CN103962074B - A kind of hollow sub-micron, its preparation method and application - Google Patents
A kind of hollow sub-micron, its preparation method and application Download PDFInfo
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- CN103962074B CN103962074B CN201410072478.5A CN201410072478A CN103962074B CN 103962074 B CN103962074 B CN 103962074B CN 201410072478 A CN201410072478 A CN 201410072478A CN 103962074 B CN103962074 B CN 103962074B
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Abstract
The invention discloses a kind of hollow sub-micron and its preparation method and application.The shell of described hollow sub-micron is organo-mineral complexing structure; thermodynamic stability is good; structural stability is high; simultaneously; it has inner hydrophobic and external hydrophilic characteristics; can be applicable to the fields such as water-oil separating, dewatering medicament conveying, catalyst protection, nano-reactor, is a kind of material with broad prospect of application.And preparation method's technique that the present invention adopts is simple, reproducible, template removing mild condition, employing water is decentralized medium, low in the pollution of the environment.
Description
Technical field
The present invention relates to a kind of hollow sub-micron and preparation method thereof and application, be specifically related to a kind of organic inorganic hybridization hollow sub-micron and preparation method thereof and application.
Background technology
A kind of novel partculate material that hollow microsphere is twentieth century five, the sixties grow up, diameter is in nanometer to hundreds of micrometer range, and inner hollow is a kind of material with special construction.Compared with the medicine ball of same size or nonspherical particle, hollow microsphere has the advantages such as density is low, specific area is large.In addition, owing to having large hollow volume, its object load capacity increases greatly, and large scale object can be held, produce microcosmic " parcel " effect, tiny balloon is had broad application prospects, as light filler, parting material, Co ntrolled release capsule, artificial cell, microelectronic element, high-selectivity catalyst and carrier and heat-insulating and noise-insulating material etc. as a kind of new function material.
Silicon dioxide hollow microsphere, owing to itself having nontoxic, the special nature such as acid-alkali-corrosive-resisting, good physical stability, excellent biocompatibility, makes it have wide application prospect.Such as make fire-resistant, light filler and dielectric materials etc. and be applied to high-end encapsulation field; Or at its cavity internal burden functional compounds, the targeted drug with slow-release function both can be prepared, certain value can be had in diagnosis of disease, artificial cell etc. again, be applied to medical treatment, medicine, spices and the industry such as false proof; And utilize its " parcel " effect make efficient stable catalyst or be applied to biological medium and chemical microreactor etc.
Hollow microsphere generally adopts template synthesis, and its principle is in template surface deposition or forms nucleocapsid structure by chemical reaction, removes core template, obtain hollow microsphere further by high-temperature calcination or chemical method.Template can be polymer particle, inorganic salts particle, emulsion droplets, micella, bubble etc.Employing inorganic salts particle or polymeric colloid particle are that the process of template is called hard template method, and the removing of its template adopts high-temperature calcination or chemical etching more.Hollow microsphere uniform particle sizes prepared by hard template method, hollow volume controllability is good, but can impact shell structurre or product property in removing template procedure, and preparation method mostly is the complex process of multistep.Use emulsion droplets, micella etc. are that the process of template is called soft template method, and the removing of its template can adopt gentle solvent clean method, destroys little to shell, and process is simple, does not need strict controlled condition.But the hollow microsphere domain size distribution that soft template method obtains is wide, system component is complicated, and controllability is relatively poor.In addition, in removing template or preparation emulsion process, need a large amount of organic solvent, environmental pollution is large.In view of above reason, develop that a kind of technique is simple, the preparation method of the hollow microsphere of mild condition is very necessary.
Summary of the invention
The object of the invention is to the shortcoming overcoming above-mentioned prior art, provide that a kind of technique is simple, the preparation method of the hollow sub-micron of mild condition, and the hollow sub-micron providing described method to prepare and application thereof.Above-mentioned preparation method's simple process, template remove mild condition, environmental pollution is little, product is reproducible, system is simple and controllability is good, with the obvious advantage compared with conventional method.
