CN102718413B - Water repellent agent and preparation method of water repellent agent as well as hydrophobic glass and preparation method of hydrophobic glass - Google Patents
Water repellent agent and preparation method of water repellent agent as well as hydrophobic glass and preparation method of hydrophobic glass Download PDFInfo
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- CN102718413B CN102718413B CN201210219657.8A CN201210219657A CN102718413B CN 102718413 B CN102718413 B CN 102718413B CN 201210219657 A CN201210219657 A CN 201210219657A CN 102718413 B CN102718413 B CN 102718413B
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- water
- hydrophobizing agent
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- 239000011521 glass Substances 0.000 title claims abstract description 239
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 113
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 230000002940 repellent Effects 0.000 title abstract 7
- 239000005871 repellent Substances 0.000 title abstract 7
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 229920002545 silicone oil Polymers 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 claims abstract description 5
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 238000007711 solidification Methods 0.000 claims description 14
- 230000008023 solidification Effects 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- -1 methyl trifluoro propyl Chemical group 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims description 5
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- XLXGCFTYXICXJF-UHFFFAOYSA-N ethylsilicon Chemical compound CC[Si] XLXGCFTYXICXJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 26
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000001035 drying Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention provides a water repellent agent and a preparation method of the repellent agent as well as hydrophobic glass and a preparation method of the hydrophobic glass. The preparation method of the water repellent agent comprises the following steps of: (1) mixing a silicon-containing substance, acid, water and an organic solvent and agitating to obtain a mixture, wherein the silicon-containing substance is R-SiX3 or silicone oil; the R in the R-SiX3 is alkyl or halogenated alkyl with the carbon atom number which is more than or equal to 8; and the X is any one of halogen atom, alkoxy, acyloxy, amino and aminoxy; and (2) adding a silane coupling agent into the mixture of the step (1) and agitating to obtain the water repellent agent for the glass. A sliding angle of the hydrophobic glass prepared by the water repellent agent is greatly reduced and even tiny water drops can easily slip off on the surface of the hydrophobic glass, so that the hydrophobic performance of the glass is greatly improved.
Description
Technical field
The present invention relates to Hydrophobic glass technical field, be specifically related to a kind of hydrophobizing agent and preparation method thereof, Hydrophobic glass and preparation method thereof.
Background technology
Silicate glass surface is high energy, water-wetted surface, and water droplet can make glass transmission be deteriorated on glass during unordered expansion, bring a lot of inconvenience to people's live and work.Automobile is when the rainy day travels, and rainwater can form water curtain on windshield glass, side door glass and back-mirror glass surface.Especially, under night rain environment, the water curtain of glass surface can reflect various light and have a strong impact on pilot's line of vision.Even if glass surface adopts wiper also can there is a lot of dead angle, the dead angle of these glass surfaces can increase traffic accident probability when running into the globule and gathering.And for side door and rear vision mirror, wiper is then helpless.
At present, most of automobile can travel visual field fuzzy problem at its Qianmen glass surface plating hydrophobic coating to solve the rainy day when dispatching from the factory.Simultaneously, market also there is the rainproof coated product of glass for Motor Maintenance, but all there is the excessive shortcoming of slide angle in these products at present, namely small water droplet drops on film surface can not landing rapidly, can stick to film surface on the contrary, even sitting down at certain wind-force and vibration still can not landing.Especially during light rain, the water droplet that small rain droplets drops on glass surface formation is very tiny, small water droplet sticks to glass surface and is more difficult to landing, has a strong impact on the degree of getting a clear view of officer, thus the visual field fuzzy problem making hydrophobic film layer can not solve glass surface water accumulation pearl and cause.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of hydrophobizing agent and preparation method thereof, Hydrophobic glass and preparation method thereof are provided, preparation method is simple for this hydrophobizing agent, the surface of the Hydrophobic glass obtained by this hydrophobizing agent has submissive type chain alkyl low-surface energy substance, the liquid film layer that this material is formed significantly reduces water droplet slide angle thereon, even small water droplet is also easy to landing, improve the hydrophobic function of hydrophobic film layer.
