CN109678379A

CN109678379A - A kind of modifying titanium dioxide and preparation method thereof

Info

Publication number: CN109678379A
Application number: CN201710971778.0A
Authority: CN
Inventors: 封丽娟
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-10-18
Filing date: 2017-10-18
Publication date: 2019-04-26
Anticipated expiration: 2037-10-18
Also published as: CN109678379B

Abstract

The present invention provides a kind of modifying titanium dioxide and preparation method thereof applied in mortar, and the preparation method includes the following steps: that (1) pre-processes commercial silica titanium material；(2) TiO that step (1) is obtained₂Carry out pore-creating processing；(3) by step (2) by one layer of TiO of silica kernel external sheath₂；(4) step (3) are obtained into TiO₂One layer of Cr of external sheath₂O₃；(5) one layer of TiO of titanium dioxide external sheath that step (4) obtains₂.The features such as finished titanium dioxide prepared by the present invention has mechanical strength good, and photocatalysis is energetic, it is contaminated applied to can effectively prevent its coating in mortar.

Description

A kind of modifying titanium dioxide and preparation method thereof

Technical field:

The invention belongs to commercial silica titanium fields, and in particular to a kind of titanium dioxide in lime mortar.

Background technique:

Titanium dioxide is considered as a kind of white pigment that performance is best in the world, covering power with higher, weatherability, Reducing power etc. is widely used in coating, plastics, papermaking, printing ink, chemical fibre, rubber, ceramics, cosmetics, food and medicine etc. Fine Chemical.

In the research of forefathers, discovery titanium dioxide has very strong photocatalysis performance, such as purifies air, processing waste water etc. (nano-TiO₂Preparation and Photocatalytic Performance Study, Li Yidong etc.).And works as titanium dioxide and be applied to coating, or as food and medicine When equal additives, very strong photocatalytic activity again can have an adverse effect to the performance of product, need to carry out titanium dioxide Coating to avoid product aging (orthogonal experiment optimize ZrO₂Coat titanium dioxide technical study, Duan Haiting etc.).Therefore, how very The good photocatalytic activity using titanium dioxide becomes a critically important research topic of this field.

Titanium dioxide has the function of reinforced mortar whiteness, is widely used in industry as the additive in a kind of mortar In production.CN105565736A, which discloses one kind, has anti-ultraviolet function mortar, the nano-titanium dioxide added in mortar The self-cleaning performance of product can be improved.But self-cleaning performance how is further increased, while guaranteeing the white of titanium dioxide again Degree, is the difficult point in correlative study.

Summary of the invention:

In view of this, proposing the present invention.

The present invention provides a kind of modifying titanium dioxide, and the titanium dioxide includes four layers, which is characterized in that the modification two Titanium oxide kernel is silica (SiO₂), the second layer is titanium dioxide (TiO₂), third layer is chrome green (Cr₂O₃), most Outer layer is titanium dioxide (TiO₂)。

In the modifying titanium dioxide, SiO₂Content is 10-30%, Cr₂O₃Content is 5-20%, TiO₂Content is 50- 85%.

The modifying titanium dioxide is applied in mortar, and the mortar is lime mortar, in cement mortar, mixed mortar One or more.

The present invention provides a kind of preparation method of above-mentioned modifying titanium dioxide, and the preparation method includes the following steps: (1) Commercial silica titanium material is pre-processed；(2) TiO that step (1) is obtained₂Carry out pore-creating processing；(3) by silica One layer of TiO of kernel external sheath₂；(4) step (3) are obtained into TiO₂One layer of external sheath contains Cr₂O₃Outer layer；(5) in step (4) one layer of titanium dioxide external sheath obtained contains TiO₂Outer layer.

Preferably, in step (3), the TiO of external sheath₂For the TiO obtained in step (2)₂。

Preferably, in step (5), the TiO of external sheath₂For the TiO obtained in step (2)₂。

Preferably, in step (4), contain Cr₂O₃Outer layer in, Cr₂O₃Content be 100%.

Preferably, in step (5), contain TiO₂Outer layer in, TiO₂Content be 100%.

In the step (4), contain Cr₂O₃Outer layer can also be by Cr₂O₃And TiO₂It forms, wherein Cr₂O₃Content is 60- 90%.TiO₂The TiO preferably obtained in step (2)₂。

In the step (5), contain TiO₂Outer layer can also be by Cr₂O₃And TiO₂It forms, wherein TiO₂Content is 60- 90%.TiO₂The TiO preferably obtained in step (2)₂。

It is pretreated to be preferably a step in the step (1): commercial silica titanium material and deionized water are put into removing In the hollander tub of miscellaneous device, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 2-4:6-8, preferably 3:7；Agitating device forms slurry after being stirred mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration Filter, titanium dioxide, which is filtered, to be extracted；Ammonium hydroxide is added in the titanium dioxide extracted, adjusts the pH to 1.0-2.0 of solution, this When dithiocarbamate salt derivative solution is constantly added dropwise into reactor, until do not generate solid suspension stopping, after Titanium dioxide is extracted in continuous stirring 15-25min, filtering；Titanium dioxide by filtering extract after be washed with water, after washing using Ultrasonic vibration filtering, then be dried into drying device, obtain the titanium dioxide of low impurity content.

Preferably, dithiocarbamate salt derivative is dimethyl disulfide for amine sodium formate, diethyl-dithio amine The one or more of sodium formate, dibutyl dithio amine sodium formate, the thio amine sodium formate of ethylphenyl two.

The preparation step (2) are as follows: titanium dioxide and pore creating material that step (1) obtains are ground to granularity first by a. respectively For 50 μm hereinafter, being then uniformly mixed the titanium dioxide obtained after grinding with pore creating material powder, under 100-250MPa pressure Compression moulding；B. the material through step a compression moulding is warming up to 600-1100 DEG C of sintering 3h- with 5-10 DEG C/min heating rate 6h is prepared removal pore creating material and obtains porous titanium precursors；C. by the porous titanium precursors obtained through step b according to calcium and two Calcium metal is added in titanium oxide mass ratio >=2:1, is then less than or equal to 5Pa, heating rate 5- being evacuated to furnace pressure 10 DEG C/min, reduction temperature be 1000-1100 DEG C of progresss calciothermic reduction -60h for 24 hours, after cooling, take out reduzate, will and also It originates in object to leach using dilute hydrochloric acid, is washed after the completion of leaching with distilled water and dehydrated alcohol, porous two are obtained after vacuum dried Titanium oxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.

Preferably, the pore creating material is ammonium hydrogen carbonate, high purity graphite or starch, and pore creating material additional amount is titanium dioxide quality 3%-15%.

Preferably, in a step, the compression moulding under 200MPa pressure.

Preferably, in b step, the material through step a compression moulding is warming up to 800 DEG C of burnings with 6 DEG C/min heating rate Knot 4h is prepared removal pore creating material and obtains porous titanium precursors.

Preferably, in step c, calcium and titanium dioxide mass ratio are 5:1.

Preferably, in step c, being evacuated to furnace pressure is 2Pa.

The preparation step (3) are as follows: a. takes the SiO of parts by weight 0.05-0.1₂, under ultrasound condition, it is suspended in parts by weight In the ethyl alcohol of 5-15；B. 90% hexadecylamine (HDA) and 0.1-0.4 of 0.05-0.1 parts by weight are added into above-mentioned solution The ammonium hydroxide of parts by weight is stirred at room temperature 0.5-5 minutes；C. under agitation, parts by weight 0.1-1.0 is added into step b Tetraisopropyl titanate (TIP), react 5-20 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；It e. will be above-mentioned It is deposited at 450 DEG C calcination 1-4 hours, then with 10% hydrofluoric acid wash, acquisition kernel is SiO₂TiO₂Particle.

The preparation step (4) are as follows: the TiO that a. will be obtained in step (3)₂Particle is scattered in ethyl alcohol, is ultrasonically treated 10- 15min, by every g TiO₂Organo-chromium compound is added in the ratio that particle corresponds to 0.02-1mmol, forms suspension；B. the amount of taking fully Water, adjust the suspension that obtains into 4-6, with a of pH and be heated separately to 80-95 DEG C, the two is added in blender simultaneously, Reaction is hydrolyzed；C.10-30min end of reaction after collects precipitating, and calcination 1 hour, is coated at 450-750 DEG C Cr₂O₃TiO₂Particle.

Supersonic frequency is 30-80KHz.

PH adjusting agent is preferably HCl.

The organo-chromium compound is Cr (OMe)₃、Cr(OEt)₃、Cr(O·n-Pr)₃、Cr(O·n-Bu)₃One kind or It is several, preferably Cr (O-i-H₃C₇)₃Or Cr₃O(O₂CCH₃)·7H₂O。

The preparation step (5) are as follows: the titanium dioxide that a. will be obtained in step (4) takes 1-10 parts by weight, takes step (2) Middle acquisition titanium dioxide 5-20 parts by weight, are scattered in enough decamethylcyclopentaandoxanes (DMCPSI), add 1-5 weight The OctMet (OPMC) of part is uniformly mixed, obtains suspending liquid A；B. by suspending liquid A pressing and wrapping；C. to pressure Suspending liquid A after system heats -3 hours 10 minutes at 60-120 DEG C, DMCPSI is made to volatilize.

