CN111021043B - Ultraviolet-cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric and preparation method thereof - Google Patents
Ultraviolet-cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultraviolet-cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric and a preparation method thereof. The preparation method comprises the following steps: synthesizing silicon dioxide particles by ethyl orthosilicate through a sol-gel method, and carrying out surface modification on the silicon dioxide particles by using a silane coupling agent containing sulfydryl to obtain sulfydryl modified silicon dioxide particles; adding the mercapto-modified silicon dioxide particles and the terminal acryloxy polydimethylsiloxane into a solvent, uniformly stirring, and adding a photoinitiator to prepare a uniform solution; and soaking the fabric in the prepared mixed solution by adopting a dip coating method, taking out the fabric, and irradiating by using ultraviolet light to enable mercapto groups attached to modified silica particles on the fabric and C ═ C double bonds on the terminal acryloxy polydimethylsiloxane to generate mercapto-alkene click reaction. The time required by curing the fabric after soaking is only 1-3 minutes, the static contact angle of water drops on the surface of the prepared fabric is more than 150 degrees, and meanwhile, the fabric has good heat resistance and chemical resistance.
Description
Technical Field
The invention relates to a super-hydrophobic material, in particular to an ultraviolet-cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric and a preparation method thereof.
Background
Researchers have inspired researchers to prepare various super-hydrophobic surfaces by observing animals and plants (such as lotus leaves, rose petals, the legs of water striders and the wings of butterflies) which have hydrophobic phenomena in nature and combining different materials and purposes. A superhydrophobic surface refers to a surface where the contact angle (WAC) of a water droplet is greater than 150 ° and the rolling angle (WSA) is less than 10 °. The unique wettability makes the nano-porous silicon dioxide have wide application prospects in the fields of self-cleaning, corrosion prevention, ice coating prevention, oil-water separation, microfluid and the like.
The preparation routes of the super-hydrophobic surface are mainly two: firstly, constructing a micro-nano rough structure on the surface of a low surface energy material, and secondly, modifying a low surface energy substance on the surface of the rough material. For example, Wu et al use ethyl orthosilicate (TEO) hydrolytic condensation to hydrolyze iron oxide nanoparticles (Fe) by chemical vapor deposition3O4NPs) adhered tightly to the sponge, and then the sponge was soaked in a solution of fluoropolymer to obtain a magnetic superhydrophobic sponge. The contact angle of the sponge reaches 157 degrees, andcan separate oil-water mixture under magnetic drive (Wu L, Li L, Li B, et al. magnetic, durable, and super-hydrophilic polyurethane @ Fe3O4@ SiO2@ fluoropolymer spheres for selective oil adsorption and oil/water separation [ J].ACS Applied Materials&Interfaces,2015,7(8): 4936-. Pan et al grown copper stearate (CuSA) in situ on the surface of the fabric2) And then soaking the fabric into Polydimethylsiloxane (PDMS) solution, and thermally curing the fabric for 3 hours at 80 ℃ under the action of a crosslinking agent Sylgard 184 to obtain the super-hydrophobic fabric. The fabric can still keep the contact angle above 150 degrees after 24h of ultraviolet irradiation, 10 times of mechanical abrasion or 12h of ultrasonic treatment, and shows excellent durability (paper G, Xiao X, Ye Z. fabric of stable hydrophilic coating on fabric with mechanical durability, UV resistance and high-water separation efficiency [ J].Surface and Coatings Technology,2019,360:318-328.)。
However, in the preparation of these superhydrophobic materials, two types of low surface energy materials are generally selected: first, a fluorine-containing compound. However, these substances are difficult to degrade, harmful to human body and environment and expensive; second, an organosilicon compound. However, most of these materials require several hours of heat treatment at high temperature to fully cure them. Therefore, it is important to develop a silicone superhydrophobic material which can be cured rapidly during the preparation process and has excellent performance.
