution. To ensure uniform dyeing, the dyeing bath temperature was rapidly increased to 70℃ (heating rate 5℃ / min), then gradually increased to 130℃ (heating rate 2℃ / min), and finally maintained at 130℃ for 60min. The steam pressure in the container was about 280-295kPa. After dyeing, the container temperature was lowered to room temperature at a cooling rate of 5℃ / min. During the cooling process, the container rotated at a speed of 60r / min; the treated fabric was thoroughly rinsed with tap water to remove the floating redundant coating, and dried at 150℃ for 30min to obtain a self-repairing multifunctional superhydrophobic fabric.

[0063] Example 3

[0064] A method for preparing a self-repairing multifunctional super-hydrophobic fabric comprises the following steps:

[0065] S1. 9 mL of graphene oxide dispersion was added to 18 mL of distilled water, followed by stirring for 5 min, and then 3 mL of ethanol was slowly added to the prepared graphene oxide dispersion, followed by stirring for another 5 min, and then magnetically stirred for 10 min to form a graphene oxide dispersion;

[0066] S2. Hexadecyltrimethoxysilane (HDTMS) and silicone waterborne polyurethane (WPU) were sequentially added to 30 mL of graphene oxide dispersion to obtain a functionally uniform graphene oxide / HDTMS / WPU coating solution. To prepare a colored functional coating solution, 0.03 g of disperse dye red S-BR was added to the obtained GO / HDTMS / WPU / dye composite coating solution.

[0067] S3, a 5cm×5cm polyester fabric (PET) was immersed in a dyeing machine containing 30mL GO / HDTMS / WPU / dye composite coating solution. To ensure uniform dyeing, the dyeing bath temperature was rapidly increased to 70℃ (heating rate 5℃ / min), then gradually increased to 130℃ (heating rate 2℃ / min), and finally maintained at 130℃ for 60min. The steam pressure in the container was about 280-295kPa. After dyeing, the container temperature was lowered to room temperature at a cooling rate of 5℃ / min. During the cooling process, the container rotated at a speed of 60r / min; the treated fabric was thoroughly rinsed with tap water to remove the floating redundant coating, and dried at 150℃ for 30min to obtain a self-repairing multifunctional superhydrophobic fabric.

[0068] Example 4

[0069] A method for preparing a self-repairing multifunctional super-hydrophobic fabric comprises the following steps:

[0070] S1. 9 mL of graphene oxide dispersion was added to 18 mL of distilled water, followed by stirring for 5 min, and then 3 mL of ethanol was slowly added to the prepared graphene oxide dispersion, followed by stirring for another 5 min, and then magnetically stirred for 10 min to form a graphene oxide dispersion;

[0071] S2. Hexadecyltrimethoxysilane (HDTMS) and silicone waterborne polyurethane (WPU) were sequentially added to 30 mL of graphene oxide dispersion to obtain a functionally uniform graphene oxide / HDTMS / WPU coating solution. To prepare a colored functional coating solution, 0.03 g of disperse dye blue SE-2R was added to the obtained GO / HDTMS / WPU / dye composite coating solution.

[0072] S3, a 5cm×5cm polyester fabric (PET) was immersed in a dyeing machine containing 30mL GO / HDTMS / WPU / dye composite coating solution. To ensure uniform dyeing, the dyeing bath temperature was rapidly increased to 70℃ (heating rate 5℃ / min), then gradually increased to 130℃ (heating rate 2℃ / min), and finally maintained at 130℃ for 60min. The steam pressure in the container was about 280-295kPa. After dyeing, the container temperature was lowered to room temperature at a cooling rate of 5℃ / min. During the cooling process, the container rotated at a speed of 60r / min; the treated fabric was thoroughly rinsed with tap water to remove the floating redundant coating, and dried at 150℃ for 30min to obtain a self-repairing multifunctional superhydrophobic fabric.

[0073] Example 5

[0074] A method for preparing a self-repairing multifunctional super-hydrophobic fabric comprises the following steps:

[0075] S1. 9 mL of graphene oxide dispersion was added to 18 mL of distilled water, followed by stirring for 5 min, and then 3 mL of ethanol was slowly added to the prepared graphene oxide dispersion, followed by stirring for another 5 min, and then magnetically stirred for 10 min to form a graphene oxide dispersion;

[0076] S2. Hexadecyltrimethoxysilane (HDTMS) and silicone waterborne polyurethane (WPU) were sequentially added to 30 mL of graphene oxide dispersion to obtain a functionally uniform graphene oxide / HDTMS / WPU coating solution. To prepare a colored functional coating solution, 0.03 g of disperse dye purple S-FRL was added to the obtained GO / HDTMS / WPU / dye composite coating solution.

