CN107021646B - Preparation method of hydrophobic automobile glass based on organic fluorosilane material - Google Patents
Preparation method of hydrophobic automobile glass based on organic fluorosilane material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/29—Mixtures
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/445—Organic continuous phases
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/478—Silica
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/114—Deposition methods from solutions or suspensions by brushing, pouring or doctorblading
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/31—Pre-treatment
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
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Abstract
The invention discloses a preparation method of hydrophobic automobile glass based on organic fluorosilane materials, which can prepare hydrophobic glass with an initial contact angle not less than 105 degrees by adopting the organic fluorosilane materials as main raw materials, wherein the prepared hydrophobic glass has better wear resistance, high and low temperature resistance, moisture and scrubbing resistance, chemical solvent resistance, stability and aging resistance, and all performance indexes reach or even exceed the hydrophobic glass samples provided by automobile glass suppliers, thereby completely meeting the application requirements of the hydrophobic automobile glass.
Description
Technical Field
The invention belongs to the field of glass, and particularly relates to a preparation method of hydrophobic automobile glass based on an organic fluorosilane material.
Background
Automotive glass is typically soda-lime glass produced by the float glass process, the fresh glass surface being highly reactive, especially highly reactive with water, and the glass surface undergoing hydroxylation in the following manner: chemically adsorbed water reacts with suspended silicon bonds; hydrolysis of Si-O-Si chain occurs; ion exchange occurs at the non-bridging oxygens. These three reaction mechanisms promote the formation of silanol (Si-OH) groups. The silanol (Si-OH) group has higher reactivity with organic compounds, and can physically adsorb and even carry out condensation reaction. Soda-lime glass exposed to the atmosphere is often attacked by water, acids, alkalis, salts and other media in the atmosphere. Because the surface of the glass has components such as silicon dioxide, calcium oxide, magnesium oxide and the like which can increase the surface energy of the glass, the surface of the glass has higher affinity for moisture in the atmosphere, and the water adsorbed on the surface of the glass is H+Or H3O+Form of (2) and metal ion (Ca) on the glass surface2+、Mg2+、Na+Etc.) to promote diffusion of water molecules into the glass body. Meanwhile, water molecules can destroy the silicon dioxide network structure and further diffuse from the glass surface and the microcrack defect to the glass body. The change of the surface composition and microstructure of the glass results in the change of the mechanical and optical properties of the glass.
At present, in order to avoid the damage of moisture in the atmosphere to the surface of the automobile glass and improve the water and oil repellency of the glass surface, the surface of the automobile glass is usually waxed and coated with TiO2Self-cleaning film layer, coating water-proofing agent and other methods. Although the glass surface is waxed, the glass can be brighter and has a certain waterproof function, but the glass can reflect light when meeting at night, so that the driving safety is influenced; TiO 22The self-cleaning film layer works on the principle that under the irradiation of ultraviolet light, TiO2The valence band electrons are excited to the conduction band, and the electrons and holes are directed to the TiO2Surface migration to form electron-hole pairs, electrons and Ti4+Reaction, the hole is the same asThe oxygen ion bridge reaction on the surface of the film layer generates Ti respectively3+And oxygen vacancies, and organic substances adsorbed on the surface of the film layer can be decomposed by utilizing the strong oxidizing property of the oxygen vacancies, so that the self-cleaning function is realized. The self-cleaning function can be achieved only under the irradiation of ultraviolet light; the water-proofing agent can obviously reduce the surface energy of the glass and endow the glass with the characteristic of water-proof property.
The glass surface, especially the glass lens surface, whatever protection method is adopted needs to satisfy: 1) the original optical performance is ensured; 2) the chemical stability is high; 3) the wear resistance is good. The organofluorosilane material can just meet the requirement, has the advantages of organic silicon and organofluorine compound as a novel organic material, has the advantages of high heat resistance, good chemical stability, low surface free energy, low friction coefficient and the like, and is more and more concerned by people in application. The prior organofluorosilane materials for hydrophobic protection treatment of glass surface mainly comprise trifluoropropyltrimethyl (ethoxy) silane, tridecafluorooctyltrimethyl (ethoxy) silane, heptadecafluorodecyltrimethyl (ethoxy) silane, dodecafluoroheptylpropyltrimethoxysilane, hexafluorobutylpropyltrimethoxysilane and the like.