Disclosure of Invention
Aiming at the problems that (1) fluorine-containing substances are selected in the existing preparation process of the super-hydrophobic material, so that the method is not economical and environment-friendly; (2) the problems of the prior art such as high curing temperature and time consumption of organic silicon and the like are solved, and the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric which can be rapidly cured in the preparation process and has excellent performance and the preparation method thereof are provided. The time required by curing the fabric after soaking is only 1-3min, the static contact angle of a water drop on the surface of the prepared fabric is more than 150 degrees, and meanwhile, the fabric has good heat resistance and chemical resistance.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric comprises the following steps:
(1) adding 12-24 parts of ammonia water into 100-200 parts of absolute ethyl alcohol according to volume fraction, uniformly mixing, adding 10-20 parts of ethyl orthosilicate, fully stirring at room temperature, centrifuging, washing and drying to obtain silicon dioxide particles;
dispersing 2-5 parts of silicon dioxide particles in 60-100 parts of toluene by mass, adding 1-2.5 parts of silane coupling agent containing sulfhydryl, fully stirring, heating to 110-120 ℃, reacting for 20-24h, centrifuging, washing and drying to obtain sulfhydryl modified silicon dioxide particles;
(2) according to volume fraction, slowly adding 4 parts of tetrahydrofuran solution of terminal amino polydimethylsiloxane into 1 part of tetrahydrofuran solution of isocyanate in a nitrogen atmosphere, uniformly stirring at room temperature, slowly adding 2.5 parts of tetrahydrofuran solution of hydroxyethyl acrylate, continuously stirring at room temperature, washing the precipitate, and drying to obtain terminal acryloxy polydimethylsiloxane;
(3) dispersing the sulfydryl modified silicon dioxide particles and the terminal acryloxy polydimethylsiloxane in tetrahydrofuran, uniformly stirring, adding a photoinitiator, and continuously stirring to form a uniform mixed solution; soaking the fabric in the mixed solution by adopting a dip coating method, taking out the fabric, and irradiating by ultraviolet light to enable the sulfydryl of the modified silicon dioxide particles attached to the fabric and C ═ C double bonds on the terminal acryloxy polydimethylsiloxane to generate sulfydryl-alkene click reaction so as to prepare the ultraviolet light cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric.
The reaction of the ultraviolet light curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric in the preparation method is as follows:
to further achieve the object of the present invention, preferably, the mercapto group-containing silane coupling agent in step (1) is any one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldiethoxysilane.
Preferably, the centrifugation in the step (1) is performed at the rotation speed of 8000-10000r/min for 10-20min, and the washing is performed 3-5 times by using ethanol; the drying is carried out in an oven at 60-80 ℃ for 12-24 h.
Preferably, the molecular weight of the amino-terminated polydimethylsiloxane in the step (2) is 3000-5000 g/mol.
Preferably, the concentrations of the amino-terminated polydimethylsiloxane, the isocyanate and the hydroxymethyl methacrylate in the tetrahydrofuran in the step (2) are respectively 0.1mol/L, 0.8mol/L and 0.32 mol/L; the time for stirring uniformly at room temperature is 3-6 h; the thorough washing is washing with deionized water.
Preferably, the drying in step (2) is drying in a vacuum oven at 40-50 ℃ for 18-24 h.
Preferably, in the step (3), the fabric is any one of polyester, cotton, acrylic and polyurethane; the photoinitiator is any one or a mixture of two of 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone (369) and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone (907).
Preferably, in the step (3), the mass ratio of the mercapto-modified silica particles to the acryloxy-terminated polydimethylsiloxane is 0.2 to 0.5: 1, the mass concentration of the end acryloxy dimethyl siloxane in the mixed solution is 5-8 wt%, and the dosage of the photoinitiator is 1-3 wt% of the dosage of the end acryloxy dimethyl siloxane.
Preferably, the fabric in the step (3) is soaked in the mixed solution for 2-10min, and the radiation intensity of the ultraviolet light is 50-100mW/cm2The irradiation distance of the ultraviolet lamp is 5-15cm, and the irradiation time under the ultraviolet lamp is 60-180 s.
An ultraviolet light cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric is prepared by the preparation method; the static contact angle of water drops of the prepared ultraviolet curing organosilicon/silicon dioxide hybrid super-hydrophobic fabric reaches 150-155 degrees, and the super-hydrophobic property is still maintained after the fabric is treated at different temperatures and soaked in different solvents.
