CN101434410A - Preparations of nano titanium dioxide particles and titania slurry - Google Patents
Preparations of nano titanium dioxide particles and titania slurry Download PDFInfo
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- CN101434410A CN101434410A CNA2008102327277A CN200810232727A CN101434410A CN 101434410 A CN101434410 A CN 101434410A CN A2008102327277 A CNA2008102327277 A CN A2008102327277A CN 200810232727 A CN200810232727 A CN 200810232727A CN 101434410 A CN101434410 A CN 101434410A
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Abstract
The invention relates to a nano titanium dioxide material, in particular to a preparation method of a nano titanium dioxide particle and titanium dioxide slurry. The preparation method of the nano titanium dioxide particle is characterized by including the following steps: a. slowly adding acetic acid with the volume concentration of 5-8mol/L into tetrabutyl titanate with 3-8 times of volume, fully stirring for 15 minutes to 1 hour, then adding the mixture into de-ionized water with 20-30 times of volume, and then adding an alkaline solution to regulate the PH value to be 12-14; and b. putting a precursor mixture prepared in the step a into an autoclave with a polytetrafluoro lining under the condition that the compactness is 45-70 percent, reacting for 10-24 hours at 100-135 DEG C, and washing the reactant with absolute ethyl alcohol and the de-ionized water. The preparation method realizes synthesis and coating in one step by synchronously synthesizing and organically coating the nano titanium dioxide, thereby providing a new method for confecting the titanium dioxide slurry with no agglomeration and delamination and good dispersivity and stability.
Description
Technical field
The present invention relates to nanometer titanic oxide material, the preparation method of especially a kind of titanium dioxide nanoparticle and titania slurry.
Background technology
Nano titanium oxide is because of characteristics such as its good magnetic, catalytic, photoabsorption, electricity are led, hardness and fusing points, and is widely used in each field such as solar cell, photocatalytic degradation and coating, daily cosmetics, received people's very big concern.Nano titanium oxide in use, usually need mix with some solvent phase, as mix resin, Mierocrystalline cellulose or water etc. and form slurries, therefore can particle reach maximum infiltration with solvent, thereby the slurry that disperses, forms stable performance well is to weigh the major criterion whether this nano material is convenient to practical application.But because little, specific surface area of Nano titanium dioxide particle diameter and surface energy are all very big, and coordination wretched insufficiency, show extremely strong surface polarity, make powder in water, reunite easily, in organic solvent, also be difficult for disperseing, this has just limited giving full play to of nano titanium oxide advantage greatly, therefore study nano-titanium dioxide powder dispersion, stability, to prevent to reunite be the prerequisite and the basis of further improving its application performance.
In recent years, when the nano titanium oxide synthesis technique constantly makes progress, the surface treatment of nano titanium oxide also has been subjected to certain research, mainly be surface polarity, the tension force that reduces titanium dioxide by the mode of certain compound in the coating of nano titanium oxide surface, absorption or adding tensio-active agent, improve its dispersiveness.But very big shortcoming of this method is exactly it is nano-TiO to preparing
2The aftertreatment of powder is that prepared powder is carried out aftertreatment, in fact nano-TiO
2Reunion has more or less all taken place in particle before coating, think to realize on this basis the dispersion fully between single particle and coat to be difficult to.
Summary of the invention
One of purpose of the present invention provides a kind of preparation method of titanium dioxide nanoparticle, adopt titanium dioxide nanoparticle that this method makes when being mixed into organic solvent, organic carrier, titanium dioxide nanoparticle can well disperse, and keeps secular stability.
Another object of the present invention provides a kind of preparation method of titania slurry, and this slurry do not reunite, not stratified, dispersed, good stability.
A kind of preparation method of titanium dioxide nanoparticle, its special feature is, comprises the steps:
In a, the tetrabutyl titanate with 3-8 times of volumes of the slow adding of the acetic acid of 1 volumetric concentration 5-8mol/L, fully stir after 15 minutes-1 hour and add in the deionized water of 20-30 times of volumes, violent stirring is 1-1.5 hours while dripping, add strong base solution then and regulate pH value to 12-14, and, form the presoma mixed solution of hydro-thermal reaction 60-80 ℃ of lasting insulated and stirred 0.5-1 hour;
B, the presoma mixed solution of step a preparation put into the autoclave of poly-tetrafluoro liner, compactedness is 45-70%, 100-135 ℃ is reacted 10-24h, reactant is washed respectively repeatedly with dehydrated alcohol and deionized water promptly get white titanium dioxide granule 3-5 time.
Acetic acid among the step a: tetrabutyl titanate: water volume ratio 1:5:20, acetate concentration 6mol/L.
Stir among the step a to divide and carry out for three times, be stirring at room acetic acid and tetrabutyl titanate 15min-1h for the first time, be violent stirring acetic acid, tetrabutyl titanate, water and strong base solution mixed system 1-1.5h for the second time, be 60-80 ℃ of insulated and stirred 30min-1h behind the adding strong base solution for the third time, carry out the ageing of pausing of 15-30min then, generate the presoma mixed solution of hydro-thermal reaction.
