CN112080938B - Fluorine-free durable super-hydrophobic cotton cloth and preparation method and application thereof - Google Patents

Fluorine-free durable super-hydrophobic cotton cloth and preparation method and application thereof Download PDF

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CN112080938B
CN112080938B CN202010932929.3A CN202010932929A CN112080938B CN 112080938 B CN112080938 B CN 112080938B CN 202010932929 A CN202010932929 A CN 202010932929A CN 112080938 B CN112080938 B CN 112080938B
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cotton cloth
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CN112080938A (en
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贺小华
马君君
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East China Normal University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/001—Treatment with visible light, infrared or ultraviolet, X-rays
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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
    • D06M11/77—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
    • 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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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D06M13/5135—Unsaturated compounds containing silicon atoms
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    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/01—Stain or soil resistance
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    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Abstract

The invention discloses a fluorine-free durable super-hydrophobic cotton cloth and a preparation method and application thereof, and belongs to the field of super-hydrophobic materials. The method comprises the steps of carrying out hydrolysis reaction on 3-methacryloxypropyltrimethoxysilane and silicon dioxide to obtain modified silicon dioxide; secondly, modifying cotton cloth fibers by using 3-mercaptopropyltriethoxysilane to functionalize the sulfydryl on the surfaces of the fibers; and finally, under the action of a photoinitiator and the illumination of a mercury lamp, carrying out a mercapto-alkene click chemical reaction on the thiolated cotton cloth, methacryloxy polydimethylsiloxane and modified silicon dioxide to prepare the super-hydrophobic cotton cloth. The super-hydrophobic cotton cloth prepared by the method has the functions of self-cleaning and oil-water separation. The invention has the advantages of cheap and easily obtained raw materials and environmental protection, and the prepared material has stable hydrophobicity and good wear resistance. Meanwhile, the preparation method is simple, the preparation conditions are mild, the large-scale production is facilitated, and the method has great industrial application potential.

Description

Fluorine-free durable super-hydrophobic cotton cloth and preparation method and application thereof
Technical Field
The invention belongs to the field of super-hydrophobic materials, and particularly relates to fluorine-free durable super-hydrophobic cotton cloth and a preparation method and application thereof.
Background
The fabric with the super-hydrophobic function has great application value in the aspects of self-cleaning and oil-water separation. The construction of the super-hydrophobic material is started mainly from two aspects, on one hand, elements with low surface energy are introduced to reduce the surface energy of the material, and on the other hand, a micro-nano structure is constructed to increase the surface roughness. However, current superhydrophobic fabrics also have a number of limitations. Firstly, a great amount of super-hydrophobic materials utilize fluorine-containing compounds to modify the materials, and the fluorine-containing compounds are expensive and are not environment-friendly. Secondly, the mechanical properties of superhydrophobic fabrics are not strong and risk losing their hydrophobicity after abrasion. Finally, some of the reported construction methods of the superhydrophobic fabric are complicated in process or harsh in production conditions, for example, the superhydrophobic fabric is manufactured by electrostatic spinning, and the electrostatic spinning process is difficult to realize industrialization.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of fluorine-free durable super-hydrophobic cotton cloth, and the super-hydrophobic cotton cloth with self-cleaning and oil-water separation functions is prepared by the method. The method has the advantages of cheap and easily-obtained raw materials and environmental friendliness, and the prepared material has stable hydrophobicity and good wear resistance. Meanwhile, the preparation method is simple, the preparation conditions are mild, the large-scale production is facilitated, and the method has great industrial application potential.
The preparation method of the fluorine-free durable super-hydrophobic cotton cloth provided by the invention comprises the following steps: firstly, carrying out hydrolysis reaction on 3-methacryloxypropyltrimethoxysilane (KH-570) and silicon dioxide to obtain modified silicon dioxide; secondly, 3-mercaptopropyltriethoxysilane (KH-580) is used for modifying cotton cloth fibers, so that the surface sulfydryl of the fibers is functionalized; and finally, under the action of a photoinitiator and the illumination of a mercury lamp, carrying out a mercapto-alkene click chemical reaction on methacryloxy polydimethylsiloxane, modified silicon dioxide and the sulfhydrylated cotton cloth.