Compared with the prior art, the invention has the following advantages:
(1) the super-hydrophobic fabric is prepared by a dip coating-ultraviolet curing method, and has the advantages of simple and convenient method, mild conditions, environmental protection, economy and the like.
(2) The method comprises the steps of constructing sufficient roughness on the surface of a fabric by utilizing mercapto-modified silicon dioxide particles, irradiating for 1-3min by ultraviolet light, and enabling mercapto and C ═ C double bonds on the terminal acryloxy polydimethylsiloxane to generate mercapto-alkene click reaction to form a chemical cross-linking structure, so that the fabric still keeps super-hydrophobic property after being treated at different temperatures and soaked in various solvents.
(3) The time required by the fabric for curing after soaking is only 1-3 minutes, because the mercapto-alkene click reaction is a free radical polymerization reaction initiated by light, the used photoinitiator can quickly jump from a ground state to an excited singlet state after absorbing light energy and jump from the ground state to an excited triplet state through intersystem crossing; after the excited singlet or triplet state undergoes unimolecular or bimolecular chemistry, active radicals are generated which are capable of initiating the polymerization of the monomer. Thus, the photo-initiated polymerization is faster and more efficient than the conventional thermal initiated polymerization.
(4) The static contact angle of water drops on the surface of the fabric prepared by the method is more than 150 degrees, and meanwhile, the fabric has good heat resistance and chemical resistance; the mercapto-modified silica particles used in the present invention provide a coarse structure while the acryloxy-terminated polydimethylsiloxane provides a low surface energy. And the sulfydryl of the modified silicon dioxide particles and the C ═ C double bond on the terminal acryloxy polydimethylsiloxane have sulfydryl-alkene click reaction to form a chemical crosslinking structure.
Drawings
Fig. 1 is a scanning electron micrograph of the uv-curable silicone/silica hybrid superhydrophobic fabric prepared in example 1 (image magnification is 3000 times, and the inset in the lower left is a water drop static contact angle photograph).
Fig. 2 is an ir spectrum of the dip coated fabric of example 1 before and after uv curing.
Detailed Description
The present invention will be further described with reference to the following examples for better understanding of the present invention, but the embodiments of the present invention are not limited thereto.
The static contact angle of the water drop of the super-hydrophobic organic silicon/silicon dioxide hybrid fabric is tested by adopting a DSA100 contact angle tester of Germany KRUSS company, and 5 points of each sample are taken to calculate the average value.
Example 1
Adding 24mL of ammonia water into 200mL of absolute ethanol at room temperature, uniformly mixing, slowly adding 20mL of tetraethoxysilane, fully stirring for 12h at room temperature, centrifuging the obtained milky white suspension for 15min at 8000r/min, washing for 3 times by using ethanol, and drying for 12h at 60 ℃ to obtain the silicon dioxide particles. Then, 5g of silica particles were dispersed in 100g of toluene, 2.5g of 3-mercaptopropylmethyldiethoxysilane was added thereto, the mixture was sufficiently stirred, heated to 110 ℃ and reacted for 24 hours, the resulting mixture was centrifuged at 8000r/min for 15 minutes, washed with ethanol 3 times, and dried at 60 ℃ for 12 hours, to obtain mercapto group-modified silica particles.
Under nitrogen atmosphere, 16mL of tetrahydrofuran solution (0.1mol/L) of amino-terminated polydimethylsiloxane (molecular weight 3000g/mol, Shanghai Michelle chemical technology Co., Ltd.) was slowly added to 4mL of tetrahydrofuran solution (0.8mol/L) of isocyanate, and after stirring at room temperature for 3 hours, 10mL of tetrahydrofuran solution (0.32mol/L) of hydroxyethyl acrylate was slowly added, and after stirring at room temperature for 12 hours, the precipitate was sufficiently washed with deionized water, and vacuum-dried at 40 ℃ for 24 hours to obtain acryloxy-terminated polydimethylsiloxane.
