CN101058070A - Method for preparing aza-titanium oxide/fluorine-containing polymer kernel-hull composite ordered porous microspheres - Google Patents
Method for preparing aza-titanium oxide/fluorine-containing polymer kernel-hull composite ordered porous microspheres Download PDFInfo
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Abstract
The invention relates to a method making titanium nitride oxide. Firstly, adding 20 mum-200mum particles in sequence to ion removing solution, then adding monodisperse polymer with mass ratio 10%-13% with surface having carboxy group, sticking the monodisperse polymer, getting A, adding mass ratio 1:0. 1-0. 3:0. 01-0. 03:0. 01-0. 03 fluorine integral, gallant, porous making agent, initiator, forming titanium nitride oxide shell, cleaning to get the porapak. The made titanium nitride oxide is hard to be photochemical degradated.
Description
Technical field
The invention belongs to the porous photocatalytic material field, particularly a kind of method for preparing aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
Background technology
Nanometer anatase titania can decompose toxic chemical, smog residue, stench chemicals, foul, stimulus, bacterium or the like through UV-irradiation and be nontoxic, free of contamination material, (electronics the during irradiation of wavelength＜388nm) in its valence band is excited and forms electronegative high activity electronics when ultraviolet light, produce the valence band hole of positively charged simultaneously, electronics separates with the hole, moves to the diverse location of particle surface.Hole and electronics produce the hydroxyl radical free radical and the superoxide ion free radical of high reaction activity respectively with the water on surface and oxygen reaction, these free radicals can decompose toxic chemical effectively.
Titanium dioxide optical catalyst is applied to actual pollutant control, though obtained certain effect, utilize nano powder suspension system to carry out photocatalysis, because its particle is trickle, be difficult for precipitation, catalyst is difficult to reclaim, active ingredient loss is big, is unfavorable for the regeneration of catalyst and utilizes.In addition, titanium dioxide optical catalyst need just can reach good photocatalysis effect under the irradiation of ultraviolet light, and the content of natural daylight medium ultraviolet light very little, only account for the 4-6% of the solar radiation total amount that reaches ground, and, manually produce ultraviolet light power consumption greatly, also need drop into the higher device expense along with the time changes obviously.Therefore to realize the large-scale application of photocatalysis technology, with regard to load that must solve photochemical catalyst and the problem that improves catalytic activity.
Liu Changsheng, Ma Zhibin using plasma methods such as (ZL03119056.1) has prepared nanometer aza-titanium oxide powder and thin-film material, obviously improved the ultraviolet catalytic ability, at visible light is that the illumination of wavelength＜500nm is penetrated down, 10 milliliter 1% the methyl orange solution that contains 0.5 gram nanometer aza-titanium oxide, 30-50min under solar light irradiation, its color retreats to colourless.In addition, Liu Changsheng, 200710051284.7) etc. (number of patent application: also prepared ordered porous aza titania microsphere by plasma technique, the result shows that ordered porous aza titania microsphere has excellent more photocatalysis performance under condition of the same race to Li Jun.
Meanwhile, mainly adopt two kinds of inorganic carrier load and organic carrier loads for the load of photochemical catalyst.The inorganic carrier load mainly utilizes the high temperature sintering technology titanic oxide nano sintering to be carried on the adamantine layer of ceramic surface, thereby the mode perhaps by adsorption reaction is adsorbed in titanium dioxide the purpose that reaches the photochemical catalyst load in the duct of MCM-41 type molecular sieve, and people also are carried on titanium dioxide absorption on the inorganic material such as glass, carbon dust, activated carbon fiber in addition.The organic carrier load mainly is that titanium dioxide optical catalyst is carried on textile fabric fiber, coating, surface of plastic products etc., can reach antibiotic, sterilization, self-cleaning purpose by the load on this based article, but the load on the organic matter carrier, also increased carrier itself by the possibility of photocatalytic degradation when reaching above cleaning function purpose, simple in addition catalyst cupport also makes catalyst come off from carrier easily.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres, the prepared aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres of this method can keep the original catalytic performance of photochemical catalyst and its organic carrier itself to be difficult for by photocatalytic degradation.
