CN108373609B - Coating for preparing transparent super-hydrophobic coating and preparation and use methods thereof - Google Patents
Coating for preparing transparent super-hydrophobic coating and preparation and use methods thereof Download PDFInfo
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Abstract
The invention discloses a coating for preparing a transparent super-hydrophobic coating and preparation and application methods thereof, belonging to the technical field of super-hydrophobic coatings. The coating consists of a component A and a component B, wherein: the component A comprises the following components in percentage by mass: 0.5-5% of hydrophobic modified nano particles, 0.1-5% of active auxiliary agent and 90-99.4% of organic solvent A. The component B comprises the following components in percentage by mass: 0.1-5% of ammonia modified nano particles and 99.9% of organic solvent B95%. The auxiliary agent in the component A can react with the groups on the surfaces of the nanoparticles in the component B, namely, the amino groups and the epoxy groups form stable chemical bonds, so that certain crosslinking is formed between the nanoparticles and the base material, and the overall adhesive force of the coating is improved. Meanwhile, the addition amount is small, the crosslinking degree is low, a film with a certain thickness cannot be formed, and the integral light transmission cannot be influenced.
Description
Technical Field
The invention relates to the technical field of super-hydrophobic coatings, in particular to a coating for preparing a transparent super-hydrophobic coating and a preparation method and a use method thereof.
Background
The superhydrophobic surface originates from the "lotus effect" in nature. The surface micro-nano structure and the lower surface energy are the key points for obtaining the super-hydrophobic surface. At present, the most common technical means is to form a surface micro-nano structure by self-accumulation of nano particles on the surface. Whereas low surface energy characteristics are generally obtained by methods using modified nanoparticles or secondary deposition. For example, patent application CN104449357A utilizes fumed silica nanoparticles to deposit on the surface to form a micro-nano structure, and then utilizes chemical vapor deposition to deposit a hydrophobic agent on the surface, thereby obtaining a transparent superhydrophobic surface; in patent application CN104261695A, zinc oxide sol is accumulated on the surface to form a micro-nano structure, and then the micro-nano structure is soaked in an ethanol solution containing a hydrophobic modifier, taken out and dried to obtain a transparent super-hydrophobic coating. Both methods are to obtain low surface energy characteristics by a secondary deposition method. For another example, patent application CN105086537A directly uses a hydrophobic modifier to modify silica nanoparticles, and utilizes self-accumulation of the modified nanoparticles on the surface to form a transparent super-hydrophobic coating with low surface energy characteristics. The method is to obtain low surface energy characteristic by modifying the nano particles.
Regardless of the technical route adopted, the adhesion and transparency of the superhydrophobic coating are critical in determining the application performance thereof. For example, chinese patent CN103060773A has developed a number of technical routes for improving the adhesion of coatings by chemical vapor deposition polymerization, in which an initiator is added to a suspension of silica, and monomer vapor is polymerized onto the surface by chemical vapor deposition to coat the polymer. Chinese patent CN103436138A enhances the adhesion of the coating by hybridizing epoxy resin with nanoparticles, and then drying the coating at a certain temperature. However, these methods generally have complicated processes, poor practicability, and it is difficult to achieve both of the desired transmittance and adhesion.
Disclosure of Invention
The invention aims to provide a coating for preparing a transparent super-hydrophobic coating, which has a simple and mild preparation process and can effectively enhance the adhesive force and light transmittance of the super-hydrophobic coating, and a preparation method and a use method thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
in one aspect, a coating for preparing a transparent superhydrophobic coating is provided, which is composed of a component a and a component B, wherein:
the component A comprises the following components in percentage by mass:
0.5 to 5 percent of hydrophobic modified nano particles
0.1 to 5 percent of active auxiliary agent
Organic solvent A90-99.4%
The component B comprises the following components in percentage by mass:
0.1-5% of ammonia modified nano particles
95 to 99.9 percent of organic solvent B
Wherein the active assistant is (CH) with epoxy functional group2OCH-) or a mixture thereof;
or the component A comprises the following components in percentage by mass:
0.5 to 5 percent of hydrophobic modified nano particles
0.1 to 5 percent of active auxiliary agent
Organic solvent A90-99.4%
The component B comprises the following components in percentage by mass:
0.1 to 5 percent of epoxy modified nano particles
95 to 99.9 percent of organic solvent B
Wherein the active auxiliary agent is a compound with amino functional groups (-NH)2) Or a mixture thereof.