At room temperature, mercapto group-modified silica particles and terminal acryloxy polydimethylsiloxane in a mass ratio of 0.2 were dispersed in 20g of tetrahydrofuran (the mass concentration of the terminal acryloxy polydimethylsiloxane in the mixed solution was 8 wt%) and uniformly stirred, and then 16mg of a photoinitiator, 2-hydroxy-2-methyl-1-phenyl-1-propanone (1173), stirring continuously to form a homogeneous solution; finally, soaking the cotton fabric in the prepared mixed solution for 2min by adopting a dip coating method, taking out the cotton fabric, and irradiating the cotton fabric for 60s (100 mW/cm) by using ultraviolet light25cm) to finally obtain the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric.
Fig. 1 is a scanning electron micrograph of the uv-cured silicone/silica hybrid superhydrophobic fabric of this example magnified 3000 times, wherein the inset in the lower left is a photograph of the static contact angle of a water droplet. As can be seen from FIG. 1, a large number of micro-nano rough structures with the structure of mercapto-modified silica particles are formed on the surface of the fabric, and a cross-linking layer of terminated acryloxy polydimethylsiloxane is attached to the surfaces of the rough structures. The super-hydrophobic organic silicon/silicon dioxide hybrid fabric has a static contact angle of water drops of 155 degrees and super-hydrophobic performance.
Fig. 2 is an infrared contrast spectrum of the fabric obtained before and after the fabric is subjected to dip coating treatment and is irradiated under ultraviolet light in the embodiment. As can be seen from FIG. 2, the dip-coated fabric was 3365cm before and after UV irradiation-1And 1560cm-1The absorption peaks of expansion and bending vibration of imino (-NH-) are respectively shown; at 2966cm-1And 2906cm-1Respectively generate methyl (-CH)3) And methylene (-CH)2-) absorption peak of the stretching vibration; at 1735cm-1The stretching vibration absorption peak of C ═ O in the ester group (-COO-); and at 1090cm-1The stretching vibration absorption peak of Si-O-Si appears. This demonstrates that the thiol-modified silica particles and the acryloxy-terminated polydimethylsiloxane successfully attached to the fabric after dip coating. In particular, 1645cm-1Although the stretching vibration peak of C ═ O in the carbamido group (-NH-CO-NH-) covers the weak vibration absorption peak of C ═ C double bond in the terminal acryloyloxy group, the peak is obviously weakened after illumination. This fully indicates that, after being irradiated by ultraviolet light, the mercapto group on the modified silica particle and the C ═ C double bond on the terminal acryloxy polydimethylsiloxane successfully undergo a mercapto-ene click reaction, thereby forming a chemical crosslinking layer with strong adhesion on the surface of the fabric.
In order to evaluate the stability of the super-hydrophobic fabric in different environments, the fabric is placed in an oven at 170 ℃ for high-temperature treatment for 6 hours; soaking the raw materials in 50mL beakers filled with 30mL of n-hexane and toluene for 96h respectively; soaking the raw materials in 50mL beakers containing 30mL of hydrochloric acid solution (pH is 1) and 1mol/mL of sodium chloride solution for 24 hours respectively; the fabric was soaked in a 50mL beaker containing 30mL of a sodium hydroxide solution (pH 12) for 12 hours and sealed with tinfoil, and the soaked fabric was washed with ethanol and dried in an oven at 60 ℃ for 1 hour, and the contact angles thereof were measured, respectively. Table 1 shows the contact angles of the uv-cured silicone/silica hybrid superhydrophobic fabrics of this example after being treated under different conditions, washed and dried. As can be seen from table 1, the ultraviolet-cured silicone/silica hybrid superhydrophobic fabric prepared in this example has little change in water contact angle after being treated under different test conditions, which indicates that it has good heat resistance and chemical resistance.
