CN105776887A - Hydrophobic agent, hydrophobic glass, preparation method for hydrophobic agent, and preparation method for hydrophobic glass - Google Patents
Hydrophobic agent, hydrophobic glass, preparation method for hydrophobic agent, and preparation method for hydrophobic glass Download PDFInfo
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- CN105776887A CN105776887A CN201610140418.1A CN201610140418A CN105776887A CN 105776887 A CN105776887 A CN 105776887A CN 201610140418 A CN201610140418 A CN 201610140418A CN 105776887 A CN105776887 A CN 105776887A
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- 239000011521 glass Substances 0.000 title claims abstract description 113
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 42
- -1 fluoroalkyl silane Chemical compound 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 40
- 239000004744 fabric Substances 0.000 claims description 35
- 239000000835 fiber Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 239000012153 distilled water Substances 0.000 claims description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 229910008051 Si-OH Inorganic materials 0.000 claims description 14
- 229910006358 Si—OH Inorganic materials 0.000 claims description 14
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 claims description 13
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- QIROQPWSJUXOJC-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6-undecafluoro-6-(trifluoromethyl)cyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)F QIROQPWSJUXOJC-UHFFFAOYSA-N 0.000 claims description 10
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 229960004692 perflenapent Drugs 0.000 claims description 5
- NJCBUSHGCBERSK-UHFFFAOYSA-N perfluoropentane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NJCBUSHGCBERSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000001117 sulphuric acid Substances 0.000 claims description 5
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 3
- XPWHRQHBPRSUAW-UHFFFAOYSA-N 4-[5-(4-fluorophenyl)-3-[1-(1,2-oxazol-3-ylmethyl)piperidin-4-yl]imidazol-4-yl]pyrimidin-2-amine Chemical compound NC1=NC=CC(C=2N(C=NC=2C=2C=CC(F)=CC=2)C2CCN(CC3=NOC=C3)CC2)=N1 XPWHRQHBPRSUAW-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007171 acid catalysis Methods 0.000 claims description 3
- 239000003849 aromatic solvent Substances 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical group FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 claims description 3
- 229960004624 perflexane Drugs 0.000 claims description 3
- 229950011087 perflunafene Drugs 0.000 claims description 3
- LOQGSOTUHASIHI-UHFFFAOYSA-N perfluoro-1,3-dimethylcyclohexane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)C1(F)F LOQGSOTUHASIHI-UHFFFAOYSA-N 0.000 claims description 3
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 claims description 3
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 claims description 3
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 152
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 238000005507 spraying Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 abstract description 5
- 229910000077 silane Inorganic materials 0.000 abstract description 4
- 108010009736 Protein Hydrolysates Proteins 0.000 abstract 1
- 238000003618 dip coating Methods 0.000 abstract 1
- 229960004756 ethanol Drugs 0.000 description 11
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to a hydrophobic agent, hydrophobic glass, a preparation method for a hydrophobic agent, and a preparation method for hydrophobic glass. The hydrophobic agent provided by the invention is obtained by adding long-chain fluoroalkyl silane into an organic solvent/aqueous solution with the pH value of 4.0 to 5.5, stirring for 2 to 24 hours under the conditions of 500 to 1,100 rpm, then adding perfluorinated solvent into a mixture, continuously stirring for 30 to 60 minutes, standing and layering, taking upper solution for later use, using bottom solution for circulating and purifying fluoroalkyl silane hydrolysate, adding nano-silica sol into the obtained upper solution, mixing and stirring. Low-slide angle hydrophobic glass can be obtained by forming a film on the surface of automobile glass by adopting the methods such as rubbing, spraying, scrape-coating and dip-coating, so that water drops can slide down automatically; therefore, a driver can achieve good view definition when an automobile is driven in rainy weather, and the driving safety is improved.
Description
Technical field
The present invention relates to hydrophobic glass technical field, be specifically related to hydrophober and hydrophobic vehicle glass technology of preparing, particularly relate to a kind of low slide angle hydrophobic glass technology of preparing.
