CN1811049A - Nanometer titania finishing agent with photocatalytic performace and high detergency and its prepn and application - Google Patents
Nanometer titania finishing agent with photocatalytic performace and high detergency and its prepn and application Download PDFInfo
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- CN1811049A CN1811049A CN 200510111713 CN200510111713A CN1811049A CN 1811049 A CN1811049 A CN 1811049A CN 200510111713 CN200510111713 CN 200510111713 CN 200510111713 A CN200510111713 A CN 200510111713A CN 1811049 A CN1811049 A CN 1811049A
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Abstract
The present invention is one kind of nanometer titania finishing agent with photocatalytic performance and high detergency. The nanometer titania finishing agent features its core-shell structure including a core of nanometer anatase type titania crystal and a shell of microporous carbon in light grey color. It is prepared through mixing water 18 wt%, Triton X-100 5-15 wt%, sodium bis(2-ethylhexyl) sulfosucccinate 1-5 wt%, butyl titanate 3-8 wt%, n-hexanol 12-18 wt% and cyclohexane 46-78 wt% at room temperature to produce micro emulsion; soaking nanometer anatase type titania crystal in the micro emulsion; carbonizing the solid, cooling and crushing. It is used as fabric finishing agent, and the finished fabric is easy to wash and wash resistant and possesses photocatalytic deterging and ultraviolet ray absorbing characteristic.
Description
Technical field:
The object of the invention provides a kind of easy decontamination nanometer titania finishing agent, preparation and application technology with photocatalysis performance.The present invention will be applied to textile finishing after the modification of nano-titanium oxide plane of crystal or other is unwell to the carrier of high-temperature process.Still have photocatalysis decontamination and the ultraviolet radiation absorption characteristic same after making the nano-titanium oxide crystal film be fixed in their surface with former powder suspension body.For after-finishing of textile products particularly on the carrier of soil-releasing finiss and other non-refractory the applying nano crystalline titanium oxide open up a simple and easy technology.
Background information:
Nanocrystal TiO2; in ultraviolet radiation absorption; photocatalysis; the hydrogen manufacturing of photodestruciton water; gas sensor is made and solar energy has the prospect that induces one in changing and be subjected to noting widely; particularly state basic policy is classified in the application and development of the many handles in various countries " environmental protection " and " green energy resource " as in recent years, and the research of nanocrystal TiO2 has become the problem of gazing at.Particularly photocatalysis and solar cell Application and Development aspect are discussed and report a lot both at home and abroad.Nanocrystal TiO2 is when UV-irradiation, and its oxidability is only second to fluoride electrode in the electrode potential table, can make most organic dirt mineralisings, finally generates harmless simple material such as CO
2And water.(“Chem.Rev.1995。V95。First phase P69-96 ") this is fabulous approach for the decontamination and the disposal of three wastes.It is few that but nano-titanium oxide is applied to the documents and materials of textiles, this is because of nanocrystal is prepared into two kinds of methods to be arranged usually on the organic carrier (as textiles), the one, make product (as fiber) with behind it and the monomer copolymerization, this is except solving the dispersiveness of nanocrystal, prevent outside its difficulty that is gathered into piece, another problem is that cost is higher relatively, also is not suitable for natural fabric (as cotton) simultaneously.Another kind is in back arrangement nanocrystal TiO2 to be made film at fabric face, but reported in literature (Acta PhySico-Chimica Sinica (ACTAPhys.-Chim.Sin.) calendar year 2001,17 (2) P177-180.) in prepare the method for solar cell [it make colloidal sol with raw material (colloidal sol) as titanium tetrachloride or butyl titanate, is applied to the surface of electro-conductive glass, at 400 ℃ of left and right sides sintering, makes it to become the anatase nanocrystal film then.] inapplicable to textiles, because of the general non-refractory of textiles.And some textiles is also not acidproof as cotton goods.And the inorganic matter with textiles affinity difference to be fixed in the surperficial adding additives that needs of organic fabric in the method for sorting usually, but use binding agent can make binding agent (as acrylate) be wrapped in the surface of nano-titanium oxide here as directly, when illumination was penetrated, photocatalysis performance completely lost.Thereby detergency ability can not be manifested, and nanocrystal TiO2 is easily come off at fabric face without binding agent, more not washable.
