CN104016361B - The preparation method of amphiphilic nanoparticles and its application in Pickering emulsions are prepared - Google Patents
The preparation method of amphiphilic nanoparticles and its application in Pickering emulsions are prepared Download PDFInfo
- Publication number
- CN104016361B CN104016361B CN201410208096.0A CN201410208096A CN104016361B CN 104016361 B CN104016361 B CN 104016361B CN 201410208096 A CN201410208096 A CN 201410208096A CN 104016361 B CN104016361 B CN 104016361B
- Authority
- CN
- China
- Prior art keywords
- nano
- ethanol
- particle
- cleaned
- prepared
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Silicon Polymers (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Colloid Chemistry (AREA)
Abstract
A kind of preparation method the present invention relates to amphiphilic nanoparticles and its application in Pickering emulsions are prepared, the present invention is first carried out epoxy-modified by silane coupler in nano grain surface, then it is further introduced into amino using hexamethylene diamine and epoxy reaction, appropriate hydrochloric acid neutralization is eventually adding, a kind of new amphiphilic nanoparticles are formed.This particle can replace general surfactant to prepare highly stable silicon oil/water, the Pickering emulsions of toluene/water.Its preparation process is simple, good stability is difficult to be influenceed by factors such as temperature, pH value, salinity, therefore with great application prospect and industrialization ability.The preparation method of this emulsion can also further expand to prepare different types of oil/water emulsion, or even suffer from potential application prospect in emulsion polymerization field.
Description
Technical field
The present invention relates to a kind of amphiphilic nanoparticles, the preparation method of more particularly to a kind of amphiphilic nanoparticles and its
Application in Pickering emulsions are prepared.
Background technology
The preparation of traditional emulsion is to add surfactant by the middle of mutual exclusive oil/water, is lived by surface
Property the unique amphiphile, amphiphilic molecule structure of agent so that surfactant is enriched with oil/water interface, so as to play a part of stable emulsion.
But there are many researchers to find, and it is undesirable by the stability of emulsion prepared by surfactant, easily by temperature, pH
The influence of the factors such as value, salinity, oil phase composition, so as to cause emulsion breaking.In addition some surfactants also have certain
Toxicity, to animals and plants, or even all there is harm in human body, this strongly limits the practical application of surfactant.
In recent years, researcher proposes, the solid nanoparticles using amphiphilic replace traditional surfactant to prepare
Emulsion (i.e. Pickering emulsions), relative to surfactant, absorption of the amphiphilic particle at interface is typically irreversible, because
Energy of adsorption required for granular absorption reaches thousands of kT.So, there is desorption and be nearly impossible in the particle that allow on interface,
Therefore there is unsurpassed stability (B.P.Binks.Curr.Opin.Colloid by the particle stabilized emulsion of amphiphilic
In.2002,2,21-41；S.Arditty,V.Schmitt,F.Lequeux,et al.Eur.Phys.J.B,2005,44,381-
393.).Additionally, the particle stabilized stability of emulsion of amphiphilic is difficult to receive the shadow of the factors such as temperature, pH value, salinity, oil phase composition
Ring, and this amphiphilic particle does not result in pollution to environment as emulsifying agent.Therefore, amphiphilic nanoparticles emulsifying agent is secondary
The field such as oil recovery, paint, food, medicine, cosmetics has very big potential using value.
So far, the solid particle with amphiphilic structure is mainly and connects the more complicated polymer molecule of some structures
The method complex operation that branch is modified to solid particles surface, this surface, severe reaction conditions, so prepare amphiphilic particle not
The cost of particle can be only greatly improved, the preparation process of its particle is also very cumbersome and is not suitable for large-scale production, this very big limit
Popularization and practical application (C.J.Lin, R.A.Sperling, J.K.Li, the et of Pickering emulsifying technologies are made
al.Small,2008,4,334-341；E.R.Zubarev,J.Xu,A.Sayyad,et al.J.Am.Chem.Soc.2006,
128,4958-4959；J.Shan,M.Nuopponen,H.Jiang,et al.Macromolecules,2005,38,2918-
2926.)。
The content of the invention
It is it is an object of the invention to provide a kind of preparation method of amphiphilic nanoparticles and its newborn Pickering is prepared
Application in liquid, the present invention is main epoxy-modified by carrying out in nano grain surface, then further introduces amino, most
Add appropriate hydrochloric acid to neutralize afterwards, form amphiphilic nanoparticles；This amphiphilic nanoparticles can replace general surfactant
To prepare highly stable silicon oil/water, the Pickering emulsions of toluene/water；Its preparation process is simple, and prepare
Pickering good emulsion stabilities, are difficult to be influenceed by factors such as temperature, pH value, salinity, with great application prospect and
Industrialization ability.