Background technology
Glass be mainly composed of SiO2, contain Na simultaneously+、Ca2+、Mg2+Deng composition.Moisture in air very easily occurs absorption to form moisture film at glass surface, simultaneously sour gas SO2、CO2Reacting Deng diffusing to the interface of glass and water by moisture film, glass suffers erosion.It addition, the vehicle travelled in the rainy day forms uneven moisture film because of rainwater at side window and windshield glass and rear view mirror lens surface spreading and affects the human pilot visual field, and often therefore cause that accident occurs.The rete with hydrophobic (be also known as hydrophobic, scold water, refuse water) effect can be obtained in glass surface modification low-surface energy substance, rainwater can be punctured into " spherical crown shape " voluntarily on its surface, tumble voluntarily under Gravitative Loads or under wind-force effect, fly away from glass surface and take away glass surface dust, the human pilot visual field can be improved；Additionally, in snow cold weather gas, its surface frost layer of glass scribbling this hydrophobic membranous layer can be removed easily.Therefore, hydrophobic membranous layer can give vehicle glass effect easy to clean.
At present, first the realization of hydrophobic glass technology is be hydrolyzed and teos hydrolysis by silicon fluoride, then hydrophobic membranous layer is prepared in glass surface coating, such as CN200910064894.X, CN02115493.7, generally adopt this technique to prepare hydrophobic glass and need high-temperature post-treatment technique so that low-surface energy substance, with-OH, condensation reaction occurs, connecting thus setting up firmly chemical bond, obtaining that there is necessarily ageing hydrophobic membranous layer.201410205520.6,201410205566.8 disclose and a kind of adopt the perfluoro solvents such as perfluorotributylamine as extractant, silicon fluoride hydrolyzed solution to be easily separated, obtain bottom solution (i.e. the perfluoro solvent solution such as perfluorotributylamine) as hydrophober or hydrophober key component, and upper solution is removed.Owing to the perfluoro solvents such as perfluorotributylamine are expensive, and perfluorotributylamine enters in air and has notable greenhouse effect, therefore adopts the hydrophober as constituent to be unfavorable for large-scale promotion application and environmental conservation.
In sum, prior art exists following technical problem: hydrophobic glass generally adopts fluoro alkyl-silane hydrolyzed solution in acid condition to modify or adopts silicon dioxide gel and this hydrolyzed solution to be mixed with dressing agent and modifies preparation at present, for reducing the water droplet slide angle at the glass surface modified through hydrophobic, in dressing agent, also add a little silicone oil component, but add the hydrophober of this composition after vehicle glass surface filming, under light conditions, it is easily generated dazzle, affects ride comfort and safety.
Summary of the invention
It is an object of the invention to provide a kind of hydrophober, hydrophobic glass and preparation method thereof, adopts perfluoro solvent separate fluorine hydrolyzed silane solution, and upper solution is used as main component and prepares low slide angle hydrophober and hydrophobic glass, lower floor's solution circulation uses, and concrete technical scheme is as follows:
A kind of hydrophober preparation method, comprises the following steps:
(1) long-chain silicon fluoride, acid, organic solvent and water mix and blend are obtained the first solution；
(2) in the first solution, add the perfluoro solvent of 0.5～10 times amount, continue stirring and obtain the second solution；
(3) by after second solution left standstill a period of time, upper solution is taken as the 3rd solution；
(4) silicon dioxide gel added in the 3rd solution and obtain the 4th solution after stirring.
Further, described first solution, the content of long-chain silicon fluoride is 1.22wt%～4.62wt%, and the content of acid is 0.61wt%～2.38wt%, and the content of water is 0.61wt%～2.38wt%, and surplus is organic solvent.
Further, described long-chain silicon fluoride structure is as follows:
Wherein, the span of m is 6～20, and the span of n is 1～3, and the span of a is 0～2, and R is perfluor carbochain or perfluoroether chain, and X is hydrolyzable groups.
Further, n=1, a=1, R is-CF2-CF2-CF2-,-CF2-CF2-CF2-O-or-CF2-CF(CF3)-O-, X be halogeno-group or alkoxyl, R ' is H or alkoxyl, and/or, under acid catalysis ,-Si (X)3-aRa' in halogeno-group X and alkoxyl R ' be hydrolyzed, formed and there is silanol-Si-OH containing F Long carbon chain.
Further, the first solution described in described step (2) is through being sufficiently stirred for；And/or, the second solution left standstill 20～60 minutes in step (3)；And/or, step is sufficiently stirred for 10～30 minutes in (4).
