CN104987475A - Method for preparing nano titanium dioxide gel - Google Patents
Method for preparing nano titanium dioxide gel Download PDFInfo
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- CN104987475A CN104987475A CN201510423930.2A CN201510423930A CN104987475A CN 104987475 A CN104987475 A CN 104987475A CN 201510423930 A CN201510423930 A CN 201510423930A CN 104987475 A CN104987475 A CN 104987475A
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- titanium dioxide
- gel
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Abstract
The invention discloses a method for preparing a nano titanium dioxide gel. The method comprises the following steps: I, by taking a titanium compound as a main raw material, dropwise adding water and an acid inhibiting hydrolysis for hydrolysis reaction to obtain a solated and hydrolyzed compound; II, carrying out condensation polymerization on the solated and hydrolyzed compound, a polymer monomer playing a framework role, a coupling agent and an initiator to form a gel; and III, carrying out high-temperature treatment on the gel to obtain the polymer-based nano compound material. According to the method, by taking titanate as the main raw material, the nano titanium dioxide gel is produced in a primary mixing mode, so that a certain cost is lowered objectively and moreover, the purity of the product is improved. The nanoscale titanium dioxide gel can be prepared by virtue of the method, so that a series of transparent high refractive index nano titanium dioxide films are prepared. The nano titanium dioxide gel has a certain application prospect in the aspects of cosmetics, lubricants, coatings and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nano titanium oxide.
Background technology
Current nano-TiO
2preparation method mainly contain three kinds, be respectively liquid phase method, solid phase method and vapor phase process.Liquid preparation methods nano-TiO
2it is the method that current laboratory and industrial production extensively adopt.The main two kinds of methods of liquid phase method, are respectively hydrolysis method and the precipitator method, but all there is certain problem and cannot solve.Hydrolysis method prepares TiO
2simple and easy to do, but the bad control of hydrolysising condition; It is higher that the precipitator method prepare purity, but equipment cost is very high, is unfavorable for that volume industrial is produced.
Summary of the invention
In order to reduce the equipment cost problem of existing preparation method, and can improve the purity of nano titanium oxide, the problems such as whether size distribution is even, the invention provides a kind of method preparing nanometer titanium dioxide titanium gel.The method, by being main raw material with titanate ester, adopting the mode of mixed once to produce nanometer titanium dioxide titanium gel, objectively saves certain cost, improve the purity of product simultaneously.
The object of the invention is to be achieved through the following technical solutions:
Prepare a method for nanometer titanium dioxide titanium gel, comprise the steps:
One, take titanium metal compound as main raw material, drip water and suppress the acid of hydrolysis to be hydrolyzed reaction, control titanium metal compound: water=20 ~ 22: 1 (volume ratio), the rate of addition of water is 1 ~ 3 second/, titanium metal compound: acid=10 ~ 12: 1 (volume ratio), obtains the compound after solation and hydrolysis;
Two, by the compound after solation and hydrolysis with there is the polymer monomer of skeleton function, coupling agent and initiator carry out copolycondensation, the compound controlled after gel and hydrolysis is 1 ~ 1.2: 1 with the amount of substance ratio of polymer monomer, polymer monomer: coupling agent=7 ~ 7.2: 1 (mass ratio), polymer monomer: initiator=11 ~ 11.3: 1 (mass ratio), reaction times is 3 ~ 5 hours, during preliminary generation gel, need to keep certain stirring velocity (not too fast), form gel.
Two, high temperature process is carried out 2 ~ 2.5 hours at 400 DEG C to gel, for except small molecular weight impurities such as desolventizings, obtain polymer based nanocomposites.
In aforesaid method, the compound of the titanium metal compound of employing mainly titanate ester, as butyl (tetra) titanate.
In aforesaid method, suppress the acid mainly inorganic molecules acid of hydrolysis, example hydrochloric acid or acetic acid etc.
In aforesaid method, there is the polymer monomer of skeleton function, as methyl methacrylate etc.
In last time method, coupling agent can be KH560 reagent or KH570 reagent etc.