According to the invention, the two components contain nanoparticles with different sizes and different surface modification treatments, the nanoparticles are filled with each other, and the modified nanoparticles in the component B have groups capable of reacting with the active assistant, namely, the reaction of amino and epoxy functional groups, so that a super-hydrophobic coating is formed, and meanwhile, the super-hydrophobic coating has good adhesion to the surface of a base material, so that the coating is not easy to peel off and can keep excellent light transmittance.
Furthermore, the ammonia modified nanoparticles are nanoparticles with amino groups on the surface, and the particle size of the original nanoparticles is 10-1000 nm. The ammonia modified nano particles can be commercialized nano particles with amino groups, and can also be prepared in laboratories.
Preferably, the ammonia-modified nanoparticles are nanoparticles modified with an amino-functional silane coupling agent having both an amino group and a hydrolyzable functional group-SiX3Wherein X is-OCH3，-OCH2CH3Or one or more of-Cl.
The nano particles modified by the silane coupling agent with amino functional groups can be commercialized amino modified nano particles and can also be prepared by the following preparation method: adding 0.1-5 parts by weight of nanoparticles into 95-99 parts by weight of organic solvent B', ultrasonically oscillating for 10-20 min, adding 1-6 parts by weight of silane coupling agent with amino functional groups, continuously stirring, adding 1-3 parts by weight of distilled water or ammonia water, and continuously stirring at constant temperature for 15-25 h to obtain a solution containing ammonia modified nanoparticles. And separating the obtained solution by using a centrifugal machine, and removing the solvent to obtain the ammonia modified nano particles.
Preferably, the amino-functional silane coupling agent includes 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, etc., N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, etc.
Furthermore, the epoxy modified nanoparticles are nanoparticles with epoxy groups on the surface, and the particle size of the original nanoparticles is 10-1000 nm. The epoxy modified nano particles can be commercialized nano particles with epoxy groups, and can also be prepared in laboratories.
Further, the epoxy-modified nanoparticles are nanoparticles modified with an epoxy-functional silane coupling agent having both an epoxy group and a hydrolyzable functional group-SiX3Wherein X is-OCH3，-OCH2CH3Or one or more of-Cl.
The nano particles modified by the silane coupling agent containing the epoxy functional group can be commercial epoxy modified nano particles and can also be prepared by the following preparation method: adding 0.1-5 parts by weight of nanoparticles into 95-99 parts by weight of organic solvent B', ultrasonically vibrating for 10-20 min, adding 1-6 parts by weight of silane coupling agent with epoxy functional groups, continuing stirring, adding 1-3 parts by weight of distilled water or ammonia water, and continuing stirring at constant temperature for 15-25 h to obtain a solution containing epoxy modified nanoparticles. And separating the obtained solution by using a centrifugal machine, and removing the solvent to obtain the epoxy modified nano particles.
Preferably, the silane coupling agent with epoxy functional group includes 3- (2, 3-glycidoxy) propyltrimethoxysilane, 3- (2, 3-glycidoxy) propyltriethoxysilane, 3- [ (2,3) -glycidoxy) ] propylmethyldimethoxysilane, etc.
Furthermore, the hydrophobic modified nanoparticles are nanoparticles with alkane or fluorine-containing alkane on the surface, and the particle size of the original nanoparticles is 5-30 nm. The hydrophobic modified nano particles can be commercialized hydrophobic modified nano particles, and can also be prepared in a laboratory.
When the paint is used for preparing the super-hydrophobic coating, two modified nano particles, namely the hydrophobic modified nano particles and amino modified (or epoxy modified) nano particles are used, and the super-hydrophobic coating with a micro-nano composite structure and high adhesive force is obtained under the mutual filling of the two modified nano particles and the action of a reactive additive. Thus, in terms of the selection of two types of modified nanoparticles, the original nanoparticles selected by the hydrophobic modified nanoparticles have a smaller particle size, while the original nanoparticles selected by the amino-modified (or epoxy-modified) nanoparticles have a larger selection range, and when the amino-modified (or epoxy-modified) nanoparticles having a smaller particle size are selected, the hydrophobic nanoparticles having a particle size close to the original nanoparticles can be selected, which also has a better filling effect and better light transmittance, while the other more preferable situation is: the original nanoparticle size of the hydrophobic nanoparticles is smaller than that of the amino-modified (or epoxy-modified) nanoparticles by at least 5 nm. Two types of nano particles with different sizes are mutually filled and accumulated, and the small nano particles are embedded into gaps among the large nano particles, so that the adhesive force of the coating can be remarkably improved under the condition of ensuring the light transmission while generating enough micro-nano composite structures;
preferably, the hydrophobic modified nanoparticles are nanoparticles modified by using a silane coupling agent or a fluorosilane coupling agent, and the structural general formula of the silane coupling agent or the fluorosilane coupling agent is RSiX3Wherein R is a linear or branched C4-16A hydrocarbon group or a fluorine-containing hydrocarbon group, X is a hydrolyzable group comprising-OCH3，-OCH2CH3Or one or more of-Cl.