Summary of the invention
The purpose of this invention is to provide a kind of easy decontamination nanometer titania finishing agent with photocatalysis performance;
Purpose of the present invention also provides a kind of preparation method of the above-mentioned easy decontamination nanometer titania finishing agent with photocatalysis performance;
Another object of the present invention provides a kind of application of the above-mentioned easy decontamination nanometer titania finishing agent with photocatalysis performance.
Easy decontamination nanometer titania finishing agent with photocatalysis performance of the present invention is a kind of carbon of nanocrystal TiO2 powder outer wrapping one deck porous.Product is light gray.It is a kind of core-shell structure for a transmissioning electric mirror test, and skin is the carbon of micropore, examines the titanium oxide into the nano-anatase crystal formation.The carbon-coating of this porous can allow micromolecular dirt infiltration to pass through, and when UV-irradiation, the dirt molecule that arrives the TiO2 surface can be by mineralising.And little macromolecular binding agent such as the acrylate molecule of can not making in the carbon-coating hole of porous passes through, so the binding agent molecule is non-degradable, it makes the titanium oxide crystal of carbonizing and modifying be fixed in fabric face, and reaching to have the wash fast again effect of photocatalysis decontamination.Do dirt representative (Joumal of sol-gel science andtechnology 24.2002.P95-103) by the document convention with methyl orange, make under photocatalysis performance and the similarity condition of titanium oxide crystal powder of carbonizing and modifying the preceding titanium oxide crystal powder of not carbonization basic identical.
The preparation method of the easy decontamination nanometer titania finishing agent with photocatalysis performance of the present invention is different with other surface-modification method; the present invention adopts n-hexanol, cyclohexane, polyvinyl alcohol (PVA) and surfactant TritonX-100, AOT etc. to prepare micro emulsion earlier for raw material; to make by oneself or commodity nanocrystal TiO2 immersion back stirring; after the separation with powder for drying; in Muffle furnace, calcine again, need not use nitrogen protection.
Preparation technology: raw material: the anatase-type titanium oxide of (1) nanocrystal.Can use the commercial goods or make by oneself by the reported in literature the whole bag of tricks.(2) micro emulsion.
The micro emulsion preparation of parcel carbon-coating: 1%～8% water, 5%～15% Triton X-100,1%～5%AOT[promptly: two (2-ethylhexyl) sulfonic group sodium succinate], 3%～8% butyl titanate, 12%～18% n-hexyl alcohol, 46%～78% cyclohexane.Stir under the room temperature and generate microemulsion.
Nucleocapsid structure titanium oxide crystal powder preparation: the anatase-type titanium oxide of raw material nano crystal is immersed above-mentioned micro emulsion.Quantity must be with the complete submergence of crystal powder.Stir after one hour, filter, take out solid, be placed on the interior carbonization of Muffle furnace and form, heat to 300 ℃～600 ℃, constant temperature 1～5 hour is pulverized after the cooling again.Product is a light gray.
The easy decontamination nanometer titania finishing agent with photocatalysis performance that the present invention is above-mentioned is used for textile finshing agent.Using method: (1) maceration extract preparation: 1 premium on currency, add the titanium dioxide powder after the above-mentioned surface modification of 1～5 gram, add AOT5～10 grams again, binding agent (acrylate) 5～10 grams, polyvinyl alcohol 5～10 grams are dispersed into suspension.
(2) textiles is immersed, adopt padding method, two soak two rolls pressure: 2KG/CM
2, cured 90～180 seconds at 100～120 ℃.
