CN104785180A - Method for preparing hollow microsphere taking silicon dioxide as inner shell layer and titanium dioxide as outer shell layer - Google Patents
Method for preparing hollow microsphere taking silicon dioxide as inner shell layer and titanium dioxide as outer shell layer Download PDFInfo
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Abstract
The invention relates to a method for preparing hollow microspheres taking silicon dioxide as an inner shell layer and titanium dioxide as an outer shell layer. At present, the study on hollow structure materials is mostly focused on a hollow structure of a single shell layer, and the study that two materials are adopted as a shell layer together is barely reported. The method comprises the following steps: diluting polystyrene microsphere emulsion with distilled water and isopropanol, dripping tetraethoxysilane, stirring, centrifuging, washing, and drying so as to obtain polystyrene/silicon dioxide core-shell particles; performing ultrasonic dispersion on the polystyrene/silicon dioxide core-shell particles in absolute ethyl alcohol, and at the same time dripping an absolute ethyl alcohol solution of tetrabutyl titanate; enabling the components to react, performing centrifugal washing to obtain polystyrene/silicon dioxide/titanium dioxide multi-core-shell particles, and calcining so as to obtain the hollow microspheres taking silicon dioxide as the inner shell layer and titanium dioxide as the outer shell layer. As a template method and a sol-gel method are combined to prepare the hollow microspheres taking silicon dioxide as the inner shell layer and titanium dioxide as the outer shell layer, the method is simple to operate and high in repeatability.
Description
Technical field
the present invention relates to a kind of preparation method of hollow microsphere, being specifically related to a kind of take silica as the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell.
Background technology
A kind of novel partculate material that hollow structure material is twentieth century five, the sixties grow up.Because it has special hollow-core construction, therefore have a wide range of applications in fields such as medicine controlled releasing, light filler, catalysis.Silica has the advantages such as high stability, high-melting-point, specific area be large, is widely used in the fields such as building, printing.And titanium dioxide is owing to having unique anti-uv-ray, bactericidal properties, photodegradation, use also widely.Just because of the premium properties of the inorganic particulate such as silica, titanium dioxide self, so they also become the focus that hollow structure investigation of materials field is paid close attention to.Along with the development of hollow technology, about the report of hollow silica and hollow titanium dioxide is also increasing.Li etc. take polystyrene microsphere as template, polyvinylpyrrolidone p-poly-phenyl ethene microballoon is adopted to carry out modification, in alcohol/water mixed solvent, take ethyl orthosilicate as silicon source, teos hydrolysis is made to generate coated with silica at polystyrene surface, form polystyrene/silica dioxide nucleocapsid structure, at 450 DEG C, calcine 1h remove template, obtain the silicon dioxide hollow microsphere of compound with regular structure.Yang etc. take zinc oxide as template, by ultrasonic and booster action that is surface active agent tween-80, ethyl orthosilicate in-situ hydrolysis is made to generate coated with silica at zinc oxide surface, form zinc oxide/silicon dixoide nucleocapsid structure, then dissolved oxygen zinc in hydrochloric acid solution, to prepare hollow silica microsphere.Zhang etc. utilize polystyrene for template, butyl titanate is presoma, ammoniacal liquor is catalyst, prepare polystyrene/titanium dioxide core shell structure, then at 600 DEG C, 3h is calcined, final acquisition hollow titanium dioxide microballoon, and the methyl orange finding degraded 60%, hollow titanium dioxide time used 20min fewer than ordinary titanium dioxide.Chen etc. take polystyrene as template, and ammoniacal liquor is catalyst, and the hollow titanium dioxide microballoon by one-step synthesis method, in this method, the formation of shell titanium dioxide and the dissolving of template polystyrene occur in same medium, and be almost carry out simultaneously.As from the foregoing, the research at present about hollow structure material concentrates on the hollow structure studying single shell mostly, and namely shell is a kind of material, or silica, or titanium dioxide etc., about using also more rare for the research of bi-material jointly as shell.
