CN104129790A - Nano SiO2 microsphere, water-repelling agent, preparation methods of nano SiO2 microsphere and water-repelling agent, and water-repelling glass - Google Patents
Nano SiO2 microsphere, water-repelling agent, preparation methods of nano SiO2 microsphere and water-repelling agent, and water-repelling glass Download PDFInfo
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- CN104129790A CN104129790A CN201410407416.5A CN201410407416A CN104129790A CN 104129790 A CN104129790 A CN 104129790A CN 201410407416 A CN201410407416 A CN 201410407416A CN 104129790 A CN104129790 A CN 104129790A
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- 239000011521 glass Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004005 microsphere Substances 0.000 title claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 title abstract description 10
- 239000000377 silicon dioxide Substances 0.000 title abstract description 8
- 239000003795 chemical substances by application Substances 0.000 title abstract 7
- 229910052681 coesite Inorganic materials 0.000 title abstract 7
- 229910052906 cristobalite Inorganic materials 0.000 title abstract 7
- 229910052682 stishovite Inorganic materials 0.000 title abstract 7
- 229910052905 tridymite Inorganic materials 0.000 title abstract 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000007062 hydrolysis Effects 0.000 claims abstract description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 77
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 230000002209 hydrophobic effect Effects 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- -1 perfluoroalkyl silane Chemical compound 0.000 claims description 29
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 26
- 239000012153 distilled water Substances 0.000 claims description 25
- 230000001476 alcoholic effect Effects 0.000 claims description 21
- 239000004744 fabric Substances 0.000 claims description 21
- 239000000835 fiber Substances 0.000 claims description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 19
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000002203 pretreatment Methods 0.000 claims description 5
- 229910008051 Si-OH Inorganic materials 0.000 claims description 4
- 229910006358 Si—OH Inorganic materials 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 8
- 230000004913 activation Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000413 hydrolysate Substances 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 124
- 230000004087 circulation Effects 0.000 description 14
- 238000001994 activation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 238000005815 base catalysis Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000004965 Silica aerogel Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
The invention relates to a nano SiO2 microsphere, a water-repelling agent, preparation methods of the nano SiO2 microspheres and the water-repelling agent, and water-repelling glass. High-activity microspheres within a certain particle size range are formed by use of a two-step method of base catalyzed silicate hydrolysis and acid activation; appropriate perfluoroalkyl-containing silane hydrolysate is added to a sol containing the SiO2 microspheres, the surface of the SiO2 microspheres is modified by the perfluoroalkyl-containing silane by use of stirring and mixing for certain time, and then the water-repelling agent is formed; the water-repelling agent is applied to the surface of a pretreated glass substrate so that a water-repelling film having relatively high hydrophobicity and durability can be formed. The nano SiO2 microsphere and the water-repelling agent are simple in process, low in cost, remarkable in effect and capable of improving the view clarity of drivers and passengers in overcast and rain weather and improving the safety if being applied to the automobile glass.
Description
Technical field
The present invention relates to nanometer SiO
2microballoon, hydrophober and hydrophobic glass preparing technical field, be specifically related to a kind of nanometer SiO
2microballoon, hydrophober, its preparation method and hydrophobic glass.
Background technology
The vehicle travelling in the rainy day affects the navigating mate visual field because rainwater forms moisture film at side window and windshield glass surface spreading, and often therefore causes accident to occur.At glass surface modification low surface energy material, can obtain the rete with hydrophobic effect, rainwater can be punctured into ball-type voluntarily on its surface, under Gravitative Loads, landing or fly away from glass surface and take away glass surface dust under wind effect voluntarily, can improve navigating mate degree of getting a clear view; In addition,, in snow cold weather gas, its surperficial frost layer of glass that scribbles hydrophober can be removed easily.Therefore, hydrophobic membranous layer has given glass effect easy to clean.