The technical scheme that solution the technology of the present invention problem adopts is a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) silicon-containing material, acid, water are mixed with organic solvent, stir and obtain mixture,
Wherein, described silicon-containing material is R-SiX
3or silicone oil, described R-SiX
3in R be straight chained alkyl or the halogenated straight alkyl that carbonatoms is more than or equal to 8, X is any one in halogen atom, alkoxyl group, acyloxy, amino and aminooxy;
(2) in the mixture in step (1), add silane coupling agent, stir the hydrophobizing agent obtained for glass.
Above-mentioned R-SiX
3be submissive type long-chain low-surface energy substance with silicone oil, use it for and prepare glass hydrophobizing agent.This hydrophobizing agent being used for glass can reduce the slide angle of glass surface greatly, even if small water droplet is also easy to landing at glass surface, substantially increases the degree of getting a clear view of officer.
Preferably, in described step (1), the carbonatoms in R is less than or equal to 30.
Preferably, when the X in described step (1) contains carbon atom, carbonatoms is less than or equal to 10.
Preferably, the silicone oil in described step (1) is one or more mixtures in methyl-silicone oil, ethyl silicon oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil.
Preferably, described step (1) plants the acid added is one or several mixtures in hydrochloric acid, nitric acid, sulfuric acid, acetic acid or hydrofluoric acid.
Preferably, the organic solvent in described step (1) is one or more mixtures in ethanol, ethyl acetate, acetone, methyl alcohol.
Preferably, the whipping temp in described step (1) is 15 ~ 45 DEG C, and churning time is 1 ~ 5 hour.
Preferably, the churning time of described step (2) is 2 ~ 20 hours.
Preferably, silane coupling agent in described step (2) is one or more mixtures in 3-aminopropyl triethoxysilane, γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.
The mass fraction of the silicon-containing material in described step (1) is 1 ~ 5 part, and the mass fraction of acid is 0.1 ~ 2 part, and the mass fraction of water is 0.5 ~ 5 part, and the mass fraction of organic solvent is 90 ~ 98 parts; Wherein the mass fraction of acid is the mass fraction of pure acid;
The mass fraction of the silane coupling agent in described step (2) is 0.5 ~ 5 part.
The present invention also provides a kind of hydrophobizing agent for glass, and it is prepared by aforesaid method.
The present invention also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, SiX ' is added
4with the mixing solutions of water, cleaned glass is put in the atmosphere of this encloses container, wherein X ' be halogen atom, any one in alkoxyl group, acyloxy, amino and aminooxy;
(2) take out the glass in step (1), form hydrophobic film layer with the hydrophobizing agent for glass prepared by aforesaid method at glass surface, after the hydrophobic film layer solidification of glass surface, obtain Hydrophobic glass.
Preferably, time in the X ' in described step (1) containing carbon atom, carbonatoms is less than or equal to 10.
Preferably, the cleaning process of the glass in the step (1) of the preparation method of described Hydrophobic glass is specially: by 1 ~ 5 part of hydrochloric acid (or sulfuric acid, nitric acid, acetic acid and hydrofluoric acid), 1 ~ 5 part of cerium rouge and 5 ~ 50 parts of water mixing and stirring, with its cleaning glass window surface, then clean glass surface, obtain cleaned glass.
Preferably, in described step (1), described being put into by cleaned glass in the atmosphere of this encloses container is specially: cleaned glass, in the atmosphere of encloses container, places 15min ~ 60min, wherein SiX ' at 15 ~ 60 DEG C
4be (1: 1) ~ (10: 1) with the mol ratio of water.For chlorine atom, its reaction process is as follows:
SiCl
4+H
2O→Si(OH)
4
Si (OH)
4the silanol of+HO-Si-(glass surface) →-Si-O-Si (OH)
3
By this pre-treatment, increase the silanol that glass surface can react, improve active, increase the active site of glass surface by this kind of method, the smooth degree of glass surface can well be kept, contribute to the slide angle reducing glass surface.