In aforesaid method, initiator can be BPO reagent etc.
Core methed of the present invention is sol-gel (Sol-Gel) method.So-called sol-gel (Sol-Gel) method refers to that metal organic or inorganic compound is through solution, colloidal sol, gel and solidifying, then forms the method for oxide compound or other solid chemical compound through thermal treatment.General by metal alkoxide M (OR) n (M=Si, Ti, Zr, Al, Sn, Ce, V etc., OR is alkoxyl group, n is the Oxidation Number of metal) as precursor, after the hydrolysis of precursor molecule, produce active hydroxyl, form colloidal sol through shrink or acetal reaction.It directly can inject die for molding, also can adopt dip coating or spin-coating method film forming.Along with the carrying out of hydrolysis condensation reaction, the viscosity of colloidal sol increases gradually, to the last becomes gel.Gel becomes xerogel through ageing, drying.The material that can be formed is the network structure of inorganic phase and organic phase IPN, and organic constituent can improve the performance of inorganic component or make its functionalization, and the binding ability between two-phase is strengthened; Reaction conditions is gentle, at ambient temperature liquid phase reaction can occur, and two-phase mixtures is comparatively even, can reach micron order even molecular level compound, and accurately can control the ratio of each component of reactant.
Reaction mechanism is as follows:
Permutoid reaction: RCOOH+SiOEt=SiOOCR+EtOH
RCOOH+SiOH＝SiOOCR+H
2O
Esterification: RCOOH+EtOH=EtOOCR+H
2o
Hydrolysis reaction: SiOEt+H
2o=SiOH+EtOH
Condensation reaction: SiOH+SiOOCR=SiOSi+RCOOH speed of reaction is fast
2SiOH=SiOSi+H
2o is slow
SiOH+SiOEt=SiOSi+RCOOH is slow
SiOOCR+SiOEt=SiOSi+RCOO is very slow
The present invention has following beneficial effect:
1, because reaction conditions is comparatively gentle, so industrial production cost is lower, and mutually between mixing comparatively even, other compound of molecular level can be reached, thus the degree of each composition can be controlled accurately.
2, Nano titanium dioxide gel can be prepared by this method, thus prepare a series of transparent high refractive index nano titanium deoxid film, in makeup, lubricant, coating etc., have now certain application prospect.
3, the present invention adopts sol-gel method to prepare TiO
2reaction, process is easy to control, and side reaction is few, and equipment and process is simple to operate, obtained TiO
2purity is high, even particle size distribution.
Accompanying drawing explanation
Fig. 1 is reaction unit figure, 1-feed hopper, 2-three-necked bottle, 3-reflux condensate device, 4-thermometer, 5-mechanical stirring device;
Fig. 2 is process flow sheet;
Fig. 3 is the gel state structure of nano titanium oxide;
Fig. 4 is nano titanium oxide infrared test figure;
Fig. 5 is the scanning electron microscope (SEM) photograph of the nano titanium oxide of preparation.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1:
Get a and b two 50ml beakers, 10ml butyl (tetra) titanate and 10ml dehydrated alcohol add in a beaker and mix, be configured to a solution after drying by distilled water.In b beaker, add 20ml dehydrated alcohol and mix with 2ml distilled water, and add Glacial acetic acid 3ml, be configured to b solution.Ensure at 50 DEG C, b solution is slowly instilled a solution with the second speed of one.Be mixed into polymer monomer methyl methacrylate 11ml and coupling agent KH560 1ml and initiator B PO 1.5ml again.After reacting 12 hours, at room temperature sedimentation, sealing, makes gel.After drying, then by TiO
2gel, 400 DEG C of high temperature sinterings two hours, forms nano level TiO
2, as shown in Figure 1, as shown in Figure 2, as shown in Figure 3, scanning electron microscope (SEM) photograph as shown in Figure 5 for three-dimensional net structure for reaction process flow process for its reaction unit.From TiO shown in Fig. 4
2infrared spectrum is analyzed known: 3400cm
-1and 1600/cm
-1for TiO
2the hydroxyl group absorption peak that Surface Polarization produces, 400 to 700cm
-1for TiO
2charateristic avsorption band, so prove define TiO
2product.