What the present invention was realized in：A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
0.5~2.0g nano particles are dispersed in 30~60g ethanol first, then by 1~4g glycidyl ether oxygen propyls
Triethoxysilane is dropwise instilled wherein, is stirred vigorously, and 18~24h is reacted at 50~70 DEG C；Then it is centrifuged, will receives
After rice grain is separated, cleaned 1-3 times with deionized water, cleaned 1-3 times with ethanol again afterwards, it is finally true at 80~100 DEG C
Sky dries 10~16h, obtains epoxy-modified nano particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nano particles of 0.5~2.0g are dispersed in 30~60g ethanol first, add 1~2g hexamethylene diamines,
Stir, 4~10h is reacted at 50~70 DEG C；Then it is centrifuged, after nano particle is separated, uses deionization
Water is cleaned 1-3 times, is cleaned 1-3 times with ethanol again afterwards, is finally vacuum dried 10~16h at 80~100 DEG C, obtains amino modified
Nano particle；
(3) amphiphilic nanoparticles are obtained：
The amino modified nano particle of 0.5~2.0g is dispersed in 30~60g ethanol first, addition 0.8~
1.6gHCl, stirring neutralizes 1~2h；Then it is centrifuged, after nano particle is separated, 1-3 is cleaned with deionized water
It is secondary, cleaned 1-3 times with ethanol again afterwards, 10~16h finally is vacuum dried at 80~100 DEG C, obtain amphiphilic nanoparticles.
The nano particle is nano silicon, nano titanium oxide, Nano Silver, nano-sized iron oxide, nano tin dioxide
Or one kind or any combination of nano zine oxide.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
0.5~2.0g nano particles are dispersed in 30~60g ethanol first, then by 1~4g glycidyl ether oxygen propyls
Triethoxysilane is dropwise instilled wherein, is stirred vigorously, and 18~24h is reacted at 50~70 DEG C；Then it is centrifuged, will receives
After rice grain is separated, cleaned 1-3 times with deionized water, cleaned 1-3 times with ethanol again afterwards, it is finally true at 80~100 DEG C
Sky dries 10~16h, obtains epoxy-modified nano particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nano particles of 0.5~2.0g are dispersed in 30~60g ethanol first, add 1~2g hexamethylene diamines,
Stir, 4~10h is reacted at 50~70 DEG C；Then it is centrifuged, after nano particle is separated, uses deionization
Water is cleaned 1-3 times, is cleaned 1-3 times with ethanol again afterwards, is finally vacuum dried 10~16h at 80~100 DEG C, obtains amino modified
Nano particle；
(3) amphiphilic nanoparticles are obtained：
The amino modified nano particle of 0.5~2.0g is dispersed in 30~60g ethanol first, addition 0.8~
1.6gHCl, stirring neutralizes 1~2h；Then it is centrifuged, after nano particle is separated, 1-3 is cleaned with deionized water
It is secondary, cleaned 1-3 times with ethanol again afterwards, 10~16h finally is vacuum dried at 80~100 DEG C, obtain amphiphilic nanoparticles.
The nano particle is nano silicon, nano titanium oxide, Nano Silver, nano-sized iron oxide, nano tin dioxide
Or one kind or any combination of nano zine oxide.
Application of the above-mentioned amphiphilic nanoparticles in Pickering emulsions are prepared, comprises the following steps：
By above-mentioned amphiphilic nanoparticles ultrasonic disperse in water, oil phase is subsequently adding, under 2000-5000rpm rotating speeds
2~10min of dispersion, the oil/water Pickering emulsions (reference oil-in-water emulsion) stablized；Wherein oil and the volume ratio of water
It is 1:1~1:4, amphiphilic nanoparticles account for the 0.05~0.1% of oil/water Pickering emulsion gross masses.The oil phase is preferred
For toluene, hexamethylene, containing hydrogen silicone oil, hydroxy silicon oil, dimethicone, amido silicon oil and epoxy-modified silicone oil one kind or appoint
Meaning combination.
It is preferred that nano silicon prepares amphiphilic nanoparticles as nano particle.
It is preferred that dimethicone prepares Pickering emulsions as oil phase.
The preparation method of amphiphilic nanoparticles of the present invention and its application in Pickering emulsions are prepared have following excellent
Point：The present invention by silane coupler it is first carried out in nano grain surface it is epoxy-modified, it is then anti-using hexamethylene diamine and epoxy
Amino should be further introduced into, appropriate hydrochloric acid neutralization is eventually adding, a kind of new amphiphilic nanoparticles are formed.This particle can generation
Highly stable silicon oil/water, the Pickering emulsions of toluene/water are prepared for general surfactant.Its preparation technology letter
Single, good stability is difficult to be influenceed by factors such as temperature, pH value, salinity, therefore with great application prospect and industrialization
Ability.The preparation method of this emulsion can also further expand to prepare different types of oil/water emulsion, or even in emulsion polymerization
Field suffers from potential application prospect.
Pickering emulsions prepared by the present invention are placed one month at a temperature of 50 DEG C, by the layering feelings for estimating emulsion
Condition determines its stability, and its emulsion droplet form is characterized by light microscope.
Brief description of the drawings
Figure one prepares reaction equation for amphiphilic nanoparticles.
Figure two is the emulsion after 50 DEG C of heat are stored up 1 month：
(a) with surfactant as emulsifying agent,
B () is with amphiphilic nanoparticles as emulsifying agent.
Figure three is the optical microscope photograph of Pickering emulsion droplets.
Specific embodiment
With reference to specific embodiment, the present invention will be described in detail.
