CN1931448A - Method of forming hydrophobic transparent film on the surface of different substrates - Google Patents

Method of forming hydrophobic transparent film on the surface of different substrates Download PDF

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CN1931448A
CN1931448A CNA2006101165435A CN200610116543A CN1931448A CN 1931448 A CN1931448 A CN 1931448A CN A2006101165435 A CNA2006101165435 A CN A2006101165435A CN 200610116543 A CN200610116543 A CN 200610116543A CN 1931448 A CN1931448 A CN 1931448A
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fluorosilane
hydroxyl
acid
solution
hydroxylated
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CN100429009C (en
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张青红
高濂
林小华
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20Use of solutions containing silanes

Abstract

The present invention is method for forming hydrophobic transparent film on the surface of different substrates, glass, ceramic, metal, paint, etc. fluorosilane and other components are painted to the surface of plastic or paint with hydroxyl radical containing oxide film form in advance or the surface of other kind of substrate directly. Under the action of catalyst, the ethoxy group connected to the Si atom in fluorosilane is hydrolyzed into hydroxyl radical in advance, and the hydrolyzed solution is maintained in monohydric alcohol dihydrolic alcohol or other organic solvent, and the hydrolyzed fluorosilane reacts with the metal hydroxyl radical bond in the surface of the oxide to obtain high stability M-O-Si bonding. The formed film of several nanometer to decades nanometer thickness is firmly combined with the substrate chemically at normal temperature without need of heat treatment.

Description

Method for forming hydrophobic transparent film on surfaces of various substrates
Technical Field
The invention relates to a method for forming a hydrophobic transparent film on the surfaces of various substrates, wherein the substrates comprise glass, ceramics, metal and paint. The invention particularly relates to a hydroxyl fluorosilane solution and a method for forming a stable hydrophobic film after the hydroxyl fluorosilane solution is fixed on the surfaces of various materials.
Background
The contact angle of water on the surface is larger than 90 degrees, the surface is hydrophobic (also called hydrophobic), the surface is hydrophilic when the contact angle is smaller than 90 degrees, the surfaces of metal and glass are hydrophilic, and the contact angle of the upper surface of common flat sodium silicate glass is about 30 degrees. The hydrophilic or hydrophobic state of plastic and paint surfaces is then related to their composition and state of use, plastic articles such as Polyethylene (PE) are inherently hydrophobic materials. The use condition is mentioned because after long-term use in light and air, the surface of the plastic can be oxidized to form hydrophilic hydroxyl or carboxyl. In this way, the material can change from a hydrophobic state to a hydrophilic state. In addition, dust whose main component is oxide can change the surface from hydrophobic state to hydrophilic state after the dust is deposited on the surface of plastic or paint. The surface can be changed from a hydrophilic state to a hydrophobic state by coating the surface of the material with a hydrophobic substance, for example, the surface of the glass is quickly changed from the hydrophilic state to the hydrophobic state by coating the surface of the glass with silicone oil. In engineering applications, it is desirable that the hand feel of the surface of the coated material is not substantially altered, that the coated material has good adhesion to the substrate, and that the appearance, or even the optical properties, of the material are not altered. Although there are many methods for designing and changing the surface roughness, a rugged nanopattern is intentionally prepared on the surface to realize the superhydrophobic state of the surface. However, in practical application, it is also necessary to consider that the rough surface is changed in use (small particles fill the concave part and are not easy to remove), and the gas trapped by the concave part is volatilized and diffused, so that the general effectiveness of the hydrophobic surface based on the nano structure is a problem which must be solved in application. The invention mainly solves the problem of hydrophobicity of the flat surface, and the outward-oriented fluorocarbon group has very low surface energy after the flat surface is coated with the hydroxyfluorosilane, so that the coated material has the functions of hydrophobicity, stain resistance, easiness in cleaning and the like.