At present, the realization of hydrophobic glass technology normally plates a layered low-surface energy material at the glass surface through decontamination, degreasing and activation treatment, obtain the hydrophobic membranous layer that water contact angle is 105 ° of left and right, the initial effect of this hydrophobic membranous layer is better, but exists in actual use the impact of suspended particulate in atmosphere or windscreen wiper swipe and cause rapid failure.For solution initial contact angle is low and the problem of poor durability,
Following prior art for example:
1) preparation method of CN200410012854.8 submicron and nanometer spherical silicon-dioxide
2) preparing spherical SiO 2 of CN200410059518.9 surface-treated with silane-titania-based fine particle, its production method and uses thereof
3) preparation method of a CN200510000151.8 preparing spherical SiO 2 particles
4) preparation method of CN200910112653.8 silica aerogel material
In sum, have following technical problem in prior art: current commercially available vehicle glass hydrophober exists the problems such as poor durability, contact angle are low in application process, meanwhile, the application of part hydrophober need to operate under a constant temperature, humidity, complex process.
Summary of the invention
The object of the present invention is to provide a kind of nanometer SiO
2microballoon and be applicable to the good hydrophobic glass preparation method of hydrophober, weather resistance that vehicle glass surface hydrophobisation is processed.Adopt the hydrolysis of base catalysis silicic acid fat, acid activation two-step approach to form the high-activity nano microballoon with certain particle size range, to containing this SiO
2in microballoon colloidal sol, add the hydrolyzed silane solution that contains in right amount perfluoroalkyl, by being uniformly mixed of certain hour, realize perfluoroalkyl silane to nanometer SiO
2microsphere surface is modified, and forms hydrophober, and the glass basis surface that this hydrophober is coated on through pre-treatment can form the hydrophobic membranous layer having compared with high hydrophobic and weather resistance.Concrete technical scheme is as follows:
A kind of nanometer SiO
2the preparation method of microballoon, comprises the steps:
(1) tetraethoxy is scattered in and in alcohol solution, forms solution A;
(2) strong aqua is added in alcohol, form alcohol ammonia solution B;
(3) solution B added in solution A and stir;
(4) the standing spherical SiO obtaining in solution C and solution C
2particle.
Further,
In step (1), the shared mass ratio of water is 1.8%～2.0%, and the shared mass ratio of tetraethoxy is 0.4%～2.6%, and surplus is alcohol;
And/or,
Described water is deionized water or distilled water;
And/or,
Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
Further,
In step (2), NH in alcohol ammonia solution B
3mass percentage content is 3.1%～7.2%, and surplus is alcoholic solvent;
And/or,
Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
Further, in step (3), under room temperature, speed by solution B with 20～45 μ l/min adds in solution A, when solution B adds solution A, stir, stirring velocity is 500～1000 turn/min, and solution B adds that to continue churning time after solution A be 30～120min completely;
And/or,
In step (4), uncovered standing 24～72h obtains solution C.
A kind of nanometer SiO
2microballoon, adopts above-mentioned preparation method to make, and particle diameter is 10～75nm.
A kind of employing nanometer SiO
2microballoon is prepared the method for hydrophober, to containing this SiO
2in microballoon colloidal sol, add the hydrolyzed silane solution that contains in right amount perfluoroalkyl, by being uniformly mixed of certain hour, realize perfluoroalkyl silane to nanometer SiO
2microsphere surface is modified, and forms hydrophober.
Further, specifically comprise the steps:
(1) ammonia alcoholic solution is slowly splashed in ethyl acetate alcohol solution, stir hydrolysis;
(2) naturally place effusion ammonia;
(3) perfluoroalkyl silane is added in alcohol solution, and add appropriate amount of acid catalytic hydrolysis;
(4) after hydrolysis, this solution is mixed with step (1) gained solution according to certain mass ratio, form hydrophober.