Summary of the invention
The object of this invention is to provide a kind of take silica as the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell, and obtained hollow microsphere has the performance of silica and TiO 2 particles concurrently, has the correlation properties of hollow structure simultaneously.
The technical solution adopted in the present invention is:
Take silica as the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell, it is characterized in that:
Include following steps:
(1) by 2 ~ 3mL, solid content polystyrene microsphere emulsion 10 ~ 12mL distilled water and 40 ~ 42mL isopropanol between 5 ~ 10%, regulate pH to 9.8 ~ 10.3, drip 0.2 ~ 0.3g ethyl orthosilicate, in 40 ~ 50 DEG C, 300 ~ 400r/min mechanical agitation, 5 ~ 8h, product is centrifugal and by washed with isopropyl alcohol 3 ~ 5 times, in 50 ~ 70 DEG C of baking ovens, dry 4 ~ 6h, obtains polystyrene/silica dioxide core-shell particles;
(2) 0.03 ~ 0.05g polystyrene/silica dioxide core-shell particles is taken, ultrasonic disperse is in 15 ~ 17mL absolute ethyl alcohol, drip the ethanol solution of butyl titanate, in the consumption of absolute ethyl alcohol and the ethanol solution of butyl titanate, the consumption sum of absolute ethyl alcohol is 24mL thereupon; The ethanol solution of butyl titanate is scattered in by 0.12 ~ 0.18g butyl titanate and obtains in 7 ~ 9mL absolute ethyl alcohol, and time for adding is 5 ~ 10min; After dropwising, at 300 ~ 400r/min, at 75 ~ 85 DEG C, react 2 ~ 4h, product is centrifugal, and with absolute ethanol washing 3 ~ 5 times, obtain polystyrene/silica dioxide/titanium dioxide multinuclear shell particles;
(3) polystyrene/silica dioxide/titanium dioxide multinuclear shell particles obtained is calcined 3 ~ 5h in 500 ~ 600 DEG C of Muffle furnaces, obtain taking silica as hypostracum titanium dioxide the hollow microsphere being outer shell.
In step (1), the particle diameter of polystyrene microsphere is between 150 ~ 500nm.
In step (1), regulate pH with ammoniacal liquor.
The present invention has the following advantages:
Template combines with sol-gal process and prepares with silica the hollow microsphere be hypostracum titanium dioxide being outer shell by the present invention, there is simple to operate, that repeatability is high feature, and gained hollow microsphere not only has the performance characteristics of silica, also have the performance characteristics of titanium dioxide concurrently, its internal cavity structures is easy to realize controllable adjustment simultaneously, all has broad application prospects in various fields.
Accompanying drawing explanation
Fig. 1 is take silica as the stereoscan photograph of the hollow microsphere that hypostracum titanium dioxide is outer shell.
Fig. 2 is take silica as the XRD spectra of the hollow microsphere that hypostracum titanium dioxide is outer shell.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be described in detail.
That the present invention relates to take silica as the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell, includes following steps:
(1) by 2 ~ 3mL, solid content polystyrene microsphere emulsion 10 ~ 12mL distilled water and 40 ~ 42mL isopropanol between 5 ~ 10%, regulate pH to 9.8 ~ 10.3, drip 0.2 ~ 0.3g ethyl orthosilicate, in 40 ~ 50 DEG C, 300 ~ 400r/min mechanical agitation, 5 ~ 8h, product is centrifugal and by washed with isopropyl alcohol 3 ~ 5 times, in 50 ~ 70 DEG C of baking ovens, dry 4 ~ 6h, obtains polystyrene/silica dioxide core-shell particles;
(2) 0.03 ~ 0.05g polystyrene/silica dioxide core-shell particles is taken, ultrasonic disperse is in 15 ~ 17mL absolute ethyl alcohol, drip the ethanol solution of butyl titanate, in the consumption of absolute ethyl alcohol and the ethanol solution of butyl titanate, the consumption sum of absolute ethyl alcohol is 24mL thereupon; The ethanol solution of butyl titanate is scattered in by 0.12 ~ 0.18g butyl titanate and obtains in 7 ~ 9mL absolute ethyl alcohol, and time for adding is 5 ~ 10min; After dropwising, at 300 ~ 400r/min, at 75 ~ 85 DEG C, react 2 ~ 4h, product is centrifugal, and with absolute ethanol washing 3 ~ 5 times, obtain polystyrene/silica dioxide/titanium dioxide multinuclear shell particles;
(3) polystyrene/silica dioxide/titanium dioxide multinuclear shell particles obtained is calcined 3 ~ 5h in 500 ~ 600 DEG C of Muffle furnaces, obtain taking silica as hypostracum titanium dioxide the hollow microsphere being outer shell.
