CN1384152A - Titania nano-paint for photocatalytic decomposition of organic matter and its prepn - Google Patents
Titania nano-paint for photocatalytic decomposition of organic matter and its prepn Download PDFInfo
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- CN1384152A CN1384152A CN 01115625 CN01115625A CN1384152A CN 1384152 A CN1384152 A CN 1384152A CN 01115625 CN01115625 CN 01115625 CN 01115625 A CN01115625 A CN 01115625A CN 1384152 A CN1384152 A CN 1384152A
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Abstract
The present invention relates to a paint. At normal temperature, the titania nano-particle sol, organosilicon adhesive and solvent are mixed homogeneously to prepare titania paint to form photocatalytic transparent hydrophilic coating. Of the material, the total weight of titania nano-particle and organosilicon adhesive accounts 1-10 wt% of the paint material and the weight ratio between nanometer titania particle and silica in organosilicon adhesive is 50-95 to 5-50. The paint can form firm transparent titania nano-coating on the surface of base material and the coating can decompose organic matter under the irradiation of light.
Description
The invention belongs to paint field, particularly a kind of titania nano-paint that is used for the organism photocatalysis Decomposition and preparation method thereof.
A large amount of uses of organic chemicals such as gasoline, plastics, agricultural chemicals have greatly improved people's clothing, food, lodging and transportion--basic necessities of life, but in the water and air of constantly waste discharge being depended on for existence to people in the manufacturing of these products and process of consumption, have worsened existent environment of people.It is the natural cleaning system of power that nature has originally with the sunlight, but the continual renovation of Industrial products and mass production make this elements seem more and more insignificant.In order to improve existent environment of people, various environmental improvement technology are continually developed out.Utilize the ultraviolet composition in sunlight and the various source of artificial light, be that can to make water and oxygen conversion be the free radical with strong oxidation capacity for the photocatalyst of representative with titanium dioxide, can decompose the mineralising organism in wide spectrum ground, therefore just get more and more people's extensive concerning, research report, patent documentation are seen everywhere.
Because TiO 2 particles is fine, if it directly is suspended in the medium to be processed, recycling very difficulty, so generally all be titanium dioxide nano-particle to be fixed on the carrier use, is the comparison difficulty but form the high titanium deoxid film of photocatalytic activity at substrate surface.One of method is that the pure titanium plate of atmospheric oxidation or anodic oxidation forms titanium dioxide film, but pure titanizing stable in properties is difficult to oxidation, and photocatalysis performance can not get guaranteeing; Another kind method is with CVD method evaporation titanium dioxide, forms film at substrate surface, and this method is the price height not only, and can only be used for specific base material; It is that titanium dioxide nano-particle is distributed in water or the organic solvent that a kind of method is arranged again, make coating, be sprayed onto on the base material, water or organic solvent volatilization back form titanium deoxid film, but titanium dioxide nano-particle is difficult to disperse, photocatalytic activity does not reach expected effect, and the film tack is poor, and outward appearance is not good.At present, widely used a kind of method is with the titanic acid ester hydrolysis, the preparation titanium dioxide nano sol, is coated on and forms film on the matrix, but that the shortcoming of this method is a raw material is expensive that titanium dioxide nano-particle is a undefined structure in the film, there is not the photochemical catalysis effect, must could use as photocatalyst in the pyroprocessing more than 400 ℃, can not be used for base material, also not be suitable for preparation big area coating as non-refractories such as plastics.
The objective of the invention is to overcome preparation during titania nano-paint used titanic acid ester raw material expensive, titanium dioxide nano-particle does not have crystalline structure in the film of making, need pyroprocessing could possess hydrophilic property defective such as energy, provide the titanium dioxide nano coating of a kind of economic and practical, easy construction, formation to have good photocatalytic activity, and the titania nano-paint that is used for the organism photocatalysis Decomposition that adhesion property is good, appearance transparent is attractive in appearance of base material.