[0077] S3, a 5cm×5cm polyester fabric (PET) was immersed in a dyeing machine containing 30mL GO / HDTMS / WPU / dye composite coating solution. To ensure uniform dyeing, the dyeing bath temperature was rapidly increased to 70℃ (heating rate 5℃ / min), then gradually increased to 130℃ (heating rate 2℃ / min), and finally maintained at 130℃ for 60min. The steam pressure in the container was about 280-295kPa. After dyeing, the container temperature was lowered to room temperature at a cooling rate of 5℃ / min. During the cooling process, the container rotated at a speed of 60r / min; the treated fabric was thoroughly rinsed with tap water to remove the floating redundant coating, and dried at 150℃ for 30min to obtain a self-repairing multifunctional superhydrophobic fabric.

[0078] Example 6

[0079] A method for preparing a self-repairing multifunctional super-hydrophobic fabric comprises the following steps:

[0080] S1. 9 mL of graphene oxide dispersion was added to 18 mL of distilled water, followed by stirring for 5 min, and then 3 mL of ethanol was slowly added to the prepared graphene oxide dispersion, followed by stirring for another 5 min, and then magnetically stirred for 10 min to form a graphene oxide dispersion;

[0081] S2. Hexadecyltrimethoxysilane (HDTMS) and silicone waterborne polyurethane (WPU) were sequentially added to 30 mL of graphene oxide dispersion to obtain a functionally uniform graphene oxide / HDTMS / WPU coating solution. To prepare a colored functional coating solution, 0.03 g of disperse dye brown S-2RFLN was added to the obtained GO / HDTMS / WPU / dye composite coating solution;

[0082] S3, a 5cm×5cm polyester fabric (PET) was immersed in a dyeing machine containing 30mL GO / HDTMS / WPU / dye composite coating solution. To ensure uniform dyeing, the dyeing bath temperature was rapidly increased to 70℃ (heating rate 5℃ / min), then gradually increased to 130℃ (heating rate 2℃ / min), and finally maintained at 130℃ for 60min. The steam pressure in the container was about 280-295kPa. After dyeing, the container temperature was lowered to room temperature at a cooling rate of 5℃ / min. During the cooling process, the container rotated at a speed of 60r / min; the treated fabric was thoroughly rinsed with tap water to remove the floating redundant coating, and dried at 150℃ for 30min to obtain a self-repairing multifunctional superhydrophobic fabric.

[0083] Figure 2 FIG. 2 is a process diagram for preparing the super hydrophobic fabric of the present invention. Figure 2 As shown, a functional coating solution was prepared by adding HDTMS and WPU to a graphene oxide dispersion solution by magnetic stirring, while a specific color of the coating could be achieved by adding disperse dyes to the prepared graphene oxide / HDTMS / WPU solution. The obtained graphene oxide / HDTMS / WPU / dye solution showed high stability without precipitation even after being stored under ambient conditions for two weeks. The solution was then applied to polyester fabric by a disperse dyeing process at an elevated temperature of 130 °C for 60 min to form a durable coating of a predetermined color on the fabric with superhydrophobic, antibacterial and antistatic properties, while achieving in-situ reduction of graphene oxide in the coating. In order to determine the in-situ reduction of graphene oxide during the disperse dyeing process, white polyester fabric was used as a model fabric substrate and treated with a graphene oxide / HDTMS / WPU solution in the absence of disperse dyes. The color of the fabric changed from white to black, which was attributed to the partial reduction of GO promoted by the high temperature / steam pressure dyeing process and the subsequent heating treatment. In contrast, when the fabric was dip-coated with the GO / HDTMS / WPU solution and dried under ambient conditions, the fabric was brown, indicating that the GO was not reduced.