As early as the 80's of the last century, there have been reports of silane modifying the surface of a material to change the surface of the silicon to a hydrophobic state in a hydrophilic state (s.r. wasserman, et al langmuir, 1989, 5, 1074-1087.s.r. wasserman, et al j).Am. chem. Soc, 1989, 111, 5852-. Compared with alkyl silane, the material surface has lower specific surface energy (the specific surface energy of methyl and trifluoromethyl is 25 millinewton per meter (mN/m) and 15 millinewton per meter (mN/m) respectively) after being modified by fluorosilane. Therefore, replacing the silane with fluorosilane is expected to further enhance the hydrophobic effect of the surface. The Chinese patent of invention (patent number ZL 02115493.7) discloses the use of tridecafluorooctyltriethoxysilane CF3(CF2)5C2H4Si(OC2H5)3The contact angle of water and glass coated with the water repellent can reach 90 to 100 degrees, and the method is more suitable for surface modification before glass installation. Since the glass is subjected to a heat treatment at 200 to 350 ℃ after being coated with the water repellent liquid, the method is difficult to be used for coating the glass after installation and during use. The invention patent of antifouling coating and its manufacturing method, and its application in automobile glass and automobile (application No. 01111791.5) discloses a method for preparing antifouling glass by using fluorosilane chloride, the contact angle between water and antifouling glass can reach about 110 degrees, the method has the disadvantages that the Si-Cl bond of fluorosilane chloride is quickly hydrolyzed, and harmful and corrosive hydrogen chloride gas is generated in the hydrolysis process, so the construction needs to be carried out in dry inert atmosphere, and the heat treatment of 300-450 ℃ is also needed after the coating. Ethyl orthosilicate Si (OC) has been reported in the literature2H5)4Of medium-Si-OC2H5Can be hydrolyzed to silicon hydroxyl-Si-OH (Q.H.Zhang et al, chem.Lett., 2001, 1124) at 40 to 70 deg.C under the catalysis of dilute nitric acid. The invention is based on the principle that tridecafluorooctyltriethoxysilane CF is catalyzed by dilute inorganic acid in a lower monohydric alcohol or dihydric alcohol medium at the temperature of 40-70 DEG C3(CF2)5C2H4Si(OC2H5)3Or heptadecafluorodecyltriethoxysilane CF3(CF2)7C2H4Si(OC2H5)3Of medium-Si-OC2H5Pre-hydrolyzing at 40-70 deg.C under the catalysis of dilute acid to obtain hydroxylated tridecafluorooctyl trihydroxysilane CF3(CF2)5C2H4Si(OH)3Or heptadecafluorodecyltrimethyloxysilane CF3(CF2)7C2H4Si(OH)3The solution, hydroxylated fluorosilane, forms firm chemical combination with glass rich in hydroxyl, plastic rich in hydroxyl and paint surface by grafting metal oxide sol at room temperature.
Disclosure of Invention
The invention aims to provide a method for forming a stable and transparent hydrophobic transparent film on the surfaces of various materials. The method mainly comprises the steps of hydrolyzing fluorosilane in advance to prepare a hydroxylated fluorosilane solution, forming chemical combination of silicon hydroxyl bonds in the solution and metal hydroxyl bonds on the surface of a coated material at the room temperature of 10-25 ℃ after the solution is coated on the surface of the material to form a hydrophobic film, wherein fluorocarbon groups of the fluorosilane in the prepared hydrophobic film face outwards. The surfaces of plastics and paint do not contain chemical bonds of metal and hydroxyl, and the surfaces of the plastics and paint are modified by using alumina, silica, boehmite and titania sol, so that the metal hydroxyl bonds are grafted on the surfaces of the plastics and paint. The grafted surface can react with hydroxyl of fluorosilane at room temperature to form chemical combination of M-O-Si- (M represents silicon or metal elements such as aluminum, titanium and the like). The invention refers to the research result of the hydrolysis of tetraethoxysilane: tetraethoxysilane Si (OC)2H5)4Of medium-Si-OC2H5Can be hydrolyzed to silicon hydroxyl-Si-OH (Q.H.Zhang et al, chem.Lett., 2001, 1124) at 40 to 70 deg.C under the catalysis of dilute nitric acid. The tridecafluorooctyltriethoxysilane or the heptadecafluorodecyltriethoxysilane likewise contains-Si-OC2H5Therefore, the fluorosilane can be hydrolyzed in advance to obtain hydroxylated tridecafluorooctyl trishydroxysilane CF by using dilute acid as a catalyst at a certain temperature3(CF2)5C2H4Si(OH)3Or heptadecafluoroDecyl trihydroxy silane CF3(CF2)7C2H4Si(OH)3And (3) solution.
