CN104129790B - A kind of Nano-meter SiO_22microsphere, hydrophober, its preparation method and hydrophobic glass - Google Patents

A kind of Nano-meter SiO_22microsphere, hydrophober, its preparation method and hydrophobic glass Download PDF

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CN104129790B
CN104129790B CN201410407416.5A CN201410407416A CN104129790B CN 104129790 B CN104129790 B CN 104129790B CN 201410407416 A CN201410407416 A CN 201410407416A CN 104129790 B CN104129790 B CN 104129790B
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solution
glass
alcohol
hydrophober
water
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CN201410407416.5A
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CN104129790A (en
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陈大华
熊建民
洪丽
秦玉林
徐蕤
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奇瑞汽车股份有限公司
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Abstract

The present invention relates to a kind of Nano-meter SiO_22Microsphere, hydrophober, its preparation method and hydrophobic glass, use the hydrolysis of base catalysis silicic acid fat, acid activation two-step method to form the high-activity nano microsphere with certain particle size range, to containing this SiO2Microsphere colloidal sol adds the appropriate hydrolyzed silane solution containing perfluoroalkyl, is mixed by the stirring of certain time and realize perfluoroalkyl silanes to Nano-meter SiO_22Microsphere surface is modified, and forms hydrophober, is coated on by this hydrophober and can form the hydrophobic membranous layer with relatively high hydrophobic and durability through the glass basis surface of pre-treatment.Present invention process is simple, with low cost, and effect is notable, and on vehicle glass, application can improve the degree of getting a clear view of driver and crew in rainy weather, improves safety.

Description

A kind of Nano-meter SiO_22Microsphere, hydrophober, its preparation method and hydrophobic glass
Technical field
The present invention relates to Nano-meter SiO_22Microsphere, hydrophober and hydrophobic glass preparing technical field, be specifically related to a kind of Nano-meter SiO_22Microsphere, hydrophober, its preparation method and hydrophobic glass.
Background technology
The vehicle travelled in the rainy day affects the human pilot visual field because rainwater forms moisture film at side window and windshield glass surface spreading, and the most therefore causes accident to occur.The film layer with hydrophobic effect can be obtained in glass surface modification low-surface energy substance, rainwater can be punctured into ball-type voluntarily on its surface, under Gravitative Loads, landing or fly away from glass surface under wind-force effect and take away glass surface dust voluntarily, can improve human pilot degree of getting a clear view;Additionally, in snow cold weather gas, its surface frost layer of glass scribbling hydrophober can be removed easily.Therefore, hydrophobic membranous layer imparts the effect that glass is easy to clean.
At present, the realization of hydrophobic glass technology is typically to plate a layered low-surface energy material at the glass surface through decontamination, defat and activation processing, obtain the hydrophobic membranous layer that water contact angle is about 105 °, this hydrophobic membranous layer initial effect is preferable, but deposits the impact of suspended particulate substance in an atmosphere or windscreen wiper scraping in actual use and cause rapid failure.Low and the problem of poor durability for solution initial contact angle,
The most following prior art:
1) CN200410012854.8 submicron and the preparation method of nanometer spherical silicon dioxide
2) preparing spherical SiO 2 of CN200410059518.9 surface-treated with silane-titania-based fine grained, its production method and application thereof
3) preparation method of a CN200510000151.8 preparing spherical SiO 2 particles
4) preparation method of CN200910112653.8 silica aerogel material
In sum, prior art exists following technical problem: presently commercially available vehicle glass hydrophober exists the problems such as poor durability, contact angle are low in application process, and meanwhile, the application of part hydrophober needs to operate under certain epidemic disaster, complex process.
Summary of the invention
It is an object of the invention to provide a kind of Nano-meter SiO_22Microsphere and be applicable to hydrophober, the good hydrophobic glass preparation method of durability that vehicle glass surface hydrophobicization processes.The hydrolysis of base catalysis silicic acid fat, acid activation two-step method is used to form the high-activity nano microsphere with certain particle size range, to containing this SiO2Microsphere colloidal sol adds the appropriate hydrolyzed silane solution containing perfluoroalkyl, is mixed by the stirring of certain time and realize perfluoroalkyl silanes to Nano-meter SiO_22Microsphere surface is modified, and forms hydrophober, is coated on by this hydrophober and can form the hydrophobic membranous layer with relatively high hydrophobic and durability through the glass basis surface of pre-treatment.Concrete technical scheme is as follows:
A kind of Nano-meter SiO_22The preparation method of microsphere, comprises the steps:
(1) tetraethyl orthosilicate is scattered in alcohol-water solution formation solution A;
(2) strong aqua ammonia is added in alcohol, form alcohol ammonia solution B;
(3) solution B added in solution A and stir;
(4) spherical SiO obtaining in solution C and solution C is stood2Particle.