Further,
In step (1), hydrochloric acid, sulfuric acid or nitric acid and water are mixed to get to solution D according to volume ratio 1:1; Described hydrochloric acid, sulfuric acid or nitric acid are concentrated acid, and described water is deionized water or distilled water;
And/or,
In step (3), solution D, perfluoroalkyl silane and alcoholic solvent are mixed, and wherein the shared mass ratio of solution D is 6%～10%, and the shared mass ratio of perfluoroalkyl silane is 1～2%, surplus is alcoholic solvent, stirs 4～24h obtain solution E with 200～500 turn/min; Described perfluoroalkyl silane structure formula is:
The span that the span that wherein span of m is 2～30, n is 1～3, a is 0～2; R is perfluor carbochain or full fluorinated ether chain, and X is hydrolysable group; Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein;
And/or,
In step (4), solution E is mixed according to mass ratio 0.5～3:1 with solution C, with 200～500 turn/min, stir 0.5～4h and obtain hydrophober solution F.
A hydrophobic glass, further, that by aforesaid method, is prepared contains SiO
2the glass basis surface that the hydrophober of microballoon is coated on through pre-treatment forms.
Further, comprise the steps: to wipe glass basis surface dirt with ultra-fine fibre cloth, then with ultra-fine fibre cloth, dip the hydrochloric acid of 1mol/L or salpeter solution and in the even wiping of glass surface, at glass surface, form unionized state Si-OH, then clean with deionized water or distilled water flushing, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of above-mentioned hydrophober solution F in its surface uniform wiping, after wiping, at room temperature naturally place 24h or thermal treatment 10～60min at 80～150 ℃.
Compare with currently available technology, the present invention adopts the method for base catalysis, acid activation to prepare the nanometer SiO with greater activity
2microballoon, the hydrophober solution obtaining after perfluoroalkyl is hydride modified can with glass reaction, form and to have compared with the hydrophobic membranous layer of high hydrophobic and endurance quality.Technique of the present invention is simple, with low cost, and effect is remarkable, and on vehicle glass, application can improve the degree of getting a clear view of driver and crew in rainy weather, and improves security.
Specifically:
1. adopt the hydrolysis of base catalysis silicic acid fat, acid activation two-step approach to form the nanometer SiO with greater activity
2microballoon;
2. adopt the hydride modified SiO of perfluoroalkyl
2microballoon forms hydrophober;
3. will contain SiO
2the glass basis surface that the hydrophober of microballoon is coated on through pre-treatment forms hydrophobic glass;
4. hydrophobic glass water contact angle of the present invention is not less than 111 °, and under 300g/cm load, after 30,000 circulations of windscreen wiper scraping, remaining contact angle is not less than 106 °.
Accompanying drawing explanation
Fig. 1 is hydrophobic glass preparation technology flow process
Embodiment
Describe the present invention with reference to the accompanying drawings below, it is a kind of preferred embodiment in numerous embodiments of the present invention.
A kind of nanometer SiO
2microballoon and hydrophober preparation method and hydrophobic glass, its preparation process is as follows: 1. ammonia alcoholic solution is slowly splashed in ethyl acetate alcohol solution, stir hydrolysis, then naturally place effusion ammonia; 2. perfluoroalkyl silane is added in alcohol solution, and add appropriate amount of acid catalytic hydrolysis, after hydrolysis, this solution is mixed with the 1st step gained solution according to the mass ratio of 0.5～3:1, form hydrophober; 3. the 2nd step gained hydrophober solution is coated on to the glass basis surface through pre-treatment, obtains hydrophobic glass.Particularly:
1. nanometer SiO
2microballoon preparation
A kind of nanometer SiO
2method for preparing microsphere, comprises the following steps:
(1) tetraethoxy is scattered in alcohol solution and forms solution A, wherein the shared mass ratio of water is 1.8%～2.0%, and the shared mass ratio of tetraethoxy is 0.4%～2.6%, and surplus is alcohol; Described water is deionized water or distilled water; Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
(2) strong aqua is added in alcohol, form alcohol ammonia solution B, NH in this alcohol ammonia solution B
3mass percentage content is 3.1%～7.2%, and surplus is alcoholic solvent; Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
(3) under room temperature, speed by solution B with 20～45 μ l/min adds in solution A, when adding solution A, solution B stirs, stirring velocity is 500～1000 turn/min, solution B adds that to continue churning time after solution A be 30～120min completely, and then uncovered standing 24～72h obtains solution C.