Preferably, form the method for hydrophobic film layer at glass surface in described step (2) to comprise: any one in lift plated film, manual blade coating, mechanical blade coating, spraying.
Preferably, in described step (2), the curing of hydrophobic film layer be had on surface the glass of hydrophobic film layer to be placed on temperature is 80 ~ 120 DEG C, relative humidity be in the environment of 60 ~ 90% place 15 ~ 120min.
The invention provides a kind of Hydrophobic glass, it is prepared by above-mentioned method.
In the pretreatment process of glass of the present invention, silanol is formed by siliceous compounds hydrolysis, and react with the silanol of glass surface thus form network-like silanol structure at glass surface, and add more active site than original glass surface, better can also keep the smooth degree of glass surface simultaneously, be conducive to the slide angle reducing glass surface.Material containing submissive type chain alkyl in hydrophobizing agent has received glass surface by coupling agent submissive type chain alkyl, thus makes Hydrophobic glass have good hydrophobic performance, even very little water droplet is dropped in hydrophobic glass surface, is also easy to landing.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
In following embodiment, the cleaning process of sheet glass is specially: by the hydrochloric acid (or sulfuric acid, nitric acid, acetic acid and hydrofluoric acid) of 1 ~ 5 mass parts, the cerium rouge of 1 ~ 5 mass parts and the water mixing and stirring of 5 ~ 50 mass parts, with its cleaning glass window surface, then clean glass surface, obtain cleaned glass.
Embodiment 1
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 1 mass parts
18h
37siCl
3, HCl containing 1 mass parts mass percent concentration be that the hydrochloric acid soln of 30% and the water (comprising the water in hydrochloric acid soln) of 3 mass parts join in the ethyl acetate solvent of 93 mass parts, stir at 30 DEG C and obtain mixture in 5 hours;
(2) in mixture, drip N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane of 3 mass parts, be added dropwise to complete rear continuation stirring 12 hours, obtain the hydrophobizing agent for glass.
Said n-C
18h
37siCl
3for submissive type long-chain low-surface energy substance, use it for and prepare glass hydrophobizing agent.This hydrophobizing agent being used for glass can reduce the slide angle of glass surface greatly, even if small water droplet is also easy to landing at glass surface, substantially increases the degree of getting a clear view of officer.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (OCOC is added
2h
5)
4with the mixing solutions of water, wherein Si (OCOC
2h
5)
4be 5: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 15 DEG C, place 35min;
(2) stand-by after taking out glass drying, the method of lift plated film is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 120 DEG C, relative humidity is place 120min in the environment of 80% to be had on surface the glass of hydrophobic film layer to be placed on, and obtains Hydrophobic glass after the hydrophobic film layer solidification of glass surface.
In step (1), its reaction process is as follows:
Si(OCOC
2H
5)
4+H
2O→Si(OH)
4
Si (OH)
4the silanol of+HO-Si-(glass surface) →-Si-O-Si (OH)
3
In the pretreatment process of glass, silanol is formed by siliceous compounds hydrolysis, and react with the silanol of glass surface thus form network-like silanol structure at glass surface, and add more active site than original glass surface, better can also keep the smooth degree of glass surface simultaneously, be conducive to the slide angle reducing glass surface.
Material containing submissive type chain alkyl in hydrophobizing agent has received glass surface by coupling agent submissive type chain alkyl, thus makes Hydrophobic glass have good hydrophobic performance, even very little water droplet is dropped in hydrophobic glass surface, is also easy to landing.
The sample keeping level drips the water droplet of 10 μ L, and then, tilt this sample gradually, measures the angle of inclination of horizontal plane and sample when water droplet starts to slide, and record slide angle is 17 °.
Embodiment 2
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the CF of 5 mass parts
3(CF
2)
7(CH
2)
2si (NH
2)
3, H containing 2 mass parts
2sO
4mass percent concentration be that the sulphuric acid soln of 50% and the water (comprising the water in sulphuric acid soln) of 3 mass parts join in the formic acid solvent of 95 mass parts, at 15 DEG C stir within 2 hours, obtain mixture;
(2) in mixture, drip γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane of 5 mass parts, be added dropwise to complete rear continuation stirring 10 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, SiF is added
4with the mixing solutions of water, wherein SiF
4be 4: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 60 DEG C, place 60min;
(2) stand-by after taking out glass drying, the method of blade coating is by hand made to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 80 DEG C, relative humidity is place 15min in the environment of 60% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 19 °.
