CN100515556C - Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application - Google Patents
Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application Download PDFInfo
- Publication number
- CN100515556C CN100515556C CNB2004100992272A CN200410099227A CN100515556C CN 100515556 C CN100515556 C CN 100515556C CN B2004100992272 A CNB2004100992272 A CN B2004100992272A CN 200410099227 A CN200410099227 A CN 200410099227A CN 100515556 C CN100515556 C CN 100515556C
- Authority
- CN
- China
- Prior art keywords
- hollow microsphere
- inorganic carbon
- titania
- composite nano
- carbon composite
- 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.)
- Expired - Fee Related
Links
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to a titanium dioxide/inorganic carbon composite nano hollow microsphere, its preparation method and application. Said hollow microsphere shell layer includes two layers of structure, external layer is tilanium dioxide, and its internal layer is inorganic carbon skeleton. The preparation method of said hollow microsphere includes the following steps: synthesizing high polymer microsphere template system, forming inorganic carbon skeleton layer, forming titanium dioxide layer and calcinations. Said hollow microsphere can be used for loading organic small molecule to form composite, and can be extensively used in the fields of medical apparatus and instrument, interior upholstery of car, sports equipment, coating, and fabric or package material.
Description
Technical field
The present invention relates to a kind of hollow nano microballoon, relate in particular to a kind of titania/inorganic carbon composite Nano hollow microsphere and its production and application.
Background technology
Hollow microsphere is owing to its architectural feature, and its range of application expands to material science by medical science, pharmaceutics.At present, the method for preparing the titanium dioxide hollow microballoon mainly contains template and static self-assembly method (LBL).
External also very active to the research of titanium dioxide hollow microballoon.The Germany general colloid of horse and Interface Study Dr.Frank Caruso to have opened up one be template, the synthetic route of passing through the static self-assembling technique with the colloid, obtain the titanium dioxide/colloid core-shell type microballoon of micron even submicron order, and finally obtain the hollow microsphere of titanium dioxide by calcining method.What the Arnout Imhof of Holland Utrecht University adopted is to be template with the polystyrene, directly obtains titanium dioxide/polystyrene core-shell type microballoon by the isopropyl titanate hydrolysis, and obtains the titanium dioxide hollow microballoon by the method for calcining and dissolving.The titanium dioxide hollow microspherulite diameter that these two kinds of methods prepare is respectively 640nm and 380nm, and the cavity microballoon all is to be adsorbed onto by titanium dioxide to remove kernel again behind the template surface and obtain.Therefore, the thickness of the size of template and titanium dioxide shell can be controlled respectively.
At home, professor Yang Zhenzhong of Chinese Academy of Sciences's chemistry institute then adopts a kind of thinking more flexibly: as long as a step just can realize thick and controlled this target of cavity size while of titanium dioxide shell.They at first adopt the higher thiosulfonic acid of concentration to handle polystyrene microsphere, then it is dispersed in tetrabutyl titanate/ethanol (1/1 volume ratio) mixed solution, microballoon after then a therefrom taking-up part is handled is dispersed in ethanol/water (1/1 volume ratio) mixed solution and is hydrolyzed, just obtain titanium dioxide/polystyrene core-shell type microballoon, finally can obtain the titanium dioxide hollow microballoon by the method for calcining or dissolving.Experiment is found: the sulfonation time is long more, and the core-shell type microballoon shell that obtains is thick more, and internal cavities is more little.Equally, their microspherulite diameter of synthesizing is at 300～500nm.
In addition, Qingdao University of Science and Technology nano material engineering and technological research laboratory has been carried out more careful research to how controlling experiment conditions such as titanium dioxide shell thickness, and the template that is adopted is a polystyrene microsphere, the about 900nm of its particle diameter.It is that template makes the core-shell type microballoon that outermost layer is a titanium dioxide that this school applied chemistry system then adopts with argent or polyacrylic acid-galactic nucleus shell-type microballoon, and then obtains the hollow microsphere that particle diameter is 600nm.