A further object of the present invention provides titania nano-paint that is used for the organism photocatalysis Decomposition and preparation method thereof, and this method is simple to operate, easy to implement.
The titania nano-paint that the present invention is used for the organism photocatalysis Decomposition comprises titanium dioxide nano-particle, solvent and organosilicon caking agent, wherein: closing of the weight of titanium dioxide nano-particle and organosilicon caking agent accounts for 1～10% of coating total amount, and the weight ratio of the silicon-dioxide in titanium dioxide nano-particle and the organosilicon caking agent is 50～95: 50～5.
Described titanium silicon is than (TiO
2: SiO
2) be preferably 60～80.
Described titanium dioxide nano-particle median size is 3～100 nanometers; Between preferred 10～20 nanometers.
Described titanium dioxide nano-particle crystal formation is sharp titanium structure, rutile structure or their mixing crystal formation.
Described solvent is made up of water and alcohol.Described alcohol is methyl alcohol, ethanol, Virahol or their mixture.
Described organosilicon caking agent is that silicone resin or structural formula are R
1 pSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1, q+t is between 2～4, between preferred 3～4.As methyl, ethyl or sec.-propyl silicon ester and silicon halide etc.
Described silicon ester is to use with the oligopolymer form that monomer or partial hydrolysis generate, and oligopolymer is that structural formula is Si
nO
N-1(OR)
2n+2The condenses of silicon ester or their mixture, wherein n is 2～6, R is C
1～4Alkyl.
Coating of the present invention is coated on substrate surface, at room temperature dry, can form the thick coating of 100～300nm, can obtain having the material of photocatalytic activity.
Further contain organic silicone couplet or tensio-active agent in the described coating.
Being used for titanium dioxide nano-particle of the present invention is under the irradiation of light, the titanyl compound that organic redox is had katalysis, with titanium dioxide or more at a low price the state of oxidation be good, the crystal type of titanium dioxide can be anatase crystal type, rutile crystal type, brookite crystal formation or their mixing crystal formation, preferably pure anatase crystal type is because the titanium dioxide of anatase crystal type has better photocatalytic activity.
Consider that from the intensity of photocatalytic activity the particle diameter of these titanium dioxide nano-particles is good with 3～100nm, also can use but particle diameter exceeds this scope, only photocatalytic activity will have reduction in various degree.Titanium dioxide nano-particle can use with powder morphology, but preferably in advance it is made dispersion, and it can be dispersed in the silicone based tackiness agent.
The degree of scatter of titanium dioxide nano-particle in coating can directly have influence on photo-catalysis function and appearance of coat and the mechanical property thereof that forms coating in the present invention.
The manufacture method of titanium dioxide nano-particle has multiple.As 1. in the presence of crystal seed, with the method for titanium compound hydrolysis such as titanium sulfate, titanium chloride, organic titanic compound.2. in the presence of crystal seed, in titanium compounds such as titanium sulfate, titanium chloride, organic titanic compound, add alkali neutral method.3. the method for gaseous oxidation titanium chloride, organic titanic compound.4. calcine 1. above-mentioned and 2. in the method for the titanium dioxide that obtains, or the like.Especially with 1. above-mentioned and 2. in the photocatalysis performance of the titanium dioxide nano-particle that makes of the method mentioned good.For further improving photo-catalysis function, can coat metals such as platinum, gold and silver, copper on the titanium dioxide nano-particle surface.
Use special method, these titanium dioxide nano-particles are disperseed at water or organic solvent camber, for the single dispersion and do not produce the secondary aggegation in the water equal solvent of the titanium dioxide that makes super nanoparticle, should under alkalescence or acidic conditions, preserve, with pH=1～4, be good especially during acid state with 2～3.
With the titanium sulfate thermal hydrolysis, the preparation metatitanic acid, purification, dry, low temperature calcination are used the monoprotic acid dispergation then, obtain titanium dioxide nano-particle colloidal sol.This colloidal sol transparent clear, wherein titanium dioxide nano-particle is in monodisperse status, and median size is 3～100nm; Between preferred 10～20 nanometers, and crystal formation is sharp titanium or rutile structure, is specially adapted to the photocatalyst among the present invention.