Preferably, it in the step b, is suppressed using the homemade coating equipment of the application, structure such as specification is attached Fig. 1, shown in 2.Suspending liquid A is placed on plate first, under the driving of linear motor, spreader at the uniform velocity suspending liquid A is equal Even paving is dispersed on plate, and coating speed is 1.0 × 10^-2M/s is between 1m/s.Suspending liquid A is suppressed while coating Cladding, pressure adjust the temperature to 30-40 DEG C between 10Pa-1000Pa.After cladding, 60-70 DEG C is adjusted the temperature to, is dried Dry 10-30min.

The photocatalytic activity that the present invention attempts to improve titanium dioxide prevents mortar coating quilt so that it is applied after mortar Pollution, is especially polluted by soot pollutant.It is well known that titanium dioxide has very strong light absorption energy in UV light region Power, while also having very strong photocatalytic activity, the present invention attempts by way of by titanium dioxide external sheath metal oxide, The wavelength section of its light absorption is improved, so as to improve its photocatalytic activity.However it is aoxidized in titanium dioxide external sheath metal After object, whiteness is inevitably affected again, therefore again in metal oxide outer layer cladding titanium dioxide in the present invention Method studied, explore it is a kind of neither reduce whiteness, and the preparation method of photocatalytic activity can be enhanced.

The present invention is found surprisingly that, when outermost layer coats certain thickness titanium dioxide, can not only improve finished product Whiteness, or even the photocatalytic activity of product can be further increased.

Advantageous effect of the invention are as follows:

1. having silica kernel using titanium dioxide internal layer prepared by preparation method of the present invention, so that entire powder machinery Performance is more preferable.

2. being coated with chrome green using titanium dioxide internal layer prepared by preparation method of the present invention, titanium dioxide is increased The light absorpting ability of powder.

3. making final products have good whiteness, not using the outer layer titanium dioxide of preparation method of the present invention cladding It will affect the light absorpting ability of titanium dioxide powder.

Detailed description of the invention:

In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with It obtains other drawings based on these drawings.

Fig. 1 is the front view of coating equipment of the present invention

Fig. 2 is the side view of coating equipment of the present invention

Description of symbols

1, linear motor driver；11, linking arm；12, glass board support；13, shifting chute；2, glass plate；3, it is coated with Device；31, gap；32, it is coated with roller bearing；4, heating plate；5, suspension.

Description of symbols through the above attached drawings can be more clearly understood and illustrate this hair in conjunction with the embodiment of the present invention Bright technical solution.

Specific embodiment

Example embodiments are described in detail here, and the example is illustrated in the accompanying drawings.Following description is related to When attached drawing, unless otherwise indicated, the same numbers in different drawings indicate the same or similar elements.Following exemplary embodiment Described in embodiment do not represent all embodiments consistented with the present invention.On the contrary, they be only with it is such as appended The example of device and method being described in detail in claims, some aspects of the invention are consistent.

It is only to be not intended to limit the invention merely for for the purpose of describing particular embodiments in terminology used in the present invention. It is also intended in the present invention and the "an" of singular used in the attached claims, " described " and "the" including majority Form, unless the context clearly indicates other meaning.It is also understood that term "and/or" used herein refers to and wraps It may be combined containing one or more associated any or all of project listed.

It will be appreciated that though various information, but this may be described using term first, second, third, etc. in the present invention A little information should not necessarily be limited by these terms.These terms are only used to for same type of information being distinguished from each other out.For example, not departing from In the case where the scope of the invention, the first information can also be referred to as the second information, and similarly, the second information can also be referred to as One information.Depending on context, word as used in this " if " can be construed to " ... when " or " when ... When " or " in response to determination ".

The present invention will be described in detail by way of examples below.

Experimental example 1

The method of coated by titanium dioxide chromium is probed into this experimental example.

Chromium method for coating commonly used in the art is as follows: 9:1 weighs TiO in mass ratio₂And Cr₂O₃, the two is mixed, is added Enter into planetary ball mill ball-milling reaction 4h, after drying 12h, powder is taken out, is placed in Muffle furnace, is kept the temperature at 1000 DEG C 70h is to get being coated with Cr₂O₃TiO₂.By this method parallel laboratory test 5 times.

In this experiment, using following steps to TiO₂Carry out Cr₂O₃Cladding: disperse enough second for titanium dioxide granule In alcohol, it is ultrasonically treated 15min under the frequency of 40KHz, Cr is added in the ratio that every g titanium dioxide granule corresponds to 0.04mmol₃O (O₂CCH₃)·7H₂O forms suspension, is heated to 90 DEG C；The purified water for the amount of taking fully is added HCl and adjusts pH to 5, is heated to 90 DEG C, both suspension and purified water are added in blender simultaneously, reaction is hydrolyzed；End of reaction after 30min, it is heavy to collect It forms sediment, calcination 1 hour at 700 DEG C obtains the titanium dioxide granule of cladding chrome green.By this method parallel laboratory test 5 times.

At different wavelengths by the titanium dioxide of two methods preparation, absorbance test is carried out, the results are shown in Table 1.Sample The UV-vis DRS spectrum (UV-VIS DRS) of product uses Perkin Elmer-Lambda 35UV-Vis Spectrometer test.

According to the result of table 1, the TiO coated using the method for the present invention₂Have at visible light region (400-550nm) than adopting The TiO coated with conventional ball mill method₂Bigger absorbance (P < 0.01).

The absorbance of the cladding of table 1 front and back titanium dioxide at different wavelengths

Experimental example 2

During cladding of the invention, a kind of coating equipment is used.The coating equipment is by linear motor driver 1, glass plate 2, spreader 3, heating plate 4 form.Linking arm 11 is fixedly connected with spreader 3, and can be in the driving of motor Under moved in shifting chute 13, so that spreader 3 be pushed to move on glass plate 2.Between the spreader 3 and glass plate 2 31 height of gap is 5-30 μm, and preferably 15 μm, the size in gap 31 can be controlled by adjusting the height of coating roller bearing 32.It is described Glass board support 12 is set on linear motor driver 1, is used to support glass plate 3, is fixedly installed heating plate under glass plate 3 4。

It weighs and is coated with Cr₂O₃TiO₂500g and commercial silica titanium 500g, is scattered in the DMCPSI of 1L, stirring Uniformly, the OPMC of 100g is added, is uniformly mixed, obtains suspension 5.

A certain amount of suspension 5 is taken, is placed on the glass plate 2 of coating equipment, starts linear motor driver 1, passes through The conduction of linking arm 11 pushes spreader 3 at the uniform velocity to move on a glass.Gap between spreader 3 and glass plate 2 is 15 μm, is applied Rate travel of the cloth device 3 on glass plate 2 is 0.02m/s.

When observing that suspension 5 is uniformly spread on cloth and glass plate 2, heating plate 4 is opened, adjusts the temperature to 35 DEG C.Then Control linear motor driver 1 moves round about, until starting point, and so on moves 1h.Stop linear motor driving Dynamic device 1 adjusts 4 temperature of heating plate to 70 DEG C, dries 30min.

After cladding, the experiment five time is repeated.

It is coated using ball-milling method, as a comparison.Experimental method is as follows: 9:1 in mass ratio weighs commercial silica titanium and packet It is covered with Cr₂O₃TiO₂, the two is mixed, after addition the ball-milling reaction 4h into planetary ball mill, dry 12h, powder is taken Out, it is placed in Muffle furnace, keeps the temperature 70h at 1000 DEG C to get Cr₂O₃External sheath have TiO₂Titanium dioxide granule.It repeats Above-mentioned experiment five time.

It is detected with whiteness of the measuring brightness instrument to titanium dioxide, testing result is as shown in table 2.

According to the result of table 2 it is found that due to before cladding, titanium dioxide surface coats one layer of Cr₂O₃, lead to its whiteness very Low, after this field routine techniques, that is, ball-milling method cladding, titanium dioxide granule whiteness has one compared with before cladding Fixed raising, data have statistical significance (P < 0.01).After method cladding titanium dioxide of the invention, whiteness ratio There is significant raising (P < 0.01) before cladding, and reaches the level (P > 0.05) of commercial silica titanium.

The whiteness value (%) of the cladding of table 2 front and back titanium dioxide

The titanium dioxide absorbance in this experimental example is detected using the detection method of experimental example 1, testing result is such as Shown in table 3.Inventor is found surprisingly that, using method for coating of the invention, by Cr₂O₃One layer of TiO of layer outer cladding₂Afterwards, can The absorbance in light-exposed region is also risen, and absorbance has significant difference (P < compared with before cladding at 550nm 0.05), use ball-milling method by Cr₂O₃One layer of TiO of layer outer cladding₂Afterwards, visible light region absorbance compared with before cladding It is remarkably decreased (P < 0.01).