More than the synthetic microballoon size of these research institutes all at submicron order even micron order, this has limited the range of application of this hollow microsphere to a certain extent; In addition, from the experimental result that they provide, these cavity microballoons all inevitably exist structural defective; For example, titanium dioxide shell structurre imperfect especially causes the problem of subsiding of hollow structure easily after the calcining, and this can badly influence its effect.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of nano-scale and size ratio titania/inorganic carbon composite Nano hollow microsphere and its production and application uniformly for the defective that overcomes above-mentioned prior art existence.
Purpose of the present invention can be achieved through the following technical solutions:
Titania/inorganic carbon composite Nano hollow microsphere is characterized in that, this hollow microsphere shell comprises double-layer structure: outer is titanium dioxide, and internal layer is the DIC skeleton.
Described hollow microsphere particle diameter is 70～90nm.
Described titanium dioxide layer is by pure titanate Ti (OR)
4(R=-C
2H
5,-C
3H
7...-C
nH
2n+1) in a kind of hydrolysis obtain.
Described DIC casing play is obtained by polyacrylonitrile or the carbonization of 2-butene nitrile.
The preparation method of titania/inorganic carbon composite Nano hollow microsphere is characterized in that, this preparation method comprises following processing step:
(1) synthetic high polymer microsphere template system: the template monomer is added in the organic solvent, under the condition of stirring and logical inert gas, be heated to 70～90 ℃, add initator after 20～30 minutes and react, reaction continues 3～6 hours, obtains the high polymer micro balloons template system after reacting completely;
(2) in above-mentioned system, slowly add a certain amount of acrylonitrile or 2-butene nitrile, continue to react completely, can make the suspension of core-shell type microballoon, again the suspension that makes can be taken out the core-shell type microballoon and uses the ethanol carrying out washing treatment with centrifugal process;
(3) the core-shell type microballoon after will handling is dispersed in the alcohol solvent, and adds under the condition of high-speed stirred and comprise dispersant, water, titanate esters, carries out ageing after reacting completely, and just can obtain titanium dioxide/polyacrylonitrile/high polymer core-shell type microballoon;
(4) titanium dioxide/polyacrylonitrile/high polymer core-shell type microballoon that obtains is taken out, under the condition of anoxybiotic, calcine, just can obtain titania/inorganic carbon composite Nano hollow microsphere;
The ratio of described template monomer and acrylonitrile or 2-butene nitrile is 10/90～50/50 (moL/moL), and the ratio of described core-shell type microballoon and titanate esters is 60～120 (g/moL).
Described high polymer template monomer is selected from a kind of in styrene, the methyl methacrylate.
The initator that described step (1) adopts is selected from azo diisobutyl amidine hydrochloride.
The dispersant that described step (3) adopts is selected from a kind of in polyvinylpyrrolidone PVP, ethanol, isopropyl alcohol, isobutanol or the n-butanol.
Described calcine technology is constant temperature 30～60min in the time of 100 ℃, and with the intensification digit rate to 600 of 10 ℃/min ℃ and at this temperature lower calcination 120min, whole process is all carried out in the atmosphere of anoxybiotic then.
The application of titania/inorganic carbon composite Nano hollow microsphere, it is characterized in that, described hollow nano microballoon can be used for loading organic little molecule forming composite, described organic molecule is selected from one or more in antiseptic, anti ultraviolet agent, the antioxidant, and described compound can be applicable to medicine equipment, automotive upholstery, sports equipment, coating, fabric or packaging material.
Said method make TiO
2/ C is compound, and the hollow microsphere size ratio is more even, and hollow structure is more complete, and the agglomeration of microballoon is not very serious; In addition, the slowly-releasing test finds that this compound hollow microsphere has good slow release effect, obviously is better than the titanium dioxide hollow microballoon; Therefore, join again behind the organic molecules such as one or more in wherein adding antiseptic, anti ultraviolet agent, antioxidant and go in the macromolecular material, all help its application at polymeric material field.
The skin of this kind tiny balloon is TiO
2, internal layer is the C layer, because the C layer has stronger structure, can well support TiO
2Layer particularly can guarantee TiO when calcining
2Layer does not break, thereby the high product production rate is arranged.Simultaneously, can guarantee that in the product use product is not extruded fragmentation.
