CN108642869B - Preparation method of super-hydrophobic anti-ultraviolet fabric - Google Patents
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
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Abstract
The invention discloses a preparation method of a super-hydrophobic anti-ultraviolet fabric. The method comprises the following steps: firstly, synthesizing an anti-ultraviolet compound of 1, 2-epoxypropyl ether aromatic ketone, and then modifying silicon dioxide to ensure that the anti-ultraviolet compound is grafted to the surface of silicon dioxide particles to endow the silicon dioxide with anti-ultraviolet capability; then sequentially immersing the fabric into a polyelectrolyte compound aqueous solution and a silicon dioxide aqueous dispersion, and enabling silicon dioxide particles to be adsorbed on the surface of the fabric through an electrostatic self-assembly method, so that the fabric is endowed with anti-ultraviolet performance and a rough surface required by super-hydrophobicity is constructed; finally, the fabric is further treated by the fluorine-free water repellent agent to obtain the super-hydrophobic performance. The fabric obtained by the invention has excellent uvioresistant performance and hydrophobicity, and the preparation method is simple and convenient.
Description
Technical Field
The invention relates to the technical field of preparation of multifunctional fabrics, in particular to a preparation method of a super-hydrophobic anti-ultraviolet fabric.
Background
The super-hydrophobic surface has special wettability, namely the contact angle of a water drop on the surface is more than 150 degrees, and the water drop is easy to roll. When water drops roll on the super-hydrophobic surface, some pollutants adsorbed on the surface of the water drops, such as solid particles, dust and the like, are adsorbed by the water drops and are carried away along with the sliding of the water drops, so that the lotus leaf self-cleaning effect is realized. With the increasing intensity of ultraviolet radiation and the tendency of shortwave, the energy of ultraviolet reaching the earth surface is increased, and the awareness of people on the harm of ultraviolet and the awareness of self-prevention are also increased. Therefore, the fabric with both ultraviolet resistance and super-hydrophobic performance can be widely applied to daily life, such as sun umbrellas, beach umbrellas, advertising signs, mountaineering wear and the like.
At present, most of researches on super-hydrophobic ultraviolet-resistant fabrics adopt nano particles such as titanium dioxide and zinc oxide, and the ultraviolet-resistant performance of nano particles is utilizedMeanwhile, the rough surface can be constructed by utilizing the nano particles, and the super-hydrophobic and ultraviolet-resistant effects are achieved. For example, patent 103572584a discloses a method for treating polyester and cotton fabrics with nano titanium dioxide modified by silane coupling agent, which can absorb ultraviolet rays and reflect and scatter ultraviolet rays, thus having excellent ultraviolet resistance. But TiO 22And ZnO and the like have extremely strong oxidizing property and reducing property after absorbing ultraviolet rays, and can perform nonselective decomposition on a fabric substrate in contact with the ZnO and a low surface energy substance covering a surface layer, so that the service life of the material is shortened, and the fabric gradually loses hydrophobicity.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a preparation method of a super-hydrophobic ultraviolet-resistant fabric. The ultraviolet-resistant micromolecules are synthesized on the basis of the nano silicon dioxide, and then are grafted to the surface of the nano silicon dioxide, so that the nano silicon dioxide is endowed with excellent ultraviolet-resistant performance; the roughness of the surface of the fabric is increased by using silicon dioxide, and finally the fabric is subjected to hydrophobic treatment to prepare the cotton fabric with the uvioresistant performance and the super-hydrophobic performance. The fabric obtained by the method has excellent hydrophobicity and ultraviolet resistance, and has the characteristics of simple and easy operation.
The invention is realized by the following technical scheme.