Due to being unable to control outer layer TiO using ball-milling method cladding₂Thickness, lead to Cr₂O₃Outer cladding very thick one layer of layer TiO₂, it can not be played in the absorbing ability of visible light region.And the cladding mode of the method for the present invention is used, Cr₂O₃Layer outer cladding TiO₂Layer is very thin, not only smaller on its light absorpting ability influence in visible light region, while Cr₂O₃The visible light that layer absorbs Internal layer and outer layer TiO can be improved simultaneously₂Photocatalytic activity.It can be seen that dioxy can be improved using method for coating of the invention Change absorbance of the titanium in visible-range, the absorbance at especially 500-550nm.

The absorbance of the cladding of table 3 front and back titanium dioxide at different wavelengths

Experimental example 3

This experimental example probes into the pre-treatment to titanium dioxide, is coated on Cr to it₂O₃The influence of outer layer.Coat Cr₂O₃Side Method is as described in experimental example 2.

Scheme a:(1) it weighs and is coated with Cr₂O₃Titanium dioxide 500g and commercial silica titanium 1kg, be scattered in 1L's It in DMCPSI, stirs evenly, the OPMC of 100g is added, be uniformly mixed, obtain suspension.A certain amount of suspension is taken, packet is placed in On the glass plate of coating equipment, start linear motor driver, pushes spreader even on a glass by the conduction of linking arm Speed is mobile.Gap between spreader and glass plate is 15 μm, and the rate travel of spreader on a glass is 0.02m/s.Work as sight When observing on uniform suspension paving cloth and glass plate, heating plate is opened, adjusts the temperature to 35 DEG C.Then control linear motor drives Dynamic device moves round about, until starting point, and so on moves 1h.After cladding, stop linear motor driver, adjusts Temperature of heating plate is saved to 70 DEG C, dries 30min.

By this method parallel laboratory test 5 times.

Scheme b: (1) it is 50 μm hereinafter, carbon that titanium dioxide and pore creating material ammonium hydrogen carbonate are ground to granularity first by a. respectively Sour hydrogen ammonium quality is the 5% of titanium dioxide, is then uniformly mixed the titanium dioxide obtained after grinding with ammonium hydrogen carbonate, Compression moulding under 200MPa pressure；B. the material through step a compression moulding is warming up to 800 DEG C of burnings with 6 DEG C/min heating rate Knot 4h is prepared removal pore creating material and obtains porous titanium precursors；C. by the porous titanium precursors obtained through step b according to calcium with Calcium metal is added in titanium dioxide mass ratio 5:1, then to be evacuated to furnace pressure be 2Pa, heating rate is 5 DEG C/min, also Former temperature is 1000 DEG C of progress calciothermic reduction 50h, after cooling, takes out reduzate, and reduzate is leached using dilute hydrochloric acid, It is washed after the completion of leaching with distilled water and dehydrated alcohol, obtains poriferous titanium dioxide after vacuum dried.And it is porous by what is obtained Titanium dioxide is ground to partial size less than 5 μm.

(2) it weighs and is coated with Cr₂O₃Titanium dioxide 500g and previous step in the poriferous titanium dioxide 1kg for preparing, point It dissipates in the DMCPSI of 1L, stirs evenly, the OPMC of 100g is added, be uniformly mixed, obtain suspension.Take a certain amount of suspension Liquid is placed on the glass plate of coating equipment, starts linear motor driver, pushes spreader in glass by the conduction of linking arm It is at the uniform velocity moved in glass plate.Gap between spreader and glass plate is 15 μm, and the rate travel of spreader on a glass is 0.02m/s.When observing on uniform suspension paving cloth and glass plate, heating plate is opened, adjusts the temperature to 35 DEG C.Then control Linear motor driver moves round about, until starting point, and so on moves 1h.After cladding, stop straight-line electric Motivation driver adjusts temperature of heating plate to 70 DEG C, dries 30min.

By this method parallel laboratory test 5 times.

Scheme c:(1) commercial silica titanium material and deionized water are put into the hollander tub of exclusion device, titanium dioxide Between titanium material and deionized water according to the mixed proportion of weight be 3:7；Agitating device forms slurry after being stirred mashing, will Slurry, which injects in the first ultrasonic activation sieve, carries out ultrasonic vibration filtering, and titanium dioxide, which is filtered, to be extracted；By what is extracted Ammonium hydroxide is added in titanium dioxide, adjusts the pH to 2.0 of solution, dimethyl disulfide is constantly added dropwise into reactor at this time for amine sodium formate Solution continues to stir 20min, titanium dioxide is extracted in filtering until not generating solid suspension stopping；It is filtered in titanium dioxide It is washed with water after extraction, is filtered after washing using ultrasonic vibration, then be dried into drying device, obtain low impurity and contain The titanium dioxide of amount.

By this method parallel laboratory test 5 times.

Scheme d: scheme c:(1) commercial silica titanium material and deionized water are put into the hollander tub of exclusion device, Between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 3:7；Agitating device is formed after being stirred mashing Slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering by slurry, and titanium dioxide, which is filtered, to be extracted；It will mention Ammonium hydroxide is added in the titanium dioxide of taking-up, adjusts the pH to 2.0 of solution, dimethyl disulfide is constantly added dropwise into reactor at this time for amine Sodium formate solution continues to stir 20min, titanium dioxide is extracted in filtering until not generating solid suspension stopping；In titanium dioxide It is washed with water after being extracted by filtering, filters, then be dried into drying device, obtain low using ultrasonic vibration after washing The titanium dioxide of impurity content.

(2) it is 50 μm hereinafter, ammonium hydrogen carbonate that titanium dioxide and pore creating material ammonium hydrogen carbonate are ground to granularity first by a. respectively Quality is the 5% of titanium dioxide, is then uniformly mixed the titanium dioxide obtained after grinding with ammonium hydrogen carbonate, in 200MPa pressure Lower compression moulding；B. the material through step a compression moulding 800 DEG C of sintering 4h are warming up to 6 DEG C/min heating rate to be prepared into Porous titanium precursors are obtained to removal pore creating material；C. by the porous titanium precursors obtained through step b according to calcium and titanium dioxide matter Calcium metal is added than 5:1 in amount, then to be evacuated to furnace pressure be 2Pa, heating rate is 5 DEG C/min, reduction temperature is 1000 DEG C of progress calciothermic reduction 50h take out reduzate after cooling, and reduzate is leached using dilute hydrochloric acid, leaches and completes It is washed afterwards with distilled water and dehydrated alcohol, obtains poriferous titanium dioxide after vacuum dried.And the poriferous titanium dioxide that will be obtained Partial size is ground to less than 5 μm.

(3) it weighs and is coated with Cr₂O₃Titanium dioxide 500g and previous step in the poriferous titanium dioxide 1kg for preparing, point It dissipates in the DMCPSI of 1L, stirs evenly, the OPMC of 100g is added, be uniformly mixed, obtain suspension.Take a certain amount of suspension Liquid is placed on the glass plate of coating equipment, starts linear motor driver, pushes spreader in glass by the conduction of linking arm It is at the uniform velocity moved in glass plate.Gap between spreader and glass plate is 15 μm, and the rate travel of spreader on a glass is 0.02m/s.When observing on uniform suspension paving cloth and glass plate, heating plate is opened, adjusts the temperature to 35 DEG C.Then control Linear motor driver moves round about, until starting point, and so on moves 1h.After cladding, stop straight-line electric Motivation driver adjusts temperature of heating plate to 70 DEG C, dries 30min.

By this method parallel laboratory test 5 times.

Whiteness, absorbance detection are carried out to the titanium dioxide using scheme a-d preparation.Detection method such as experimental example 1, experiment Example 2.Experimental result is as shown in table 4,5.According to 4 data of table, at the same time to titanium dioxide raw material using pretreatment and pore-creating When processing, the titanium dioxide granule whiteness after cladding, which compares other schemes (individually do pore-creating processing, or individually pre-process), to be had It is significant to improve (P < 0.01).In addition, individually do pore-creating processing to titanium dioxide, or after individually pre-processing, coated, Be not processed the technical solution directly coated, the whiteness of finished product has no significant difference (P > 0.05), it was demonstrated that titanium dioxide After carrying out pretreatment and pore-creating, it is coated on outer layer and obtains the unexpected technical effect of those skilled in the art.