Advantage of the present invention:
(1) raw material can adopt commercially available nano oxidized titanium crystal.Do not need extraordinary preparation technology, only it is done surperficial modification.
(2) the nano oxidized titanium crystal after the modification can use the direct low temperature of common bond to be fixed in the surface of carrier such as organic plastics of textiles or other non-refractory, and the textiles after the arrangement has easy decontamination and wash fast performance.
(3) textiles after the arrangement is penetrated down in illumination and is had same photocatalysis decontamination and ultraviolet radiation absorption characteristic with former nanocrystal powder suspension body.
(4) this technique processing method is simple and easy, and is with low cost.
Description of drawings
The TEM photo of homemade nano-titanium oxide powder before Fig. 1 modification.
Fig. 2 is the TEM photo of the present invention after with nano-titanium oxide modification among Fig. 1.
The visible nucleocapsid structure of the section of the broken particle from figure.
The specific embodiment:
To help to understand the present invention by following examples, but not limit content of the present invention.
The preparation of the anatase-type titanium oxide of embodiment 1 nanocrystal
Can use the commercial goods or by the self-control of the method for reported in literature, specific as follows: raw material is a titanium tetrachloride, ethanol, triethanolamine, ammoniacal liquor, 145 ℃ with hydrothermal method preparation, reaction condition and technology are seen document: Acta PhySico-Chimica Sinica (ACTAPhys.-Chim.Sin.) calendar year 2001,17 (8) P713-717.The nano-titanium oxide powder that makes is made the raw material of modification.
Embodiment 2 has the preparation of the easy decontamination nanometer titania finishing agent of photocatalysis performance
Specific as follows: micro emulsion preparation: 5% water, 12% Triton X-100,2%AOT[promptly: two (2-ethylhexyl) sulfonic group sodium succinate], 6% butyl titanate, 20% n-hexyl alcohol, 55% cyclohexane.Stir under the room temperature and generate microemulsion.The anatase-type titanium oxide of raw material nano crystal is immersed above-mentioned micro emulsion.The complete submergence of solid.Stir after one hour, filter, take out solid, be placed on the interior carbonization of Muffle furnace and form, carburizing temperature control is heated earlier to 450 ℃, and constant temperature 3 hours is pulverized after the cooling again.Product is a light gray.
Embodiment 3 application examples
Adopt the foregoing description 1 preparation about 20 nanometers of particle diameter (recorded by XRD and transmission electron microscope, Fig. 1) anatase-type titanium oxide is a raw material, do to do the transmissioning electric mirror test (see figure 2) after the surperficial modification with above-mentioned second step process, be nucleocapsid structure as can be known from the cross section of fragmentation.About 40 nanometers of parcel back particle diameter, by X-ray diffraction as can be known, crystal formation still is a Detitanium-ore-type.With it adopt above-mentioned technology (maceration extract preparation: 1 premium on currency, add the titanium dioxide powder after the above-mentioned surface modification of 3 grams, add AOT 6 grams again, binding agent (acrylate) 6 grams, polyvinyl alcohol 8 grams are dispersed into suspension.)
Make binding agent with acrylate, arrangement white cotton khaki drills adopts padding method, and two soak two rolls pressure: 2KG/CM
2, cured 100 seconds at 120 ℃.Be dipped in methyl orange solution with the cotton card after the arrangement, solution composition is that hydrogen peroxide is 0.1%; Every liter contains 4.88 milligrams of methyl oranges.Under the 12W ultra violet lamp, methyl orange is faded obviously.Solution became colourless in two hours.Rate constants k/minute=0.01266; After the cotton card washing after this arrangement 50 times, catalytic effect still clearly, rate constants k/minute=0.00434; Learn that by calculating washing still has after 50 times nearly 34% photochemical catalyst to stay on the fabric.After the photocatalysis, cotton card and the cotton card of raw material (this white), color is identical.