The object of the invention is thus achieved: dissolving fluorosilane in lower monohydric alcohol, dihydric alcohol or mixture of monohydric alcohol and dihydric alcohol, wherein the monohydric alcohol comprises ethanol, n-propanol and isopropanol, and the dihydric alcohol is ethylene glycol. Before hydrolysis, inorganic acid is added as catalyst, and the acid is one or mixture of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid or trichloroacetic acid. The molar ratio of hydrogen ions released by the acid to silicon atoms in the fluorosilane is 1: 300 to 1: 10. The ethoxy in the fluorosilane is hydrolyzed into hydroxyl by hydrolysis at the temperature of 40-70 ℃, the hydrolyzed fluorosilane still has good stability, is still dissolved in the lower alcohol, does not precipitate out, and does not form colloidal particles. In order to improve the bonding strength of the fluorosilane and the material, a certain amount of tetraethoxysilane (molecular formula Si (OC)) is added before the hydrolysis of the lower alcohol solution of the fluorosilane2H5)4TEOS for short) to hydrolyze TEOS and fluorosilane together, and the hydrated silica colloidal particles generated by hydrolysis are an inorganic binder. Or mixing TEOS with one or more of butyl titanate, isopropyl titanate and aluminum isopropoxide, and co-hydrolyzing to obtain inorganic binders with different binding properties. In addition, toStabilizing the hydrolysate of fluorosilane, and adding a small amount of surfactant to the hydrolyzed solution, wherein the surfactant refers to nonionic surfactants, such as: such as polyethylene oxide, Triton (Triton), or a fluorine-containing surfactant.
The above process is now detailed as follows:
measuring fluorosilane with a certain volume, putting the fluorosilane into the stirred monohydric or dihydric lower alcohol, stirring for 10-20 minutes, and then adding diluted acid, wherein the molar ratio of hydrogen ions released by acid to silicon in the fluorosilane is 1: 300 to 1: 10. Water is added in the form of dilute acid of 0.05 to 0.1M in an amount of 1: 1 to 1: 10 in terms of a molar ratio of water to silicon in the fluorosilane. After the mixture is uniformly stirred, the temperature is increased under the condition of water bath, the temperature range is 40-70 ℃, the temperature increase rate is 1-10 ℃/min, and the temperature is kept for 0.5-12 hours after reaching the set temperature. Then, the mixture is naturally cooled to 10-25 ℃ in the air, and the ethoxy in the obtained fluorosilane is hydrolyzed into fluorosilane alcohol containing hydroxyl, which is also called as fluorosilane hydroxide. Fluorosilane can obtain transparent solution in a wide range of concentration of 0.5-50% (unless otherwise specified,% in the present document refers to mass percentage concentration), and the solution can be diluted by absolute ethyl alcohol or isopropyl alcohol to obtain directly usable diluent, wherein the concentration of the hydroxylated fluorosilane in the diluent is 0.5-5.0%.
The chemical equation for the reaction is:
(n is more than or equal to 6, and R is-CH3or-C2H50.05 to 0.1M acid as catalyst at a temperature of 40 to 70 ℃ C.)