The whiteness value (%) of the cladding of table 4 front and back titanium dioxide

Scheme a	Scheme b	Scheme c	Scheme d	Commercial silica titanium
					90.0	90.1	90.4	92.2	90.2

According to the data of table 5, scheme b, scheme c are ultra-violet (UV) band (< 400nm) and visible compared with the product of scheme a Light area (> 400nm) absorbance does not have significant difference (P > 0.05), but scheme d product titanium dioxide obtained, It is at visible region (500nm, 550nm), compared with scheme a-c, all has better absorbance (P < 0.05).

The absorbance of the cladding of table 5 front and back titanium dioxide at different wavelengths

Experimental example 4

It is influence of the silica to powder machinery performance that titanium dioxide kernel is probed into this experimental example.

Scheme 1: complete preparation method according to the invention prepares titanium dioxide.Specifically, (1) is former by commercial silica titanium Material is put into deionized water into the hollander tub of exclusion device, according to the mixing of weight between titanium dioxide raw material and deionized water Ratio is 2:8；Agitating device forms slurry after being stirred mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasound Vibration filtering, titanium dioxide, which is filtered, to be extracted；Ammonium hydroxide is added in the titanium dioxide extracted, adjusts the pH to 1.0 of solution, Dimethyl disulfide is constantly added dropwise into reactor at this time for amine sodium formate solution, until not generating solid suspension stopping, continuing 15min is stirred, titanium dioxide is extracted in filtering；It is washed with water after titanium dioxide is extracted by filtering, using ultrasound after washing Vibration filtering, then be dried into drying device, obtain the titanium dioxide of low impurity content.(2) a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding that the titanium dioxide and pore creating material ammonium hydrogen carbonate obtained is ground to granularity respectively It is uniformly mixed with the ammonium hydrogen carbonate powder for being equivalent to titanium dioxide quality 3%, the compression moulding under 100MPa pressure；It b. will be through step The material of rapid a compression moulding with 5 DEG C/min heating rate be warming up to 600 DEG C of sintering 3h be prepared remove pore creating material obtain it is porous Titanium precursors；C. calcium metal is added according to calcium and titanium dioxide mass ratio 2:1 in the porous titanium precursors obtained through step b, so Afterwards to be evacuated to furnace pressure be 1Pa, heating rate is 5 DEG C/min, reduction temperature be 1000 DEG C of progress calciothermic reduction for 24 hours, After cooling, reduzate is taken out, reduzate is leached using dilute hydrochloric acid, is washed after the completion of leaching with distilled water and dehydrated alcohol It washs, obtains poriferous titanium dioxide after vacuum dried.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): A. the SiO of 50g is taken₂, under ultrasound condition, it is suspended in the ethyl alcohol of 5000g；B. the 90%0 of 50g is added into above-mentioned solution The ammonium hydroxide of six alkylamines (HDA) and 100g is stirred at room temperature 0.5 minute；C. under agitation, it is added into step b The tetraisopropyl titanate (TIP) of 100g reacts 5 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；It e. will be upper It states and is deposited in calcination 1 hour at 450 DEG C, then with 10% hydrofluoric acid wash, acquisition kernel is SiO₂TiO₂Particle.(4) a. will The TiO obtained in step (3)₂Particle is scattered in ethyl alcohol, and 30KHz is ultrasonically treated 10min, by every g TiO₂Particle is corresponding Cr is added in the ratio of 0.02mmol₃O(O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts pH to 4 with HCl, with The suspension obtained in a is heated separately to 80 DEG C, and the two is added in blender simultaneously, reaction is hydrolyzed；C.10min after End of reaction, collects precipitating, and calcination 1 hour at 450 DEG C obtains cladding Cr₂O₃TiO₂Particle.(5) a. will be in step (4) The titanium dioxide of acquisition, takes 100g, takes and obtains titanium dioxide 2000g in step (2), is scattered in the decamethylcyclopentaandoxane of 1L (DMCPSI) in, the OctMet (OPMC) of 100g is added, is uniformly mixed, obtains suspending liquid A；B. it takes certain The suspending liquid A of amount, is placed on the glass plate of coating equipment, starts linear motor driver, is pushed by the conduction of linking arm Spreader at the uniform velocity moves on a glass.Gap between spreader and glass plate is 15 μm, the movement of spreader on a glass Rate is 0.01m/s；C. when observing that suspending liquid A is uniformly spread on cloth and glass plate, heating plate is opened, adjusts the temperature to 30 ℃.Then control linear motor driver moves round about, until starting point, and so on moves 30min.Stop straight line Motor driver adjusts temperature of heating plate to 60 DEG C, dries 30min.It is prepared in parallel by this method 5 times.

Scheme 2: according to (3) the step of 1 preparation method of scheme, preparation is coated with the silica of titanium dioxide.By we Method is prepared 5 times in parallel.

Scheme 3: according to (3)-(4) the step of 1 preparation method of scheme, preparation is by being silica-dioxy respectively except interior Change titanium-chrome green powder.It is prepared in parallel by this method 5 times.

Scheme 4: by 1 step of scheme (3) method for coating, being changed to the ball-milling method cladding titanium dioxide of this field routine, used Titanium dioxide is step (2) acquisition.It is prepared in parallel by this method 5 times.

The Mohs' hardness of detection scheme 1-4 finished product, testing result are as shown in table 6.As shown in 6 data of table, scheme 1-3, After titanium dioxide is exactly wrapped in silica with the method for the present invention, the product hardness of preparation has aobvious than titanium dioxide raw material It writes and promotes (P < 0.01).Moreover, titanium dioxide is wrapped in by (scheme 4) after silica using conventional method, the machinery of product Intensity is substantially less than the product (scheme 1-3) (P < 0.01) after using the method for the present invention to coat.

The Mohs' hardness of 6 scheme 1-4 finished product of table

Comparative example 1

CN102641220A discloses a kind of titanium dioxide with very intensive ultraviolet absorbability.By its method preparation two Titanium oxide product the, specific steps are as follows: 1) synthesis of amphipathic triblock polymer PEO-b-PDMA-b-PS: using Polyoxyethylene (PEO-Br) after 0.500g bromination is macromole evocating agent, by the catalyst cuprous bromide (CuBr) of 0.036g, The monomer methacrylic acid dimethylamino ethyl ester (DMA) and 4mL solvent of the ligand PMDETA, 1.580g of 0.044g are added to 50mL Round-bottomed flask in, carry out atom transfer radical polymerization (ATRP), 30 DEG C of temperature, by 3.800g styrene after reaction 6 hours After dilution, it is added in reaction flask that the reaction was continued 24 hours.Acquisition polymer revolving, cross silicon gel column, concentration, precipitating, Pumping finally puts vacuum drying oven 24 hours, obtains block polymer PEO₄₃-b-PDMA₄₀-b-PS₁₄₀.2) polymer self assembles shape At micella: polymer is dissolved in tetrahydrofuran (THF), the solution of 20mg/mL is prepared, under stirring conditions with 10d/min Speed the methanol of 60 times of THF volumes is added dropwise into THF solution, stirring obtained opalescent solution after 24 hours.3) it polymerize Object micellar surface deposits titanium source: the use of butyl titanate being titanium source, is dissolved in butyl titanate (TBT) with the concentration of 10mg/mL In ethyl alcohol, TBT and DMA are instilled with the molar ratio of 0.2:1 in the solution of micella, and are obtained after being vigorously stirred 24 hours milky Solution.4) required product will be obtained after the nanoparticles solution drying of obtained organic inorganic hybridization.

Comparative example 2

CN1454939A discloses a kind of titanium dioxide product that ultraviolet screening ability is strong.Titanium dioxide is prepared by its method Titanium products, specific steps are as follows: 250gTi (OC₄H₉)₄It is dissolved in 2500ml ethyl alcohol, obtains Ti (OC₄H₉)₄Solution A； The ethyl alcohol of 1320ml is dissolved in the water of 1320ml, is solution B；Prepare sodium aluminate alkali solution C (mass percentage concentration: Al₂O₃%= 0.28%, NaOH%=0.45%), at room temperature, solution A is pumped into the solution B being vigorously stirred in 50 minutes, continues to stir It 15 minutes, filters, the xerogel of drying in 15 hours at 110 DEG C.Above-mentioned xerogel is ground, 80 mesh Microtraps are sieved, and roast at 500 DEG C Obtain nanometer anatase titania within 1 hour.It disperses above-mentioned nano-titanium dioxide 10g in the water of 300ml, by P₂O₅∶TiO₂ =0.1% is added sodium hexametaphosphate dispersant, and it is 10 that the NaOH of 1M, which adjusts PH, and ultrasonic disperse 50 minutes.By nano-TiO₂Slurries, Under stiring, 85 DEG C are heated to, then adjusting pH value is 8.5, solution C then is added in 40 minutes, with Al₂O₃Poidometer, Al₂O₃∶TiO₂=10%, it cures 3 hours.It is 7.0 with the pH value that sulfuric acid solution adjusts slurries, then stirs 30 minutes.Filtering, Secondary deionized water washing washing is to inspection without SO₄ ^2-, drying in 15 hours is to get monodispersed surface-coating aluminium oxide at 120 DEG C Titanium dioxide nanoparticle.