Implementation of an application example (B): raw material terylene poplin cloth, the finishing agent of dipping usefulness soaks two with example (A) two and rolls pressure: 2KG/CM
2, cured 100 seconds at 110 ℃.It is the same to be dipped in blue solution (dirt representative) (concentration is 0.002%, and containing hydrogen peroxide concentration in the solution is 0.4%) the irradiation condition of methine with the terylene poplin cloth after the arrangement, and solution became colourless in two hours.Rate constants k/minute=0.01314; Rate constants k after washing 40 times/minute=0.01096.After the photocatalysis, the terylene poplin cloth is identical with raw material terylene poplin cloth color.
Implementation of an application example (C): the raw material nano titanium oxide powder prepares the same, micro emulsion preparation: 7% water, 15% Triton X-100,3%AOT[promptly: two (2-ethylhexyl) sulfonic group sodium succinate], 6% butyl titanate, 16% n-hexyl alcohol, 53% cyclohexane.Stir under the room temperature and generate microemulsion.The anatase-type titanium oxide of raw material nano crystal is immersed above-mentioned micro emulsion.The complete submergence of solid.Stir after one hour, filter, take out solid, be placed on the interior carbonization of Muffle furnace and form, carburizing temperature control is heated earlier to 500 ℃, and constant temperature 3 hours is pulverized after the cooling again.Product is a light gray.Make raw material with the white cotton khaki drills: maceration extract preparation: 1 premium on currency, add the titanium dioxide powder after the above-mentioned surface modification of 3 grams, add AOT 5 grams again, binding agent (acrylate) 5 grams, polyvinyl alcohol 5.5 grams are dispersed into suspension.Two soak two rolls pressure: 2KG/CM
2, cured 100 seconds at 110 ℃.It is the same to be dipped in blue solution (dirt representative) (concentration is 0.002%, and containing hydrogen peroxide concentration in the solution is 0.4%) the irradiation condition of methine with the cotton card after the arrangement, and solution became colourless in two hours.Rate constants k/minute=0.01410; Test after washing 50 times rate constants k/minute=0.0049.After the photocatalysis, cotton card is identical with the cotton card of raw material color.
Embodiment 4 application examples
Raw material terylene poplin cloth, dipping finishing agent of usefulness and finishing technique are done the dirt representative with example (C) with methyl orange, (methyl orange and hydrogen peroxide concentration are with routine (A)) the bleach solution that fades in two hours.Rate constants k/minute=0.01210; After the photocatalysis, the terylene poplin cloth is compared no change with raw material terylene poplin cloth color, wash 30 times after, rate constants k/minute=0.01050.
Illustrate: the intensity of photocatalytic speed constant and irradiation is relevant, and sunshine medium ultraviolet light accounts for 3～5%; Anatase-type titanium oxide only absorbs ultraviolet ray, makes the dirt of its surface absorption be oxidized to nontoxic simple molecules, and it is the most practical to use sunshine to do measurement, but a difficulty is arranged, Strength Changes is big throughout the year, also is subjected to cloudy partly cloudy influence of weather, and testing used portable uviol lamp is 12W.Experiment experience shows with make peace greatly in the methyl orange solution of same concentration and oxidants hydrogen peroxide solution spring and autumn sky fine day solar irradiation catalytic effect of same catalyst similar.
Claims (6)
1, a kind of easy decontamination nanometer titania finishing agent with photocatalysis performance is characterized in that a kind of core-shell structure, examines the TiOx nano crystal into the nano-anatase crystal formation, and the carbon of the carbon porous of outer wrapping one deck micropore is light gray; Described carbon is formed through carbonization by the water microemulsion of Triton X-100, two (2-ethylhexyl) sulfonic group sodium succinate, butyl titanate, n-hexyl alcohol and cyclohexane.