Embodiment 3
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) be that the hydrofluoric acid solution of 40% and the water (comprising the water in hydrofluoric acid solution) of 3 mass parts join in the alcohol solvent of 94 mass parts by the mass percent concentration of the methyl-silicone oil of 2.5 mass parts and methylhydroxy silicone oil (mass ratio of methyl-silicone oil and methylhydroxy silicone oil is 1: 1), HF containing 0.5 mass parts, stir at 45 DEG C and obtain mixture in 3 hours;
(2) in mixture, drip the 3-aminopropyl triethoxysilane of 0.5 mass parts, be added dropwise to complete rear continuation stirring 2 hours, obtain the hydrophobizing agent for glass.
Above-mentioned methyl-silicone oil and methylhydroxy silicone oil are submissive type long-chain low-surface energy substance, use it for and prepare glass hydrophobizing agent.This hydrophobizing agent being used for glass can reduce the slide angle of glass surface greatly, even if small water droplet is also easy to landing at glass surface, substantially increases the degree of getting a clear view of officer.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, SiCl is added
4with the mixing solutions of water, wherein SiCl
4be 6: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 30 DEG C, place 20min;
(2) stand-by after taking out glass drying, the method of spraying is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 110 DEG C, relative humidity is place 30min in the environment of 65% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 15 °.
Embodiment 4
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the hydrochloric acid of the methyl trifluoro propyl silicone oil of 3 mass parts, HCl and HF containing 0.1 mass parts and hydrofluoric acid mixing solutions, (mass ratio of HCl and HF is 2: 1, mixing solutions is mixed by the hydrochloric acid soln of 30% and the hydrofluoric acid solution of 40%), the water of 0.5 mass parts (comprising the water in hydrochloric acid and hydrofluoric acid mixing solutions) joins in the propanol solvent of 90 mass parts, stir at 20 DEG C and obtain mixture in 1 hour;
(2) in mixture, drip 3-aminopropyl triethoxysilane and 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane (mass ratio of 3-aminopropyl triethoxysilane and 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane is 1: 3) of 0.5 mass parts, be added dropwise to complete rear continuation stirring 20 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (OCH is added
3)
4with the mixing solutions of water, wherein Si (OCH
3)
4be 10: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 40 DEG C, place 15min;
(2) stand-by after taking out glass drying, the method of mechanical blade coating is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 105 DEG C, relative humidity is place 50min in the environment of 90% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 20 °.
Embodiment 5
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 5 mass parts
16h
33si (ONH
2)
3, HNO containing 0.8 mass parts
3mass percent concentration be that the salpeter solution of 50% and the water of 2.5 mass parts join (comprising the water in salpeter solution) in the ethanol of 91 mass parts and the mixed solvent (mass ratio of ethanol and ethyl acetate is 2: 3) of ethyl acetate, at 35 DEG C stir within 2.5 hours, obtain mixture;
(2) in mixture, drip 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane of 4.5 mass parts, be added dropwise to complete rear continuation stirring 15 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (OC is added
10h
21)
4with the mixing solutions of water, wherein Si (OC
10h
21)
4be 8: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 35 DEG C, place 50min;
(2) stand-by after taking out glass drying, the method of mechanical blade coating is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 100 DEG C, relative humidity is place 90min in the environment of 85% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 18 °.
