CN102641220A - Method for preparing high-efficiency ultraviolet-resistant titanium-dioxide nano granules - Google Patents
Method for preparing high-efficiency ultraviolet-resistant titanium-dioxide nano granules Download PDFInfo
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- CN102641220A CN102641220A CN2012101014799A CN201210101479A CN102641220A CN 102641220 A CN102641220 A CN 102641220A CN 2012101014799 A CN2012101014799 A CN 2012101014799A CN 201210101479 A CN201210101479 A CN 201210101479A CN 102641220 A CN102641220 A CN 102641220A
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Abstract
The invention belongs to the technical field of materials and particularly relates to a method for preparing titanium-dioxide nano granules with the performance of high-efficiency ultraviolet resistance. An amphiphilic three-block polymer PEO-b-PDMA-b-PS is synthesized by an atom transfer radical polymerization (ATRP) reaction, and polymeric micelles with uniform particle-size distribution are also formed by macromolecular self-assembly. Then, the sol-gel reaction of deposited titanate occurs on the micelles in situ, organic/inorganic hybrid titanium-dioxide nano granules are obtained after drying, and then inorganic titanium-dioxide nano granules can also be obtained after further calcining. According to the method for preparing the titanium-dioxide nano granules with the performance of the high-efficiency ultraviolet resistance, the titanium-dioxide nano granules with the performance of the high-efficiency ultraviolet resistance can be prepared; and moreover, the magnitude of the particle size of the nano granules can be controlled by controlling the pH value of an environment and the polymerization degree of each chain segment of the polymer. The method has a simple preparing process and low cost and is convenient to operate, and the prepared product is safe and nontoxic, has favorable dispersing performance in water and can be applied to the fields of sun-screen cosmetics, catalytic degradation and the like.
Description
Technical field
The present invention relates to a kind of method for preparing efficient uvioresistant titania nanoparticles.
Background technology
Along with increasing of the toxic gas that discharges in the modern industry, the ozone layer in the atmosphere is constantly destroyed, and makes increasing ultraviolet radiation to the human body skin surface.The photochemical reaction that excessive ultraviolet radiation causes makes function of human body that a series of variation take place, and especially possibly damage skin, eyes and immune system.In order to reduce the injury of sunlight middle-ultraviolet lamp to human body, sunscreen becomes a kind of very useful product.It comprises the active component that can absorb or stop ultraviolet radiation, can make skin avoid the sunlight injury.Present sunscreen comprises organic and inorganic sunscreen products, and organic principle often is difficult to degraded, and may produce injury to human body skin, and the hydrophilicity of inorganic sunscreen is better, and nontoxic, therefore is used as sunscreen product more and more.Inorganic sunscreen product commonly used has titanium dioxide and zinc oxide.Titanium dioxide single-activity composition can be made into high SPF product, and zinc oxide can not improve SPF.
Titania nanoparticles is a kind of novel photocatalysis agent, UV resistant agent; Under the irradiation of ultraviolet light, sunlight, daylight lamp; Can excite the electron transition on the valence band; And on valence band, produce corresponding hole; Generation has the superoxide ion free radical of extremely strong Oxidation, ultra oxygen hydroxyl radical free radical, hydroxyl radical free radical, can oxidation Decomposition such as harmful organic substances such as formaldehyde, benzene,toluene,xylene, ammonia, VOC, antibacterial, pollutant, foul smell be become harmless carbon dioxide (CO
2) and water (H
2Micromolecule such as O); Simultaneously, it also has the antiseptic property of high-efficiency broad spectrum, effectively controls the cross infection of antibacterial, virus, reaches control bacterial reproduction and the purpose that purifies air, and has been widely used in finishing pollution and has administered.Therefore nano titanium oxide is as a kind of catalyst, and any variation and loss do not take place for itself, has lasting, continuous action of time, safe, nontoxic advantage, does not produce secondary pollution, is the free of contamination product of internationally recognized environmental protection.Its safety non-toxic, in water good dispersion, can be used for preparing sunscreen products.
In recent years, the polymer micelle that is formed by self-assembling technique has caused widely to be paid close attention to.The shell of this nanometer spherical structure possess hydrophilic property and hydrophobic kernel constitute, and the polymer micelle particle diameter is even, can also regulate and control micellar size as required.Recently, polymer micelle is used as the template of diversified organic-inorganic hybrid material.