TiO provided by the invention
2The purposes of/C composite Nano hollow microsphere is: load organic molecule (be selected from antiseptic, anti ultraviolet agent, the antioxidant one or more) to cavity inside, then it is added in the middle of the macromolecular material, can obviously improve some characteristic performance of base material.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
In the 250mL there-necked flask, add deionized water 60mL, acetone 30mL, styrene 5mL (handling) and stir (rotating speed is 300r/min) through decompression distillation, logical then nitrogen 30min is with deoxygenation, then it is put in 80 ℃ the thermostat water bath and heat, behind about 20min, (concentration is 4.82 * 10 to add 10mL initator azo diisobutyl amidine hydrochloride (AIBA) solution to system
-2Mol/L), in system, drip 10.2mL acrylonitrile (rate of addition is 20D/min) behind the lasting 4h of reaction and then react 4h; Reaction ends, and it is centrifugal and with ethanolic solution (analyzing pure) carrying out washing treatment to take out suspension.Getting 0.5906g core-shell type microballoon then is dispersed in the 100mL ethanolic solution, add polyethylene of dispersing agent pyrrolidones PVP 1g, deionized water 2.8mL and isopropyl titanate 2.2mL under the condition of high-speed stirred, be swift in response, allow after its ageing a period of time, just obtain TiO its centrifugal treating
2/ PAN/PS core-shell type microballoon; Calcine in the anoxybiotic atmosphere then, at first be warming up to 100 ℃ and keep 30min, then with the heating rate to 600 of 10 ℃/min ℃ and keep 120min, it cools off relief naturally; The final TiO that just can obtain structural integrity
2/ C composite Nano hollow microsphere.This TiO
2The diameter of/C composite Nano hollow microsphere is about 80～100nm, the about 15nm of C layer thickness wherein, TiO
2The about 15nm of layer thickness.
Embodiment 2
In the 250mL there-necked flask, add deionized water 60mL, ethanol 30mL, styrene 5mL (handling) and stir (rotating speed is 300r/min) through decompression distillation, logical then nitrogen 30min is with deoxygenation, then it is put in 80 ℃ the thermostat water bath and heat, behind about 20min, (concentration is 5.17 * 10 to add 10mL initator azo diisobutyl amidine hydrochloride solution to system
-2Mol/L), reaction continues to drip 10.2mL acrylonitrile (rate of addition is 20D/min) continuation reaction 4h behind the 4h in system; Reaction ends, and it is centrifugal and with ethanolic solution (analyzing pure) carrying out washing treatment to take out suspension.Getting 1.024g core-shell type microballoon then is dispersed in the 100mL ethanolic solution, add polyethylene of dispersing agent pyrrolidones 1g, deionized water 0.8mL and isopropyl titanate 1.8mL under the condition of high-speed stirred, be swift in response, allow after its ageing a period of time, just obtain TiO its centrifugal treating
2/ PAN/PS core-shell type microballoon; Then in the anoxybiotic atmosphere, calcine; At first be warming up to 100 ℃ and keep 30min, again with the heating rate to 600 of 10 ℃/min ℃ and keep 120min, it cools off relief naturally; The final TiO that just can obtain structural integrity
2/ C composite Nano hollow microsphere.This TiO
2The diameter of/C composite Nano hollow microsphere is about 80～100nm, the about 15nm of C layer thickness wherein, TiO
2The about 10nm of layer thickness.