The method comprises the following steps:
(1) preparation of modified silica (denoted KH-570@ SiO)2)
In a solvent containing ammonia water, silica and 3-methacryloxypropyltrimethoxysilane (KH-570) are subjected to hydrolysis reaction at a certain temperature, so that the surface of the silica has carbon-carbon double bonds, and a reaction solution containing modified silica is obtained.
And centrifuging the reaction solution by using an ethanol-containing aqueous solution, repeating the centrifugation for 2-4 times, and drying at a certain temperature to obtain the white solid modified silicon dioxide.
(2) Pretreatment of cotton cloth
In a first solvent containing acetic acid, cotton cloth with a large number of hydroxyl groups on the surface is subjected to hydrolysis reaction with KH-580 at a certain temperature, so that the surface of the cotton cloth has sulfydryl. And taking out the cotton cloth, washing with a second solvent and drying.
(3) Fluorine-free durable super-hydrophobic cotton cloth prepared by sulfydryl-alkene click chemistry method
KH-570@ SiO prepared in the step (1)2Dissolving in a solvent, adding methacryloxy polydimethylsiloxane and a photoinitiator, carrying out ultrasonic treatment on the solution, soaking the cotton cloth pretreated in the step (2) in the solution after ultrasonic treatment, taking out the cotton cloth, and illuminating the cotton cloth under a mercury lamp to obtain the fluorine-free durable super-hydrophobic cotton cloth.
The reaction mechanism of the present invention is shown by the following formula (I): the nanosilica was modified with 3-methacryloxypropyltrimethoxysilane (KH-570) as shown in Step 1. The raw cotton was subjected to a sulfhydrylation treatment with 3-mercaptopropyltriethoxysilane (KH-580) as shown in Step 2. As shown in Step3, sulfhydrylated cotton cloth, methacryloxy Polydimethylsiloxane (PDMS) and modified silica (KH-570@ SiO) are subjected to the action of ultraviolet light and a photoinitiator by using the principle of sulfhydryl-alkene click chemistry2) And carrying out thiol-ene click chemical reaction to prepare the super-hydrophobic cotton cloth. The modified silicon dioxide containing carbon-carbon double bonds and the methacryloxy polydimethylsiloxane are grafted on the cotton cloth, so that the hydrophobic component is introduced to the surface of the cotton cloth.
Figure BDA0002670895210000021
In step (1) of the present invention, the solvent is one or more selected from tetrahydrofuran, ethyl acetate, ethanol, n-propanol, isopropanol, 1, 4-butanediol, etc.; preferably, it is ethanol.
In the step (1), the particle size of the silicon dioxide is 20nm-100 nm; preferably, 20nm, 40nm, 80nm, 100nm, etc.; further preferably 20 nm.
In the step (1), the ammonia water is used in an amount of 40-60 parts; preferably 50 parts.
In the step (1), the mass ratio of the silicon dioxide, the solvent, the ammonia water and the 3-methacryloxypropyltrimethoxysilane is (0.5-2): (100-200): (40-60): (0.5 to 3); preferably, 1: 150: 50: 1.5.
in the step (1), the temperature of the hydrolysis reaction is 25-40 ℃; preferably, it is 40 ℃.
In the step (1), the hydrolysis reaction time is 12-24 h; preferably 24 h.
In the step (1), the rotating speed of the centrifugation is 5000-7000 r/min; preferably, it is 6000 r/min.
In the step (1), the centrifugation time is 5-10 min; preferably, it is 5 min.
In the step (1), the mass fraction of ethanol in the ethanol-containing aqueous solution is 50-75%; preferably, it is 75%.