The present invention adopts following technical scheme:
A kind of hollow sub-micron, it has hydrophobic cavity and hydrophilic surface, and the shell of described hollow sub-micron is organo-mineral complexing structure, and primarily of silicon-containing polymer composition, silica colloidal particles is embedded in shell, and has partial denudation outside.
According to the present invention, in described shell, also has nano pore.
According to the present invention, the particle diameter of described hollow sub-micron is about 100-300 nanometer.The even particle size distribution of described hollow sub-micron.
According to the present invention, described organo-mineral complexing structure is that the raw material comprising silica colloidal particles is obtained by emulsion polymerisation.
According to the present invention, described emulsion polymerisation adopts a kind of thermodynamically stable Pickering emulsion system, and template is a kind of volatile solvent.
According to the present invention, the emulsion in described emulsion polymerisation comprises the volatile solvent of silane coupler, silica colloidal particles and one.
According to the present invention, described volatile solvent is selected from isoamyl acetate etc.
According to the present invention, described silane coupler is methoxy silane or the Ethoxysilane with double bond structure.Preferably there is the methoxy silane of double bond structure, more preferably 3-methacryloyl oxygen propyl trimethoxy silicane.
According to the present invention, the mass ratio of described volatile solvent and silane coupler is 1:1 ~ 6:1.Preferred 2:1 ~ 4:1.
According to the present invention, the mass ratio of described silica colloidal particles and silane coupler is 1:2 ~ 1:14.Be preferably 1:2.5 ~ 1:5.
According to the present invention, the particle size range of described silica colloidal particles is 10 ~ 100 nanometers.Preferably, the silica colloidal particles of 10 ~ 50 nanometers is adopted.
According to the present invention, above-mentioned hollow sub-micron has hydrophobic cavity and hydrophilic surface, and shell is organo-mineral complexing structure, thus has good thermodynamic stability and structural stability, after 700 DEG C of calcinings or organic solvent are soaked, still can keep its hollow-core construction.
The invention also discloses following technical scheme:
A kind of preparation method of hollow sub-micron of the present invention, it adopts a kind of thermodynamically stable Pickering emulsion system, with the volatile solvent of one for template, adopt the method for emulsion polymerisation, obtained a kind of hollow sub-micron with inner hydrophobic external hydrophilic structure.
According to the present invention, the shell of described hollow sub-micron is organo-mineral complexing structure, and primarily of silicon-containing polymer composition, silica colloidal particles is embedded in shell, and has partial denudation outside.
According to the present invention, the emulsion in described emulsion polymerisation process comprises the volatile solvent of silane coupler, silica colloidal particles and one.
According to the present invention, described volatile solvent is selected from isoamyl acetate etc.
According to the present invention, described silane coupler is methoxy silane or the Ethoxysilane with double bond structure.Preferably there is the methoxy silane of double bond structure, more preferably 3-methacryloyl oxygen propyl trimethoxy silicane.
According to the present invention, the mass ratio of described volatile solvent and silane coupler is 1:1 ~ 6:1.Preferred 2:1 ~ 4:1.
According to the present invention, the mass ratio of described silica colloidal particles and silane coupler is 1:2 ~ 1:14.Be preferably 1:2.5 ~ 1:5.
According to the present invention, the particle size range of described silica colloidal particles is 10 ~ 100 nanometers.Preferably, the silica colloidal particles of 10 ~ 50 nanometers is adopted.
According to the present invention, in described preparation method, silane coupler, silica colloidal particles, volatile solvent stir and form emulsion in water, add initator (preferred persulfate) initiated polymerization after emulsion is formed, and form hollow sub-micron.
According to the present invention, described preparation method specifically comprises the steps:
(1) silane coupler, silica colloidal particles, isoamyl acetate are added to the water, stir, form emulsion;
(2) emulsion is heated to above 60 DEG C, adding persulfate is initator, initiated polymerization;
(3) drying obtains powdery product.
According to the present invention, temperature when stirring in above-mentioned steps (1) is 10 ~ 30 DEG C.
