CN103897435A - Surface modified silicon dioxide and preparation method thereof - Google Patents
Surface modified silicon dioxide and preparation method thereof Download PDFInfo
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- CN103897435A CN103897435A CN201410122183.4A CN201410122183A CN103897435A CN 103897435 A CN103897435 A CN 103897435A CN 201410122183 A CN201410122183 A CN 201410122183A CN 103897435 A CN103897435 A CN 103897435A
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- silicon
- silane compound
- dioxide
- surface modified
- silicon dioxide
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Abstract
The invention relates to a surface modified nano silicon dioxide. The nano silicon dioxide is composed of the following substrates: silane compound modified silicon dioxide, a silazane compound and water; a preparation method of the surface modified nano silicon dioxide comprises the following steps: providing silicon dioxide and dispersing the silicon dioxide in a non-aqueous solvent, adding a silane compound, mixing thoroughly for reacting, and drying to obtain the silane compound modified silicon dioxide, next, dispersing the silane compound modified silicon dioxide in the water, adding the silazane compound, mixing thoroughly for reacting, and drying to obtain the surface modified silicon dioxide. The surface modified nano silicon dioxide is characterized in that the silicon dioxide is sequentially modified by the silane compound and the silazane compound, and consequently, the number of hydroxyls on the surface of the silicon dioxide is greatly reduced.
Description
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Technical field
The present invention relates to surface modification silicon-dioxide and preparation method thereof.
Background technology
Silicon-dioxide has extensive use in a lot of fields, comprises the various organic materialss of filling, increment, thickening and enhancing, for example plastics, resin, rubber, wet goods.Particle diameter is at the nano silicon of 1-100nm, it has the common feature of nano material, be small-size effect, quantum size effect, surface effects, macroscopic quantum effect etc., shown great application prospect in all many-sides such as catalysis, absorption, separation, bio-sensing, nano molecular device and other functional materialss.
But in actual applications, there are a large amount of activated silica hydroxyls in nano-silica surface, make nano-silica surface present the characteristic of oleophobic, also be easy to reunite simultaneously, in medium, be difficult to infiltrate and disperse, directly be filled in organic materials, be difficult to its effect of performance, this has limited nano silicon in industrial application.
Summary of the invention
In order to obtain the nano silicon that performance is more superior, the invention provides a kind of new surface modification silicon-dioxide and preparation method thereof.
Surface modification silicon-dioxide, is made through the further modification of silicon nitrogen silane compound in the aqueous solution by silane compound improved silica.
Surface modification silicon-dioxide, is prepared from by following material:
Silane compound improved silica
Silicon nitrogen silane compound
Water
Surface modification silicon-dioxide, is prepared from by following material:
Silicon-dioxide
Silane compound
Non-aqueous solvent
Silicon nitrogen silane compound
Water
The preparation method of surface modification silicon-dioxide, comprises the following steps:
S10., silicon-dioxide is provided, is scattered in non-aqueous solvent, add silane compound, mix fully reaction, dry, obtain silane compound improved silica;
S20. silane compound improved silica, is scattered in water, adds silicon nitrogen silane compound, mixes fully reaction, dry, obtains surface modification silicon-dioxide.
Due to polymerization easily occurring after silane compound hydrolysis, silane compound can not be reacted with the hydroxyl of silica sphere fully, the present invention, by silane compound, silicon nitrogen silane compound successively improved silica, greatly reduces the hydroxyl quantity of silica sphere.Meanwhile, using water as solvent, the hydroxyl quantity of silicon-dioxide increases, and makes silicon nitrogen silane compound modification more effective.
Embodiment
The present invention relates to surface modification silicon-dioxide, made through the further modification of silicon nitrogen silane compound in the aqueous solution by silane compound improved silica.
As the preferred technical scheme of one, silicon-dioxide of the present invention has about 2 to about 150 nanometers, for example, for example, about 3 to about 60, about 5 to about 40 or about 5 for example, to about 25 nanometers, about 6 median sizes to about 18 nanometers.
Silicon dioxide granule can have narrow size-grade distribution, i.e. low Relative Size standard deviation.The relative standard deviation of size-grade distribution is the standard deviation ratio with mean particle size by the size-grade distribution of number.The relative standard deviation of size-grade distribution can be lower than about 60%(by number), especially lower than about 30%(by number), more especially lower than about 15 quantity %(by number).