In the step (1), the washing times are 2-4 times; preferably 3 times.
In the step (1), the drying temperature is 40-70 ℃; preferably, it is 40 ℃.
In the step (1), the drying time is 12-24 h; preferably 24 h.
In one embodiment, performing step (1) comprises: ultrasonically dispersing 0.5-2 parts of silicon dioxide in 100-200 parts of solvent, adding 40-60 parts of ammonia water, adding 0.5-3 parts of 3-methacryloxypropyltrimethoxysilane, and stirring at 25-40 ℃ for 12-24 hours. And after the solution is cooled, centrifuging, and washing with an ethanol aqueous solution with the mass fraction of 50-75%. Repeating for 2-4 times, and drying at 40-70 ℃ to obtain white solid modified silicon dioxide. Wherein, the ratio of silicon dioxide: solvent: ammonia water: the mass ratio of the 3-methacryloxypropyltrimethoxysilane to the 3-methacryloxypropyltrimethoxysilane is (0.5-2): (100-200): (40-60): (0.5 to 3).
In step (2) of the present invention, the first solvent is one or more selected from tetrahydrofuran, ethyl acetate, ethanol, n-propanol, isopropanol, 1, 4-butanediol, etc.; preferably, it is ethanol.
In the step (2), the amount of the first solvent is 20-40 parts; preferably 40 parts.
In the step (2), the amount of acetic acid is 5-10 parts; preferably 10 parts.
In the step (2), the using amount of the KH-580 is 2-5 parts; preferably, it is 3 parts.
In the step (2) of the invention, the cotton cloth is AATCC standard white cotton cloth. The "AATCC standard white cotton cloth" refers to american association of dyers and chemists (american association of dyers and chemists and colors) standard white cotton cloth, which is abbreviated as AATCC standard white cotton cloth.
In step (2) of the present invention, the second solvent is one or more selected from tetrahydrofuran, ethyl acetate, ethanol, n-propanol, isopropanol, 1, 4-butanediol, etc.; preferably, it is ethanol.
In the step (2), the temperature of the hydrolysis reaction is 40-70 ℃; preferably, it is 40 ℃.
In the step (2), the hydrolysis reaction time is 2-4 h; preferably, it is 2 h.
In the step (2), the drying temperature is 70-120 ℃; preferably 70 deg.c.
In the step (2), the drying time is 2-4 h; preferably, it is 3 h.
In one embodiment, the performing step (2) comprises: adding 5-10 parts of acetic acid into a mixed solution of 2-5 parts of KH-580 and 20-40 parts of a solvent, soaking cotton cloth in the solution, heating to react at 40-70 ℃ for 2-4 h, taking out the cotton cloth, washing off excessive KH-580 with the solvent, and drying at 70-120 ℃ for 2-4 h. Wherein the mass ratio of the solvent to the acetic acid to the KH-580 is 20-40: 5-10: 2 to 5.
In step (3) of the present invention, the solvent is one or more selected from tetrahydrofuran, acetone, dichloromethane, N-dimethylformamide, ethyl acetate, etc.; preferably, acetone.
In the step (3), the photoinitiator is selected from one or more of benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, benzoin dimethyl ether and the like; preferably benzoin dimethyl ether.
In the step (3), the solvent is KH-570@ SiO2The mass ratio of methacryloxy polydimethylsiloxane to photoinitiation is 1-5: 0.1-0.5: 0.05-0.5: 0.0025 to 0.005; preferably, 3: 0.1: 0.05: 0.0025.
in the step (3), the illumination time is 1-2 h; preferably for 2 hours.
In one embodiment, the performing step (3) comprises: 0.1 to 0.5 portion of KH-570@ SiO2Dissolved inAdding 0.05-0.5 part of methacryloxy dimethyl siloxane and 0.0025-0.005 part of photoinitiator into 1-5 parts of solvent, carrying out ultrasonic treatment on the solution, soaking the pretreated cotton cloth into the solution after ultrasonic treatment, taking out the cotton cloth, and then, illuminating the cotton cloth for 1-2 hours under a mercury lamp. The solvent is KH-570@ SiO2The mass ratio of the methacryloxy polydimethylsiloxane to the photoinitiator is 1-5: 0.1-0.5: 0.05-0.5: 0.0025 to 0.005.
