CN102174276B - Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper - Google Patents
Method for preparing cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper Download PDFInfo
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- CN102174276B CN102174276B CN 201110056091 CN201110056091A CN102174276B CN 102174276 B CN102174276 B CN 102174276B CN 201110056091 CN201110056091 CN 201110056091 CN 201110056091 A CN201110056091 A CN 201110056091A CN 102174276 B CN102174276 B CN 102174276B
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Abstract
The invention relates to a method for preparing a cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper, which comprises the following steps of: hydrolyzing titanate on the outer layers of polystyrene microspheres serving as a template in an alcohol/nitrile mixed solvent containing ammonia water and distilled water to prepare polystyrene and titanium dioxide composite particles; immersing and stirring the composite particles in a cerium sol for 4 to 12 hours, performing centrifugal separation, and drying at the temperature of between 60 and 100 DEG C; and roasting at the temperature of between 500 and 600 DEG C for 2 to 6 hours to prepare cerium-doped titanium dioxide pigment microspheres with a hollow structure, wherein the microspheres are yellow and have the particle size of 100 to 400nm and the relative density of 1.4 to 2.8g/cm<3>. The yield of the polystyrene and titanium dioxide composite particles is controlled by adjusting the addition amount of water, so that the yield of cerium-doped hollow nano titanium dioxide yellow pigment particles is improved, and the problem that the content of secondary particles in the polystyrene and titanium dioxide core-shell composite particles is high at present is solved. The yellow hollow microspheres prepared by the method have a regular shape and low relative density, and the particle size is easy to control. The invention has the advantages that: raw materials are readily available, and the method is environment-friendly.
Description
One, technical field
The invention belongs to the electronic paper technology field, particularly a kind of preparation method of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper.
Two, background technology
Electronic Paper is a kind of novel indicating meter, has less energy-consumption, flexible shows, the characteristics such as ultra-thin light, high-contrast, high-res.The approach that realizes at present electronic paper technology mainly includes cholesterol liquid crystal technique of display, electrophoretic display technology (EPD) and electric wetting technique of display etc.Wherein with the micro encapsulation electrophoretic display technology for the most potential technological approaches.It will be coated among the microcapsule by the electrophoresis disclosing solution that electrophoresis particle, suspension, charge control agent and stablizer etc. form, and utilize electrophoresis particle to be subjected to electric field action in painted suspension and electrophoretic migration occurs realize showing.The colored demonstration is the main direction of present electronic paper technology research, usually adopts colored filter to realize.But spectral filter not only can reduce the brightness of reflection-type electric paper display, also can reduce the saturation ratio of color.Doing electrophoresis particle with colored organic pigments also is one of method that realizes full-color demonstration, but mineral dye size distribution commonly used is wide, surface irregularity and density are larger, dispersion stabilization in suspension is poor, can reduce the contrast gradient of prepared electronic paper display device, shorten its work-ing life.
Utilizing metal ion mixing is one of method for preparing on the colored organic pigments particle, and metal ion commonly used mainly contains Cr at present
3+, Co
2+, Al
3+, Fe
3+Deng.But contain Cr
3+, contain Co
2+Pigment has certain toxicity, so its use is more and more restricted, simultaneously, the transition metals such as Fe, Co cause the impact that chromatic effect is subjected to the character of the variation of ligancy and adjacent ions significantly, be difficult to reliably, stably control the color development effect.
In order to improve the density matching of electrophoresis particle and organic solvent, improve its dispersion stabilization in organic solvent, usually can adopt electrophoresis particle is carried out organics coating modification or it is prepared into the method for hollow microsphere.Template is a kind of common method of preparation hollow microsphere, and it at first is at the basis of selected template preparation nuclear (template)/shell (target wall) composite particles, then by the method for physics or chemistry the kernel template is removed, thereby is obtained the target hollow-particle.The key of the method is will prepare to coat complete, uniform particle diameter and disturb the nuclear (template) of particles (such as the secondary particle of spontaneous nucleation etc.)/shell (target wall) composite particles without other.
Three, summary of the invention
Technical problem:
The object of the present invention is to provide a kind of preparation method of eco-friendly cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper.
