CN104387812A - Fluoroalkyl silane-modified metal oxide nano material and preparation method and application thereof - Google Patents
Fluoroalkyl silane-modified metal oxide nano material and preparation method and application thereof Download PDFInfo
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- CN104387812A CN104387812A CN201410670427.2A CN201410670427A CN104387812A CN 104387812 A CN104387812 A CN 104387812A CN 201410670427 A CN201410670427 A CN 201410670427A CN 104387812 A CN104387812 A CN 104387812A
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Abstract
The invention discloses a fluoroalkyl silane-modified metal oxide nano material, which is prepared by grafting fluorine-modified alkylsilane on the surfaces of metal oxide particles. The reaction materials comprise a nano-sized metal oxide and the fluorine-modified alkylsilane according to the mass ratio of (3 to 7) to 1. In addition, the invention also discloses a preparation method and an application of the fluoroalkyl silane-modified metal oxide nano material. Fluoroalkyl silane is successfully grafted on the nano metal oxide surface through a chemical modification method; and the obtained fluoroalkyl silane-modified metal oxide nano material has the advantages of small particle size, even distribution, good dispersion stability, wide application scope and the like, and also has the properties of hydrophobic performance, lipophobicity, fingerprint resistance and the like when being used as a coating. The fluoroalkyl silane-modified metal oxide nano material is simple in production process, convenient to use, safe, environmentally friendly, and suitable for large-scale popularization and application.
Description
Technical field
The present invention relates to technical field of nano material, particularly relate to a kind of silicon fluoride modified metal-oxide nano material and its preparation method and application.
Background technology
Along with the raising of people's living standard, multifunctional material is more and more subject to people's attention, and wherein nano-metal-oxide is because having the special propertys such as surface effects, small-size effect, optical effect, and coated coating can be made to obtain new function.But, nano-metal-oxide specific surface area is large, surface energy is high, be in thermodynamic (al) unsteady state, by the effect of Van der Waals force between particle, make them be easy to reunite together and form the larger-size coacervate with some loosely-boned interface, so just the practical application effect even eliminating nano particle is greatly reduced, its application on industrial circle is greatly limited, and therefore, it is necessary for carrying out surface modification to nano-metal-oxide.
At present, the surface modification of prior art nano-metal-oxide, is mainly bondd with adsorptive power by nano particle and tensio-active agent and realized, but the improvement of material property is still limited, in particular for the process of substrate surface.Because applied environment is day by day complicated, thus the requirement of effects on surface process material is also more and more higher, needs to possess multifunctionality and excellent performance, otherwise is difficult to adapt to higher more complicated application demand.Therefore, how to carry out modification to material and make it possess multifunctionality, and provide the environment for use of simple production technique and safety, be direction and the problem that material supplier author is devoted to research always.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of silicon fluoride modified metal-oxide nano material with good hydro-oleophobicity is provided, to adapt to complicated and multi-functional application demand.Another object of the present invention is to the preparation method and application that above-mentioned silicon fluoride modified metal-oxide nano material is provided.
Object of the present invention is achieved by the following technical programs:
A kind of silicon fluoride modified metal-oxide nano material provided by the invention, by being prepared from metal oxide particle surface grafting fluorine richness alkyl silane, its reaction raw materials is as follows:
Nanosize metal oxide;
Fluorine richness alkyl silane, structural formula is R
f-(CH
2)
n-Si (OR
1)
3, wherein, R
1for methyl or ethyl, R
ffor C
mf
2m+1or C
6f
5, 0≤n≤3,1≤m≤13, n, m are integer;
Described reaction raw materials nanosize metal oxide in mass ratio: fluorine richness alkyl silane=3 ~ 7: 1;
Described preparation process is: joined in the mixing solutions be made up of solvent and water by described nanosize metal oxide, and the pH value of regulator solution system is in alkalescence; Then in solution system, add fluorine richness alkyl silane obtain silicon fluoride modified metal-oxide nano material to carry out surface graft modification to metal oxide particle.
Nano material of the present invention is the colourless transparent solution with good stability, and its activeconstituents is nano level silicon fluoride modified metal-oxide particle.
Further, the median size of nanosize metal oxide of the present invention is 1 ~ 100nm.Described metal oxide is one in zinc, aluminium, manganese, titanium, magnesium, zirconium, ferroelectric metal oxide or its combination.
Another object of the present invention is achieved by the following technical programs:
The preparation method of above-mentioned silicon fluoride modified metal-oxide nano material provided by the invention, comprises the following steps:
(1) joined by nanosize metal oxide in the mixing solutions be made up of solvent and water, at 35 ~ 65 DEG C of temperature, stir 30 ~ 60min, then keeping this temperature and adding basic catalyst regulator solution system pH is 8 ~ 13, continues stirring 1 ~ 3h;
(2) in solution system, add fluorine richness alkyl silane, at 35 ~ 65 DEG C of temperature, continue stirring reaction 2 ~ 6h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modified metal-oxide nano material.
