CN106854042B - Preparation method of super-hydrophobic glass surface treating agent - Google Patents
Preparation method of super-hydrophobic glass surface treating agent Download PDFInfo
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- CN106854042B CN106854042B CN201611178246.3A CN201611178246A CN106854042B CN 106854042 B CN106854042 B CN 106854042B CN 201611178246 A CN201611178246 A CN 201611178246A CN 106854042 B CN106854042 B CN 106854042B
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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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a preparation method of a super-hydrophobic glass surface treating agent, which comprises the following steps: dissolving dialkoxy silane as an initial material in alcohol and water, adding acid to adjust the pH value to acidity, and heating and hydrolyzing for 2-8 hours at 40-70 ℃; adding alkali to make the solution alkaline, making silane undergo the polycondensation reaction, at 40-80 deg.C for 1-4 hr. Adding acid to adjust pH value to acidity, adding trialkoxysilane, heating and hydrolyzing at 40-70 deg.C for 2-8 hr; adding alkali to make the solution alkaline, then polycondensing at 40-80 deg.C for 1-4 hr, adding acid to regulate pH value of the solution to acidity. The molar ratio of dialkoxysilane to trialkoxysilane is between 10:1 and 20: 1. The invention solves the problems of poor surface durability, high production cost and poor applicability of the transparent super-hydrophobic glass. The super-hydrophobic coating with the contact angle larger than 120 degrees, the rolling angle lower than 10 degrees and good visible light transmission is achieved by covering the surface of the glass with the reticular nano-scale polymer.
Description
Technical Field
The invention relates to a preparation method of a super-hydrophobic glass surface treating agent, and also relates to a preparation method of a glass surface hydrophobic coating, in particular to a method for realizing the super-hydrophobic property of a glass surface by eliminating hydrophilic hydroxyl groups on the glass surface and simultaneously forming transparent nano-scale network-shaped cross-linked polysilane on the surface.
Background
The super-hydrophobic material is a material with a surface water contact angle larger than 150 degrees and a rolling angle smaller than 10 degrees, and has wide application potential in the field of surface modification of windshields of automobiles, airplanes and the like, high-rise building wall glass, common door and window glass, shower room glass, glasses and the like. At present, superhydrophobic surfaces can be prepared by two approaches, one is to modify a low surface energy substance on a surface with a certain roughness; the other is achieved by changing the roughness and surface micro-morphology of the material surface.
The main low surface energy materials are silicones and fluororesins and their corresponding modified resins. The organosilicon series compounds include siloxane resin, organosilicon rubber and modified substances thereof. The organic silicon resin has organopolysiloxane with highly branched chain structure, and has the characteristics of high and low temperature resistance, weather resistance, excellent electrical insulation, ozone resistance, chemical corrosion resistance, water resistance, moisture resistance, surface activity and the like, so the organic silicon resin is widely applied to antifouling paint.
Research shows that the contact angle between the surface of the material adopting the fluorosilane compound with the lowest surface energy and water is only 120 degrees to the maximum, namely, the low-surface-energy material is only the basic condition for preparing the super-hydrophobic surface, and the surface has enough roughness or the micro-nano structure with the surface similar to a lotus leaf can realize real surface hydrophobization.
The superhydrophobic and self-cleaning effects of lotus leaf surfaces have been well known as early as 90 s in the 20 th century. The deionized water drops are spherical on the lotus leaf surface, the lotus leaf surface is provided with a plurality of papilla with the diameter of 5-9 μm, the papilla is covered by a plurality of nano-scale waxy crystals, a large amount of air is stored between the convexo-concave, and when the water drops on the lotus leaf surface, the water drops can not penetrate into the lotus leaf but can freely roll on the lotus leaf surface due to the combined action of the air layer, the papilla and the waxy layer. However, for the glass surface, it is very challenging to construct a surface with micro-nano structure, transparency and low surface energy.
The following methods are adopted in the literature which have been reported so far: rao【1】And preparing the silica sol with the surface covered by Si-CH3 groups by a sol-gel method by using methyltrimethoxysilane as a precursor and ammonium hydroxide as a catalyst. Shirtcliffe【2】The organic silicon super-hydrophobic film is prepared by using a sol-gel method and combining a phase separation technology and using methyltriethoxysilane as a precursor, and the conversion condition between hydrophobicity and water absorbability is discussed. Karuppuchamay【3】Preparing amorphous super-hydrophilic titanium dioxide coatings and hydrophobic amorphous titanium dioxide coatings on the surfaces of Indium Tin Oxide (ITO) glass substrates from aqueous solutions of titanium peroxide complexes by an electrodeposition method. Tsoi【4】The method comprises depositing a layer of Si0 with columnar structure on a conductive glass substrate by GLAD deposition2The contact angle between the surface of the film and water reaches more than 150 degrees after the surface of the film is modified by fluoroalkyl silane. The method generally has the defects of complex process, high production cost and the like.