Specifically, the preparation method of the fluorine-free durable super-hydrophobic cotton cloth comprises the following specific steps:
step 1: preparation of modified silica (denoted KH-570@ SiO)2)
Ultrasonically dispersing 0.5-2 parts of silicon dioxide in 100-200 parts of solvent, adding 40-60 parts of ammonia water, adding 0.5-3 parts of 3-methacryloxypropyltrimethoxysilane, and stirring at 25-40 ℃ for 12-24 hours. And finally, cooling the solution, centrifuging, and washing with an ethanol aqueous solution with the mass fraction of 50-75%. Repeating for 2-3 times, and drying at 50-70 ℃ for 12-24 h to obtain the white solid modified silicon dioxide.
Step 2: pretreatment of cotton cloth
Adding 5-10 parts of acetic acid into a mixed solution of 2-5 parts of KH-580 and 20-40 parts of a solvent, soaking cotton cloth in the solution, heating at 40-70 ℃ for reaction for 2-4 h, taking out the cotton cloth, washing off excessive KH-580 with the solvent, and drying at 70-120 ℃ for 2-4 h.
And step 3: preparation of super-hydrophobic cotton cloth
0.1 to 0.5 portion of KH-570@ SiO2Dissolving in 1-5 parts of solvent, adding 0.05-0.5 part of methacryloxy dimethyl silicone polymer and 0.0025-0.005 part of photoinitiator, carrying out ultrasonic treatment on the solution, soaking the pretreated cotton cloth in the solution after ultrasonic treatment, taking out the cotton cloth, and then, illuminating the cotton cloth under a mercury lamp for 1-2 hours to obtain the fluorine-free durable superhydrophobic cotton cloth.
The invention also provides the fluorine-free durable super-hydrophobic cotton cloth prepared by the method. The fluorine-free durable super-hydrophobic cotton cloth has self-cleaning performance and an oil-water separation function.
The invention also provides application of the fluorine-free durable super-hydrophobic cotton cloth in self-cleaning and oil-water separation.
Compared with the prior art, the invention has the following remarkable beneficial effects:
(1) the cotton cloth is modified by 3-mercaptopropyltriethoxysilane, and reactive group sulfydryl is added on the surface of the cotton cloth; the silica is modified by 3-methacryloxypropyltrimethoxysilane, and double bonds are added on the surface of the silica. And click chemistry is utilized to bond the cotton cloth with the modified silicon dioxide and the methacryloxy polydimethylsiloxane by chemical bonds, so that the super-hydrophobicity of the cotton cloth is more stable. The mercapto-alkene click chemistry reaction conditions are mild, the reaction rate is high, the time consumption is short, and no by-product is generated.
(2) The preparation method is simple and feasible, has cheap and easily obtained raw materials, is environment-friendly, has mild preparation conditions, is convenient for large-scale production, has practical value and has huge industrial application potential. The prepared super-hydrophobic cotton cloth is stable in hydrophobicity and good in abrasion resistance, and can be used as an oil-water separation material. The super-hydrophobic cotton cloth has double functions of oil absorption and water resistance, can be used as an absorbent of oily substances (such as petroleum ether), can also be used for separating a mixture of water and oil (such as carbon tetrachloride), and has potential application value in solving the problem of marine petroleum pollution.
(3) The prepared super-hydrophobic cotton cloth has good self-cleaning capability, can resist liquid stains such as milk, cola, tea and other daily beverages, and can also clean solid dirt (such as sand) on the surface. Meanwhile, even if the super-hydrophobic cotton cloth is subjected to physical damage such as knife scraping, abrasive paper friction and the like, the cotton cloth still can keep good hydrophobic capacity.