The present invention is used for the preparation method of the titania nano-paint of organism photocatalysis Decomposition:
Under the normal temperature, titanium dioxide nano-particle colloidal sol, organosilicon binding agent and solvent is even, make the titania nano-paint that is used for the organism photocatalysis Decomposition; Wherein: the weight of titanium dioxide nano-particle and organosilicon caking agent close the weight percent 1～10% that accounts for the coating total amount, the weight ratio of the silicon-dioxide in titanium dioxide nano-particle and the organosilicon caking agent is 50～95: 50～5.
Use suitable method to mix titanium dioxide nano-particle dispersion and organosilicon caking agent, such as maintaining the temperature at 10～50 ℃, give to drip silicone resin or silicon ester or silicon ester hydrolytie polycondensation body in the titanium dioxide sour water dispersion, dropwise the back stirring reaction and made coating in 1～5 hour.When adding silicon ester or its partial hydrolysis condensation polymer, can add the silicon ester hydrolyst, the acid-basicity of the catalyzer of selecting for use should be consistent with the acid-basicity of titanium dioxide dispersion, example hydrochloric acid or ammoniacal liquor also can utilize acid or alkali in the titanium oxide dispersion to come catalytic hydrolysis.Preferably separately the hydrolyzable silicon compound is carried out prehydrolysis, the alcohols dispersion liquid of prehydrolysis thing is under agitation mixed with the water/pure dispersion liquid of titanium dioxide.
Titanium silicon is than (TiO in coating of the present invention
2: SiO
2Weight) it was 50～95: 50～5 (adding up to 100, weight), if titanium silicon is than (TiO
2: SiO
2) being lower than 50: 50, its photo-catalysis function can diminish and lack practicality.This is because the ratio of silicon oxide particle increases in the final coating that forms, and has hindered titanium dioxide nano-particle and has wanted contacting of oxygenolysis material.If titanium silicon is than (TiO
2: SiO
2) surpassed 95: 5 and the bonding strength of base material jail inadequately, just may come off through friction and vibrations, only be applicable to Special Circumstances, titanium silicon is than (TiO
2: SiO
2) be preferably 60～80.
Solid content is 1～10% (weight) in the coating of the present invention, and this solid content can pass through to burn coating 400 ℃ of dry down bakings, and weight obtained before and after the calculating baking was burnt.The solid content of coating is relevant with coat-thickness, and generally speaking, solid content is high more, and coating is thick more.After coat-thickness surpasses certain value, just can not increase again with the contacted titanium dioxide nano-particle amount of compound of wanting oxygenolysis in the coating, thereby photo-catalysis capability just can not increase again.Titanium dioxide nano-particle density on the too thin then coatingsurface of coating can reduce, and does not have enough photocatalytic activities, is difficult to bring into play necessary photo-catalysis function.Therefore suitable solid content is 0.5～2%, and solid content is transparent in the coating of this scope, can not influence the original outward appearance of base material.Though solid content 0.5% can use when following, the thickness low LCL of coating can increase thickness by application repeatedly.If solid content surpasses 10%, can make the film-forming properties variation, the coating of formation and the adhesivity of base material reduce greatly, once rubbing with the hands it are peeled off with finger.Concrete solid content can be done corresponding selection by concrete purposes.
Coating of the present invention forms coating at substrate surface through coating, drying.Coating process can adopt rolling method, spraying method, pickling process etc. according to the shape of coated base material.
The operable base material range of coating is very wide among the present invention, as glass, metal, cement concrete, slabstone, plasterboard, stone material, timber, pottery or plastics etc., its shape can be arbitrarily, as tabular, tubulose, reticulation, spherical, cellular etc., should thorough drying remove solvent, moisture etc. after the application.
