CN104177867B - A kind of Nano-meter SiO_2 2method of modifying - Google Patents
A kind of Nano-meter SiO_2 2method of modifying Download PDFInfo
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- CN104177867B CN104177867B CN201410468265.4A CN201410468265A CN104177867B CN 104177867 B CN104177867 B CN 104177867B CN 201410468265 A CN201410468265 A CN 201410468265A CN 104177867 B CN104177867 B CN 104177867B
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Abstract
The invention discloses a kind of Nano-meter SiO_2
2method of modifying, belong to nano-material modified technical field.These method of modifying concrete steps comprise the preparation of HF gas, HF gas and Nano-meter SiO_2
2nano-meter SiO_2 after reaction, HF process
2with the aftertreatment of olefinic organic hydrocarbon reaction, modified sample.The present invention utilizes HF in anhydrous conditions to the Nano-meter SiO_2 be dispersed in dehydrated alcohol
2process, make surface be connected with a large amount of active hydrogens, then react with the isometric chain end monoolefine of 1-octene, can at Nano-meter SiO_2 by addition reaction
2surface connects a large amount of oil loving Long carbon chain, makes modified Nano-meter SiO_2
2can be dispersed in organic phase, and effectively overcome the problems such as stability is bad.
Description
Technical field:
The invention belongs to nano-material modified technical field, be specifically related to adopt organic alkene to Nano-meter SiO_2
2carry out the method for surface chemical modification.
Background technology:
Nano-meter SiO_2
2as the unbodied white powder of one, it is a kind of nano-powder material that large-scale industrial production output is the highest in the world at present, there is very special rheological property, optical property and photocatalysis characteristic, equally also can be used as important inorganic toughen and intensify functional filler.Therefore, Nano-meter SiO_2
2be widely used in the fields such as pharmaceutical carrier, pigment, makeup.But Nano-meter SiO_2
2surface energy is high, easily reunite and fully can not mix with organism, and surface exists the hydroxyl of undersaturated residual bond and different bond styles, surface exhibits is hydrophilic oleophobic performance, is difficult to be evenly dispersed in organic medium, affects the filling effect of material, therefore, must to Nano-meter SiO_2
2carry out surface chemical modification, to solve Nano-meter SiO_2
2dispersiveness and problem with organic medium consistency.
To Nano-meter SiO_2
2the principle of chemical modification is by adding properties-correcting agent, making itself and Nano-meter SiO_2
2the hydroxyl generation chemical action on surface, reduces SiO
2the hydroxyl value on surface, reduces and reunites, make nanoparticle dispersion even.At present, conventional chemical modifier has alcohol, silicoorganic compound and silane coupling agent etc.One hexamethyldisilazane is proposed to Nano-meter SiO_2 in the paper " hmds is to the surface modification of thermal silica " that " East China University of Science's journal " (2001,27 (6)) are delivered
2carry out the method for surface coating modification, SiO after surface treatment
2pH value and carbon content increase, surface hydroxyl number obviously reduces, and agglomeration obviously improves." the Nano-meter SiO_2 that " New Chemical Materials " (2007,35 (11)) are delivered
2research on Surface Modification " paper disclose a kind of by KH-560 to Nano-meter SiO_2
2the method of surface modification, using ethanol as dispersion medium, utilizes KH-560 and Nano-meter SiO_2
2the hydroxyl reaction on surface, connect epoxy group(ing) on its surface, the group obtained open loop under certain condition generates adjacent hydroxyl, thus improves SiO
2dispersion effect.Chinese patent CN101338082A discloses a kind of surface modifying method of silicon-dioxide, specifically by after the mixing of silicon dioxide gel, tensio-active agent, silane coupling agent containing cycloalkyl groups and deionized water, for some time is stirred under different pH value condition, the silicon dioxide gel of modification, particle diameter is between tens to hundreds of nanometer.As mentioned above, although Nano-meter SiO_2
2surface modifying method numerous, but modified Nano-meter SiO_2
2mostly disperse in aqueous phase only, and be difficult to reach ideal effect, the stability after dispersion is bad.
Summary of the invention:
Object of the present invention is exactly to overcome existing Nano-meter SiO_2
2the deficiency of method of modifying, provide one can in oil phase finely dispersed Nano-meter SiO_2
2method of modifying.Nano-meter SiO_2
2modified by the inventive method, can not only be dispersed in organic phase medium, and after dispersion, there is good stability.