(4) Compared with the fluorine-containing super-hydrophobic material with high price, the raw material prepared from the super-hydrophobic cotton cloth is mainly a silicon-containing compound, has wider sources, and is cheap and easy to obtain. Meanwhile, the silicon-containing material is relatively more environment-friendly and does not bring threat to the environment and organisms like a fluorine-containing material.
Drawings
FIG. 1 shows the contact angle of 5uL of water dropped on the superhydrophobic cotton cloth prepared by examples 1-4 of the present invention.
FIG. 2 is a pattern of "ECNU" formed by 10uL of water dropped onto various locations on a superhydrophobic cotton cloth made using examples 1-4 of the present invention.
FIG. 3 shows 10uL of tea, cola, milk, water dripping onto super-hydrophobic cotton cloth made according to examples 1-4 of the present invention.
FIG. 4 shows the floating behavior in water of the original cotton (lower layer) and the superhydrophobic cotton made using examples 1-4 of the present invention.
FIG. 5 shows the oil absorption process of the superhydrophobic cotton cloth prepared by examples 1-4 of the present invention.
FIG. 6 is a partial enlarged view of an oil-water separation process and an oil-water separation apparatus of the superhydrophobic cotton cloth manufactured in examples 1-4 of the present invention.
FIG. 7 shows the self-cleaning process of the super-hydrophobic cotton cloth made according to examples 1-4 of the present invention.
FIG. 8 shows the hydrophobicity of the super-hydrophobic cotton cloth prepared by examples 1-4 of the present invention after knife grinding.
FIG. 9 shows the hydrophobicity of the superhydrophobic cotton cloth prepared by examples 1-4 of the present invention after being abraded by sandpaper.
FIG. 10 is an SEM photograph of superhydrophobic cotton cloth and virgin cotton cloth made using examples 1-4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following specific examples and the accompanying drawings. The procedures, conditions, experimental methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited.
The present invention will be described in further detail by way of examples.
Example 1
1 part of silicon dioxide with the particle size of 20nm is ultrasonically dispersed in 150 parts of solvent, 50 parts of ammonia water is added, 1.5 parts of 3-methacryloxypropyltrimethoxysilane is added, and the mixture is stirred for 24 hours at the temperature of 40 ℃. To be dissolvedCooling, centrifuging at 6000r/min for 5min, and washing with 75% ethanol water solution. This was repeated 3 times, and dried at 40 ℃ for 24 hours to obtain a modified silica as a white solid. Adding 10 parts of acetic acid into a mixed solution of 3 parts of KH-580 and 40 parts of ethanol, soaking cotton cloth in the solution, heating at 40 deg.C for 2h, taking out the cotton cloth, washing off excessive KH-580 with ethyl acetate, and oven drying at 70 deg.C for 3 h. Mixing 0.1 part of KH-570@ SiO2Dissolving in 3 parts of acetone, adding 0.05 part of methacryloxypolydimethylsiloxane and 0.0025 part of benzoin dimethyl ether, carrying out ultrasonic treatment on the solution, soaking the pretreated cotton cloth in the ultrasonic-treated solution, taking out the cotton cloth, and then irradiating the cotton cloth for 2 hours under a mercury lamp.
Example 2
0.5 part of silica with the particle size of 40nm is ultrasonically dispersed in 100 parts of ethyl acetate, 40 parts of ammonia water is added, 0.5 part of 3-methacryloxypropyltrimethoxysilane is added, and the mixture is stirred for 12 hours at the temperature of 25 ℃. And after the solution is cooled, centrifuging at the rotating speed of 7000r/min for 10min, and washing by using an aqueous solution of 50% ethanol in mass fraction. This was repeated 2 times and dried at 40 ℃ for 22 hours to obtain a modified silica as a white solid. Adding 5 parts of acetic acid into a mixed solution of 2 parts of KH-580 and 20 parts of ethyl acetate, soaking cotton cloth in the solution, heating at 40 deg.C for 2h, taking out the cotton cloth, washing off excessive KH-580 with ethanol, and oven drying at 40 deg.C for 4 h. Mixing 0.1 part of KH-570@ SiO2Dissolving in 1 part of tetrahydrofuran, adding 0.05 part of methacryloxypolydimethylsiloxane and 0.0025 part of benzoin butyl ether, carrying out ultrasonic treatment on the solution, soaking the pretreated cotton cloth in the ultrasonic-treated solution, taking out the cotton cloth, and then irradiating the cotton cloth for 1 hour under a mercury lamp.