Embodiment 6
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 4 mass parts
45h
91si (OCH
3)
3, HAc containing 1.5 mass parts mass percent concentration be that the acetic acid solution of 70% and the water (comprising the water in acetic acid solution) of 1.5 mass parts join in the formic acid solvent of 98 mass parts, stir at 25 DEG C and obtain mixture in 4 hours;
(2) in mixture, drip γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane of 4 mass parts, be added dropwise to complete rear continuation stirring 18 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (OC is added
3h
7)
4, Si (OC
9h
19)
4(Si (OC
3h
7)
4with Si (OC
9h
19)
4ratio of quality and the number of copies be 2: 1) and the mixing solutions of water, wherein Si (OC
3h
7)
4with Si (OC
9h
19)
4mixture and the mol ratio of water be 1: 1, cleaned glass is put in the atmosphere of this encloses container, at 45 DEG C, places 40min;
(2) stand-by after taking out glass drying, the method of spraying is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 115 DEG C, relative humidity is place 60min in the environment of 70% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 16 °.
Embodiment 7
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the hydrochloric acid of the MethylethoxylsiliconFluid Fluid of 2 mass parts and methyl vinyl silicon oil (mass ratio of MethylethoxylsiliconFluid Fluid and methyl vinyl silicon oil is 2: 1), HCl and HF containing 1.5 mass parts and hydrofluoric acid mixing solutions, (mass ratio of HCl and HF is 1: 2, mixing solutions is mixed by the hydrochloric acid soln of 30% and the hydrofluoric acid solution of 40%) and the water (comprising the water in hydrochloric acid and hydrofluoric acid mixing solutions) of 3.5 mass parts join in the propanol solvent of 97 mass parts, at 20 DEG C stir within 2 hours, obtain mixture;
(2) in mixture, drip the 3-aminopropyl triethoxysilane of 3.5 mass parts, be added dropwise to complete rear continuation stirring 19 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (OCOC is added
4h
9)
4with the mixing solutions of water, wherein Si (OCOC
4h
9)
4be 7: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 55 DEG C, place 60min;
(2) stand-by after taking out glass drying, the method of blade coating is by hand made to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 95 DEG C, relative humidity is place 15min in the environment of 90% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 15 °.
Embodiment 8
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the CF of 2 mass parts
3(CF
2)
5(CH
2)
2siF
3, HCl containing 1 mass parts mass percent concentration be that the hydrochloric acid soln of 30% and the water (comprising the water in hydrochloric acid soln) of 4.5 mass parts join in the ethyl acetate solvent of 94 mass parts, stir at 15 DEG C and obtain mixture in 5 hours;
(2) in mixture, drip 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane of 1 mass parts, be added dropwise to complete rear continuation stirring 6 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (OCOC is added
6h
13)
4with the mixing solutions of water, wherein Si (OCOC
6h
13)
4be 5: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 20 DEG C, place 30min;
(2) stand-by after taking out glass drying, the method of lift plated film is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 85 DEG C, relative humidity is place 35min in the environment of 75% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 20 °.
Embodiment 9
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 3 mass parts
20h
41si (OC
10h
21)
3and n-C
30h
61si (OC
2h
5)
3(n-C
20h
41si (OC
10h
21)
3and n-C
30h
61si (OC
2h
5)
3ratio of quality and the number of copies be 2: 1), the mass percent concentration of HAc containing 2 mass parts is that the acetic acid solution of 70% and the water (comprising the water in acetic acid solution) of 4 mass parts join in the alcohol solvent of 96 mass parts, stir at 45 DEG C and obtain mixture in 4 hours;
(2) in mixture, drip N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane of 5 mass parts, be added dropwise to complete rear continuation stirring 8 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (NH is added
2)
4with the mixing solutions of water, wherein Si (NH
2)
4be 9: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 50 DEG C, place 15min;
(2) stand-by after taking out glass drying, the method of mechanical blade coating is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 90 DEG C, relative humidity is place 70min in the environment of 75% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 17 °.
Embodiment 10
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 0.5 mass parts
30h
61si (OC
2h
5)
3, HNO containing 1.8 mass parts
3mass percent concentration be that the salpeter solution of 50% and the water (comprising the water in salpeter solution) of 5 mass parts join in the ethyl acetate solvent of 92 mass parts, at 30 DEG C stir within 3 hours, obtain mixture;
(2) in mixture, drip the 3-aminopropyl triethoxysilane of 2 mass parts, be added dropwise to complete rear continuation stirring 11 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, Si (ONH is added
2)
4with the mixing solutions of water, wherein Si (ONH
2)
4be 10: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 60 DEG C, place 35min;
(2) stand-by after taking out glass drying, the method of lift plated film is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 80 DEG C, relative humidity is place 55min in the environment of 60% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 20 °.