(1) specific embodiment is as follows：
A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
0.5~2.0g nano particles are dispersed in 30~60g ethanol first, then by 1~4g glycidyl ether oxygen propyls
Triethoxysilane is dropwise instilled wherein, is stirred vigorously, and 18~24h is reacted at 50~70 DEG C；Then it is centrifuged, will receives
After rice grain is separated, cleaned 1-3 times with deionized water, cleaned 1-3 times with ethanol again afterwards, it is finally true at 80~100 DEG C
Sky dries 10~16h, obtains epoxy-modified nano particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nano particles of 0.5~2.0g are dispersed in 30~60g ethanol first, add 1~2g hexamethylene diamines,
Stir, 4~10h is reacted at 50~70 DEG C；Then it is centrifuged, after nano particle is separated, uses deionization
Water is cleaned 1-3 times, is cleaned 1-3 times with ethanol again afterwards, is finally vacuum dried 10~16h at 80~100 DEG C, obtains amino modified
Nano particle；
(3) amphiphilic nanoparticles are obtained：
The amino modified nano particle of 0.5~2.0g is dispersed in 30~60g ethanol first, addition 0.8~
1.6gHCl, stirring neutralizes 1~2h；Then it is centrifuged, after nano particle is separated, 1-3 is cleaned with deionized water
It is secondary, cleaned 1-3 times with ethanol again afterwards, 10~16h finally is vacuum dried at 80~100 DEG C, obtain amphiphilic nanoparticles.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
0.5~2.0g nano particles are dispersed in 30~60g ethanol first, then by 1~4g glycidyl ether oxygen propyls
Triethoxysilane is dropwise instilled wherein, is stirred vigorously, and 18~24h is reacted at 50~70 DEG C；Then it is centrifuged, will receives
After rice grain is separated, cleaned 1-3 times with deionized water, cleaned 1-3 times with ethanol again afterwards, it is finally true at 80~100 DEG C
Sky dries 10~16h, obtains epoxy-modified nano particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nano particles of 0.5~2.0g are dispersed in 30~60g ethanol first, add 1~2g hexamethylene diamines,
Stir, 4~10h is reacted at 50~70 DEG C；Then it is centrifuged, after nano particle is separated, uses deionization
Water is cleaned 1-3 times, is cleaned 1-3 times with ethanol again afterwards, is finally vacuum dried 10~16h at 80~100 DEG C, obtains amino modified
Nano particle；
(3) amphiphilic nanoparticles are obtained：
The amino modified nano particle of 0.5~2.0g is dispersed in 30~60g ethanol first, addition 0.8~
1.6gHCl, stirring neutralizes 1~2h；Then it is centrifuged, after nano particle is separated, 1-3 is cleaned with deionized water
It is secondary, cleaned 1-3 times with ethanol again afterwards, 10~16h finally is vacuum dried at 80~100 DEG C, obtain amphiphilic nanoparticles.
The nano particle is nano silicon, nano titanium oxide, Nano Silver, nano-sized iron oxide, nano tin dioxide
Or one kind or any combination of nano zine oxide.
Application of the above-mentioned amphiphilic nanoparticles in Pickering emulsions are prepared, comprises the following steps：
By above-mentioned amphiphilic nanoparticles ultrasonic disperse in water, oil phase is subsequently adding, under 2000-5000rpm rotating speeds
2~10min of dispersion, the oil/water Pickering emulsions (reference oil-in-water emulsion) stablized；Wherein oil and the volume ratio of water
It is 1:1~1:4, amphiphilic nanoparticles account for the 0.05~0.1% of oil/water Pickering emulsion gross masses.The oil phase is preferred
For toluene, hexamethylene, containing hydrogen silicone oil, hydroxy silicon oil, dimethicone, amido silicon oil and epoxy-modified silicone oil one kind or appoint
Meaning combination.
Refer to shown in Fig. 1-3, wherein Fig. 1 prepares reaction equation for amphiphilic nanoparticles.
Fig. 2 is the emulsion after 50 DEG C of heat are stored up 1 month：
(a) with surfactant as emulsifying agent,
B () is with amphiphilic nanoparticles as emulsifying agent.
Fig. 3 is the optical microscope photograph of Pickering emulsion droplets.
