CN1982349A - Nano-titanium dioxide surface treatment - Google Patents
Nano-titanium dioxide surface treatment Download PDFInfo
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- CN1982349A CN1982349A CN 200510134271 CN200510134271A CN1982349A CN 1982349 A CN1982349 A CN 1982349A CN 200510134271 CN200510134271 CN 200510134271 CN 200510134271 A CN200510134271 A CN 200510134271A CN 1982349 A CN1982349 A CN 1982349A
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- titanium oxide
- nano titanium
- surface treatment
- titanium dioxide
- treatment method
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Abstract
Nano-titanium dioxide surface treatment is carried out by surface pre-treating for nano-titanium dioxide by butyrin titanate and surface polymerizing by methyl acrylate. It has excellent dispersibilty, stability and ultraviolet-absorbing ability in organic medium.
Description
Technical field
The present invention relates to a kind of surface treatment of nano titanium oxide, belong to the nanosecond science and technology field.
Background technology
Nano titanium oxide is because of its volume effect is led at magnetic, catalytic, photoabsorption, electricity with surface effects, hardness is compared with conventional material with aspects such as fusing points and demonstrated many specific performances, as catalytic performance, uv absorption property and effect etc., at present be widely used in the metallized finish of catalyzer, high-grade car, sun-proof daily cosmetics etc., thereby received people's very big concern.But, because little, specific surface area of nano titanium oxide particle diameter and surface energy are all very big, and coordination wretched insufficiency, thereby show extremely strong surfactivity, reunite easily in dispersion medium, form big aggregate, the existence of reunion will hinder giving full play to of nano titanium oxide advantage again greatly, therefore thereby influence effect in the practical application, study dispersing nanometer titanium dioxide, stability will be the prerequisite and the basis of further improving material property.
In recent years, when the nano titanium oxide synthesis technique constantly makes further progress, the research of aftertreatment technology also has been subjected to attention.By coating certain compound on nano titanium oxide surface, receive the application performance of material titanium dioxide with raising, as weathering resistance, photostabilization, dispersiveness, surfactivity etc.To existing many relevant report and the application of nano titanium oxide surface modification, five kinds of methods of the many employings of various surface treatments: solution deposition desiccating method, SURFACTANT ADSORPTION method, chemical precipitation method, surface reaction method and polymer capsule method.The titanium dioxide granule that makes like this, particle diameter is difficult for Be Controlled, and the every controlled variable in the surface treatment process is not clear, causes top coat inhomogeneous, and it is not good particularly just to be used in the makeup dispersiveness, and many indexs do not reach expected effect.
Summary of the invention
Purpose of the present invention just is to propose the good surface treatment method of receiving material titanium dioxide of a kind of new shielding ultraviolet rays performance.
With the coupling agent butyl (tetra) titanate titanium dioxide nanoparticle is carried out pre-treatment, butyl (tetra) titanate and the reaction of titanium dioxide granule surface hydroxyl, form firm chemical bond and be linked to titanium dioxide nanoparticle, make the titanium dioxide nanoparticle surface generate a plurality of active function groups that can carry out polyreaction, add methyl methacrylate monomer and amount of initiator again and carry out graft polymerization reaction on titanium dioxide nanoparticle surface through surface preparation with polymer monomer.The titanium dioxide nanoparticle surface can form the layer of even polymeric film, the lipophilicity and the space steric effect of a plurality of superpolymer long-chains by being grafted on the titanium dioxide nanoparticle surface, improve greatly based on the dispersiveness in the sun care preparations base-material of organic substance and stable, bring into play titanium dioxide nanoparticle better and absorb ultraviolet function.
In order to achieve the above object, the surface treatment method of a kind of nano titanium oxide of the present invention, with the nano titanium oxide is raw material, and its key step is: the nano titanium oxide purifying, with butyl (tetra) titanate nano titanium oxide is carried out surface preparation and carries out surface aggregate with methyl methacrylate (MMA).
Because Cl is contained on the nano titanium oxide surface that the high temperature gas phase makes
-, SO
4 2-Harmful, therefore need before use it is carried out purifying.In the aqueous solution of titanium dioxide, be heated with stirring to 60 ℃, add alkali to pH be add after 9,20 minutes acid to pH be after 7,10 minutes with the solution suction filtration, oven dry is stand-by down at 100 ℃ with the titania powder of gained behind the repetitive scrubbing.
It generally is to carry out in organic solvent system that the butyl (tetra) titanate of titanium dioxide surface is handled, titanium ester butyl ester is as a kind of coupling agent, its effect is in inorganic materials and organic materials or different organic materials compound system, by chemical action or chemical reaction, the two incorporated affinity of the two that makes is improved, thereby improve the matrix material function.The consumption of butyl (tetra) titanate is different because of the granularity and the surface appearance of inorganic particle, and the amount of butyl (tetra) titanate is 2～3% (by weight) of titanium dioxide amount among the present invention.Nano titanium oxide contacts the generation hydration with water makes its surface produce hydroxyl, in methylene chloride, butyl (tetra) titanate can with the hydroxyl reaction of titanium dioxide surface, form chemical bond, make butyl (tetra) titanate be linked to the titanium dioxide granule surface, make its surface have the active function groups that carries out polyreaction with polymer monomer.
