CN103755152B - A kind of super-hydrophobic SiO 2the preparation method of aerogel - Google Patents
A kind of super-hydrophobic SiO 2the preparation method of aerogel Download PDFInfo
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- CN103755152B CN103755152B CN201310695739.4A CN201310695739A CN103755152B CN 103755152 B CN103755152 B CN 103755152B CN 201310695739 A CN201310695739 A CN 201310695739A CN 103755152 B CN103755152 B CN 103755152B
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Abstract
The present invention adopts the mixing solutions of hydrochloric acid and hexamethyldisiloxane to SiO
2film carries out hydrophobically modified, and use the vitriol oil as catalyzer, promote that reaction is carried out to the right, namely more trimethylchlorosilane is generated, trimethylchlorosilane is more, and during modification, activity is stronger, thus makes trimethylchlorosilane can be spread to film inside, reduce the capillary force of material internal, realize film complete modification from inside to outside.Relative to existing hydrophobically modified method, the present invention saves expensive solvent replacing step, enormously simplify technique, easily realize industrialization and produce, and environmental pollution is little, has tempting application prospect.
Description
Technical field
The present invention relates to thin film technique field, particularly relate to a kind of super-hydrophobic SiO
2the preparation method of aerogel.
Background technology
Hydrophobic glass can be widely used in the surface of various waterproof, frost prevention and efflorescence prevention, as the glassworks such as automobile and aircraft windshield, building doors and windows glass, cladding glass, mirror and glasses all exist a difficult problem for waterproof and cleaning.Use the daily life that Hydrophobic glass can not only be convenient for people to greatly, and can larger economic benefit be created.Mostly being used in material surface is coated with the method for thin film to obtain Hydrophobic glass both at home and abroad at present.
SiO
2aerogel is a kind of novel nano-porous materials, is a kind of hydrophobic film having utilization prospect.Secondly, SiO
2aerogel also has the characteristics such as low thermal conductivity, high light transmittance, high porosity and low density, and glass applies one deck SiO
2aerogel is one of effective way improving the heat insulation and preservation effect such as energy saving building window glass and windshield.Therefore, SiO
2the research of aerogel has become a study hotspot in domestic and international inorganic functional heat-insulating heat-preserving material field.
SiO
2the hydrophobicity of aerogel is relevant with the network structure of its inside with thermal insulation, and due to SiO
2-OH the hydrophilic radical to ambient moisture and moisture-sensitive is there is in aerogel network internal structure, make the moisture of film in absorbed air, the contraction of film is caused even to occur crackle, damage its porous network structure, thus the heat-proof quality of deleterious film, namely heat-proof quality is also relevant with hydrophobicity to a certain extent.Therefore, SiO can be improved
2the hydrophobicity of aerogel is the emphasis of research at present.
When constant pressure and dry, the condensation between hydroxyl can cause aerogel that serious contraction occurs, cave in and the situation such as fragmentation, thus affects it and obtain the excellent properties such as low density, high-specific surface area, therefore, adopts hydrophobic modifier to SiO
2aerogel oh group carries out modifying and decorating, keeps the porous network structure of film, effectively improves its hydrophobic performance.
Publication number is the preparation method that CN103359954 discloses a kind of hexa-methyldisilazane graft modified silicon sol and super-hydrophobic silica film, and it utilizes intermolecular dehydration reaction by-Si(CH in hexamethyldisilazane
3)
3group is grafted in silicon sol molecule, makes the micelle surface of silicon sol be covered with-Si(CH
3)
3group, obtains the hydrophobic colloidal silica of modification, is finally coated in matrix surface.But the properties-correcting agent that this method uses is hexamethyldisilazane, and environmental pollution is larger.
Tongji University Liu Guang force waits people, and (water glass is the super-hydrophobic SiO in source
2aerogel block body UV absorber, silicate journal, the 40th volume the 1st phase, in January, 2012) adopt the mixed solution modification wet gel of hexamethyldisiloxane (HMDSO) and a small amount of hydrochloric acid to prepare SiO
2aerogel block body, gained aerogel block body surface contact angle can reach more than 150 °, and this method of modifying adopts the mixing solutions of hydrochloric acid and hexamethyldisiloxane, and modified effect is good, and environmental pollution is little.But this method of modifying speed of response is gentleer, and modification efficiency is low, being difficult to be diffused into bulk inner to properties-correcting agent during block modification, so have to pass through solvent replacing step in advance, with the ethanol replacement SiO that surface tension is little
2the water that aerogel block body interior surface tension force is large, avoids the effect due to capillary force in drying process to there will be phenomenon of caving in.
Summary of the invention
For the deficiencies in the prior art, of the present inventionly provide a kind of super-hydrophobic SiO
2the preparation method of aerogel.