A preparation method of a super-hydrophobic ultraviolet-resistant fabric comprises the following steps:
(1) synthesis of the uvioresistant compound: adding 2, 4-dihydroxy benzophenone, epoxy chloropropane and a solvent into a reactor, dripping a catalyst under the condition of stirring, heating to 80-90 ℃, reacting for 2-6 h, and separating and purifying a product to obtain 1, 2-epoxypropyl ether aromatic ketone (HEPBP);
(2) amino-modified silica: adding silicon dioxide, a solvent and an aminosilane coupling agent into a reactor, heating to 100-120 ℃, reacting for 4-8 hours, and centrifugally washing the product for multiple times to obtain amino modified silicon dioxide;
(3) grafting of silica with 1, 2-epoxypropyl ether aryl ketone: dispersing the amino modified silicon dioxide obtained in the step (2) in a solvent, pouring the solvent into a three-necked bottle, uniformly stirring, adding the 1, 2-epoxypropyl ether aromatic ketone obtained in the step (1), reacting at 35-50 ℃ for 12-24 h, centrifuging for many times, washing, and drying to obtain silicon dioxide grafted with anti-ultraviolet micromolecules;
(4) preparation of silica dispersion: adding the silicon dioxide obtained in the step (3) into deionized water, and homogenizing and carrying out ultrasonic treatment to obtain a light yellow dispersion liquid with the mass percentage concentration of 0.5-2%;
(5) and (3) treating the fabric: preparing a cationic polyelectrolyte solution with the mass concentration of 0.3-0.7%, uniformly stirring, soaking the fabric in the solution at the soaking temperature of 30-50 ℃ for 1-5 min, taking out, and drying at the temperature of not higher than 80 ℃; soaking the dried fabric in the dispersion liquid obtained in the step (4) at the soaking temperature of 30-50 ℃ for 3-7 min, taking out, and drying at the temperature of not higher than 80 ℃; repeating the above steps for 2-6 times;
(6) and (3) dipping the fabric obtained in the step (5) in the fluorine-free water repellent agent emulsion or solution for 1-10 min, taking out, drying at 60-85 ℃, and baking at 125-135 ℃ for 3-8 min to obtain the super-hydrophobic ultraviolet-resistant fabric.
In the method, the solvent in the step (1) is acetone; the catalyst is sodium hydroxide or potassium hydroxide.
In the method, in the step (2), the silica refers to silica with a particle size of 10-100 nm; the solvent is toluene, cyclohexane or chloroform; the aminosilane coupling agent is one of gamma-aminopropyltriethoxysilane (KH-550), N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane (KH-792) and g-aminopropyltrimethoxysilane (KH-551), and the dosage of the added aminosilane coupling agent is 5-10% of the mass of silicon dioxide.
In the method, in the step (3), the amount of the 1, 2-epoxypropyl ether aromatic ketone is 5-13% of the mass of the silicon dioxide.
In the method, in the step (4), the homogenizing is performed for 3-5 min by using a homogenizer, and the rotating speed is 5000-12000 r/min.
In the above method, in the step (5), the cationic polyelectrolyte is one of polydimethyldiallylammonium chloride (PDDA), polyvinylamine (PVAm), and Polyethyleneimine (PEI).
In the method, in the step (6), the fluorine-free water repellent agent emulsion or solution is one of emulsions or solutions of polycarbodiimide, fluorine-free long-chain siloxane, amino-modified polysiloxane, hydroxyl-terminated polysiloxane and polydimethylsiloxane.
In the method, in the step (6), the solvent in the fluorine-free water repellent agent solution is one or more of ethanol, ethyl acetate and cyclohexane.
In the method, in the step (6), the mass fraction of the fluorine-free water repellent agent in the fluorine-free water repellent agent emulsion or solution is 3-8%.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, the 1, 2-epoxypropyl ether aryl ketone is used for grafting the silicon dioxide, so that the ultraviolet resistance of the fabric is greatly enhanced by utilizing the reflection effect of silicon dioxide nano particles on ultraviolet rays and the absorption capacity of benzophenone compounds on the ultraviolet rays.
2. The 1, 2-epoxypropyl ether group aromatic ketone grafted silicon dioxide nano particle prepared by the invention has an anti-ultraviolet function, and also serves as a basic particle for constructing the rough surface of the fabric, so that the basic particle becomes the basis for obtaining the super-hydrophobic performance of the fabric. The silicon dioxide is non-toxic and has no photocatalytic activity, and does not damage the fabric substrate.
3. According to the invention, the strong cationic polyelectrolyte is used for adsorbing the silica nanoparticles, and the loading capacity of the silica particles on the surface of the fabric can be improved by increasing the cycle times; and through the electrostatic attraction and hydrogen bond action between the polyelectrolyte and the silicon dioxide, the silicon dioxide can be better adsorbed on the surface of the fabric, and the durability of the fabric is improved.
4. The low surface energy modification material adopted by the invention does not contain fluorine and has environmental friendliness.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1, 2-epoxypropyl ether aryl ketone in example 1;
FIG. 2 is an infrared spectrum of the modified silica in example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
The static contact angle and the rolling angle of the fabric described in the examples were measured using a contact angle tester model JC2000D1, Shanghai, with a drop of 5. mu.L deionized water, 3 points per sample and the average. The ultraviolet resistance test of the fabric in the embodiment is operated according to national standard GB/T18830-.