Example 3
2 parts of silicon dioxide with the particle size of 100nm are dispersed in 200 parts of tetrahydrofuran by ultrasonic, 60 parts of ammonia water is added, 3 parts of 3-methacryloxypropyltrimethoxysilane is added, and the mixture is stirred for 24 hours at 40 ℃. And after the solution is cooled, centrifuging for 8min at the rotating speed of 5000r/min, and washing by using an ethanol aqueous solution with the mass fraction of 75%. Repeating the above steps for 4 times, and drying at 70 deg.C for 12 hr to obtain white solidAnd (3) silicon dioxide. Adding 10 parts of acetic acid into a mixed solution of 5 parts of KH-580 and 40 parts of tetrahydrofuran, soaking cotton cloth in the solution, heating at 70 deg.C for 4h, taking out the cotton cloth, washing off excessive KH-580 with isopropanol, and oven drying at 120 deg.C for 2 h. Mixing 0.5 part of KH-570@ SiO2Dissolving in 5 parts of dichloromethane, adding 0.5 part of methacryloxypolydimethylsiloxane and 0.005 part of benzoin isopropyl ether, ultrasonically treating the solution, soaking the pretreated cotton cloth in the ultrasonically treated solution, taking out the cotton cloth, and irradiating the cotton cloth for 2 hours under a mercury lamp.
Example 4
1.5 parts of silica with a particle size of 80nm are ultrasonically dispersed in 180 parts of ethanol, 55 parts of ammonia water are added, 2 parts of 3-methacryloxypropyltrimethoxysilane are added, and the mixture is stirred at 30 ℃ for 18 hours. And after the solution is cooled, centrifuging at the rotating speed of 5500r/min for 6min, and washing by using an ethanol aqueous solution with the mass fraction of 60%. Drying at 60 deg.C for 18h was repeated 3 times to obtain modified silica as a white solid. Adding 8 parts of acetic acid into a mixed solution of 4 parts of KH-580 and 30 parts of ethanol, soaking cotton cloth in the solution, heating at 60 ℃ for reaction for 1.5h, taking out the cotton cloth, washing off excessive KH-580 with ethanol, and drying at 100 ℃ for 2.5 h. Mixing 0.3 part of KH-570@ SiO2Dissolving in 3 parts of acetone, adding 0.25 part of methacryloxypolydimethylsiloxane and 0.003 part of benzoin dimethyl ether, carrying out ultrasonic treatment on the solution, soaking the pretreated cotton cloth in the ultrasonic-treated solution, taking out the cotton cloth, and then irradiating the cotton cloth for 1.5 hours under a mercury lamp.
FIG. 1 shows the contact angle of 5uL of water dropped on the superhydrophobic cotton cloth prepared by examples 1-4 of the present invention. The prepared super-hydrophobic cotton cloth has hydrophobic angles (namely, contacts, abbreviated as 'CA' in the figure) of 153 DEG, 155 DEG, 152 DEG and 151 DEG respectively, and has a good hydrophobic function.
FIG. 2 is a pattern of "ECNU" formed by 10uL of water dropped onto various locations on a superhydrophobic cotton cloth made using examples 1-4 of the present invention. As can be seen from the figure, all the positions of the cotton cloth have good hydrophobic capacity, so that water is similar to 'ball shape' on the surface of the cotton cloth.