Further, described acid is one or more in hydrochloric acid, sulphuric acid, acetic acid, nitric acid, and organic solvent/pH value of water solution is adjusted to 4.0～5.5；Described organic solvent is the aromatic solvent such as toluene, dimethylbenzene；The ketones solvent such as acetone, butanone；The esters solvent such as ethyl acetate, butyl acetate；The ether solvents such as ether, n-butyl ether, petroleum ether；The alcohols solvents such as dehydrated alcohol, normal propyl alcohol, isopropanol, n-butyl alcohol, or the mixture of several solvent；Described water is deionized water or distilled water；Described perfluoro solvent is perfluorotributylamine, perfluoro butyl oxolane, perflenapent, perflexane, perfluoromethylcyclohexane (PFMCH), perfluorodimethylcyclohexane, PFO, perfluorodecalin, perfluor-1-methyl naphthalane, perfluor dimethyl naphthalane etc.；Nano-meter SiO_2 in described silicon dioxide gel2Particle diameter is 10～75nm, SiO2Content is 1wt%～10wt%, and silicon dioxide gel and the 3rd solution mix according to mass ratio, and mixed proportion is 1:1～1:3.
Further, described first solution is that stirring mixing velocity is 500～1100 revs/min, mixing time 2～24 hours in order to be hydrolyzed to by long-chain silicon fluoride containing F Long carbon chain silanol and hydrogen halides or short carbon chain alcohol, and/or,
Described second solution is that mixing speed when being sufficiently mixed is 1000～1100 revs/min, mixing time 30～60 minutes in order to allow perfluoro solvent and the first solution be sufficiently mixed, and/or,
Described 3rd solution is through the sufficiently cleaned up organic solvent solution containing F Long carbon chain silanol of perfluoro solvent, there is the oligosiloxane containing Si-OH in this solution, and/or,
4th solution is addition nano silicon dioxide sol on the basis of the 3rd solution, and mixing speed is 1000～1600 revs/min, mixing time 30～60 minutes.
A kind of hydrophober, for vehicle glass, adopts above-mentioned hydrophober preparation method to prepare.
The preparation method of a kind of hydrophobic glass, comprises the steps:
A. glass basis surface dirt is wiped；
B. dip acid solution and in the uniform wiping of glass surface, form non-electrical amorph Si-OH at glass surface；
C. rinse well；
D. treat that glass surface is dried, dip the 4th solution as described in claim 1-7 in the uniform wiping in its surface；
E. dry and obtain hydrophobic membranous layer.
A kind of hydrophobic glass, adopts above-mentioned hydrophober preparation method to prepare, or adopts and prepare with the following method:
A. glass basis surface dirt is wiped with superfine fibre cloth；
B. dip the hydrochloric acid of 1mol/L or salpeter solution and in the uniform wiping of glass surface with superfine fibre cloth, form non-electrical amorph Si-OH at glass surface；
C. clean with deionized water or distilled water flushing；
D. treat that glass surface is dried, dip a small amount of the 4th solution as described in claim 1-7 in the uniform wiping in its surface with superfine fibre cloth；
E. at room temperature natural drying 5～10 minutes；
F. use superfine fibre cloth in the glass surface wiping of coated 4th solution；
G. natural drying can obtain the hydrophobic membranous layer that is firmly combined with for more than 12 hours.
Compared with currently available technology, present invention ensure that human pilot can obtain good degree of getting a clear view when rainy weather middle rolling car, improve travel safety.Utilize perfluoro solvent the impurity introduced when adding silicon fluoride and non-complete hydrolysis material to be dissolved in organic solvent/aqueous solution immiscible feature and wherein realize dedoping step, be conducive to obtaining low slide angle hydrophobic membranous layer；Simultaneously because the distribution that the Long carbon chain silanol containing F is in organic solvent/aqueous solution and perfluoro solvent exists an equilibrium state, therefore perfluoro solvent can be recycled and loses containing F Long carbon chain silanol without causing；To mainly comprise composition containing organic solvent/aqueous solution containing F Long carbon chain silanol for hydrophober of the present invention after separating, avoid the sky high cost adopting the hydrophober being main component with perfluoro solvent to bring, avoid perfluoro solvent simultaneously and enter the greenhouse effect brought in air.Therefore, present invention process is simple, with low cost, and effect is notable, environmental friendliness, and on vehicle glass, application can improve the degree of getting a clear view of driver and crew in rainy weather, improves safety.
Accompanying drawing explanation
Fig. 1 is hydrophobic glass preparation process schematic diagram of the present invention
Detailed description of the invention
Describing the present invention below according to accompanying drawing, it is a kind of preferred embodiment in numerous embodiments of the present invention.