The nano particles modified by the silane coupling agent or the fluorosilane coupling agent can be commercial hydrophobic modified nano particles and can also be prepared by the following method: adding 0.5-5 parts by weight of nano particles into 90-99 parts by weight of organic solvent A', carrying out ultrasonic oscillation for 10-20 min, adding 1-6 parts by weight of silane coupling agent or fluorosilane coupling agent, continuing stirring, adding 1-3 parts by weight of distilled water or ammonia water, continuing stirring at constant temperature for 15-25 h, and obtaining the solution containing the hydrophobic modified nano particles. And separating the obtained solution by using a centrifugal machine, and removing the solvent to obtain the hydrophobic modified nano particles.
Preferably, the silane coupling agent or fluorosilane coupling agent includes one or more of octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, tridecafluorooctyltriethoxysilane, perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, etc.
Further, the organic solvent A or the organic solvent B is selected from one or more of acetone, methyl ethyl ketone, butanone, ethyl acetate, n-butyl acetate, methanol, ethanol, butanol, isopropanol, ethylene glycol, toluene and xylene. The organic solvent a may be the same as or different from the organic solvent B. The organic solvent A' may be the same as or different from the organic solvent A; the organic solvent B 'or B' may be the same as or different from the organic solvent B.
Further, the nano particles comprise one or more of nano silicon dioxide, nano aluminum oxide, nano zinc oxide and nano titanium dioxide.
In another aspect, there is provided a method for preparing a coating material for preparing a transparent superhydrophobic coating layer, the method comprising the steps of:
1) preparation of component A: adding the hydrophobic modified nanoparticles into an organic solvent A, carrying out ultrasonic oscillation for 10-30 min, and adding the compound active auxiliary agent containing epoxy functional groups to obtain a component A;
2) preparation of the component B: adding the ammonia modified nanoparticles into an organic solvent B, and performing ultrasonic oscillation for 10-30 min to obtain a component B;
alternatively, the preparation method comprises the following steps:
1) preparation of component A: adding the hydrophobic modified nanoparticles into an organic solvent A, carrying out ultrasonic oscillation for 10-30 min, and adding the compound active auxiliary agent containing amino functional groups to obtain a component A;
2) preparation of the component B: and adding the epoxy modified nanoparticles into the organic solvent B, and performing ultrasonic oscillation for 10-30 min to obtain a component B.
In another aspect, an application method of the paint for preparing the transparent super-hydrophobic coating is provided, wherein A, B components are mixed according to the proportion of (1-10) to (10-1), and the mixture is sprayed on a substrate to obtain the super-hydrophobic coating.
The substrate can be a substrate such as glass, steel and the like, and is particularly suitable for a transparent substrate such as glass.
In conclusion, the beneficial effects of the invention are as follows:
1) the auxiliary agent in the component A can react with the groups on the surfaces of the nanoparticles in the component B, namely, the amino groups and the epoxy groups form stable chemical bonds, so that certain crosslinking is formed between the nanoparticles and the base material, and the overall adhesive force of the coating is improved. Meanwhile, because the addition amount is small and the crosslinking degree is low, a film with a certain thickness cannot be formed, and the integral light transmission cannot be influenced;
2) the nanoparticles in the component B are nanoparticles with larger particles, the particle size of the nanoparticles in the component A is smaller, the two types of nanoparticles can be mutually filled and stacked, the small nanoparticles are embedded into gaps among the large nanoparticles, and the adhesion of the coating is improved while enough micro-nano composite structures are generated;
3) the preparation process of the super-hydrophobic coating is simple, easy to operate, low in operation cost, easy to realize and capable of being widely popularized and used.