Will be very firm with the coating drying that coating of the present invention forms, can form more firm film at organosilicon caking agent more than 100 ℃, so as required, 100～300 ℃ of bakings.The photocatalytic activity of noting nanoparticle titanium dioxide descends gradually 150 ℃ of baking meetings, and surpassing 400 ℃ will sharply descend, so answer balance coating firmness and photocatalytic activity, suitably selects drying or storing temperature.
The coating of the present invention's preparation is of many uses.Such as the function that can bring into play the self-purging wall when the wall material, can be used to prepare material in hospital with sterilizing function, the insulating board that is used for motorway, can decompose and remove harmful organic substance, microorganism in the air, coating in ceramic hole can be removed obnoxious flavoures such as sulfide hydrogen, stick to and can be used as the material of purifying liquid waste on globular glass, float stone, the pottery, be coated with and be contained in ashtray etc. and also can decompose tobacco tar, the inwall that is used for the pond can prevent algae.
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.
Fig. 1. the embodiment of the invention 2 coating solid contents are to the influence of photocatalytic activity;
Fig. 2. the embodiment of the invention 3 titanium silicon are than (TiO
2: SiO
2) to the influence of photocatalytic activity.
The preparation and the coating preparation of embodiment 1. coating
Get methyl alcohol 20ml, add silicone resin (silicone glass resin, Shanghai Resin Factory produces) 2ml (SiO
2Content 30%), stir, (the Shanghai titanium powder plant produces, TiO to add titanium colloidal sol
2Content 200g/l, particle diameter are 20 nanometers) 2ml, add methyl alcohol to 30ml, stirred one hour, be made into coating.
Coating coating:, be coated on the slide glass that microscope uses, normal temperature seasoning with dip coating with the above-mentioned coating of preparing.
Photocatalytic activity is measured:
The preparation of photocatalytic activity working sample: the above-mentioned slide glass that coats is used ultra violet lamp 2 hours, decompose the organism that the surface may exist, immerse the Methylene blue solution 20～60 minutes of 1mmol/l then, take out and dry the water droplet at back, thorough drying, to be analyzed.
Analytical instrument is with " antifouling activity with photocatalyst evaluating and measuring instrument " (PCC-1, Japanese vacuum science and engineering Co., Ltd. system).Instrument carries the detection light source of ultraviolet lamp and 650nm.The detection light source of 650nm is used to measure the absorbancy of slide glass, and ultraviolet lamp is used for the exciting light catalyzed reaction.The photocatalyst that contains in the filming of slide glass is decomposing the Methylene blue that adsorbs on the slide glass under the irradiation of ultraviolet lamp, the reduction of Methylene blue content causes the reduction of slide glass absorbancy.Slide glass photochemical catalysis effect is good more, and the Methylene blue of decomposition is many more, and then absorbancy reduces manyly more.Instrument is worth the photocatalytic activity that characterizes slide glass by the reduction that detects the certain hour internal absorbance.
Embodiment 2. coating solid contents are to the influence of photocatalytic activity:
Press example 1 method preparation solid content (TiO
2: SiO
2=80: 20) be respectively the coating of 2g/l, 5g/l, 10g/l, 15g/l, 20g/l, coating also is prepared to working sample, detects photocatalytic activity.Result such as Fig. 1 and table 1.
Table 1. coating solid content is to the influence of photocatalytic activity
| Sequence number | Solid content g/l | Outward appearance | Relative rate of decomposition (annotating 1) |
| ????1 | ????2 | Transparent | ????0.1 |
| ????2 | ????5 | Transparent | ????0.4 |
| ????3 | ????10 | Interference color are arranged, and film is even | ????1 |
| ????4 | ????15 | Interference color are arranged, and film is even | ????2.5 |
| ????5 | ????20 | Interference color are arranged, and film is inhomogeneous | ????3 |
Annotate 1: rate of decomposition is each slope of a curve ratio among Fig. 1 relatively, is 10g/l's with the solid content
Rate of decomposition is 1.
By the result as can be known, the photocatalytic activity of coating is relevant with the coating solid content, and the solid content height helps photocatalytic activity; But solid content is too high, is unfavorable for the outward appearance and the homogeneity of coating.