Disclosure of Invention
The invention aims to avoid the damage of water in the atmosphere to the surface of automobile glass and improve the water and oil repellency of the glass surface, and provides a preparation method of automobile hydrophobic glass based on an organic fluorosilane material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of hydrophobic automobile glass based on an organic fluorosilane material comprises the following steps:
degreasing glass by absolute ethyl alcohol, repeatedly polishing the glass by using polishing solution for a plurality of times, washing the glass by using deionized water to remove the polishing solution, drying a glass sample by using hot air, dipping hydrophobic modifier solution into dust-free paper to wipe the glass sample in a criss-cross mode, and drying the glass at the temperature of 100 ℃ to 120 ℃ for 10-30 minutes after wiping to obtain the glass.
The preparation method of the hydrophobic automobile glass based on the organic fluorosilane material comprises the following steps of:
5-7 parts of heptadecafluorodecyltriethoxysilane, 21-30 parts of tetraethyl orthosilicate, 10-15 parts of n-methyl pyrrolidone, 0.6-1 part of methyl tin mercaptide, 1-2 parts of triethanolamine oleate soap, 3-4 parts of a film-forming assistant, 0.7-1 part of a catalyst, 10-13 parts of aniline and 1-2 parts of an initiator;
the catalyst is stannous sulfide;
the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate;
the film-forming additive is propylene glycol phenyl ether;
the preparation method of the hydrophobic modifier solution comprises the following steps:
(1) adding tetraethyl orthosilicate into deionized water with the weight 35-40 times of that of tetraethyl orthosilicate, uniformly stirring, adding methyl tin mercaptide, raising the temperature to 50-60 ℃, dropwise adding 10-13mol/l of ammonia water, adjusting the pH to 10-12, keeping the temperature, stirring for 1-2 hours, adding triethanolamine oleic soap, and stirring to normal temperature to obtain a saponification sol dispersion liquid;
(2) adding the film-forming aid into deionized water which is 107 times of 100 times of the weight of the film-forming aid, uniformly stirring, adding aniline and n-methylpyrrolidone, and carrying out ultrasonic treatment for 3-5 minutes to obtain a monomer dispersion liquid;
(3) mixing the monomer dispersion liquid and the saponification sol dispersion liquid, stirring uniformly, adding an initiator, feeding into a reaction kettle, introducing nitrogen, stirring for 2-3 hours at the temperature of 70-80 ℃, and discharging to obtain a saponification polymer solution;
(4) mixing the saponified polymer solution with heptadecafluorodecyltriethoxysilane and a catalyst, feeding the mixture into a polytetrafluoroethylene reaction kettle, adjusting the temperature of the reaction kettle to 35-40 ℃, magnetically stirring the mixture for 20-30 hours, discharging the mixture, and cooling the mixture to the normal temperature to obtain the hydrophobic modifier solution.
The invention has the advantages that:
according to the invention, tetraethyl orthosilicate is used as a precursor, the obtained sol is treated by triethanolamine oleate soap to obtain a saponified sol dispersion liquid, the dispersion liquid has high strength and good viscosity and dispersibility, aniline is used as a monomer and is dispersed into the saponified sol, and then polymerization is carried out under the action of an initiator, so that the contact angle of a polyaniline coating to water is increased, the adhesive force and the water resistance are improved, and the surface hydrophobicity of the polyaniline sol coating is further improved by treatment of heptadecafluorodecyltriethoxysilane;
the invention adopts the organic fluorosilane-based material as the main raw material to prepare the hydrophobic glass with the initial contact angle not less than 105 degrees, and the prepared hydrophobic glass has better abrasion resistance, high and low temperature resistance, moisture and scrubbing resistance, chemical solvent resistance, stability and aging resistance, and all performance indexes reach or even exceed the hydrophobic glass sample provided by an automobile glass supplier, thereby completely meeting the application requirements of the hydrophobic automobile glass.
Detailed Description
Example 1
A preparation method of hydrophobic automobile glass based on an organic fluorosilane material comprises the following steps:
degreasing glass by absolute ethyl alcohol, repeatedly polishing the glass by using polishing solution for a plurality of times, washing the glass by using deionized water to remove the polishing solution, drying a glass sample by using hot air, dipping hydrophobic modifier solution into dust-free paper to wipe the glass sample in a criss-cross mode, and drying the glass for 30 minutes at 120 ℃ after wiping to obtain the glass.