The innovative point of present technique invention is for utilizing polymer template original position generation solgel reaction; Thereby obtain having the titania nanoparticles of the organic inorganic hybridization of efficient anti-ultraviolet property, through further making inorganic titania nanoparticles after the calcining.Method for preparing is simple, and the products obtained therefrom particle diameter is even, size adjustable, and in water good dispersion.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing efficient uvioresistant titania nanoparticles.
The method of the efficient uvioresistant titania nanoparticles of preparation that the present invention proposes; Utilize polymer template to prepare the hydridization titania nanoparticles, utilize ATRP (ATRP) method to obtain amphipathic triblock copolymer PEO-by bromo polyoxyethylene (PEO-Br), dimethylaminoethyl methacrylate (DMA) and styrene (Styrene)
b-PDMA-
b-PS.This polymer is dissolved in certain good solvent, and dropwise splashes into poor solvent and carry out self assembly and form the uniform amphipathic nature polyalcohol micelle of particle diameter.Wherein, hydrophobic PS forms the micelle kernel, and hydrophilic PEO and PDMA segment form shell and subshell respectively, thereby makes micelle keep stability.Behind the titanium source diluting, dropwise splash in the polymer micelle solution, and constantly stir, obtain the titania nanoparticles of organic inorganic hybridization after the drying, under ppm level concentration, its uv absorption rate can reach 70%.Further can also obtain titania nanoparticles after the calcining.
The method of the efficient uvioresistant titania nanoparticles of preparation that the present invention proposes, concrete steps are following:
(1) amphipathic triblock polymer PEO-
b-PDMA-
b-PS's is synthetic
Macromole evocating agent PEO-Br, catalyst, catalyst ligand and monomer Dimethylaminoethyl Methacrylate (DMA) are with 1:1: (1～5): the mol ratio of (15～150) joins in the round-bottomed flask; Add 1 ~ 100mL solvent, polymerization temperature is 20～100 ℃, reacts after 1～100 hour; Styrene is dissolved in 4 ~ 40mL xylol; Join after the degassing and continue reaction in the round-bottomed flask, polymerization temperature is 30～120 ℃, and the time is 12～72 hours; The polymer that makes is revolved steaming, dissolving, peroxidating aluminum pillar, deposition, filtration, vacuum drying, obtain triblock polymer PEO-
b-PDMA-
b-PS; Wherein: the mol ratio of styrene and PEO-Br is (20 ~ 200): 1;
(2) self assembly forms polymer micelle
The polymer P EO-that step (1) is obtained with the concentration of 10～50mg/mL
b-PDMA-
b-PS is dissolved among the good solvent A, under stirring condition, drips 1 ~ 100 times to the poor solvent B of good solvent A volume with the speed of 10～50d/min, obtains milky micellar solution after the stirring;
(3) polymer micelle surface deposition titanium source
Concentration with 10～20mg/mL is dissolved in the titanium source in the solvent C, and titanium source and DMA are with (0.2 ~ 10.0): 1 mol ratio splashes in the micellar solution, and vigorous stirring obtains milky solution after a period of time;
(3) drying obtains the titania nanoparticles of organic inorganic hybridization
After the nano-particle solution drying with the organic inorganic hybridization that obtains, promptly obtain required product.
Among the present invention, the molecular weight of the polyoxyethylene PEO described in the step (1) is 1900～5000, said block copolymer PEO-
b-PDMA-
bThe molecular weight of-PS is 8000～50000.
Among the present invention, the good solvent A of the triblock polymer of the self assembly described in the step (2) be oxolane,
In dichloromethane, dimethyl formamide (DMF), chloroform or the dimethyl sulfoxine one or more; Poor solvent B is one or more in water, acetone, methanol, ethanol, glycerin or the butanols.
Among the present invention, employed solvent C is to be in oxolane, methanol, ethanol, glycerin or the butanols one or more in the step (3).
Among the present invention, the solvent that uses in the step (1) is one to several kinds in toluene, dichloromethane, oxolane, methanol, ethanol, dimethyl sulfoxine or the dimethyl formamide (DMF).
