CN101209843A - Method for preparing anhydrous silicon dioxide organic solvent dispersion - Google Patents
Method for preparing anhydrous silicon dioxide organic solvent dispersion Download PDFInfo
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- CN101209843A CN101209843A CNA2007101727422A CN200710172742A CN101209843A CN 101209843 A CN101209843 A CN 101209843A CN A2007101727422 A CNA2007101727422 A CN A2007101727422A CN 200710172742 A CN200710172742 A CN 200710172742A CN 101209843 A CN101209843 A CN 101209843A
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Abstract
The invention discloses a preparation method of an organic solvent dispersion liquid of anhydrous silicon dioxide, comprising the steps: (1) silica sol with pH value of 6-12 is dissolved in an organic solvent A, added with an organic solvent B that forms azeotrope with water and a coupling agent C and stirred for 10-60 minutes; (2) the mixed solution acquired from step(1) is distilled, dehydrated by a water segregator at 60-140 DEG C, then the organic solution B of the solution is removed by heating or vacuum distillation; the solution A with uniformly dispersed anhydrous silicon dioxide is obtained. The invention has simple manufacturing technique and low cost.
Description
Technical field
The invention belongs to organic chemical industry's nanotechnology preparation field, relate in particular to a kind of preparation method of waterless nano silicon dioxide organic solvent dispersion.
Background technology
Because surface effects, small-size effect and the quantization effect etc. of nanoparticle make nano material become the research focus and the new growth point of 21 century material science.But because small particle size, bigger serface and the high surface energy of nano material, nano material is very easily reunited, and therefore often needs before use through complicated loaded down with trivial details depolymerization, dispersing technology, as surface treatment, mechanical dispersion etc.But although used these methods, the nanoparticle that obtains often also is the coacervate of nanoparticle, rather than the dispersion of single nanoparticle, can't really embody the effect of nanoparticle.
Nanoparticle is distributed in water or the organic solvent, and then prepares the focus that various nano materials become the research nano-hybrid material gradually.A step crucial in this method is exactly the preparation of nanoparticulate dispersion.
CN1678525A discloses a kind of silica aqueous dispersion, it makes last SiO 2 powder being sneaked in the aqueous solution by diverting device of silicon dioxide powder by flame hydrolysis and prepares under acidic conditions, finally having obtained a kind of hydroxy density that comprises is 2.5～4.7OH/nm
2The stable aqueous dispersion system of SiO 2 powder.
CN1692074A discloses a kind of aqueous silicon dioxide dispersion liquid, and it is that one or more silane compounds are formed dispersion liquid with mixing with colloidal silica particle after water prepares clear solution again.
CN1517411A has announced a kind of water dispersion nano silicon dioxde solution of room temperature long-term stability, and it is to be raw material with water glass, the method preparation of usefulness ion-exchange.The dispersion liquid room temperature that obtains can store more than 18 months, silicon-dioxide quality concentration greater than 20% and particle diameter less than 5nm.
CN1675128A discloses a kind of aqueous dispersion of SiO 2 powder, and it is to make with at least a the contact when providing cationic compound to move in water-bearing media by SiO 2 powder.This dispersion liquid is stable in 2～6 PH scope.
CN1907851A has announced the method for organosol of silica, it is by preparing the organosol of silica that is combined with alkaline-earth metal ionic silica colloidal particle on a kind of surface, solved because the effect of the solid acid on colloidal silica particles surface causes resin qualitative change by the time, decompose and the generation variable color, crack problem and silicon dioxide gel is scattered in ketone, ester, during the acid amides equal solvent, owing to the katalysis of the solid acid of silicon-dioxide is decomposed the dispersion medium as colloidal sol, painted and cause resin through the time rotten, the problem of decomposing.
The silica dispersions system that above-mentioned patent obtains only is a silicon-dioxide in aqueous systems or contain dispersion liquid in the organic solvent system of water, can't directly apply to the most widely used organic materials system of non-aqueous system, particularly nano material.
CN1800010A discloses a kind of silicon dioxde propanol solution.It is to add the propyl alcohol wiring solution-forming in silicon sol, to the solution heating, with water and propyl alcohol evaporation, is evaporated to water-content in the solution and is not more than 15% and obtains.Silicon-dioxide is present in the propyl alcohol with colloidal solid in the dispersion liquid, and the particle median size is 5～20nm, and the weight content of silicon-dioxide is 5～35%.