The present invention adds the water yield with the yield of control polystyrene and titanium dioxide core-shell composite particles by regulating, thereby improve the yield of cerium doping hollow titanium dioxide yellow ultramarine particle, solve the many defectives of secondary particle in present polystyrene and titanium dioxide core-shell composite particles, simultaneously, by introducing Rare-Earth Ce
4+Ion is to give the hollow microsphere yellow nature, the preparation non-toxic pigment, simultaneously since rare earth element painted be the transition of electron that relies in the inner f shell, seldom be subjected to the impact of adjacent ions character, thereby solve the unmanageable defective of transition metal pigment color development effect that contains commonly used.Its technical scheme:
The preparation method of a kind of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper of the present invention may further comprise the steps:
1) be that the alcohol/nitrile mixed solution of 2:1 ~ 4:1 mixes with ammoniacal liquor, distilled water and volume ratio, wherein ammoniacal liquor and distilled water account for respectively 0.33% ~ 0.44% and 0.25% ~ 0.50% of ammoniacal liquor, distilled water and alcohol/nitrile mixed solution three total mass, namely obtain containing the alcohol of ammoniacal liquor and distilled water/nitrile mixed solvent
2) polystyrene microsphere is dispersed in the described mixed solvent, is mixed with mass percent and is 0.02% ~ 0.2% polystyrene dispersion liquid; The preparation mass percent is the ethanol solution of 3% ~ 7% titanic acid ester, under stirring it is splashed in the described polystyrene dispersion liquid, and the quality of the titanic acid ester solution that drips accounts for 15% ~ 18% of titanic acid ester solution and polystyrene dispersion liquid total mass, 20 ~ 35 ℃ of lower reactions 2 ~ 12 hours, centrifugation, the absolute ethanol washing post-drying obtains white spherical polystyrene and titanium dioxide complex particle
3) be to add ceric ammonium nitrate in the dehydrated alcohol of 7:1 and the distilled water mixed solvent in volume ratio, the ceric ammonium nitrate solution of preparation 0.1 ~ 0.2mmol/L, then add 2 times of mol ratios to the citric acid of ceric ammonium nitrate, the rear adding volume that stirs accounts for ethylene glycol or the polyoxyethylene glycol of described ceric ammonium nitrate solution 10% ~ 30%, 20 ℃ ~ 35 ℃ lower reactions obtained transparent yellow cerium colloidal sol in 2 hours
4) with step 2) spherical polystyrene that obtains and titanium dioxide complex particle be immersed in the cerium colloidal sol that step 3) obtains, wherein, the quality of the composite particles that adds accounts for 0.05% ~ 0.1% of composite particles and cerium colloidal sol total mass, stirred 4 ~ 12 hours, 60 ℃ ~ 100 ℃ oven dry, be prepared into the cerium doped titanium dioxide yellow ultramarine microballoon with hollow structure in 2 ~ 6 hours 500 ℃ ~ 600 ℃ roastings at last after the centrifugation.
Surfaces of Polystyrene Microparticles used in the present invention shows electronegativity.
Alcohol used in the present invention/nitrile mixed solvent is dehydrated alcohol/acetonitrile mixed solvent.
Titanic acid ester used in the present invention is isopropyl titanate or tetrabutyl titanate.
Raw material polystyrene used in the present invention, titanic acid ester and doping agent ceric ammonium nitrate all are nontoxic or low toxicity, environmental friendliness.
Beneficial effect:
React according to technique scheme: the starting material toxicological harmless, environmental friendliness, reaction conditions is gentle, and product postprocessing is simple; The yellow hollow pigment microballoon regular shape for preparing, any surface finish, relative density are at 1.4 ~ 2.8g/cm
3Between, median size is at 100 ~ 400nm.
In the present invention, the adding of suitable quantity of water, can effectively be controlled at Surfaces of Polystyrene Microparticles and carry out coated by titanium dioxide: take tetrabutyl titanate as example, an amount of water can promote the hydrolysis of tetrabutyl titanate, produces (the C of capacity
4H
9O)
3TiOH monomer, itself and ammoniacal liquor further act on and produce electronegative (C
4H
9O)
3TiO
-, because the aobvious electronegativity of Surfaces of Polystyrene Microparticles can be impelled the NH in the mixed solvent
4+In a large amount of enrichments in its surface, thereby make electronegative (C
4H
9O)
3TiO
-Cause and NH
4+Interaction and by quick adsorption to Surfaces of Polystyrene Microparticles and at NH
4+Catalysis under the original position condensation, thereby form polystyrene and titanic oxide composite microsphere.