Comparative example 3

CN105565736A discloses a kind of anti-ultraviolet mortar, prepares titanium dioxide product by its method, specific to grasp Steps are as follows for work: (1) prepare modification infusorial earth: 10 ︰ in mass ratio, 1 ︰, 20 ︰, 0.5 ︰ 1 takes diatomite, chitin, water, idol respectively Join agent and nano-titanium dioxide；Then, diatomite, chitin, water and coupling agent are added in blender, are 3000r/ in revolving speed Under the mixing speed of min, it is uniformly mixed；Later, the revolving speed of blender is down to 500r/min, is slowly added to nanometer titanium dioxide Titanium stirs 30min, slurry is made under the mixing speed of 500r/min；Obtained slurry is dried in 100 DEG C of baking ovens again It is dry, then powder grinds to get.It (2) is in 100kg powder stirrer to bulk density, successively feed intake quartz sand powder 45kg, P.O42.5 Ordinary portland cement 30kg, desulfurized gypsum 10kg, flyash 5kg, anti-crack fiber 1kg, cellulose ether 2kg, modification infusorial earth Powder component A is made to being uniformly mixed in 5kg, lithium bentonite 2kg, stirring 15min.It (3) is 50kg, revolving speed 30r/ to bulk density In min blender, 13kg methyl acrylate lotion, alcohol ester 12 coalescing agent 0.1kg, defoaming agent 0.1kg, dispersion are successively put into Lotion material B component is made to being uniformly mixed in agent 0.5kg, stirring 15min.(4) it by powder component A and lotion material B component, is applying Working hour, scene 1 ︰ 1-2 in mass ratio are mixed and stirred for uniformly being formulated.

Embodiment 1

Titanium dioxide is prepared as follows: (1) being put into commercial silica titanium material and deionized water to exclusion device Hollander tub in, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 2:8；Agitating device is stirred Slurry is formed after mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide, which is filtered, to be mentioned It takes out；Ammonium hydroxide is added in the titanium dioxide extracted, the pH to 1.0 of solution is adjusted, is constantly added dropwise two into reactor at this time The thio amine sodium formate solution of methyl two continues to stir 15min, titanium dioxide is extracted in filtering until not generating solid suspension stopping Titanium；Titanium dioxide by filtering extract after be washed with water, filtered after washing using ultrasonic vibration, then into drying device into Row drying obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore creating material carbonic acid that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide quality 3% that hydrogen ammonium is ground to granularity respectively Ammonium hydrogen carbonate powder be uniformly mixed, the compression moulding under 100MPa pressure；B. by the material through step a compression moulding with 5 DEG C/ Min heating rate be warming up to 600 DEG C of sintering 3h be prepared removal pore creating material obtain porous titanium precursors；C. it will be obtained through step b Calcium metal is added according to calcium and titanium dioxide mass ratio 2:1 in the porous titanium precursors arrived, is then being evacuated to furnace pressure 1Pa, heating rate are 5 DEG C/min, reduction temperature be 1000 DEG C of progress calciothermic reduction for 24 hours, after cooling, take out reduzate, Reduzate is leached using dilute hydrochloric acid, is washed, is obtained after vacuum dried more with distilled water and dehydrated alcohol after the completion of leaching Porous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes the SiO of 50g₂, in ultrasonic item Under part, it is suspended in the ethyl alcohol of 5000g；B. 90% hexadecylamine (HDA) and 100g of 50g are added into above-mentioned solution Ammonium hydroxide is stirred at room temperature 0.5 minute；C. under agitation, the tetraisopropyl titanate (TIP) of 100g is added into step b, Reaction 5 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. it is deposited in calcination 1 hour at 450 DEG C by above-mentioned, Again with 10% hydrofluoric acid wash, acquisition kernel be SiO₂TiO₂Particle.(4) TiO that a. will be obtained in step (3)₂Particle point It dissipates in ethyl alcohol, 30KHz is ultrasonically treated 10min, by every g TiO₂Cr is added in the ratio that particle corresponds to 0.02mmol₃O (O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 4, with a with HCl and adds respectively Heat is added in blender simultaneously to 80 DEG C, by the two, and reaction is hydrolyzed；C.10min end of reaction after collects precipitating, Calcination 1 hour at 450 DEG C obtains cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4), takes 100g takes and obtains titanium dioxide 2000g in step (2), is scattered in the decamethylcyclopentaandoxane (DMCPSI) of 1L, adds The OctMet (OPMC) of 100g is uniformly mixed, obtains suspending liquid A；B. a certain amount of suspending liquid A is taken, is placed in On the glass plate of coating equipment, start linear motor driver, spreader is pushed on a glass by the conduction of linking arm At the uniform velocity move.Gap between spreader and glass plate is 15 μm, and the rate travel of spreader on a glass is 0.01m/s；c. When observing that suspending liquid A is uniformly spread on cloth and glass plate, heating plate is opened, adjusts the temperature to 30 DEG C.Then control straight-line electric Motivation driver moves round about, until starting point, and so on moves 30min.Stop linear motor driver, adjusts Temperature of heating plate dries 30min to 60 DEG C.

Embodiment 2

Titanium dioxide is prepared as follows: (1) being put into commercial silica titanium material and deionized water to exclusion device Hollander tub in, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 4:6；Agitating device is stirred Slurry is formed after mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide, which is filtered, to be mentioned It takes out；Ammonium hydroxide is added in the titanium dioxide extracted, the pH to 2.0 of solution is adjusted, is constantly added dropwise two into reactor at this time The thio amine sodium formate solution of methyl two continues to stir 25min, titanium dioxide is extracted in filtering until not generating solid suspension stopping Titanium；Titanium dioxide by filtering extract after be washed with water, filtered after washing using ultrasonic vibration, then into drying device into Row drying obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore creating material carbonic acid that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide quality 3% that hydrogen ammonium is ground to granularity respectively Ammonium hydrogen carbonate powder be uniformly mixed, the compression moulding under 250MPa pressure；B. by the material through step a compression moulding with 10 DEG C/min heating rate be warming up to 1100 DEG C of sintering 6h be prepared removal pore creating material obtain porous titanium precursors；It c. will be through step Calcium metal is added according to calcium and titanium dioxide mass ratio 10:1 in the porous titanium precursors that b is obtained, and is then being evacuated to furnace internal pressure Power is 5Pa, heating rate is 10 DEG C/min, reduction temperature is 1100 DEG C of progress calciothermic reduction 60h, after cooling, takes out reduction Reduzate is leached using dilute hydrochloric acid, is washed after the completion of leaching with distilled water and dehydrated alcohol, obtained after vacuum dried by product To poriferous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes the SiO of 100g₂, Under ultrasound condition, it is suspended in the ethyl alcohol of 15000g；B. 90% hexadecylamine (HDA) of 100g is added into above-mentioned solution, And the ammonium hydroxide of 400g, it is stirred at room temperature 5 minutes；C. under agitation, four isopropyl of metatitanic acid of 1000g is added into step b Ester (TIP) reacts 20 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. it is deposited in above-mentioned at 450 DEG C Calcination 4 hours, then with 10% hydrofluoric acid wash, acquisition kernel is SiO₂TiO₂Particle.(4) a. will be obtained in step (3) TiO₂Particle is scattered in ethyl alcohol, and 80KHz is ultrasonically treated 15min, by every g TiO₂Cr is added in the ratio that particle corresponds to 1mmol₃O (O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 6, with a with HCl and adds respectively Heat is added in blender simultaneously to 95 DEG C, by the two, and reaction is hydrolyzed；C.30min end of reaction after collects precipitating, Calcination 1 hour at 750 DEG C obtains cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4), takes 1000g takes and obtains titanium dioxide 500g in step (2), is scattered in the decamethylcyclopentaandoxane (DMCPSI) of 10L, then plus Enter the OctMet (OPMC) of 500g, is uniformly mixed, obtains suspending liquid A；B. a certain amount of suspending liquid A is taken, is set In on the glass plate of coating equipment, start linear motor driver, pushes spreader in glass plate by the conduction of linking arm On at the uniform velocity move.Gap between spreader and glass plate is 50 μm, and the rate travel of spreader on a glass is 1m/s；C. when When observing that suspending liquid A is uniformly spread on cloth and glass plate, heating plate is opened, adjusts the temperature to 40 DEG C.Then control straight line electric Machine driver moves round about, until starting point, and so on moves 2h.Stop linear motor driver, adjusts heating Plate temperature dries 30min to 70 DEG C.