Colloid silica particle is in this article also referred to as silicon sol, can be generated by precipitated silica, SILICA FUME (silicon powder), pyrolytic silicon dioxide (pyrogenic silica) or silica gel, the aerosil for example with sufficient purity and composition thereof.
As the preferred technical scheme of one, silane compound is optional from small molecules organosilane or small molecules siloxanes.
The molecular formula of described small molecules organosilane or small molecules siloxanes is HR
1 bsiR
2 3-bor R
ar
1 bsiR
2 4-a-b,
A and b are an integer in 0-4, and (a+b)≤4;
And, described R, R
1and R
2can be selected from Cl, Br, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, the alkyl of C5-C18 and thiazolinyl, cyclopentyl, cyclohexyl, phenyl, vinyl, allyl group, 2-alkene butyl, 3-alkene butyl, 2-methacrylic, acryloyl-oxy methyl, methacryloxypropyl methyl, acrylyl oxy-ethyl, methylacryoyloxyethyl, acryloyl-oxy propyl group, methacryloxypropyl, acetyl oxygen propyl group, acetyl oxygen ethyl, acetyl-o-methyl, aminomethyl, β-aminoethyl, γ-aminopropyl, brine alkyl, mercapto alkyl, N-(β-aminoethyl)-γ-aminopropyl, γ-2,3-epoxypropoxy, beta-hydroxyethyl, γ-hydroxypropyl, 4-hydroxyl butyl, 5-hydroxyl amyl group, N-phenyl-aminomethyl, N-phenyl-β-aminoethyl, N-phenyl-γ-aminopropyl, (N-perfluorooctyl sulfonyl)-aminopropyl, containing fluoroalkyl, isocyanic acid alkyl, cyanogen alkyl, alkoxyl group, acyloxy, any one in ketoxime acyloxy and amido or multiple, but be not limited to this.
Wherein, the molecular formula of brine alkyl is XR-, and R is C1-C18 alkyl, and X is chlorine, bromine,
The molecular formula of mercapto alkyl is HSR-, and R is C1-C18 alkyl,
Molecular formula containing fluoroalkyl is C
xh
2x+1-yf
y, x=1-18,0 < y < 2x+2, x, y are natural number,
The molecular formula of isocyanic acid alkyl is OCNR-, and R is C1-C18 alkyl,
The molecular formula of cyanogen alkyl is CNR-, and R is C1-C18 alkyl,
The molecular formula of alkoxyl group is-OR, the alkyl that R is C1-C10,
The molecular formula of acyloxy is-O-COR, the alkyl that R is C1-C10,
The molecular formula of ketoxime acyloxy is-ON=CR
'r
", R
'and R
"for identical or different C1-C10 alkyl,
The molecular formula of amido is-NH-COR, the alkyl that R is C1-C10.
The aqueous solution of the present invention refers to and contains the solution that quality % is 5%-100%, can contain water-soluble or be slightly soluble in water or water-fast liquid in the aqueous solution, is not restricted.
Silicon nitrogen silane compound, is selected from one or more of hexamethyldisilazane, pregnancy basic ring three silazane, octamethylcyclotetrasilazane.The reaction of typical silicon nitrogen silane compound is as follows:
The ammonia that silazane is produced, is conducive to improve the alkalescence of solution, is more conducive to produce more silicon hydroxyl.Under the aqueous solution, silica sphere can the more siloxanes of grafting.
As the preferred technical scheme of one, surface modification silicon-dioxide, is prepared from by following material:
Silane compound improved silica
Silicon nitrogen silane compound
Water
As the preferred technical scheme of one, surface modification silicon-dioxide, is prepared from by following material:
Silicon-dioxide
Silane compound
Non-aqueous solvent
Silicon nitrogen silane compound
Water
The preparation method of surface modification silicon-dioxide, comprises the following steps:
S10., silicon-dioxide is provided, is scattered in non-aqueous solvent, add silane compound, mix fully reaction, dry, obtain silane compound improved silica;
S20. silane compound improved silica, is scattered in water, adds silicon nitrogen silane compound, mixes fully reaction, dry, obtains surface modification silicon-dioxide.
Between the preferred 40-85 of hybrid reaction temperature degree Celsius.Reaction times 1-3 hour.
Described silane compound, the preferably 0.1%-70% of silicon-dioxide quality.Preferably 5%-35%.