Further,
In step (1), mass ratio shared by water is 0.4%~2.6%, and mass ratio shared by tetraethyl orthosilicate is 1.8%~2.0%, and surplus is alcohol;
And/or,
Described water is deionized water or distilled water;
And/or,
Described alcohol is a kind of or the most several mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
Further,
In step (2), NH in alcohol ammonia solution B3Mass percentage content is 3.1%~7.2%, and surplus is alcoholic solvent;
And/or,
Described alcohol is a kind of or the most several mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
Further, in step (3), under room temperature, solution B is added in solution A with the speed of 20~45 μ l/min, adding while solution A in solution B and stir, mixing speed is 500~1000 turns/min, solution B after being added completely into solution A the continuously stirred time be 30~120min;
And/or,
In step (4), uncovered standing 24~72h obtains solution C.
A kind of Nano-meter SiO_22Microsphere, uses above-mentioned preparation method to prepare, and particle diameter is 10~75nm.
A kind of employing Nano-meter SiO_22The method of hydrophober prepared by microsphere, to containing this SiO2Microsphere colloidal sol adds the appropriate hydrolyzed silane solution containing perfluoroalkyl, is mixed by the stirring of certain time and realize perfluoroalkyl silanes to Nano-meter SiO_22Microsphere surface is modified, and forms hydrophober.
Further, following steps are specifically included:
(1) ammonia alcoholic solution is slowly dropped in tetraethyl orthosilicate alcohol-water solution, stirring hydrolysis;
(2) naturally place, escape ammonia;
(3) perfluoroalkyl silanes is added in alcohol-water solution, and add appropriate amount of acid catalyzing 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, sulphuric acid or nitric acid and water are mixed to get solution D according to volume ratio 1:1;Described hydrochloric acid, sulphuric acid or nitric acid is concentrated acid, and described water is deionized water or distilled water;
And/or,
In step (3), solution D, perfluoroalkyl silanes and alcoholic solvent being mixed, wherein mass ratio shared by solution D is 6%~10%, and mass ratio shared by perfluoroalkyl silanes is 1~2%, surplus is alcoholic solvent, obtains solution E with 200~500 turns/min stirring 4~24h;Described perfluoroalkyl silanes structural formula is:
Wherein the span of m is 2~30, and the span of n is 1~3, and the span of a is 0~2;R is perfluor carbochain or perfluoroether chain, and X is hydrolyzable groups;Described alcohol is a kind of or the most several mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol;
And/or,
In step (4), solution E is mixed according to mass ratio 0.5~3:1 with solution C, obtain hydrophober solution F with 200~500 turns/min stirring 0.5~4h.
A kind of hydrophobic glass, further, by said method prepare containing SiO2The hydrophober of microsphere is coated on and is formed through the glass basis surface of pre-treatment.
Further, comprise the steps: to wipe glass basis surface dirt 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, dip a small amount of above-mentioned hydrophober solution F in the uniform wiping in its surface with superfine fibre cloth, the most naturally place after wiping 24h or at 80~150 DEG C heat treatment 10~60min.
Compared with currently available technology, the present invention uses base catalysis, the method for acid activation prepares the Nano-meter SiO_2 with greater activity2Microsphere, the hydrophober solution obtained after perfluoroalkyl silanes is modified can form the hydrophobic membranous layer with relatively high hydrophobic and endurance quality with glass reaction.Present invention process is simple, with low cost, and effect is notable, and on vehicle glass, application can improve the degree of getting a clear view of driver and crew in rainy weather, improves safety.
Specifically:
1. use the hydrolysis of base catalysis silicic acid fat, acid activation two-step method to form the Nano-meter SiO_2 with greater activity2Microsphere;
2. use perfluoroalkyl silanes to modify SiO2Microsphere forms hydrophober;
3. will be containing SiO2The hydrophober of microsphere is coated on and forms hydrophobic glass through the glass basis surface of pre-treatment;
Hydrophobic glass water contact angle the most of the present invention is not less than 111 °, and after under 300g/cm loads, windscreen wiper is swiped 30,000 and circulated, remaining contact angle is not less than 106 °.
