CN101823719A - Two-step preparation method of hollow silica particles - Google Patents
Two-step preparation method of hollow silica particles Download PDFInfo
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- CN101823719A CN101823719A CN201010175242.6A CN201010175242A CN101823719A CN 101823719 A CN101823719 A CN 101823719A CN 201010175242 A CN201010175242 A CN 201010175242A CN 101823719 A CN101823719 A CN 101823719A
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- Prior art keywords
- water
- silicon
- hollow silica
- dioxide
- reaction
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims description 31
- 229960001866 silicon dioxide Drugs 0.000 claims description 19
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 3
- XQMTUIZTZJXUFM-UHFFFAOYSA-N tetraethoxy silicate Chemical group CCOO[Si](OOCC)(OOCC)OOCC XQMTUIZTZJXUFM-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- -1 vinyl pyridine-polyethylene Chemical group 0.000 description 2
- 239000000592 Artificial Cell Substances 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Silicon Compounds (AREA)
Abstract
The invention relates to a two-step preparation method of hollow silica particles, comprising the following steps of: heating ammonia-water to 25-75 DEG C; slowly dripping a part of silica precursor in the ammonia-water for reaction for 5-10 minutes; then adding rest silica precursor at constant temperature; stirring for reaction for a couple of hours; and centrifuging, washing, and drying in vacuum to obtain hollow silica particles. In the system, the weight percentage: water and ammonia-water (25 percent) is 15-150: 1; and the weight percentage of water and silica precursor is 10-30: 1. The silica precursor which is firstly added accounts for 2-20 percent of total amount of silica precursor; and the reaction temperature is 25-75 DEG C.
Description
(1) technical field
The invention belongs to the nano-functional material technical field, be specifically related to a kind of preparation method of hollow silica particle.
(2) technical background
The hollow-particle material is paid close attention to greatly because of its special structure, pattern and surface and interface character are subjected to people.Compare with the hollow organic filler, the hollow inorganic particle has very superior heat, light, electricity, mechanical property and acid, alkaline stability.Therefore, they are widely used in the controlled transportation and the delivery systme of medicine, dyestuff, makeup, susceptibility reagent (enzyme and protein) as microencapsulation material, also can be used as light-weight filler, high selection type catalyzer or support of the catalyst simultaneously.In addition, they also have extremely important value at aspects such as artificial cell, medicals diagnosis on disease.
The silicon-dioxide hollow microsphere promptly is wherein important and a class that extensively paid close attention to, and its preparation method is a lot, but mainly is the template of widely using, and can be divided into soft template and hard template two classes.The hard template rule must be through removing the last handling process of template kernel; usually adopt means such as calcination or dissolving; become complexity and deleterious, efficient of preparation process is reduced, increased the difficulty of large-scale production, thereby made its application prospect be subjected to certain restriction.Compare with it, be that the soft template rule of template becomes simply the step of removing template with drop, bubble or amphipathy macromolecule micella, thereby can remedy the deficiency of this respect, become simpler, more effective synthesizing mean of a class and technological approaches.
In soft template method, utilize the water-oily interfacial effect and the possible surface reaction thereof of emulsion system, be one of important method of preparation silicon-dioxide hollow microsphere.But, based on the chemical reaction of silicon-dioxide presoma and the characteristics of reaction process, product has stronger diffusibility at aqueous phase in the middle of it, makes it be difficult for being bound on water-oily interface, thereby is difficult to make up effectively hollow microsphere.Therefore, how the surface reaction of the diffusion of silicon-dioxide precursor, hydrolysis, polycondensation and product thereof effectively being controlled in the many-sides such as selective deposition of interface zone is the key that successfully prepares hollow-particle.Poulin etc. adopt the reversed-phase emulsion system, utilize water droplet to be template, water miscible emulsifying agent cetyl trimethylammonium bromide and a kind of oil-soluble emulsifying agent (DowCorning 3225C) act synergistically and have successfully prepared hollow silica particle (reference 1:PhilippePoulin etc., Advanced Materials, 2004,16,1094-1097).Nakashima is preparation polystyrene-poly vinyl pyridine-polyethylene oxide triblock copolymer (PS-PVP-PEO) earlier, constitute micella as template with it again, the silicon-dioxide precursor optionally is deposited in the PVP segment and is hydrolyzed and polycondensation, product is removed above-mentioned block copolymer micelle template by calcining after drying, obtain hollow silica particle (reference 2:Kenichi Nakashima etc., Journal of American Chemical Society, 2007,129,1534-1535).In the above-mentioned example, emulsifying agent and template micella play keying action to the formation of hollow silicon dioxide granule, but their existence can influence the application performance of hollow silica particle.Simultaneously, specific emulsifying agent is selected or the preparation of functional micella material also can increase production cost accordingly.Secondly, the organic solvent as external phase in water/fat liquor system also can produce serious pollution to environment.