The hydrophobic modifier solution is composed of the following raw materials in parts by weight:
heptadecafluorodecyltriethoxysilane 7, tetraethyl orthosilicate 30, n-methyl pyrrolidone 15, methyl tin mercaptide 1, triethanolamine oleate soap 2, film-forming assistant 4, catalyst 0.7-1, aniline 13 and initiator 2;
the catalyst is stannous sulfide;
the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate;
the film-forming additive is propylene glycol phenyl ether;
the preparation method of the hydrophobic modifier solution comprises the following steps:
(1) adding tetraethyl orthosilicate into deionized water 40 times of tetraethyl orthosilicate, uniformly stirring, adding methyl tin mercaptide, raising the temperature to 60 ℃, dropwise adding 13mol/l of ammonia water, adjusting the pH to 12, keeping the temperature and stirring for 2 hours, adding triethanolamine oleic acid soap, and stirring to normal temperature to obtain a saponification sol dispersion liquid;
(2) adding a film-forming aid into deionized water with the weight 107 times that of the film-forming aid, uniformly stirring, adding aniline and n-methylpyrrolidone, and carrying out ultrasonic treatment for 5 minutes to obtain a monomer dispersion liquid;
(3) mixing the monomer dispersion liquid and the saponified sol dispersion liquid, uniformly stirring, adding an initiator, feeding into a reaction kettle, introducing nitrogen, keeping the temperature at 80 ℃, stirring for 3 hours, and discharging to obtain a saponified polymer solution;
(4) mixing the saponified polymer solution with heptadecafluorodecyltriethoxysilane and a catalyst, feeding the mixture into a polytetrafluoroethylene reaction kettle, adjusting the temperature of the reaction kettle to 40 ℃, magnetically stirring the mixture for 30 hours, discharging the mixture, and cooling the mixture to the normal temperature to obtain the hydrophobic modifier solution.
Example 2
A preparation method of hydrophobic automobile glass based on an organic fluorosilane material is characterized by comprising the following steps:
degreasing glass by absolute ethyl alcohol, repeatedly polishing the glass by using polishing solution for a plurality of times, washing the glass by using deionized water to remove the polishing solution, drying a glass sample by using hot air, dipping hydrophobic modifier solution into dust-free paper, wiping the glass in a criss-cross mode, and drying the glass at 100 ℃ for 10 minutes after wiping to obtain the glass.
The preparation method of the hydrophobic automobile glass based on the organic fluorosilane material comprises the following steps of:
heptadecafluorodecyltriethoxysilane 5, tetraethyl orthosilicate 21, n-methylpyrrolidone 10, methyl tin mercaptide 0.6, triethanolamine oleate soap 1, film-forming assistant 3, catalyst 0.7, aniline 10 and initiator 1;
the catalyst is stannous sulfide; the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate; the film-forming additive is propylene glycol phenyl ether; the preparation method of the hydrophobic modifier solution comprises the following steps:
(1) adding tetraethyl orthosilicate into deionized water with the weight 35 times that of tetraethyl orthosilicate, uniformly stirring, adding methyl tin mercaptide, raising the temperature to 50 ℃, dropwise adding 10mol/l of ammonia water, adjusting the pH to 10, keeping the temperature and stirring for 1 hour, adding triethanolamine oleic acid soap, and stirring to normal temperature to obtain a saponification sol dispersion liquid;
(2) adding a film-forming aid into deionized water with the weight of 100 times that of the film-forming aid, uniformly stirring, adding aniline and n-methylpyrrolidone, and carrying out ultrasonic treatment for 3 minutes to obtain a monomer dispersion liquid;
(3) mixing the monomer dispersion liquid and the saponified sol dispersion liquid, uniformly stirring, adding an initiator, feeding into a reaction kettle, introducing nitrogen, keeping the temperature at 70 ℃, stirring for 2 hours, and discharging to obtain a saponified polymer solution;
(4) mixing the saponified polymer solution with heptadecafluorodecyltriethoxysilane and a catalyst, feeding the mixture into a polytetrafluoroethylene reaction kettle, adjusting the temperature of the reaction kettle to 35 ℃, magnetically stirring the mixture for 20 hours, discharging the mixture, and cooling the mixture to the normal temperature to obtain the hydrophobic modifier solution.