In a preferred embodiment, in silicon fluoride hydrolyzed solution, add perfluoro solvent be sufficiently stirred for, utilize perfluoro solvent that the non-hydrolysis substance in silicon fluoride hydrolyzed solution and other impurity are purified by the immiscible character of the material such as alcohol, water, obtaining supernatant as hydrophobic modifier main component, bottom solution can recycle as purification medium.Long-chain silicon fluoride is added in organic solvent/aqueous solution that pH value is 4.0～5.5, stirs 2～24 hours under 600～1100 revs/min of conditions, then perfluoro solvent is added wherein, continue stirring 30～60 minutes, stratification, take upper solution standby；Being added by nano silicon dioxide sol in gained upper solution, mix and blend obtains hydrophober of the present invention, adopts the methods such as erasing, spraying, blade coating, lift can low slide angle hydrophobic glass at vehicle glass surface filming.
In a further advantageous embodiment, long-chain silicon fluoride is added in organic solvent/aqueous solution that pH value is 4.0～5.5, stir 2～24 hours under 500～1100 revs/min of conditions, then perfluoro solvent is added wherein, continue stirring 30～60 minutes, stratification, takes upper solution standby, and bottom solution uses for silicon fluoride hydrolyzed solution circularly purifying；Nano silicon dioxide sol is added in gained upper solution, mix and blend obtains hydrophober of the present invention, adopt the method such as erasing, spraying, blade coating, lift can low slide angle hydrophobic glass at vehicle glass surface filming, to guarantee that water droplet can landing voluntarily, so that it is guaranteed that human pilot can obtain good degree of getting a clear view when rainy weather middle rolling car, improve travel safety.Wherein:
1. prepared by hydrophober
A kind of hydrophober preparation method for vehicle glass, comprises the following steps:
(1) long-chain silicon fluoride, acid, organic solvent and water mix and blend are obtained the first solution；
(2) to the perfluoro solvent adding 0.5～10 times amount in well-beaten first solution, continue stirring and obtain the second solution；
(3) by after the second solution left standstill 20～60 minutes, upper solution is taken as the 3rd solution；
(4) the 4th solution is obtained after being added in the 3rd solution and be sufficiently stirred for 10～30 minutes by silicon dioxide gel.
The first solution in described step (1), the content of long-chain silicon fluoride is 1.22wt%～4.62wt%, and the content of acid is 0.61wt%～2.38wt%, and the content of water is 0.61wt%～2.38wt%, and surplus is organic solvent.
Described long-chain silicon fluoride structure is as follows:
Wherein the span of m is 6～20, and the span of n is 1～3, it is preferable that the span of n=1, a is 0～2, it is preferable that a=0 or 1, it is most preferred that a=0；R is perfluor carbochain or perfluoroether chain, such as-CF2-CF2-CF2-,-CF2-CF2-CF2-O-or-CF2-CF(CF3)-O-；X is hydrolyzable groups, and such as halogeno-group or alkoxyl, R ' is H or alkoxyl.Under acid catalysis ,-Si (X)3-aRa' in halogeno-group X and alkoxyl R ' be hydrolyzed, formed and there is silanol-Si-OH containing F Long carbon chain.
Described acid is one or more in hydrochloric acid, sulphuric acid, acetic acid, nitric acid, and organic solvent/pH value of water solution is adjusted to 4.0～5.5.
Described organic solvent is the aromatic solvent such as toluene, dimethylbenzene；The ketones solvent such as acetone, butanone；The esters solvent such as ethyl acetate, butyl acetate；The ether solvents such as ether, n-butyl ether, petroleum ether；The alcohols solvents such as dehydrated alcohol, normal propyl alcohol, isopropanol, n-butyl alcohol, or the mixture of several solvent.Preferred organic solvent is one or several the mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
Described water is deionized water or distilled water.
Described perfluoro solvent is perfluorotributylamine, perfluoro butyl oxolane, perflenapent, perflexane, perfluoromethylcyclohexane (PFMCH), perfluorodimethylcyclohexane, PFO, perfluorodecalin, perfluor-1-methyl naphthalane, perfluor dimethyl naphthalane etc..
Nano-meter SiO_2 in described silicon dioxide gel2Particle diameter is 10～75nm, SiO2Content is 1wt%～10wt%, and silicon dioxide gel and the 3rd solution mix according to mass ratio, and mixed proportion is 1:1～1:3.
Described first solution is that stirring mixing velocity is 500～1100 revs/min, mixing time 2～24 hours in order to be hydrolyzed to by long-chain silicon fluoride containing F Long carbon chain silanol and hydrogen halides or short carbon chain alcohol.