Example 2
Adding 24mL of ammonia water into 150mL of absolute ethanol at room temperature, uniformly mixing, slowly adding 15mL of ethyl orthosilicate, fully stirring for 18h at room temperature, centrifuging the obtained milky white suspension at 9000r/min for 10min, washing with ethanol for 3 times, and drying at 70 ℃ for 20h to obtain the silicon dioxide particles. Then, 4g of silica particles were dispersed in 80g of toluene, 2.5g of 3-mercaptopropylmethyldiethoxysilane was added thereto, the mixture was sufficiently stirred, heated to 110 ℃ and reacted for 24 hours, and the resulting mixture was similarly centrifuged at 9000r/min for 10 minutes, washed with ethanol 3 times, and dried at 70 ℃ for 18 hours, to obtain mercapto group-modified silica particles.
Under nitrogen atmosphere, 16mL of tetrahydrofuran solution (0.1mol/L) of amino-terminated polydimethylsiloxane (molecular weight is 3000g/mol) is slowly added into 4mL of tetrahydrofuran solution (0.8mol/L) of isocyanate, after stirring for 3h at room temperature, 10mL of tetrahydrofuran solution (0.32mol/L) of hydroxyethyl acrylate is slowly added, after stirring for 6h at room temperature, the precipitate is fully washed by deionized water, and after drying at 40 ℃ for 1824 h in vacuum, the acryloxy-terminated polydimethylsiloxane is obtained.
Mercapto group-modified silica particles at a mass ratio of 0.3 at room temperatureDispersing the seed and the terminal acryloyloxy polydimethylsiloxane into 20g of tetrahydrofuran (the mass concentration of the terminal acryloyloxy polydimethylsiloxane in the mixed solution is 5wt percent), uniformly stirring, adding 15mg of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), and continuously stirring to form a uniform solution; finally, soaking the cotton fabric in the prepared mixed solution by adopting a dip coating method for 8min, taking out the cotton fabric, and irradiating the cotton fabric for 100s (80 mW/cm) by using ultraviolet light210cm) to finally obtain the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric.
The scanning electron microscope image of the ultraviolet-cured organosilicon/silica hybrid superhydrophobic fabric prepared in the embodiment and the infrared contrast spectrogram of the fabric before and after ultraviolet curing after dip coating are basically the same as those in fig. 1 and fig. 2, which shows that the prepared fabric has superhydrophobic performance, and mercapto groups on modified silica particles and C ═ C double bonds on end acryloxy polydimethylsiloxane successfully generate mercapto-alkene click reaction, so that a chemical crosslinking layer with strong adhesive force is formed on the surface of the fabric.
In order to evaluate the stability of the super-hydrophobic fabric in different environments, the fabric is placed in an oven at 170 ℃ for high-temperature treatment for 6 hours; soaking the raw materials in 50mL beakers filled with 30mL of n-hexane and toluene for 96h respectively; soaking the raw materials in 50mL beakers containing 30mL of hydrochloric acid solution (pH is 1) and 1mol/mL of sodium chloride solution for 24 hours respectively; the fabric was soaked in a 50mL beaker containing 30mL of a sodium hydroxide solution (pH 12) for 12 hours and sealed with tinfoil, and the soaked fabric was washed with ethanol and dried in an oven at 60 ℃ for 1 hour, and the contact angles thereof were measured, respectively. Table 1 shows the contact angles of the uv-cured silicone/silica hybrid superhydrophobic fabrics of this example after being treated under different conditions, washed and dried. As can be seen from table 1, the ultraviolet-cured silicone/silica hybrid superhydrophobic fabric prepared in this example has little change in water contact angle after being treated under different test conditions, which indicates that it has good heat resistance and chemical resistance.
Example 3
Adding 12mL of ammonia water into 100mL of absolute ethyl alcohol at room temperature, uniformly mixing, slowly adding 15mL of ethyl orthosilicate, fully stirring for 20h at room temperature, centrifuging the obtained milky white suspension for 20min at 8000r/min, washing for 4 times by using ethanol, and drying for 18h at 70 ℃ to obtain the silicon dioxide particles. Then, 3g of silica particles were dispersed in 50g of toluene, 1.5g of 3-mercaptopropyltriethoxysilane was added thereto, the mixture was sufficiently stirred, heated to 120 ℃ and reacted for 24 hours, and the resulting mixture was centrifuged at 9000r/min for 10 minutes, washed 5 times with ethanol, and dried at 75 ℃ for 20 hours to obtain mercapto group-modified silica particles.