(3) summary of the invention
The object of the present invention is to provide a kind of preparation method of hollow silica particle, do not use emulsifying agent, organic solvent and template thing in the process, design and regulation and control by the presoma feeding mode, certainly the consumption of the self stabilization of realization system and template, thereby the simplification preparation process reduces production costs and reduces environmental pollution.
The process of method proposed by the invention was divided into for two steps: at first, a part of silicon-dioxide precursor slowly is added drop-wise in the ammonia soln, forms the homogeneous phase solution of silicate oligopolymer.Then, add the remaining silica precursor in this system, forming with water is that external phase, precursor drop are that disperse phase, silicate oligopolymer are the oil-in-water-type suspension system of stablizer.After hydrolysis, polycondensation, promptly obtain shell thickness evenly and have a hollow silica particle of sufficient intensity.
Design philosophy of the present invention and technological core are: from the characteristics of polymerization mechanism and polymerization process, appropriate design by feeding mode, form the oil-aqueous dispersion of self stabilization, and by effective regulation and control to diffusion and interfacial polymerization, with the drop is the shell that template makes up hollow-particle, and then obtains hollow silica particle.
Characteristics of the present invention are: (1) need not to add extra emulsifying agent, reduces production costs, and reduces the influence to the material application performance; (2) drop of silicon-dioxide precursor is the template that makes up hollow-particle, provides reactant for making up shell again, has simplified last handling process; (3) by regulating the feeding mode and the proportioning of silicon-dioxide precursor, control the thickness of silica shell effectively.
The synthetic method of hollow silica particle proposed by the invention and the concrete steps that adopted thereof are as follows:
1. after ammonia soln being heated to 25～75 ℃, earlier a part of silicon-dioxide presoma is added drop-wise in the ammonia soln lentamente, dripped off in 30-50 minute, reacted 5-10 minute, obtain transparent homogeneous phase solution.
2. add the silicon-dioxide presoma of remainder, keep temperature-resistant, stir reaction down 5-7 hour.
3. through centrifugal, washing, vacuum-drying obtains hollow silica particle.
Among the present invention, select tetraethoxy or methyl silicate as the silicon-dioxide presoma.
In the system of the present invention, the part by weight scope between each component is: water: ammoniacal liquor (25%)=15～150: 1; Water: silicon-dioxide precursor=10～30: 1; The first part's silicon-dioxide presoma that drips accounts for 2～20% of its total amount; Temperature of reaction is 25～75 ℃.
(4) embodiment
Among the following embodiment,, be weight part as not specified.
Embodiment 1:
With 5 parts of concentration is that ammoniacal liquor and 90 parts of distilled water of 25% join in the flask, the above-mentioned solution to 25 of heating in water bath ℃.Stir down, in flask, drip first 0.06 part of tetraethoxy lentamente, add in 30 minutes, continue reaction 5 minutes, then, remaining 2.94 parts of tetraethoxys are joined in the above-mentioned system, keep temperature-resistant, stir reaction down 7 hours.Product distilled water centrifuge washing, 60 ℃ of following vacuum-dryings obtain hollow silica particle.Be viewed as hollow-particle under the transmission electron microscope, particle diameter 200～800nm, shell thickness is about 18nm.
Embodiment 2:
With 5 parts of concentration is that ammoniacal liquor and 90 parts of distilled water of 25% join in the flask, the above-mentioned solution to 50 of heating in water bath ℃.Stir down, in flask, drip first 0.1 part of tetraethoxy lentamente, add in 50 minutes, continue reaction 10 minutes, then, remaining 2.9 parts of tetraethoxys are joined in the above-mentioned system, keep temperature-resistant, stir reaction down 5 hours.Product distilled water centrifuge washing, 60 ℃ of following vacuum-dryings obtain hollow silica particle.Be viewed as hollow-particle under the transmission electron microscope, particle diameter 200～800nm, shell thickness is about 33nm.