Among the present invention, the titanium source of using in the step (3) is to several kinds in butyl titanate, tetraethyl titanate, titanium tetrachloride or the metatitanic acid methyl ester.
Among the present invention, catalyst described in the step (1) is cuprous bromide (CuBr) or Cu-lyt. (CuCl), and said catalyst ligand is PMDETA.
The polymer micelle particle diameter that utilizes the inventive method to make is 20 ~ 200nm, and the titania nanoparticles particle diameter of organic inorganic hybridization is 20 ~ 200nm, and the titania nanoparticles particle diameter that obtains after the calcining is that 20 ~ 200nm is adjustable.
With respect to scheme of the prior art, advantage of the present invention is:
1) synthetic triblock polymer PEO-
b-PDMA-
bAmong-the PS, PDMA has the pH response, can come the micellar size of controlling polymers through the pH regulator of environment;
2) the polymer self-assembling technique can access the uniform micelle of particle diameter, thereby can effectively control particle size distribution and size;
3), can access the hydridization titania nanoparticles that is evenly distributed of a series of different-grain diameters through control micellar size;
4) method for preparing is simple, and anti-ultraviolet property is good.
Description of drawings
Fig. 1 for calcining after the transmission electron microscope picture of the titania nanoparticles that obtains.Wherein: (a) be titania nanoparticles under the low range, (b) be the titania nanoparticles under the high magnification.
Fig. 2 is the uv absorption figure of organic inorganic hybridization titania nanoparticles.
The specific embodiment
Further specify the present invention through embodiment below.
1) amphipathic triblock polymer PEO-
b-PDMA-
b-PS's is synthetic
With the polyoxyethylene after the 0.500g bromination (PEO-Br) is macromole evocating agent; Catalyst cuprous bromide (CuBr) with 0.036g; 0.044g part PMDETA; 1.580g monomer Dimethylaminoethyl Methacrylate (DMA) and 4mL solvent join in the round-bottomed flask of 50mL, carry out ATRP (ATRP), temperature 30
oC reacts after 6 hours after the dilution of 3.800g styrene, joins and continues reaction 24 hours in the reaction flask.The polymer that obtains revolves steamings, crosses the silica gel pillar, concentrated, deposition, pump are taken out, and puts vacuum drying oven at last 24 hours, obtains block polymer PEO
43-
b-PDMA
40-
b-PS
140
2) the polymer self assembly forms micelle
Polymer dissolution is prepared the solution of 20mg/mL in oxolane (THF), the speed with 10d/min under stirring condition drips 60 times to the methanol of THF volume in THF solution, stir and obtain milky solution after 24 hours.
3) polymer micelle surface deposition titanium source
Use butyl titanate to be the titanium source, with the concentration of 10mg/mL butyl titanate (TBT) is dissolved in the ethanol, TBT and DMA splash in the micellar solution with the mol ratio of 0.2:1, and vigorous stirring obtains milky solution after 24 hours.
4) promptly obtain required product after the nanoparticles solution drying with the organic inorganic hybridization that obtains.
As shown in Figure 1, the clear in structure of the titania nanoparticles that process obtains after further calcining, grain size is even.
As shown in Figure 2, under ppm level concentration, the uv absorption rate of the titania nanoparticles of organic inorganic hybridization can reach 70%.
Embodiment 2
1) amphipathic triblock polymer PEO-
b-PDMA-
b-PS's is synthetic
0.500g macromole evocating agent PEO
43-Br; 0.036g catalyst cuprous bromide (CuBr), the part PMDETA of 0.044g, monomer Dimethylaminoethyl Methacrylate (DMA) and the 3mL methanol solvate of 1.180g join in the round-bottomed flask of 50mL; Carry out ATRP (ATRP), temperature 30
oC reacts and after 6 hours 2.800g styrene is dissolved in the 3mL xylol continuation reaction 24 hours.The polymer that obtains revolves steamings, crosses the silica gel pillar, concentrated, deposition, pump are taken out, and puts vacuum drying oven at last 24 hours, obtains block polymer PEO
43-
b-PDMA
30-
b-PS
100
2) the polymer self assembly forms micelle
Polymer dissolution is prepared the solution of 30mg/mL in dichloromethane, the speed with 10d/min under stirring condition drips 80 times to the ethanol of methylene chloride volume in above-mentioned solution, stir and obtain milky white solution after 24 hours.