Thehydrolysis of fluorosilane is affected by its concentration, catalyst concentration and hydrolysis temperature, the hydrolysis temperature is set to 40 ℃, 12 hours are required for the reaction to be complete, and at 70 ℃, the hydrolysis reaction can be completed in 0.5 hour.
In the process for preparing the hydroxylated fluorosilane, ethyl orthosilicate, aluminum isopropoxide, butyl titanate or isopropyl titanate is introduced before heating, and the substances and the fluorosilane are subjected to cohydrolysis to obtain the hydroxylated fluorosilane containing inorganic nano-particles, wherein the introduction of the inorganic nano-particles can improve the binding force of a film and substrates such as glass, ceramic and the like, and can also regulate and control the thickness of a coated film.
The hydroxylated fluorosilane obtained by pre-hydrolysis can be diluted by absolute ethyl alcohol, isopropanol and the like according to any proportion, so that a hydroxylated fluorosilane dilute solution is obtained, and the concentration of a relatively proper diluent of the transparent hydrophobic film can be obtained and is 0.5-5.0%.
In order to enhance the hydrophobic effect, 0.1 to 1.0% of aerosol of inorganic nanoparticles, which are loose nanoparticle aggregates with a low apparent density, may also be added to the dilution. The aerosol of the inorganic nano particles is dispersed in absolute ethyl alcohol or isopropanol, and is directly mixed with the diluent of the hydroxylated fluorosilane, and the suspension can be stabilized by stirring, so that the hydrophobic effect is better after the aerosol is coated on the surface of glass.
The surface of the plastic or paint is not rich in hydroxyl, and after the hydroxylated fluorosilane is directly coated on the surface of the plastic or paint, the hydroxyl and the fluoroalkyl of the fluorosilane are randomly oriented, so that a good hydrophobic effect is difficult to obtain. In order to solve the problem of orientation of fluorocarbon groups, the organic surface may be coated beforehand with a transparent hydrosol of silica, alumina, boehmite or titania, which is itself a preferred inorganic binder, the particles of which are very fine and suitable for forming a transparent and stable film on the paint surface. The hydrosol may be a commercial hydrosol product or may be prepared by a conventional sol-gel process. After treatment according to this process, it is equivalent to "grafting" a layer of oxide rich in hydroxyl groups (referred to as silica, alumina or titania) onto the paint surface. After the treatment, the diluent of the hydroxylated fluorosilane is coated on the surface of the oxide layer, so that the outward arrangement of fluorocarbon groups is realized. For certain glasses whose surface is not rich in hydroxyl groups, the above hydrosol may also be precoated to bring the surface to a hydroxyl-rich state.
The transparency is an important performance index of the surface of glass and the like, and the change of the optical performance of the glass is quantitatively evaluated by measuring the transmittance before and after the two sides of the glass are coated with the hydroxyl fluorosilane in an ultraviolet-visible light region. The contact angle of water and glass is a static advancing contact angle, 5 different positions are tested, the average value is calculated, and the error of the contact angle is not more than +/-0.5 degrees. The durability test included two groups, and the contact angle did not decrease for the time of one day to one year of coating in room environment at normal temperature. The results of the insolation experiment in outdoor air show that under the outdoor insolation condition, the contact angle is changed from 108 degrees to 103 degrees in 6 months (from 12 months to the bottom of 5 months in the next year in Shanghai region),and the contact angle is not obviously reduced.
The invention provides a hydrophobic transparent film formed on the surfaces of various base materials, which is characterized in that:
1. the hydroxyl fluorinated silane solution is prepared by pre-hydrolysis, and can be directly used for forming transparent hydrophobic films on the surfaces of various materials at room temperature after being diluted by absolute ethyl alcohol or isopropyl alcohol, and the heat treatment at the temperature of 300-450 ℃ in the literature cited in the background art is no longer a necessary process for forming the films.