(2) embodiment is as follows：
Embodiment 1：A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 1.5g is dispersed in the ethanol of 40g, then by 2g glycidyl ether oxygen propyls three
Ethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 24h is reacted at 50 DEG C；Then it is centrifuged, by nanometer
After silica dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 2 times, then 10h is vacuum dried at 100 DEG C, obtained
To epoxy-modified nanometer silicon dioxide particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 1.5g is scattered in 40g ethanol, adds 1g hexamethylene diamines, stirring
Uniformly, 6h is reacted at 50 DEG C；Then it is centrifuged, it is clear with deionized water after nanometer silicon dioxide particle is separated
Wash 1 time, ethanol is cleaned 2 times, then 10h is vacuum dried at 100 DEG C, obtain amino modified nanometer silicon dioxide particle；
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 1.5g is dispersed in 40g ethanol, 1g HCl are added, stirred
Mix neutralization 1h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 1 time, ethanol is cleaned with deionized water
Cleaning 2 times, is finally vacuum dried 10h at 100 DEG C, obtains amphiphilic nano silica particle.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 1.5g is dispersed in the ethanol of 40g, then by 2g glycidyl ether oxygen propyls three
Ethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 24h is reacted at 50 DEG C；Then it is centrifuged, by nanometer
After silica dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 2 times, then 10h is vacuum dried at 100 DEG C, obtained
To epoxy-modified nanometer silicon dioxide particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 1.5g is scattered in 40g ethanol, adds 1g hexamethylene diamines, stirring
Uniformly, 6h is reacted at 50 DEG C；Then it is centrifuged, it is clear with deionized water after nanometer silicon dioxide particle is separated
Wash 1 time, ethanol is cleaned 2 times, then 10h is vacuum dried at 100 DEG C, obtain amino modified nanometer silicon dioxide particle；
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 1.5g is dispersed in 40g ethanol, 1g HCl are added, stirred
Mix neutralization 1h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 1 time, ethanol is cleaned with deionized water
Cleaning 2 times, is finally vacuum dried 10h at 100 DEG C, obtains amphiphilic nano silica particle.
Application of the above-mentioned amphiphilic nano silica particle in Pickering emulsions are prepared, comprises the following steps：
The amphiphilic nano silica particle of above-mentioned preparation is soluble in water, and ultrasonic disperse is uniform, is subsequently adding diformazan
Base silicone oil, 10min is disperseed under 5000rpm speed, the silicone oil Pickering emulsions stablized；Wherein dimethicone with
The volume ratio of water is 1:3, amphiphilic nano silica particle accounts for the 0.05% of emulsion gross mass.
Embodiment 2：A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
The titanium dioxide nanoparticle of 1.0g is dispersed in the ethanol of 50g, then by 1.5g glycidyl ether oxygen propyls
Triethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 20h is reacted at 50 DEG C；Then it is centrifuged, will receives
After rice titanium dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 2 times, then 10h be vacuum dried at 100 DEG C,
Obtain epoxy-modified titanium dioxide nanoparticle.
(2) amino modified nano particle is prepared：
The epoxy-modified titanium dioxide nanoparticle for weighing 1.0g is dispersed in 50g ethanol, adds 1.5g hexamethylene diamines, is stirred
Mix uniform, 6h is reacted at 50 DEG C；Then it is centrifuged, after titanium dioxide nanoparticle is separated, uses deionized water
Cleaning 1 time, ethanol is cleaned 2 times, then is vacuum dried 12h at 100 DEG C, obtains amino modified titanium dioxide nanoparticle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified titanium dioxide nanoparticle of 1.0g is dispersed in 50g ethanol, 1.0g HCl are added,
Stirring neutralizes 2h；Then it is centrifuged, after titanium dioxide nanoparticle is separated, 1 time, second is cleaned with deionized water
Alcohol is cleaned 2 times, is finally vacuum dried 10h at 100 DEG C, you can obtain amphiphilic nano titanium dioxide granule.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
The titanium dioxide nanoparticle of 1.0g is dispersed in the ethanol of 50g, then by 1.5g glycidyl ether oxygen propyls
Triethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 20h is reacted at 50 DEG C；Then it is centrifuged, will receives
After rice titanium dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 2 times, then 10h be vacuum dried at 100 DEG C,
Obtain epoxy-modified titanium dioxide nanoparticle.
(2) amino modified nano particle is prepared：
The epoxy-modified titanium dioxide nanoparticle for weighing 1.0g is dispersed in 50g ethanol, adds 1.5g hexamethylene diamines, is stirred
Mix uniform, 6h is reacted at 50 DEG C；Then it is centrifuged, after titanium dioxide nanoparticle is separated, uses deionized water
Cleaning 1 time, ethanol is cleaned 2 times, then is vacuum dried 12h at 100 DEG C, obtains amino modified titanium dioxide nanoparticle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified titanium dioxide nanoparticle of 1.0g is dispersed in 50g ethanol, 1.0g HCl are added,
Stirring neutralizes 2h；Then it is centrifuged, after titanium dioxide nanoparticle is separated, 1 time, second is cleaned with deionized water
Alcohol is cleaned 2 times, is finally vacuum dried 10h at 100 DEG C, you can obtain amphiphilic nano titanium dioxide granule.
Application process of the above-mentioned amphiphilic nano titanium dioxide granule in Pickering emulsions are prepared, including following step
Suddenly：
The amphiphilic nano titanium dioxide granule of above-mentioned preparation is soluble in water, and ultrasonic disperse is uniform, is subsequently adding toluene,
Disperse 10min under 5000rpm speed, the toluene/water Pickering emulsions stablized, wherein oil is with the volume ratio of water
1:2, amphiphilic nano titanium dioxide granule accounts for the 0.05% of emulsion gross mass.
Embodiment 3：A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 0.5g is dispersed in the ethanol of 30g, then by 1.0g glycidyl ether oxygen propyls
Triethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 24h is reacted at 50 DEG C；Then it is centrifuged, will receives
After rice silica dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 2 times, then 10h be vacuum dried at 100 DEG C,
Obtain epoxy-modified nanometer silicon dioxide particle.