2, a kind of easy decontamination nanometer titania finishing agent with photocatalysis performance, it is characterized in that described water microemulsion contains 5%～15%Triton X-100,1%～5%AOT[is promptly: two (2-ethylhexyl) sulfonic group sodium succinate], 3%～8% butyl titanate, 12%～18% n-hexyl alcohol, 46%～78% cyclohexane.All the other are water.
3, a kind of preparation method as claimed in claim 1 with easy decontamination nanometer titania finishing agent of photocatalysis performance, it is characterized in that with
1%～8% water, 5%～15%Triton X-100,1%～5%AOT[is promptly: two (2-ethylhexyl) sulfonic group sodium succinate], 3%～8% butyl titanate, 12%～18% n-hexyl alcohol, 46%～78% cyclohexane.Stir under the room temperature and generate microemulsion.
With the anatase-type titanium oxide of above-mentioned micro emulsion submergence nanocrystal, stir after one hour then, filter, solid is at 300 ℃～600 ℃, and constant temperature carbonization in 1～5 hour is cooled off, and pulverizes.
4, a kind of preparation method with easy decontamination nanometer titania finishing agent of photocatalysis performance as claimed in claim 1 is characterized in that described carbonization carries out in Muffle furnace.
5, a kind of purposes with easy decontamination nanometer titania finishing agent of photocatalysis performance as claimed in claim 1 is characterized in that being used for textile finshing agent.
6, a kind of purposes as claimed in claim 5 with easy decontamination nanometer titania finishing agent of photocatalysis performance, it is characterized in that with contain described easy decontamination nanometer titania finishing agent 1～5 grams per liter with photocatalysis performance of claim 1, AOT 5～10 grams per liters, acrylate 5～10 grams per liters, polyvinyl alcohol 5～10 grams per liters, all the other are the suspension maceration extract of water; Textiles is immersed above-mentioned maceration extract, adopt padding method, two soak two rolls pressure: 2KG/CM
2, cured 90～180 seconds at 100～120 ℃.
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| CN 200510111713 CN1811049A (en) | 2005-12-20 | 2005-12-20 | Nanometer titania finishing agent with photocatalytic performace and high detergency and its prepn and application |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413212B (en) * | 2008-11-27 | 2011-03-16 | 东华大学 | Method for preparing air self-purifying function fabric of photochemical catalyst coating |
| CN103184685A (en) * | 2013-03-19 | 2013-07-03 | 浙江理工大学 | Preparation method of photocatalytic functional fabric based on titanium dioxide/magnesium oxide core-shell nanorod |
| CN103790000A (en) * | 2013-12-24 | 2014-05-14 | 东华大学 | Preparation method of photo-cured titanate air purification finishing agent specially used for fiber fabric |
| CN109054617A (en) * | 2018-07-05 | 2018-12-21 | 吕莉 | A kind of preparation method of nano paint |
-
2005
- 2005-12-20 CN CN 200510111713 patent/CN1811049A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101413212B (en) * | 2008-11-27 | 2011-03-16 | 东华大学 | Method for preparing air self-purifying function fabric of photochemical catalyst coating |
| CN103184685A (en) * | 2013-03-19 | 2013-07-03 | 浙江理工大学 | Preparation method of photocatalytic functional fabric based on titanium dioxide/magnesium oxide core-shell nanorod |
| CN103184685B (en) * | 2013-03-19 | 2014-11-19 | 浙江理工大学 | Preparation method of photocatalytic functional fabric based on titanium dioxide/magnesium oxide core-shell nanorod |
| CN103790000A (en) * | 2013-12-24 | 2014-05-14 | 东华大学 | Preparation method of photo-cured titanate air purification finishing agent specially used for fiber fabric |
| CN103790000B (en) * | 2013-12-24 | 2015-10-28 | 东华大学 | A kind of preparation method of fabric dedicated optical solidification titanate purification of air finishing agent |
| CN109054617A (en) * | 2018-07-05 | 2018-12-21 | 吕莉 | A kind of preparation method of nano paint |
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