Drawings
FIG. 1 shows the appearance of water on the surface of glass after the coating prepared by the present invention is applied on the surface of glass;
FIG. 2 is a side view of the contact angle to water of a coating prepared in accordance with the present invention;
FIG. 3 is a graph showing the transmittance of light before and after a coating is formed on the surface of glass according to the present invention;
fig. 4 is a side view of the contact angle to water of a coating prepared according to the present invention after a shakeout test.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the embodiments of the present invention clearer, the following detailed description will be given with reference to the accompanying drawings and specific embodiments. The invention is in no way limited to these examples. The following description is only a preferred embodiment of the present invention, and is only for the purpose of explaining the present invention, and should not be construed as limiting the scope of the present invention. It should be understood that 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 present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
In order to confirm the transparent hydrophobic effect of the super-hydrophobic coating, the hydrophobicity of water on the surface is represented by using a static contact angle test, and the visible light transmittance is measured by using a transmittance meter. In addition, in order to further confirm that the super-hydrophobic coating disclosed by the invention has excellent adhesion, a glass sheet coated with the coating is subjected to an abrasion resistance test by using a shakeout method experimental device (GBT23988-2009), and specifically, after the shakeout test is performed by using 100mL of standard sand, the contact angle of the impacted part is measured.
Some embodiments of the invention are as follows:
example one
Adding 2g of nano silicon dioxide with the average particle size of about 20nm into 93g of acetone, carrying out ultrasonic oscillation for 15min, adding 4g of n-octyl trimethoxy silane, continuing stirring, slowly adding 2mL of distilled water, and carrying out constant-temperature stirring reaction for 20h to obtain a solution containing the hydrophobic modified nanoparticles. The resulting solution was separated using a centrifuge and after removal of the solvent, approximately 6g of hydrophobically modified nanoparticles were obtained. And (3) completely adding the obtained hydrophobic modified nanoparticles into 200g of ethyl acetate, performing ultrasonic oscillation for 20min, and then adding 6g of glycerol glycidyl ether to obtain the component A.
Adding 2g of silicon dioxide particles with the particle size of 100nm into 93g of ethanol, carrying out ultrasonic oscillation for 15min, adding 4g of gamma-aminopropyltriethoxysilane, slowly adding 2mL of distilled water, and continuously stirring at constant temperature for reaction for 15h to obtain a solution containing ammonia modified nanoparticles. The resulting solution was separated using a centrifuge and after removal of the solvent, approximately 6g of ammonia-modified nanoparticles were obtained. The obtained ammonia modified nano particles are added into 200g of butyl acetate to obtain a component B.
The AB components are mixed according to the mass ratio of 5:1, and the mixture is sprayed on the surface of a common glass slide to obtain a transparent super-hydrophobic effect. As shown in fig. 1, the text below the slide is clearly visible and the surface coating has good light transmission. Meanwhile, the water drops on the glass slide are spherical, which shows that the glass slide has a better super-hydrophobic effect. Fig. 2 shows the contact angle of water at the surface, about 155 deg.. Fig. 3 shows the transmittance curves of the raw glass in the visible light band and the glass coated with the coating, the transmittance of the raw glass in the visible light band of 380nm-800nm is about 89%, and the overall transmittance can be maintained above 80% after the coating is sprayed. Fig. 4 shows the contact angle of a drop of water at the surface of the impact, about 136 °, after a shakeout test. Therefore, the coating has better adhesive force and can resist certain external friction.
Example two
Adding 3g of nano silicon dioxide with the particle size of 7nm into 93g of ethanol, carrying out ultrasonic oscillation for 15min, adding 5g of dodecyl trimethoxy silane, continuing stirring, slowly adding 2mL of ammonia water, and carrying out constant-temperature stirring reaction for 20h to obtain a solution containing the hydrophobic modified nanoparticles. The resulting solution was separated using a centrifuge and after removal of the solvent, approximately 8g of hydrophobically modified nanoparticles were obtained. And (3) completely adding the obtained hydrophobic modified nanoparticles into 191.8g of ethanol, and carrying out ultrasonic oscillation for 20 min. Additional 0.2g C12-C14 alkyl glycidyl ether (trade designation Epodil 748) was added to obtain component A.
Adding 0.1g of silicon dioxide particles with the particle size of about 300nm into 93g of isopropanol, oscillating for 15min by ultrasonic waves, adding 0.1g of 3-aminopropyltriethoxysilane, slowly adding 2mL of ammonia water, and continuously stirring at constant temperature for reaction for 15h to obtain a solution containing ammonia modified nanoparticles. The resulting solution was separated using a centrifuge to obtain about 0.2g of ammonia-modified nanoparticles. And (3) completely adding the obtained ammonia modified nanoparticles into 198.8g of n-butanol, and carrying out ultrasonic oscillation for 20min to obtain a component B.
The AB components are mixed according to the mass ratio of 3:1, and sprayed on the surface of common glass (the original light transmittance is about 89%), so that the transparent super-hydrophobic effect can be obtained, the contact angle of water is about 152%, and the visible light transmittance is about 79%. After the shakeout test, the contact angle of water on the surface was about 130 °.