Embodiment 3
In the 250mL there-necked flask, add deionized water 60mL, ethanol 30mL, styrene 5mL (handling) and stir (rotating speed is 300r/min) through decompression distillation, logical then nitrogen 30min is with deoxygenation, then it is put in 80 ℃ the thermostat water bath and heat, behind about 20min, (concentration is 5.17 * 10 to add 10mL initator azo diisobutyl amidine hydrochloride solution to system
-2Mol/L), reaction continues to drip 6.0mL acrylonitrile (rate of addition is 20D/min) continuation reaction 4h behind the 4h in system; Reaction ends, and it is centrifugal and with ethanolic solution (analyzing pure) carrying out washing treatment to take out suspension.Getting 0.5906g core-shell type microballoon then is dispersed in the 100mL ethanolic solution, add polyethylene of dispersing agent pyrrolidones 1g, deionized water 2.8mL and isopropyl titanate 2.2mL under the condition of high-speed stirred, be swift in response, allow after its ageing a period of time, just obtain TiO its centrifugal treating
2/ PAN/PS core-shell type microballoon; Then in the anoxybiotic atmosphere, calcine; At first be warming up to 100 ℃ and keep 30min, again with the heating rate to 600 of 10 ℃/min ℃ and keep 120min, it cools off relief naturally; The final TiO that just can obtain structural integrity
2/ C composite Nano hollow microsphere.This TiO
2The diameter of/C composite Nano hollow microsphere is about 70～90nm, the about 10nm of C layer thickness wherein, TiO
2The about 17nm of layer thickness.
Embodiment 4
In the 250mL there-necked flask, add deionized water 60mL, ethanol 30mL, styrene 5mL (handling) and stir (rotating speed is 300r/min) through decompression distillation, logical then nitrogen 30min is with deoxygenation, then it is put in 80 ℃ the thermostat water bath and heat, behind about 20min, (concentration is 5.17 * 10 to add 10mL initator azo diisobutyl amidine hydrochloride solution to system
-2Mol/L), reaction continues to drip 6.0mL acrylonitrile (rate of addition is 20D/min) continuation reaction 4h behind the 4h in system; Reaction ends, and it is centrifugal and with ethanolic solution (analyzing pure) carrying out washing treatment to take out suspension.Getting 1.024g core-shell type microballoon then is dispersed in the 100mL ethanolic solution, add polyethylene of dispersing agent pyrrolidones 1g, deionized water 0.8mL and isopropyl titanate 1.8mL under the condition of high-speed stirred, be swift in response, allow after its ageing a period of time, just obtain TiO its centrifugal treating
2/ PAN/PS core-shell type microballoon; Then in the anoxybiotic atmosphere, calcine; At first be warming up to 100 ℃ and keep 30min, again with the heating rate to 600 of 10 ℃/min ℃ and keep 120min, it cools off relief naturally; The final TiO that just can obtain structural integrity
2/ C composite Nano hollow microsphere.This TiO
2The diameter of/C composite Nano hollow microsphere is about 70～90nm, the about 10nm of C layer thickness wherein, TiO
2The about 13nm of layer thickness.
Embodiment 5
In the 250mL there-necked flask, add deionized water 60mL, ethanol 30mL, styrene 5mL (handling) and stir (rotating speed is 300r/min) through decompression distillation, logical then nitrogen 30min is with deoxygenation, then it is put in 80 ℃ the thermostat water bath and heat, behind about 20min, (concentration is 5.17 * 10 to add 10mL initator azo diisobutyl amidine hydrochloride solution to system
-2Mol/L), reaction continues to drip 3.9mL acrylonitrile (rate of addition is 20D/min) continuation reaction 4h behind the 4h in system; Reaction ends, and it is centrifugal and with ethanolic solution (analyzing pure) carrying out washing treatment to take out suspension.Getting 0.5906g core-shell type microballoon then is dispersed in the 100mL ethanolic solution, add polyethylene of dispersing agent pyrrolidones 1g, deionized water 2.8mL and isopropyl titanate 2.2mL under the condition of high-speed stirred, be swift in response, allow after its ageing a period of time, just obtain TiO its centrifugal treating
2/ PAN/PS core-shell type microballoon; Then in the anoxybiotic atmosphere, calcine; At first be warming up to 100 ℃ and keep 30min, again with the heating rate to 600 of 10 ℃/min ℃ and keep 120min, it cools off relief naturally; The final TiO that just can obtain structural integrity
2/ C composite Nano hollow microsphere.This TiO
2The diameter of/C composite Nano hollow microsphere is about 70～80nm, the about 5nm of C layer thickness wherein, TiO
2The about 20nm of layer thickness.