Example 1
(1) Synthesizing uvioresistant small molecules: dissolving 1g of 2, 4-dihydroxy benzophenone in 10ml of acetone, pouring the acetone into a three-neck flask, sequentially adding 2.3g of epichlorohydrin and 10ml of NaOH aqueous solution with the concentration of 0.25g/ml, heating to 80 ℃, carrying out reflux reaction for 2 hours, carrying out separation and purification steps such as extraction, rotary evaporation, column chromatography and the like on the obtained product, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a light yellow powdery solid.
(2) Modification of silica: adding 4g of silicon dioxide into a round-bottom flask, adding 100ml of toluene, ultrasonically dispersing, heating to 100 ℃, adding 0.2g of KH-550, carrying out reflux reaction for 5 hours, centrifugally washing the obtained product, re-dispersing the product in the toluene, adding 0.2g of the product obtained in the step (1), reacting for 12 hours at 40 ℃, centrifugally washing, and vacuum drying for 5 hours at 70 ℃.
(3) Preparation of silica dispersion: and (3) taking 0.1g of the modified silicon dioxide powder obtained in the step (2), adding 20ml of deionized water, homogenizing for 3min, and then carrying out ultrasonic dispersion for 5 min.
(4) And (3) treating the fabric: preparing 20ml of PDDA aqueous solution with the concentration of 3mg/ml, soaking the fabric in the solution for 3min, taking out and drying at 60 ℃; soaking the dried fabric in the suspension obtained in the step (3) at 35 ℃ for 3min, taking out and drying at 60 ℃; the cycle is 2 times.
(5) And (3) soaking the fabric obtained in the step (4) in an ethanol solution of hexadecyl trimethoxy silane (HDTMS) with the mass fraction of 3% for 1min, taking out, drying at 60 ℃, and baking at 125 ℃ for 6min to obtain the fabric.
The product obtained in step (1) was characterized by nuclear magnetic resonance hydrogen spectroscopy, the results are shown in fig. 1, and the characterization data were analyzed as follows:1h NMR (600MHz, CDCl3)12.65(s,1H), 7.64-7.62 (m,2H),7.57(t, J ═ 7.5Hz,1H),7.53(s,1H),7.49(dd, J ═ 10.5,4.6Hz,2H),6.52(d, J ═ 2.5Hz,1H),6.45(dd, J ═ 9.0,2.5Hz,1H),4.32(dd, J ═ 11.1,2.9Hz,1H),3.99(dd, J ═ 11.1,5.9Hz,1H),3.38(ddt, J ═ 5.8,4.1,2.8Hz,1H), 2.94-2.93 (m,1H),2.77(dd, 4.8, 6.8, 1H). Wherein, the 12.65ppm is the characteristic peak of the proton on the phenolic hydroxyl, the 7.64, 7.57, 7.53, 7.49, 6.52 and 6.45ppm are the characteristic peaks of the proton on the benzene ring, the 4.32 and 3.99ppm are the characteristic peaks of the proton on the methylene, and the 3.38, 2.93 and 2.77ppm are the characteristic peaks of the proton on the epoxypropyl. In view of the above, the product from which the target structure is synthesized can be determined.
The product obtained in step (2) was characterized by infrared spectroscopy, the results of which are shown in fig. 2, and the characterization data were analyzed as follows: first of all, SiO in comparison with unmodified silica2-NH2In the curve (i.e. amino-modified silica) at 2925cm-1And 2848cm-1A new absorption peak appears, which is-CH on KH5502The peak of stretching vibration absorption of KH-550 was confirmed to be successfully grafted on silica. Second, with SiO2-NH2Curve comparison, SiO2HEPBP curve (i.e. silica grafted with 1, 2-epoxypropyl aryl ketone) at 1600cm-1A new absorption peak appears, namely a stretching vibration peak of C ═ O on the 1, 2-epoxypropyl ether aromatic ketone, which indicates that HEPBP is successfully grafted on the surface of the silicon dioxide.