EXAMPLE III
Adding 0.5g of aluminum oxide with the particle size of 30nm into 93g of ethanol, carrying out ultrasonic oscillation for 15min, adding 0.5g of perfluorodecyl triethoxysilane, continuing stirring, slowly adding 1mL of ammonia water, and carrying out constant-temperature stirring reaction for 20h to obtain a solution containing the hydrophobic modified nanoparticles. The resulting solution was separated using a centrifuge to obtain about 1g of hydrophobically modified nanoparticles. Adding the obtained hydrophobic modified nanoparticles into 198g of acetone, ultrasonically oscillating for 20min, and then adding 1g of ethylene glycol glycidyl ether to obtain a component A.
Adding 1g of aluminum oxide nanoparticles with the particle size of 100nm into 93g of isopropanol, oscillating for 15min by ultrasonic waves, adding 1g of N- (2-aminoethyl) -3-aminopropyltriethoxysilane, slowly adding 2mL of ammonia water, and continuously stirring at constant temperature for reaction for 15h to obtain a solution containing ammonia modified nanoparticles. The resulting solution was separated using a centrifuge to obtain about 2g of ammonia-modified nanoparticles. And adding the obtained hydrophobic modified nanoparticles into 200g of isopropanol, and performing ultrasonic oscillation for 20min to obtain a component B.
The AB components are mixed according to the mass ratio of 10:1, and sprayed on the surface of common glass (the visible light transmittance is about 89%), so that the transparent super-hydrophobic effect can be obtained, the contact angle of water is about 160 degrees, and the visible light transmittance is about 78%. After the shakeout test, the contact angle of water on the surface was about 137 °.
Example four
2g of hydrophobically modified nano-silica (model DNS-2, manufactured by Henan Wang House nanotechnology, Ltd.) having an average particle size of about 15-25nm was added to 93g of xylene, and subjected to ultrasonic oscillation for 15 min. 5g of glycerol glycidyl ether was added to obtain component A.
Adding 1g of silicon dioxide nano particles with the particle size of 600nm into 93g of ethanol, carrying out ultrasonic oscillation for 15min, adding 2g of gamma-aminopropyltriethoxysilane, and continuously stirring at constant temperature for reaction for 15h to obtain a solution containing ammonia modified nano particles. The resulting solution was separated using a centrifuge and after removal of the solvent, approximately 3g of ammonia-modified nanoparticles were obtained. And (3) completely adding the obtained ammonia modified nanoparticles into 97g of isopropanol, and performing ultrasonic oscillation for 20min to obtain a component B.
The AB components are mixed according to the mass ratio of 5:1, and sprayed on the surface of common glass (the visible light transmittance is about 89%), so that the transparent super-hydrophobic effect can be obtained, the contact angle of water is about 150 degrees, and the visible light transmittance is about 78%. After the shakeout test, the contact angle of water on the surface was about 128 °.
EXAMPLE five
Adding 2g of silicon dioxide with the particle size of 15nm into 93g of isopropanol, carrying out ultrasonic oscillation for 15min, adding 4g of perfluorodecyl triethoxysilane, continuing stirring, slowly adding 1mL of distilled water, and carrying out constant-temperature stirring reaction for 20h to obtain a solution containing the hydrophobic modified nanoparticles. The resulting solution was separated using a centrifuge and after removal of the solvent, approximately 6g of hydrophobically modified nanoparticles were obtained. And adding the obtained hydrophobic modified nanoparticles into 200g of ethanol, performing ultrasonic oscillation for 20min, and adding 2g of triethylene tetramine to obtain a component A.
Adding 2g of silicon dioxide nanoparticles with the particle size of 400nm into 93g of ethanol, carrying out ultrasonic oscillation for 15min, adding 3g of 3- (2, 3-epoxypropoxy) propyltriethoxysilane, continuing stirring, slowly adding 1mL of distilled water, continuing stirring at constant temperature for reaction for 15h, and obtaining a solution containing epoxy modified nanoparticles. The resulting solution was separated using a centrifuge to obtain about 5g of epoxy modified nanoparticles. And adding the obtained epoxy modified nanoparticles into 95g of ethanol, and performing ultrasonic oscillation for 20min to obtain a component B.
The AB components are mixed according to the mass ratio of 10:1, and sprayed on the surface of common glass (the visible light transmittance is about 89%), so that the transparent super-hydrophobic effect can be obtained, the contact angle of water is about 155 degrees, and the visible light transmittance is about 80 percent. After the shakeout test, the contact angle of water on the surface was about 135 °.
