CN111392736A - Silicon dioxide-based Janus particle and preparation method and application thereof - Google Patents
Silicon dioxide-based Janus particle and preparation method and application thereof Download PDFInfo
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- CN111392736A CN111392736A CN202010231693.0A CN202010231693A CN111392736A CN 111392736 A CN111392736 A CN 111392736A CN 202010231693 A CN202010231693 A CN 202010231693A CN 111392736 A CN111392736 A CN 111392736A
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
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Abstract
The invention discloses a silicon dioxide-based Janus particle and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a mixture of 1: dissolving 0.007-0.014 silicate ester and alkoxy silane in a solvent, uniformly stirring, adding a certain amount of weak alkaline solution, reacting at 20-30 ℃ for 6-12 h, centrifuging, and drying to obtain the silicon dioxide-based Janus particle. The method has the advantages of low reaction temperature, mild conditions and few reaction steps, the prepared Janus particles are uniform spheres, the surfaces of the spheres have obviously different shapes, one side of each sphere is smooth, the other side of each sphere is rough, the smooth surface has hydrophilicity, and the rough surface has lipophilicity, so that the method can be applied to the fields of stable emulsion, supported catalyst, controlled drug release and the like.
Description
Technical Field
The invention relates to the technical field of inorganic functional nanoparticles, in particular to a silicon dioxide-based Janus particle and a preparation method and application thereof.
Background
Janus particles are small solid particles which have amphiphilicity and are asymmetric in nature, namely, one surface of the particles is hydrophilic, and the other surface of the particles is hydrophobic, and the solid particles with partial lipophilicity and partial hydrophilicity can be adsorbed at the interface of an aqueous phase and an oil phase, and are mainly used as a stabilizer, a thickening agent and a catalyst of a Pickering emulsion.
The advantages of Janus particles are: (1) the concentration of colloid particles needed by the emulsion is far lower than that of the surfactant, so that the dosage of the emulsifier can be reduced, and the cost is saved; (2) the toxic action of the colloidal particles to human bodies and the environment is far less than that of the surfactant; (3) the emulsion system with stable Janus particles is not easily influenced by external acidity and alkalinity, salt concentration, temperature and oil phase composition, and has stronger stability; (4) janus particles can be easily modified to have acid-base, temperature or magnetic responsiveness, and separation and recovery of the particles can be achieved by changing stimulation conditions.
At present, the methods for preparing Janus particles based on inorganic compound particles mainly include: the method comprises the steps of topology selection surface modification, a microfluid technology, a nucleation growth control method and the like, wherein the topology selection surface modification method is complex to operate, the microfluid technology has high requirements on equipment, the size of prepared ions is single, the nucleation growth control method is simple to operate, and the size of the ions can be adjusted.
Chinese patent CN201210347232.5 discloses a method for preparing modified nano-silica, which is a selective surface modification method, and is characterized by adopting sol-gel method acid-base co-catalysis to prepare nano-silica, and using silane coupling agent to carry out in-situ modification on nano-silica, so that nano-silica is converted from hydrophilicity to lipophilicity. However, this method is cumbersome, the reaction temperature is high, and the resulting particles do not have the regional amphiphilicity that is characteristic of Janus particles.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and shortcomings of high reaction temperature and complicated reaction steps in the existing preparation of the silicon dioxide-based Janus particles, and provide a preparation method of the silicon dioxide-based Janus particles, wherein the regional modification of the silicon dioxide particles is realized by controlling the use amounts of the precursor and the modifier, the reaction temperature is low, the conditions are mild, and the preparation method has few steps.
It is another object of the present invention to provide a silica-based Janus particle.
It is yet another object of the present invention to provide the use of silica-based Janus particles in the preparation of an emulsion.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of silica-based Janus particles comprises the following steps:
mixing a mixture of 1: dissolving 0.007-0.014 silicate ester and alkoxy silane in a solvent, uniformly stirring, adding a weak alkaline solution with the volume of 1-3 times that of the silicate ester, reacting at 20-30 ℃ for 6-12 h, centrifuging, and drying to obtain the silicon dioxide-based Janus particle.
The invention provides a method for preparing silicon dioxide based Janus particles, which is characterized in that in a mixed solution of silicate and a modifier, a weakly alkaline solution is added by regulating and controlling the ratio of the silicate to the modifier to provide the most appropriate reaction environment, and the silicon dioxide based Janus particles can be generated after reaction.
Preferably, the silicate and alkoxysilane are present in a molar ratio of 1: 0.01.
preferably, the silicate is one of tetraethyl silicate, tetramethoxysilane, propyl orthosilicate and isopropyl orthosilicate as a precursor of the reaction.
More preferably, the silicate is tetraethyl silicate.
Preferably, the alkoxy silane is one of hexadecyl trimethoxy silane, octadecyl triethoxy silane and n-octyl trimethoxy silane as a modifier of the reaction.
More preferably, the alkoxysilane is hexadecyltrimethoxysilane.