Accompanying drawing explanation
Fig. 1 is hydrophobic glass preparation technology flow process
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.
A kind of Nano-meter SiO_22Microsphere and hydrophober preparation method and hydrophobic glass, its preparation process is as follows: 1. be slowly dropped in ethyl acetate alcohol-water solution by ammonia alcoholic solution, stirring hydrolysis, the most naturally places, effusion ammonia;2. perfluoroalkyl silanes is added in alcohol-water solution, and add appropriate amount of acid catalyzing hydrolysis, after hydrolysis, this solution is mixed according to mass ratio and the 1st step gained solution of 0.5~3:1, form hydrophober;3. second step gained hydrophober solution is coated on the glass basis surface through pre-treatment, obtains hydrophobic glass.Specifically:
1. Nano-meter SiO_22Prepared by microsphere
A kind of Nano-meter SiO_22Method for preparing microsphere, comprises the following steps:
(1) tetraethyl orthosilicate is scattered in alcohol-water solution formation solution A, and wherein mass ratio shared by water is 0.4%~2.6%, and mass ratio shared by tetraethyl orthosilicate is 1.8%~2.0%, and surplus is alcohol;Described water is deionized water or distilled water;Described alcohol is a kind of or the most several mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
(2) strong aqua ammonia is added in alcohol, form alcohol ammonia solution B, NH in this alcohol ammonia solution B3Mass percentage content is 3.1%~7.2%, and surplus is alcoholic solvent;Described alcohol is a kind of or the most several mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
(3) under room temperature, solution B is added in solution A with the speed of 20~45 μ l/min, stir while solution B adds solution A, mixing speed is 500~1000 turns/min, solution B after being added completely into solution A the continuously stirred time be 30~120min, the most uncovered standing 24~72h obtains solution C.
Said method is used to can get the spherical SiO that particle diameter is 10~75nm2Particle.
2. prepared by hydrophober
Hydrophober preparation method comprises the following steps:
(1) hydrochloric acid, sulphuric acid or nitric acid and water are mixed to get solution D according to volume ratio 1:1;Described hydrochloric acid, sulphuric acid or nitric acid is concentrated acid, and described water is deionized water or distilled water.
(2) solution D, perfluoroalkyl silanes and alcoholic solvent being mixed, wherein mass ratio shared by solution D is 6%~10%, and mass ratio shared by perfluoroalkyl silanes is 1~2%, and surplus is alcoholic solvent, obtains solution E with 200~500 turns/min stirring 4~24h;Described perfluoroalkyl silanes structural formula is represented by:
Wherein the span of m is 2~30, and the span of n is 1~3, and the span of preferably n=1, a is 0~2, preferably a=0 or 1, most preferably 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.
Described alcohol is a kind of or the most several mixture in the alcohols solvents such as ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
(3) solution E is mixed according to mass ratio 0.5~3:1 with solution C, obtain hydrophober solution F with 200~500 turns/min stirring 0.5~4h.
3. 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, a small amount of above-mentioned hydrophober solution F is dipped in the uniform wiping in its surface with superfine fibre cloth, after wiping the most naturally place 24h or at 80~150 DEG C heat treatment 10~60min, due to the Nano-meter SiO_2 in hydrophober solution F2There is a large amount of non-electrical amorph-OH in microsphere surface, partly the perfluoroalkyl silanes hydrolyzed reaction product after-OH and hydrolysis in hydrophober solution, and the Si-OH of another part-OH and glass surface reacts and forms-Si-O-Si-structure, i.e. Nano-meter SiO_22The existence of microsphere is equivalent to add the asperity of glass surface, adds reaction site, i.e. adds the quantity of unit are glass surface hydrophobic group, therefore can obtain the hydrophobic glass with preferable hydrophobicity performance and endurance quality.