According to the present invention, the time of stirring in above-mentioned steps (1) is 10 ~ 30 hours, preferably 16 ~ 24 hours.
According to the present invention, the polymerization temperature in above-mentioned steps (2), higher than 65 DEG C, is preferably 65 ~ 80 DEG C.
According to the present invention, the polymerization reaction time in above-mentioned steps (2) is 8 ~ 24 hours, is preferably 14 ~ 20 hours.
The invention also discloses following technical scheme:
The application of above-mentioned hollow sub-micron, can be applicable to the aspects such as hydrophobic guest parcel, water-oil separating, dewatering medicament conveying, catalyst protection, microreactor.
According to the present invention, described hollow sub-micron has the special construction of inner hydrophobic external hydrophilic; Its shell is inlaid with silica colloidal particles, and has partial denudation in surface, can be used for further modification and finishing; In addition, leave the nano pore that solvent volatilization is formed in described shell, make hollow sub-micron have comparatively bigger serface.Said structure feature, makes described hollow sub-micron be particularly suitable for the fields such as hydrophobic guest parcel, water-oil separating, dewatering medicament conveying, catalyst protection, microreactor.
Hollow sub-micron prepared by the present invention and preparation method thereof has the following advantages:
1. the hollow sub-micron that prepared by the present invention has the special construction of inner hydrophobic external hydrophilic, can be applicable to the aspects such as hydrophobic guest parcel, water-oil separating, dewatering medicament conveying, catalyst protection, microreactor.In addition, hollow sub-micron shell is inlaid with silica colloidal particles, and has partial denudation in surface, can be used for further modification and finishing.And the particle diameter of described hollow sub-micron is about 100-300 nanometer and even particle size distribution.
2. preparation method of the present invention, employ a kind of thermodynamically stable emulsion system, product is reproducible, and system composition is simple, and process control is good, is convenient to large-scale production.
3. the present invention uses a kind of volatile solvent (as isoamyl acetate) to be template, and in dry run, realize the removing of template, mild condition, process is simple.Without the need to the process of follow-up removing template, can not damage shell.In addition, template, in volatilization process, leaves nano pore at shell, makes hollow sub-micron have comparatively bigger serface.
4. in method of the present invention, adopt water to be decentralized medium, low in the pollution of the environment.
Accompanying drawing explanation
Fig. 1 is the electron microscopic picture of the hollow sub-micron of gained in embodiment 1.In figure, a is transmission electron microscope picture, and b is scanning electron microscopic picture
Fig. 2 is the electron microscopic picture of the hollow sub-micron of gained in embodiment 2.In figure, a is transmission electron microscope picture, and b is scanning electron microscopic picture
Fig. 3 is the electron microscopic picture of the hollow sub-micron of gained in embodiment 3.In figure, a is transmission electron microscope picture, and b is scanning electron microscopic picture
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Detailed description of the invention
Protection scope of the present invention is not limited only to following examples.According to content disclosed by the invention, those skilled in the art will recognize that when the technical characteristic do not departed from given by technical solution of the present invention and scope, to the above embodiment make many changes and amendment all belong to protection scope of the present invention.
Embodiment 1
Raw material adopts 3-methacryloyl oxygen propyl trimethoxy silicane (TPM), particle diameter is 30 nanometers silica colloidal particles (LudoxTM40), isoamyl acetate (PEA), initator is potassium peroxydisulfate.By 0.5mLTPM, 0.65mL silica colloidal particles dispersion liquid, 1mLPEA adds in 40mL water, and 15 DEG C are stirred 16 hours, and logical nitrogen deoxygenation, after 30 minutes, is warmed up to 70 DEG C, adds 10mg potassium peroxydisulfate initiated polymerization, and polymerisation continues 12 hours.By the centrifugation of gained emulsion, after ethanol purge 3 times, be scattered in water, freeze drying obtains white powdery solids.