Preferably, the solvent is one of isopropanol, methanol, ethanol, n-propanol, ethylene glycol and tert-butanol.
More preferably, the solvent is isopropanol, which is cheaper and more environmentally friendly, and is most preferably water-soluble and oil-soluble.
Preferably, the weak alkaline solution is an ammonia water solution with the mass fraction of 25% -30%.
Preferably, the reaction temperature is 20-30 ℃, and the reaction time is 6-12 h.
Further preferably, the reaction temperature is 30 ℃ and the reaction time is 6 h.
Preferably, after centrifugation, the particles are washed for 3 times by ethanol and distilled water respectively, and the silica-based Janus particles are obtained after drying.
Further preferably, after the reaction is finished, the system is in a white emulsion state, centrifugation is carried out, a supernatant is discarded, solid residues are respectively washed three times by ethanol and distilled water, and after washing, drying is carried out until the weight is constant, so that the silicon dioxide-based Janus particles are obtained.
The invention also protects the silicon dioxide-based Janus particle prepared by the preparation method.
The invention also protects the application of the silicon dioxide-based Janus particle in preparing the emulsion.
Janus particles have amphipathy, can be dispersed at an oil-water interface, are similar to small molecular surfactants, and have better stability of a prepared emulsion system.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a preparation method of a silicon dioxide based Janus particle, which is characterized in that a weak alkaline solution is added into a mixed solution of silicate and a modifier to react to generate the silicon dioxide based Janus particle, so that regional modification is realized.
Drawings
Fig. 1 is a scanning electron micrograph of silica-based Janus particles prepared in example 1, comparative example 1 and comparative example 2 (fig. 1a. example 1; fig. 1b. comparative example 1; fig. 1c. comparative example 2).
FIG. 2 is a microscope photograph of a stabilized emulsion of Janus particles prepared in example 1.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
Example 1
A preparation method of silica-based Janus particles comprises the following steps:
8m L tetraethyl silicate and 0.1m L hexadecyl trimethoxy silane are respectively added into 100m L isopropanol, wherein the molar ratio of the tetraethyl silicate to the hexadecyl trimethoxy silane is 1: 0.007, after stirring for 10 minutes, a water bath is controlled at 30 ℃, 24m L ammonia water (the mass fraction is 25%) is dropwise added, after 1 hour of dropwise addition, the stirring is continued for 6 hours under controlled temperature.
And after the reaction is finished, the system is in a white emulsion state, centrifuging, removing supernatant, respectively washing solid residues with ethanol and distilled water for three times, and drying to constant weight after washing to obtain the silicon dioxide-based Janus particles.
Example 2
This example was prepared in the same manner as example 1 except that isopropanol was replaced with methanol, tetraethyl silicate was replaced with tetramethoxysilane, 0.1m L hexadecyltrimethoxysilane was replaced with 0.15m L octadecyltrimethoxysilane, and the molar ratio of tetramethoxysilane to octadecyltrimethoxysilane was 1: 0.01.
Example 3
This example was prepared in the same manner as example 1 except that isopropanol was replaced with n-propanol, tetraethyl orthosilicate was replaced with propyl orthosilicate, 0.1m L hexadecyltrimethoxysilane was replaced with 2m L octadecyltriethoxysilane, and the molar ratio of propyl orthosilicate to octadecyltriethoxysilane was 1: 0.014.
Example 4
The preparation method of the embodiment is the same as that of the embodiment 1, except that the temperature control of the water bath is replaced by 20 ℃, the stirring time is replaced by 12 hours, the isopropanol is replaced by the ethylene glycol, and the ammonia water with the mass fraction of 25% is replaced by the ammonia water with the mass fraction of 30%.
Example 5
The procedure of this example is the same as in example 1 except that the temperature of the water bath is controlled to 25 ℃ and stirring is carried out for 9 hours, and isopropanol is replaced by tert-butanol.
Example 6
The procedure of this example is the same as in example 1, except that isopropanol is replaced by ethanol, tetraethyl silicate is replaced by isopropyl n-silicate, and hexadecyltrimethoxysilane is replaced by n-octyltrimethoxysilane.
Comparative example 1
This comparative example was prepared in the same manner as example 1, except that 0.1m L hexadecyltrimethoxysilane was not added.
Comparative example 2
This comparative example was prepared by the same method as example 1 except that 0.1m L hexadecyltrimethoxysilane was replaced with 3m L hexadecyltrimethoxysilane, the molar ratio of tetraethyl silicate to hexadecyltrimethoxysilane being 1: 0.021.
Comparative example 3
The comparative example was prepared in the same manner as in example 1 except that 25% by mass of aqueous ammonia was used in place of 0.05 mol/L of the sodium hydroxide solution.
Comparative example 4
The preparation method of this comparative example is the same as that of example 1 except that ammonia water of 25% by mass is substituted for ammonia water of 10% by mass.