Preferred embodiment one: the present embodiment provides a kind of Nano-meter SiO_22The preparation method of microsphere, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) being scattered in ethanol/distilled water by tetraethyl orthosilicate and obtain solution A, wherein tetraethyl orthosilicate mass percentage content is 1.88%, and distilled water mass percentage content is 2.53%, and surplus is ethanol;Strong aqua ammonia is added in ethanol, obtain NH3Mass percentage content is the solution B of 6.60%;Adding in solution A by solution B with the speed of 20 μ l/min, stir with 1000 turns/min simultaneously, continuously stirred 30min after solution B all adds in solution A, the most uncovered standing 72h obtain solution C, SiO in solution C2Microspherulite diameter is about 75nm.
(2) hydrochloric acid and distilled water are mixed to get solution D according to the ratio of 1:1;By perfluoroalkyl silanesIt is mixed to get perfluoroalkyl silanes/mixed alkoxide solution with ethanol, solution D is added in perfluoroalkyl silanes/mixed alkoxide solution according to the mass ratio of 6% and stirs with 500 turns/min, stirring 24h obtains solution E, and wherein perfluoroalkyl silanes mass percentage content in solution E is 1%.
(3) solution E is mixed according to the mass ratio of 0.5:1 with solution C, obtain hydrophober solution F with 500 turns/min stirring 4h.
(4) glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid solution of 1mol/L is dipped and in the uniform wiping of glass surface with superfine fibre cloth, after wiping clean with distilled water flushing, treat that glass surface dips a small amount of hydrophober solution F with superfine fibre cloth after drying, then in the uniform wiping of glass surface, after wiping, glass is placed the most naturally 24h and obtains hydrophobic glass.3 μ l water droplets are 116.24 ° at this hydrophobic glass surface initial contact angle, carry the load applying 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, reciprocal 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 Nano-meter SiO_22The preparation method of microsphere, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) being scattered in ethanol/distilled water by tetraethyl orthosilicate and obtain solution A, wherein tetraethyl orthosilicate mass percentage content is 1.90%, and distilled water mass percentage content is 1.63%, and surplus is ethanol;Strong aqua ammonia is added in ethanol, obtain NH3Mass percentage content is the solution B of 5.55%;Adding in solution A by solution B with the speed of 25 μ l/min, stir with 800 turns/min simultaneously, continuously stirred 60min after solution B all adds in solution A, the most uncovered standing 72h obtain solution C, SiO in solution C2Microspherulite diameter is about 63nm.
(2) hydrochloric acid and distilled water are mixed to get solution D according to the ratio of 1:1;By perfluoroalkyl silanesIt is mixed to get perfluoroalkyl silanes/alcohol mixed solution with ethanol, solution D is added in perfluoroalkyl silanes/alcohol mixed solution according to the mass ratio of 10% and stirs with 400 turns/min, stirring 4h obtains solution E, and wherein perfluoroalkyl silanes mass percentage content in solution E is 1.5%.
(3) solution E is mixed according to the mass ratio of 1:1 with solution C, obtain hydrophober solution F with 500 turns/min stirring 2h.
(4) glass basis surface dirt is wiped with superfine fibre cloth, then the salpeter solution of 1mol/L is dipped and in the uniform wiping of glass surface with superfine fibre cloth, after wiping clean with distilled water flushing, treat that glass surface dips a small amount of hydrophober solution F with superfine fibre cloth after drying, then in the uniform wiping of glass surface, after wiping, glass is placed at 80 DEG C 60min and obtains hydrophobic glass.3 μ l water droplets are 115.39 ° at this hydrophobic glass surface initial contact angle, carry the load applying 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, reciprocal 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 Nano-meter SiO_22The preparation method of microsphere, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) being scattered in ethanol/distilled water by tetraethyl orthosilicate and obtain solution A, wherein tetraethyl orthosilicate mass percentage content is 1.91%, and distilled water mass percentage content is 1.03%, and surplus is ethanol;Strong aqua ammonia is added in ethanol, obtain NH3Mass percentage content is the solution B of 4.39%;Adding in solution A by solution B with the speed of 30 μ l/min, stir with 500 turns/min simultaneously, continuously stirred 90min after solution B all adds in solution A, the most uncovered standing 48h obtain solution C, SiO in solution C2Microspherulite diameter is about 24nm.
(2) hydrochloric acid and distilled water are mixed to get solution D according to the ratio of 1:1;By perfluoroalkyl silanes CF3-(CF2)7-(CH2)2-Si[OCH(CH3)2]3It is mixed to get perfluoroalkyl silanes/isopropyl alcohol mixture with isopropanol, solution D is added in perfluoroalkyl silanes/isopropyl alcohol mixture according to the mass ratio of 8% and stirs with 500 turns/min, stirring 12h obtains solution E, and wherein perfluoroalkyl silanes mass percentage content in solution E is 2%.