Strong base solution is the aqueous solution of NaOH or KOH among the step a, and the concentration of strong alkali aqueous solution is 10-20mol/L.
A kind of preparation method of titania slurry, its special feature is, comprises the steps:
A, be that constant temperature stirs 1-2h again in the organic solvent that at the uniform velocity stirs under 1:7-9 slowly adds 60-80 ℃ by mass ratio, form evenly, have the organic carrier of certain extensional viscosity ethyl cellulose;
B, with any titanium dioxide granule that makes in the claim 1 to 4, the mass ratio of pressing 1:3-1:5 adds in the organic carrier of step a preparation, even with the abundant agitation grinding of stirrer, agate mortar or ball mill, promptly form required titania slurry.
Organic solvent is higher pure lipid or an arene of boiling point among the step b.
Wherein organic solvent is Terpineol 350 or glycol ether dibenzoic acid fat.
The present invention is based on hydro-thermal reaction, in reaction process, the coupling agent tetrabutyl titanate is in hydrolysis, again with the hydroxyl reaction on the titanium dioxide nanoparticle surface that generates, 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 with the high-energy polymer monomer, adding Terpineol 350 and ethyl cellulose again forms in the process of slurry, the good complexing of the hydroxyl on esters monomer and nano titanium oxide surface, thus the layer of even polymeric film formed on the nano titanium oxide surface.Therefore when being mixed into organic solvent, organic carrier, titanium dioxide nanoparticle can well disperse, and keeps secular stability.
The present invention with the surface treatment of nano titanium oxide be blended in the hydro-thermal of nano titanium oxide synthetic in, the synthetic of nano titanium oxide carried out synchronously with organic coating, one step realized synthetic and had coated, and pass through the outfit of oiliness slurry and place experiment, the nano-titanium dioxide powder of a kind of preparation, processing is provided, preparation do not reunite, the novel method of the titania slurry of not stratified, dispersed, good stability.
Description of drawings
Fig. 1 is the stereoscan photograph of the prepared nano titanium oxide of the embodiment of the invention 1.
Fig. 2 is that the slurry of the embodiment of the invention 1 configuration is placed after 0 day the TiO that coating sintering obtains
2Film scanning electron microscope picture;
Fig. 3 is that the slurry of the embodiment of the invention 1 configuration is placed after 15 days the TiO behind the coating sintering
2Film scanning electron microscope picture;
Fig. 4 is that the slurry of the embodiment of the invention 1 configuration is placed after 30 days the TiO behind the coating sintering
2Film scanning electron microscope picture.
Embodiment
The preparation method of titanium dioxide nanoparticle of the present invention and titania slurry is as follows:
Embodiment 1:
(1) configuration of presoma
Under the room temperature, acetic acid (concentration 6mol/L) is slowly added in the tetrabutyl titanate, acetic acid and tetrabutyl titanate volume ratio are 1:5, and the limit edged stirs, and add the back that finishes and continue to stir 15min.Under the violent stirring of 600r/min, said mixture is added then in the deionized water of 20 volumes, i.e. acetic acid: tetrabutyl titanate: water volume ratio=1:5:20.Continue to stir the mixture solution 1h that this adularescent precipitation generates, so that its hydrolysis reaction carries out fully.To the KOH solution that wherein adds 1/2-1 volume 10mol/L, regulate ph value of mixture to 13 behind the 1h, simultaneously this mixture is warmed up to 80 ℃ and be incubated 1h in whipping process, form the presoma mixed solution of hydro-thermal reaction.
(2) hydro-thermal of nano titanium oxide is synthetic
Forerunner's mixed solution of step (1) preparation is put into the autoclave that gathers the tetrafluoro liner, and compactedness is 68%, 110 ℃ of constant temperature 12h, and reactant is washed the titanium dioxide drying for standby that had both obtained white for 3 times respectively repeatedly with dehydrated alcohol and deionized water.
(3) configuration of the organic carrier of titania slurry
Under 60 ℃ of heating in water bath stir, ethyl cellulose (EC7) is slowly added in the Terpineol 350 ethyl cellulose: Terpineol 350 mass ratio 1:8, mix and stir 2h, form the organic carrier of the about 5.9cP of viscosity.
(4) preparation of titania slurry
TiO with step (2) preparation
2Powder, the mass ratio of pressing 1:3 adds in the organic carrier of step (3) preparation, after stirring with planetary ball mill, fully grinds evenly with mortar or three-high mill again, promptly forms required titania slurry.
By the prepared titanium dioxide nanoparticle of the foregoing description dispersiveness, crystallization shape and uniform particles degree preferably, particle diameter 15-20nm (Fig. 1) are arranged.Pressed by this titanium dioxide nanoparticle in the titania slurry of embodiment preparation, nano titanium oxide is uniformly dispersed, the long period (15-30 days) place do not reunite, not stratified, this slurry was placed after 0,15,30 day, the TiO that coating sintering forms
2The surface topography of film is shown in Fig. 2,3,4.