By above-mentioned powder dispersion in ethanol, make sample for use in transmitted electron microscope and scanning electron microscope example, observe particle morphology.As shown in Figure 1, described particle has the structure of obvious hollow, and has nano particle to be embedded in shell, and has partial denudation outside; The nano pore that solvent volatilization is formed also is left in described shell; The particle diameter of described hollow sub-micron is about 100-300 nanometer and even particle size distribution.
Embodiment 2
Raw material adopts 3-methacryloyl oxygen propyl trimethoxy silicane (TPM), particle diameter is 12 nanometers silica colloidal particles (LudoxHS40), isoamyl acetate (PEA), initator is potassium peroxydisulfate.By 1mLTPM, 0.28mL silica colloidal particles dispersion liquid, 2mLPEA adds in 40mL water, and 20 DEG C are stirred 24 hours, and logical nitrogen deoxygenation, after 30 minutes, is warmed up to 65 DEG C, adds 10mg potassium peroxydisulfate initiated polymerization, and polymerisation continues 12 hours.By the centrifugation of gained emulsion, after ethanol purge 3 times, be scattered in water, freeze drying obtains white powdery solids.
By above-mentioned powder dispersion in ethanol, make sample for use in transmitted electron microscope and scanning electron microscope example, observe particle morphology.As shown in Figure 2, described particle has the structure of obvious hollow, and has nano particle to be embedded in shell, and has partial denudation outside; The nano pore that solvent volatilization is formed also is left in described shell; The particle diameter of described hollow sub-micron is about 100-300 nanometer and even particle size distribution.
Embodiment 3
Raw material adopts 3-methacryloyl oxygen propyl trimethoxy silicane (TPM), particle diameter is 7 nanometers silica colloidal particles (LudoxHS40), isoamyl acetate (PEA), initator is potassium peroxydisulfate.By 1mLTPM, 0.225mL silica colloidal particles dispersion liquid, 2mLPEA adds in 40mL water, and 20 DEG C are stirred 24 hours, and logical nitrogen deoxygenation, after 30 minutes, is warmed up to 65 DEG C, adds 10mg potassium peroxydisulfate initiated polymerization, and polymerisation continues 12 hours.By the centrifugation of gained emulsion, after ethanol purge 3 times, be scattered in water, freeze drying obtains white powdery solids.
By above-mentioned powder dispersion in ethanol, make sample for use in transmitted electron microscope and scanning electron microscope example, observe particle morphology.As shown in Figure 3, described particle has the structure of obvious hollow, and has nano particle to be embedded in shell, and has partial denudation outside; The nano pore that solvent volatilization is formed also is left in described shell; The particle diameter of described hollow sub-micron is about 100-300 nanometer and even particle size distribution.
Embodiment 4
Raw material adopts 3-methacryloyl oxygen propyl trimethoxy silicane (TPM), particle diameter is 30 nanometers silica colloidal particles (LudoxTM40), isoamyl acetate (PEA), initator is potassium peroxydisulfate.By 0.5mLTPM, 0.65mL silica colloidal particles dispersion liquid, 2mLPEA adds in 40mL water, and 25 DEG C are stirred 24 hours, and logical nitrogen deoxygenation, after 30 minutes, is warmed up to 70 DEG C, adds 10mg potassium peroxydisulfate initiated polymerization, and polymerisation continues 18 hours.By the centrifugation of gained emulsion, after ethanol purge 3 times, be scattered in water, freeze drying obtains white powdery solids.
Embodiment 5
Raw material adopts 3-methacryloyl oxygen propyl trimethoxy silicane (TPM), particle diameter is 30 nanometers Nano particles of silicon dioxide (LudoxTM40), isoamyl acetate (PEA), initator is potassium peroxydisulfate.By 1mLTPM, 0.65mL silica colloidal particles dispersion liquid, 1mLPEA adds in 40mL water, and 10 DEG C are stirred 28 hours, and logical nitrogen deoxygenation, after 30 minutes, is warmed up to 70 DEG C, adds 10mg potassium peroxydisulfate initiated polymerization, and polymerisation continues 18 hours.By the centrifugation of gained emulsion, after ethanol purge 3 times, be scattered in water, freeze drying obtains white powdery solids.