Adopt aforesaid method can obtain the spherical SiO that particle diameter is 10～75nm
2particle.
2. hydrophober preparation
Hydrophober is preparation method comprise the following steps:
(1) hydrochloric acid, sulfuric acid or nitric acid and water are mixed to get to solution D according to volume ratio 1:1; Described hydrochloric acid, sulfuric acid or nitric acid are concentrated acid, and described water is deionized water or distilled water.
(2) solution D, perfluoroalkyl silane and alcoholic solvent are mixed, wherein the shared mass ratio of solution D is 6%～10%, and the shared mass ratio of perfluoroalkyl silane is 1～2%, and surplus is alcoholic solvent, stirs 4～24h obtain solution E with 200～500 turn/min; Described perfluoroalkyl silane structure formula can be expressed as:
The span that wherein span of m is 2～30, n is 1～3, preferred n=1, and the span of a is 0～2, preferably a=0 or 1, most preferably a=0; R is perfluor carbochain or full fluorinated ether chain, as-CF
2-CF
2-CF
2-,-CF
2-CF
2-CF
2-O-or-CF
2-CF (CF
3)-O-; X is hydrolysable group, and as halogeno-group or alkoxyl group, R ' is H or alkoxyl group.
Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
(3) solution E is mixed according to mass ratio 0.5～3:1 with solution C, with 200～500 turn/min, stir 0.5～4h and obtain hydrophober solution F.
3. hydrophobic glass preparation
First with ultra-fine fibre cloth, wipe glass basis surface dirt, then with ultra-fine fibre cloth, dip the hydrochloric acid of 1mol/L or salpeter solution and in the even wiping of glass surface, at glass surface, form unionized state Si-OH, then clean with deionized water or distilled water flushing, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of above-mentioned hydrophober solution F in its surface uniform wiping, after wiping, at room temperature naturally place 24h or at 80～150 ℃ thermal treatment 10～60min, due to the nanometer SiO in hydrophober solution F
2there are a large amount of unionized state-OH in microsphere surface, partly-OH reacts with the perfluoroalkyl silane hydrolyzate product after hydrolysis in hydrophober solution, and another part-OH reacts formation-Si-O-Si-structure, i.e. nanometer SiO with the Si-OH of glass surface
2the existence of microballoon has been equivalent to increase the nano and micro relief of glass surface, has increased reaction site, has increased the quantity of unit surface glass surface hydrophobic grouping, therefore can obtain having the hydrophobic glass of better hydrophobicity performance and endurance quality.
Preferred embodiment one: the present embodiment provides a kind of nanometer SiO
2the preparation method of microballoon, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) tetraethoxy is scattered in ethanol/distilled water and obtains solution A, wherein tetraethoxy mass percentage content is 1.88%, and distilled water mass percentage content is 2.53%, and surplus is ethanol; Strong aqua is added in ethanol, obtain NH
3mass percentage content is 6.60% solution B; Speed by solution B with 20 μ l/min adds in solution A, stirs with 1000 turn/min simultaneously, continues to stir 30min after solution B all adds in solution A, and then uncovered standing 72h obtains solution C, SiO in solution C
2microspherulite diameter is about 75nm.
(2) hydrochloric acid and distilled water are mixed to get to solution D according to the ratio of 1:1; By perfluoroalkyl silane
be mixed to get perfluoroalkyl silane/mixed alkoxide solution with ethanol, solution D is added in perfluoroalkyl silane/mixed alkoxide solution and with 500 turn/min and stirred according to 6% mass ratio, stir 24h and obtain solution E, wherein the mass percentage content of perfluoroalkyl silane in solution E is 1%.