The surface aggregate reaction is to carry out in solid-liquid system, therefore must consider the dispersion of solid particulate in solvent, make simultaneously monomer molecule reach titanium dioxide surface as early as possible again to reduce the self-polymerization between the polymer monomer in solution as far as possible, so stir favourable to graft polymerization, but rotating speed is excessive, owing to contain tensio-active agent in system, is easy to generate foam, thereby cause reaction medium outwards to overflow from there-necked flask, appropriate rotating speed is got 480～500rpm among the present invention.In titanium dioxide add-on one regularly, the monomer add-on is big more, and then clad ratio is big more.Usually can reach modified effect for clad ratio reaches 20%, the surface just can obtain polymeric film, so monomer and titanium dioxide weight ratio are 0.4～0.45 to get final product.In whole system, exist two parallel reactors of carrying out simultaneously all the time: the monomer polymerization in solution and in the polymerization on titanium dioxide granule surface.Obviously the rising of temperature helps the former and is unfavorable for the latter, so temperature rising clad ratio reduces on the contrary.The clad ratio that is reached and consider that higher speed of reaction will be arranged as requested, the present invention adopts 58～60 ℃ temperature of reaction.Also need add tensio-active agent sodium lauryl sulphate (SDS) in the present invention in the polyreaction, its objective is that SURFACTANT ADSORPTION forms adsorption layer with the place as monomer polymerization at titanium dioxide surface.Initiator is one of most important component in the polymerization formula, concerning polymerization process, requires used initiator to be insoluble to monomer, and is dissolved in external phase, so will adopt water soluble starter.For K
2S
2O
8-Na
2S
2O
5Redox initiation system, it with singly use K
2S
2O
8The mechanism that thermal decomposition initiating produces free radical is different.K
2S
2O
8-Na
2S
2O
5To produce sulfate ion free radical and bisulfite free radical, these two kinds of free radicals can initiated polymerization.Under the same polymeric condition, only use K by the clad ratio ratio that redox initiation system obtains
2S
2O
8The clad ratio height.Therefore polyreaction adopts K among the present invention
2S
2O
8-Na
2S
2O
5Composite initiator.Adopt K
2S
2O
8-Na
2S
2O
5Redox initiation system, to the MMA polyreaction, the free radical that generates in initiating stage initiator and monomer effect and other chain monomer addition and increase, exhaust and stop up to monomer, evenly form many long-chain macromolecules on the titanium dioxide granule surface, oxygen among the MMA in carbon atom and the titanium dioxide lattice forms covalent linkage, and obtaining with titanium dioxide is number nuclear, and polymethylmethacrylate (PMMA) is the nano particle TiO of the nucleocapsid composite structure of wall material
2-PMMA.
In order to estimate effect to the nano titanium oxide surface modification, be its in organic medium dispersiveness, stability and absorb ultraviolet effect, we use means of testing such as transmission electron microscope, infrared absorption spectrum, thermogravimetric analysis, contact angle analysis, hydrophilic and oleophilic test and ultra-violet absorption spectrum and respectively the titanium dioxide nanoparticle that surface modification is crossed are tested in the present invention, confirm through the modifying titanium dioxide particle in organic medium dispersiveness, stability and absorb ultraviolet performance and improve greatly.
Embodiment
A kind of surface treatment of nano titanium oxide:
(1) nano titanium oxide purifying: titania powder and the deionized water ratio (weight ratio) with 1: 5 is added in the there-necked flask, and stirring heating is warming up to 60 ℃, keeps constant temperature, drip the NaOH aqueous solution of 1M/L, regulating the pH value is 9, reacts 20 minutes, drips the H of 1M/L
2SO
4The aqueous solution, regulating the pH value is 7, filtering and washing, with gained titanium dioxide 100 ℃ of oven dry.
(2) with butyl (tetra) titanate nano titanium oxide is carried out surface preparation: in the 1000ml large beaker, add the titania powder that the 25g purifying is crossed, add methylene dichloride 250ml ultra-sonic dispersion and drip 1 of 6 of butyl (tetra) titanates and dispersion agent diethanolamine after 10 minutes, with high speed dispersor with solution (rotating speed is 640rpm) dispersion 30 minutes at a high speed.With the reaction system suction filtration, filter solid oven dry stand-by.