Embodiment 3:
With 5 parts of concentration is that ammoniacal liquor and 90 parts of distilled water of 25% join in the flask, the above-mentioned solution to 75 of heating in water bath ℃.Stir down, in flask, drip first 0.6 part of tetraethoxy lentamente, add in 30 minutes, continue reaction 5 minutes, then, remaining 2.4 parts of tetraethoxys are joined in the above-mentioned system, keep temperature-resistant, stir reaction down 5 hours.Product distilled water centrifuge washing, 60 ℃ of following vacuum-dryings obtain hollow silica particle.Be viewed as hollow-particle under the transmission electron microscope, particle diameter 200～800nm, shell thickness is about 50nm.
Embodiment 4:
With 0.5 part of concentration is that ammoniacal liquor and 90 parts of distilled water of 25% join in the flask, the above-mentioned solution to 50 of heating in water bath ℃.Stir down, in flask, drip first 0.6 part of methyl silicate lentamente, add in 30 minutes, continue reaction 10 minutes, then, remaining 2.4 parts of methyl silicates are joined in the above-mentioned system, keep temperature-resistant, stir reaction down 7 hours.Product distilled water centrifuge washing, 60 ℃ of following vacuum-dryings obtain hollow silica particle.Be viewed as hollow-particle under the transmission electron microscope, particle diameter 200～800nm, shell thickness is about 28nm.
Embodiment 5:
With 5 parts of concentration is that ammoniacal liquor and 90 parts of distilled water of 25% join in the flask, the above-mentioned solution to 75 of heating in water bath ℃.Stir down, in flask, drip first 0.06 part of tetraethoxy lentamente, add in 30 minutes, continue reaction 5 minutes, then, remaining 2.94 parts of tetraethoxys are joined in the above-mentioned system, keep temperature-resistant, stir reaction down 5 hours.Product distilled water centrifuge washing, 60 ℃ of following vacuum-dryings obtain hollow silica particle.Be viewed as hollow-particle under the transmission electron microscope, particle diameter 200～800nm, shell thickness is about 25nm.
Claims (1)
1. the two-step preparation method of hollow silica particle, it is characterized in that: ammonia soln is heated to 25～75 ℃, earlier a part of silicon-dioxide presoma slowly is added drop-wise in the ammonia soln, dripped off in 30-50 minute, react after 5-10 minute, add the silicon-dioxide presoma of remainder, keep temperature-resistant, stir down, reacted 5-7 hour, through centrifuge washing, vacuum-drying obtains hollow silica particle; In the system, the part by weight scope between each component is: water: ammoniacal liquor (25%)=15～150: 1; Water: silicon-dioxide precursor=10～30: 1; The a part of silicon-dioxide presoma that drips accounts for 2～20% of its total amount earlier; Temperature of reaction is 25～75 ℃; The silicon-dioxide presoma is tetraethoxy or methyl silicate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101752426A CN101823719B (en) | 2010-05-18 | 2010-05-18 | Two-step preparation method of hollow silica particles |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101752426A CN101823719B (en) | 2010-05-18 | 2010-05-18 | Two-step preparation method of hollow silica particles |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0891821A (en) * | 1994-02-25 | 1996-04-09 | Agency Of Ind Science & Technol | Production of spherical hollow porous silica particles |
| JP2006256921A (en) * | 2005-03-18 | 2006-09-28 | Nagoya Institute Of Technology | Manufacturing method of silica hollow particle |
| CN101045537A (en) * | 2007-05-08 | 2007-10-03 | 浙江大学 | Preparation method of size controlled hollow silicon oxide microsphere |
| CN101549871A (en) * | 2009-05-05 | 2009-10-07 | 南京大学 | Preparation method of nanometer silica hollow microspheres |
-
2010
- 2010-05-18 CN CN2010101752426A patent/CN101823719B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0891821A (en) * | 1994-02-25 | 1996-04-09 | Agency Of Ind Science & Technol | Production of spherical hollow porous silica particles |
| JP2006256921A (en) * | 2005-03-18 | 2006-09-28 | Nagoya Institute Of Technology | Manufacturing method of silica hollow particle |
| CN101045537A (en) * | 2007-05-08 | 2007-10-03 | 浙江大学 | Preparation method of size controlled hollow silicon oxide microsphere |
| CN101549871A (en) * | 2009-05-05 | 2009-10-07 | 南京大学 | Preparation method of nanometer silica hollow microspheres |
Non-Patent Citations (1)
| Title |
|---|
| 《有机硅材料》 20090831 顾文娟等 中空二氧化硅微球的制备方法研究进展 第257-264页 1 第23卷, 第4期 2 * |
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Granted publication date: 20110831 Termination date: 20120518 |