A kind of Nano-meter SiO_2 provided by the present invention
2method of modifying concrete steps as follows:
(1) preparation of HF gas:
Calcium fluoride powder is placed in reactor, vacuumize under sealed state, again the vitriol oil of 98wt% is joined in reactor, stir and be heated to 48 ~ 52 DEG C and carry out reacting obtained HF gas, reaction times is 5 ~ 6h, and the mass ratio of the vitriol oil of described Calcium Fluoride (Fluorspan) and 98wt% is: 1:(1.1 ~ 1.2).
(2) HF gas and Nano-meter SiO_2
2reaction:
By Nano-meter SiO_2
2be placed in another reactor, in this reactor, add dehydrated alcohol as dispersion agent, vacuumize under air-tight state, and logical nitrogen protection; HF gas obtained for step (1) is imported to by conduit and is dispersed with Nano-meter SiO_2
2dehydrated alcohol in, stir and be heated to 67 ~ 73 DEG C and react, the reaction times is 5 ~ 6h, and carries out tail gas recycle, described Nano-meter SiO_2
2with the mass ratio of dehydrated alcohol be: 1:(55 ~ 65), preferably; Described 1:60, Nano-meter SiO_2
2with the mass ratio of HF gas be: 1:(4.5 ~ 5.5).
(3) Nano-meter SiO_2 after HF process
2with olefinic organic hydrocarbon reaction:
In step (2) reacted reactant, slowly add organic alkene, continue logical nitrogen protection, and be warming up to 105 ~ 115 DEG C, reflux condensation mode 7 ~ 8h, under agitation continue to be obtained by reacting modified Nano-meter SiO_2
2; The mass ratio of described nanosized SiO_2 and organic alkene is: 1:(60 ~ 80).
(4) aftertreatment of modified sample:
By Nano-meter SiO_2 modified for step (3)
2carry out centrifugation, and with n-hexane 3 ~ 5 times, finally in vacuum drying oven, dry obtained target product: modified Nano SiO
2.
In the preparation of HF gas, the mass ratio of Calcium Fluoride (Fluorspan) and the vitriol oil is with n (CaF
2): n (dense H
2sO
4)=1:1.2 is good, can ensure that the vitriol oil is excessive like this, make Calcium Fluoride (Fluorspan) complete reaction.
Described organic alkene is a kind of or any two the above mixture in 1-octene, 1-decene, 1-laurylene, 1-tetradecylene; Described Nano-meter SiO_2
2particle diameter be 15 ± 5nm, content is 99.5%.
The Ethylene recov of described tail gas recycle is the NaOH solution of 5wt%.
Described HF and Nano-meter SiO_2
2temperature of reaction is in ethanol good with 70 DEG C, because the boiling point of ethanol is 78.4 DEG C, prevents boiling and volatilizees; When with olefinic organic hydrocarbon reaction, temperature is advisable with 110 DEG C, because the boiling point of 1-octene is minimum in organic alkene, is 121.3 DEG C, and one is that two is that temperature can cause polymerization reaction take place between organic alkene very much in order to prevent boiling from volatilizing.
The present invention utilizes HF in anhydrous conditions to the Nano-meter SiO_2 be dispersed in dehydrated alcohol
2process, make surface be connected with a large amount of active hydrogens, then react with the isometric chain end monoolefine of 1-octene, can at Nano-meter SiO_2 by addition reaction
2surface connects a large amount of oil loving Long carbon chain, makes modified Nano-meter SiO_2
2can be dispersed in organic phase, and effectively overcome the problems such as stability is bad.The present invention has following technical characterstic:
(1) with existing Nano-meter SiO_2
2method of modifying is compared, and the present invention uses HF gas to Nano-meter SiO_2
2carry out surface treatment, make surface be connected with active hydrogen, then react with organic alkene.
(2) existing Nano-meter SiO_2
2the modified product that method of modifying obtains disperses only in aqueous phase, and the modified Nano SiO that the present invention obtains
2then can be uniformly dispersed in oil phase, this has not only filled up the deficiency of existing method of modifying, and makes modified Nano-meter SiO_2
2be applicable to more system, widen Nano-meter SiO_2
2application Areas.
(3) Nano-meter SiO_2 that the present invention is modified
2can have good dispersiveness in the organic phase such as chloroform, tetrahydrofuran (THF), long-time placement also produces without precipitation.
Accompanying drawing illustrates:
Fig. 1 is mechanism of modification figure of the present invention.
Fig. 2 is the infrared light collection of illustrative plates of modification gained sample of the present invention, and wherein every bar collection of illustrative plates represents with different organic alkene Nano-meter SiO_2
2carry out modification.
Fig. 3 is the scanning electron microscope diagram of unmodified sample.
Fig. 4 is the scanning electron microscope (SEM) photograph through 1-octene modification gained sample.
Fig. 5 is the scanning electron microscope (SEM) photograph through 1-decene modification gained sample.