Embodiment 3

Titanium dioxide is prepared as follows: (1) being put into commercial silica titanium material and deionized water to exclusion device Hollander tub in, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 3:7；Agitating device is stirred Slurry is formed after mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide, which is filtered, to be mentioned It takes out；Ammonium hydroxide is added in the titanium dioxide extracted, the pH to 1.5 of solution is adjusted, is constantly added dropwise two into reactor at this time The thio amine sodium formate solution of methyl two continues to stir 20min, titanium dioxide is extracted in filtering until not generating solid suspension stopping Titanium；Titanium dioxide by filtering extract after be washed with water, filtered after washing using ultrasonic vibration, then into drying device into Row drying obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore creating material carbonic acid that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide quality 3% that hydrogen ammonium is ground to granularity respectively Ammonium hydrogen carbonate powder be uniformly mixed, the compression moulding under 200MPa pressure；B. by the material through step a compression moulding with 6 DEG C/ Min heating rate be warming up to 800 DEG C of sintering 4h be prepared removal pore creating material obtain porous titanium precursors；C. it will be obtained through step b Calcium metal is added according to calcium and titanium dioxide mass ratio 5:1 in the porous titanium precursors arrived, is then being evacuated to furnace pressure 5Pa, heating rate are 6 DEG C/min, reduction temperature is 1050 DEG C of progress calciothermic reduction 48h, after cooling, take out reduzate, Reduzate is leached using dilute hydrochloric acid, is washed, is obtained after vacuum dried more with distilled water and dehydrated alcohol after the completion of leaching Porous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes the SiO of 80g₂, in ultrasonic item Under part, it is suspended in the ethyl alcohol of 10000g；B. 90% hexadecylamine (HDA) and 200g of 80g are added into above-mentioned solution Ammonium hydroxide is stirred at room temperature 2 minutes；C. under agitation, the tetraisopropyl titanate (TIP) of 500g is added into step b, instead It answers 10 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. calcination 2 hours at 450 DEG C are deposited in by above-mentioned, Again with 10% hydrofluoric acid wash, acquisition kernel be SiO₂TiO₂Particle.(4) TiO that a. will be obtained in step (3)₂Particle point It dissipates in ethyl alcohol, 50KHz is ultrasonically treated 10min, by every g TiO₂Cr is added in the ratio that particle corresponds to 0.1mmol₃O (O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 5, with a with HCl and adds respectively Heat is added in blender simultaneously to 90 DEG C, by the two, and reaction is hydrolyzed；C.20min end of reaction after collects precipitating, Calcination 1 hour at 600 DEG C obtains cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4), takes 500g takes and obtains titanium dioxide 1000g in step (2), is scattered in the decamethylcyclopentaandoxane (DMCPSI) of 5L, adds The OctMet (OPMC) of 200g is uniformly mixed, obtains suspending liquid A；B. a certain amount of suspending liquid A is taken, is placed in On the glass plate of coating equipment, start linear motor driver, spreader is pushed on a glass by the conduction of linking arm At the uniform velocity move.Gap between spreader and glass plate is 30 μm, and the rate travel of spreader on a glass is 0.1m/s；C. when When observing that suspending liquid A is uniformly spread on cloth and glass plate, heating plate is opened, adjusts the temperature to 35 DEG C.Then control straight line electric Machine driver moves round about, until starting point, and so on moves 1h.Stop linear motor driver, adjusts heating Plate temperature dries 20min to 65 DEG C.

Embodiment 4

Titanium dioxide is prepared as follows: (1) being put into commercial silica titanium material and deionized water to exclusion device Hollander tub in, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 3:7；Agitating device is stirred Slurry is formed after mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide, which is filtered, to be mentioned It takes out；Ammonium hydroxide is added in the titanium dioxide extracted, the pH to 1.5 of solution is adjusted, is constantly added dropwise two into reactor at this time The thio amine sodium formate solution of methyl two continues to stir 20min, titanium dioxide is extracted in filtering until not generating solid suspension stopping Titanium；Titanium dioxide by filtering extract after be washed with water, filtered after washing using ultrasonic vibration, then into drying device into Row drying obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore creating material carbonic acid that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide quality 3% that hydrogen ammonium is ground to granularity respectively Ammonium hydrogen carbonate powder be uniformly mixed, the compression moulding under 200MPa pressure；B. by the material through step a compression moulding with 6 DEG C/ Min heating rate be warming up to 800 DEG C of sintering 4h be prepared removal pore creating material obtain porous titanium precursors；C. it will be obtained through step b Calcium metal is added according to calcium and titanium dioxide mass ratio 5:1 in the porous titanium precursors arrived, is then being evacuated to furnace pressure 5Pa, heating rate are 6 DEG C/min, reduction temperature is 1050 DEG C of progress calciothermic reduction 48h, after cooling, take out reduzate, Reduzate is leached using dilute hydrochloric acid, is washed, is obtained after vacuum dried more with distilled water and dehydrated alcohol after the completion of leaching Porous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes the SiO of 80g₂, in ultrasonic item Under part, it is suspended in the ethyl alcohol of 10000g；B. 90% hexadecylamine (HDA) and 200g of 80g are added into above-mentioned solution Ammonium hydroxide is stirred at room temperature 2 minutes；C. under agitation, the tetraisopropyl titanate (TIP) of 500g is added into step b, instead It answers 10 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. calcination 2 hours at 450 DEG C are deposited in by above-mentioned, Again with 10% hydrofluoric acid wash, acquisition kernel be SiO₂TiO₂Particle.(4) TiO that a. will be obtained in step (3)₂Particle point It dissipates in ethyl alcohol, 50KHz is ultrasonically treated 10min, by every g TiO₂Cr (O-i-H is added in the ratio that particle corresponds to 0.1mmol₃C₇ )₃, form suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 5, with a with HCl and is heated separately to 90 DEG C, will The two is added in blender simultaneously, and reaction is hydrolyzed；C.20min end of reaction after collects precipitating, the calcination 1 at 600 DEG C Hour, obtain cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4), takes 500g, takes in step (2) Obtain titanium dioxide 1000g, be scattered in the decamethylcyclopentaandoxane (DMCPSI) of 5L, add 200g to methoxyl group meat Cinnamate (OPMC) is uniformly mixed, obtains suspending liquid A；B. a certain amount of suspending liquid A is taken, the glass plate of coating equipment is placed in On, start linear motor driver, pushes spreader at the uniform velocity to move on a glass by the conduction of linking arm.Spreader with Gap between glass plate is 30 μm, and the rate travel of spreader on a glass is 0.1m/s；C. when observing that suspending liquid A is uniform When spreading on cloth and glass plate, heating plate is opened, adjusts the temperature to 35 DEG C.Then control linear motor driver round about It is mobile, until starting point, and so on moves 1h.Stop linear motor driver, adjusts temperature of heating plate to 65 DEG C, dry 20min。

Embodiment 5

Titanium dioxide is prepared as follows: (1) being put into commercial silica titanium material and deionized water to exclusion device Hollander tub in, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 3:7；Agitating device is stirred Slurry is formed after mashing, and slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide, which is filtered, to be mentioned It takes out；Ammonium hydroxide is added in the titanium dioxide extracted, the pH to 1.5 of solution is adjusted, is constantly added dropwise two into reactor at this time The thio amine sodium formate solution of methyl two continues to stir 20min, titanium dioxide is extracted in filtering until not generating solid suspension stopping Titanium；Titanium dioxide by filtering extract after be washed with water, filtered after washing using ultrasonic vibration, then into drying device into Row drying obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore creating material carbonic acid that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide quality 3% that hydrogen ammonium is ground to granularity respectively Ammonium hydrogen carbonate powder be uniformly mixed, the compression moulding under 200MPa pressure；B. by the material through step a compression moulding with 6 DEG C/ Min heating rate be warming up to 800 DEG C of sintering 4h be prepared removal pore creating material obtain porous titanium precursors；C. it will be obtained through step b Calcium metal is added according to calcium and titanium dioxide mass ratio 5:1 in the porous titanium precursors arrived, is then being evacuated to furnace pressure 5Pa, heating rate are 6 DEG C/min, reduction temperature is 1050 DEG C of progress calciothermic reduction 48h, after cooling, take out reduzate, Reduzate is leached using dilute hydrochloric acid, is washed, is obtained after vacuum dried more with distilled water and dehydrated alcohol after the completion of leaching Porous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes the SiO of 80g₂, in ultrasonic item Under part, it is suspended in the ethyl alcohol of 10000g；B. 90% hexadecylamine (HDA) and 200g of 80g are added into above-mentioned solution Ammonium hydroxide is stirred at room temperature 2 minutes；C. under agitation, the tetraisopropyl titanate (TIP) of 500g is added into step b, instead It answers 10 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. calcination 2 hours at 450 DEG C are deposited in by above-mentioned, Again with 10% hydrofluoric acid wash, acquisition kernel be SiO₂TiO₂Particle.(4) TiO that a. will be obtained in step (3)₂Particle point It dissipates in ethyl alcohol, 50KHz is ultrasonically treated 10min, by every g TiO₂Cr is added in the ratio that particle corresponds to 0.1mmol₃O (O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 5, with a with HCl and adds respectively Heat is added in blender simultaneously to 90 DEG C, by the two, and reaction is hydrolyzed；C.20min end of reaction after collects precipitating, Calcination 1 hour at 600 DEG C obtains cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4), takes 500g takes and obtains titanium dioxide 1000g in step (2), is scattered in the decamethylcyclopentaandoxane (DMCPSI) of 5L, adds The OctMet (OPMC) of 200g is uniformly mixed, obtains suspending liquid A；B. by suspending liquid A pressing and wrapping, pressure For 500Pa；C. it to pressed suspending liquid A at 80 DEG C, heats 2 hours, DMCPSI is made to volatilize.