(3) carry out surface aggregate with methyl methacrylate (MMA): in the 500ml there-necked flask, add 15g above-mentioned filter solid and the surfactant SDS of 0.433g, add the 300ml deionized water, with the rotating speed is that 300rpm is heated with stirring to 25 ℃, isothermal reaction 50～60 minutes.Be warming up to 60 ℃ then.Feed nitrogen to drive away the oxygen in the system.Regulate agitator speed to 500rpm, add 6g MMA monomer, and good initiator solution (K has been dissolved in dropping
2S
2O
80.051g and Na
2S
2O
50.057g add the small amount of deionized water dissolving), isothermal reaction 90 minutes.Solid particulate with solution suction filtration gained is the nano titanium oxide of crossing through surface modification at last.
Claims (8)
1. the surface treatment method of a nano titanium oxide is characterized in that: with butyl (tetra) titanate nano titanium oxide is carried out surface preparation and carries out surface aggregate with methyl methacrylate.
2. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that surface treatment is to carry out in liquid phase.
3. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that be 2～3% (by weight) of titanium dioxide amount with butyl (tetra) titanate to the amount that nano titanium oxide carries out butyl (tetra) titanate in the surface preparation.
4. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that surface aggregate reacts medium speed and gets 480～500rpm.
5. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that monomer and titanium dioxide weight ratio are 0.4～0.45 in the surface aggregate reaction.
6. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that adopting 58～60 ℃ temperature of reaction in the surface aggregate reaction.
7. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that also need adding the tensio-active agent sodium lauryl sulphate in the surface aggregate reaction.
8. the surface treatment method of a kind of nano titanium oxide according to claim 1 is characterized in that adopting K in the surface aggregate reaction
2S
2O
8-Na
2S
2O
5Redox initiation system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510134271 CN1982349A (en) | 2005-12-16 | 2005-12-16 | Nano-titanium dioxide surface treatment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510134271 CN1982349A (en) | 2005-12-16 | 2005-12-16 | Nano-titanium dioxide surface treatment |
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|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070920A (en) * | 2009-11-23 | 2011-05-25 | 中国科学院福建物质结构研究所 | Nano titanium oxide surface treatment method |
| CN101469140B (en) * | 2007-12-29 | 2012-03-07 | 比亚迪股份有限公司 | Preparation of active titanium dioxide |
| CN105778569A (en) * | 2016-05-05 | 2016-07-20 | 中钛集团洛阳市裕星化工有限公司 | Method for preparing composite titanium dioxide powder with titanium-coated light calcium carbonate |
| CN107383941A (en) * | 2017-08-04 | 2017-11-24 | 中钛化工集团有限公司 | The special titanium dioxide process of chemical fibre |
| CN107400381A (en) * | 2017-08-04 | 2017-11-28 | 中钛化工集团有限公司 | The special titanium dioxide process of Masterbatch |
| CN110684332A (en) * | 2019-10-24 | 2020-01-14 | 温岭市科珵机械股份有限公司 | Lampshade of motorcycle headlamp and preparation method thereof |
-
2005
- 2005-12-16 CN CN 200510134271 patent/CN1982349A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101469140B (en) * | 2007-12-29 | 2012-03-07 | 比亚迪股份有限公司 | Preparation of active titanium dioxide |
| CN102070920A (en) * | 2009-11-23 | 2011-05-25 | 中国科学院福建物质结构研究所 | Nano titanium oxide surface treatment method |
| CN105778569A (en) * | 2016-05-05 | 2016-07-20 | 中钛集团洛阳市裕星化工有限公司 | Method for preparing composite titanium dioxide powder with titanium-coated light calcium carbonate |
| CN105778569B (en) * | 2016-05-05 | 2017-10-31 | 中钛集团洛阳市裕星化工有限公司 | A kind of preparation method of the composite titanium dioxide of titanium cladding precipitated calcium carbonate |
| CN107383941A (en) * | 2017-08-04 | 2017-11-24 | 中钛化工集团有限公司 | The special titanium dioxide process of chemical fibre |
| CN107400381A (en) * | 2017-08-04 | 2017-11-28 | 中钛化工集团有限公司 | The special titanium dioxide process of Masterbatch |
| CN107400381B (en) * | 2017-08-04 | 2019-03-26 | 西藏亚吐克工贸有限公司 | The dedicated titanium dioxide process of Masterbatch |
| CN107383941B (en) * | 2017-08-04 | 2019-03-26 | 西藏亚吐克工贸有限公司 | The dedicated titanium dioxide process of chemical fibre |
| CN110684332A (en) * | 2019-10-24 | 2020-01-14 | 温岭市科珵机械股份有限公司 | Lampshade of motorcycle headlamp and preparation method thereof |
| CN110684332B (en) * | 2019-10-24 | 2021-10-29 | 温岭市科珵机械股份有限公司 | Lampshade of motorcycle headlamp and preparation method thereof |
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Open date: 20070620 |