Under nitrogen atmosphere, 16mL of tetrahydrofuran solution (0.1mol/L) of amino-terminated polydimethylsiloxane (molecular weight 5000g/mol) is slowly added into 4mL of tetrahydrofuran solution (0.8mol/L) of isocyanate, after stirring for 3h at room temperature, 10mL of tetrahydrofuran solution (0.32mol/L) of hydroxyethyl acrylate is slowly added, after stirring for 10h at room temperature, the precipitate is fully washed by deionized water, and vacuum drying is carried out at 45 ℃ for 24h, so as to obtain the terminal acryloxy polydimethylsiloxane.
At room temperature, dispersing mercapto-modified silicon dioxide particles and terminal acryloxy polydimethylsiloxane in a mass ratio of 0.4 in 20g of tetrahydrofuran (the mass concentration of the terminal acryloxy polydimethylsiloxane in the mixed solution is 7 wt%) and uniformly stirring, then adding 28mg of photoinitiator 1-hydroxycyclohexyl phenyl ketone (184), and continuously stirring to form a uniform solution; finally, soaking the cotton fabric in the prepared mixed solution by adopting a dip coating method for 4min, taking out the cotton fabric, and irradiating the cotton fabric for 60s (90 mW/cm) by using ultraviolet light210cm) to finally obtain the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric.
The scanning electron microscope image of the ultraviolet-cured organosilicon/silica hybrid superhydrophobic fabric prepared in the embodiment and the infrared contrast spectrogram of the fabric before and after ultraviolet curing after dip coating are basically the same as those in fig. 1 and fig. 2, which shows that the prepared fabric has superhydrophobic performance, and mercapto groups on modified silica particles and C ═ C double bonds on end acryloxy polydimethylsiloxane successfully generate mercapto-alkene click reaction, so that a chemical crosslinking layer with strong adhesive force is formed on the surface of the fabric.
In order to evaluate the stability of the super-hydrophobic fabric in different environments, the fabric is placed in an oven at 170 ℃ for high-temperature treatment for 6 hours; soaking the raw materials in 50mL beakers filled with 30mL of n-hexane and toluene for 96h respectively; soaking the raw materials in 50mL beakers containing 30mL of hydrochloric acid solution (pH is 1) and 1mol/mL of sodium chloride solution for 24 hours respectively; the fabric was soaked in a 50mL beaker containing 30mL of a sodium hydroxide solution (pH 12) for 12 hours and sealed with tinfoil, and the soaked fabric was washed with ethanol and dried in an oven at 60 ℃ for 1 hour, and the contact angles thereof were measured, respectively. Table 1 shows the contact angles of the uv-cured silicone/silica hybrid superhydrophobic fabrics of this example after being treated under different conditions, washed and dried. As can be seen from table 1, the ultraviolet-cured silicone/silica hybrid superhydrophobic fabric prepared in this example has little change in water contact angle after being treated under different test conditions, which indicates that it has good heat resistance and chemical resistance.
Example 4
Adding 15mL of ammonia water into 200mL of absolute ethyl alcohol at room temperature, uniformly mixing, slowly adding 10mL of ethyl orthosilicate, fully stirring for 24h at room temperature, centrifuging the obtained milky white suspension for 10min at 10000r/min, washing for 3 times by using ethanol, and drying for 24h at 80 ℃ to obtain the silicon dioxide particles. Then, 2g of silica particles were dispersed in 60g of toluene, 1g of 3-mercaptopropyltrimethoxysilane was added thereto, the mixture was sufficiently stirred, heated to 120 ℃ and reacted for 20 hours, and the resulting mixture was centrifuged at 8000r/min for 20 minutes, washed with ethanol 4 times, and dried at 80 ℃ for 24 hours, to obtain mercapto group-modified silica particles.