EXAMPLE six
Adding 4g of nano zinc oxide particles with the particle size of 30nm into 90g of dimethylbenzene, carrying out ultrasonic oscillation for 15min, adding 6g of dodecyl triethoxysilane, continuing stirring, slowly adding 1mL of distilled water, and carrying out constant-temperature stirring reaction for 16h to obtain a solution containing the hydrophobic modified nanoparticles. The resulting solution was separated with a centrifuge and after removal of the solvent, approximately 10g of hydrophobically modified nanoparticles were obtained. Adding the obtained hydrophobic modified nanoparticles into 185g of dimethylbenzene, carrying out ultrasonic oscillation for 20min, and then adding 5g of m-xylylenediamine to obtain a component A.
Adding 2g of nano zinc oxide particles with the particle size of 800nm into 93g of butyl acetate, oscillating for 15min by ultrasonic waves, adding 3g of 3- [ (2,3) -glycidoxy) ] propyl methyldimethoxysilane, continuing stirring, slowly adding 1mL of distilled water, continuing stirring at constant temperature for reacting for 15h, and obtaining a solution containing epoxy modified nano particles. The resulting solution was separated with a centrifuge and after removal of the solvent, approximately 5g of epoxy modified nanoparticles were obtained. And adding the obtained epoxy modified nanoparticles into 200g of ethanol, and performing ultrasonic oscillation for 20min to obtain a component B.
The AB components are mixed according to the mass ratio of 6:1, and sprayed on the surface of common glass (the visible light transmittance is about 89%), so that the transparent super-hydrophobic effect can be obtained, the contact angle of water is about 151 degrees, and the visible light transmittance is about 81%. After the shakeout test, the contact angle of water on the surface was about 131 °.
Comparative example 1
Adding 2g of nano silicon dioxide with the average particle size of about 25nm into 93g of acetone, carrying out ultrasonic oscillation for 15min, adding 4g of n-octyl trimethoxy silane, continuing stirring, slowly adding 2mL of distilled water, and carrying out constant-temperature stirring reaction for 20h to obtain a solution containing the hydrophobic modified nanoparticles. The resulting solution was separated using a centrifuge and after removal of the solvent, approximately 6g of hydrophobically modified nanoparticles were obtained. And adding the obtained hydrophobic modified nanoparticles into 200g of ethyl acetate, performing ultrasonic oscillation for 20min, and adding 6g of glycerol glycidyl ether to obtain the component A.
Adding 2g of silicon dioxide particles with the average particle size of about 15nm into 93g of ethanol, carrying out ultrasonic oscillation for 15min, adding 4g of gamma-aminopropyltriethoxysilane, slowly adding 2mL of distilled water, and continuously stirring at constant temperature for reaction for 15h to obtain a solution containing ammonia modified nanoparticles. The resulting solution was separated using a centrifuge to obtain about 6g of ammonia-modified nanoparticles. The obtained ammonia modified nano particles are added into 200g of butyl acetate to obtain a component B.
The AB components are mixed according to the mass ratio of 5:1, and the mixture is sprayed on the surface of a common glass slide to obtain a transparent super-hydrophobic effect. The contact angle of water is about 155 deg., and the visible light transmittance is about 82%. But after the shakeout test, the contact angle of water on the surface was only 105 °.
Therefore, compared with the super-hydrophobic coating prepared in the first embodiment, the super-hydrophobic coating has the advantages that the particle size is relatively close, and even when the particle size of the ammonia modified nanoparticles in the component B is smaller than that of the hydrophobic modified nanoparticles in the component A, the super-hydrophobic effect and the light transmittance effect are good, but the adhesion of the super-hydrophobic coating is poor.
Comparative example two (same CN103436138B example one)
Blending 30nm of silicon dioxide nanoparticles, bisphenol A type epoxy resin and acetone to obtain an epoxy resin hybrid solution, wherein the mass ratio of the nanoparticles to the epoxy resin to the acetone is 1:0.1: 1; and simultaneously dissolving 1H, 1H-heptadecafluorononanamine and triethylamine in acetone to obtain a fluorine-containing solution, wherein the mass ratio of the 1H, 1H-heptadecafluorononanamine to the triethylamine to the acetone is 1:20: 20. And spraying the epoxy resin hybrid coating on the surface of a substrate, then placing the substrate in an oven, drying for 0.5h at 80 ℃, then spraying the fluorine-containing solution on the surface of the substrate, after the solvent is volatilized, placing the substrate in the oven, and drying for 0.5h at 80 ℃. And finally, washing the surface of the base material by using a solvent to obtain the transparent super-hydrophobic coating. The contact angle of water on the surface is about 155 deg., and the visible light transmittance is about 80%.