CN1800012A has announced a kind of silicon dioxde acetone solution.It is to add the acetone wiring solution-forming in silicon sol, to the solution heating, with water and acetone evaporated, is evaporated to water-content in the solution and is not more than 15% and obtains.Silicon-dioxide is present in the acetone with colloidal solid in the dispersion liquid,, the weight content of silicon-dioxide is 5～35%, the weight content of water is 1～15%.
CN1785804A has announced a kind of silicon-dioxide ethanolic soln.It is to add alcohol solution-forming in silicon sol, and heating evaporation carries out condensation to vaporize water and ethanol and reclaims, and is evaporated to water-content in the solution and is not more than 15% and obtains.Silicon-dioxide is present in the ethanol with colloidal solid in the dispersion liquid, the weight content of silicon-dioxide is 15～28%, the median size of colloidal solid is 5～20nm, and colloidal solid is compared with median size, and deviation is no more than 10% of colloid total amount at most greater than the particle of 3nm.
CN1800011A discloses a kind of Virahol dispersion liquid.It is to add the Virahol wiring solution-forming in silicon sol, to the solution heating, with water and Virahol evaporation, the water of evaporation and Virahol is carried out condensation reclaim, and is evaporated to water-content in the solution and is not more than 15% and obtains.Silicon-dioxide is present in the Virahol with colloidal solid in the dispersion liquid, and the weight content of silicon-dioxide is 5～35%, and the median size of colloidal solid is 5～20nm.
The silica dispersions system of above-mentioned patent preparation, wherein acetone because of not with the water generates azeotropism, so can't prepare complete water-free silicon dioxde acetone dispersion liquor, and propyl alcohol, ethanol and Virahol since can with water generation azeotropism, can prepare complete moisture free silicon dioxde propanol, ethanol and Virahol dispersion liquid.
Organic solvent commonly used such as N ' N-N,N-DIMETHYLACETAMIDE, ethylene glycol etc. can not with the water azeotropic, all can't prepare complete moisture free silicon dioxide organic solvent (can not with water azeotropic organic solvent) dispersion liquid with above-mentioned all patents.
This patent relates to a kind of anhydrous silicon dioxide organic solvent dispersion and preparation method thereof, this dispersion liquid contains silicon-dioxide and organic solvent, silicon-dioxide is present in the organic solvent with the form of colloidal solid, the content of silicon-dioxide is 1～30%, and the median size of silicon dioxide colloid particle diameter is less than 100 nanometers.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of waterless nano silicon dioxide organic solvent dispersion, overcome prior art in preparation during silicon dioxide organic solvent dispersion, do not break away from Aquo System or be confined to can and the restriction of water generates azeotropic organic solvent system.This method technology is simple, and cost is low.
Technical scheme
The preparation method of a kind of waterless nano silicon dioxide organic solvent dispersion provided by the invention, specifically realize by the following technical solutions:
(1) be that the colloidal sol of 6～12 silicon-dioxide is dissolved in the organic solvent A with pH value, add the organic solvent B and the coupling agent C that can form azeotrope with water then, stir 10～60min, wherein the mass ratio of colloidal sol and coupling agent is 1: 0.013～1: 0.025;
(2) with above-mentioned mixed solution distillation, under 60～140 ℃, heat up again or underpressure distillation after removing moisture in (1) with water trap, remove the organic solvent B in the solution, make the homodisperse A solution of anhydride silica.
Polar organic solvent A in the described step (1) is ethylene glycol, polyoxyethylene glycol, polypropylene glycol, glycerine, N, N '-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N-methyl arsenic pyrrolidone etc.
The organic solvent B that can form azeotrope with water of described step (1) is chloroform, toluene, n-propyl alcohol, isopropylcarbinol, propyl carbinol, benzene, dimethylbenzene, pyridine, primary isoamyl alcohol, Pentyl alcohol, Virahol, ether, ethanol etc.
Coupling agent C in the described step (1) is KH-550, KH-560, KH-570 or their mixture.
The boiling point of polar organic solvent A in the described step (1) is higher more than 10 ℃ than organic solvent B.
Water content in the silicon dioxide organic solvent dispersion that described step (2) obtains is≤100ppm.
The weight content of silicon-dioxide is 1～30% in the silicon dioxide organic solvent dispersion that described step (2) obtains.