Further, preparation method of the present invention is according to water described in volume ratio: solvent: fluorine richness alkyl silane=1 ~ 3: 20 ~ 60: 1.Described solvent is one in ethanol, ethylene glycol, Virahol, Isopropanediol or its combination.Described basic catalyst is sodium hydroxide, strong aqua or sodium ethylate.
Above-mentioned silicon fluoride modified metal-oxide applications to nanostructures provided by the invention, is applicable to the surface treatment of glass, pottery, metal, plastics, rubber, electronic devices and components etc.
The present invention has following beneficial effect:
(1) the present invention is by chemical modification method, at the successful grafting fluorine richness alkyl silane in nano-metal-oxide surface, gained modified nano metal oxide have granularity little, be evenly distributed, the advantage such as dispersion stabilization is good, suitable application area is wide; And stable performance, stability in storage is good, at room temperature place 6 months not stratified, without obvious sediment, there is resistant of high or low temperature, the ageing resistance of the excellence that metallic substance and organosilicon material possess.
(2) nano material of the present invention and substrate surface are with chemical bonds, strong adhesion, on the surface of glass, pottery, metal, plastics, rubber, electronic devices and components etc., all there is good sticking power (test according to GB/T 9286-1998, sticking power all reaches 0 grade).And, the excellent properties such as coating solvent resistant, chemically stable, lower surface energy are imparted due to the introducing of fluoro-containing group, water, wet goods pollutent are difficult to be attached on surface, thus there is good resistance to soiling, the performances such as there is hydrophobic, oleophobic, anti-fingerprint are used as coating, be greater than 115 ° with the contact angle of water, be greater than 100 ° with the contact angle of oil, can give substrate surface dust-proof, antifouling and self-cleaning function.
(3) production technique of the present invention is simple, and easy to use, volatile matter is mainly alcohols that is substantially nontoxic or low toxicity, safety and environmental protection.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment one:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 30g nano level (1 ~ 100nm) titanium dioxide is joined in the mixing solutions be made up of 150ml ethanol and 10ml water, 30min is stirred at 35 DEG C of temperature, then keeping this temperature and adding strong aqua regulator solution system pH is 10, continues to stir 1h;
(2) in solution system, add 10g (7ml) ten trifluoro octyl group Trimethoxy silane, at 35 DEG C of temperature, continue stirring reaction 2h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modifying titanium dioxide nano material.
Embodiment two:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 50g nano level (1 ~ 100nm) zinc oxide is joined in the mixing solutions be made up of 250ml ethylene glycol and 15ml water, 45min is stirred at 45 DEG C of temperature, then keeping this temperature and adding sodium hydrate regulator solution system pH is 11, continues to stir 1.5h;
(2) in solution system, add 10g (7ml) ten trifluoro octyltri-ethoxysilane, at 45 DEG C of temperature, continue stirring reaction 3h, obtain clear solution, filter reaction product and namely obtain the modified oxidized zinc nano material of silicon fluoride.
Embodiment three:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 70g nano level (1 ~ 100nm) aluminium sesquioxide is joined in the mixing solutions be made up of 420ml Virahol and 20ml water, 60min is stirred at 55 DEG C of temperature, then keeping this temperature and adding sodium ethylate regulator solution system pH is 12, continues to stir 2h;
(2) in solution system, add 10g (7ml) 17 fluorine decyl Trimethoxy silane, at 55 DEG C of temperature, continue stirring reaction 4h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modification aluminium sesquioxide nano material.
Embodiment four:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 70g nano level (1 ~ 100nm) Manganse Dioxide is joined in the mixing solutions be made up of 420ml Isopropanediol and 21ml water, 50min is stirred at 65 DEG C of temperature, then keeping this temperature and adding sodium hydrate regulator solution system pH is 13, continues to stir 2.5h;
(2) in solution system, add 10g (7ml) 17 fluorine decyl triethoxyl silane, at 65 DEG C of temperature, continue stirring reaction 5h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modified manganese dioxide nano material.
Embodiment five:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 60g nano level (1 ~ 100nm) magnesium oxide is joined in the mixing solutions be made up of 360ml Virahol and 15ml water, 45min is stirred at 60 DEG C of temperature, then keeping this temperature and adding strong aqua regulator solution system pH is 9, continues to stir 3h;
(2) in solution system, add 10g (7ml) (CH
3o)
3si-(CH
2)
3-C
6f
5, at 60 DEG C of temperature, continue stirring reaction 6h, obtain clear solution, filter reaction product and namely obtain the modified oxidized magnesium nano material of silicon fluoride.
Embodiment six:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 50g nano level (1 ~ 100nm) zirconium white is joined in the mixing solutions be made up of 300ml ethylene glycol and 20ml water, 40min is stirred at 50 DEG C of temperature, then keeping this temperature and adding strong aqua regulator solution system pH is 8, continues to stir 1h;
(2) in solution system, add 10g (7ml) (CH
3cH
2o)
3si-(CH
2)
3-C
6f
5, at 50 DEG C of temperature, continue stirring reaction 4h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modified zirconia nano material.