Therefore, compared with the example of the invention, the comparative example II needs two times of drying treatment when preparing the super-hydrophobic coating, has a complex preparation process, and cannot be applied in a large area at low cost.
COMPARATIVE EXAMPLE III (same as CN102702553B example I)
0.51g of titanium dioxide particles, 0.84g of silica particles, 6.63g of gamma-aminopropyltriethoxysilane and 5.61g of ammonia water were added to 100g of an ethanol solvent, stirred and reacted at room temperature for 8 hours, dried and pulverized at 100 ℃ to obtain aminated titanium dioxide and silica particles, which were added to 35mL of an ethanol solvent, and 14g of an aqueous epoxy resin was added to obtain a coating sol.
And uniformly coating the coating sol on a glass sheet, and standing at room temperature for later use. And (3) immersing the glass sheet with the coating film into a tetrahydrofuran solution of perfluoro-n-butyltriethoxysilane with the mass fraction of 5%, soaking for 30 minutes, taking out the glass sheet, putting the glass sheet into a vacuum drying oven with the temperature of 150 ℃ for curing and crosslinking to obtain the glass sheet with the super-hydrophobic film, wherein the contact angle of water is about 155 degrees, but the visible light transmittance is only about 23 percent. After the shakeout test, the contact angle of water on the surface was only about 117 °.
Therefore, compared with the example of the invention, the third comparative example also needs high-temperature drying treatment when preparing the super-hydrophobic coating, and needs to spray fluorine-containing solution for coating, so that the preparation process is complex, and the prepared super-hydrophobic coating has low light transmittance and poor adhesive force.
Therefore, the transparent super-hydrophobic coating comprises two components AB, wherein the two components contain nanoparticles with different sizes and different surface modification treatments. The adhesion of the nanoparticles on the surface is improved through the mutual filling of the two types of nanoparticles and the reaction of partial nanoparticles and the auxiliary agent. The technical route of the invention has simple process, does not need high-temperature heating and curing, only needs one-time spraying and forming, is suitable for large-area spraying application, and simultaneously has excellent transparency.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A coating for preparing a transparent super-hydrophobic coating, which is characterized by consisting of a component A and a component B, wherein:
the component A comprises the following components in percentage by mass:
0.5 to 5 percent of hydrophobic modified nano particles
0.1 to 5 percent of active auxiliary agent
90 to 99.4 percent of organic solvent A
The component B comprises the following components in percentage by mass:
0.1-5% of ammonia modified nano particles
95 to 99.9 percent of organic solvent B
Wherein the coagent is a compound containing an epoxy functional group or a mixture thereof;
or the component A comprises the following components in percentage by mass:
0.5 to 5 percent of hydrophobic modified nano particles
0.1 to 5 percent of active auxiliary agent
90 to 99.4 percent of organic solvent A
The component B comprises the following components in percentage by mass:
0.1 to 5 percent of epoxy modified nano particles
95 to 99.9 percent of organic solvent B
Wherein the coagent is a compound with an amino functional group or a mixture thereof;
the original nanoparticles of the hydrophobic modified nanoparticles in the component A have the particle size of 5-30 nm;
the original nanoparticles of the ammonia modified nanoparticles or the epoxy modified nanoparticles in the component B have the particle size of 100-1000 nm;
the mass ratio of the component A to the component B is (3-10) to 1;
the hydrophobic modified nano particles are nano particles with alkane or fluorine-containing alkane on the surface;
the ammonia modified nanoparticles are nanoparticles with amino groups on the surface;
the epoxy modified nanoparticles are nanoparticles with epoxy groups on the surface.
2. The coating for preparing a transparent superhydrophobic coating of claim 1, wherein the ammonia-modified nanoparticles are nanoparticles modified with an amino-functional silane coupling agent bearing both amino and hydrolysable functional groups-SiX3Wherein X is-OCH3，-OCH2CH3Or one or more of-Cl.
3. The coating for preparing a transparent superhydrophobic coating according to claim 1, characterized in that said epoxy-modified nanoparticles are nanoparticles modified with an epoxy-functional silane coupling agent carrying both epoxy and hydrolysable functional groups-SiX3Wherein X is-OCH3，-OCH2CH3Or one or more of-Cl.
4. The coating for preparing the transparent super-hydrophobic coating according to claim 1, wherein the hydrophobically modified nanoparticles are nanoparticles modified by a silane coupling agent or a fluorosilane coupling agent, and the structural general formula of the silane coupling agent or fluorosilane coupling agent is RSiX3Wherein R is a linear or branched C4-16A hydrocarbon group or a fluorine-containing hydrocarbon group, X is a hydrolyzable group comprising-OCH3，-OCH2CH3Or one or more of-Cl.