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 0.5g is scattered in 30g ethanol, adds 1.0g hexamethylene diamines, is stirred
Mix uniform, 6h is reacted at 50 DEG C；Then it is centrifuged, after nanometer silicon dioxide particle is separated, uses deionized water
Cleaning 1 time, ethanol is cleaned 2 times, then is vacuum dried 10h at 100 DEG C, obtains amino modified nanometer silicon dioxide particle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 0.5g is dispersed in 30g ethanol, 1g HCl are added, stirred
Mix neutralization 1h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 1 time, ethanol is cleaned with deionized water
Cleaning 2 times, is finally vacuum dried 10h at 100 DEG C, obtains amphiphilic nano silica particle.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 0.5g is dispersed in the ethanol of 30g, then by 1.0g glycidyl ether oxygen propyls
Triethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 24h is reacted at 50 DEG C；Then it is centrifuged, will receives
After rice silica dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 2 times, then 10h be vacuum dried at 100 DEG C,
Obtain epoxy-modified nanometer silicon dioxide particle.
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 0.5g is scattered in 30g ethanol, adds 1.0g hexamethylene diamines, is stirred
Mix uniform, 6h is reacted at 50 DEG C；Then it is centrifuged, after nanometer silicon dioxide particle is separated, uses deionized water
Cleaning 1 time, ethanol is cleaned 2 times, then is vacuum dried 10h at 100 DEG C, obtains amino modified nanometer silicon dioxide particle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 0.5g is dispersed in 30g ethanol, 1g HCl are added, stirred
Mix neutralization 1h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 1 time, ethanol is cleaned with deionized water
Cleaning 2 times, is finally vacuum dried 10h at 100 DEG C, obtains amphiphilic nano silica particle.
Application process of the above-mentioned amphiphilic nano silica particle in Pickering emulsions are prepared, including following step
Suddenly：
By above-mentioned preparation to obtain amphiphilic nano silica particle soluble in water, ultrasonic disperse is uniform, is subsequently adding
Containing hydrogen silicone oil, 10min is disperseed under 5000rpm speed, the silicone oil Pickering emulsions stablized, wherein containing hydrogen silicone oil with
The volume ratio of water is 1:1, amphiphilic nano silica particle accounts for the 0.08% of emulsion gross mass.
Embodiment 4：A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 0.5g is dispersed in the ethanol of 30g, then by 1g glycidyl ether oxygen propyls three
Ethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 24h is reacted at 50 DEG C；Then it is centrifuged, by nanometer
After silica dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 1 time, then 16h is vacuum dried at 80 DEG C, obtained
Epoxy-modified nanometer silicon dioxide particle.
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 0.5g is scattered in 30g ethanol, adds 1g hexamethylene diamines, stirring
Uniformly, 10h is reacted at 50 DEG C；Then it is centrifuged, it is clear with deionized water after nanometer silicon dioxide particle is separated
Wash 1 time, ethanol is cleaned 1 time, then 16h is vacuum dried at 80 DEG C, obtain amino modified nanometer silicon dioxide particle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 0.5g is dispersed in 30g ethanol, 0.8g HCl are added,
Stirring neutralizes 1h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 1 time, second is cleaned with deionized water
Alcohol is cleaned 1 time, is finally vacuum dried 16h at 80 DEG C, obtains amphiphilic nano silica particle.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 0.5g is dispersed in the ethanol of 30g, then by 1g glycidyl ether oxygen propyls three
Ethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 24h is reacted at 50 DEG C；Then it is centrifuged, by nanometer
After silica dioxide granule is separated, cleaned with deionized water 1 time, ethanol is cleaned 1 time, then 16h is vacuum dried at 80 DEG C, obtained
Epoxy-modified nanometer silicon dioxide particle.
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 0.5g is scattered in 30g ethanol, adds 1g hexamethylene diamines, stirring
Uniformly, 10h is reacted at 50 DEG C；Then it is centrifuged, it is clear with deionized water after nanometer silicon dioxide particle is separated
Wash 1 time, ethanol is cleaned 1 time, then 16h is vacuum dried at 80 DEG C, obtain amino modified nanometer silicon dioxide particle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 0.5g is dispersed in 30g ethanol, 0.8g HCl are added,
Stirring neutralizes 1h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 1 time, second is cleaned with deionized water
Alcohol is cleaned 1 time, is finally vacuum dried 16h at 80 DEG C, obtains amphiphilic nano silica particle.
Application process of the above-mentioned amphiphilic nano silica particle in Pickering emulsions are prepared, including following step
Suddenly：
By above-mentioned preparation to obtain amphiphilic nano silica particle soluble in water, ultrasonic disperse is uniform, is subsequently adding
Containing hydrogen silicone oil, 10min is disperseed under 2000rpm speed, the silicone oil Pickering emulsions stablized, wherein containing hydrogen silicone oil with
The volume ratio of water is 1:1, amphiphilic nano silica particle accounts for the 0.05% of emulsion gross mass.