(3) solution E is mixed according to the mass ratio of 0.5:1 with solution C, with 500 turn/min, stir 4h and obtain hydrophober solution F.
(4) with ultra-fine fibre cloth, wipe glass basis surface dirt, then with ultra-fine fibre cloth, dip the hydrochloric acid soln of 1mol/L and in the even wiping of glass surface, clean with distilled water flushing after wiping, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of hydrophober solution F, then in the even wiping of glass surface, after wiping, glass is at room temperature placed to 24h naturally and obtain hydrophobic glass.3 μ l water droplets are 116.24 ° at this hydrophobic glass surface initial contact angle, carry the load that applies 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, back and forth friction is once designated as a circulation, after 30,000 circulation frictions, remaining contact angle is 107.44 °, after 50,000 circulation frictions, remaining contact angle is 106.69 °, and after 150,000 circulation frictions, remaining contact angle is 99.30 °.
Preferred embodiment two: the present embodiment provides a kind of nanometer SiO
2the preparation method of microballoon, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) tetraethoxy is scattered in ethanol/distilled water and obtains solution A, wherein tetraethoxy mass percentage content is 1.90%, and distilled water mass percentage content is 1.63%, and surplus is ethanol; Strong aqua is added in ethanol, obtain NH
3mass percentage content is 5.55% solution B; Speed by solution B with 25 μ l/min adds in solution A, stirs with 800 turn/min simultaneously, continues to stir 60min after solution B all adds in solution A, and then uncovered standing 72h obtains solution C, SiO in solution C
2microspherulite diameter is about 63nm.
(2) hydrochloric acid and distilled water are mixed to get to solution D according to the ratio of 1:1; By perfluoroalkyl silane
be mixed to get perfluoroalkyl silane/alcohol mixed solution with ethanol, solution D is added in perfluoroalkyl silane/alcohol mixed solution and with 400 turn/min and stirred according to 10% mass ratio, stir 4h and obtain solution E, wherein the mass percentage content of perfluoroalkyl silane in solution E is 1.5%.
(3) solution E is mixed according to the mass ratio of 1:1 with solution C, with 500 turn/min, stir 2h and obtain hydrophober solution F.
(4) with ultra-fine fibre cloth, wipe glass basis surface dirt, then with ultra-fine fibre cloth, dip the salpeter solution of 1mol/L and in the even wiping of glass surface, clean with distilled water flushing after wiping, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of hydrophober solution F, then in the even wiping of glass surface, after wiping, glass is placed to 60min at 80 ℃ and obtain hydrophobic glass.3 μ l water droplets are 115.39 ° at this hydrophobic glass surface initial contact angle, carry the load that applies 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, back and forth friction is once designated as a circulation, after 30,000 circulation frictions, remaining contact angle is 108.83 °, and after 50,000 circulation frictions, remaining contact angle is 105.02 °.
Preferred embodiment three: the present embodiment provides a kind of nanometer SiO
2the preparation method of microballoon, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) tetraethoxy is scattered in ethanol/distilled water and obtains solution A, wherein tetraethoxy mass percentage content is 1.91%, and distilled water mass percentage content is 1.03%, and surplus is ethanol; Strong aqua is added in ethanol, obtain NH
3mass percentage content is 4.39% solution B; Speed by solution B with 30 μ l/min adds in solution A, stirs with 500 turn/min simultaneously, continues to stir 90min after solution B all adds in solution A, and then uncovered standing 48h obtains solution C, SiO in solution C
2microspherulite diameter is about 24nm.
(2) hydrochloric acid and distilled water are mixed to get to solution D according to the ratio of 1:1; By perfluoroalkyl silane CF
3-(CF
2)
7-(CH
2)
2-Si[OCH (CH
3)
2]
3be mixed to get perfluoroalkyl silane/isopropyl alcohol mixture with Virahol, solution D is added in perfluoroalkyl silane/isopropyl alcohol mixture and with 500 turn/min and stirred according to 8% mass ratio, stir 12h and obtain solution E, wherein the mass percentage content of perfluoroalkyl silane in solution E is 2%.