Experimental example
The hollow sub-micron that embodiment 1-5 obtains has hydrophobic cavity and hydrophilic surface, and shell forms primarily of silicon-containing polymer, and silica colloidal particles is embedded in shell, and has partial denudation outside, is a kind of organo-mineral complexing structure.Hollow submicron microsphere surface inserting has silica colloidal particles, can carry out further modification or finishing.In addition, in solvent volatilization process, in shell, leave nano pore, make hollow sub-micron have large specific area.
The structure of these embodiments is detected, after 700 DEG C of calcinings or organic solvent are soaked, still can keep its hollow-core construction.
Thermodynamic stability and the display of structural stability result: the specific area of embodiment 1-5 is respectively:
Claims (33)
1. a hollow sub-micron, it has hydrophobic cavity and hydrophilic surface, and the shell of described hollow sub-micron is organo-mineral complexing structure, and primarily of silicon-containing polymer composition, silica colloidal particles is embedded in shell, and has partial denudation outside.
2. hollow sub-micron according to claim 1, also has nano pore in described shell.
3. hollow sub-micron according to claim 1 and 2, the particle diameter of described hollow sub-micron is 100-300 nanometer and even particle size distribution.
4. hollow sub-micron according to claim 1 and 2, described organo-mineral complexing structure is that the raw material comprising silica colloidal particles is obtained by emulsion polymerisation.
5. hollow sub-micron according to claim 4, adopts a kind of thermodynamically stable Pickering emulsion system in described emulsion polymerisation, template is a kind of volatile solvent.
6. hollow sub-micron according to claim 5, the emulsion in described emulsion polymerisation comprises the volatile solvent of silane coupler, silica colloidal particles and one.
7. hollow sub-micron according to claim 6, described volatile solvent is selected from isoamyl acetate.
8. hollow sub-micron according to claim 6, described silane coupler is methoxy silane or the Ethoxysilane with double bond structure.
9. hollow sub-micron according to claim 8, described silane coupler is the methoxy silane with double bond structure.
10. hollow sub-micron according to claim 9, described silane coupler is 3-methacryloyl oxygen propyl trimethoxy silicane.
11. the hollow sub-micron according to any one of claim 6-10, the mass ratio of described volatile solvent and silane coupler is 1:1 ~ 6:1.
12. hollow sub-microns according to claim 11, the mass ratio of described volatile solvent and silane coupler is 2:1 ~ 4:1.
13. hollow sub-microns according to any one of claim 6-10, the mass ratio of described silica colloidal particles and silane coupler is 1:2 ~ 1:14.
14. hollow sub-microns according to claim 13, the mass ratio of described silica colloidal particles and silane coupler is 1:2.5 ~ 1:5.
15. hollow sub-microns according to any one of claim 6-10, the particle size range of described silica colloidal particles is 10 ~ 100 nanometers.
16. hollow sub-microns according to claim 15, adopt the silica colloidal particles of 10 ~ 50 nanometers.
The preparation method of the hollow sub-micron of 17. 1 kinds of any one of claim 1-16, it adopts a kind of thermodynamically stable Pickering emulsion system, with the volatile solvent of one for template, adopt the method for emulsion polymerisation, obtained a kind of hollow sub-micron with inner hydrophobic external hydrophilic structure;
The shell of described hollow sub-micron is organo-mineral complexing structure, and primarily of silicon-containing polymer composition, silica colloidal particles is embedded in shell, and has partial denudation outside.
18. preparation methods according to claim 17, the emulsion in described emulsion polymerisation process comprises the volatile solvent of silane coupler, silica colloidal particles and one.
19. preparation methods according to claim 18, described volatile solvent is selected from isoamyl acetate.
20. preparation methods according to claim 18, described silane coupler is the methoxy silane with double bond structure.
21. preparation methods according to claim 20, described silane coupler is 3-methacryloyl oxygen propyl trimethoxy silicane.
22. the preparation method according to any one of claim 18-21, the mass ratio of described volatile solvent and silane coupler is 1:1 ~ 6:1.