Embodiment 5：A kind of amphiphilic nanoparticles, it is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 2.0g is dispersed in the ethanol of 60g, then by 4g glycidyl ether oxygen propyls three
Ethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 18h is reacted at 70 DEG C；Then it is centrifuged, by nanometer
After silica dioxide granule is separated, cleaned with deionized water 3 times, ethanol is cleaned 3 times, then 10h is vacuum dried at 100 DEG C, obtained
To epoxy-modified nanometer silicon dioxide particle.
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 2.0g is scattered in 60g ethanol, adds 2g hexamethylene diamines, stirring
Uniformly, 4h is reacted at 70 DEG C；Then it is centrifuged, it is clear with deionized water after nanometer silicon dioxide particle is separated
Wash 3 times, ethanol is cleaned 3 times, then 10h is vacuum dried at 100 DEG C, obtain amino modified nanometer silicon dioxide particle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 2.0g is dispersed in 60g ethanol, 1.6g HCl are added,
Stirring neutralizes 2h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 3 times, second is cleaned with deionized water
Alcohol is cleaned 3 times, is finally vacuum dried 10h at 100 DEG C, obtains amphiphilic nano silica particle.
The preparation method of above-mentioned amphiphilic nanoparticles, it is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
The nanometer silicon dioxide particle of 2.0g is dispersed in the ethanol of 60g, then by 4g glycidyl ether oxygen propyls three
Ethoxysilane (GPTEOS) is dropwise instilled wherein, is stirred vigorously, and 18h is reacted at 70 DEG C；Then it is centrifuged, by nanometer
After silica dioxide granule is separated, cleaned with deionized water 3 times, ethanol is cleaned 3 times, then 10h is vacuum dried at 100 DEG C, obtained
To epoxy-modified nanometer silicon dioxide particle.
(2) amino modified nano particle is prepared：
The epoxy-modified nanometer silicon dioxide particle for weighing 2.0g is scattered in 60g ethanol, adds 2g hexamethylene diamines, stirring
Uniformly, 4h is reacted at 70 DEG C；Then it is centrifuged, it is clear with deionized water after nanometer silicon dioxide particle is separated
Wash 3 times, ethanol is cleaned 3 times, then 10h is vacuum dried at 100 DEG C, obtain amino modified nanometer silicon dioxide particle.
(3) amphiphilic nanoparticles are obtained：
Finally the above-mentioned amino modified nanometer silicon dioxide particle of 2.0g is dispersed in 60g ethanol, 1.6g HCl are added,
Stirring neutralizes 2h；Then it is centrifuged, after nanometer silicon dioxide particle is separated, 3 times, second is cleaned with deionized water
Alcohol is cleaned 3 times, is finally vacuum dried 10h at 100 DEG C, obtains amphiphilic nano silica particle.
Application process of the above-mentioned amphiphilic nano silica particle in Pickering emulsions are prepared, including following step
Suddenly：
By above-mentioned preparation to obtain amphiphilic nano silica particle soluble in water, ultrasonic disperse is uniform, is subsequently adding
Containing hydrogen silicone oil, 2min is disperseed under 5000rpm speed, the silicone oil Pickering emulsions stablized, wherein containing hydrogen silicone oil and water
Volume ratio be 1:4, amphiphilic nano silica particle accounts for the 0.1% of emulsion gross mass.
Above-mentioned specific embodiment is that technical scheme is explained in detail, the present invention not only only office
It is limited to above-described embodiment, every any improvement or replacement according to the principle of the invention all should be within protection scope of the present invention.
Claims (6)
1. a kind of amphiphilic nanoparticles, it is characterised in that：It is prepared in accordance with the following methods：
(1) epoxy-modified nano particle is prepared：
0.5~2.0g nano particles are dispersed in 30~60g ethanol first, then by the second of 1~4g glycidyl ether oxygen propyls three
TMOS is dropwise instilled wherein, is stirred vigorously, and 18~24h is reacted at 50~70 DEG C；Then it is centrifuged, by nanometer
After grain is separated, cleaned 1-3 times with deionized water, cleaned 1-3 times with ethanol again afterwards, it is finally dry in 80~100 DEG C of vacuum
Dry 10~16h, obtains epoxy-modified nano particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nano particles of 0.5~2.0g are dispersed in 30~60g ethanol first, add 1~2g hexamethylene diamines, stirring
Uniformly, 4~10h is reacted at 50~70 DEG C；Then it is centrifuged, it is clear with deionized water after nano particle is separated
Wash 1-3 times, cleaned 1-3 times with ethanol again afterwards, be finally vacuum dried 10~16h at 80~100 DEG C, obtain amino modified nanometer
Particle；
(3) amphiphilic nanoparticles are obtained：
The amino modified nano particle of 0.5~2.0g is dispersed in 30~60g ethanol first, adds 0.8~1.6gHCl, stirred
Mix 1~2h of neutralization；Then it is centrifuged, after nano particle is separated, is cleaned 1-3 times with deionized water, Zhi Houzai
Cleaned 1-3 times with ethanol, be finally vacuum dried 10~16h at 80~100 DEG C, obtain amphiphilic nanoparticles.
2. amphiphilic nanoparticles according to claim 1, it is characterised in that：The nano particle is nanometer titanium dioxide
One kind or any combination of silicon, nano titanium oxide, Nano Silver, nano-sized iron oxide, nano tin dioxide or nano zine oxide.