(3) solution E is mixed according to the mass ratio of 2:1 with solution C, with 500 turn/min, stir 4h and obtain hydrophober solution F.
(4) with ultra-fine fibre cloth, wipe glass basis surface dirt, then with ultra-fine fibre cloth, dip the hydrochloric acid soln of 1mol/L and in the even wiping of glass surface, clean with distilled water flushing after wiping, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of hydrophober solution F, then in the even wiping of glass surface, after wiping, glass is naturally placed at 120 ℃ to 10min and obtained hydrophobic glass.3 μ l water droplets are 113.61 ° at this hydrophobic glass surface initial contact angle, carry the load that applies 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, back and forth friction is once designated as a circulation, after 30,000 circulation frictions, remaining contact angle is 108.37 °, and after 50,000 circulation frictions, remaining contact angle is 104.08 °.
Preferred embodiment four: the present embodiment provides a kind of nanometer SiO
2the preparation method of microballoon, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) tetraethoxy is scattered in ethanol/distilled water and obtains solution A, wherein tetraethoxy mass percentage content is 1.92%, and distilled water mass percentage content is 0.41%, and surplus is ethanol; Strong aqua is added in ethanol, obtain NH
3mass percentage content is 3.09% solution B; Speed by solution B with 45 μ l/min adds in solution A, stirs with 600 turn/min simultaneously, continues to stir 120min after solution B all adds in solution A, and then uncovered standing 24h obtains solution C, SiO in solution C
2microspherulite diameter is about 10nm.
(2) hydrochloric acid and distilled water are mixed to get to solution D according to the ratio of 1:1; By perfluoroalkyl silane CF
3-(CF
2)
7-(CH
2)
2-Si[OCH (CH
3)
2]
3be mixed to get perfluoroalkyl silane/isopropyl alcohol mixture with Virahol, solution D is added in perfluoroalkyl silane/isopropyl alcohol mixture and with 500 turn/min and stirred according to 8% mass ratio, stir 24h and obtain solution E, wherein the mass percentage content of perfluoroalkyl silane in solution E is 2%.
(3) solution E is mixed according to the mass ratio of 3:1 with solution C, with 500 turn/min, stir 4h and obtain hydrophober solution F.
(4) with ultra-fine fibre cloth, wipe glass basis surface dirt, then with ultra-fine fibre cloth, dip the hydrochloric acid soln of 1mol/L and in the even wiping of glass surface, clean with distilled water flushing after wiping, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of hydrophober solution F, then in the even wiping of glass surface, after wiping, glass is at room temperature placed to 24h naturally and obtain hydrophobic glass.3 μ l water droplets are 111.66 ° at this hydrophobic glass surface initial contact angle, carry the load that applies 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, back and forth friction is once designated as a circulation, after 30,000 circulation frictions, remaining contact angle is 107.02 °, and after 50,000 circulation frictions, remaining contact angle is 103.24 °.
By reference to the accompanying drawings the present invention is exemplarily described above; obviously specific implementation of the present invention is not subject to the restrictions described above; as long as the various improvement that adopted method design of the present invention and technical scheme to carry out; or directly apply to other occasion without improvement, all within protection scope of the present invention.
Claims (10)
1. a nanometer SiO
2the preparation method of microballoon, is characterized in that, comprises the steps:
(1) tetraethoxy is scattered in and in alcohol solution, forms solution A;
(2) strong aqua is added in alcohol, form alcohol ammonia solution B;
(3) solution B added in solution A and stir;
(4) the standing spherical SiO obtaining in solution C and solution C
2particle.