3) polymer micelle surface deposition titanium source
Use tetraethyl titanate to be the titanium source, with the concentration of 10mg/mL tetraethyl titanate is dissolved in the glycerin, tetraethyl titanate and DMA splash in the solution of vesicle with the mol ratio of 0.5:1, and vigorous stirring is after 24 hours, and milky is constant.
4) promptly obtain required product after the nano-particle solution drying with the organic inorganic hybridization that obtains.
Embodiment 3
1) amphipathic triblock polymer PEO-
b-PDMA-
b-PS's is synthetic
With the polyoxyethylene after the 1.000g bromination (PEO-Br) is macromole evocating agent, the catalysis of 0.072g
Agent cuprous bromide (CuBr), the part PMDETA of 0.088g, monomer Dimethylaminoethyl Methacrylate (DMA) and the 5mL methanol solvate of 3.160g join in the round-bottomed flask of 50mL, carry out ATRP (ATRP), temperature 30
oC reacts and after 6 hours 3.300g styrene is dissolved in the 6mL xylol, joins to continue reaction 24 hours in the reaction flask.After post processing, obtain block polymer PEO
43-
b-PDMA
40-
b-PS
120
2) the polymer self assembly forms micelle
Polymer dissolution is prepared the solution of 20mg/mL in dichloromethane, the speed with 10d/min under stirring condition drips 80 times to the ethanol of methylene chloride volume in THF solution, stir and obtain milky white solution after 24 hours.
3) polymer micelle surface deposition titanium source
With the butyl titanate is the titanium source, with the concentration of 20mg/mL butyl titanate (TBT) is dissolved in the methanol, and butyl titanate and DMA splash in the micellar solution with the mol ratio of 1.0:1, and vigorous stirring is after 24 hours, and milky is constant.
4) promptly obtain required product after the nano-particle solution drying with the organic inorganic hybridization that obtains.
Above-mentioned instance only is explanation technical conceive of the present invention and characteristics, and its purpose is to let the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (8)
1. method for preparing efficient uvioresistant titania nanoparticles is characterized in that concrete steps are following:
(1) amphipathic triblock polymer PEO-
b-PDMA-
b-PS's is synthetic
Macromole evocating agent PEO-Br, catalyst, catalyst ligand and monomer Dimethylaminoethyl Methacrylate are with 1:1: (1～5): the mol ratio of (15～150) joins in the round-bottomed flask; Add 1 ~ 100mL solvent, polymerization temperature is 20～100 ℃, reacts after 1～100 hour; Styrene is dissolved in 4 ~ 40mL xylol; Join after the degassing and continue reaction in the round-bottomed flask, polymerization temperature is 30～120 ℃, and the time is 12～72 hours; The polymer that makes is revolved steaming, dissolving, peroxidating aluminum pillar, deposition, filtration, vacuum drying, obtain triblock polymer PEO-
b-PDMA-
b-PS; Wherein: the mol ratio of styrene and PEO-Br is (20 ~ 200): 1;
(2) self assembly forms polymer micelle
The polymer P EO-that step (1) is obtained with the concentration of 10～50mg/mL
b-PDMA-
b-PS is dissolved among the good solvent A, under stirring condition, drips 1 ~ 100 times to the poor solvent B of good solvent A volume with the speed of 10～50d/min, obtains milky micellar solution after the stirring;
(3) polymer micelle surface deposition titanium source
Concentration with 10～20mg/mL is dissolved in the titanium source in the solvent C, and titanium source and Dimethylaminoethyl Methacrylate are with (0.2 ~ 10.0): 1 mol ratio splashes in the micellar solution, and vigorous stirring obtains milky solution after a period of time;
(4) drying obtains the titania nanoparticles of organic inorganic hybridization
After the nano-particle solution drying with the organic inorganic hybridization that obtains, promptly obtain required product.
2. method according to claim 1, its characteristic have in the polyoxyethylene PEO described in the step (1)
Molecular weight be 1900～5000, said block copolymer PEO-
b-PDMA-
bThe molecular weight of-PS is 8000～50000.