Embodiment 6

In the step (5), contain TiO₂Outer layer by Cr₂O₃And TiO₂Composition.

Titanium dioxide is specifically prepared as follows: (1) being put into commercial silica titanium material and deionized water to removing In the hollander tub of miscellaneous device, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 4:6；Agitating device into Slurry is formed after row stirring to pulp, slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide quilt Filtering extracts；Ammonium hydroxide is added in the titanium dioxide extracted, adjusts the pH to 2.0 of solution, constantly into reactor at this time Dimethyl disulfide is added dropwise for amine sodium formate solution, until not generating solid suspension stopping, continuing to stir 25min, filtering is extracted Titanium dioxide；It is washed with water after titanium dioxide is extracted by filtering, is filtered after washing using ultrasonic vibration, then filled to dry It is dried in setting, obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore-creating that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide matter that agent ammonium hydrogen carbonate is ground to granularity respectively The ammonium hydrogen carbonate powder of amount 3% is uniformly mixed, the compression moulding under 250MPa pressure；B. by the material through step a compression moulding With 10 DEG C/min heating rate be warming up to 1100 DEG C of sintering 6h be prepared removal pore creating material obtain porous titanium precursors；It c. will be through Calcium metal is added according to calcium and titanium dioxide mass ratio 10:1 in the porous titanium precursors that step b is obtained, and is then being evacuated to furnace Interior pressure is 5Pa, heating rate is 10 DEG C/min, reduction temperature is 1100 DEG C of progress calciothermic reduction 60h, after cooling, is taken out Reduzate is leached using dilute hydrochloric acid, is washed after the completion of leaching with distilled water and dehydrated alcohol by reduzate, vacuum dried After obtain poriferous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes 100g's SiO₂, under ultrasound condition, it is suspended in the ethyl alcohol of 15000g；B. 90% hexadecylamine of 100g is added into above-mentioned solution (HDA) and the ammonium hydroxide of 400g it, is stirred at room temperature 5 minutes；C. under agitation, the metatitanic acid of 1000g is added into step b Tetra-isopropyl (TIP) is reacted 20 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. it is deposited in above-mentioned Calcination 4 hours at 450 DEG C, then with 10% hydrofluoric acid wash, acquisition kernel is SiO₂TiO₂Particle.(4) a. is by step (3) The TiO of middle acquisition₂Particle is scattered in ethyl alcohol, and 80KHz is ultrasonically treated 15min, by every g TiO₂Particle corresponds to the ratio of 1mmol Cr is added₃O(O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 6, with a with HCl Liquid is heated separately to 95 DEG C, and the two is added in blender simultaneously, reaction is hydrolyzed；C.30min end of reaction after is collected Precipitating, calcination 1 hour at 750 DEG C obtain cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4) Titanium takes 600g；Take the Cr of the titanium dioxide 300g and 200g that obtain in step (2)₂O₃, it is scattered in five silicon of decamethyl ring of 10L In oxygen alkane (DMCPSI), the OctMet (OPMC) of 500g is added, is uniformly mixed, obtains suspending liquid A；B. it takes A certain amount of suspending liquid A, is placed on the glass plate of coating equipment, starts linear motor driver, passes through the conduction of linking arm Spreader is pushed at the uniform velocity to move on a glass.Gap between spreader and glass plate is 50 μm, and spreader is on a glass Rate travel is 1m/s；C. when observing that suspending liquid A is uniformly spread on cloth and glass plate, heating plate is opened, adjusts the temperature to 40 ℃.Then control linear motor driver moves round about, until starting point, and so on moves 2h.Stop straight-line electric Motivation driver adjusts temperature of heating plate to 70 DEG C, dries 30min.

Embodiment 7

In the step (5), contain TiO₂Outer layer by Cr₂O₃And TiO₂Composition.

Titanium dioxide is specifically prepared as follows: (1) being put into commercial silica titanium material and deionized water to removing In the hollander tub of miscellaneous device, between titanium dioxide raw material and deionized water according to the mixed proportion of weight be 4:6；Agitating device into Slurry is formed after row stirring to pulp, slurry is injected in the first ultrasonic activation sieve and carries out ultrasonic vibration filtering, titanium dioxide quilt Filtering extracts；Ammonium hydroxide is added in the titanium dioxide extracted, adjusts the pH to 2.0 of solution, constantly into reactor at this time Dimethyl disulfide is added dropwise for amine sodium formate solution, until not generating solid suspension stopping, continuing to stir 25min, filtering is extracted Titanium dioxide；It is washed with water after titanium dioxide is extracted by filtering, is filtered after washing using ultrasonic vibration, then filled to dry It is dried in setting, obtains the titanium dioxide of low impurity content.(2) titanium dioxide and pore-creating that a. first obtains step (1) It is 50 μm hereinafter, then weighing the titanium dioxide after grinding and being equivalent to titanium dioxide matter that agent ammonium hydrogen carbonate is ground to granularity respectively The ammonium hydrogen carbonate powder of amount 3% is uniformly mixed, the compression moulding under 250MPa pressure；B. by the material through step a compression moulding With 10 DEG C/min heating rate be warming up to 1100 DEG C of sintering 6h be prepared removal pore creating material obtain porous titanium precursors；It c. will be through Calcium metal is added according to calcium and titanium dioxide mass ratio 10:1 in the porous titanium precursors that step b is obtained, and is then being evacuated to furnace Interior pressure is 5Pa, heating rate is 10 DEG C/min, reduction temperature is 1100 DEG C of progress calciothermic reduction 60h, after cooling, is taken out Reduzate is leached using dilute hydrochloric acid, is washed after the completion of leaching with distilled water and dehydrated alcohol by reduzate, vacuum dried After obtain poriferous titanium dioxide.And obtained poriferous titanium dioxide is ground to partial size less than 5 μm.(3): a. takes 100g's SiO₂, under ultrasound condition, it is suspended in the ethyl alcohol of 15000g；B. 90% hexadecylamine of 100g is added into above-mentioned solution (HDA) and the ammonium hydroxide of 400g it, is stirred at room temperature 5 minutes；C. under agitation, the metatitanic acid of 1000g is added into step b Tetra-isopropyl (TIP) is reacted 20 minutes；D. centrifugation is precipitated, and is precipitated with water and ethanol washing；E. it is deposited in above-mentioned Calcination 4 hours at 450 DEG C, then with 10% hydrofluoric acid wash, acquisition kernel is SiO₂TiO₂Particle.(4) a. is by step (3) The TiO of middle acquisition₂Particle is scattered in ethyl alcohol, and 80KHz is ultrasonically treated 15min, by every g TiO₂Particle corresponds to the ratio of 1mmol Cr is added₃O(O₂CCH₃)·7H₂O forms suspension；B. the water for the amount of taking fully adjusts the suspension that pH is obtained into 6, with a with HCl Liquid is heated separately to 95 DEG C, and the two is added in blender simultaneously, reaction is hydrolyzed；C.30min end of reaction after is collected Precipitating, calcination 1 hour at 750 DEG C obtain cladding Cr₂O₃TiO₂Particle.(5) titanium dioxide that a. will be obtained in step (4) Titanium takes 600g；Take the Cr of the titanium dioxide 450g and 50g that obtain in step (2)₂O₃, it is scattered in the five silicon oxygen of decamethyl ring of 10L In alkane (DMCPSI), the OctMet (OPMC) of 500g is added, is uniformly mixed, obtains suspending liquid A；B. one is taken Quantitative suspending liquid A, is placed on the glass plate of coating equipment, starts linear motor driver, is pushed away by the conduction of linking arm Dynamic spreader at the uniform velocity moves on a glass.Gap between spreader and glass plate is 50 μm, the shifting of spreader on a glass Dynamic rate is 1m/s；C. when observing that suspending liquid A is uniformly spread on cloth and glass plate, heating plate is opened, adjusts the temperature to 40 DEG C. Then control linear motor driver moves round about, until starting point, and so on moves 2h.Stop linear motor Driver adjusts temperature of heating plate to 70 DEG C, dries 30min.