Compared with the prior art, the invention combines the mechanism of glass surface hydrophilicity, and provides a method for constructing the crosslinked silane nano-film while eliminating the hydroxyl on the glass surface to realize the super-hydrophobic property of the glass surface.
Reference to the literature
【1】Satoh J K Nakazumi H，Morita M，Preparation of super water repellent fluor inated inorganic organic coating films on nylon 66by the sol gel methodusing micropHase separation[J].Journal of Sol Gel and Technology,2003，27：327-329.
【2】Rao A V Manish M K Amalnerkar D P，SuperhydropHobic silica aerogels based on methyltrimethoxysilane precursor[J].Journal of Non Crystalline Solids，2003，330(1-3)：187-195.
【3】Shirtliffe N J，Mchale Isl Newton M I，Intrinsically super hydropHobic organosilica sol gel Foams[J].Langmuir,2003，19(14)：5626-5631.
【4】Tsoi S，Fok E，Sit C，SuperhydropHobic，high surface area，3-D Si02nanostructurcs through siloxane based surface functionalization[J].Langmuir,2004，20：10771-10774.
Disclosure of Invention
The invention aims to provide a simple preparation method of a transparent super-hydrophobic coating which is easy to put into practical application, and solves the problems of poor durability, high production cost and poor applicability of the transparent super-hydrophobic surface. The super-hydrophobic coating with the contact angle larger than 150 degrees, the rolling angle lower than 10 degrees and good visible light transmission is achieved by covering the surface of the glass with the reticular nano-scale polymer.
The technical scheme for realizing the purpose of the invention is that a silane prepolymer is prepared by utilizing the characteristic of high reaction activity of silicon hydroxyl obtained by hydrolyzing silane and hydroxyl on the surface of glass, and silane crosslinking is realized by utilizing polyfunctional silane at the later stage of reaction.
The preparation method of the super-hydrophobic glass surface treating agent is characterized by comprising the following steps:
dissolving dialkoxy silane serving as an initiator in alcohol and water to form a solution with the mass percent concentration of 20-40%, wherein the mass ratio of the alcohol to the water is 12:1-15: 1; adding acid to adjust pH value to acidity, heating and hydrolyzing at 40-70 deg.C for 2-8 hr; adding alkali to make the solution alkaline, performing silane polycondensation, and performing polycondensation for 1-4 hours at 40-80 ℃; adding acid to adjust pH value to acidity, adding trialkoxysilane, heating and hydrolyzing at 40-70 deg.C for 2-8 hr; adding alkali to make the solution alkaline, then polycondensing at 40-80 deg.C for 1-4 hr, adding acid to regulate pH value of the solution to make mole ratio of acidic dialkoxysilane and trialkoxysilane be between 10:1 and 20: 1. And finally adding ethanol for dilution for later use.
The molecular formula of the dialkoxysilane is R1R2Si(OR3)2,R1、R2＝CH3,C2H5,C3H7,C8H17，C12H25，C16H33，C18H37，F3C3H4，F13C8H4，F17C10H4，R3＝CH3,C2H5Or C3H7The molecular formula of the trialkoxysilane is R1′Si(OR2′)3,R1′、R2′＝CH3,C2H5Or C3H7。
The added alcohol is ethanol, propanol or isopropanol.
The acid added is acetic acid, oxalic acid, phosphoric acid, hydrochloric acid, sulfuric acid or nitric acid.
The alkali is ammonia water, triethanolamine, sodium ethoxide or sodium hydroxide.
Compared with the prior art, the invention has the advantages that:
(1) the glass surface hydrophobic treatment agent prepared by the invention has the advantages of simple process, good durability and low cost.
(2) The super-hydrophobic surface prepared by the invention has a very large contact angle and a very small rolling angle, and water drops can roll freely on the surface and take away dust.
(3) The super-hydrophobic transparent coating prepared by the method has good visible light transmission, and can be applied to windshields of automobiles, airplanes and the like, and door and window glass, partition glass, show window glass, glass curtain walls, shower room glass and other occasions of buildings and structures.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
(1) Preparation of the coating
To 5g of methylhexadecyl dimethoxysilane were added 12g of ethanol and 1g of water, and oxalic acid (C)2H2O4) Adjusting the pH value of the solution to 2, heating and hydrolyzing for 2h at 65 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 60 ℃, adding oxalic acid to adjust the pH value of the solution to 2, then adding 0.2g of methyltrimethoxysilane, heating and hydrolyzing for 2h at 65 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 60 ℃, adding oxalic acid to adjust the pH value of the solution to 2, and finally adding ethanol for later use.