And (3) performance testing:
initial contact Angle test:
the contact angle of the obtained sample was measured with a contact angle measuring instrument (CAM 101 of KSV, finland), and the surface of the sample was photographed optically with a CAM101 lens with a measurement accuracy of ± 0.1 °. The testing environment is 23 +/-2) DEG C and RH is 50 +/-5 percent, the testing method is based on a sitting drop method, the principle is that water drops are placed on the surface of glass according to Young's equation, and the volume of the water drops is controlled to be 2-3
The test was completed within 2 s of the droplet contacting the glass.
And (3) testing the abrasion resistance:
the test was carried out in a specific testing machine, the friction head being a cylinder with a diameter of 16. + -. 0.1mm, the specimen being subjected to a load of 9. + -. 0.2N and a linear reciprocating stroke of 104. + -.3 mm. The rubbing cloth is cotton rubbing cloth, and meets the GB/T7568.2 standardThe grid is (50 +/-2) × (50 +/-2) mm2. During testing, the sample is fixed on the tester platform by the clamping device, so that the motion direction of the friction head is consistent with the length direction of the sample. The running speed was 1 reciprocating rubbing cycle per second for 10 cycles of rubbing. After the rubbing was completed, the contact angle was measured in the same manner as before the rubbing.
High and low temperature resistance:
the high and low temperature resistance performance is respectively used for testing the contact angle change conditions of the sample in low-temperature, high-temperature and high-low temperature circulating environments, and the specific test method is as follows:
placing the sample in an environment at (-40 +/-3) DEG C for 24 h, taking out the sample, placing the sample at room temperature for 1h, and testing the contact angle of the sample;
the sample was placed in a hot circulating air at 90. + -. 2 ℃ for 240 hours, and then the contact angle was measured after the sample was taken out and placed at room temperature for 1 hour.
High and low temperature cycle resistance: the cycle test was performed according to the following test conditions:
① storing in 40 + -2) deg.C RH 95% circulating air for 6 h;
② is stored at (-20 + -2) deg.C for 3 h;
③ storing in 40 + -2 deg.C RH 95% circulating air for 6 h;
④ is stored for 6h at the temperature of 85 plus or minus 2 ℃;
after 5 cycles, the sample was removed and the contact angle was measured after 1h at room temperature.
Moisture and scrub resistance:
moisture resistance: and testing by adopting a humidity tester, controlling the temperature of a water tank to be (60 +/-1) DEG C, testing for 100h, taking out a sample, standing for 1h at room temperature, and testing the contact angle.
Scrub resistance: the scrub resistance tester is adopted for testing, 0.5% of washing powder aqueous solution is dripped on the surface of hydrophobic glass through a water pump in the process of moving a brush back and forth and scrubbing, the hydrophobic glass sample is washed after 3000 times of circulation, the hydrophobic glass sample is dried for 20 min at the temperature of 105 ℃, the hydrophobic glass sample is taken out and placed for 1h at room temperature, and then the contact angle of the hydrophobic glass sample is tested.
High pressure cleaning resistance: and (3) testing by adopting a high-pressure cleaning machine, wherein the water pressure is 85 +/-5 bar, the water outlet temperature is 70 +/-5 ℃, and the distance between the nozzle of the spray pipe and the sample is 100 +/-5 mm, drying for 20 min at 105 ℃ after testing, taking out, standing for 1h at room temperature, and testing the contact angle.
Chemical solvent resistance:
the test method and the test period are respectively as follows:
①0.1 mol/L H2SO4soaking at 20 +/-2 ℃ for 2 h, soaking at ② 0.1.1 mol/L NaOH at 20 +/-2 ℃ for 2 h, soaking at ③ percent of vehicle window cleaning solution at 50 percent for 20 +/-2 ℃ for 168 h;
and after each test period is finished, washing the test sample by using deionized water and absolute ethyl alcohol respectively, and carrying out contact angle test after drying.
Xenon lamp aging resistance:
the xenon lamp aging resistance test is carried out according to GB/T1865, continuous illumination is carried out, and the drying period is 102 min; the wetting period is 18min, the black standard temperature is (65 +/-2) DEG C, the space temperature of the test chamber is (38 +/-3) DEG C, the relative air humidity is 40% -60% in the drying stage, and the illumination intensity is 0.51W/m2Wavelength 340 nm and test time 1000 h. After the test, the contact angle was measured.