Embodiment 6
In the 250mL there-necked flask, add deionized water 60mL, ethanol 30mL, methyl methacrylate 4.6mL (handling) and stir (rotating speed is 300r/min) through decompression distillation, logical then nitrogen 30min is with deoxygenation, then it is put in 80 ℃ the thermostat water bath and heat, behind about 20min, (concentration is 5.17 * 10 to add 10mL initator azo diisobutyl amidine hydrochloride solution to system
-2Mol/L), reaction continues to drip 3.9mL acrylonitrile (rate of addition is 20D/min) continuation reaction 4h behind the 4h in system; Reaction ends, and it is centrifugal and with ethanolic solution (analyzing pure) carrying out washing treatment to take out suspension.Getting 1.024g core-shell type microballoon then is dispersed in the 100mL ethanolic solution, add polyethylene of dispersing agent pyrrolidones 1g, deionized water 0.8mL and isopropyl titanate 1.8mL under the condition of high-speed stirred, be swift in response, allow after its ageing a period of time, just obtain TiO its centrifugal treating
2/ PAN/PS core-shell type microballoon; Then in the anoxybiotic atmosphere, calcine; At first be warming up to 100 ℃ and keep 30min, again with the heating rate to 600 of 10 ℃/min ℃ and keep 120min, it cools off relief naturally; The final TiO that just can obtain structural integrity
2/ C composite Nano hollow microsphere.This TiO
2The diameter of/C composite Nano hollow microsphere is about 70～80nm, the about 5nm of C layer thickness wherein, TiO
2The about 15nm of layer thickness.
Subordinate list 1
Annotate: data shown in the table 1 are experiment consumption and test result.
Claims (9)
1. titania/inorganic carbon composite Nano hollow microsphere is characterized in that, this hollow microsphere shell comprises double-layer structure: outer is titanium dioxide, and internal layer is the DIC skeleton.
2. titania/inorganic carbon composite Nano hollow microsphere according to claim 1 is characterized in that described hollow microsphere particle diameter is 70～90nm.
3. titania/inorganic carbon composite Nano hollow microsphere according to claim 1 is characterized in that, described DIC casing play is obtained by polyacrylonitrile or the carbonization of 2-butene nitrile.
4. the preparation method of a titania/inorganic carbon composite Nano hollow microsphere as claimed in claim 1 is characterized in that, this preparation method comprises following processing step:
(1) synthetic high polymer microsphere template system: the template monomer is added in the organic solvent, under the condition of stirring and logical inert gas, be heated to 70～90 ℃, add initator after 20～30 minutes and react, reaction continues 3～6 hours, obtains the high polymer micro balloons template system after reacting completely;
(2) in above-mentioned system, slowly add a certain amount of acrylonitrile or 2-butene nitrile, continue to react completely, can make the suspension of core-shell type microballoon, again the suspension that makes can be taken out the core-shell type microballoon and uses the ethanol carrying out washing treatment with centrifugal process;
(3) the core-shell type microballoon after will handling is dispersed in the alcohol solvent, and under the condition of high-speed stirred, add dispersant, water and titanate esters, carry out ageing after reacting completely, just can obtain titanium dioxide/polyacrylonitrile/high polymer core-shell type microballoon;
(4) titanium dioxide/polyacrylonitrile/high polymer core-shell type microballoon that obtains is taken out, under the condition of anoxybiotic, calcine, just can obtain titania/inorganic carbon composite Nano hollow microsphere;
The ratio of described template monomer and acrylonitrile or 2-butene nitrile is 10/90～50/50 (moL/moL), and the ratio of described core-shell type microballoon and titanate esters is 60～120 (g/moL).
5. the preparation method of titania/inorganic carbon composite Nano hollow microsphere according to claim 4 is characterized in that, described template monomer is selected from a kind of in styrene, the methyl methacrylate.
6. the preparation method of titania/inorganic carbon composite Nano hollow microsphere according to claim 4 is characterized in that, the initator that described step (1) adopts is selected from azo diisobutyl amidine hydrochloride.