A kind of super-hydrophobic SiO
2the preparation method of aerogel, comprises the following steps:
(1) alkaline silicon solution is prepared acidic silicasol by ion exchange resin, be then 5.0-6.0 by basic solution adjust ph, obtain SiO
2colloidal sol;
(2) SiO described in utilization
2colloidal sol, adopts dipping-pulling method to prepare SiO on substrate
2wet gel film;
(3) by SiO that step (2) prepares
2carry out aging in wet gel film immersion deionized water;
(4) by the SiO after aging
2wet gel film be soaked in the mixed solution of hexamethyldisiloxane and hydrochloric acid, add the vitriol oil as catalyzer, carry out hydrophobically modified;
(5) SiO after hydrophobically modified will be carried out
2wet gel film is dry 24h at normal temperatures, forms super-hydrophobic SiO
2aerogel.
There is following reaction in aqueous in hydrochloric acid and hexamethyldisiloxane:
(CH
3)
3SiOSi(CH
3)
3+2HCl—2(CH
3)
3SiCl+2H
2O。
Because reaction is from left to right thermo-negative reaction, therefore hydrochloric acid (HCl) and hexamethyldisiloxane ((CH
3)
3siOSi (CH
3)
3) reaction generation trimethylchlorosilane ((CH
3)
3siCl) efficiency is very low, and trimethylchlorosilane is the Main Function agent of hydrophobically modified, so adopt hydrochloric acid and the modification of hexamethyldisiloxane mixing solutions to need certain temperature and longer time could realize hydrophobically modified more completely, and be difficult to be deep into bulk inner modification.
The present invention adopts the mixing solutions of hydrochloric acid and hexamethyldisiloxane to SiO
2film carries out hydrophobically modified, and use the vitriol oil as catalyzer, promote that reaction is carried out from left to right, namely more properties-correcting agent (trimethylchlorosilane) is generated, properties-correcting agent is more, and during modification, activity is stronger, thus makes properties-correcting agent can be spread to film inside (film thickness is at micron order), reduce the capillary force of material internal, realize film complete modification from inside to outside.Relative to existing hydrophobically modified method, the present invention saves expensive solvent replacing step, enormously simplify technique, easily realize industrialization and produce, and environmental pollution is little, has tempting application prospect.
In described step (1), the pH value of acidic silicasol is 1.0 ~ 3.0, and then use basic solution adjust ph, the PH making the solution finally obtained is 5.0 ~ 6.0, namely obtains SiO
2silicon sol (SiO
2colloidal sol).
The present invention also directly can adopt the silicon sol of purchase.
Before preparing wet gel film in described step (2) on substrate, substrate need through cleaning, drying treatment, and described substrate can be common slide glass.
Dipping-pulling method is adopted to prepare SiO in described step (2)
2during wet gel film, first substrate to be immersed in silicon sol and to keep 10 ~ 50s, then with the speed of 2.0 ~ 3.0cm/s, substrate being lifted out, thus prepare SiO on substrate
2wet gel film.The speed of lift determines the SiO of preparation
2the thickness of aerogel.
In described step (3), digestion time is 4 ~ 48h.
In mixed solution in described step (4), the volume ratio of hexamethyldisiloxane and hydrochloric acid is 2 ~ 8:1, and the mass percent concentration of described hydrochloric acid is 36% ~ 38%.As preferably, in mixed solution, the volume ratio of hexamethyldisiloxane and hydrochloric acid is 2:1.
Described vitriol oil mass percent concentration is 70% ~ 99%.General employing percentage concentration is the vitriol oil of 98%.
The volume ratio of the described vitriol oil and described mixing solutions is 0.1% ~ 5%.When the vitriol oil is more, reacts faster, but react too fast, the quality of the aerogel prepared can be reduced.Generally, the volume ratio of the vitriol oil and described mixing solutions is less than 5%.As preferably, the volume ratio of the vitriol oil and described mixing solutions is 5%.
When adopting the properties-correcting agent of the mixing solutions of hydrochloric acid and hexamethyldisiloxane as hydrophobically modified, reaction conditions is gentle, but needing certain temperature, after interpolation catalyzer, just can carry out modification at normal temperatures, can carry out in a heated condition for accelerating hydrophobically modified efficiency.Therefore, as preferably, in described step (4), the temperature of hydrophobically modified is 25 ~ 80 DEG C.
As preferably, in described step (4), the time of hydrophobically modified is 4 ~ 48h.
Due to water glass (Na
2siO
3) wide material sources, can preparation cost be reduced.Therefore, described step (1) neutral and alkali silicon solution is Na
2siO
3the aqueous solution.