23. preparation methods according to claim 22, the mass ratio of described volatile solvent and silane coupler is 2:1 ~ 4:1.
24. preparation methods according to any one of claim 18-21, the mass ratio of described silica colloidal particles and silane coupler is 1:2 ~ 1:14.
25. preparation methods according to claim 24, the mass ratio of described silica colloidal particles and silane coupler is 1:2.5 ~ 1:5.
26. preparation methods according to any one of claim 18-21, the particle size range of described silica colloidal particles is 10 ~ 100 nanometers.
27. preparation methods according to claim 26, adopt the silica colloidal particles of 10 ~ 50 nanometers.
28. preparation methods according to claim 18, wherein, silane coupler, silica colloidal particles, volatile solvent stir and form emulsion in water, add initator initiated polymerization after emulsion is formed, and form hollow sub-micron.
29. preparation methods according to claim 28, described initator is persulfate.
30. preparation methods according to claim 19, is characterized in that, described method comprises the steps:
(1) silane coupler, silica colloidal particles, isoamyl acetate are added to the water, stir, form emulsion;
(2) emulsion is heated to above 60 DEG C, adding persulfate is initator, initiated polymerization;
(3) drying obtains powdery product.
31. preparation methods according to claim 30, temperature when stirring in described step (1) is 10 ~ 30 DEG C;
The time of stirring in described step (1) is 10 ~ 30 hours;
Polymerization temperature in described step (2) is higher than 60 DEG C;
Polymerization reaction time in described step (2) is 8 ~ 24 hours.
32. preparation methods according to claim 31, the time of stirring in described step (1) is 16 ~ 24 hours;
Polymerization temperature in described step (2) is 65 ~ 80 DEG C;
Polymerization reaction time in described step (2) is 14 ~ 20 hours.
The application of the hollow sub-micron described in 33. any one of claim 1 to 16, is characterized in that, described application comprises hydrophobic guest parcel, water-oil separating, dewatering medicament conveying, catalyst protection, microreactor.
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| CN104448168B (en) * | 2014-12-02 | 2017-07-21 | 中国科学院化学研究所 | A kind of preparation method of organic inorganic hybridization hollow microsphere and its product and application |
| CN106317425B (en) * | 2015-06-16 | 2018-11-23 | 中国科学院化学研究所 | A method of organic inorganic hybridization hollow nanospheres are prepared by ultrasound |
| CN106317964B (en) * | 2015-06-25 | 2018-10-02 | 中国科学院化学研究所 | A kind of sub-micron composite balls and preparation method thereof and as silicon rubber at the application of porcelain filling |
| CN110960503B (en) * | 2018-09-30 | 2021-09-17 | 中国科学院化学研究所 | Colloidal particles with low protein adsorption and preparation method and application thereof |
| CN110054227B (en) * | 2019-04-16 | 2021-05-25 | 常州大学 | Method for preparing composite shell nano hollow sphere from Pickering miniemulsion |
| CN112973650B (en) * | 2021-02-08 | 2022-02-08 | 厦门大学 | Nano-micro composite ball and preparation method and application thereof |
| CN114130317A (en) * | 2021-12-01 | 2022-03-04 | 北京吾星球科技有限公司 | Submicron hollow microsphere containing aromatic |
| WO2023189800A1 (en) * | 2022-03-30 | 2023-10-05 | 日本ゼオン株式会社 | Hollow particles and production method therefor |
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| CN102430372A (en) * | 2011-08-29 | 2012-05-02 | 浙江理工大学 | Preparation method of strawberry-shaped organic-inorganic nanometer composite microsphere |
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| CN102083306A (en) * | 2008-03-13 | 2011-06-01 | 辛根塔有限公司 | Microencapsulation |
| CN102430372A (en) * | 2011-08-29 | 2012-05-02 | 浙江理工大学 | Preparation method of strawberry-shaped organic-inorganic nanometer composite microsphere |
| CN102617769A (en) * | 2012-02-29 | 2012-08-01 | 华南理工大学 | Nanometer composite porous gel microsphere and preparation method thereof |
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