[0084] Figure 3 The following are scanning electron microscope images and hydrophobic performance images of the super hydrophobic fabric of the present invention. Figure 3 a is a scanning electron microscope image, b is an image of water droplets on the treated fabric, c is an image of various aqueous phase droplets, d is a physical image of Example 1, e is a physical image of Example 2, f is a physical image of Example 3, g is a physical image of Example 4, h is a physical image of Example 5, and i is a physical image of Example 6. Figure 3As shown in a, a stratified surface can be observed, indicating that a thin layer of reduced graphene oxide / HDTMS / WPU coating is formed on the PET fabric, and the resulting high surface roughness can improve the liquid repellency of the coating. In contrast, the original fiber shows a smooth fiber morphology. Figure 3 As shown in b, after dyeing, the reduced graphene oxide / HDTMS / WPU coated fabric has superhydrophobicity, WCA is 158°, and the minimum SA is only 5; Figure 3 As shown in c, the fabric also has good liquid repellency to various aqueous solutions, such as hydrochloric acid aqueous solution (pH=1), sodium hydroxide aqueous solution (pH=14), salt water, juice, milk and coffee, with CAs exceeding 150° and SAs less than 6. When the water jet splashes the coated fabric, it splashes out immediately and no trace of water is left on the surface, indicating that the coating has strong liquid repellency, which also gives the fabric self-cleaning properties. In addition, the fabric still maintains satisfactory flexibility. Although the treated fabric is dark due to the presence of reduced graphene oxide in the coating, it can still be dyed into different colors. Figure 3 As shown in Figure 2, different dark disperse dyes, such as blue, purple, yellow, red, navy blue, black, etc., have been introduced into the GO / HDTMS / WPU coating system. After dyeing and curing, the synthesized fabrics showed different colors, and they all had superhydrophobicity, with WCA greater than 155° and SA less than 5.

[0085] The crystal structure of graphene oxide was studied by X-ray diffraction (XRD). Figure 4 Figure 2 is the XRD diagram of the graphene oxide flakes before and after the dispersion dyeing treatment of the present invention. Figure 4 As shown in the figure, there is a characteristic peak at about 11.5°, which represents the typical diffraction pattern (001) of the graphene oxide crystal structure; for the treated fabric, there is another peak near 2θ = 15°, which is also considered to be the crystal diffraction peak of graphene oxide

[29] . The characteristic (001) peak disappears, and a broad new peak appears at about 23°, corresponding to the (002) diffraction, indicating that the oxygen-containing groups on the basal plane of graphene oxide are partially removed and the graphene oxide is partially reduced.

[0086] The surface chemical properties of the fabrics treated with reduced graphene oxide / HDTMS / WPU were analyzed by X-ray photoelectron spectroscopy (XPS). Figure 5 This is the X-ray photoelectron spectrum of the super-hydrophobic fabric dyeing treatment in Example 1 of the present invention, Figure 5 a is the full XPS spectrum, b is the C1s spectrum, c is the Si2p spectrum, d is the N1s spectrum, e is the EDX dispersion diagram of C, f is the EDX dispersion diagram of O, g is the EDX dispersion diagram of N, and h is the EDX dispersion diagram of Si. Figure 5As shown in a, after dyeing treatment, C, N, O and Si elements can be observed in the XPS measurement spectrum, among which N and Si elements can verify the existence of WPU and HDTMS molecules; Figure 5 In the high-resolution C1s spectrum shown in (b), the four peaks with binding energies of CC (284.9 eV, 285.6 eV, 287.1 eV, and 289.1 eV) are assigned to CC (CH), CO, C=O, and OC=O, respectively; Figure 5 Figure c shows the high-resolution Si2p spectrum, and the peaks at 100.2 eV and 101.6 eV are attributed to the Si-C and Si-O bonds of the HDTMS molecules, respectively; Figure 5 The d in the figure is the N1s spectrum of the treated fabric. The peaks with binding energies of 399.7 eV and 397.9 eV are NC=O and CN bonds, respectively, confirming the presence of WPU. The surface chemical composition of the treated fabric was also analyzed by FTIR spectroscopy. The results of energy dispersive spectroscopy (EDS) are shown in Figure 2. Figure 5 The eh in the graphene oxide / HDTMS / WPU coating is consistent with the XPS results. The graphene oxide / HDTMS / WPU coating contains C, O, Si, and N elements, which are evenly distributed on the surface of the treated fabric, with atomic ratios of 35.98%, 52.12%, 1.07%, and 10.83%, respectively. In contrast, the original fabric only contains C and O elements, with atomic ratios of 47.93% and 52.07%, respectively.