Alkalescence silicon solution filters water glass (Na by ion exchange resin
2siO
3) wide material sources, and Na
2during the excessive concentration of SiO3, viscosity is strong, not easily passs through ion exchange resin, and when concentration is lower, viscosity is inadequate, cannot form network-like gel structure again.So as preferred, described Na
2siO
3the mass percent concentration of the aqueous solution is 5% ~ 22%.
For avoiding introducing impurity in preparation process, the basic solution in described step (1) is aqueous sodium hydroxide solution or ammoniacal liquor.Because ammoniacal liquor can volatilize, water-soluble being easy to of sodium ion is removed, and therefore, as preferred aqueous sodium hydroxide solution or ammoniacal liquor, can not bring a lot of impurity in final product aerogel into.
Present invention also offers the super-hydrophobic SiO prepared by this preparation method
2aerogel, this super-hydrophobic SiO
2the thickness of aerogel is 100nm ~ 30 μm, visible light transmissivity 80% ~ 96%, and surface contact angle is 120 ° ~ 153 °.
Compared with prior art, the invention has the advantages that:
One, adopt technical grade water glass as silicon source, prepare silicon dioxide gel by ion exchange method, raw materials cost is low, technical maturity, simple.
Two, adopt deionized water aging, effect is better, and eliminates common solvent exchange step.
Three, in hydrophobically modified process, adopt the mixing solutions of hydrochloric acid and hexamethyldisiloxane as modifier, and using the vitriol oil as catalyzer, other modifier environmental pollutions are little relatively, and can recycle and reuse, and greatly reduce costs.
Four, dry under normal temperature and pressure in air atmosphere, while reducing costs, risk is lower, easily operates, and applicability is strong, is applicable to industrialization scale operation.
Five, SiO
2aerogel shows to possess higher transmitance, in certain temperature range, have more stable ultra-hydrophobicity after tested.
Accompanying drawing explanation
Fig. 1 be embodiment 1 prepare there is super-hydrophobic SiO
2the SEM image of aerogel, its magnification is × 50K;
Fig. 2 be embodiment 1 prepare there is super-hydrophobic SiO
2the glass static contact angle photo of aerogel.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with the drawings and specific embodiments, but the present invention is not limited to embodiment, those skilled in the art can adjust according to practical situation.
Embodiment 1
(1) SiO is prepared
2colloidal sol
Be the Na of 10% by mass percent
2siO
3the aqueous solution is 1.5(and acidic silicasol by the solution ph after ion exchange resin Filtration Filtration), then aqueous sodium hydroxide solution (in the present embodiment, the mass percent concentration of aqueous sodium hydroxide solution is 8%) adjust ph is used dropwise to be instilled in acidic silicasol by sodium hydroxide solution to 5.0(), can silicon sol be obtained;
(2) plated film
Adopt dipping-pulling method dried for wash clean slide glass to be immersed in silicon sol and keep 30s, then being lifted out with the speed of 2.2cm/s and obtain wet gel film;
(3) wet gel is aging
The slide glass being coated with wet gel film is immersed in deionized water again and carries out aging 12h;
(4) wet gel modification
By be coated with aging after the slide glass of wet gel film be soaked in 30ml hexamethyldisiloxane and 15ml mass percent is in the mixed solution (namely methyl two silicon ether and hydrochloric acid volume ratio are 2:1) of the hydrochloric acid of 37%, and to add 2ml mass percent be 98% vitriol oil, carry out the modification of wet gel film surface, at 60 DEG C, modify 24h;
(5) Air drying
Finally, by sample dry 24h at normal temperatures, super-hydrophobic SiO is obtained
2aerogel.
The super-hydrophobic SiO that the present embodiment prepares
2the thickness of aerogel is 113nm, and the transmitance of visible ray is 92%.
Fig. 1 is this super-hydrophobic SiO
2the SEM image of aerogel, can find out, this super-hydrophobic SiO
2the surface uniform of aerogel.
Fig. 2 is this super-hydrophobic SiO
2the glass static contact angle photo of aerogel, can find out this super thin SiO
2the contact angle of aerogel is 153.0 °.
Embodiment 2
Step (1) mesosilicic acid na concn is 15%, and all the other are identical with example 1.
The super thin SiO prepared in the present embodiment
2the super-hydrophobic SiO of aerogel
2the thickness of aerogel is 113nm, and the transmitance of visible ray is 93%, and contact angle is 143 °.
Embodiment 3
In step (2), pull rate is 2.8cm/s, and all the other are identical with example 1.
The super thin SiO prepared in the present embodiment
2the super-hydrophobic SiO of aerogel
2the thickness of aerogel is 100nm, and the transmitance of visible ray is 91%, and contact angle is about 134 °.
Embodiment 4
Step (3) digestion time is 20h, and all the other are identical with example 1.