FIG. 3 shows 10uL of tea, cola, milk, water dripping onto super-hydrophobic cotton cloth made according to examples 1-4 of the present invention. As can be seen from the figure, the cotton cloth has certain anti-fouling capacity on tea, cola, milk and water, so that the liquid of the tea, the cola, the milk and the water is not impregnated on the cotton cloth, and the cleanness of the surface of the cotton cloth is ensured.
FIG. 4 shows the floating behavior in water of the original cotton (lower layer) and the superhydrophobic cotton made using examples 1-4 of the present invention. It can be seen from the figure that the original cotton cloth directly sinks in water due to its hydrophilicity, while the cotton cloth prepared in the example of the present invention does not directly sink in water but floats on the water surface due to its hydrophobicity, which indicates that the superhydrophobic cotton cloth prepared in the example of the present invention has good hydrophobic ability.
FIG. 5 shows the oil absorption process of the superhydrophobic cotton cloth prepared by examples 1-4 of the present invention. The lower colorless transparent liquid is water, and the upper dark liquid is petroleum ether (dyed by oil red O). The super-hydrophobic cotton cloth is oleophilic and hydrophobic, so the cotton cloth can absorb petroleum ether from an oil-water mixture.
FIG. 6 is a partial enlarged view of an oil-water separation process and an oil-water separation apparatus of the superhydrophobic cotton cloth manufactured in examples 1-4 of the present invention. The lower colorless transparent liquid is carbon tetrachloride and the upper dark liquid is water (dyed by methylene blue). Because the super-hydrophobic cotton cloth is oleophylic and hydrophobic, the cotton cloth can block water on the cotton cloth, and absorb carbon tetrachloride to enable the carbon tetrachloride to smoothly leak downwards, thereby realizing the function of oil-water separation.
FIG. 7 shows the self-cleaning process of the super-hydrophobic cotton cloth made according to examples 1-4 of the present invention. The solid pollutants are simulated by sand, water drops are dripped on the surface of the super-hydrophobic cotton cloth containing the sand, and the sand can be taken away by rolling water drops, so that the super-hydrophobic surface is kept clean.
FIG. 8 shows the hydrophobicity of the super-hydrophobic cotton cloth prepared by examples 1-4 of the present invention after knife grinding. After knife grinding, the cotton cloth surface was damaged. However, even after the cotton cloth is damaged, water drops can not be soaked on the cotton cloth after dropping, and the hydrophobic performance of the cotton cloth is still maintained, which shows that the hydrophobic performance has certain stability.
FIG. 9 shows the hydrophobicity of the superhydrophobic cotton cloth prepared by examples 1-4 of the present invention after being abraded by sandpaper. The cotton was moved fifteen centimeters with horizontal force, and the cycle was recorded twice back and forth. After the friction cycle is carried out for 100 times, even if the surface of the cotton cloth is damaged, the cotton cloth still has good hydrophobicity.
FIG. 10 is an SEM photograph of superhydrophobic cotton cloth and virgin cotton cloth made using examples 1-4 of the present invention. In FIG. 10, a1And a2SEM pictures of different scales of the super-hydrophobic cotton cloth, b1And b2SEM images of different dimensions of the original cotton cloth. From the SEM image with the scale of 200um, it can be seen that the original cotton cloth surface is smooth, while the super-hydrophobic cotton cloth surface has coarse particulate matter, which is caused by grafting PDMS and modified silica on the cotton cloth surface. As can be seen from the SEM image with the size of 1um, compared with the original cotton cloth, the nano-scale bulges are uniformly dispersed on the surface of the super-hydrophobic cotton cloth. Therefore, the roughness of the surface of the superhydrophobic cotton cloth is greatly increased, which is advantageous for enhancing the hydrophobic property of the cotton cloth.
The protection of the invention is not limited to the above embodiments. Variations and advantages that may occur to those skilled in the art may be incorporated into the invention without departing from the spirit and scope of the inventive concept, and the scope of the appended claims is intended to be protected.