Under nitrogen atmosphere, 16mL of tetrahydrofuran solution (0.1mol/L) of amino-terminated polydimethylsiloxane (molecular weight 4000g/mol) is slowly added into 4mL of tetrahydrofuran solution (0.8mol/L) of isocyanate, after stirring for 3h at room temperature, 10mL of tetrahydrofuran solution (0.32mol/L) of hydroxyethyl acrylate is slowly added, after stirring for 12h at room temperature, the precipitate is fully washed with deionized water, and after vacuum drying for 20h at 5040 ℃, the acryloxy-terminated polydimethylsiloxane is obtained.
Mercapto group-modified silica particles and acryloxy-terminated polydimethylsiloxane at a mass ratio of 0.45 were dispersed in 20g of tetrahydro at room temperatureUniformly stirring furan (the mass concentration of the terminal acryloyloxy polydimethylsiloxane accounts for 6 wt% of the mixed solution), adding 36mg of photoinitiator 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone (907), and continuously stirring to form a uniform solution; finally, the cotton fabric is soaked in the prepared mixed solution for 10min by adopting a dip coating method, and is taken out and irradiated by ultraviolet light for 180s (50 mW/cm)25cm) to finally obtain the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric.
The scanning electron microscope image of the ultraviolet-cured organosilicon/silica hybrid superhydrophobic fabric prepared in the embodiment and the infrared contrast spectrogram of the fabric before and after ultraviolet curing after dip coating are basically the same as those in fig. 1 and fig. 2, which shows that the prepared fabric has superhydrophobic performance, and mercapto groups on modified silica particles and C ═ C double bonds on end acryloxy polydimethylsiloxane successfully generate mercapto-alkene click reaction, so that a chemical crosslinking layer with strong adhesive force is formed on the surface of the fabric.
In order to evaluate the stability of the super-hydrophobic fabric in different environments, the fabric is placed in an oven at 170 ℃ for high-temperature treatment for 6 hours; soaking the raw materials in 50mL beakers filled with 30mL of n-hexane and toluene for 96h respectively; soaking the raw materials in 50mL beakers containing 30mL of hydrochloric acid solution (pH is 1) and 1mol/mL of sodium chloride solution for 24 hours respectively; the fabric was soaked in a 50mL beaker containing 30mL of a sodium hydroxide solution (pH 12) for 12 hours and sealed with tinfoil, and the soaked fabric was washed with ethanol and dried in an oven at 60 ℃ for 1 hour, and the contact angles thereof were measured, respectively. Table 1 shows the contact angles of the uv-cured silicone/silica hybrid superhydrophobic fabrics of this example after being treated under different conditions, washed and dried. As can be seen from table 1, the ultraviolet-cured silicone/silica hybrid superhydrophobic fabric prepared in this example has little change in water contact angle after being treated under different test conditions, which indicates that it has good heat resistance and chemical resistance.
Table 1 shows water contact angles of the uv-cured silicone/silica hybrid superhydrophobic fabrics of the examples of the invention under different treatment conditions.
TABLE 1
With reference to fig. 1, fig. 2 and table 1, the water contact angles of the uv-cured silicone/silica hybrid superhydrophobic fabrics prepared in the embodiments of the present invention are all greater than 150 °, which is mainly attributed to the micro-nano rough structure of the surface structure of the mercapto-modified silica particles and the hydrophobicity of the siloxane segment in the terminal acryloxy polydimethylsiloxane; the good heat resistance and chemical resistance of the ultraviolet light cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric are mainly due to the fact that sulfydryl on modified silicon dioxide particles and C ═ C double bonds on the terminal acryloxy polydimethylsiloxane are subjected to sulfydryl-alkene click reaction, and therefore a chemical crosslinking layer with strong adhesive force is formed on the surface of the fabric.