Embodiment 8

To comparative example 1-2, prepared titanium dioxide carries out absorbance test in embodiment 1-7, and test method is as tested Described in example 1.According to the result of table 7 it is found that using the method for the present invention prepare titanium dioxide, whether in ultra-violet (UV) band, or Visible region, light-absorbing ability is very strong, especially in visible light region (400-550nm), embodiment 1-7 titanium dioxide The absorbance of titanium is above comparative example 1, comparative example 2, and its result with statistical significance (P < 0.01).Wherein embodiment 5 exists At 500nm, 550nm, absorbance will lack (P < 0.05) compared with embodiment 1-4 again, illustrate during the cladding of step (5), use Device better effect provided by the invention.

The absorbance of 7 titanium dioxide of table at different wavelengths

Titanium dioxide and NO gas are placed in quartz reactor, irradiated with the light of wavelength 300nm or the light of wavelength 500nm 8 hours, present invention device is interior to be reacted as follows: 3NO+hv → (1/2) N₂+N₂O+O₂.It measures to decompose by gas chromatography and produce Object N₂The amount of O, N₂O production quantity is bigger, illustrates that optically catalytic TiO 2 ability is stronger, the results are shown in Table 8.According to the result of table 8 It is shown, comparative example 1-2, embodiment 1-7, at 300nm, N₂O production quantity is very close to and data there was no significant difference (P > 0.05), illustrate that photocatalytic activity of these titanium dioxide at 300nm is not much different；But at wavelength 500nm, embodiment Its catalytic activity of the titanium dioxide of 1-7 is significantly higher than comparative example 1,2 (P < 0.01), it was demonstrated that titanium dioxide provided in the present invention Catalytic activity is stronger under visible light.

Table 8N₂O production quantity

Embodiment 9

By comparative example 1-2, the titanium dioxide of embodiment 1-7 preparation prepares mortar according to the method for comparative example 1-3.By powder Material component A and lotion material B component, in mass ratio 1 ︰ 2 are mixed and stirred for uniformly, being coated on 10cm × 10cm plate, thickness control For system in 1.8-2.2cm, each sample is coated with 30 sample panels, is divided into ultraviolet light experimental group and visible light experimental group, and every group 15 Plate.By even spread 1g soot in each sample panel.

Different mortars are tested under ultraviolet light (300nm) and visible light (500nm) to the contamination resistance of soot.Detection Method is as described below: being distinguished irradiating sample 30 days with ultraviolet light and visible light, with portable spectral photometric colour measuring agent test sample face Color, and the sample color change situation of sample is calculated, calculation formula is as follows: Δ E^* _ab=[(Δ L^*)²+(Δa^*)²+(Δb^*)²]^1/2, Middle L is whiteness (0 is black, and 100 be white), Δ L^*=L^* _f-L^* ₀；a^*For red and green area domain (+a^*For red ,-a^*For green), Δ a^*=a^* _f-a^* ₀；b^*For champac region (+b^*For yellow ,-b^*For blue), Δ b^*=b^* _f-b^* ₀。ΔE^* _abValue is bigger, illustrates in reality It tests middle color sample and becomes deeper, that is, contamination resistance is weaker.Experimental result is as shown in table 9,10.

According to table 9,10 as a result, in visible light region, comparative example 1-3 is compared, the mortar of embodiment 1-5 preparation can be more Good prevents soot chronic pollution (P < 0.01), prevents the further blackening of coating, this in embodiment 8, the two of embodiment 1-5 Titanium oxide also matches in the stronger result of visible light region absorbance.However in ultraviolet region, comparative example 1,2, with embodiment 1-5 absorbance is similar, and photocatalytic activity is also similar (data are shown in embodiment 8), it was unexpected that as shown in table 9, embodiment 1-5 exists Under 300nm, soot is prevented to be significantly stronger than comparative example 1,2 (P < 0.01) and 3 (P of comparative example to the ability of coating chronic pollution < 0.01), it was demonstrated that titanium dioxide prepared by the present invention is preventing mortar coating contaminated, especially by carbon smoke pollution, has There is unexpected superior technique effect.

The situation of change of color sample after 9 UV treatment of table

The situation of change of color sample after the processing of 10 luminous ray of table

It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, may be used also With several improvements and modifications are made to the present invention, these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. a kind of modifying titanium dioxide, the titanium dioxide includes four layers, which is characterized in that the modifying titanium dioxide kernel is Silica, the second layer are titanium dioxide, and third layer is chrome green, and outermost layer is titanium dioxide.

2. titanium dioxide according to claim 1, it is characterised in that: in the modifying titanium dioxide, SiO₂Content is 10- 30%, Cr₂O₃Content is 5-20%, TiO₂Content is 50-85%.

3. titanium dioxide according to claim 1 or 2, it is characterised in that: the modifying titanium dioxide is applied to mortar In, the mortar is one or more of lime mortar, cement mortar, mixed mortar.

4. a kind of preparation method of the modifying titanium dioxide as described in any in claim 1-3, the preparation method includes such as Lower step: (1) commercial silica titanium material is pre-processed；(2) TiO that step (1) is obtained₂Carry out pore-creating processing；(3) By one layer of TiO of silica kernel external sheath₂；(4) step (3) are obtained into TiO₂One layer of Cr of external sheath₂O₃；(5) by step (2) TiO obtained₂It is coated on the titanium dioxide outer layer of step (4) acquisition.

5. preparation method according to claim 4, it is characterised in that: in the step (1), pretreated step are as follows: Commercial silica titanium material and deionized water are put into the hollander tub of exclusion device, titanium dioxide raw material and deionized water it Between according to weight mixed proportion be 2-4:6-8；Agitating device forms slurry after being stirred mashing, and slurry injection the first is surpassed Ultrasonic vibration filtering is carried out in acoustic vibration sieve, titanium dioxide, which is filtered, to be extracted；Ammonia is added in the titanium dioxide extracted Water adjusts the pH to 1.0-2.0 of solution, and dithiocarbamate salt derivative solution is constantly added dropwise into reactor at this time, Until not generating solid suspension stopping, continuing to stir 15-25min, titanium dioxide is extracted in filtering；It is filtered and is mentioned in titanium dioxide It is washed with water after taking, is filtered after washing using ultrasonic vibration, then be dried into drying device, obtain low impurity content Titanium dioxide.

6. preparation method according to claim 4, it is characterised in that: the preparation step (2) are as follows: a. is first by step (1) it is 50 μm hereinafter, the titanium dioxide that then will be obtained after grinding that the titanium dioxide and pore creating material obtained is ground to granularity respectively It is uniformly mixed with pore creating material powder, the compression moulding under 100-250MPa pressure；B. by the material through step a compression moulding with 5- 10 DEG C/min heating rate be warming up to 600-1100 DEG C of sintering 3h-6h be prepared removal pore creating material obtain porous titanium precursors； C. calcium metal is added according to calcium and titanium dioxide mass ratio >=2:1 in the porous titanium precursors obtained through step b, then taken out very It is 5-10 DEG C/min that sky to furnace pressure, which is less than or equal to 5Pa, heating rate, reduction temperature is 1000-1100 DEG C of progress calcium heat Reductase 12 4h-60h takes out reduzate after cooling, and reduzate is leached using dilute hydrochloric acid, distilled water is used after the completion of leaching It is washed with dehydrated alcohol, poriferous titanium dioxide is obtained after vacuum dried, and obtained poriferous titanium dioxide is ground to partial size Less than 5 μm.

7. preparation method according to claim 6, it is characterised in that: the pore creating material is ammonium hydrogen carbonate, high purity graphite Or starch, pore creating material additional amount are the 3%-15% of titanium dioxide quality.

8. preparation method according to claim 6, it is characterised in that: in step c, calcium and titanium dioxide mass ratio are 5: 1。

9. preparation method according to claim 4, it is characterised in that: the preparation step (4) are as follows: a. is by step (3) The TiO of middle acquisition₂Particle is scattered in ethyl alcohol, 10-15min is ultrasonically treated, by every g TiO₂Particle corresponds to the ratio of 0.02-1mmol Organo-chromium compound is added in example, forms suspension；B. the water for the amount of taking fully adjusts the suspension difference that pH is obtained into 4-6, with a It is heated to 80-95 DEG C, the two is added in blender simultaneously, reaction is hydrolyzed；C.10-30min end of reaction after is collected Precipitating, calcination 1 hour at 450-750 DEG C obtain cladding Cr₂O₃TiO₂Particle.

10. preparation method according to claim 4, it is characterised in that: the preparation step (5) are as follows: a. is by step (4) The titanium dioxide of middle acquisition takes 1-10 parts by weight, takes and obtains titanium dioxide 5-20 parts by weight in step (2), is scattered in enough In decamethylcyclopentaandoxane, the OctMet of 1-5 parts by weight is added, is uniformly mixed, obtains suspending liquid A； B. by suspending liquid A pressing and wrapping；C. it to pressed suspending liquid A at 60-120 DEG C, heats 1-3 hours, DMCPSI is made to volatilize.