The size of silicon-dioxide is≤100nm in the silicon dioxide organic solvent dispersion that described step (2) obtains.
The present invention can obtain inorganic phase size in nanometer scale, and finely dispersed waterless nano silicon dioxide organic solvent dispersion.It contains silicon-dioxide and organic solvent, and silicon-dioxide is present in the organic solvent with the form of colloidal solid, and the content of silicon-dioxide is 1～30%, and the median size of silicon dioxide colloid particle diameter is less than 100nm.Organic solvent in the waterless nano silicon dioxide organic solvent dispersion can be energy and water azeotropic, also can be to use organic solvent always with the water azeotropic, and silica dioxide granule is uniformly dispersed in the dispersion liquid, can long-term stability deposit under the room temperature.
Beneficial effect
Compared with prior art, the preparation method of waterless nano silicon dioxide organic solvent dispersion provided by the invention has following advantage:
1, silicon dioxide gel adopts industry silicasol, and the silicon source is more cheap.
2, the present invention has been distributed to the silicon-dioxide in the silicon sol in the organic solvent dexterously uniformly, obtained particle diameter little, be uniformly dispersed and anhydrous silicon-dioxide organic dispersions.
3, organic solvent is more extensive, no matter can with the water azeotropic, can be used for obtaining anhydrous silicon dioxide organic solvent dispersion.
4, present method technology is simple, and being used for the azeotropic organic solvent can recycle, and manufacturing cost is lower.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Silicon-dioxide particle diameter in the silicon dioxide organic solvent dispersion comprises median size and deviation among the present invention, is equal to the micelle situation of primary industry silicon sol basically.Select for use the silicon sol of 10～100nm to make raw material, can make the silicon dioxide organic solvent dispersion of corresponding particle diameter by technology of the present invention.
Embodiment 1:
With 530ml N, the N-dimethylacetamide solvent, 0.5g coupling agent KH-560 and 172ml toluene join in the silicon sol that the 33.4g particle diameter is 10nm, controlled temperature is about 130 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is steamed, the toluene in the solution is removed in last underpressure distillation, obtains anhydride silica N,N-dimethylacetamide dispersion liquid, wherein dioxide-containing silica is 2%, and particle diameter is 10nm.
Embodiment 2:
With 530ml N, the N-dimethylacetamide solvent, 0.5g coupling agent KH-550 and 172ml toluene join in the silicon sol that the 33.4g particle diameter is 10nm, controlled temperature is about 130 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is steamed, the toluene in the solution is removed in last underpressure distillation, obtains anhydride silica N,N-dimethylacetamide dispersion liquid, wherein dioxide-containing silica is 2%, and particle diameter is 20～50nm.
Embodiment 3:
With 530ml N, the N-dimethylacetamide solvent, 2.5g coupling agent KH-560 and 800ml toluene join in the silicon sol that the 166.7g particle diameter is 10nm, controlled temperature is about 130 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is taken out of, last underpressure distillation steams toluene, obtain anhydride silica N,N-dimethylacetamide dispersion liquid.Wherein dioxide-containing silica is 10%, and particle diameter is 10～50nm.
Embodiment 4:
With 530ml N, the N-dimethylacetamide solvent, 0.75g coupling agent KH-560 and 365ml benzene join in the silicon sol that the 50g particle diameter is 10nm, controlled temperature is about 110 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is taken out of, last underpressure distillation steams toluene, obtain anhydride silica N,N-dimethylacetamide dispersion liquid.Wherein the content of silicon-dioxide is 3%, and particle diameter is 10～20nm.
Embodiment 5:
With 530ml N, the N-dimethylacetamide solvent, 2.5g coupling agent KH-560 and 1205ml benzene join in the silicon sol that the 166.7g particle diameter is 10nm, controlled temperature is about 110 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is taken out of, last underpressure distillation steams benzene, obtain anhydride silica N,N-dimethylacetamide dispersion liquid.Wherein the content of silicon-dioxide is 10%, and particle diameter is 10～60nm.
Embodiment 6:
With the 900ml ethylene glycol solvent, 2.5g coupling agent KH-560 and 800ml toluene join in the silicon sol that the 166.7g particle diameter is 10nm, controlled temperature is about 120 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is taken out of, last underpressure distillation steams toluene, obtains anhydride silica ethylene glycol dispersion liquid.Wherein the content of silicon-dioxide is 5%, and particle diameter is 10nm.