(2) Surface coating film for base material
And (2) preparing a membrane by adopting a smearing method, soaking a soft cloth in the solution prepared in the step (1), and repeatedly wiping the surface of the glass sheet by using the soft cloth to clean the surface of the glass sheet to obtain the transparent cross-linked nano super-hydrophobic membrane on the surface of the glass sheet.
The visible light transmittance of the untreated glass sheet was measured to be 87.2 and the visible light transmittance of the coated glass sheet was measured to be 87.2 according to GB/T2680-1994 standard.
The contact angle of the coated glass sheet was found to be 132 ℃ according to GB/T31815-2015 standard.
Example 2
(1) Preparation of the coating
To 5g of methylhexadecyl dimethoxysilane were added 15g of ethanol and 1g of water, and oxalic acid (C)2H2O4) Adjusting pH to 4, heating at 70 deg.C for hydrolysis for 2h, adding 25% ammonia water dropwise to adjust pH to 10, polymerizing at 65 deg.C for 2h, adding oxalic acid to adjust pH to 4, adding 0.2g methyltrimethoxysilane, heating at 70 deg.C for hydrolysis for 2h, adding 25% ammonia water dropwise to adjust pHRegulating the pH value of the solution to 10, polymerizing for 2 hours at 65 ℃, adding oxalic acid to regulate the pH value of the solution to 4, and finally adding ethanol for later use.
(2) Surface coating film for base material
And (2) preparing a membrane by adopting a smearing method, soaking a soft cloth in the solution prepared in the step (1), and repeatedly wiping the surface of the glass sheet by using the soft cloth to clean the surface of the glass sheet to obtain the transparent cross-linked nano super-hydrophobic membrane on the surface of the glass sheet.
The visible light transmittance of the untreated glass sheet was measured to be 87.2 and the visible light transmittance of the coated glass sheet was measured to be 87.2 according to GB/T2680-1994 standard.
The contact angle of the coated glass sheet was found to be 132 ℃ according to GB/T31815-2015 standard.
Example 3
(1) Preparation of the coating
To 8g of heptadecafluorodecylmethyldimethoxysilane were added 12g of ethanol and 1g of water, and acetic acid (C)2H4O2) Adjusting the pH value of the solution to 3, heating and hydrolyzing for 2h at 70 ℃, then dripping 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 80 ℃, adding oxalic acid to adjust the pH value of the solution to 3, then adding 0.2g of methyltrimethoxysilane, heating and hydrolyzing for 2h at 70 ℃, then dripping 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 80 ℃, adding oxalic acid to adjust the pH value of the solution to 3, and finally adding ethanol for later use.
(2) Surface coating film for base material
And (2) preparing a membrane by adopting a smearing method, soaking a soft cloth in the solution prepared in the step (1), and repeatedly wiping the surface of the glass sheet by using the soft cloth to clean the surface of the glass sheet to obtain the transparent cross-linked nano super-hydrophobic membrane on the surface of the glass sheet.
The visible light transmittance of the untreated glass sheet was measured to be 87.2 and the visible light transmittance of the coated glass sheet was measured to be 87.2 according to GB/T2680-1994 standard.
The contact angle of the coated glass sheet was measured to be 135 ℃ according to GB/T31815-2015 standard.
Example 4
(1) Preparation of the coating
5g of 8g heptadecafluorodecylmethyldimethoxysilane were added with 12g of isopropanol and1g of water, and oxalic acid (C) was added2H2O4) Adjusting the pH value of the solution to 3, heating and hydrolyzing for 2h at 40 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 45 ℃, adding oxalic acid to adjust the pH value of the solution to 3, then adding 0.15g of methyltrimethoxysilane, heating and hydrolyzing for 2h at 40 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 45 ℃, adding oxalic acid to adjust the pH value of the solution to 3, and finally adding isopropanol for later use.
(2) Surface coating film for base material
And (2) preparing a membrane by adopting a smearing method, soaking a soft cloth in the solution prepared in the step (1), and repeatedly wiping the surface of the glass sheet by using the soft cloth to clean the surface of the glass sheet to obtain the transparent cross-linked nano super-hydrophobic membrane on the surface of the glass sheet.
The visible light transmittance of the untreated glass sheet was measured to be 87.2 and the visible light transmittance of the coated glass sheet was measured to be 87.2 according to GB/T2680-1994 standard.
The contact angle of the coated glass sheet was measured to be 133 ℃ according to GB/T31815-2015 standard.
Example 5
(1) Preparation of the coating
To 4g of methyldodecyldiethoxysilane were added 12g of ethanol and 1g of water, and oxalic acid (C)2H2O4) Adjusting the pH value of the solution to 2, heating and hydrolyzing for 2h at 50 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 40 ℃, adding oxalic acid to adjust the pH value of the solution to 2, then adding 0.2g of methyltrimethoxysilane, heating and hydrolyzing for 2h at 50 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 40 ℃, adding oxalic acid to adjust the pH value of the solution to 2, and finally adding ethanol for later use.