Described second solution is to allow perfluoro solvent and the first solution be sufficiently mixed, by the impurity introduced when adding long-chain silicon fluoride be not hydrolyzed silane completely and be dissolved in wherein.By long-chain silicon fluoride hydrolyze to form containing F Long carbon chain silanol owing to mixing with organic solvent/aqueous solution containing Si-OH, simultaneously because containing low-surface-energy containing F Long carbon chain, therefore part Long carbon chain silanol containing F is also had to be dissolved in perfluoro solvent, there is an equilibrium state in the distribution in organic solvent/aqueous solution and perfluoro solvent of the Long carbon chain silanol containing F, therefore perfluoro solvent can be recycled and loses containing F Long carbon chain silanol without causing.Mixing speed when being sufficiently mixed is 1000～1100 revs/min, mixing time 30～60 minutes.
Described 3rd solution is through the sufficiently cleaned up organic solvent solution containing F Long carbon chain silanol of perfluoro solvent, there is the oligosiloxane containing Si-OH in this solution.
4th solution is addition nano silicon dioxide sol on the basis of the 3rd solution, to forming the low-surface-energy rete of micro-rough at glass surface,-the OH on the Si-OH in the Si-OH on silicon dioxide gel surface and oligosiloxane and glass basis surface forms hydrogen bond, in solidifying dehydration, form firmly covalent bond with glass basis be connected, namely obtain high hydrophobic, low slide angle hydrophobic glass rete.Mixing speed is 1000～1600 revs/min, mixing time 30～60 minutes.
2. prepared by hydrophobic glass
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, non-electrical amorph Si-OH is formed at glass surface, then clean with deionized water or distilled water flushing, treat that glass surface is dried, with superfine fibre cloth dip on a small quantity above-mentioned 4th solution in the uniform wiping in its surface, at room temperature natural drying 5～10 minutes after wiping, then use superfine fibre cloth in the glass surface wiping of coated 4th solution, obtain the glass surface of transparent light, then natural drying can obtain the hydrophobic membranous layer that is firmly combined with for more than 12 hours again.
Above-mentioned erasing process also can use the methods such as spraying, blade coating, lift plated film to replace.
Preferred embodiment one: the present embodiment provides a kind of hydrophober and low slide angle hydrophobic glass preparation method, comprises the following steps:
Being mixed with sulphuric acid, distilled water and ethanol by long-chain silicon fluoride, wherein long-chain silicon fluoride structural formula is F3C-(CF2)6-(CH2-CH2)-Si(OCH2CH3)3, wherein the addition of long-chain silicon fluoride is 1.22wt%, and the addition of sulphuric acid is 0.61wt%, and the addition of distilled water is 0.61wt%, and surplus is ethanol, and solution ph is 4.0, stirs 2 hours, obtain the first solution under 500 revs/min；Adding perfluorotributylamine in the first solution, the addition of perfluorotributylamine is 1 times of the first solution total amount, stirs 30 minutes, obtain the second solution under 1000 revs/min；Upper solution being separated after second solution left standstill layering, isolated upper solution is as the 3rd solution；Silicon dioxide gel is added in the 3rd solution according to the mass ratio of 1:3, wherein Nano-meter SiO_22Particle diameter is 20nm, SiO2Content is 10wt%, is sufficiently stirred for 30 minutes with the speed of 1200 revs/min, obtains the 4th solution after mixing.
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, then rinse well with deionized water, treat that glass surface is dried, with superfine fibre cloth dip on a small quantity above-mentioned 4th solution in the uniform wiping in its surface, at room temperature natural drying 10 minutes after wiping, then use superfine fibre cloth in the glass surface wiping of coated 4th solution, obtain the glass surface of transparent light, then natural drying 12 hours again, obtaining contact angle is 110 °, slide angle is the hydrophobic glass of 5 °.
Preferred embodiment two: the present embodiment provides a kind of hydrophober and low slide angle hydrophobic glass preparation method, comprises the following steps:
Being mixed with hydrochloric acid, distilled water and ethanol/isopropanol by long-chain silicon fluoride, wherein long-chain silicon fluoride structural formula is F3C-(CF2)12-(CH2-CH2)-Si(OCH2CH3)3Wherein the addition of long-chain silicon fluoride is 2.31wt%, the addition of hydrochloric acid is 0.61wt%, the addition of distilled water is 1.19wt%, surplus is ethanol/isopropanol mixed liquor (mixing according to the volume ratio of 90:10), solution ph is 4.5, stirs 6 hours, obtain the first solution under 800 revs/min；Adding perfluorotributylamine in the first solution, the addition of perfluorotributylamine is 0.5 times of the first solution total amount, stirs 30 minutes, obtain the second solution under 1100 revs/min；Upper solution being separated after second solution left standstill layering, isolated upper solution is as the 3rd solution；Silicon dioxide gel is added in the 3rd solution according to the mass ratio of 1:1, wherein Nano-meter SiO_22Particle diameter is 50nm, SiO2Content is 10wt%, is sufficiently stirred for 30 minutes with the speed of 1200 revs/min, obtains the 4th solution after mixing.