Embodiment 2:
(1) configuration of presoma
Under the room temperature, with Glacial acetic acid (density: 1.0492g/cm
3) slowly add tetrabutyl titanate (density: 0.996g/cm
3) in, acetic acid and tetrabutyl titanate volume ratio are 1:8, the limit edged stirs, and adds the back that finishes and continues to stir 30min.Under the violent stirring of 800r/min, said mixture is added then in the deionized water of 30 volumes, i.e. Glacial acetic acid: tetrabutyl titanate: water volume ratio=1:8:30.Continue to stir the mixture solution 1h that this adularescent precipitation generates, so that its hydrolysis reaction carries out fully.To the NaOH solution that wherein adds 1/3-1/2 volume 20mol/L, regulate ph value of mixture to 14 behind the 1h, simultaneously this mixture is warmed up to 60 ℃ in whipping process, and insulation 1.5h, the presoma mixed solution of formation hydro-thermal reaction.
(2) hydro-thermal of nano titanium oxide is synthetic
Forerunner's mixed solution of step (1) preparation is put into the autoclave that gathers the tetrafluoro liner, and compactedness is 45%, 135 ℃ of constant temperature 24h, and reactant is washed the titanium dioxide that had both obtained white for 3 times repeatedly with dehydrated alcohol and deionized water.Drying for standby.
(3) configuration of the organic carrier of titania slurry
Ethyl cellulose (EC7) is pressed in the glycol ether dibenzoic acid fat that mass ratio 1:9 at the uniform velocity stirs under slowly adding 80 ℃, and constant temperature stirs 1.5h, forms the organic carrier system of viscosity about 6.2.
(4) preparation of titania slurry
TiO with step (2) preparation
2Powder is put into agate mortar, splashes into the glycol ether dibenzoic acid fat of minute quantity (about 0.5-1g), grinds and makes TiO earlier twice
2Powder disperses at glycol ether dibenzoic acid fat; Press organic carrier system then: nano-TiO
2The mass ratio of powder 4:1 joins organic carrier system in the said mixture mucus, continues to grind evenly with agate mortar, promptly forms required titania slurry after placing away bubble.
Claims (7)
1, a kind of preparation method of titanium dioxide nanoparticle is characterized in that, comprises the steps:
In a, the tetrabutyl titanate with 3-8 times of volumes of the slow adding of the acetic acid of 1 volumetric concentration 5-8mol/L, fully stir after 15 minutes-1 hour and add in the deionized water of 20-30 times of volumes, violent stirring is 1-1.5 hours while dripping, add strong base solution then and regulate pH value to 12-14, and, form the presoma mixed solution of hydro-thermal reaction 60-80 ℃ of lasting insulated and stirred 0.5-1 hour;
B, the presoma mixed solution of step a preparation put into the autoclave of poly-tetrafluoro liner, compactedness is 45-70%, 100-135 ℃ is reacted 10-24h, reactant is washed respectively repeatedly with dehydrated alcohol and deionized water promptly get white titanium dioxide granule 3-5 time.
2, the preparation method of a kind of titanium dioxide nanoparticle as claimed in claim 1 is characterized in that:
Acetic acid among the step a: tetrabutyl titanate: water volume ratio 1:5:20, acetate concentration 6mol/L.
3, the preparation method of a kind of titanium dioxide nanoparticle as claimed in claim 1 is characterized in that:
Stir among the step a to divide and carry out for three times, be stirring at room acetic acid and tetrabutyl titanate 15min-1h for the first time, be violent stirring acetic acid, tetrabutyl titanate, water and strong base solution mixed system 1-1.5h for the second time, be 60-80 ℃ of insulated and stirred 30min-1h behind the adding strong base solution for the third time, carry out the ageing of pausing of 15-30min then, generate the presoma mixed solution of hydro-thermal reaction.
4, the preparation method of a kind of titanium dioxide nanoparticle as claimed in claim 1 is characterized in that:
Strong base solution is the aqueous solution of NaOH or KOH among the step a, and the concentration of strong alkali aqueous solution is 10-20mol/L.
5, a kind of preparation method of titania slurry is characterized in that, comprises the steps:
A, be that constant temperature stirs 1-2h again in the organic solvent that at the uniform velocity stirs under 1:7-9 slowly adds 60-80 ℃ by mass ratio, form evenly, have the organic carrier of certain extensional viscosity ethyl cellulose;
B, with any titanium dioxide granule that makes in the claim 1 to 4, the mass ratio of pressing 1:3-1:5 adds in the organic carrier of step a preparation, even with the abundant agitation grinding of stirrer, agate mortar or ball mill, promptly form required titania slurry.
6, the preparation method of a kind of titania slurry as claimed in claim 5 is characterized in that: organic solvent is higher pure lipid or an arene of boiling point among the step b.
7, the preparation method of a kind of titania slurry as claimed in claim 6 is characterized in that: wherein organic solvent is Terpineol 350 or glycol ether dibenzoic acid fat.
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