Claims (11)

1. A preparation method of fluorine-free durable super-hydrophobic cotton cloth is characterized by comprising the following steps:
(1) modified silicon dioxide KH-570@ SiO2Preparation of
In a solvent containing ammonia water, carrying out hydrolysis reaction on silicon dioxide and 3-methacryloxypropyltrimethoxysilane at a certain temperature; then centrifuging the mixture by using an ethanol water solution, and drying the mixture to obtain modified silicon dioxide KH-570@ SiO2；
(2) Pretreatment of cotton cloth
In a first solvent containing acetic acid, cotton cloth with a large number of hydroxyl groups on the surface and 3-mercaptopropyltriethoxysilane are subjected to hydrolysis reaction at a certain temperature; then taking out the cotton cloth, washing with a second solvent and drying;
(3) preparation of super-hydrophobic cotton cloth
KH-570@ SiO prepared in the step (1)2Dissolving in a solvent, adding methacryloxy polydimethylsiloxane and a photoinitiator, carrying out ultrasonic treatment on the solution, soaking the cotton cloth pretreated in the step (2) in the solution after ultrasonic treatment, taking out the cotton cloth, and illuminating the cotton cloth under a mercury lamp to obtain the fluorine-free durable super-hydrophobic cotton cloth.
2. The preparation method according to claim 1, wherein in the step (1), the solvent is one or more selected from tetrahydrofuran, ethyl acetate, ethanol, n-propanol, isopropanol, and 1, 4-butanediol; and/or the particle size of the silicon dioxide is 20nm-100 nm; and/or the using amount of the ammonia water is 40-60 parts.
3. The production method according to claim 1, wherein in step (1), the silica: solvent: ammonia water: the mass ratio of the 3-methacryloxypropyltrimethoxysilane to the 3-methacryloxypropyltrimethoxysilane is (0.5-2): (100-200): (40-60): (0.5 to 3).
4. The method according to claim 1, wherein in the step (1), the temperature of the hydrolysis reaction is 25 to 40 ℃; and/or the time of the hydrolysis reaction is 12-24 hours; and/or the drying temperature is 40-70 ℃; and/or the drying time is 12-24 h; and/or the rotating speed of the centrifugation is 5000-7000 r/min; and/or the centrifugation time is 5-10 min.
5. The preparation method according to claim 1, wherein in the step (2), the first solvent is one or more selected from tetrahydrofuran, ethyl acetate, ethanol, n-propanol, isopropanol, and 1, 4-butanediol; and/or the second solvent is selected from one or more of tetrahydrofuran, ethyl acetate, ethanol, n-propanol, isopropanol and 1, 4-butanediol; and/or the temperature of the hydrolysis reaction is 40-70 ℃; and/or the hydrolysis reaction time is 2-4 h; and/or the drying temperature is 70-120 ℃; and/or the drying time is 2-4 h.
6. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the first solvent to the acetic acid to the KH-580 is 20-40: 5-10: 2 to 5.
7. The preparation method according to claim 1, wherein in the step (3), the solvent is one or more selected from tetrahydrofuran, acetone, dichloromethane, N-dimethylformamide and ethyl acetate; and/or the photoinitiator is selected from one or more of benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether and benzoin dimethyl ether.
8. The preparation method according to claim 1, wherein in the step (3), the illumination time is 1 to 2 hours.
9. The process according to claim 1, wherein in the step (3), the solvent is KH-570@ SiO2The mass ratio of the methacryloxy polydimethylsiloxane to the photoinitiator is 1-5: 0.1-0.5: 0.05-0.5: 0.0025 to 0.005.
10. A fluorine-free durable superhydrophobic cotton cloth prepared according to the method of any one of claims 1-9.
11. The use of the fluorine-free durable superhydrophobic cotton cloth of claim 10 in self-cleaning and oil-water separation.
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