In step (1), the particle diameter of polystyrene microsphere is between 150 ~ 500nm;
In step (1), regulate pH with ammoniacal liquor.
Embodiment 1:
(1) by 2mL, solid content polystyrene microsphere emulsion 10mL distilled water and 42mL isopropanol between 10%, regulate pH to 9.8, drip 0.3g ethyl orthosilicate, in 40 DEG C, 400r/min mechanical agitation 5h, product is centrifugal and by washed with isopropyl alcohol 5 times, dry 6h in 50 DEG C of baking ovens, obtains polystyrene/silica dioxide core-shell particles;
(2) 0.03g polystyrene/silica dioxide core-shell particles is taken, ultrasonic disperse is in 17mL absolute ethyl alcohol, drip the ethanol solution of butyl titanate, in the consumption of absolute ethyl alcohol and the ethanol solution of butyl titanate, the consumption sum of absolute ethyl alcohol is 24mL thereupon; The ethanol solution of butyl titanate is scattered in by 0.12g butyl titanate and obtains in 9mL absolute ethyl alcohol, and time for adding is 5min; After dropwising, at 400r/min, at 75 DEG C, react 4h, product is centrifugal, and with absolute ethanol washing 3 times, obtain polystyrene/silica dioxide/titanium dioxide multinuclear shell particles;
(3) polystyrene/silica dioxide of acquisition/titanium dioxide multinuclear shell particles is calcined 3h in 600 DEG C of Muffle furnaces, obtain taking silica as hypostracum titanium dioxide the hollow microsphere being outer shell.
In step (1), the particle diameter of polystyrene microsphere is at 500nm;
In step (1), regulate pH with ammoniacal liquor.
Embodiment 2:
(1) by 2mL, solid content polystyrene microsphere emulsion 11mL distilled water and 41mL isopropanol between 7%, regulate pH to 10, drip 0.2g ethyl orthosilicate, in 45 DEG C, 350r/min mechanical agitation 6h, product is centrifugal and by washed with isopropyl alcohol 4 times, dry 5h in 60 DEG C of baking ovens, obtains polystyrene/silica dioxide core-shell particles;
(2) 0.04g polystyrene/silica dioxide core-shell particles is taken, ultrasonic disperse is in 16mL absolute ethyl alcohol, drip the ethanol solution of butyl titanate, in the consumption of absolute ethyl alcohol and the ethanol solution of butyl titanate, the consumption sum of absolute ethyl alcohol is 24mL thereupon; The ethanol solution of butyl titanate is scattered in by 0.15g butyl titanate and obtains in 8mL absolute ethyl alcohol, and time for adding is 7min; After dropwising, at 350r/min, at 80 DEG C, react 3h, product is centrifugal, and with absolute ethanol washing 4 times, obtain polystyrene/silica dioxide/titanium dioxide multinuclear shell particles;
(3) polystyrene/silica dioxide of acquisition/titanium dioxide multinuclear shell particles is calcined 4h in 550 DEG C of Muffle furnaces, obtain taking silica as hypostracum titanium dioxide the hollow microsphere being outer shell.
In step (1), the particle diameter of polystyrene microsphere is at 320nm;
In step (1), regulate pH with ammoniacal liquor.