(3) solution E is mixed according to the mass ratio of 2:1 with solution C, obtain hydrophober solution F with 500 turns/min stirring 4h.
(4) glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid solution of 1mol/L is dipped and in the uniform wiping of glass surface with superfine fibre cloth, after wiping clean with distilled water flushing, treat that glass surface dips a small amount of hydrophober solution F with superfine fibre cloth after drying, then in the uniform wiping of glass surface, after wiping, glass is placed at 120 DEG C naturally 10min and obtains hydrophobic glass.3 μ l water droplets are 113.61 ° at this hydrophobic glass surface initial contact angle, carry the load applying 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, reciprocal 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 Nano-meter SiO_22The preparation method of microsphere, hydrophobic modifier and hydrophobic glass, comprises the following steps:
(1) being scattered in ethanol/distilled water by tetraethyl orthosilicate and obtain solution A, wherein tetraethyl orthosilicate mass percentage content is 1.92%, and distilled water mass percentage content is 0.41%, and surplus is ethanol;Strong aqua ammonia is added in ethanol, obtain NH3Mass percentage content is the solution B of 3.09%;Adding in solution A by solution B with the speed of 45 μ l/min, stir with 600 turns/min simultaneously, continuously stirred 120min after solution B all adds in solution A, the most uncovered standing 24h obtain solution C, SiO in solution C2Microspherulite diameter is about 10nm.
(2) hydrochloric acid and distilled water are mixed to get solution D according to the ratio of 1:1;By perfluoroalkyl silanes CF3-(CF2)7-(CH2)2-Si[OCH(CH3)2]3It is mixed to get perfluoroalkyl silanes/isopropyl alcohol mixture with isopropanol, solution D is added in perfluoroalkyl silanes/isopropyl alcohol mixture according to the mass ratio of 8% and stirs with 500 turns/min, stirring 24h obtains solution E, and wherein perfluoroalkyl silanes mass percentage content in solution E is 2%.
(3) solution E is mixed according to the mass ratio of 3:1 with solution C, obtain hydrophober solution F with 500 turns/min stirring 4h.
(4) glass basis surface dirt is wiped with superfine fibre cloth, then the hydrochloric acid solution of 1mol/L is dipped and in the uniform wiping of glass surface with superfine fibre cloth, after wiping clean with distilled water flushing, treat that glass surface dips a small amount of hydrophober solution F with superfine fibre cloth after drying, then in the uniform wiping of glass surface, after wiping, glass is placed the most naturally 24h and obtains hydrophobic glass.3 μ l water droplets are 111.66 ° at this hydrophobic glass surface initial contact angle, carry the load applying 300g/cm on windscreen wiper bar, then prepared hydrophobic glass is rubbed, reciprocal 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 °.
Above in conjunction with accompanying drawing, the present invention is exemplarily described; obviously the present invention implements and is not subject to the restrictions described above; if the various improvement that the method design that have employed the present invention is carried out with technical scheme; or it is the most improved that directly apply to other occasion, all within protection scope of the present invention.

Claims (6)

1. a Nano-meter SiO_22The preparation method of microsphere, it is characterised in that comprise the steps:
(1) tetraethyl orthosilicate is scattered in alcohol-water solution formation solution A;
(2) strong aqua ammonia is added in alcohol, form alcohol ammonia solution B;
(3) solution B added in solution A and stir;
(4) spherical SiO obtaining in solution C and solution C is stood2Particle;
In step (1), mass ratio shared by water is 0.4%~2.6%, mass ratio shared by tetraethyl orthosilicate be 1.8%~ 2.0%, surplus is alcohol;
And/or,
Described water is deionized water or distilled water;
And/or,
Described alcohol is a kind of or the most several mixture in ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol;
In step (2), NH in alcohol ammonia solution B3Mass percentage content is 4.39% or 5.55%~7.2%, Surplus is alcoholic solvent;
And/or,
Described alcohol is a kind of or the most several mixture in ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol.