7. the preparation method of titania/inorganic carbon composite Nano hollow microsphere according to claim 4, it is characterized in that the dispersant that described step (3) adopts is selected from a kind of in polyvinylpyrrolidone PVP, ethanol, isopropyl alcohol, isobutanol or the n-butanol.
8. the preparation method of titania/inorganic carbon composite Nano hollow microsphere according to claim 4, it is characterized in that, described calcine technology is constant temperature 30～60min in the time of 100 ℃, with the intensification digit rate to 600 of 10 ℃/min ℃ and at this temperature lower calcination 120min, whole process is all carried out in the atmosphere of anoxybiotic then.
9. the application of a titania/inorganic carbon composite Nano hollow microsphere as claimed in claim 1, it is characterized in that, described hollow nano microballoon can be used for loading organic little molecule forming composite, described organic molecule is selected from one or more in antiseptic, anti ultraviolet agent, the antioxidant, and described compound can be applicable to medicine equipment, automotive upholstery, sports equipment, coating, fabric or packaging material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100992272A CN100515556C (en) | 2004-12-29 | 2004-12-29 | Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100992272A CN100515556C (en) | 2004-12-29 | 2004-12-29 | Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1795978A CN1795978A (en) | 2006-07-05 |
| CN100515556C true CN100515556C (en) | 2009-07-22 |
Family
ID=36817424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100992272A Expired - Fee Related CN100515556C (en) | 2004-12-29 | 2004-12-29 | Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100515556C (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100453166C (en) * | 2006-12-19 | 2009-01-21 | 武汉理工大学 | Method for preparing unidimensional TiO2 hollow structured photocatalyst using vanadium oxide nanobelt as template |
| CN101323444B (en) * | 2007-06-15 | 2011-05-25 | 中国科学院化学研究所 | Carbon or carbon composite hollow ball and preparation thereof |
| TWI395714B (en) * | 2009-09-16 | 2013-05-11 | Univ Nat Chunghsing | Inorganic hollow microspheres and its preparation method |
| CN102059082B (en) * | 2010-11-30 | 2012-06-27 | 重庆大学 | Method for preparing nano manganese dioxide/carbon composite microsphere |
| CN105047860B (en) * | 2014-12-19 | 2019-08-06 | 上海杉杉科技有限公司 | Battery cathode titanium dioxide carbonaceous mesophase spherules composite material and preparation method |
| CN105216389A (en) * | 2015-08-25 | 2016-01-06 | 无锡市长安曙光手套厂 | A kind of fabric, Its Preparation Method And Use |
| CN105820602B (en) * | 2016-03-24 | 2018-05-04 | 青岛科技大学 | A kind of preparation method of nano-titanium dioxide modified hollow glass micropearl |
| CN106587917A (en) * | 2016-12-14 | 2017-04-26 | 苏州纽东精密制造科技有限公司 | Decorative ceramic for automotive trims |
| CN108219394B (en) * | 2017-12-22 | 2020-09-18 | 东莞市基烁实业有限公司 | Yellow-eliminating, whitening and brightening master batch, polyester reclaimed material and preparation method |
| CN109225185A (en) * | 2018-09-13 | 2019-01-18 | 扬州大学 | One kind having TiO2The hollow complex microsphere and preparation method thereof of/carbon double-layer spherical shell |
| CN109621853A (en) * | 2018-12-27 | 2019-04-16 | 中国电子科技集团公司第十八研究所 | Oxide with porous core-shell structure and preparation method thereof |
| CN110227434A (en) * | 2019-07-05 | 2019-09-13 | 浙江迈实科技有限公司 | A kind of preparation method of the hollow type photocatalytic nanometer particle of core-shell structure |
| CN110983557A (en) * | 2019-11-27 | 2020-04-10 | 江阴龙阳纺织有限公司 | Photodynamic antibacterial knitted underwear fabric and preparation method thereof |
| CN113493220A (en) * | 2020-04-02 | 2021-10-12 | 杨洋 | Hollow metal oxide microsphere, preparation method thereof and drug sustained-release application |