[0087] The super-hydrophobic fabrics were subjected to washing and abrasion durability tests after dyeing. The washing durability tests were conducted according to the standard washing procedures specified by the American Association of Textile Chemists and Colorists (AATCC, Test Method 61-2006 Test No. 2A). All tests were conducted in a standard washing machine equipped with a 500 mL stainless steel tank (750 mm × 75 mm). Fabric samples (5 × 5 cm 2 ) were washed in 150 mL of aqueous solution. The washing temperature was set at 49 °C and the stirring speed was 40 ± 2 rpm. The standard laundry cycle was 45 min long, equivalent to 5 home laundry cycles. The abrasion resistance of the fabric coating was evaluated using a commercial Martindale abrasion tester using the Martindale method (ASTM D4966) at a loading pressure of 9 kPa.

[0088] The SW-24E washing color fastness instrument and ISO105-C10-C10:2001 and ISO 105X-12:2001 textile color fastness standards were used for evaluation. Color fastness test: The treated fabric was washed in a standard soap solution (5g / L) at 50°C for 45min; the color fastness was tested under dry and wet friction. The dry friction method is as follows: the fabric is fixed on a 104mm friction channel, a cylinder (16mm in diameter) is wrapped with white cotton fabric, a friction force of 9N is applied, and the friction finger is reciprocated 20 times on the fabric fixed on the friction channel. For wet friction, the fabric is first soaked in distilled water, and then rubbed 20 times under the same conditions as dry friction.

[0089] Figure 6 The super-hydrophobicity of the super-hydrophobic fabric of Example 1 of the present invention after repeated washing cycles and the scanning electron microscope image after the cycles are shown. Figure 6 a is the super hydrophobicity after repeated washing cycles, b is the scanning electron microscopy after 100 washing cycles, and c is the color fastness after washing cycles. Figure 6 As shown in a in FIG, the increase in the washing cycle causes the WCA to remain almost unchanged and the SA to increase slightly. After 100 washing cycles, the WCA of the fabric is still 153.8° and the SA is 10.5; Figure 6 As shown in Figure b, the delaminated coating on the washed fabric is almost undamaged, indicating strong adhesion between the coating and the fabric substrate; Figure 6 As shown in Figure c, the K / S value of the washed fabric decreases significantly with the amount of washing and drops to 19.63 in the first 40 washing cycles. This is because some over-dispersed dye particles remaining on the coating surface are removed by washing. As the washing cycle further increases to 100, the K / S value only decreases slightly and stabilizes at 18.20, indicating high color fastness.

[0090] Figure 7 This is a graph showing the wear resistance of the super hydrophobic fabric of Example 1 of the present invention. Figure 7 a is the effect of abrasion cycles on superhydrophobicity, b is the scanning electron micrograph after 2000 abrasion cycles, and c is the color fastness after abrasion. Figure 7 As shown in a, the coating also has excellent wear resistance, which is evaluated according to the Martindale wear test with a load of 9 kPa. After increasing the wear cycle, the WCA remains almost unchanged, and the SA increases. After 2000 wear cycles, the WCA of the fabric is 151.2° and the SA is 13.5; Figure 7 As shown in (b), after 2000 abrasion cycles, some fibers on the top surface of the coating were damaged and the coating partially fell off, resulting in an increase in the SA value. However, the unexposed fibers were still firmly covered by the coating with high surface roughness, which made the abraded fabric show superhydrophobicity; Figure 7As shown in Figure c, the effect of abrasion on the color fastness of the coated fabric, the K / S value drops sharply in the first 800 abrasion cycles, and then begins to gradually decrease as the abrasion cycles gradually increase to 2000. After 2000 cycles, the K / S value of the fabric is 18.98.

[0091] The coated fabrics were immersed in various solvents (such as hydrochloric acid (pH = 1), sodium hydroxide (pH = 14), ethanol, ethanol, N-methylpyridone (NMP), dimethylformamide (DMF), tetrahydrofuran (THF) and cyclohexane (CYH)) for 24 h, then rinsed with water and dried under ambient conditions. Figure 8 This is a diagram showing the hydrophobic properties of the super hydrophobic fabric of Example 1 of the present invention after being immersed in an organic solvent. Figure 8 As shown, all treated fabrics maintained superhydrophobicity with WCA greater than 150° and SA no greater than 10 for all liquids. At the same time, the K / S values ​​of the treated fabrics changed slightly, indicating that the coatings had good color fastness against chemical attack.