The scanning electron micrograph of the silica-based Janus particles prepared in example 1 is shown in fig. 1a to be uniform spherical, with a diameter range of 450 ± 20nm, one side of which is rough and the other side of which is smooth, and the particles have amphiphilicity. Janus particles prepared in examples 1-6 are amphiphilic and therefore can be dispersed at the oil-water interface, similar to small molecule surfactants.
The scanning electron microscope of the silica particles prepared in comparative example 1 is shown in fig. 1b, the diameter is 1180 ± 20nm, the surfaces of the particles are all smooth surfaces, and the particles are hydrophilic particles.
The silica particles prepared in comparative example 2 had a diameter of 480. + -.20 nm and all the surfaces thereof were rough and hydrophobic as shown in FIG. 1c.
The silica particles prepared in comparative example 3 had a non-uniform particle size distribution, and the particle surfaces were all rough and hydrophobic.
The silica particles prepared in comparative example 4 were slightly smaller in particle size, and the particle surfaces were all rough surfaces, which were hydrophobic particles.
The 4 types of particles prepared in comparative examples 1 to 4 were hydrophilic particles, hydrophobic particles, and hydrophobic particles, respectively.
Based on the above characteristics of the Janus particles, the invention uses the Janus particles prepared in example 1 as an emulsifier to prepare a high internal phase water-in-oil emulsion, the external phase is a mixture of styrene and divinylbenzene, the internal phase is water, the internal phase volume ratio can reach 90%, and the obtained emulsion is placed for two months, so that no obvious oil-water separation phenomenon is found, and the stability of the Janus particles in example 1 is strong. The optical micrograph of the resulting emulsion is shown in FIG. 2.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of silica-based Janus particles is characterized by comprising the following steps:
mixing a mixture of 1: dissolving 0.007-0.014 silicate ester and alkoxy silane in a solvent, uniformly stirring, adding a weak alkaline solution with the volume of 1-3 times that of the silicate ester, reacting at 20-30 ℃ for 6-12 h, centrifuging, and drying to obtain the silicon dioxide-based Janus particle.
2. The method according to claim 1, wherein the silicate and the alkoxysilane are present in a molar ratio of 1: 0.01.
3. the method according to claim 1 or 2, wherein the silicate is one of tetraethyl silicate, tetramethoxysilane, propyl orthosilicate, and isopropyl orthosilicate.
4. The method according to claim 1 or 2, wherein the alkoxysilane is one of hexadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and n-octyltrimethoxysilane.
5. The method according to claim 1, wherein the solvent is one of isopropyl alcohol, methanol, ethanol, n-propyl alcohol, ethylene glycol, and t-butyl alcohol.
6. The method according to claim 1, wherein the weakly alkaline solution is an aqueous ammonia solution with a mass fraction of 25% to 30%.
7. The method according to claim 1, wherein the reaction temperature is 30 ℃ and the reaction time is 6 hours.
8. The method according to claim 1, wherein the silica-based Janus particles are obtained by washing the particles with ethanol and distilled water for 3 times, respectively, after centrifugation, and drying the washed particles.
9. The bis-silyl Janus particle prepared by the preparation method of any one of claims 1 to 8.
10. Use of the silica-based Janus particles of claim 9 in the preparation of an emulsion.
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Citations (8)
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| CN101792147A (en) * | 2010-01-12 | 2010-08-04 | 清华大学深圳研究生院 | Surface modification method of silica particles and method for displaying latent fingerprints |
| CN102863823A (en) * | 2012-09-19 | 2013-01-09 | 常州大学 | Preparation method of modified nano silicon dioxide |
| CN103665269A (en) * | 2013-11-12 | 2014-03-26 | 江南大学 | Preparation method of amphiphilic acrylate copolymer surface grafting modified nano silicon dioxide |
| CN107416844A (en) * | 2017-08-09 | 2017-12-01 | 中国石油天然气股份有限公司 | Nano silicon dioxide dispersion and preparation method with parents characteristic and double grains minor structure |
| US20180200689A1 (en) * | 2015-07-30 | 2018-07-19 | Dwi-Leibniz-Institut Für Interaktive Materialien E.V. | Method for the encapsulation of substances in silica-based capsules and the products obtained thereof |
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2020
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| CN101792147A (en) * | 2010-01-12 | 2010-08-04 | 清华大学深圳研究生院 | Surface modification method of silica particles and method for displaying latent fingerprints |
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| CN107416844A (en) * | 2017-08-09 | 2017-12-01 | 中国石油天然气股份有限公司 | Nano silicon dioxide dispersion and preparation method with parents characteristic and double grains minor structure |
| CN108383129A (en) * | 2018-01-30 | 2018-08-10 | 南京工业大学 | A kind of preparation method of flexibility Hydrophobic silica aeroge |
| CN109666455A (en) * | 2019-01-16 | 2019-04-23 | 中国海洋大学 | The preparation method of amphipathic silica solid particle base marine oil spill dispersing agent |
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