2. Fluorosilane or fluorosilane and ethyl orthosilicate, aluminum isopropoxide, butyl titanate and isopropyl titanate are cohydrolyzed at 40-70 ℃, and alkoxy groups are partially or completely hydrolyzed into hydroxyl groups under the catalytic action of dilute acid.
3. The dispersion liquid in the alcohol medium of the inorganic nano-particle aerosol is introduced into the hydrolyzed fluorosilane, so that the hydrophobic effect of the surface of the base material is enhanced.
4. The surface of the paint is grafted with silica, alumina, titanium oxide or sol of a mixture of the silica, the alumina and the titanium oxide, so that the firm combination of the hydroxylated fluorosilane and the paint surface at normal temperature and the outward arrangement of fluorocarbon groups in the fluorosilane due to the vertical arrangement of the fluorocarbon groups on the base material are realized. The fluorocarbon group is trifluoromethyl (-CF)3) And difluoromethylene (-CF)2-)。
5. The film has good light transmission, and the change of the light transmission of the double-sided single-layer coated glass in a visible light area is less than 0.5 percent.
6. The method provided by the invention takes fluorosilane and inorganic nano-particle sol as main components, and forms a film with the thickness of several nanometers to dozens of nanometers on the surfaces of various materials which are coated with glass, ceramics, metal, plastics or paint after being wiped by soft cloth.
7. The contact angle of water on the coated glass is 105-111 degrees, which is obviously larger than 30 degrees when the coated glass is not coated, and the coated glass shows good hydrophobic effect.
Drawings
FIG. 1 is a graph comparing light transmittance in the UV-visible region before and after double-sided coating of hydroxylated fluorosilane on glass.
FIG. 2 is a photograph of a bead of water on hydroxylated fluorosilane coated glass from which a contact angle of 108 degrees can be calculated. The contact angle of water on uncoated glass was about 30 degrees.
Fig. 3 is a photograph of water droplets on hydroxylated fluorosilane coated glass, from which the contact angle can be calculated as 111 degrees.
Detailed Description
The following examples are merely illustrative of specific aspects of the invention and are not intended to be limiting in scope or detail.
Example 1:
10g of tridecafluorooctyltriethoxysilane CF are weighed3(CF2)5C2H4Si(OC2H5)3And 5g of tetraethoxyorthosilicate (formula Si (OC)2H5)4Adding into 82.2g isopropanol, and adding 2.8g 0.1M HNO3Refluxing at 40 deg.C for 12 hr to obtain hydroxylated fluorosilane containing silica nanoparticles (10% of fluorine-containing silane)(calculated as tridecafluorooctyltriethoxysilane). After cooling, the mixture was diluted with isopropyl alcohol at a mass ratio of 1: 5 so that 2% of fluorosilane (based on tridecafluorooctyltriethoxysilane) was contained. Coating the glass on both sides at normal temperature, wherein the dosage is 15ml/m2. After wiping with a soft cloth, the contact angle was measured to be 108 degrees without heat treatment for 24 hours. The transmittance curve of the glass after transparent coating with this liquid is given at 2 in fig. 1, and the transmittance of the coated glass is not reduced but slightly improved. Figure 2 shows a photograph of a water bead on glass coated with this liquid, and the contact angle can be calculated to be 108 degrees.