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, then clean with distilled water flushing, treat that glass surface is dried, with superfine fibre cloth dip on a small quantity above-mentioned 4th solution in the uniform wiping in its surface, at room temperature natural drying 5 minutes after wiping, then use superfine fibre cloth in the glass surface wiping of coated 4th solution, obtain the glass surface of transparent light, then natural drying 12 hours again, obtaining contact angle is 115 °, slide angle is the hydrophobic glass of 3 °.
Preferred embodiment three: the present embodiment provides a kind of hydrophober and low slide angle hydrophobic glass preparation method, comprises the following steps:
Being mixed with hydrochloric acid, distilled water and isopropanol by long-chain silicon fluoride, wherein long-chain silicon fluoride structural formula is F3C-(CF2)7-(CH2-CH2)-Si(OCH(CH3)2)3, wherein the addition of long-chain silicon fluoride is 2.31wt%, and the addition of hydrochloric acid is 0.61wt%, and the addition of distilled water is 1.19wt%, and surplus is isopropanol, and solution ph is 4.5, stirs 2 hours, obtain the first solution under 500 revs/min；Adding perfluorotributylamine in the first solution, the addition of perfluorotributylamine is 5 times of the first solution total amount, stirs 30 minutes, obtain the second solution under 1000 revs/min；Upper solution being separated after second solution left standstill layering, isolated upper solution is as the 3rd solution；Silicon dioxide gel is added in the 3rd solution according to the mass ratio of 1:1, wherein Nano-meter SiO_22Particle diameter is 75nm, SiO2Content is 5wt%, is sufficiently stirred for 30 minutes with the speed of 1400 revs/min, obtains the 4th solution after mixing.
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, then clean with distilled water flushing, treat that glass surface is dried, with superfine fibre cloth dip on a small quantity above-mentioned 4th solution in the uniform wiping in its surface, at room temperature natural drying 7 minutes after wiping, then use superfine fibre cloth in the glass surface wiping of coated 4th solution, obtain the glass surface of transparent light, then natural drying 12 hours again, obtaining contact angle is 112 °, slide angle is the hydrophobic glass of 3 °.
Preferred embodiment four: the present embodiment provides a kind of hydrophober and low slide angle hydrophobic glass preparation method, comprises the following steps:
Being mixed with hydrochloric acid, distilled water and ethanol/isopropanol by long-chain silicon fluoride, wherein long-chain silicon fluoride structural formula is F3C-(CF2)6-(CH2-CH2)-Si(OCH(CH3)2)3Wherein the addition of long-chain silicon fluoride is 4.62wt%, the addition of hydrochloric acid is 1.19wt%, the addition of distilled water is 2.38wt%, surplus is ethanol/isopropanol (mixing according to the volume ratio of 70:30), solution ph is 5, stirs 24 hours, obtain the first solution under 800 revs/min；Adding perflenapent in the first solution, the addition of perflenapent is 10 times of the first solution total amount, stirs 30 minutes, obtain the second solution under 1100 revs/min；Upper solution being separated after second solution left standstill layering, isolated upper solution is as the 3rd solution；Silicon dioxide gel is added in the 3rd solution according to the mass ratio of 1:2, wherein Nano-meter SiO_22Particle diameter is 45nm, SiO2Content is 10wt%, is sufficiently stirred for 60 minutes with the speed of 1600 revs/min, obtains the 4th solution after mixing.
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, then clean with distilled water flushing, treat that glass surface is dried, above-mentioned 4th solution is sprayed on dry glass surface, at room temperature natural drying 10 minutes after spraying, then with superfine fibre cloth in the glass surface wiping through spraying, obtain the glass surface of transparent light, then natural drying 12 hours again, obtain contact angle be 120 °, slide angle be the hydrophobic glass of 2 °.