In the present invention, select Rare-Earth Ce
4+Ion doping is to give the hollow microsphere yellow nature.Compare with transition metal such as Cr, Fe, Co, rare earth element is painted to be the transition of electron that relies in the inner f shell, seldom is subjected to the impact of adjacent ions character.Because the yellow nature of prepared hollow microsphere itself when therefore being used for the Electronic Paper demonstration, can not reduce the saturation ratio of its brightness and color.Simultaneously, compare with transition metal such as Cr, Co, the toxicity of Rare-Earth Ce is very little, and prepared yellow ultramarine is environmentally friendly.
In the present invention, select the styrene polymer microballoon to do template, can control by the polystyrene microsphere of selecting different-grain diameter the size of hollow microsphere inner chamber.Simultaneously, can regulate by the consumption of control titanic acid ester the wall thickness of final hollow microsphere.Thereby the yellow hollow microsphere pigment that can prepare the different size requirement is to satisfy the demand of Electronic Paper industry.
Four, description of drawings
Fig. 1 is the transmission electron microscope picture of the product that made by the present invention;
Fig. 2 is the wide-angle X-ray diffraction curve of the product that made by the present invention;
Fig. 3 is the UV-Vis DRS spectrogram of the product that made by the present invention;
Fig. 4 is polystyrene and the titanium dioxide complex particle that is made by the present invention;
Fig. 5 is polystyrene and the titanium dioxide complex particle for preparing when not adding distilled water in the preparation process;
Fig. 6 adds in the preparation process to account for polystyrene and the titanium dioxide complex particle for preparing when the mixed solvent mass percent is 0.70% distilled water.
Five, embodiment
Embodiment 1
A kind of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper, this pigment particle size are 100nm, 200nm, 300nm, 400nm, and relative density is 1.4g/cm
3, 1.6g/cm
3, 2.2g/cm
3, 2.8g/cm
3, its preparation method is take the styrene polymer microballoon as template, prepares polystyrene and titanium dioxide complex particle at its outer Hydrolysis of Titanium acid esters.The submergence in cerium colloidal sol of this composite particles was stirred 4 ~ 12 hours, and centrifugation is by oven dry, and roasting is prepared from.
Embodiment 2
A kind of preparation method of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper may further comprise the steps:
1) be that the alcohol/nitrile mixed solution of 2:1,3:1 or 4:1 mixes with ammoniacal liquor, distilled water and volume ratio, wherein ammoniacal liquor and distilled water account for respectively 0.33% or 0.44% and 0.25%, 0.30% or 0.50% of ammoniacal liquor, distilled water and alcohol/nitrile mixed solution three total mass, namely obtain containing the alcohol of ammoniacal liquor and distilled water/nitrile mixed solvent
2) the styrene polymer microballoon is dispersed in the described mixed solvent, is mixed with mass percent and is 0.02%, 0.05%, 0.10%, 0.15% or 0.2% polystyrene dispersion liquid; The preparation mass percent is the ethanol solution of 3%, 5% or 7% titanic acid ester, under stirring it is splashed in the described polystyrene dispersion liquid, and the quality of the titanic acid ester solution that drips accounts for 15%, 16%, 17% or 18% of titanic acid ester solution and polystyrene dispersion liquid total mass, 20 ℃, 25 ℃, 30 ℃ or 35 ℃ of lower reactions 2,6,10 or 12 hours, centrifugation, the absolute ethanol washing post-drying obtains white spherical polystyrene and titanium dioxide complex particle
3) be to add ceric ammonium nitrate in the dehydrated alcohol of 7:1 and the distilled water mixed solvent in volume ratio, the ceric ammonium nitrate solution of preparation 0.1mmol/L, 0.15mmol/L or 0.2mmol/L, then add 2 times of mol ratios to the citric acid of ceric ammonium nitrate, the rear adding volume that stirs accounts for described ceric ammonium nitrate solution 10%, 20% or 30% ethylene glycol or polyoxyethylene glycol, reaction obtained transparent yellow cerium colloidal sol in 2 hours under 20 ℃, 25 ℃, 30 ℃ or 35 ℃
4) with step 2) spherical polystyrene that obtains and titanium dioxide complex particle be immersed in the cerium colloidal sol that step 3) obtains, wherein, the quality of the composite particles that adds accounts for 0.05%, 0.08% or 0.1% of composite particles and cerium colloidal sol total mass, stirred 4,8 or 12 hours, after the centrifugation 60 ℃, 80 ℃ or 100 ℃ of oven dry, at last 500 ℃ or 600 ℃ of roastings 2, be prepared into the cerium doped titanium dioxide yellow ultramarine microballoon with hollow structure in 4 or 6 hours.