| CN113488651B (en) * | 2020-08-31 | 2022-11-25 | 中南大学 | Titanium oxide @ C hollow composite framework embedded with noble metal silver, and preparation method and application thereof |
| CN112094623B (en) * | 2020-09-27 | 2022-07-19 | 山东大学 | Preparation method and application of titanium dioxide coated nickel-carbon hollow core-shell nano microsphere wave-absorbing material |
-
2004
- 2004-12-29 CN CNB2004100992272A patent/CN100515556C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| 模板法制备水凝胶微粒三维有序结构. 李君，纪立军，容建华，马劲，杨振忠.科学通报，第48卷第13期. 2003 |
| 模板法制备水凝胶微粒三维有序结构. 李君，纪立军，容建华，马劲，杨振忠.科学通报，第48卷第13期. 2003 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1795978A (en) | 2006-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100515556C (en) | Nano hollow microsphere of composite titania / inorganic carbon, preparation method and application | |
| US20210237145A1 (en) | Method of producing a metal form containing dispersed aerogel particles impregnated with polymers | |
| US6720007B2 (en) | Polymeric microspheres | |
| CN103771470B (en) | Synthesis method for aluminium oxide nano hollow ball-in-ball | |
| CN103962074B (en) | A kind of hollow sub-micron, its preparation method and application | |
| CN103588920B (en) | Novel preparation method for monodisperse porous polymer nano microcapsule | |
| Wang et al. | Direct encapsulation of water-soluble drug into silica microcapsules for sustained release applications | |
| CN107163268B (en) | Hollow bowl-shaped nano silicon dioxide two-dimensional array structure and preparation and application thereof | |
| CN102115508A (en) | Synthetic method for micro-size polymer fluorescent microspheres | |
| Liu et al. | Facile fabrication of well-defined hydrogel beads with magnetic nanocomposite shells | |
| CN105801886A (en) | Preparation method of hydrophobic nano porous cellulose microspheres | |
| Cheng et al. | Chemical template-assisted synthesis of monodisperse rattle-type Fe3O4@ C hollow microspheres as drug carrier | |
| CN104439276A (en) | Method for fast preparing hollow porous silicon dioxide/silver nanoparticle composite and product | |
| Wang et al. | Hollow particles templated from Pickering emulsion with high thermal stability and solvent resistance: Young investigator perspective | |
| Pei et al. | Preparation of TiO2 nanocapsules for loading and release of antimicrobial triclosan molecules | |
| CN106115779A (en) | A kind of hollow nano-TiO2the preparation method of bag carbon Yolk shell structure | |
| Chen et al. | Magnetic hollow mesoporous silica nanospheres: Facile fabrication and ultrafast immobilization of enzymes | |
| CN113929599A (en) | Precise block polymer nano assembly and preparation method thereof | |
| KR20190087174A (en) | Hollow Silica Nanospheres and Preparation Method Thereof | |
| CN106392096B (en) | A kind of gold nano cup or gold nano bottle and preparation method thereof | |
| Wang et al. | Well-dispersed hollow silica microspheres synthesis with silica sol as precursor by template method | |
| CN112156730B (en) | Preparation method of high-purity monodisperse porous silicon oxide spheres | |
| CN106867021B (en) | Preparation method of magnetic porous polymer microspheres | |
| CN109810259B (en) | Egg shell structure metal-organic framework composite material and preparation method thereof | |
| CN113979466A (en) | ZnO@SiO2Preparation method of nano capsule |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANGHAI GENIUS ADVANCED MATERIAL (GROUP) CO., LTD Free format text: FORMER NAME: JIESHIJIE NEW MATERIALS CO., LTD., SHANGHAI |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 201109, No. 800, North Song Road, North Qiao Town, Shanghai, Minhang District Patentee after: Shanghai Genius Advanced Material (Group) Co., Ltd. Address before: 201109, No. 800, North Song Road, North Qiao Town, Shanghai, Minhang District Patentee before: Jieshijie New Materials Co., Ltd., Shanghai |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090722 Termination date: 20141229 |
|
| EXPY | Termination of patent right or utility model |