(2) Surface coating film for base material
And (2) preparing a membrane by adopting a smearing method, soaking a soft cloth in the solution prepared in the step (1), and repeatedly wiping the surface of the glass sheet by using the soft cloth to clean the surface of the glass sheet to obtain the transparent cross-linked nano super-hydrophobic membrane on the surface of the glass sheet.
The visible light transmittance of the untreated glass sheet was measured to be 87.2 and the visible light transmittance of the coated glass sheet was measured to be 87.2 according to GB/T2680-1994 standard.
The contact angle of the coated glass sheet was found to be 132 ℃ according to GB/T31815-2015 standard.
Example 6
(1) Preparation of the coating
To 4g of methyldodecyldiethoxysilane were added 12g of ethanol and 1g of water, and oxalic acid (C)2H2O4) Adjusting the pH value of the solution to 3, heating and hydrolyzing for 2h at 60 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9, polymerizing for 2h at 65 ℃, adding oxalic acid to adjust the pH value of the solution to 3, then adding 0.2g of methyltrimethoxysilane, heating and hydrolyzing for 2h at 60 ℃, then dropwise adding 25% ammonia water to adjust the pH value of the solution to 9-10, polymerizing for 2h at 65 ℃, adding oxalic acid to adjust the pH value of the solution to 2-4, and finally adding ethanol for later use.
(2) Surface coating film for base material
And (2) preparing a membrane by adopting a smearing method, soaking a soft cloth in the solution prepared in the step (1), and repeatedly wiping the surface of the glass sheet by using the soft cloth to clean the surface of the glass sheet to obtain the transparent cross-linked nano super-hydrophobic membrane on the surface of the glass sheet.
The visible light transmittance of the untreated glass sheet was measured to be 87.2 and the visible light transmittance of the coated glass sheet was measured to be 87.2 according to GB/T2680-1994 standard.
The contact angle of the coated glass sheet was found to be 132 ℃ according to GB/T31815-2015 standard.
Claims (5)
1. The preparation method of the super-hydrophobic glass surface treating agent is characterized by comprising the following steps:
dissolving dialkoxy silane serving as an initiator in alcohol and water to form a solution with the mass percent concentration of 20-40%, wherein the mass ratio of the alcohol to the water is 12:1-15: 1; adding acid to adjust pH value to acidity, heating and hydrolyzing at 40-70 deg.C for 2-8 hr; adding alkali to make the solution alkaline, performing silane polycondensation, and performing polycondensation for 1-4 hours at 40-80 ℃; adding acid to adjust pH value to acidity, adding trialkoxysilane, heating and hydrolyzing at 40-70 deg.C for 2-8 hr; adding alkali to make the solution alkaline, polycondensing at 40-80 deg.C for 1-4 hr, adding acid to adjust pH value of the solution to acidity, and the molar ratio of dialkoxysilane to trialkoxysilane is 10: 1-20: 1.
2. The method of claim 1, wherein said dialkoxysilane has the formula R1R2Si(OR3)2,R1、R2＝CH3,C2H5,C3H7,C8H17，C12H25，C16H33，C18H37，F3C3H4，F13C8H4，F17C10H4，R3＝CH3,C2H5Or C3H7The molecular formula of the trialkoxysilane is R1′Si(OR2′)3,R1′、R2′＝CH3,C2H5Or C3H7。
3. The process according to claim 1, wherein the alcohol is ethanol, propanol or isopropanol.
4. The method according to claim 1, wherein the acid added is acetic acid, oxalic acid, phosphoric acid, hydrochloric acid, sulfuric acid or nitric acid.
5. The method according to claim 1, wherein the base is ammonia, triethanolamine, sodium ethoxide or sodium hydroxide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101817980A (en) * | 2010-04-22 | 2010-09-01 | 复旦大学 | Sol-gel preparation method of silica-based superhydrophobic thin films |
| CN101863625A (en) * | 2009-04-17 | 2010-10-20 | 信义汽车玻璃(东莞)有限公司 | Hydrophobic solution, hydrophobic glass for vehicle and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2015013464A1 (en) * | 2013-07-23 | 2015-01-29 | Lotus Leaf Coatings, Inc. | Process for preparing an optically clear superhydrophobic coating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863625A (en) * | 2009-04-17 | 2010-10-20 | 信义汽车玻璃(东莞)有限公司 | Hydrophobic solution, hydrophobic glass for vehicle and manufacturing method thereof |
| CN101817980A (en) * | 2010-04-22 | 2010-09-01 | 复旦大学 | Sol-gel preparation method of silica-based superhydrophobic thin films |
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