In the present embodiment,
Employed Surfaces of Polystyrene Microparticles shows electronegativity.
Employed alcohol/nitrile mixed solvent is dehydrated alcohol/acetonitrile mixed solvent.
Employed titanic acid ester is isopropyl titanate or tetrabutyl titanate.
Comparative Examples 1
Adopt to prepare cerium doped titanium dioxide hollow nanospheres yellow ultramarine with above-described embodiment 2 identical methods, difference is not add distilled water in the reaction.Measurement result is shown in Fig. 5.
Comparative Examples 2
Adopt to prepare cerium doped titanium dioxide hollow nanospheres yellow ultramarine with above-described embodiment 2 identical methods, difference has added in being to react that to account for the mixed solvent mass percent be 0.70% distilled water.Measurement result is shown in Fig. 6.
With reference to Fig. 1, the analysis showed that product of the present invention according to the transmission electron microscope picture, its edge is obviously different with the contrast that the center shows in the transmission electron microscope picture, and the color of edge is darker, and the center color is more shallow, proves that product has hollow structure.
With reference to Fig. 2, show that according to the wide-angle x-ray diffraction analysis product of the present invention has the crystallization phases of titanium dioxide and cerium dioxide, prove that product is the titanium dioxide hollow microballoon that cerium mixes.
With reference to Fig. 3, spectroscopic analysis shows that product of the present invention has strong reflection to the visible light more than the 580nm according to UV-Vis DRS, proves that product can be used as yellow ultramarine.
With reference to Fig. 4, the analysis showed that by the present invention according to the transmission electron microscope picture to prepare in the process of polystyrene and titanium dioxide complex particle that the adding of suitable quantity of water can promote the hydrolysis of tetrabutyl titanate, thereby produce more (C
4H
9O)
3TiOH monomer, itself and ammoniacal liquor further act on and produce electronegative (C
4H
9O)
3TiO
-, because Surfaces of Polystyrene Microparticles NH
4+A large amount of enrichments, electronegative (C
4H
9O)
3TiO
-By quick adsorption to Surfaces of Polystyrene Microparticles and at NH
4+Catalysis under the original position condensation, show polystyrene and the titanic oxide composite microsphere that coats evenly, do not have secondary TiO 2 particles thereby form.
Contrast Fig. 5 and Fig. 6, the analysis showed that in the preparation process of polystyrene and titanium dioxide complex particle according to the transmission electron microscope picture, if except adding ammoniacal liquor, no longer add distilled water, then tetrabutyl titanate can't effectively be hydrolyzed, and can not form the coated by titanium dioxide layer of significant effective at the outside surface of polystyrene moulding; Add too much distilled water and then can significantly reduce (C
4H
9O)
3The solubleness of TiOH monomer, this just means that the nucleation rate of secondary TiO 2 particles improves greatly in the system, thereby affects prepared polystyrene and the yield of titanium dioxide complex particle.