Preferred embodiment five: the present embodiment provides a kind of hydrophober and low slide angle hydrophobic glass preparation method, comprises the following steps:
Being mixed with hydrochloric acid, distilled water and ethanol by long-chain silicon fluoride, wherein long-chain silicon fluoride structural formula is F3C-(CF2-CF2-CF2-O)6-(CH2-CH2)-SiCl2(OCH2CH3), wherein the addition of long-chain silicon fluoride is 2.31wt%, and the addition of hydrochloric acid is 0.61wt%, and the addition of distilled water is 2.38wt%, and surplus is ethanol, and solution ph is 5, stirs 12 hours, obtain the first solution under 1100 revs/min；Adding PFO in the first solution, the addition of PFO is 3 times of the first solution total amount, stirs 30 minutes, obtain the second solution under 1000 revs/min；Upper solution being separated after second solution left standstill layering, isolated upper solution is as the 3rd solution；Silicon dioxide gel is added in the 3rd solution according to the mass ratio of 1:1, wherein Nano-meter SiO_22Particle diameter is 75nm, SiO2Content is 1wt%, is sufficiently stirred for 30 minutes with the speed of 1600 revs/min, obtains the 4th solution after mixing.
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, then clean with distilled water flushing, treat that glass surface is dried, with superfine fibre cloth dip on a small quantity above-mentioned 4th solution in the uniform wiping in its surface, at room temperature natural drying 5 minutes after wiping, then use superfine fibre cloth in the glass surface wiping of coated 4th solution, obtain the glass surface of transparent light, then natural drying 12 hours again, obtaining contact angle is 111 °, slide angle is the hydrophobic glass of 3 °.
Preferred embodiment six: the present embodiment provides a kind of hydrophober and low slide angle hydrophobic glass preparation method, comprises the following steps:
Being mixed with hydrochloric acid, distilled water and ethanol by long-chain silicon fluoride, wherein long-chain silicon fluoride structural formula is F3C-(CF2)20-(CH2-CH2)-SiCl(OCH2CH3)2, wherein the addition of long-chain silicon fluoride is 2.31wt%, and the addition of hydrochloric acid is 0.61wt%, and the addition of distilled water is 2.38wt%, and surplus is ethanol, and solution ph is 4.5, stirs 10 hours, obtain the first solution under 1100 revs/min；Adding perfluoromethylcyclohexane (PFMCH) in the first solution, the addition of perfluoromethylcyclohexane (PFMCH) is 2 times of the first solution total amount, stirs 30 minutes, obtain the second solution under 1000 revs/min；Upper solution being separated after second solution left standstill layering, isolated upper solution is as the 3rd solution；Silicon dioxide gel is added in the 3rd solution according to the mass ratio of 1:1, wherein Nano-meter SiO_22Particle diameter is 75nm, SiO2Content is 3wt%, is sufficiently stirred for 60 minutes with the speed of 1200 revs/min, obtains the 4th solution after mixing.
First glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid of 1mol/L or salpeter solution are dipped and in the uniform wiping of glass surface with superfine fibre cloth, then clean with distilled water flushing, treat that glass surface is dried, with superfine fibre cloth dip on a small quantity above-mentioned 4th solution in the uniform wiping in its surface, at room temperature natural drying 5 minutes after wiping, then use superfine fibre cloth in the glass surface wiping of coated 4th solution, obtain the glass surface of transparent light, then natural drying 12 hours again, obtaining contact angle is 118 °, slide angle is the hydrophobic glass of 3 °.
Above in conjunction with accompanying drawing, the present invention is exemplarily described; the obvious present invention implements and is not subject to the restrictions described above; as long as have employed the various improvement that the design of the method for the present invention carries out with technical scheme; or not improved that directly apply to other occasion, all within protection scope of the present invention.
Claims (10)
1. a hydrophober preparation method, it is characterised in that comprise the following steps:
(1) long-chain silicon fluoride, acid, organic solvent and water mix and blend are obtained the first solution；
(2) in the first solution, add the perfluoro solvent of 0.5～10 times amount, continue stirring and obtain the second solution；
(3) by after second solution left standstill a period of time, upper solution is taken as the 3rd solution；
(4) silicon dioxide gel added in the 3rd solution and obtain the 4th solution after stirring.
2. hydrophober preparation method as claimed in claim 1, it is characterised in that described first solution, the content of long-chain silicon fluoride is 1.22wt%～4.62wt%, the content of acid is 0.61wt%～2.38wt%, and the content of water is 0.61wt%～2.38wt%, and surplus is organic solvent.
3. hydrophober preparation method as claimed in claim 2, it is characterised in that described long-chain silicon fluoride structure is as follows:
Wherein, the span of m is 6～20, and the span of n is 1～3, and the span of a is 0～2, and R is perfluor carbochain or perfluoroether chain, and X is hydrolyzable groups.