And (3) testing the abrasion resistance:
table 1 shows the contact angles before and after the abrasion resistance test of the hydrophobic glass sample of the present invention and the conventional hydrophobic glass sample, respectively. Taking the contact angle value measured before the abrasion resistance performance test as an initial contact angle; and the difference value between the contact angle measured after the abrasion resistance test and the initial contact angle reflects the abrasion resistance of the hydrophobic film layer. As can be seen from the data in Table 1, the average contact angle of the conventional sample after friction is reduced by about 1.0%, while the average contact angle of the sample of the invention after friction is reduced by about 0.4%, so that the friction has no obvious influence on the hydrophobic performance of the hydrophobic film layer; the average initial contact angle of the traditional sample is 101.80 degrees, while the average initial contact angle of the sample of the invention is 107.18 degrees, which is higher than the former by about 5 degrees.
And (3) testing high and low temperature resistance:
table 2 shows the test data of heat resistance, cold resistance and high and low temperature cycle resistance of the hydrophobic glass sample of the present invention and the conventional hydrophobic glass sample, respectively. As can be seen from Table 2, after the high temperature, low temperature and high and low temperature cycling tests are carried out on the hydrophobic glass sample, the average contact angle is kept above 100 degrees, and the high and low temperature cycling resistance is only greatly reduced by about 3.2 percent; the traditional hydrophobic glass sample has good low temperature resistance and high and low temperature cycle resistance, basically does not change before and after the test, and has an average contact angle of 93.52 degrees after the high temperature resistance test, which is reduced by 8.1 percent compared with the initial performance. However, the average contact angle of the conventional hydrophobic glass samples was lower than that of the hydrophobic glass samples of the present invention both before and after the test.
Moisture and scrub resistance test:
table 3 shows the data of the moisture resistance, high pressure cleaning resistance and scrub resistance of the conventional hydrophobic glass sample and the hydrophobic glass sample of the present invention, respectively. As can be seen from Table 3, the initial average contact angle of the hydrophobic glass samples of the present invention was about 105, while the initial average contact angle of the conventional hydrophobic glass samples was about 101; after moisture resistance, high pressure cleaning resistance and scrubbing resistance tests, the average contact angles of the hydrophobic glass sample are 105.28 degrees, 103.46 degrees and 102.35 degrees respectively, the average contact angles of the traditional hydrophobic glass sample are 54.91 degrees, 103.14 degrees and 101.68 degrees respectively, and compared with the initial average contact angle, the hydrophobicity of the sample and the traditional sample after the tests are respectively attenuated by-0.6 percent, 2.1 percent, 2.6 percent and 46.0 percent, -1.8 percent and-0.8 percent. Therefore, the high pressure cleaning resistance and scrubbing resistance of the traditional hydrophobic glass sample are similar to those of the hydrophobic glass sample, and the humidity resistance of the traditional hydrophobic glass sample is poorer.
Chemical solvent resistance test:
table 4 shows the stability test data of the chemical solvent resistance of the conventional hydrophobic glass sample and the hydrophobic glass sample of the present invention, respectively. As can be seen from Table 4, the initial average contact angle of the hydrophobic glass samples of the present invention was about 105, while the initial average contact angle of the conventional hydrophobic glass samples was about 101; after acid resistance, alkali resistance and vehicle window cleaning fluid resistance tests, the average contact angles of the hydrophobic glass sample are respectively 103.14 degrees, 104.24 degrees and 103.76 degrees, the average contact angles of the traditional hydrophobic glass sample are respectively 98.99 degrees, 97.84 degrees and 104.97 degrees (the contact angles are increased after the test and are possibly abnormal values), and compared with the initial average contact angle, the hydrophobicity of the traditional sample and the sample of the invention are respectively attenuated by 2.1 percent, 0.5 percent, 1.3 percent, 2.6 percent, 3.4 percent and 3.5 percent after the test. Therefore, the acid and alkali resistance of the traditional hydrophobic glass sample is lower than that of the hydrophobic glass sample, and the performance of the traditional hydrophobic glass sample and the performance of the hydrophobic glass sample are similar to those of the hydrophobic glass sample.