3. the preparation method of amphiphilic nanoparticles described in a kind of claim 1, it is characterised in that：It is comprised the steps of：
(1) epoxy-modified nano particle is prepared：
0.5~2.0g nano particles are dispersed in 30~60g ethanol first, then by the second of 1~4g glycidyl ether oxygen propyls three
TMOS is dropwise instilled wherein, is stirred vigorously, and 18~24h is reacted at 50~70 DEG C；Then it is centrifuged, by nanometer
After grain is separated, cleaned 1-3 times with deionized water, cleaned 1-3 times with ethanol again afterwards, it is finally dry in 80~100 DEG C of vacuum
Dry 10~16h, obtains epoxy-modified nano particle；
(2) amino modified nano particle is prepared：
The epoxy-modified nano particles of 0.5~2.0g are dispersed in 30~60g ethanol first, add 1~2g hexamethylene diamines, stirring
Uniformly, 4~10h is reacted at 50~70 DEG C；Then it is centrifuged, it is clear with deionized water after nano particle is separated
Wash 1-3 times, cleaned 1-3 times with ethanol again afterwards, be finally vacuum dried 10~16h at 80~100 DEG C, obtain amino modified nanometer
Particle；
(3) amphiphilic nanoparticles are obtained：
The amino modified nano particle of 0.5~2.0g is dispersed in 30~60g ethanol first, adds 0.8~1.6gHCl, stirred
Mix 1~2h of neutralization；Then it is centrifuged, after nano particle is separated, is cleaned 1-3 times with deionized water, Zhi Houzai
Cleaned 1-3 times with ethanol, be finally vacuum dried 10~16h at 80~100 DEG C, obtain amphiphilic nanoparticles.
4. the preparation method of amphiphilic nanoparticles according to claim 3, it is characterised in that：The nano particle is to receive
One kind of rice silica, nano titanium oxide, Nano Silver, nano-sized iron oxide, nano tin dioxide or nano zine oxide is any
Combination.
5. application of the amphiphilic nanoparticles described in claim 1 in Pickering emulsions are prepared, it is characterised in that：Bag
Include following steps：
By the amphiphilic nanoparticles ultrasonic disperse described in claim 1 in water, oil phase is subsequently adding, in 2000-5000rpm
Disperse 2~10min, the oil/water Pickering emulsions stablized under rotating speed；Wherein oil and the volume ratio of water is 1:1~1:4,
Amphiphilic nanoparticles account for the 0.05~0.1% of oil/water Pickering emulsion gross masses.
6. application of the amphiphilic nanoparticles according to claim 5 in Pickering emulsions are prepared, its feature exists
In：The oil phase is toluene, hexamethylene, containing hydrogen silicone oil, hydroxy silicon oil, dimethicone, amido silicon oil and epoxy-modified silicone
One kind or any combination of oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208096.0A CN104016361B (en) | 2014-05-16 | 2014-05-16 | The preparation method of amphiphilic nanoparticles and its application in Pickering emulsions are prepared |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410208096.0A CN104016361B (en) | 2014-05-16 | 2014-05-16 | The preparation method of amphiphilic nanoparticles and its application in Pickering emulsions are prepared |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104016361A CN104016361A (en) | 2014-09-03 |
| CN104016361B true CN104016361B (en) | 2017-06-23 |
Family
ID=51433425
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410208096.0A Active CN104016361B (en) | 2014-05-16 | 2014-05-16 | The preparation method of amphiphilic nanoparticles and its application in Pickering emulsions are prepared |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104016361B (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525061B (en) * | 2014-11-07 | 2016-08-24 | 陕西师范大学 | Based on ionic liquid and the magnetic responsiveness pickering emulsion of amphipathic Fe3O4 nano particle |
| CN104947229B (en) * | 2015-07-02 | 2017-05-03 | 武汉工程大学 | Method for preparing medicine-carrying nanofibers of core-shell structure by virtue of Pickering emulsion electrospinning |
| CN105363495B (en) * | 2015-11-20 | 2017-10-31 | 中北大学 | A kind of amphiphilic nano TiO2Fine catalyst and preparation method thereof and application method |
| CN105817152A (en) * | 2016-03-18 | 2016-08-03 | 东华大学 | Pickering emulsion with biocompatibility and biodegradability and preparation method thereof |
| CN106084215B (en) * | 2016-06-20 | 2018-03-06 | 陕西师范大学 | The bionical method for constructing functionalization Janus particles |
| CN107141429B (en) * | 2017-05-08 | 2019-11-29 | 苏州科技大学 | A kind of modified magnetic nano silica and its application in water-oil separating |
| CN107413279A (en) * | 2017-06-28 | 2017-12-01 | 江南大学 | A kind of compound emulsifying agent with redox stimuli responsive performance |
| CN107399740B (en) * | 2017-09-01 | 2020-03-24 | 东北石油大学 | Fluorinated amphiphilic nano-particles and application thereof |
| CN109485092B (en) * | 2017-09-11 | 2020-12-01 | 中南民族大学 | Method for enriching chlorophenol organic pollutants by titanium dioxide self-assembled microcapsules |
| CN107880867B (en) * | 2017-09-22 | 2021-03-19 | 中国石油大学(华东) | Pickering emulsion fracturing fluid and preparation method and application thereof |