Claims (4)
1. the preparation method of a cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper is characterized in that it may further comprise the steps:
1) be that the alcohol/nitrile mixed solution of 2:1 ~ 4:1 mixes with ammoniacal liquor, distilled water and volume ratio, wherein ammoniacal liquor and distilled water account for respectively 0.33% ~ 0.44% and 0.25% ~ 0.50% of ammoniacal liquor, distilled water and alcohol/nitrile mixed solution three total mass, namely obtain containing the alcohol of ammoniacal liquor and distilled water/nitrile mixed solvent, employed alcohol/nitrile mixed solvent is dehydrated alcohol/acetonitrile mixed solvent
2) polystyrene microsphere is dispersed in the described mixed solvent, is mixed with mass percent and is 0.02% ~ 0.2% polystyrene dispersion liquid; The preparation mass percent is the ethanol solution of 3% ~ 7% titanic acid ester, under stirring it is splashed in the described polystyrene dispersion liquid, and the quality of the titanic acid ester solution that drips accounts for 15% ~ 18% of titanic acid ester solution and polystyrene dispersion liquid total mass, 20 ~ 35 ℃ of lower reactions 2 ~ 12 hours, centrifugation, the absolute ethanol washing post-drying obtains white spherical polystyrene and titanium dioxide complex particle
3) be to add ceric ammonium nitrate in the dehydrated alcohol of 7:1 and the distilled water mixed solvent in volume ratio, the ceric ammonium nitrate solution of preparation 0.1 ~ 0.2mmol/L, then add 2 times of mol ratios to the citric acid of ceric ammonium nitrate, the rear adding volume that stirs accounts for ethylene glycol or the polyoxyethylene glycol of described ceric ammonium nitrate solution 10% ~ 30%, 20 ℃ ~ 35 ℃ lower reactions obtained transparent yellow cerium colloidal sol in 2 hours
4) with 2) spherical polystyrene and the titanium dioxide complex particle that obtain be immersed in 3) in the cerium colloidal sol that obtains, wherein, the quality of the composite particles that adds accounts for 0.05% ~ 0.1% of composite particles and cerium colloidal sol total mass, stirred 4 ~ 12 hours, 60 ℃ ~ 100 ℃ oven dry, be prepared into the cerium doped titanium dioxide yellow ultramarine microballoon with hollow structure in 2 ~ 6 hours 500 ℃ ~ 600 ℃ roastings at last after the centrifugation.
2. the preparation method of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper according to claim 1 is characterized in that employed Surfaces of Polystyrene Microparticles shows electronegativity.
3. the preparation method of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper according to claim 1 is characterized in that employed titanic acid ester is isopropyl titanate or tetrabutyl titanate.
4. the preparation method of cerium-doped hollow nano titanium dioxide yellow pigment for electronic paper according to claim 1 is characterized in that employed raw material polystyrene, titanic acid ester and doping agent ceric ammonium nitrate all are nontoxic or low toxicity, environmental friendliness.
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| CN103613958B (en) * | 2013-11-29 | 2015-01-21 | 深圳清华大学研究院 | Environment-friendly titanium pigment prepared by using complexation-precipitation process |
| CN105086518A (en) * | 2015-07-27 | 2015-11-25 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing bamboo charcoal powder and preparation method thereof |
| CN105111794A (en) * | 2015-07-27 | 2015-12-02 | 安徽明珠颜料科技有限公司 | Black iron oxide pigment containing tourmalinite powder and preparation method thereof |
| CN106082317B (en) * | 2016-05-31 | 2017-12-12 | 陕西科技大学 | A kind of preparation method of hollow hemisphere titanium dioxide |
Citations (1)
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| CN101210120A (en) * | 2007-12-25 | 2008-07-02 | 天津大学 | Hollow titanium dioxide white electrophoresis ion for electrophoresis displaying and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210120A (en) * | 2007-12-25 | 2008-07-02 | 天津大学 | Hollow titanium dioxide white electrophoresis ion for electrophoresis displaying and preparing method thereof |
Non-Patent Citations (4)
| Title |
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| Facile preparation of titania hollow spheres by combination of the mixed solvent method and the sol-gel process and post-calcination;Xin Du et al;《Materials Research Bulletin》;20090124;第44卷;1238-1243 * |
| Hollow titania spheres with movable silica spheres inside;Kai Zhang et al;《Langmuir》;20041112;第20卷;11312-11314 * |
| Kai Zhang et al.Hollow titania spheres with movable silica spheres inside.《Langmuir》.2004,第20卷11312-11314. |
| Xin Du et al.Facile preparation of titania hollow spheres by combination of the mixed solvent method and the sol-gel process and post-calcination.《Materials Research Bulletin》.2009,第44卷1238-1243. |
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