Example 2
(1) Synthesizing uvioresistant small molecules: 2.14g of 2, 4-dihydroxy benzophenone is dissolved in 20ml of acetone, the mixture is poured into a three-neck flask, then 4.16g of epichlorohydrin and 20ml of NaOH aqueous solution with the concentration of 0.25g/ml are sequentially added, the temperature is increased to 80 ℃, reflux reaction is carried out for 4 hours, the obtained product is subjected to separation and purification steps such as extraction, rotary evaporation, column chromatography and the like, and vacuum drying is carried out at 60 ℃ for 12 hours to obtain light yellow powdery solid.
(2) Modification of silica: adding 4g of silicon dioxide into a round-bottom flask, adding 100ml of toluene, ultrasonically dispersing, heating to 110 ℃, adding 0.3g of KH-550, carrying out reflux reaction for 4 hours, centrifugally washing the obtained product, re-dispersing the product in the toluene, adding 0.5g of the product obtained in the step (1), reacting for 20 hours at 40 ℃, centrifugally washing, and vacuum drying for 5 hours at 70 ℃.
(3) Preparation of silica dispersion: and (3) taking 0.15g of the modified silicon dioxide powder obtained in the step (2), adding 20ml of deionized water, homogenizing for 3min, and then carrying out ultrasonic dispersion for 5 min.
(4) And (3) treating the fabric: preparing 20ml of PDDA aqueous solution with the concentration of 3mg/ml, soaking the fabric in the solution for 2min, taking out and drying at 60 ℃; soaking the dried fabric in the suspension obtained in the step (3) at 40 ℃ for 3min, taking out and drying at 60 ℃; this was repeated 4 times.
(5) And (3) soaking the fabric obtained in the step (4) in PM-3705 emulsion with the mass fraction of 3% for 3min, taking out, drying at 60 ℃, and baking at 130 ℃ for 3min to obtain the fabric.
Example 3
(1) Synthesizing uvioresistant small molecules: dissolving 4.28g of 2, 4-dihydroxy benzophenone in 30ml of acetone, pouring the acetone into a three-neck flask, sequentially adding 9.26g of epoxy chloropropane and 20ml of NaOH aqueous solution with the concentration of 0.25g/ml, heating to 85 ℃, carrying out reflux reaction for 4 hours, carrying out separation and purification steps such as extraction, rotary evaporation, column chromatography and the like on the obtained product, and carrying out vacuum drying for 12 hours at 60 ℃ to obtain a light yellow powdery solid.
(2) Modification of silica: adding 4g of silicon dioxide into a round-bottom flask, adding 100ml of cyclohexane, performing ultrasonic dispersion, heating to 115 ℃, adding 0.4g of KH-550, performing reflux reaction for 3 hours, centrifugally washing the obtained product, re-dispersing the product in toluene, adding 0.5g of the product obtained in the step (1), reacting for 24 hours at 45 ℃, centrifugally washing, and performing vacuum drying for 5 hours at 70 ℃.
(3) Preparation of silica dispersion: and (3) taking 0.1g of the modified silicon dioxide powder obtained in the step (2), adding 20ml of deionized water, homogenizing for 5min, and then carrying out ultrasonic dispersion for 5 min.
(4) And (3) treating the fabric: preparing 20ml of PDDA aqueous solution with the concentration of 5mg/ml, soaking the fabric in the solution for 1min, taking out and drying at the temperature of 80 ℃; soaking the dried fabric in the suspension obtained in the step (3) at 40 ℃ for 5min, taking out and drying at 80 ℃; the cycle is 6 times.
(5) And (3) soaking the fabric obtained in the step (4) in amino modified polysiloxane with the mass fraction of 3% for 1min, taking ethyl acetate and ethanol as a cosolvent (the volume ratio of ethyl acetate to ethanol is 2:1), drying at 80 ℃ after taking out, and baking at 130 ℃ for 5min to obtain the fabric.
TABLE 1 static contact and roll angles of the fabrics
Note: the control was an untreated swatch.