Embodiment 3:
(1) by 3mL, solid content polystyrene microsphere emulsion 12mL distilled water and 40mL isopropanol between 5%, regulate pH to 10.3, drip 0.2g ethyl orthosilicate, in 50 DEG C, 300r/min mechanical agitation 8h, product is centrifugal and by washed with isopropyl alcohol 3 times, dry 4h in 70 DEG C of baking ovens, obtains polystyrene/silica dioxide core-shell particles;
(2) 0.05g polystyrene/silica dioxide core-shell particles is taken, ultrasonic disperse is in 15mL absolute ethyl alcohol, drip the ethanol solution of butyl titanate, in the consumption of absolute ethyl alcohol and the ethanol solution of butyl titanate, the consumption sum of absolute ethyl alcohol is 24mL thereupon; The ethanol solution of butyl titanate is scattered in by 0.18g butyl titanate and obtains in 7mL absolute ethyl alcohol, and time for adding is 10min; After dropwising, at 300r/min, at 85 DEG C, react 2h, product is centrifugal, and with absolute ethanol washing 5 times, obtain polystyrene/silica dioxide/titanium dioxide multinuclear shell particles;
(3) polystyrene/silica dioxide of acquisition/titanium dioxide multinuclear shell particles is calcined 5h in 500 DEG C of Muffle furnaces, obtain taking silica as hypostracum titanium dioxide the hollow microsphere being outer shell.
In step (1), the particle diameter of polystyrene microsphere is at 150nm;
In step (1), regulate pH with ammoniacal liquor.
Adopt the present invention to prepare with silica be the stereoscan photograph of the hollow microsphere that hypostracum titanium dioxide is outer shell as shown in Figure 1, regular, the uniform particle diameter of this micro-sphere structure and there is obvious hollow structure as seen from the figure.Fig. 2 is the XRD spectra of this hollow microsphere, and the main component of this microballoon is titanium dioxide and silica as we know from the figure, and titanium dioxide mainly Detitanium-ore-type, there is a small amount of rutile-type, silica is unformed.
Content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading description of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (3)
1. be the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell with silica, it is characterized in that:
Include following steps:
(1) by 2 ~ 3mL, solid content polystyrene microsphere emulsion 10 ~ 12mL distilled water and 40 ~ 42mL isopropanol between 5 ~ 10%, regulate pH to 9.8 ~ 10.3, drip 0.2 ~ 0.3g ethyl orthosilicate, in 40 ~ 50 DEG C, 300 ~ 400r/min mechanical agitation, 5 ~ 8h, product is centrifugal and by washed with isopropyl alcohol 3 ~ 5 times, in 50 ~ 70 DEG C of baking ovens, dry 4 ~ 6h, obtains polystyrene/silica dioxide core-shell particles;
(2) 0.03 ~ 0.05g polystyrene/silica dioxide core-shell particles is taken, ultrasonic disperse is in 15 ~ 17mL absolute ethyl alcohol, drip the ethanol solution of butyl titanate, in the consumption of absolute ethyl alcohol and the ethanol solution of butyl titanate, the consumption sum of absolute ethyl alcohol is 24mL thereupon; The ethanol solution of butyl titanate is scattered in by 0.12 ~ 0.18g butyl titanate and obtains in 7 ~ 9mL absolute ethyl alcohol, and time for adding is 5 ~ 10min; After dropwising, at 300 ~ 400r/min, at 75 ~ 85 DEG C, react 2 ~ 4h, product is centrifugal, and with absolute ethanol washing 3 ~ 5 times, obtain polystyrene/silica dioxide/titanium dioxide multinuclear shell particles;
(3) polystyrene/silica dioxide/titanium dioxide multinuclear shell particles obtained is calcined 3 ~ 5h in 500 ~ 600 DEG C of Muffle furnaces, obtain taking silica as hypostracum titanium dioxide the hollow microsphere being outer shell.
2. according to claim 1 take silica as the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell, it is characterized in that:
In step (1), the particle diameter of polystyrene microsphere is between 150 ~ 500nm.