3. method according to claim 1, its characteristic have in three embeddings of the self assembly described in the step (2)
The good solvent A of section polymer is one or more in oxolane, dichloromethane, dimethyl formamide, chloroform or the dimethyl sulfoxine; Poor solvent B is one or more in water, acetone, methanol, ethanol, glycerin or the butanols.
4. it is to be in oxolane, methanol, ethanol, glycerin or the butanols one or more that method according to claim 1, its characteristic have in step (3) employed solvent C.
5. method according to claim 1, its characteristic have the solvent that in step (1), uses to be one to several kinds in toluene, dichloromethane, oxolane, methanol, ethanol, dimethyl sulfoxine or the dimethyl formamide (DMF).
6. it is to several kinds in butyl titanate, tetraethyl titanate, titanium tetrachloride or the metatitanic acid methyl ester that method according to claim 1, its characteristic have the titanium source of in step (3), using.
7. it is cuprous bromide or Cu-lyt. that method according to claim 1, its characteristic have in catalyst described in the step (1).
8. it is 20 ~ 200nm that method according to claim 1, its characteristic have in prepared polymer micelle particle diameter, and the titania nanoparticles particle diameter of organic inorganic hybridization is 20 ~ 200nm, and the titania nanoparticles particle diameter that obtains after the calcining is 20 ~ 200nm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214634A (en) * | 2013-04-01 | 2013-07-24 | 北京化工大学 | Preparation method of three-block amphiphilic copolymer |
| CN103820990A (en) * | 2014-02-25 | 2014-05-28 | 南京邮电大学 | Uvioresistant yarns prepared by confinement induced self-assembly and preparation method thereof |
| CN104784058A (en) * | 2015-05-08 | 2015-07-22 | 苏润文 | Photocatalytic sunscreen essence and preparation method thereof |
| CN107260560A (en) * | 2017-07-17 | 2017-10-20 | 中钛化工集团有限公司 | The special titanium dioxide process of cosmetics |
| CN108192299A (en) * | 2018-01-12 | 2018-06-22 | 浙江东太新材料有限公司 | A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof |
| CN109395704A (en) * | 2018-11-06 | 2019-03-01 | 济南大学 | A method of mesoporous TiO 2 is prepared with template crosslinked method |
-
2012
- 2012-04-10 CN CN 201210101479 patent/CN102641220B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| DOMINIQUE SCALARONE ET AL.: "《Porous and worm-like titanium dioxide nanostructures from PS-b-PEO block copolymer micellar solutions》", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
| WILSON A. LEE ET AL.: "《Multicomponent polymer coating to block photocatalytic activity of TiO2 nanoparticles》", 《CHEM COMM》 * |
| YU ZHANG ET AL.: "《Hybrid Titania Microspheres of Novel Superstructures Templated by Block Copolymers》", 《CHEM.MATER》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214634A (en) * | 2013-04-01 | 2013-07-24 | 北京化工大学 | Preparation method of three-block amphiphilic copolymer |
| CN103820990A (en) * | 2014-02-25 | 2014-05-28 | 南京邮电大学 | Uvioresistant yarns prepared by confinement induced self-assembly and preparation method thereof |
| CN103820990B (en) * | 2014-02-25 | 2016-07-06 | 南京邮电大学 | Ultraviolet resistance yarn and preparation method thereof is prepared in a kind of confinement induction self assembly |
| CN104784058A (en) * | 2015-05-08 | 2015-07-22 | 苏润文 | Photocatalytic sunscreen essence and preparation method thereof |
| CN104784058B (en) * | 2015-05-08 | 2018-07-06 | 苏润文 | A kind of sun-proof Essence of photocatalyst and preparation method thereof |
| CN107260560A (en) * | 2017-07-17 | 2017-10-20 | 中钛化工集团有限公司 | The special titanium dioxide process of cosmetics |
| CN107260560B (en) * | 2017-07-17 | 2020-06-30 | 西藏亚吐克工贸有限公司 | Preparation method of titanium dioxide special for cosmetics |
| CN108192299A (en) * | 2018-01-12 | 2018-06-22 | 浙江东太新材料有限公司 | A kind of delustring uvioresistant high-performance PET master batch and preparation method thereof |
| CN109395704A (en) * | 2018-11-06 | 2019-03-01 | 济南大学 | A method of mesoporous TiO 2 is prepared with template crosslinked method |
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