The embodiments of the present invention are not limited to the embodiments described above, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (10)
1. The preparation method of the ultraviolet curing organic silicon/silicon dioxide hybrid super-hydrophobic fabric is characterized by comprising the following steps of:
(1) adding 12-24 parts of ammonia water into 100-200 parts of absolute ethyl alcohol according to volume fraction, uniformly mixing, adding 10-20 parts of ethyl orthosilicate, fully stirring at room temperature, centrifuging, washing and drying to obtain silicon dioxide particles;
dispersing 2-5 parts of silicon dioxide particles in 60-100 parts of toluene by mass, adding 1-2.5 parts of silane coupling agent containing sulfhydryl, fully stirring, heating to 110-120 ℃, reacting for 20-24h, centrifuging, washing and drying to obtain sulfhydryl modified silicon dioxide particles;
(2) according to volume fraction, slowly adding 4 parts of tetrahydrofuran solution of terminal amino polydimethylsiloxane into 1 part of tetrahydrofuran solution of isocyanate in a nitrogen atmosphere, uniformly stirring at room temperature, slowly adding 2.5 parts of tetrahydrofuran solution of hydroxyethyl acrylate, continuously stirring at room temperature, washing the precipitate, and drying to obtain terminal acryloxy polydimethylsiloxane;
(3) dispersing the sulfydryl modified silicon dioxide particles and the terminal acryloxy polydimethylsiloxane in tetrahydrofuran, uniformly stirring, adding a photoinitiator, and continuously stirring to form a uniform mixed solution; soaking the fabric in the mixed solution by adopting a dip-coating method, taking out the fabric, and irradiating the fabric by ultraviolet light to enable the sulfydryl of the modified silicon dioxide particles attached to the fabric and C ═ C double bonds on the terminal acryloxy polydimethylsiloxane to generate sulfydryl-alkene click reaction so as to prepare the ultraviolet light cured organic silicon/silicon dioxide hybrid super-hydrophobic fabric; the radiation intensity of the ultraviolet light is 50-100mW/cm2The irradiation distance of the ultraviolet lamp is 5-15cm, and the irradiation time under the ultraviolet lamp is 60-180 s.
2. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: the mercapto-containing silane coupling agent in the step (1) is any one of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane and 3-mercaptopropylmethyldiethoxysilane.
3. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: the centrifugation in the step (1) is carried out for 10-20min at the rotating speed of 8000-10000r/min, and the washing is carried out for 3-5 times by using ethanol; the drying is carried out in an oven at 60-80 ℃ for 12-24 h.
4. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: the molecular weight of the amino-terminated polydimethylsiloxane in the step (2) is 3000-5000 g/mol.
5. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: in the step (2), the concentrations of the amino-terminated polydimethylsiloxane, the isocyanate and the hydroxyethyl acrylate in tetrahydrofuran are respectively 0.1mol/L, 0.8mol/L and 0.32 mol/L; the time for stirring uniformly at room temperature is 3-6 h; the washing of the washed precipitate is with deionized water.
6. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: in the step (2), the drying is carried out for 18-24h in a vacuum oven at 40-50 ℃.
7. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: in the step (3), the fabric is any one of polyester, cotton, acrylic fiber and polyurethane; the photoinitiator is any one or a mixture of two of 1-hydroxycyclohexyl phenyl ketone (184), 2-hydroxy-2-methyl-1-phenyl-1-acetone (1173), 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butanone (369) and 2-methyl-1- (4-methylthiophenyl) -2-morpholine-1-acetone (907).
8. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: in the step (3), the mass ratio of the mercapto-modified silica particles to the terminal acryloxy polydimethylsiloxane is 0.2-0.5: 1, the mass concentration of the end acryloxy dimethyl siloxane in the mixed solution is 5-8 wt%, and the dosage of the photoinitiator is 1-3 wt% of the dosage of the end acryloxy dimethyl siloxane.
9. The preparation method of the ultraviolet curing organosilicon/silicon dioxide hybrid superhydrophobic fabric according to claim 1, characterized in that: and (4) soaking the fabric in the mixed solution in the step (3) for 2-10 min.
10. An ultraviolet-cured organosilicon/silica hybrid superhydrophobic fabric, characterized by being prepared by the preparation method of any one of claims 1-9; the static contact angle of water drops of the prepared ultraviolet curing organosilicon/silicon dioxide hybrid super-hydrophobic fabric reaches 150-155 degrees, and the super-hydrophobic property is still maintained after the fabric is treated at different temperatures and soaked in different solvents.
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