Fig. 6 is the scanning electron microscope (SEM) photograph through 1-laurylene modification gained sample.
Fig. 7 is the scanning electron microscope (SEM) photograph through 1-tetradecylene modification gained sample.
Embodiment:
Embodiment 1: the consumption of each component is as follows:
Method of modifying concrete steps are as follows:
(1) preparation of HF gas: the Calcium Fluoride (Fluorspan) powder taking 5.032g is placed in there-necked flask, vacuumize under sealed state, dropwise joined in there-necked flask by dropping funnel by the vitriol oil of 6.523g, magnetic agitation 5h, oil bath is heated to 50 DEG C and reacts again.
(2) HF gas and Nano-meter SiO_2
2reaction: take 0.503g Nano-meter SiO_2
2be placed in another there-necked flask, in flask, add 30g dehydrated alcohol as dispersion agent, vacuumize under air-tight state, and logical nitrogen protection.The HF gas produced in (1) is imported to by plastic catheter and is dispersed with Nano-meter SiO_2
2dehydrated alcohol in, react 5h under magnetic agitation, oil bath is heated to 70 DEG C and reacts, and carries out tail gas recycle.
(3) Nano-meter SiO_2 after HF process
2with olefinic organic hydrocarbon reaction: by dropping funnel, slowly drip the 1-octene of 32.230g in reacted (2), continue logical nitrogen protection, reflux condensation mode 7h, oil bath is warming up to 110 DEG C, makes reaction proceed under magnetic stirring.
(4) aftertreatment of modified sample: by modified Nano-meter SiO_2
2centrifugation, and with n-hexane three times, the Nano-meter SiO_2 of finally drying modified in vacuum drying oven
2sample.
Embodiment 2: the following institute of consumption of each component:
The implementation method of the present embodiment comprises the preparation of HF gas, HF gas and Nano-meter SiO_2
2reaction, Nano-meter SiO_2 after HF process
2with the aftertreatment of olefinic organic hydrocarbon reaction and modified sample, concrete working method is with embodiment 1.
Embodiment 3: the consumption of each component is as follows:
The implementation method of the present embodiment comprises the preparation of HF gas, HF gas and Nano-meter SiO_2
2reaction, Nano-meter SiO_2 after HF process
2with the aftertreatment of olefinic organic hydrocarbon reaction and modified sample, concrete working method is with embodiment 1.
Embodiment 4: the following institute of consumption of each component:
The implementation method of the present embodiment comprises the preparation of HF gas, HF gas and Nano-meter SiO_2
2reaction, Nano-meter SiO_2 after HF process
2with the aftertreatment of olefinic organic hydrocarbon reaction and modified sample, concrete working method is with embodiment 1.
As seen from Figure 2, the Nano-meter SiO_2 of and 1-ten four rare modification rare through 1-octene, 1-decene, 1-12
2with unmodified Nano-meter SiO_2
2compare, modified Nano-meter SiO_2
2be 2900cm at wavelength
-1near have strong absorption peak, be the stretching vibration peak of alkane c h bond, be 750cm at wavelength herein
-1neighbouring absorption peak strengthens, and is the flexural vibration peak of alkane c h bond herein, can shows alkene success and Nano-meter SiO_2 thus
2the active hydrogen on surface completes addition reaction, makes Long carbon chain be connected to Nano-meter SiO_2
2surface.
By Fig. 3 and Fig. 4, Fig. 5, Fig. 6, Fig. 7 through different alkene modified Nano SiO
2sEM figure can find out, unmodified Nano-meter SiO_2
2when SEM amplifies 50000 times, sample is obvious particulate state and particle diameter is less, but modified through different alkene, under SEM amplifies identical multiple, can see that sample has in block trend, and particle diameter increases.Modified is Nano-meter SiO_2 in block reason
2with olefine reaction before, first with go HF to react, HF can corrode SiO
2surface, makes its surface become coarse, and superficial attractive forces increases, and intergranular spacing is reduced; Nano-meter SiO_2
2react behind rear surface with HF and be connected a large amount of active hydrogen, addition reaction is carried out again with alkene, surface is made to connect a large amount of Long carbon chain, Long carbon chain can the space between filler particles and the interlaced effect between Long carbon chain, the spacing of particle and particle is reduced further, therefore, the Nano-meter SiO_2 after olefin-modified
2bulk can be presented.Due to modified Nano-meter SiO_2
2there is a large amount of Long carbon chain on surface, is hydrophobic oleophilic oil group, therefore can has good dispersion effect in oil phase.