Embodiment 7:
With the 450ml ethylene glycol solvent, 2.5g coupling agent KH-560 and 800ml toluene join in the silicon sol that the 166.7g particle diameter is 10nm, controlled temperature is about 120 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is taken out of, last underpressure distillation steams toluene, obtains anhydride silica ethylene glycol dispersion liquid.Wherein the content of silicon-dioxide is 10%, and particle diameter is 10～20nm.
Embodiment 8:
With the 450ml ethylene glycol solvent, 3.75g coupling agent KH-560 and 1300ml toluene join in the silicon sol that the 250g particle diameter is 10nm, controlled temperature is about 120 ℃, under the continuously stirring, by water trap the moisture in the silicon sol is taken out of, last underpressure distillation steams toluene, obtains anhydride silica ethylene glycol dispersion liquid.Wherein the content of silicon-dioxide is 15%, and particle diameter is 10～30nm.
Claims (8)
1. the preparation method of an anhydrous silicon dioxide organic solvent dispersion comprises following step:
(1) silicon dioxide gel with pH value 6～12 is dissolved in the organic solvent A, and adding and water form the organic solvent B and the coupling agent C of azeotrope, stir 10～60 minutes:
(2) with above-mentioned mixed solution distillation, under 60～140 ℃, heat up or underpressure distillation after removing moisture with water trap, remove the organic solvent B in the solution, make the homodisperse A solution of anhydride silica.
2. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1, it is characterized in that: the mass ratio of described silicon dioxide gel and coupling agent is 1: 0.013～1: 0.025.
3. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1, it is characterized in that: the organic solvent A in the described step (1) is ethylene glycol, polyoxyethylene glycol, polypropylene glycol, glycerine, N, N '-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) or N-methyl arsenic pyrrolidone.
4. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1, it is characterized in that: the organic solvent B of described step (1) is chloroform, toluene, n-propyl alcohol, isopropylcarbinol, propyl carbinol, benzene, dimethylbenzene, pyridine, primary isoamyl alcohol, Pentyl alcohol, Virahol, ether or ethanol.
5. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1 is characterized in that: the coupling agent C in the described step (1) is selected from a kind of in KH-550, KH-560, KH-570 or their mixture.
6. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1, it is characterized in that: the boiling point of the polar organic solvent A in the described step (1) is higher more than 10 ℃ than organic solvent B.
7. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1 is characterized in that: the water content in the silicon dioxide organic solvent dispersion that described step (2) obtains is≤100ppm.
8. the preparation method of anhydrous silicon dioxide organic solvent dispersion as claimed in claim 1, it is characterized in that: the weight content of silicon-dioxide is 1～30% in the silicon dioxide organic solvent dispersion that described step (2) obtains, and is of a size of≤100nm.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101727422A CN101209843A (en) | 2007-12-21 | 2007-12-21 | Method for preparing anhydrous silicon dioxide organic solvent dispersion |
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| CNA2007101727422A CN101209843A (en) | 2007-12-21 | 2007-12-21 | Method for preparing anhydrous silicon dioxide organic solvent dispersion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111976A (en) * | 2018-09-25 | 2019-01-01 | 天津大学 | Nano SiO 2 particle lubricating additive more purification dispersing method |
| CN113474288A (en) * | 2019-02-25 | 2021-10-01 | 日产化学株式会社 | Inorganic oxide particles, inorganic oxide particle dispersion liquid, method for producing inorganic oxide particle dispersion liquid, and method for producing surface modifier |
-
2007
- 2007-12-21 CN CNA2007101727422A patent/CN101209843A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109111976A (en) * | 2018-09-25 | 2019-01-01 | 天津大学 | Nano SiO 2 particle lubricating additive more purification dispersing method |
| CN113474288A (en) * | 2019-02-25 | 2021-10-01 | 日产化学株式会社 | Inorganic oxide particles, inorganic oxide particle dispersion liquid, method for producing inorganic oxide particle dispersion liquid, and method for producing surface modifier |
| CN113474288B (en) * | 2019-02-25 | 2023-11-17 | 日产化学株式会社 | Inorganic oxide particles, inorganic oxide particle dispersion, method for producing same, and method for producing surface modifier |
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Open date: 20080702 |