[0092] In addition, the color fastness of the coating against dry and wet friction was evaluated according to textile standards ISO 105-C10: 2006 and ISO 105X-12: 2001. The calculated grayscale evaluation showed that the reduced graphene oxide / HDTMS / WPU / dye composite coating had a color fastness level of 4-5, which showed good color fastness. The superhydrophobicity of the coating can also withstand long-term UV exposure without degradation.

[0093] Fig. 9 Graph showing the hydrophobic performance of the super hydrophobic fabric of Example 5 of the present invention under ultraviolet irradiation. Fig. 9 As shown in Figure 2, after irradiation with 365 nm UV light for 72 h, the fabric still exhibited superhydrophobicity with a WCA of 152.8° and a SA of 9.4. In order to further study the durability of the coating, the coated fabric was treated with ultrasound in tap water.

[0094] Fig.10 The hydrophobic properties and color fastness of the super hydrophobic fabric of Example 5 of the present invention under ultrasonic treatment are shown in FIG. Fig.10 Where a is the hydrophobicity under ultrasonic treatment, and b is the color fastness of the fabric after 30 minutes of ultrasonic treatment. Fig.10 As shown in a, with the extension of ultrasonic treatment time, WCA decreased slightly and SA increased, but after 30 minutes of ultrasonic treatment, the fabric still maintained superhydrophobicity, with WCA of 153° and SA of 9); Fig.10 Figure b is a photograph of the coated fabric immersed in water after 30 minutes of ultrasonic treatment. The water is clear and colorless, indicating that the dispersed dye is safely embedded in the coating and the fabric has extremely high color fastness to ultrasonic treatment.

[0095] Fig.11 This is a diagram showing the hydrophobic performance of the super-hydrophobic fabric of Example 5 of the present invention at high and low temperatures. Fig.11 In a, heating at 180℃ for 30min, and in b, freezing with liquid nitrogen for 3min. Fig.11 As shown, the coating is also stable under high and low temperature conditions. After heating at 180°C for 30 minutes and freezing in liquid nitrogen for 3 minutes, the WCA of the coated fabric is still over 150° and the color change is not obvious.

[0096] The antibacterial zone and antibacterial activity of the super-hydrophobic fabric of Example 1 were evaluated by the AGAR diffusion method after the super-hydrophobic fabric was dyed. Staphylococcus aureus (Gram-positive) was used as a model bacterium. The antibacterial zone was measured after the bacteria grew for 24 hours. The antibacterial rate (R, %) was calculated using the following formula:

[0097]

[0098] Among them, A and B are the number of viable bacteria on the fabric before and after coating treatment after 24 hours of culture, respectively.

[0099] According to the standard GB / T 12703.1-2008 (Evaluation of electrostatic properties of textiles - Part 1: Half-life of electrostatic voltage), the electrostatic voltage and half-life of the super-hydrophobic fabric of Example 1 were tested on a YG(L)342D electrostatic tester. The discharge voltage was 10 kV, the rotation speed was 1500 rpm, and the test duration was about 30 s.

[0100] Due to the presence of conductive reduced graphene oxide flakes, the prepared reduced graphene oxide / HDTMS / WPU / dye coating exhibits good antistatic properties. The static voltage and half-life of the fabric and dyeing treatment were measured. Fig.12 The electrostatic voltage and half-life performance diagram of the super-hydrophobic fabric before and after treatment in Example 1 of the present invention are shown in FIG. Fig.12 Where a is the static voltage and b is the half-life. Fig.12 As shown, the standard antistatic performance of the original fabric is 500V, the half-life is 160s, and there is no antistatic performance. After dyeing, the static voltage of the fabric is greatly reduced to 130V, and the half-life is only 0.01s; this is because the reduced graphene oxide embedded in the coating establishes a large number of conductive channels for the transmission of electrons, thereby improving the conductivity of the coated fabric.

[0101] Fig.13 The antibacterial performance diagram of the super hydrophobic fabric of Example 1 of the present invention is shown in FIG. Fig.13As shown, bacteria grow rapidly in agar plates, indicating that untreated PET does not show antibacterial ability, while most Staphylococcus aureus can be effectively killed by the treated fabrics; the antibacterial activity of the coating was calculated using the viable cell counting method (ASTM E2180), and the antibacterial rate of the reduced graphene oxide / HDTMS / WPU / dye treated fabric was above 98%. It can be seen that when Staphylococcus aureus is used as a model bacterium, the GO / HDTMS / WPU / dye composite coating also shows good antibacterial properties.