And (3) xenon lamp aging resistance test:
table 5 shows the xenon lamp aging resistance test data of the hydrophobic glass sample of the present invention and the conventional hydrophobic glass sample, respectively. As can be seen from Table 5, the average contact angle of the conventional hydrophobic glass sample is obviously attenuated after the xenon lamp aging resistance test, and is reduced by about 8% compared with the initial average contact angle, while the xenon lamp aging resistance of the hydrophobic glass sample of the invention is relatively stable, and the hydrophobic property is only attenuated by 1.6%. In addition, the initial average contact angle of the sample is about 4 degrees higher than that of the traditional sample, and the average contact angle of the sample after aging test is about 10 degrees higher than that of the traditional sample.
Claims (1)
1. A preparation method of hydrophobic automobile glass based on an organic fluorosilane material is characterized by comprising the following steps:
degreasing glass by absolute ethyl alcohol, repeatedly polishing the glass by using polishing solution for a plurality of times, washing the glass by using deionized water to remove the polishing solution, drying a glass sample by using hot air, dipping hydrophobic modifier solution into dust-free paper to wipe the glass sample in a criss-cross manner, drying the glass for 10 to 30 minutes at the temperature of 100 ℃ plus material and 120 ℃ after wiping the glass sample to obtain the glass,
the hydrophobic modifier solution comprises the following raw materials in parts by weight:
5-7 parts of heptadecafluorodecyltriethoxysilane, 21-30 parts of tetraethyl orthosilicate, 10-15 parts of n-methyl pyrrolidone, 0.6-1 part of methyl tin mercaptide, 1-2 parts of triethanolamine oleate soap, 3-4 parts of a film-forming assistant, 0.7-1 part of a catalyst, 10-13 parts of aniline and 1-2 parts of an initiator;
the catalyst is stannous sulfide;
the initiator is one of ammonium persulfate, potassium persulfate and sodium persulfate;
the film-forming additive is propylene glycol phenyl ether;
the preparation method of the hydrophobic modifier solution comprises the following steps:
(1) adding tetraethyl orthosilicate into deionized water with the weight 35-40 times of that of tetraethyl orthosilicate, uniformly stirring, adding methyl tin mercaptide, raising the temperature to 50-60 ℃, dropwise adding 10-13mol/l of ammonia water, adjusting the pH to 10-12, keeping the temperature, stirring for 1-2 hours, adding triethanolamine oleic soap, and stirring to normal temperature to obtain a saponification sol dispersion liquid;
(2) adding the film-forming aid into deionized water which is 107 times of 100 times of the weight of the film-forming aid, uniformly stirring, adding aniline and n-methylpyrrolidone, and carrying out ultrasonic treatment for 3-5 minutes to obtain a monomer dispersion liquid;
(3) mixing the monomer dispersion liquid and the saponification sol dispersion liquid, stirring uniformly, adding an initiator, feeding into a reaction kettle, introducing nitrogen, stirring for 2-3 hours at the temperature of 70-80 ℃, and discharging to obtain a saponification polymer solution;
(4) mixing the saponified polymer solution with heptadecafluorodecyltriethoxysilane and a catalyst, feeding the mixture into a polytetrafluoroethylene reaction kettle, adjusting the temperature of the reaction kettle to 35-40 ℃, magnetically stirring the mixture for 20-30 hours, discharging the mixture, and cooling the mixture to the normal temperature to obtain the hydrophobic modifier solution.
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| CN105776887A (en) * | 2016-03-11 | 2016-07-20 | 奇瑞汽车股份有限公司 | Hydrophobic agent, hydrophobic glass, preparation method for hydrophobic agent, and preparation method for hydrophobic glass |
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| DE69709800T2 (en) * | 1996-08-19 | 2002-09-26 | Central Glass Co., Ltd. | Water-repellent glass pane and process for its manufacture |
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| CN102643029A (en) * | 2012-04-24 | 2012-08-22 | 奇瑞汽车股份有限公司 | Hydrophobic modification agent and hydrophobic glass modified by hydrophobic modification agent and method for preparing hydrophobic glass |
| CN103045079A (en) * | 2013-01-17 | 2013-04-17 | 奇瑞汽车股份有限公司 | Hydrophobic modifier for glass, preparation method thereof, hydrophobic glass as well as preparation method thereof |
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