Example 2:
15g of tridecafluorooctyltriethoxysilane CF are weighed out3(CF2)5C2H4Si(OC2H5)3And 2g of tetraethoxyorthosilicate (formula Si (OC)2H5)4Adding into 80.7g of isopropanol, adding 2.3g of 0.1M HCl, and refluxing at 70 ℃ for 0.5 hour to obtain the silicon oxide nano-particle-containing hydroxyfluorosilane with 15 percent of fluorine-containing silane (calculated by tridecafluorooctyltriethoxysilane). After cooling, the mixture was diluted with isopropyl alcohol at a mass ratio of 1: 10 so that fluorosilane was contained at 1.5% (based on tridecafluorooctyltriethoxysilane). Taking 50g of fluorosilane containing 1.5 percent (by tridecafluorooctyl triethoxy)Silane) was mixed with 50g of a 1.0% isopropyl alcohol colloidal dispersion containing silica aerosol, 0.75% fluorine-containing silane and 0.5% silica after mixing. Coating the glass on both sides at normal temperature, wherein the dosage is 15ml/m2. After wiping with a soft cloth, the contact angle was measured to be 111 degrees without heat treatment for 24 hours. The transmittance curve of the glass after transparent coating with this liquid is given at 2 in fig. 1, with an anti-reflection effect below 700 nm, with a slight decrease in transmittance in the range of 700 to 800 nm, with a decrease of less than 0.3%. Figure 3 shows a photograph of a water bead on glass coated with this liquid, and the contact angle can be calculated as 111 degrees.
Example 3:
diluting commercial silica sol to 1.0% silica oxide with primary particle size of about 10nm, and coating paint surface at room temperature with 20ml/m2. The resulting mixture was rubbed with a soft cloth and after 15 minutes diluted fluorosilane containing silica aerogel was applied, the preparation was the same as in example 2, wherein the fluorosilane was 0.75% and the silica was 0.5%. Coating the paint surface at normal temperature, wherein the dosage is 20ml/m2. After wiping with a soft cloth, the contact angle was measured at 105 degrees for 24 hours, and the measurement and calculation of the contact angle are described in the text.
Example 4:
the silica and titanium oxide composite hydrosol (containing 0.75 percent of silica and 0.25 percent of titanium dioxide) prepared by a sol-gel method is prepared, wherein the primary particle size of the silica is about 10nm, and the primary particle size of the titanium dioxide is less than 15 nm. Coating the paint surface at normal temperature, wherein the dosage is 20ml/m2. The resulting mixture was rubbed with a soft cloth and after 15 minutes diluted fluorosilane containing silica aerogel was applied, the preparation was the same as in example 2, wherein the fluorosilane was 1.00% and the silica was 0.5%. Coating the paint surface at normal temperature, wherein the dosage is 15ml/m2. After wiping with a soft cloth, the contact angle was measured at 106 degrees for 24 hours, and the measurement and calculation of the contact angle are described in the text.
Example 5:
weighing 10g of heptadecafluorodecyltriethoxysilane CF3(CF2)5C2H4Si(OC2H5)3And 6g of tetraethoxyorthosilicate (formula Si (OC)2H5)4Adding into 80.2g of absolute ethyl alcohol, and then adding 1.6g of 0.1M HNO3And 2.2g of 0.1M HCl, and refluxing at 50 ℃ for 4 hours, to obtain a silica-containing nanoparticle-containing hydroxyfluorosilane containing 10% of fluorine-containing silane (based on heptadecafluorodecyltriethoxysilane). After cooling, the mixture was diluted with isopropyl alcohol at a mass ratio of 1: 10 so that fluorosilane was contained at 1.0% (based on heptadecafluorodecyltriethoxysilane). Coating the glass on both sides at normal temperature, wherein the dosage is 18ml/m2. After wiping with a soft cloth, the contact angle was measured to be 107 degrees after wiping for 24 hours without heat treatment.