[0102] Fig.14 This is a self-repairing characteristic diagram of the super-hydrophobic fabric of Example 1 of the present invention, Fig.14 a in the figure is after vacuum plasma treatment, b is after plasma treatment and heating at 150°C for 10 min, and c is repeated plasma heating treatment cycle. Fig.14 As shown in Figure 2, after 3 min of vacuum plasma treatment, the fabric becomes hydrophilic and the water droplets diffuse into the fabric immediately when the WCA is 0 ( Fig.14 a); however, when the plasma-treated fabric was heated at 150 °C for 10 min, its superhydrophobicity was restored at a WCA of 153° ( Fig.14 This process was reproducible and after 10 cycles of plasma / heat treatment, the fabric exhibited superhydrophobicity with a WCA of 151° ( Fig.14 e) in.

[0103] As shown in the above, the present invention can not only realize the in-situ reduction of graphene oxide and fabric dyeing in the dyeing process, but also can apply colorful multifunctional composite coating on the fabric surface. Due to the synergy between all coating materials, the treated fabric shows super hydrophobicity, WCA is more than 158 °, SA is 5, in this composite coating system, micro-scale reduced graphene oxide has a higher surface roughness, hydrophobic WPU is used as an adhesive, the composite coating is firmly adhered to the fabric substrate, and HDTMS and reduced graphene oxide are combined together. The fluorine-free long carbon chain HDTMS embedded in the WPU matrix reduces the surface free energy and increases the super hydrophobicity of the coating. In addition, the uniform dispersion of dyes in the coating gives it different colors, and has almost no effect on function (such as super hydrophobic, antibacterial, antistatic). The developed functional coating has excellent durability to various serious damages, and can recover its super hydrophobicity from chemical damage.

[0104] Although the preferred embodiments of the present invention have been described, those skilled in the art may make other changes and modifications to these embodiments once they have learned the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0105] Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the present invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include these modifications and variations.

Claims

1. A method for preparing a self-repairing multifunctional super-hydrophobic fabric, characterized in that: The following steps are involved: A graphene oxide dispersion, a hydrophobic long-chain silane with a carbon atom number n≥6, an aqueous polyurethane and a disperse dye are mixed to form a composite coating solution, and the fabric is reduced and finished by a one-step disperse dyeing method. A self-repairing antibacterial and antistatic super-hydrophobic composite coating is formed on the surface of the fabric. During the formation of the composite coating, the graphene oxide is reduced in situ, and the aqueous polyurethane is used as an adhesive to combine the hydrophobic long-chain silane and the reduced graphene oxide to construct a rough structure and reduce the surface free energy, thereby obtaining a self-repairing multifunctional super-hydrophobic fabric.

2. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 1, characterized in that: The usage ratio of the graphene oxide dispersion, the hydrophobic long-chain silane and the aqueous polyurethane is 30 mL: 0.1-1.0 g: 0.5-1.0 g.

3. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 1, characterized in that: The hydrophobic long-chain silane is a silane coupling agent with a carbon atom number n≥6, and the waterborne polyurethane is an organic silicon-modified waterborne polyurethane.

4. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 1, characterized in that: The mass ratio of the disperse dye to the waterborne polyurethane is 1-5:

20.

5. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 1, characterized in that: The concentration of the graphene oxide dispersion is 2-3 g / L.

6. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 1, characterized in that: The fabric is a fiber fabric that can be dyed with disperse dyes.

7. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 1, characterized in that: During the reduction finishing process, the fabric is immersed in the composite coating solution, first heated to 50-70°C, then heated to 120-150°C and kept warm for 60 minutes. After the end, it is rotated at 60r / min and cooled to room temperature, and dried to obtain a self-repairing multifunctional super-hydrophobic fabric.

8. The method for preparing the self-repairing multifunctional super-hydrophobic fabric according to claim 7, characterized in that: The heating rate to 50-70°C is 5-10°C / min, the heating rate to 120-150°C is 2-3°C / min, the pressure is 280-295KPa, and the cooling rate to room temperature is 5°C / min.

9. A self-repairing antibacterial and antistatic multifunctional super-hydrophobic fabric prepared by the preparation method according to any one of claims 1 to 8.

10. The self-repairing multifunctional super-hydrophobic fabric according to claim 9, characterized in that: The hydrophobicity of the super-hydrophobic fabric is self-repairing under thermal induction.

Images