Further describe the present invention below in conjunction with specific embodiment, advantage and disadvantage of the present invention will be more clear along with description.But these embodiment are only exemplary, scope of the present invention are not formed to any restriction.It will be understood by those skilled in the art that lower without departing from the spirit and scope of the present invention and can the details of technical solution of the present invention and form be modified or be replaced, but these amendments and replacement all fall within the scope of protection of the present invention.
Surface hydroxyl measuring method: the SiO that takes 2.0g (m) modification
2sample adds and in 200mL beaker, adds 25mL ethanol wetting, then adds the NaCl solution of 75mL massfraction 20%, stirs; Regulate pH to 4 with the HCl of 0.1mol/L, finally use 0.1mol/L(C) NaOH to be titrated to pH be nondiscoloration in 9,3min.Obtain pH value from 4 fade to 9 consume the volume V of NaOH.Calculate the surface hydroxyl number of every square nanometers by specific surface area S.Calculation formula is as follows:
N
afor Avogadro constant.
Material source:
Nano silicon NH-200 Yangzhou sky energy chemical industry, the surface hydroxyl number 1.435 of every square nanometers;
Dimethyldichlorosilane(DMCS) Tianjin recovery fine chemistry industry;
The precious chemical industry of methyltrimethoxy silane Hangzhou silicon;
The precious chemical industry of hexamethyldisilazane Hangzhou silicon.
Embodiment 1
Get 20g silicon-dioxide NH-200, be scattered in acetone, add 5g dimethyldichlorosilane(DMCS), mix fully reaction 1 hour, be dried to weight, obtain silane compound improved silica, the silane compound improved silica obtaining is scattered in water, adds 5g hexamethyldisilazane, mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.152.
Embodiment 2
Get 20g silicon-dioxide NH-200, be scattered in ethanol, add 10g dimethyldichlorosilane(DMCS), mix fully reaction 1 hour, be dried to weight, obtain silane compound improved silica, the silane compound improved silica obtaining is scattered in water, adds 2g hexamethyldisilazane, mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.189.
Embodiment 3
Get 20g silicon-dioxide NH-200, be scattered in acetone, add 20g methyltrimethoxy silane, mix fully reaction 1 hour, be dried to weight, obtain silane compound improved silica, the silane compound improved silica obtaining is scattered in water, adds 0.3g hexamethyldisilazane, mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.214.
Embodiment 4
Get 20g silicon-dioxide NH-200, be scattered in ethanol, add 5g dimethyldichlorosilane(DMCS), mix fully reaction 1 hour, be dried to weight, obtain silane compound improved silica, the silane compound improved silica obtaining is scattered in water, adds 10g hexamethyldisilazane, mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.187.
Comparative example 1
Get 20g silicon-dioxide NH-200, be scattered in acetone, add 5g dimethyldichlorosilane(DMCS), and 5g hexamethyldisilazane, mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.562.
Comparative example 2
Get 20g silicon-dioxide NH-200, be scattered in acetone, add 5g dimethyldichlorosilane(DMCS), mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.855.
Comparative example 3
Get 20g silicon-dioxide NH-200, be scattered in acetone, add 2g hexamethyldisilazane, mix fully reaction 2 hours, be dried to weight, obtain surface modification silicon-dioxide.The improved silica that the surface hydroxyl number that obtains every square nanometers is 0.320.
Can find out, preparation method of the present invention can significantly reduce the hydroxyl value of silica sphere.
Although the present invention is fully described in above-mentioned explanation, be apparent that, above-described embodiment can change in many ways.These changes should not be regarded as deviating from the spirit and scope of the invention, and the apparent all such amendments of those skilled in the art are intended within the scope of the present invention.
Claims (6)
1. a surface modified nano silicon, is characterized in that, described nano silicon is made up of following material:
Silane compound improved silica
Silicon nitrogen silane compound
Water.
2. a surface modified nano silicon, is characterized in that, described nano silicon is made up of following material:
Silicon-dioxide
Silane compound
Non-aqueous solvent
Silicon nitrogen silane compound
Water.
3. according to a kind of surface modified nano silicon described in any one claim in claim 1 or 2, it is characterized in that, described silicon-dioxide has 2 median sizes to about 150 nanometers.