When embodiment 3. coating solid contents were identical, titanium silicon was than (TiO
2: SiO
2) to the influence of photocatalytic activity
By example 1 method preparation solid content is the coating of 10g/l, and titanium silicon is than (TiO
2: SiO
2) be respectively 100: 0,90: 10,70: 30,50: 50 coating, and be mixed with the analysis experiment slice, detect photocatalytic activity.Result such as Fig. 2 and table 2.
The different titanium silicon of table 2 are than (TiO
2: SiO
2) to the influence of photocatalytic activity
| Sequence number | Titanium silicon ratio | Relative rate of decomposition (annotating 2) | Sticking power (annotating 3) |
| 1 | ?100∶0 | ?1 | × |
| 2 | ?90∶10 | ?0.5 | ○ |
| 3 | ?60∶40 | ?0.5 | ◎ |
| 4 | ?50∶50 | ?0.3 | ◎ |
Annotate 2: rate of decomposition is each slope of a curve ratio among the figure two relatively, with titanium silicon than (TiO
2
SiO
2) be that 100: 0 rate of decomposition is 1.
Annotate 3: the coating adhesion that obtains in the example shows with following master meter.
*. just can make breakdown of coating with the finger wiping
Zero. with the finger wiping cut is arranged
◎. there is not cut with the finger wiping
By the result as can be known, the silicone content height helps the bonding strength of coating, but under identical solid content, the increase of silicone content can reduce the content of titanium dioxide in the coating, reduces photocatalytic activity.
Claims (10)
1. titania nano-paint that is used for the organism photocatalysis Decomposition, it is characterized in that: this coating comprises titanium dioxide nano-particle, solvent and organosilicon caking agent, wherein: the weight sum of titanium dioxide nano-particle and organosilicon caking agent accounts for 1～10% of coating total amount, and the weight ratio of the silicon-dioxide in titanium dioxide nano-particle and the organosilicon caking agent is 50～95: 50～5.
2. coating as claimed in claim 1 is characterized in that: described titanium dioxide nano-particle median size is 3～100 nanometers.
3. coating as claimed in claim 1 is characterized in that: described titanium silicon ratio is 60～80.
4. coating as claimed in claim 1 or 2 is characterized in that: described titanium dioxide nano-particle crystal formation is sharp titanium structure, rutile structure or their mixing crystal formation.
5. coating as claimed in claim 1 is characterized in that: described solvent is made up of water and alcohol.
6. coating as claimed in claim 5 is characterized in that: described alcohol is methyl alcohol, ethanol, Virahol or their mixture.
7. coating as claimed in claim 1 is characterized in that: described organosilicon caking agent is that silicone resin or structural formula are R
1 pSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof, wherein: R
1Be C
1～C
18Alkyl, X is a halogen atom, OR
2Be C
1～C
4Organic alkoxy, p+q+t=4,4 〉=q+t 〉=1, q+t is between 2～4.
8. coating as claimed in claim 7 is characterized in that: described structural formula is R
1 pSiX
q(OR
2)
tHydrolyzable silicon compound and partial hydrolysate thereof be methyl, ethyl or sec.-propyl silicon ester and silicon halide.
9. coating as claimed in claim 1 is characterized in that: described titanium dioxide nano-particle surface scribbles platinum, gold and silver or copper metal.