Embodiment seven:
The preparation method of the present embodiment silicon fluoride modified metal-oxide nano material, its step is as follows:
(1) 40g nano level (1 ~ 100nm) ferric oxide is joined in the mixing solutions be made up of 300ml ethanol and 10ml water, 30min is stirred at 40 DEG C of temperature, then keeping this temperature and adding sodium ethylate regulator solution system pH is 9, continues to stir 2h;
(2) in solution system, add 10g (7ml) pentafluorophenyl group triethoxyl silane, at 40 DEG C of temperature, continue stirring reaction 5h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modification ferric oxide nano-material.
Performance test:
The silicon fluoride modified metal-oxide nano material prepared with the above embodiment of the present invention, adopt crystal pulling method to prepare silicon fluoride modified metal-oxide film at transparent glass surface, and test sticking power, acid resistance, resistant of high or low temperature, artificial accelerated aging and the contact angle with water and glycerine.Test result is as shown in table 1.
The performance index of silicon fluoride modified metal-oxide nano material prepared by table 1 various embodiments of the present invention
A kind of silicon fluoride modified metal-oxide of the present invention nano material and its preparation method and application, its reaction raw materials composition and preparation method's processing parameter are not limited to the above-mentioned embodiment enumerated.
Claims (8)
1. a silicon fluoride modified metal-oxide nano material, is characterized in that: by being prepared from metal oxide particle surface grafting fluorine richness alkyl silane, its reaction raw materials is as follows:
Nanosize metal oxide;
Fluorine richness alkyl silane, structural formula is R
f-(CH
2)
n-Si (OR
1)
3, wherein, R
1for methyl or ethyl, R
ffor C
mf
2m+1or C
6f
5, 0≤n≤3,1≤m≤13, n, m are integer;
Described reaction raw materials nanosize metal oxide in mass ratio: fluorine richness alkyl silane=3 ~ 7: 1;
Described preparation process is: joined in the mixing solutions be made up of solvent and water by described nanosize metal oxide, and the pH value of regulator solution system is in alkalescence; Then in solution system, add fluorine richness alkyl silane obtain silicon fluoride modified metal-oxide nano material to carry out surface graft modification to metal oxide particle.
2. silicon fluoride modified metal-oxide nano material according to claim 1, is characterized in that: the median size of described nanosize metal oxide is 1 ~ 100nm.
3. silicon fluoride modified metal-oxide nano material according to claim 1 and 2, is characterized in that: described metal oxide is one in zinc, aluminium, manganese, titanium, magnesium, zirconium, ferroelectric metal oxide or its combination.
4. the preparation method of one of claim 1-3 described silicon fluoride modified metal-oxide nano material, is characterized in that comprising the following steps:
(1) joined by nanosize metal oxide in the mixing solutions be made up of solvent and water, at 35 ~ 65 DEG C of temperature, stir 30 ~ 60min, then keeping this temperature and adding basic catalyst regulator solution system pH is 8 ~ 13, continues stirring 1 ~ 3h;
(2) in solution system, add fluorine richness alkyl silane, at 35 ~ 65 DEG C of temperature, continue stirring reaction 2 ~ 6h, obtain clear solution, filter reaction product and namely obtain silicon fluoride modified metal-oxide nano material.
5. the preparation method of silicon fluoride modified metal-oxide nano material according to claim 4, is characterized in that: according to water described in volume ratio: solvent: fluorine richness alkyl silane=1 ~ 3: 20 ~ 60: 1.
6. the preparation method of the silicon fluoride modified metal-oxide nano material according to claim 4 or 5, is characterized in that: described solvent is one in ethanol, ethylene glycol, Virahol, Isopropanediol or its combination.
7. the preparation method of silicon fluoride modified metal-oxide nano material according to claim 4, is characterized in that: described basic catalyst is sodium hydroxide, strong aqua or sodium ethylate.
8. one of claim 1-3 described silicon fluoride modified metal-oxide applications to nanostructures, is characterized in that: described nano material is used for the surface treatment of glass, pottery, metal, plastics, rubber, electronic devices and components etc.
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| CN109390457A (en) * | 2018-09-10 | 2019-02-26 | 天津大学 | Automatically cleaning LED encapsulation coating and preparation method thereof |
| CN116676807A (en) * | 2023-05-17 | 2023-09-01 | 中国人民大学 | Paper deacidification dispersion liquid and preparation method and application thereof |
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Effective date of registration: 20200528 Address after: Workshop 3 and 4, no.6, Tonglin Road, Nanhai national ecological industry demonstration park, Danzao Town, Nanhai District, Foshan City, Guangdong Province Patentee after: Foshan Nanhai Yile Engineering Plastics Co.,Ltd. Address before: 213 room 12, 510663 research road, Science City, Guangzhou hi tech Industrial Development Zone, Guangdong, China Patentee before: GUANGZHOU QIANCHENG CHEMICAL TECHNOLOGY DEVELOPMENT Co.,Ltd. |
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