Embodiment 11
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 1 mass parts
8h
17si (OCOC
7h
15)
3with methyl-silicone oil (n-C
8h
17si (OCOC
7h
15)
3be 1: 2 with the ratio of quality and the number of copies of methyl-silicone oil), the mass percent concentration of HF containing 1.7 mass parts is that the hydrofluoric acid solution of 40% and the water (comprising the water in hydrofluoric acid solution) of 3 mass parts join in the alcohol solvent of 98 mass parts, stir at 35 DEG C and obtain mixture in 1 hour;
(2) in mixture, drip γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane of 1.5 mass parts, be added dropwise to complete rear continuation stirring 14 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, SiCl is added
4with the mixing solutions of water, wherein SiCl
4be 1: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 15 DEG C, place 55min;
(2) stand-by after taking out glass drying, the method of spraying is used to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 120 DEG C, relative humidity is place 65min in the environment of 85% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 15 °.
Embodiment 12
The present embodiment provides a kind of preparation method of the hydrophobizing agent for glass, comprises the following steps:
(1) by the n-C of 5 mass parts
40h
81si (OCOC
4h
9)
3, H containing 1.2 mass parts
2sO
4mass percent concentration be that the sulphuric acid soln of 50% and the water (comprising the water in sulphuric acid soln) of 5 mass parts join in the propanol solvent of 90 mass parts, at 25 DEG C stir within 2.5 hours, obtain mixture;
(2) in mixture, drip N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane of 2.5 mass parts, be added dropwise to complete rear continuation stirring 20 hours, obtain the hydrophobizing agent for glass.
The present embodiment also provides a kind of preparation method of Hydrophobic glass, comprises the following steps:
(1) in encloses container, SiF is added
4with the mixing solutions of water, wherein SiF
4be 3: 1 with the mol ratio of water, cleaned glass be put in the atmosphere of this encloses container, at 35 DEG C, place 45min;
(2) stand-by after taking out glass drying, the method of blade coating is by hand made to form hydrophobic film layer at glass surface the hydrophobizing agent being used for glass of above-mentioned preparation, temperature is 100 DEG C, relative humidity is place 30min in the environment of 65% to be had on surface the glass of hydrophobic film layer to be placed on, obtain Hydrophobic glass after the hydrophobic film layer solidification of glass surface, the slide angle recording Hydrophobic glass is 16 °.
Be understandable that, the illustrative embodiments that above embodiment is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (8)
1. a preparation method for Hydrophobic glass, is characterized in that, comprises the following steps:
(1) in encloses container, SiX ' is added
4with the mixing solutions of water, cleaned glass is put in the atmosphere of this encloses container, wherein X ' be halogen atom, any one in alkoxyl group, acyloxy, amino and aminooxy;
(2) take out the glass in step (1), the hydrophobizing agent being used for glass is formed hydrophobic film layer at glass surface, the hydrophobic film layer solidification of glass surface obtains Hydrophobic glass;
Wherein, the preparation method of the described hydrophobizing agent for glass, comprises the following steps:
(1) silicon-containing material, acid, water are mixed with organic solvent, stir and obtain mixture,
Wherein, described silicon-containing material is R-SiX
3or silicone oil, described R-SiX
3in R be straight chained alkyl or the halogenated straight alkyl that carbonatoms is more than or equal to 8, X is any one in halogen atom, alkoxyl group, acyloxy, amino and aminooxy;
(2) in the mixture in step (1), add silane coupling agent, stir the hydrophobizing agent obtained for glass.
2. the preparation method of Hydrophobic glass according to claim 1, is characterized in that, in the described step (1) of the preparation method of the described hydrophobizing agent for glass, the carbonatoms in R is less than or equal to 30.