10. as the described preparation method for coating of claim 1-9, it is characterized in that: under the normal temperature that titanium dioxide nano-particle colloidal sol, organosilicon binding agent and solvent is even, make the titania coating that is used to form photocatalytic transparent hydrophilic coating; Wherein: the weight of titanium dioxide nano-particle and organosilicon caking agent close the weight percent 1～10% that accounts for the coating total amount, the weight ratio of the silicon-dioxide in titanium dioxide nano-particle and the organosilicon caking agent is 50～95: 50～5.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011156252A CN1147543C (en) | 2001-04-28 | 2001-04-28 | Titania nano-paint for photocatalytic decomposition of organic matter and its prepn |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011156252A CN1147543C (en) | 2001-04-28 | 2001-04-28 | Titania nano-paint for photocatalytic decomposition of organic matter and its prepn |
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| Publication Number | Publication Date |
|---|---|
| CN1384152A true CN1384152A (en) | 2002-12-11 |
| CN1147543C CN1147543C (en) | 2004-04-28 |
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ID=4662114
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|---|---|---|---|
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|---|---|---|---|---|
| CN100422278C (en) * | 2005-08-26 | 2008-10-01 | 中国科学院金属研究所 | Nano SiO2-organosilicon coating and preparation method thereof |
| CN100999624B (en) * | 2007-01-05 | 2010-05-19 | 福州大学 | Compounding of inorganic anti-pollution coating for high pressure insulator surface and preparation process thereof |
| CN102093794A (en) * | 2010-12-31 | 2011-06-15 | 东莞市明天纳米科技有限公司 | Method for preparing nano-titanium dioxide photocatalytic bactericidal coating |
| CN101450343B (en) * | 2007-12-04 | 2013-03-13 | 日吉华株式会社 | Coating method of building materials |
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-
2001
- 2001-04-28 CN CNB011156252A patent/CN1147543C/en not_active Ceased
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|---|---|---|---|---|
| CN100422278C (en) * | 2005-08-26 | 2008-10-01 | 中国科学院金属研究所 | Nano SiO2-organosilicon coating and preparation method thereof |
| CN100999624B (en) * | 2007-01-05 | 2010-05-19 | 福州大学 | Compounding of inorganic anti-pollution coating for high pressure insulator surface and preparation process thereof |
| CN101450343B (en) * | 2007-12-04 | 2013-03-13 | 日吉华株式会社 | Coating method of building materials |
| US8568870B2 (en) | 2007-12-04 | 2013-10-29 | Nichiha Corporation | Coating film for building material |
| CN102093794A (en) * | 2010-12-31 | 2011-06-15 | 东莞市明天纳米科技有限公司 | Method for preparing nano-titanium dioxide photocatalytic bactericidal coating |
| CN105439152A (en) * | 2014-08-18 | 2016-03-30 | 中国科学院化学研究所 | Liquid-solid phase photocatalytic purification method for purifying SiCl4 and / or SiHCl3 crude product |
| CN104893375A (en) * | 2015-06-03 | 2015-09-09 | 福州大学 | Organic-inorganic hybrid photocatalysis top coating as well as preparation method and application thereof |
| CN105833920B (en) * | 2016-04-27 | 2018-06-29 | 天津蕙俐邦环保科技有限公司 | A kind of ultra-dispersed photochemical catalyst and preparation method and application |
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| CN106563430A (en) * | 2016-11-08 | 2017-04-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Honeycomb ceramic monolithic photocatalyst as well as preparation method and application of honeycomb ceramic monolithic photocatalyst |
| CN108816228A (en) * | 2018-06-28 | 2018-11-16 | 江苏朗逸环保科技有限公司 | A kind of modified Nano grade catalysis material and preparation method thereof |
| CN109225785A (en) * | 2018-08-24 | 2019-01-18 | 金华市东瑞新材料有限公司 | A kind of vacuum cup |
| CN109437752A (en) * | 2018-12-07 | 2019-03-08 | 江西科技学院 | Photo catalytic cement based composites, preparation method and applications |
| CN111826002A (en) * | 2019-09-23 | 2020-10-27 | 法国圣戈班玻璃公司 | Coating dispersion liquid, preparation method and application thereof |
| CN111203218A (en) * | 2020-01-17 | 2020-05-29 | 珠海益佳生物科技有限公司 | TiO with photocatalysis function2Coating and preparation method |
| CN111203218B (en) * | 2020-01-17 | 2022-10-21 | 珠海益佳生物科技有限公司 | TiO with photocatalysis function 2 Coating and preparation method |
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