4. according to a kind of surface modified nano silicon described in any one claim in claim 1 or 2, it is characterized in that, described silane compound is optional from small molecules organosilane or small molecules siloxanes;
The molecular formula of described small molecules organosilane or small molecules siloxanes is HR
1 bsiR
2 3-bb or R
ar
1 bsiR
2 4-a-b, wherein a and b are an integer in 0-4, and (a+b)≤4;
Described R, R1 and R2 can be selected from Cl, Br, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, the alkyl of C5-C18 and thiazolinyl, cyclopentyl, cyclohexyl, phenyl, vinyl, allyl group, 2-alkene butyl, 3-alkene butyl, 2-methacrylic, acryloyl-oxy methyl, methacryloxypropyl methyl, acrylyl oxy-ethyl, methylacryoyloxyethyl, acryloyl-oxy propyl group, methacryloxypropyl, acetyl oxygen propyl group, acetyl oxygen ethyl, acetyl-o-methyl, aminomethyl, β-aminoethyl, γ-aminopropyl, brine alkyl, mercapto alkyl, N-(β-aminoethyl)-γ-aminopropyl, γ-2,3-epoxypropoxy, beta-hydroxyethyl, γ-hydroxypropyl, 4-hydroxyl butyl, 5-hydroxyl amyl group, N-phenyl-aminomethyl, N-phenyl-β-aminoethyl, N-phenyl-γ-aminopropyl, (N-perfluorooctyl sulfonyl)-aminopropyl, containing fluoroalkyl, isocyanic acid alkyl, cyanogen alkyl, alkoxyl group, acyloxy, any one in ketoxime acyloxy and amido or multiple.
5. according to a kind of surface modified nano silicon described in any one claim in claim 1 or 2, it is characterized in that, described silicon nitrogen silane compound, is selected from one or more of hexamethyldisilazane, pregnancy basic ring three silazane, octamethylcyclotetrasilazane.
6. a surface modified nano silicon, is characterized in that, described method for preparing nano silica is as follows:
S10., silicon-dioxide is provided, is scattered in non-aqueous solvent, add silane compound, mix fully reaction, dry, obtain silane compound improved silica;
S20. silane compound improved silica, is scattered in water, adds silicon nitrogen silane compound, mixes fully reaction, dry, obtains surface modification silicon-dioxide.
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Cited By (3)
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| CN105038927A (en) * | 2015-07-06 | 2015-11-11 | 天门市天宝化工科技有限公司 | Composite modified nano particle transformer oil, and preparation method thereof |
| CN113539689A (en) * | 2020-04-15 | 2021-10-22 | 深圳新宙邦科技股份有限公司 | Silica lactone sol, preparation method and electrolyte for aluminum electrolytic capacitor |
| CN115010155A (en) * | 2022-04-20 | 2022-09-06 | 兰州石化职业技术学院 | Method for modifying surface of carrier silicon dioxide |
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| CN101517012A (en) * | 2006-09-15 | 2009-08-26 | 卡伯特公司 | Method of preparing hydrophobic silica |
| CN102872847A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for modifying titanium silicon oxide material |
| CN103073927A (en) * | 2013-01-31 | 2013-05-01 | 沈阳化工股份有限公司 | Surface-modified fumed silica capable of improving tearing strength of silicone rubber and production method of silicon dioxide |
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Patent Citations (4)
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| CN101410461A (en) * | 2005-10-31 | 2009-04-15 | 赢创德固赛有限责任公司 | Improved processing compositions and method of forming the same |
| CN101517012A (en) * | 2006-09-15 | 2009-08-26 | 卡伯特公司 | Method of preparing hydrophobic silica |
| CN102872847A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for modifying titanium silicon oxide material |
| CN103073927A (en) * | 2013-01-31 | 2013-05-01 | 沈阳化工股份有限公司 | Surface-modified fumed silica capable of improving tearing strength of silicone rubber and production method of silicon dioxide |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038927A (en) * | 2015-07-06 | 2015-11-11 | 天门市天宝化工科技有限公司 | Composite modified nano particle transformer oil, and preparation method thereof |
| CN113539689A (en) * | 2020-04-15 | 2021-10-22 | 深圳新宙邦科技股份有限公司 | Silica lactone sol, preparation method and electrolyte for aluminum electrolytic capacitor |
| CN113539689B (en) * | 2020-04-15 | 2023-04-18 | 深圳新宙邦科技股份有限公司 | Silica lactone sol, preparation method and electrolyte for aluminum electrolytic capacitor |
| CN115010155A (en) * | 2022-04-20 | 2022-09-06 | 兰州石化职业技术学院 | Method for modifying surface of carrier silicon dioxide |
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Application publication date: 20140702 |