Claims (3)
1. a Nano-meter SiO_2
2method of modifying, it is characterized in that these method of modifying concrete steps are as follows:
(1) preparation of HF gas: calcium fluoride powder is placed in reactor, vacuumize under sealed state, again the vitriol oil of 98wt% is joined in reactor, stir and be heated to 48 ~ 52 DEG C and carry out reacting obtained HF gas, reaction times is 5 ~ 6h, and the mass ratio of the vitriol oil of described Calcium Fluoride (Fluorspan) and described 98wt% is: 1:1.1 ~ 1.2;
(2) HF gas and Nano-meter SiO_2
2reaction: by Nano-meter SiO_2
2be placed in another reactor, in this reactor, add dehydrated alcohol as dispersion agent, vacuumize under air-tight state, and logical nitrogen protection; HF gas obtained for step (1) is imported to by conduit and is dispersed with Nano-meter SiO_2
2dehydrated alcohol in, stir and be heated to 67 ~ 73 DEG C and react, the reaction times is 5 ~ 6h, and carries out tail gas recycle, described Nano-meter SiO_2
2with the mass ratio of described dehydrated alcohol be: 1:55 ~ 65, described Nano-meter SiO_2
2with the mass ratio of described HF gas be: 1:4.5 ~ 5.5;
(3) Nano-meter SiO_2 after HF process
2with olefinic organic hydrocarbon reaction: in step (2) reacted reactant, slowly add organic alkene, continue logical nitrogen protection, and be warming up to 105 ~ 115 DEG C, reflux condensation mode 7 ~ 8h, under agitation continue to be obtained by reacting modified Nano-meter SiO_2
2; Described organic alkene is a kind of or any two the above mixture in 1-octene, 1-decene, 1-laurylene, 1-tetradecylene; Described Nano-meter SiO_2
2with the mass ratio of organic alkene be: 1:60 ~ 80;
(4) modified Nano-meter SiO_2
2aftertreatment: by Nano-meter SiO_2 modified for step (3)
2carry out centrifugation, and with n-hexane 3 ~ 5 times, finally in vacuum drying oven, dry obtained target product: modified Nano SiO
2.
2. a kind of Nano-meter SiO_2 according to claim 1
2method of modifying, it is characterized in that described Nano-meter SiO_2
2particle diameter be 15 ± 5nm, mass content is 99.5%.
3. a kind of Nano-meter SiO_2 according to claim 1
2method of modifying, it is characterized in that the Ethylene recov of tail gas recycle is the NaOH solution of 5wt% in described step (2).
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|---|---|---|---|
| CN201410468265.4A CN104177867B (en) | 2014-09-15 | 2014-09-15 | A kind of Nano-meter SiO_2 2method of modifying |
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| CN104177867B true CN104177867B (en) | 2015-09-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054689A (en) * | 1976-10-07 | 1977-10-18 | The Dow Chemical Company | Method of preparing hydrophobic silica |
| CN1417249A (en) * | 2002-12-13 | 2003-05-14 | 清华大学 | Composite polyolefin/sio2 nano particle and its prepn |
| CN1468870A (en) * | 2003-06-09 | 2004-01-21 | 清华大学 | Composite nano epoxy functional polymer/SiO2 particle and its prepn process |
| EP2067743A1 (en) * | 2007-12-03 | 2009-06-10 | Evonik Degussa GmbH | Surface modified silicon nanoparticles |
| CN102826513A (en) * | 2012-09-03 | 2012-12-19 | 南通市明鑫化工有限公司 | Production process of hydrofluoric acid |
| CN103288087A (en) * | 2013-05-28 | 2013-09-11 | 浙江大学 | Surface modification process for improving luminance and dispersity of porous silicon |
-
2014
- 2014-09-15 CN CN201410468265.4A patent/CN104177867B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4054689A (en) * | 1976-10-07 | 1977-10-18 | The Dow Chemical Company | Method of preparing hydrophobic silica |
| CN1417249A (en) * | 2002-12-13 | 2003-05-14 | 清华大学 | Composite polyolefin/sio2 nano particle and its prepn |
| CN1468870A (en) * | 2003-06-09 | 2004-01-21 | 清华大学 | Composite nano epoxy functional polymer/SiO2 particle and its prepn process |
| EP2067743A1 (en) * | 2007-12-03 | 2009-06-10 | Evonik Degussa GmbH | Surface modified silicon nanoparticles |
| CN102826513A (en) * | 2012-09-03 | 2012-12-19 | 南通市明鑫化工有限公司 | Production process of hydrofluoric acid |
| CN103288087A (en) * | 2013-05-28 | 2013-09-11 | 浙江大学 | Surface modification process for improving luminance and dispersity of porous silicon |
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