2. nanometer SiO as claimed in claim 1
2the preparation method of microballoon, is characterized in that,
In step (1), the shared mass ratio of water is 1.8%～2.0%, and the shared mass ratio of tetraethoxy is 0.4%～2.6%, and surplus is alcohol;
And/or,
Described water is deionized water or distilled water;
And/or,
Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
3. nanometer SiO as claimed in claim 1 or 2
2the preparation method of microballoon, is characterized in that,
In step (2), NH in alcohol ammonia solution B
3mass percentage content is 3.1%～7.2%, and surplus is alcoholic solvent;
And/or,
Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein.
4. the nanometer SiO as described in any one in claim 1-3
2the preparation method of microballoon, it is characterized in that, in step (3), under room temperature, speed by solution B with 20～45 μ l/min adds in solution A, when solution B adds solution A, stir, stirring velocity is 500～1000 turn/min, and solution B adds that to continue churning time after solution A be 30～120min completely;
And/or,
In step (4), uncovered standing 24～72h obtains solution C.
5. a nanometer SiO
2microballoon, is characterized in that, adopts the preparation method as described in claim 1-4 to make, and particle diameter is 10～75nm.
6. one kind adopts nanometer SiO described in claim 5
2microballoon is prepared the method for hydrophober, it is characterized in that, to containing this SiO
2in microballoon colloidal sol, add the hydrolyzed silane solution that contains in right amount perfluoroalkyl, by being uniformly mixed of certain hour, realize perfluoroalkyl silane to nanometer SiO
2microsphere surface is modified, and forms hydrophober.
7. nanometer SiO as claimed in claim 6
2microballoon is prepared the method for hydrophober, it is characterized in that, specifically comprises the steps:
(1) ammonia alcoholic solution is slowly splashed in ethyl acetate alcohol solution, stir hydrolysis;
(2) naturally place effusion ammonia;
(3) perfluoroalkyl silane is added in alcohol solution, and add appropriate amount of acid catalytic hydrolysis;
(4) after hydrolysis, this solution is mixed with step (1) gained solution according to certain mass ratio, form hydrophober.
8. nanometer SiO as described in claim 6 or 7
2microballoon is prepared the method for hydrophober, it is characterized in that,
In step (1), hydrochloric acid, sulfuric acid or nitric acid and water are mixed to get to solution D according to volume ratio 1:1; Described hydrochloric acid, sulfuric acid or nitric acid are concentrated acid, and described water is deionized water or distilled water;
And/or,
In step (3), solution D, perfluoroalkyl silane and alcoholic solvent are mixed, and wherein the shared mass ratio of solution D is 6%～10%, and the shared mass ratio of perfluoroalkyl silane is 1～2%, surplus is alcoholic solvent, stirs 4～24h obtain solution E with 200～500 turn/min; Described perfluoroalkyl silane structure formula is:
The span that the span that wherein span of m is 2～30, n is 1～3, a is 0～2; R is perfluor carbochain or full fluorinated ether chain, and X is hydrolysable group; Described alcohol is a kind of in the alcoholic solvents such as ethanol, n-propyl alcohol, Virahol, propyl carbinol or several mixture wherein;
And/or,
In step (4), solution E is mixed according to mass ratio 0.5～3:1 with solution C, with 200～500 turn/min, stir 0.5～4h and obtain hydrophober solution F.
9. a hydrophobic glass, is characterized in that, that by method described in claim 6-8, is prepared contains SiO
2the glass basis surface that the hydrophober of microballoon is coated on through pre-treatment forms.
10. the preparation method of hydrophobic glass as claimed in claim 9, it is characterized in that, comprise the steps: to wipe glass basis surface dirt with ultra-fine fibre cloth, then with ultra-fine fibre cloth, dip the hydrochloric acid of 1mol/L or salpeter solution and in the even wiping of glass surface, at glass surface, form unionized state Si-OH, then clean with deionized water or distilled water flushing, after glass surface is dry, with ultra-fine fibre cloth, dip a small amount of above-mentioned hydrophober solution F in its surface uniform wiping, after wiping, at room temperature naturally place 24h or thermal treatment 10～60min at 80～150 ℃.
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