4. hydrophober preparation method as claimed in claim 3, it is characterised in that n=1, a=1, R are-CF2-CF2-CF2-,-CF2-CF2-CF2-O-or-CF2-CF(CF3)-O-, X be halogeno-group or alkoxyl, R ' is H or alkoxyl, and/or, under acid catalysis ,-Si (X)3-aR′aIn halogeno-group X and alkoxyl R ' be hydrolyzed, formed and there is silanol-Si-OH containing F Long carbon chain.
5. the hydrophober preparation method as according to any one of claim 1-4, it is characterised in that described in described step (2), the first solution is through being sufficiently stirred for；And/or, the second solution left standstill 20～60 minutes in step (3)；And/or, step is sufficiently stirred for 10～30 minutes in (4).
6. the hydrophober preparation method as according to any one of claim 1-5, it is characterised in that described acid is one or more in hydrochloric acid, sulphuric acid, acetic acid, nitric acid, and organic solvent/pH value of water solution is adjusted to 4.0～5.5；Described organic solvent is the aromatic solvent such as toluene, dimethylbenzene；The ketones solvent such as acetone, butanone；The esters solvent such as ethyl acetate, butyl acetate；The ether solvents such as ether, n-butyl ether, petroleum ether；The alcohols solvents such as dehydrated alcohol, normal propyl alcohol, isopropanol, n-butyl alcohol, or the mixture of several solvent；Described water is deionized water or distilled water；Described perfluoro solvent is perfluorotributylamine, perfluoro butyl oxolane, perflenapent, perflexane, perfluoromethylcyclohexane (PFMCH), perfluorodimethylcyclohexane, PFO, perfluorodecalin, perfluor-1-methyl naphthalane, perfluor dimethyl naphthalane etc.；Nano-meter SiO_2 in described silicon dioxide gel2Particle diameter is 10～75nm, SiO2Content is 1wt%～10wt%, and silicon dioxide gel and the 3rd solution mix according to mass ratio, and mixed proportion is 1:1～1:3.
7. the hydrophober preparation method as according to any one of claim 1-6, it is characterised in that described first solution is to be hydrolyzed to by long-chain silicon fluoride containing F Long carbon chain silanol and hydrogen halides or short carbon chain alcohol, stirring mixing velocity is 500～1100 revs/min, mixing time 2～24 hours, and/or
Described second solution is that mixing speed when being sufficiently mixed is 1000～1100 revs/min, mixing time 30～60 minutes in order to allow perfluoro solvent and the first solution be sufficiently mixed, and/or,
Described 3rd solution is through the sufficiently cleaned up organic solvent solution containing F Long carbon chain silanol of perfluoro solvent, there is the oligosiloxane containing Si-OH in this solution, and/or,
4th solution is addition nano silicon dioxide sol on the basis of the 3rd solution, and mixing speed is 1000～1600 revs/min, mixing time 30～60 minutes.
8. a hydrophober, it is characterised in that for vehicle glass, adopts the hydrophober preparation method as described in claim 1-7 to prepare.
9. the preparation method of a hydrophobic glass, it is characterised in that comprise the steps:
A. glass basis surface dirt is wiped；
B. dip acid solution and in the uniform wiping of glass surface, form non-electrical amorph Si-OH at glass surface；
C. rinse well；
D. treat that glass surface is dried, dip the 4th solution as described in claim 1-7 in the uniform wiping in its surface；
E. dry and obtain hydrophobic membranous layer.
10. a hydrophobic glass, it is characterised in that adopt hydrophober preparation method as claimed in claim 9 to prepare, or adopt and prepare with the following method:
A. glass basis surface dirt is wiped with superfine fibre cloth；
B. dip the hydrochloric acid of 1mol/L or salpeter solution and in the uniform wiping of glass surface with superfine fibre cloth, form non-electrical amorph Si-OH at glass surface；
C. clean with deionized water or distilled water flushing；
D. treat that glass surface is dried, dip a small amount of the 4th solution as described in claim 1-7 in the uniform wiping in its surface with superfine fibre cloth；
E. at room temperature natural drying 5～10 minutes；
F. use superfine fibre cloth in the glass surface wiping of coated 4th solution；
G. natural drying can obtain the hydrophobic membranous layer that is firmly combined with for more than 12 hours.
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| CN109355012A (en) * | 2018-10-31 | 2019-02-19 | 西安近代化学研究所 | A kind of preparation method and application containing Nano diamond fluorine-containing organic silicon hydrophobing agent |
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