| CN108070368B (en) * | 2018-01-18 | 2020-09-29 | 中国石油大学(华东) | Self-emulsifying emulsion and preparation method thereof |
| CN108841364B (en) * | 2018-08-01 | 2021-03-02 | 西南石油大学 | Reversible pickering emulsion, preparation method thereof and reversible high-temperature high-density drilling fluid |
| CN108690573B (en) * | 2018-08-01 | 2022-01-04 | 西南石油大学 | Reversible Pickering emulsion, preparation method thereof and reversible Pickering emulsion type drilling fluid |
| CN111543672B (en) * | 2020-05-21 | 2022-02-08 | 中国烟草总公司郑州烟草研究院 | Preparation method of novel filter stick capable of reducing release amount of phenol in smoke and filter stick product |
| CN111632405B (en) * | 2020-05-28 | 2021-10-22 | 清华大学 | Oil-water separation method based on magnetic Janus particles |
| CN111701586B (en) * | 2020-06-09 | 2021-07-02 | 山西大学 | Photocatalytic reduction of CO2Construction method and application of Pickering microbubble system for preparing methanol |
| CN112194949B (en) * | 2020-09-18 | 2022-02-22 | 三棵树涂料股份有限公司 | Titanium dioxide and silver loaded acrylic acid composite emulsion and preparation method and application thereof |
| CN113930265A (en) * | 2021-09-29 | 2022-01-14 | 华中科技大学 | Emulsion, application thereof and method for preparing emulsion by using nano-particles to emulsify biomass pyrolysis oil |
| TWI802109B (en) * | 2021-11-26 | 2023-05-11 | 財團法人工業技術研究院 | Composite material, film, and light-emitting device |
| CN116948112B (en) * | 2023-07-29 | 2024-08-30 | 河南正佳能源环保股份有限公司 | Instant polyacrylamide for offshore oil displacement and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101302296B (en) * | 2008-06-03 | 2010-08-25 | 江南大学 | Preparation of amphiphilic copolymer self-assembled micelle wedding agent |
| CN101704529B (en) * | 2009-11-05 | 2011-06-22 | 西北工业大学 | Method for preparing amphiphilic nano silica powder and method for preparing Pickering emulsion using same |
-
2014
- 2014-05-16 CN CN201410208096.0A patent/CN104016361B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104016361A (en) | 2014-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104016361B (en) | The preparation method of amphiphilic nanoparticles and its application in Pickering emulsions are prepared | |
| Pal et al. | Recent trends in morphology-controlled synthesis and application of mesoporous silica nanoparticles | |
| Hyde et al. | Colloidal silica particle synthesis and future industrial manufacturing pathways: a review | |
| Halas | Nanoscience under glass: the versatile chemistry of silica nanostructures | |
| CN104386672B (en) | A kind of preparation method with the graphene oxide composite material of unsymmetric structure | |
| CN107140650B (en) | Silicon dioxide nano surfactant and preparation method thereof | |
| Modrzejewska-Sikorska et al. | Lignosulfonate-stabilized selenium nanoparticles and their deposition on spherical silica | |
| Aich et al. | Aggregation kinetics of higher-order fullerene clusters in aquatic systems | |
| CN105236467B (en) | A kind of a large amount of technique and its applications for preparing nano zine oxide | |
| TW200846394A (en) | Polyalkylsilsesquioxane particulates and a preparation method thereof | |
| CN106587691A (en) | Method for preparing modified micro particles coated with graphene oxide | |
| JP2007217258A (en) | Carbon nanoparticle dispersion and its production method, and core/shell type carbon nanoparticle and its production method | |
| CN105567227B (en) | A kind of method that graphene quantum dot is extracted in the solid waste from coffee grounds | |
| Wheeler et al. | Thermodynamic driving force in the spontaneous formation of inorganic nanoparticle solutions | |
| CN104076073A (en) | Short-bar-shaped nano-zinc oxide/graphene compound and preparation method thereof | |
| CN108440322B (en) | Star-shaped carboxylic acid group zwitterionic surfactant and preparation method and application thereof | |
| CN107267007A (en) | A kind of haze sealing wax and preparation method thereof | |
| CN108774413A (en) | Nano silicon dioxide dispersion and preparation method thereof | |
| CN107824218B (en) | Metal composite Janus nanosheet catalyst and preparation method and application thereof | |
| CN104119545B (en) | Silicone compound particle and its manufacture method | |
| CN103464782A (en) | Method utilizing shaddock ped extracting solution to synthesize silver nanoparticles in microwave | |
| CN104147986A (en) | Long-chain-thioether-bond-containing mesoporous organic-inorganic hybrid ball of core-hollow-shell structure and preparation method thereof | |
| CN102876088A (en) | Preparation method of novel organic acryl-chlorinated titanium dioxide nanoparticles | |
| Lei et al. | Facile synthesis of ionic liquid modified silica nanoparticles for fast removal of anionic organic dyes with extremely high adsorption capacity | |
| Karakuş | Preparation and rheological characterization of Chitosan-Gelatine@ ZnO-Si nanoparticles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |