CN1844001B - TiO2/PI hybridized film with optic catalytic self-cleaning function and preparation method thereof - Google Patents
TiO2/PI hybridized film with optic catalytic self-cleaning function and preparation method thereof Download PDFInfo
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- CN1844001B CN1844001B CN2006100260771A CN200610026077A CN1844001B CN 1844001 B CN1844001 B CN 1844001B CN 2006100260771 A CN2006100260771 A CN 2006100260771A CN 200610026077 A CN200610026077 A CN 200610026077A CN 1844001 B CN1844001 B CN 1844001B
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Abstract
The invention provides a TiO2/PI hybridization film with photocatalysis and self-cleaning function and the process for preparing it, which is characterized in that adding organic monomer in the process of preparing thin films with sol-gel processing, with titanium collosol hydrolytic polymerization happening, forming medlin phase (PAA) in original position polyreaction, finally, forming a nanometer crystal phase TiO2/PI hybridization film after heat treating. The thickness of hybridization film is not less than 300nm, which higher than anatase nanometer crystal phase obtained from common puretitanium collosol. There isn't crackle and flake for film in the process of heat treating. Chosing a suitable medlin leading body, a Ti-S bond is formed at the same time of forming a hydrogen bond inthe hybridization film, which endowing film with photocatalysis and self-cleansing effect under the visible light. And the photocatalysis and self-cleansing effect of the film are higher than the photocatalysis activity of common titanium oxide nanometer crystal phase film, meanwhile, the film has good radiation resistant and chemical stability.
Description
Technical field
The present invention relates to the brilliant and polyimide (TiO of a kind of original position synthetic TiOx nano
2/ PI) hybrid film particularly relates to and a kind ofly is coated on various glass such as building glass, vehicle glass, opticglass, and various inorganic material surfaces such as architectural pottery, snitaryware have the self-cleaning net work of photocatalytic degradation can film.The hybridized film that the present invention relates to has significant photocatalytic degradation function under the irradiation of ultraviolet-visible light wave.
Background technology
The brilliant film of nanoscale titanium oxide powder and TiOx nano has the organic and inorganic pollutant characteristic of photocatalytic degradation under UV-irradiation, the various materials that the surface scribbles the brilliant film of TiOx nano are regarded as having self-cleaning net work energy.
The brilliant film of preparation TiOx nano can adopt methods such as magnetron sputtering, vapour deposition and sol-gel.Can obtain to have the nanoscale anatase crystal structure of remarkable self-cleaning net effect with sol-gel method, the then easier usually formation amorphous structure of other technological process, its self-cleaning net effect relatively a little less than.But sol-gel processing is attended by a large amount of organic volatilizations in the process that adds thermosetting anatase nanometer crystal structure, cause the contraction of thin film layer.Thin film layer that shrinks and basal body interface produce stress, and when the blocked up interfacial stress of rete was excessive, defectives such as cracking peels off may appear in film.Generally a coating film thickness for preparing the brilliant film of TiOx nano with sol-gel method need be controlled in 100 nanometers, and needs strict control temperature rise rate, just might obtain evenly complete film.Because the self-cleaning net effect of photocatalytic degradation is relevant with the thickness of thin film of titanium oxide within the specific limits, have only the thin film of titanium oxide of working as to reach the hundreds of nanometer thickness, just might obtain best photocatalytic effect, therefore need to reach practical self-cleaning net effect by behind the plated film several times.
The restriction of sol-gel process one-pass film-forming thickness makes present coating process adopt crystal pulling method and centrifugal rotational method usually.But the more trial-production that is used for laboratory sample of centrifugal rotational method is not suitable for suitability for industrialized production.Only can be used for the step off-line mode of production and lift rule.For the on-line continuous plated film mode that large-scale commercial production requires, comparatively the ideal coating process is the colloidal sol spraying.Because the thicknesses of layers of the preparation of colloidal sol spraying at present is higher, can not be used for the preparation of the brilliant film of TiOx nano, therefore improves colloidal sol character, improves the thickness of a plated film, becomes the key of improving the collosol and gel coating process.A kind of film formation technology of having invented relates to hydrothermal method alkalescence peptization and prepares titanium dioxide water coating, at low temperatures plated film (CN200510012123.8).With this interfacial stress of avoiding thermal treatment to cause.Yet the film that film formation at low temp and high-temperature heat treatment form is compared, and the bonding state of its film and matrix is different, through heat treated film and matrix better bonding can be arranged, and film can be more firm in adhering to of matrix surface.
The pure zirconia titanium is nanocrystalline just the photocatalytic degradation effect can to take place under less than the UV-irradiation of 400nm wavelength.In actual applications, the ratio of light source medium ultraviolet light such as sunlight only is about 5%, therefore develops the photocatalytic effect under the visible light wave range rayed, has important use for the photocatalytic effect that improves the TiOx nano crystalline substance and is worth.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can form coating film thickness at the inorganic materials matrix surface and reach nanocrystalline TiO more than the 300nm
2/ PI hybridized film and preparation method thereof.Titania precursor thing that the present invention relates to use in sol-gel process and polyimide precursor monomer mix, and prepare nanocrystalline TiO with polymerization of titanium sol-hydrolysis and polyimide original position polymerization process
2/ PI hybridized film.Thickness reaches the above hybridized film of 300nm, and after heat treatment structure is intact, flawless and defective such as peel off.
The present invention relates to form TiO with different polyimide precursor monomer polymerizations
2/ PI hybridized film.The add-on of polyimide is 1～30% in the hybridized film.Hybridized film is a transparent film, and increases with polyimide content, and hybridized film is light brown gradually.TiO
2The photochemical catalysis of/PI hybridized film excites wave band to extend to visible light wave range from UV-light, and corresponding photocatalytic activity can reach 4～5 times of pure zirconia titanium nano thin-film.The TiO that the present invention relates to
2/ PI hybridized film has favorable durability under solar light irradiation.
The sol-gel in-situ polymerization film preparation process that the present invention relates to not only can be used for the thin film preparation process of crystal pulling method, centrifugal rotational method, also can be used for being fit to the thin film preparation processes such as spraying method of suitability for industrialized production, and various film coating method all can not make TiO
2Defectives such as/PI hybridized film cracks and peels off.
The present invention is achieved in that with inorganic materials such as glass or potteries be matrix, with titania precursor thing and the monomeric mixing solutions of polyimide precursor, form specific titanium colloidal sol through sol-gel and in-situ polymerization process, this titanium colloidal sol is coated in inorganic materials matrix surfaces such as glass or pottery, obtains TiO through Overheating Treatment
2/ PI hybrid film.Whole film preparation process comprises: the preparation of titania precursor thing and polyimide precursor monomer mixed sols, mixed sols form TiO in coating, the thermal treatment of inorganic materials matrix surface
2/ PI hybridized film.
The TiOx nano crystalline precursor solution that the present invention relates to comprises: titanium alkoxide raw materials such as tetrabutyl titanate, titanium ethanolate; The vehicle substance of dissolving such as ethanol, Virahol, propyl alcohol, butanols titanium alkoxide; The stabilizing agentof sol of control titanium sol-hydrolysis polymerization process is as one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid etc.
The polyimide precursor monomer solution that the present invention relates to comprises: pyromellitic dianhydride, Tetra hydro Phthalic anhydride, maleic anhydride, nitro phthalic anhydride, chloro-benzoic anhydride, 4,4 '-diphenyl sulfide dianhydride and 4, the monomer of one or more acid anhydrides such as 4-diaminodiphenyl oxide, diaminodiphenylsulfone(DDS), thiocarbamide, aniline and amine, solvent is dimethyl formamide, N, one or more mixed solvents such as N-dimethyl acetyl ammonia, N-Methyl pyrrolidone, tetrahydrofuran (THF).
A kind of TiO with photocatalytic self-cleaning function
2The preparation method of/PI hybridized film, wherein,
1) mixed with titanium alkoxide, various additive and solvent form titanium alkoxide solution;
2) mix various presoma monomers of polyimide and solvent, stir at normal temperatures, form polyimide precursor solution;
3) mixed with titanium alkoxide solution and polyimide precursor solution carry out the hydrolytic-polymeric reaction of titanium alkoxide and the home position polymerization reaction of polyamic acid, form mixed sols;
4) on glass or ceramic matrix material, apply mixed sols with rotational method, crystal pulling method or spraying method;
5) at 100 ℃ of oven dry mixed sols films;
6) the mixed sols film was 400～600 ℃ of thermal treatments 15 minutes to 1 hour, and forming with the nanostructured anatase is the hybrid film of polyimide of principal crystalline phase.
The present invention relates to above-mentioned titanium precursor liquid solution and polyimide precursor monomer solution are mixed back formation mixing solutions, the content of polyimide precursor can be 1%～30% in the mixing solutions.Mixing solutions at low temperatures through a few hours to a couple of days home position polymerization reaction, the titanyl of formation and polyamic acid (PAA) mixed sols can be used for plated film.It is as follows that typical polyamic acid forms reaction:
Propose after the glass of cleaning surfaces or pottery immersed mixed sols, or a certain amount of colloidal sol is spread over glass or ceramic matrix surface according to film thickness, or at glass or the certain thickness sol layer of ceramic matrix surface spraying.The different thickness colloid mixture layer that forms with different methods is heat-treated, there is anatase nanometer crystal to form mutually in the heat treatment process, and having the polyamic acid dehydration reaction to form polyimide, sol layer changes transparent anatase nanometer crystal and polyimide hybrid film gradually into.The reaction that typical polyamic acid dehydration forms polyimide is as follows:
According to the variation of coating process condition, hybridized film thickness can reach more than tens nm to 300nm, and thickness increases to 300nm when above, and hybridized film is flawless and defective such as peel off still.Meanwhile, thickness increase within the specific limits can improve the photocatalytic self-cleaning function of hybridized film.
The TiO that the present invention relates to
2/ PI hybridized film wherein connects with hydrogen bond or Ti-S key between anatase phase and the polyimide phase.Ti-S key in the hybridized film can increase the photocatalytic effect that visible light wave range excites, thereby significantly improves the photocatalytic self-cleaning function of hybridized film.
The TiO that the present invention relates to
2Polyimide in the/PI hybridized film has high temperature resistant fast light radiating characteristic mutually, can stand solar light irradiation over a long time, and photocatalytic activity does not have noticeable change, so hybridized film has favorable durability.
The TiO that the present invention relates to
2/ PI hybridized film need not significantly to change sol-gel process, need not repeatedly plated film, and on the basis of the original sol gel process of basic maintenance, the transparent photocatalyzing that can prepare flawless and defectives such as peeling off is from clean film.The photocatalytic activity of hybridized film can reach 4～5 times of pure zirconia titanium film.
The TiO that the present invention relates to
2/ PI hybridized film preparation method also is applicable to the preparation of other inorganic nano structure-polyimide hybrid film.
Embodiment
Under the room temperature, in one or more mixed solvents of the ethanol that is dissolved with the titanium alkoxide, Virahol, propyl alcohol, butanols etc., add the wherein stabilizing agentof sol of one or more combination such as methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, sulfuric acid again, mix more than 20 minutes, the solution of formation is called titanium alkoxide solution.With 4, one or more mixtures of 4-diaminodiphenyl oxide, diaminodiphenylsulfone(DDS), thiocarbamide join an amount of dimethyl formamide, N, in one or more mixed solvents such as N-dimethyl acetyl ammonia, N-Methyl pyrrolidone, tetrahydrofuran (THF), add pyromellitic dianhydride, Tetra hydro Phthalic anhydride, maleic anhydride, nitro phthalic anhydride, chloro-benzoic anhydride, 4 again, one or more mixtures of 4 '-diphenyl sulfide dianhydride etc., make it to dissolve fully, the solution of formation is called the polyimide precursor solution.The polyimide precursor solution is slowly added titanium alkoxide solution, and the solution of formation is called mixing solutions.Add suitable quantity of water in mixing solutions, polyreaction is hydrolyzed.It is about more than one hour constantly to mix solution in this process, and mixing solutions carries out home position polymerization reaction and forms polyamic acid at titanium hydrolysis of alkoxide polymeric simultaneously.The mixed sols that is formed by titanium colloidal sol and polyamic acid can be used to prepare film in a few hours or a couple of days.Slowly taking out behind free of contamination glass of surface clean or the ceramic member immersion colloid, make it surface-coated one deck colloidal sol, or with centrifugal rotational method at glass or ceramic member surface-coated sol layer, or form sol layer at glass or ceramic surface with spraying method, then in succession 100 ℃ of dryings 10 minutes, 400～600 ℃ of thermal treatments 15～60 minutes.The cooling back forms TiO at glass or ceramic surface
2/ PI hybridized film, this hybridized film have good photocatalytic self-cleaning performance.
Embodiment 1, and a certain amount of butyl (tetra) titanate (20ml), concentrated hydrochloric acid (1ml), methyl ethyl diketone (1ml) are dissolved in ethanol (40ml), mixes 30 minutes, and adds suitable quantity of water and ethanol (about 10ml); An amount of diaminodiphenylsulfone(DDS) (1g) joins in the N,N-dimethylacetamide solvent (50mL), makes it to dissolve fully, adds a certain proportion of pyromellitic dianhydride and Tetra hydro Phthalic anhydride (each 0.6g) again, is stirred to dissolving; After mixing above-mentioned solution, stirred 2 hours, form the light brown mixed sols.The glass sample of cleaning is immersed in the above-mentioned colloidal solution and proposes; Or some amount colloidal sol dropped in glass surface, form the film of the above-mentioned colloidal sol of one deck at glass surface with rotational method (＜800 rev/mins).This film after about 10 minutes, 500 ℃ of thermal treatments 30 minutes, can be obtained the TiO of thickness greater than 300nm 100 ℃ of dryings
2/ PI hybridized film.The photocatalytic activity of hybridized film degraded tropeolin-D can reach more than 3 times of common titanium oxide nano thin-film.
Embodiment 2, and a certain amount of butyl (tetra) titanate (20ml), concentrated hydrochloric acid (1ml), methyl ethyl diketone (0.6ml) are dissolved in ethanol (40ml), mix 30 minutes; Add thiocarbamide and N,N-dimethylacetamide solution (50mL), add a certain proportion of pyromellitic dianhydride and Tetra hydro Phthalic anhydride (each 0.6g) then, add suitable quantity of water and ethanol (about 10ml) again, continuously stirring 3 hours forms even colloidal sol.This colloidal sol is made film by embodiment 1, can obtain the light brown TiO of thickness greater than 300nm
2/ PI hybridized film.Increase darkening of hybridized film with the PI add-on, its photochemical catalysis degrading activity under visible light shines also improves thereupon.Hybridized film can reach 4～5 times of common titanium oxide nano thin-film at the descend photocatalytic activity separate tropeolin-D of ultraviolet lighting.
Photocatalytic activity test in above-mentioned two examples selects for use the degradation rate of colored compound methyl orange solution to express.Concrete test process is: the methyl orange aqueous solution of preparation 10mg/L concentration will be coated with TiO
22.5 * 2.5cm glass specimen of/PI hybridized film places the 50ml methyl orange solution.The ultraviolet high-pressure mercury lamps of two 125W is placed 25cm place, test soln top, fill the logical recirculated cooling water cooling of container outer wall of methyl orange solution, and place water-bath, monitor bath temperature with temperature measurer, make the methyl orange solution temperature remain on 23 ℃ ± 2 ℃, guarantee can not influence the degradation rate test of tropeolin-D because ultraviolet lighting causes the solution intensification with this.Feed little air in the methyl orange solution, be beneficial to the carrying out of titanium oxide photochemical catalyst reaction in the solution.After the methyl orange solution of certain hour light-catalyzed reaction takes out, with the absorbancy of spectrophotometer test methyl orange solution at the 470nm place.Because dissolved tropeolin-D concentration is proportional to absorbancy in the solution, can calculate the degradation rate of tropeolin-D according to the variation of absorbancy.
Claims (3)
1. TiO with photocatalytic self-cleaning function
2/ PI hybridized film, it is characterized in that: the matrix of hybridized film is glass and ceramic inorganic materials, is mixed by various ingredients and forms titanium colloidal sol, and add the polyimide precursor mixture therein, through Overheating Treatment, matrix surface forms the nanocrystalline TiO of thickness greater than 300nm
2/ PI hybridized film, the add-on of polyimide is 1～30% in the hybridized film, wherein,
The various ingredients of described composition titanium colloidal sol is: the titanium alkoxide is butyl (tetra) titanate, titanium ethanolate, and alcoholic solvent is ethanol, propyl alcohol, butanols; The stabilizing agentof sol of control hydrolysis polymerization process is one or more the combination in methyl ethyl diketone, quadrol, citric acid, acetate, hydrochloric acid, nitric acid, the sulfuric acid, forms mixing solutions more and forms titanium sol-fraction in the mixed sols through hydrolysis and polyreaction;
Described polyimide precursor and solvent thereof, wherein, the polyimide precursor monomer solution is pyromellitic dianhydride, Tetra hydro Phthalic anhydride, maleic anhydride, nitro phthalic anhydride, chloro-benzoic anhydride, 4, one or more acid anhydrides in 4 '-diphenyl sulfide dianhydride, diaminodiphenylsulfone(DDS), thiocarbamide, the aniline and the monomer of amine, solvent is dimethyl formamide, N, one or more mixed solvents in N-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, the tetrahydrofuran (THF), organic precursors original position in mixed sols aggregates into the polyamic acid part.
2. at the described a kind of TiO of claim 1 with photocatalytic self-cleaning function
2The preparation method of/PI hybridized film is characterized in that:
1) mixed with titanium alkoxide, various additive and solvent form titanium alkoxide solution;
2) mix various presoma monomers of polyimide and solvent, stir at normal temperatures, form polyimide precursor solution;
3) mixed with titanium alkoxide solution and polyimide precursor solution carry out the hydrolytic-polymeric reaction of titanium alkoxide and the home position polymerization reaction of polyamic acid, form mixed sols;
4) on glass or ceramic matrix material, apply mixed sols with rotational method, crystal pulling method or spraying method;
5) at 100 ℃ of oven dry mixed sols films;
6) the mixed sols film was 400～600 ℃ of thermal treatments 15 minutes to 1 hour, and forming with the nanostructured anatase is the hybrid film of polyimide of principal crystalline phase.
3. a kind of TiO according to claim 2 with photocatalytic self-cleaning function
2The preparation method of/PI hybridized film is characterized in that:
The mixed sols of the hybridized film that forms, through suitable hydrolysis and polyreaction, through Overheating Treatment, in the anatase octahedrite of titanium oxide and polyimide hybrid structure, obtain hydrogen bond and Ti-S key, this structure hybridization film has significant catalytic self-cleaning net effect under UV-light and radiation of visible light.
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| CN106633129A (en) * | 2016-11-18 | 2017-05-10 | 浙江理工大学 | Method for preparing polyimide/TiO2 composite material nanometer film |
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