Claims (12)

1. A method for forming hydrophobic transparent film on the surface of multiple base materials is characterized in that any one of the following two methods can be adopted according to different base materials,
A. the process for forming the hydrophobic transparent film on the substrate with the surface having the metal hydroxyl bond comprises the following steps:
(1) preparation of hydroxylated fluorosilane solution
Firstly, measuring a certain volume of desflurane, pouring into the stirred monohydric alcohol, dihydric alcohol or the mixture of the monohydric alcohol and the dihydric alcohol, stirring, then adding dilute acid, wherein the molar ratio of hydrogen ions released by the dilute acid to silicon in the fluorosilane is 1: 300 to 1: 10, the concentration of the dilute acid is 0.05-0.1M, uniformly stirring, hydrolyzing ethoxy in the fluorosilane to obtain hydroxyl-containing fluorosilanol at the temperature of 40-70 ℃, cooling to 10-25 ℃, and diluting the solution until the mass percentage concentration of the hydroxylated fluorosilane in the diluent is 0.5-5.0%;
(2) coating the hydroxylated fluorosilane solution prepared in the step (1) on the surface of a base material, forming chemical combination of silicon hydroxyl bonds and metal bonds on the surface of the coated material at room temperature of 10-25 ℃ to form a film, and arranging fluorocarbon groups in fluorosilane in the prepared hydrophobic film because the fluorocarbon groups are vertical to the base material and face outwards;
B. the process for forming the hydrophobic transparent film on the paint or plastic substrate without metal hydroxyl bonds on the surface comprises the following steps:
(1) preparation of hydroxylated fluorosilane solution
Firstly, measuring a certain volume of desflurane, pouring into the stirred monohydric alcohol, dihydric alcohol or the mixture of the monohydric alcohol and the dihydric alcohol, stirring, then adding dilute acid, wherein the molar ratio of hydrogen ions released by the dilute acid to silicon in the fluorosilane is 1: 300 to 1: 10, the concentration of the dilute acid is 0.05-0.1M, uniformly stirring, hydrolyzing ethoxy in the fluorosilane to obtain hydroxyl-containing fluorosilanol at the temperature of 40-70 ℃, cooling to 10-25 ℃, and diluting the solution until the mass percentage concentration of the hydroxylated fluorosilane in the diluent is 0.5-5.0%;
(2) modifying the surface ofthe base material by using alumina, silica, boehmite or titania sol to graft a metal hydroxyl bond on the surface;
(3) and (3) forming M-o-Si chemical combination on the surface of the grafted base material by using the hydroxyl fluorosilicone solution prepared in the step (1) at the room temperature of 10-25 ℃, wherein M is one metal element of silicon, aluminum or titanium.
2. The method of claim 1, wherein said fluorosilane is tridecafluorooctyltriethoxysilane or heptadecafluorodecyltriethoxysilane.
3. The method of claim 1, wherein the monohydric alcohol is ethanol, n-propanol or isopropanol; the dihydric alcohol is ethylene glycol.
4. The method of claim 1, wherein said dilute acid is one or a mixture of hydrochloric acid, nitric acid, phosphoric acid, acetic acid, and trichloroacetic acid.
5. The method of claim 1, wherein the hydroxyl-fluorinated silane solution is prepared by adding ethyl orthosilicate, or a mixture of ethyl orthosilicate, isopropyl titanate, and/or aluminum isopropoxide before hydrolysis.
6. The method of claim 1, wherein polyethylene oxide, triton or a fluorine-containing surfactant is added to the hydrolyzed solution to stabilize the hydrolysis product of fluorosilane.
7. The method of claim 1, wherein the stirring time is 10 to 20 minutes.
8. The method of claim 1, wherein the hydrolysis is carried out in a water bath for a period of 0.5 to 12 hours.
9. The method of claim 1, wherein the molar ratio of water to silicon in the fluorosilane is from 1: 1 to 1: 10 in the solution after addition of the dilute acid.
10. The method of claim 8, wherein the temperature of the water bath is increased to 40-70 ℃ at a rate of 1-10 ℃/min.
11. The method for forming a hydrophobic transparent thin film on the surfaces of various substrates as claimed in claim 1, wherein the thickness of the nano-thin film formed on the surface of different substrates is several nanometers to several tens of nanometers.
12. The method as claimed in claim 1, wherein the contact angle of water on said coated glass is 105-111 degrees.
CNB2006101165435A 2006-09-27 2006-09-27 Method of forming hydrophobic transparent film on the surface of different substrates Expired - Fee Related CN100429009C (en)

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