2. Nano-meter SiO_2 as claimed in claim 12The preparation method of microsphere, it is characterised in that step (3) In, under room temperature, solution B is added in solution A with the speed of 20~45 μ l/min, adds molten in solution B Stirring while liquid A, mixing speed is 500~1000 turns/min, and solution B is added completely into solution A The rear continuously stirred time is 30~120min;
And/or,
In step (4), uncovered standing 24~72h obtains solution C.
3. a Nano-meter SiO_22Microsphere, it is characterised in that use the side of preparation as claimed in claim 1 or 2 Method prepares, and particle diameter is 24~75nm.
4. one kind uses Nano-meter SiO_2 described in claim 32The method of hydrophober prepared by microsphere, it is characterised in that To containing this SiO2Microsphere colloidal sol adds the appropriate hydrolyzed silane solution containing perfluoroalkyl, passes through certain time Stirring mixing realize perfluoroalkyl silanes to Nano-meter SiO_22Microsphere surface is modified, and forms hydrophober;Concrete bag Include following steps:
(1) ammonia alcoholic solution is slowly dropped in tetraethyl orthosilicate alcohol-water solution, stirring hydrolysis;
(2) naturally place, escape ammonia;
(3) perfluoroalkyl silanes is added in alcohol-water solution, and add appropriate amount of acid catalyzing hydrolysis;
(4) being mixed with step (1) gained solution according to certain mass ratio by this solution after hydrolysis, formation is hated Water preparation;
In step (1), hydrochloric acid, sulphuric acid or nitric acid and water are mixed to get solution D according to volume ratio 1:1; Described hydrochloric acid, sulphuric acid or nitric acid is concentrated acid, and described water is deionized water or distilled water;
And/or,
In step (3), solution D, perfluoroalkyl silanes and alcoholic solvent are mixed, wherein matter shared by solution D Amount ratio is 6%~10%, and mass ratio shared by perfluoroalkyl silanes is 1~2%, and surplus is alcoholic solvent, with 200~ 500 turns/min stirring 4~24h obtains solution E;Described perfluoroalkyl silanes structural formula is:
Wherein the span of m is 10~30, and the value of n is 1, and the value of a is 0 or 1;R is perfluor Carbochain or perfluoroether chain, X is hydrolyzable groups, and R ' is H or alkoxyl;Described alcohol be ethanol, positive third A kind of or the most several mixture in alcohol, isopropanol, n-butyl alcohol;
And/or,
In step (4), solution E is mixed according to mass ratio 0.5~1:1 with solution C, with 200~500 Turn/min stirring 0.5~4h obtains hydrophober solution F.
5. a hydrophobic glass, it is characterised in that by method described in claim 4 prepare containing SiO2Micro- The hydrophober of ball is coated on and is formed through the glass basis surface of pre-treatment.
6. the preparation method of hydrophobic glass described in a claim 5, it is characterised in that comprise the steps: Wipe glass basis surface dirt with superfine fibre cloth, then with superfine fibre cloth dip 1mol/L hydrochloric acid or Salpeter solution in the uniform wiping of glass surface, forms non-electrical amorph Si-OH at glass surface, then spend from Sub-water or distilled water flushing are clean, treat that glass surface is dried, dip a small amount of above-mentioned hydrophober with superfine fibre cloth Solution F in the uniform wiping in its surface, after wiping the most naturally place 24h or at 80~120 DEG C heat Process 10~60min, increase the quantity of unit are glass surface hydrophobic group, obtain that there is preferable hydrophobicity Energy and the hydrophobic glass of endurance quality.
CN201410407416.5A 2014-08-18 2014-08-18 A kind of Nano-meter SiO_22microsphere, hydrophober, its preparation method and hydrophobic glass CN104129790B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN106291911A (en) * 2016-08-10 2017-01-04 华南师范大学 Hydrophobicity dielectric layer, its preparation method and the Electrowetting device of lamination layer structure

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* Cited by examiner, † Cited by third party
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Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN103964448A (en) * 2014-05-09 2014-08-06 奇瑞汽车股份有限公司 Method for preparing monodisperse silicon dioxide nanoparticle sol for paint

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CN106291911A (en) * 2016-08-10 2017-01-04 华南师范大学 Hydrophobicity dielectric layer, its preparation method and the Electrowetting device of lamination layer structure
CN106291911B (en) * 2016-08-10 2019-06-11 华南师范大学 Hydrophobicity dielectric layer, preparation method and the Electrowetting device of lamination layer structure

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