5. The coating for preparing a transparent super-hydrophobic coating according to any one of claims 1 to 4, wherein the organic solvent A or B is one or more selected from acetone, methyl ethyl ketone, butanone, ethyl acetate, n-butyl acetate, methanol, ethanol, butanol, isopropanol, ethylene glycol, toluene and xylene.
6. The method for preparing a coating material for preparing a transparent superhydrophobic coating according to any one of claims 1 to 5, characterized in that the steps of the preparation method comprise:
1) preparation of component A: adding the hydrophobic modified nanoparticles into an organic solvent A, carrying out ultrasonic oscillation for 10-30 min, and adding the compound active auxiliary agent containing epoxy functional groups to obtain a component A;
2) preparation of the component B: adding the ammonia modified nanoparticles into an organic solvent B, and performing ultrasonic oscillation for 10-30 min to obtain a component B;
alternatively, the preparation method comprises the following steps:
1) preparation of component A: adding the hydrophobic modified nanoparticles into an organic solvent A, carrying out ultrasonic oscillation for 10-30 min, and adding the compound active auxiliary agent containing amino functional groups to obtain a component A;
2) preparation of the component B: and adding the epoxy modified nanoparticles into an organic solvent B, and performing ultrasonic oscillation for 10-30 min to obtain a component B.
7. The use method of the coating for preparing the transparent super-hydrophobic coating according to any one of claims 1 to 5, characterized in that A, B components are mixed according to the proportion of (3-10) to 1 and sprayed on a substrate to obtain the super-hydrophobic coating.
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| CN201611028879.6A CN108373609B (en) | 2016-11-18 | 2016-11-18 | Coating for preparing transparent super-hydrophobic coating and preparation and use methods thereof |
| PCT/CN2016/110382 WO2018090420A1 (en) | 2016-11-18 | 2016-12-16 | Coating for preparing transparent superhydrophobic coating layer, and preparation and usage method therefor |
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| CN201611028879.6A CN108373609B (en) | 2016-11-18 | 2016-11-18 | Coating for preparing transparent super-hydrophobic coating and preparation and use methods thereof |
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| CN110467830B (en) * | 2019-07-23 | 2021-11-09 | 北京易净星科技有限公司 | Wear-resistant hydrophobic coating and method for preparing same |
| CN111621120A (en) * | 2020-07-16 | 2020-09-04 | 贵阳学院 | Composite flame-retardant material and preparation method thereof |
| CN114425508B (en) * | 2020-10-13 | 2023-08-01 | 中国石油化工股份有限公司 | Metal material with superhydrophobic surface, preparation method and application thereof, and oil-water separation method |
| CN115124872A (en) * | 2021-03-26 | 2022-09-30 | 宁波激智科技股份有限公司 | Anti-fouling flame-retardant coating composition, preparation method thereof and anti-fouling flame-retardant film |
| CN115198516A (en) * | 2022-03-11 | 2022-10-18 | 天津仁爱学院 | Modified epoxy resin solution and super-hydrophobic fiber felt prepared by applying modified epoxy resin solution |
| CN115011154B (en) * | 2022-06-20 | 2023-03-21 | 常州大学 | Preparation method of novel nano organic silicon composite coating capable of being cured at normal temperature with high efficiency |
| CN115748237B (en) * | 2022-11-08 | 2024-07-09 | 杭州传化精细化工有限公司 | Fluorine-free super-hydrophobic material and preparation method thereof |
| CN116769396B (en) * | 2023-05-10 | 2024-08-23 | 中国华能集团清洁能源技术研究院有限公司 | Super-hydrophobic wind power blade surface protective coating and preparation method thereof |
| CN116769413B (en) * | 2023-06-27 | 2024-04-19 | 广东中鼎科技发展有限公司 | Anti-fouling TPU high-low temperature film and preparation method thereof |
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| CN104513585B (en) * | 2013-09-27 | 2017-12-19 | 无锡市耐密特新材料有限公司 | Super hydrophobic coating composition and the super-hydrophobic coat with its formation |
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| CN101838496A (en) * | 2010-04-09 | 2010-09-22 | 南京工业大学 | Super-hydrophobic polyurethane/oxide nanoparticle hybrid coating material and preparation method thereof |
| CN103555012A (en) * | 2013-10-23 | 2014-02-05 | 三棵树涂料股份有限公司 | Super-amphiphobic transparent nano coating and preparation method thereof |
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