3. the preparation method of Hydrophobic glass according to claim 1, is characterized in that, when the X in the described step (1) of the preparation method of the described hydrophobizing agent for glass contains carbon atom, carbonatoms is less than or equal to 10.
4. the preparation method of Hydrophobic glass according to claim 1, it is characterized in that, the silicone oil in the described step (1) of the preparation method of the described hydrophobizing agent for glass is one or more mixtures in methyl-silicone oil, ethyl silicon oil, MethylethoxylsiliconFluid Fluid, methyl trifluoro propyl silicone oil, methyl vinyl silicon oil, methylhydroxy silicone oil.
5. the preparation method of Hydrophobic glass according to claim 1, it is characterized in that, silane coupling agent in the described step (2) of the preparation method of the described hydrophobizing agent for glass is one or more mixtures in 3-aminopropyl triethoxysilane, γ-(2,3 epoxy third oxygen) propyl trimethoxy silicane, 3-(iso-butylene acyl-oxygen) propyl trimethoxy silicane, N-β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.
6. the preparation method of the Hydrophobic glass according to Claims 1 to 5 any one, is characterized in that,
The mass fraction of the silicon-containing material in the described step (1) of the preparation method of the described hydrophobizing agent for glass is 1 ~ 5 part, and the mass fraction of acid is 0.1 ~ 2 part, and the mass fraction of water is 0.5 ~ 5 part, and the mass fraction of organic solvent is 90 ~ 98 parts;
The mass fraction of the silane coupling agent in described step (2) is 0.5 ~ 5 part.
7. the preparation method of Hydrophobic glass according to claim 1, it is characterized in that, in described step (1), described being put into by cleaned glass in the atmosphere of this encloses container is specially: cleaned glass is in the atmosphere of encloses container, 15min ~ 60min is placed, wherein SiX ' at 15 ~ 60 DEG C
4be 1: 1 ~ 10: 1 with the mol ratio of water.
8. a Hydrophobic glass, is characterized in that, it is prepared by the method described in claim 1 ~ 7 any one.
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| CN103043919B (en) * | 2012-11-07 | 2014-12-03 | 北京化工大学 | Method for preparing waterproof and antifogging surface modified glass |
| CN103332871B (en) * | 2013-06-13 | 2015-08-12 | 奇瑞汽车股份有限公司 | Hydrophobic vehicle glass that a kind of low water droplet is residual and preparation method thereof |
| CN103433188B (en) * | 2013-08-28 | 2015-03-25 | 奇瑞汽车股份有限公司 | Preparation method for easily-cleaned hydrophobic membrane used on surface of automotive body |
| CN104150785B (en) * | 2014-07-29 | 2017-08-04 | 奇瑞汽车股份有限公司 | A kind of preparation method of Hydrophobic glass |
| CN104129790B (en) * | 2014-08-18 | 2016-08-24 | 奇瑞汽车股份有限公司 | A kind of Nano-meter SiO_22microsphere, hydrophober, its preparation method and hydrophobic glass |
| CN105347693B (en) * | 2014-08-22 | 2019-07-02 | 北京易净星科技有限公司 | Long-acting glass hydrophobing agent and its preparation and application |
| CN105585928B (en) * | 2015-05-19 | 2018-05-15 | 北京易净星科技有限公司 | Super hydrophobic coating and its preparation and application |
| DE102016000243A1 (en) * | 2016-01-12 | 2017-07-13 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Leather hydrophobization process and leather produced therewith |
| CN110790935A (en) * | 2019-08-28 | 2020-02-14 | 中国科学院兰州化学物理研究所 | Fluorine-free hydrophobic treatment agent, preparation method and application thereof, and self-cleaning glass |
| CN111574068B (en) * | 2020-05-19 | 2022-07-26 | 天津德祥生物技术有限公司 | Method for treating glass beads and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1778749A (en) * | 2005-10-14 | 2006-05-31 | 浙江大学 | Glass hydrophobic film coating liuqid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1778749A (en) * | 2005-10-14 | 2006-05-31 | 浙江大学 | Glass hydrophobic film coating liuqid |
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