TABLE 2 UV resistance of the fabrics
Note: the control was an untreated swatch.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (9)
1. A preparation method of a super-hydrophobic ultraviolet-resistant fabric is characterized by comprising the following steps:
(1) synthesis of the uvioresistant compound: adding 2, 4-dihydroxy benzophenone, epoxy chloropropane and a solvent into a reactor, dropwise adding a catalyst under the condition of stirring, heating to 80-90 ℃, reacting for 2-6 h, and separating and purifying a product to obtain 1, 2-epoxypropyl ether aromatic ketone;
(2) amino-modified silica: adding silicon dioxide, a solvent and an aminosilane coupling agent into a reactor, heating to 100-120 ℃, reacting for 4-8 hours, and centrifugally washing the product for multiple times to obtain amino modified silicon dioxide;
(3) grafting of silica with 1, 2-epoxypropyl ether aryl ketone: dispersing the amino modified silicon dioxide obtained in the step (2) in a solvent, pouring the solvent into a three-necked bottle, uniformly stirring, adding the 1, 2-epoxypropyl ether aromatic ketone obtained in the step (1), reacting at 35-50 ℃ for 12-24 h, centrifuging for many times, washing, and drying to obtain silicon dioxide grafted with anti-ultraviolet micromolecules;
(4) preparation of silica dispersion: adding the silicon dioxide obtained in the step (3) into deionized water, and homogenizing and carrying out ultrasonic treatment to obtain a light yellow dispersion liquid with the mass percentage concentration of 0.5-2%;
(5) and (3) treating the fabric: preparing a cationic polyelectrolyte solution with the mass concentration of 0.3-0.7%, uniformly stirring, soaking the fabric in the solution at the soaking temperature of 30-50 ℃ for 1-5 min, taking out, and drying at the temperature of not higher than 80 ℃; soaking the dried fabric in the dispersion liquid obtained in the step (4) at the soaking temperature of 30-50 ℃ for 3-7 min, taking out, and drying at the temperature of not higher than 80 ℃; repeating the above steps for 2-6 times;
(6) and (3) dipping the fabric obtained in the step (5) in the fluorine-free water repellent agent emulsion or solution for 1-10 min, taking out, drying at 60-85 ℃, and baking at 125-135 ℃ for 3-8 min to obtain the super-hydrophobic ultraviolet-resistant fabric.
2. The method for preparing the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein the solvent in the step (1) is acetone; the catalyst is sodium hydroxide or potassium hydroxide.
3. The preparation method of the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (2), the silicon dioxide is silicon dioxide with a particle size of 10-100 nm; the solvent is toluene, cyclohexane or chloroform; the aminosilane coupling agent is one of gamma-aminopropyltriethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane and g-aminopropyltrimethoxysilane, and the dosage of the added aminosilane coupling agent is 5-10% of the mass of silicon dioxide.
4. The method for preparing the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (3), the amount of the 1, 2-epoxypropyl ether aromatic ketone added is 5-13% of the mass of the silicon dioxide.
5. The method for preparing the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (4), the homogenization is performed by a homogenizer for 3-5 min at a rotation speed of 5000-12000 r/min.
6. The method for preparing the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (5), the cationic polyelectrolyte is one of polydimethyldiallylammonium chloride, polyvinylamine and polyethyleneimine.
7. The method for preparing the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (6), the fluorine-free water repellent agent emulsion or solution is one of emulsions or solutions of polycarbodiimide, fluorine-free long-chain siloxane, amino modified polysiloxane, hydroxyl terminated polysiloxane and polydimethylsiloxane.
8. The method for preparing the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (6), the solvent in the fluorine-free water repellent agent solution is one or more of ethanol, ethyl acetate and cyclohexane.
9. The preparation method of the superhydrophobic ultraviolet-resistant fabric according to claim 1, wherein in the step (6), the mass fraction of the fluorine-free water repellent agent in the fluorine-free water repellent agent emulsion or solution is 3% -8%.
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| CN111421920B (en) * | 2019-04-30 | 2021-08-27 | 浙江东进新材料有限公司 | Waterproof and light-shielding composite fabric |
| CN111172747A (en) * | 2019-12-30 | 2020-05-19 | 比音勒芬服饰股份有限公司 | Anti-ultraviolet fabric and preparation method and application thereof |
| CN111576036B (en) * | 2020-05-20 | 2021-01-01 | 浙江海明实业有限公司 | Nano antifouling, antibacterial and breathable environment-friendly fabric and preparation process thereof |
| CN112779780A (en) * | 2021-01-04 | 2021-05-11 | 李学梅 | Manufacturing process of antibacterial non-woven fabric |
| CN114106219B (en) * | 2021-12-09 | 2023-12-26 | 中石化石油工程技术服务有限公司 | Nanocomposite initiator, thickening agent for fracturing fluid and application |
| CN114990885B (en) * | 2022-06-30 | 2023-08-15 | 苏州大学 | Ultraviolet-resistant superhydrophobic fabric and preparation method thereof |
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