3. according to claim 2 take silica as the preparation method of the hollow microsphere that hypostracum titanium dioxide is outer shell, it is characterized in that:
In step (1), regulate pH with ammoniacal liquor.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080469A (en) * | 2015-09-06 | 2015-11-25 | 江苏大学 | Preparation method and application of dual-layer hollow TiO2/SiO2 spheres |
| CN106866992A (en) * | 2017-03-31 | 2017-06-20 | 陕西科技大学 | A kind of preparation method of the titania modified polyacrylate dispersion of hollow spheres |
| CN106882811A (en) * | 2017-03-31 | 2017-06-23 | 陕西科技大学 | A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof |
| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108686592A (en) * | 2018-05-21 | 2018-10-23 | 陕西科技大学 | A kind of preparation method of sea urchin shape bivalve layer hollow microsphere |
| CN109761239A (en) * | 2019-01-18 | 2019-05-17 | 齐鲁工业大学 | It is a kind of sensing, photoelectricity or lithium ion battery composite material and preparation method |
| CN111320905A (en) * | 2020-03-12 | 2020-06-23 | 陕西科技大学 | Preparation method of polyacrylate/flower-shaped hollow silicon dioxide @ titanium dioxide microsphere composite building coating |
| CN114213961A (en) * | 2021-12-21 | 2022-03-22 | 合肥乐凯科技产业有限公司 | Ultraviolet-proof hardening film |
| CN115872718A (en) * | 2022-12-26 | 2023-03-31 | 安徽朗凯奇科技股份有限公司 | Preparation method of waterproof heat-insulation building roof material |
Citations (1)
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| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
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- 2015-04-17 CN CN201510182827.3A patent/CN104785180A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101274246A (en) * | 2007-12-26 | 2008-10-01 | 中国科学院上海硅酸盐研究所 | Sol-gel method for preparing earth silicon/titanic oxide hollow microballoon |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080469A (en) * | 2015-09-06 | 2015-11-25 | 江苏大学 | Preparation method and application of dual-layer hollow TiO2/SiO2 spheres |
| CN106866992A (en) * | 2017-03-31 | 2017-06-20 | 陕西科技大学 | A kind of preparation method of the titania modified polyacrylate dispersion of hollow spheres |
| CN106882811A (en) * | 2017-03-31 | 2017-06-23 | 陕西科技大学 | A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof |
| CN106882811B (en) * | 2017-03-31 | 2019-04-12 | 陕西科技大学 | A kind of sea urchin shape bivalve layer hollow microsphere and preparation method thereof |
| CN106866992B (en) * | 2017-03-31 | 2019-05-17 | 陕西科技大学 | A kind of preparation method of the titania modified polyacrylate dispersion of hollow spheres |
| CN108134104A (en) * | 2017-12-26 | 2018-06-08 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108134104B (en) * | 2017-12-26 | 2020-05-12 | 成都新柯力化工科技有限公司 | Composite catalyst carrier for fuel cell and preparation method and application thereof |
| CN108686592B (en) * | 2018-05-21 | 2020-11-13 | 陕西科技大学 | Preparation method of sea urchin-shaped double-shell hollow microspheres |
| CN108686592A (en) * | 2018-05-21 | 2018-10-23 | 陕西科技大学 | A kind of preparation method of sea urchin shape bivalve layer hollow microsphere |
| CN109761239A (en) * | 2019-01-18 | 2019-05-17 | 齐鲁工业大学 | It is a kind of sensing, photoelectricity or lithium ion battery composite material and preparation method |
| CN111320905A (en) * | 2020-03-12 | 2020-06-23 | 陕西科技大学 | Preparation method of polyacrylate/flower-shaped hollow silicon dioxide @ titanium dioxide microsphere composite building coating |
| CN114213961A (en) * | 2021-12-21 | 2022-03-22 | 合肥乐凯科技产业有限公司 | Ultraviolet-proof hardening film |
| CN114213961B (en) * | 2021-12-21 | 2023-12-08 | 合肥乐凯科技产业有限公司 | Ultraviolet-proof hardening film |
| CN115872718A (en) * | 2022-12-26 | 2023-03-31 | 安徽朗凯奇科技股份有限公司 | Preparation method of waterproof heat-insulation building roof material |
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