The super thin SiO prepared in the present embodiment
2the super-hydrophobic SiO of aerogel
2the thickness of aerogel is 115nm, and the transmitance of visible ray is 92%, and contact angle is 140 °.
Embodiment 5
Modification temperature 27 DEG C in step (4), modification time is 36h, and all the other are with example 1.
The super thin SiO prepared in the present embodiment
2the super-hydrophobic SiO of aerogel
2the thickness of aerogel is 112nm, and the transmitance of visible ray is 90%, and contact angle is 151.1 °.
Claims (7)
1. a super-hydrophobic SiO
2the preparation method of aerogel, is characterized in that, comprises the following steps:
(1) alkaline silicon solution is prepared acidic silicasol by ion exchange resin, be then 5.0-6.0 by basic solution adjust ph, obtain SiO
2colloidal sol;
(2) SiO described in utilization
2colloidal sol, adopts dipping-pulling method to prepare SiO on substrate
2wet gel film;
(3) by SiO that step (2) prepares
2carry out aging in wet gel film immersion deionized water;
(4) by the SiO after aging
2wet gel film is soaked in the mixed solution of hexamethyldisiloxane and hydrochloric acid, adds the vitriol oil as catalyzer, carries out hydrophobically modified;
Described vitriol oil mass percent concentration is 70% ~ 99%, and the volume ratio of the described vitriol oil and described mixing solutions is 0.1% ~ 5%;
(5) SiO after hydrophobically modified will be carried out
2wet gel film is dry 24h at normal temperatures, forms super-hydrophobic SiO
2aerogel.
2. super-hydrophobic SiO as claimed in claim 1
2the preparation method of aerogel, is characterized in that, in the mixed solution in described step (4), the volume ratio of hexamethyldisiloxane and hydrochloric acid is 2 ~ 8:1, and the mass percent concentration of described hydrochloric acid is 36% ~ 38%.
3. super-hydrophobic SiO as claimed in claim 2
2the preparation method of aerogel, is characterized in that, in described step (4), the temperature of hydrophobically modified is 25 ~ 80 DEG C.
4. super-hydrophobic SiO as claimed in claim 3
2the preparation method of aerogel, is characterized in that, in described step (4), the time of hydrophobically modified is 4 ~ 48h.
5. super-hydrophobic SiO as claimed in claim 4
2the preparation method of aerogel, is characterized in that, described step (1) neutral and alkali silicon solution is Na
2siO
3the aqueous solution.
6. super-hydrophobic SiO as claimed in claim 5
2the preparation method of aerogel, is characterized in that, described Na
2siO
3the mass percent concentration of the aqueous solution be 5% ~ 22%.
7. super-hydrophobic SiO as claimed in claim 6
2the preparation method of aerogel, is characterized in that, the basic solution in described step (1) is aqueous sodium hydroxide solution or ammoniacal liquor.
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| CN103755152B true CN103755152B (en) | 2015-08-26 |
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| CN111515107A (en) * | 2020-04-22 | 2020-08-11 | 江苏百瑞尔包装材料有限公司 | Oxide film with ultrahigh transparent barrier and preparation method thereof |
| KR20220049841A (en) * | 2020-10-15 | 2022-04-22 | 주식회사 엘지화학 | Method of preparing aerogel blanket and the same prepared therefrom |
| CN114315248B (en) * | 2021-12-29 | 2023-03-17 | 上海暖丰保温材料有限公司 | Concrete block and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0490011A1 (en) * | 1990-12-14 | 1992-06-17 | Foret, S.A. | A process to obtain zeolite 4A starting from bauxite |
| CN1865136A (en) * | 2005-05-19 | 2006-11-22 | 同济大学 | Surface activity adjustable nano porous silicon dioxide aerogel and its preparation method |
| CN103359954A (en) * | 2012-04-01 | 2013-10-23 | 比亚迪股份有限公司 | Preparation method of silicon dioxide super-hydrophobic thin film and super-hydrophobic material |
-
2013
- 2013-12-17 CN CN201310695739.4A patent/CN103755152B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0490011A1 (en) * | 1990-12-14 | 1992-06-17 | Foret, S.A. | A process to obtain zeolite 4A starting from bauxite |
| CN1865136A (en) * | 2005-05-19 | 2006-11-22 | 同济大学 | Surface activity adjustable nano porous silicon dioxide aerogel and its preparation method |
| CN103359954A (en) * | 2012-04-01 | 2013-10-23 | 比亚迪股份有限公司 | Preparation method of silicon dioxide super-hydrophobic thin film and super-hydrophobic material |
Non-Patent Citations (1)
| Title |
|---|
| 水玻璃为源的超疏水型SiO2气凝胶块体制备与表征;刘光武等;《硅酸盐学报》;20120131;第40卷(第1期);第160-164页 * |
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