Claims (8)
1. prepare a method for nanometer titanium dioxide titanium gel, it is characterized in that described method steps is as follows:
One, take titanium metal compound as main raw material, drip water and suppress the acid of hydrolysis to be hydrolyzed reaction, control titanium metal compound: water=20 ~ 22: 1 (volume ratio), the rate of addition of water is 1 ~ 3 second/, titanium metal compound: acid=10 ~ 12: 1 (volume ratio), obtains the compound after solation and hydrolysis;
Two, by the compound after solation and hydrolysis with there is the polymer monomer of skeleton function, coupling agent and initiator carry out copolycondensation, the compound controlled after gel and hydrolysis is 1 ~ 1.2: 1 with the amount of substance ratio of polymer monomer, polymer monomer: coupling agent=7 ~ 7.2: 1 (mass ratio), polymer monomer: initiator=11 ~ 11.3: 1 (mass ratio), reaction times is 3 ~ 5 hours, forms gel;
Three, high temperature process is carried out 2 ~ 2.5 hours at 400 DEG C to gel, obtain polymer based nanocomposites.
2. the method preparing nanometer titanium dioxide titanium gel according to claim 1, is characterized in that described titanium metal compound is the compound of titanate ester.
3. the method preparing nanometer titanium dioxide titanium gel according to claim 2, is characterized in that the compound of described titanate ester is butyl (tetra) titanate.
4. the method preparing nanometer titanium dioxide titanium gel according to claim 1, is characterized in that the acid of described suppression hydrolysis is inorganic molecules acid.
5. the method preparing nanometer titanium dioxide titanium gel according to claim 4, is characterized in that the acid of described inorganic molecules is for hydrochloric acid or acetic acid.
6. the method preparing nanometer titanium dioxide titanium gel according to claim 1, the polymer monomer described in it is characterized in that with skeleton function is methyl methacrylate.
7. the method preparing nanometer titanium dioxide titanium gel according to claim 1, is characterized in that described coupling agent is KH560 or KH570.
8. the method preparing nanometer titanium dioxide titanium gel according to claim 1, is characterized in that described initiator is BPO.
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| CN201510423930.2A CN104987475A (en) | 2015-07-18 | 2015-07-18 | Method for preparing nano titanium dioxide gel |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794773A (en) * | 2018-06-29 | 2018-11-13 | 四川理工学院 | A kind of preparation method of conductive hydrogel |
| CN109880171A (en) * | 2019-03-07 | 2019-06-14 | 武汉理工大学 | Have effects that toughening and reduces the double epoxy resin additive of solidification temperature and its preparation, application method |
| CN110734643A (en) * | 2018-10-29 | 2020-01-31 | 嘉兴学院 | Preparation method of rare earth doped modified polyimide film |
-
2015
- 2015-07-18 CN CN201510423930.2A patent/CN104987475A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 赵明亮: "高介电聚偏氟乙烯/Ti02/PMMA复合薄膜的制备与表征", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108794773A (en) * | 2018-06-29 | 2018-11-13 | 四川理工学院 | A kind of preparation method of conductive hydrogel |
| CN108794773B (en) * | 2018-06-29 | 2021-03-23 | 四川理工学院 | Preparation method of conductive hydrogel |
| CN110734643A (en) * | 2018-10-29 | 2020-01-31 | 嘉兴学院 | Preparation method of rare earth doped modified polyimide film |
| CN110734643B (en) * | 2018-10-29 | 2022-03-25 | 嘉兴学院 | Preparation method of rare earth doped modified polyimide film |
| CN109880171A (en) * | 2019-03-07 | 2019-06-14 | 武汉理工大学 | Have effects that toughening and reduces the double epoxy resin additive of solidification temperature and its preparation, application method |
| CN109880171B (en) * | 2019-03-07 | 2021-03-23 | 武汉理工大学 | Epoxy resin additive with double effects of toughening and curing temperature reduction and preparation and use methods thereof |
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Application publication date: 20151021 |