To achieve these goals, technical scheme of the present invention is: the preparation of aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres, it comprises the steps:
1) at first, with particle diameter is ordered porous aza titania microsphere (the abbreviation aza-titanium oxide of 20 μ m-200 μ m, be prior art) add in the deionized water, wherein the mass ratio of ordered porous aza titania microsphere and deionized water is 0.2-0.4: 100-120, after stirring treats that it fully is uniformly dispersed, adding mass fraction again is the surperficial carboxylic monodisperse polymer micro-sphere emulsion of 10%-13%, the mass ratio of monodisperse polymer micro-sphere emulsion and ordered porous aza titania microsphere is 10-20: 0.2-0.4, and the pH value of regulating mixed solution is 2-3, in 25-30 ℃, stir 6-8h, because aza-titanium oxide and carboxylic monodisperse polymer micro-sphere surface band xenogenesis electric charge, thereby contain carboxyl monodisperse polymer micro-sphere out-phase and condense in the porous aza titania surface, then stir 6-8h in 90 ℃, make between the monodisperse polymer micro-sphere inter-adhesive, thing A;
2) adding mass ratio in thing A is 1: the fluorochemical monomer of 0.1-0.3: 0.01-0.03: 0.01-0.03, crosslinking agent, pore-foaming agent, initator (effect is that the carboxylic monodisperse polymer micro-sphere in surface is carried out swelling), wherein fluorochemical monomer and ordered porous aza titania microsphere mass ratio are 5-10: 0.2-0.4, swelling time be behind the 12h in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex;
3) successively be the shell of deionized water washing aza-titanium oxide/fluoropolymer nuclear-shell complex of 60 ℃ with carrene and temperature, remove polymer uncrosslinked in the complex shell and pore-foaming agent, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
The carboxylic monodisperse polymer micro-sphere in described surface disperses poly (methyl methacrylate) micro-sphere for containing the carboxyl monodisperse polystyrene microsphere or containing the carboxyl list.
Described fluorochemical monomer is acrylic acid trifluoro ethyl ester, acrylic acid hexafluoro isopropyl ester, acrylic acid seven fluorine normal butane base esters, trifluoroethyl methacrylate or methacrylic acid hexafluoro isopropyl ester.
Described crosslinking agent is divinylbenzene, ethylene glycol diacrylate or pentaerythritol acrylate.
Described initator is ammonium persulfate or potassium peroxydisulfate.
Described pore-foaming agent is 1-chlorinated dodecane or dimethylbenzene.
The characteristics of the inventive method are:
1, catalyst surface is carried out the modification of organic facies capacitive, its easier and organic carrier are combined, improved the binding ability of photochemical catalyst and organic carrier.
2, fluoropolymer exists on the ordered porous aza titania microsphere surface with the form of crosslinked body, owing to be fluorine-containing cross-linked polymer, therefore the polymer of shell is difficult for by photocatalytic degradation (utilize the advantage of fluoropolymer at aspects such as resistance to chemical attack degradeds, carrier itself is not produced and destroy).
3, fluoropolymer itself also is that the hole, hole communicates, and has guaranteed that ordered porous aza titania communicates with the external world, makes the aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres of preparation can keep the original catalytic performance of photochemical catalyst.
Description of drawings
Fig. 1 is a process chart of the present invention.
Among the figure: 1. add surperficial carboxylic monodisperse polymer micro-sphere emulsion; 2. add fluorochemical monomer, crosslinking agent, initator and pore-foaming agent and carry out swelling containing the carboxyl monodisperse polymer micro-sphere; 3. initiated polymerization; 4. be that 60 ℃ deionized water is removed polymer uncrosslinked in the complex shell and pore-foaming agent with carrene and temperature respectively.
The specific embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
As shown in Figure 1, at first, with the 0.2g particle diameter is in the ordered porous aza titania microsphere adding 100g deionized water of 20 μ m, after stirring treats that it fully is uniformly dispersed, add the 10g mass fraction again and be 11% contain carboxyl monodisperse polystyrene microsphere emulsion, and the pH value of regulating mixed solution is 2, stir 6h in 25 ℃, since aza-titanium oxide with contain carboxyl monodisperse polystyrene microsphere surface band xenogenesis electric charge, thereby contain carboxyl monodisperse polystyrene microsphere out-phase and condense in the porous aza titania surface, then stir 6h in 90 ℃, make contain between the carboxyl monodisperse polystyrene microsphere inter-adhesive, thing A.Secondly adding 5g acrylic acid trifluoro ethyl ester, 0.6g divinylbenzene, 0.2g 1-chlorinated dodecane, 0.06g ammonium persulfate carry out swelling (the carboxyl monodisperse polystyrene microsphere out-phase that contains after the swelling is condensed in the porous aza titania microsphere surface) to containing the carboxyl monodisperse polystyrene microsphere in thing A, in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex behind the swelling 12h.At last, be that 60 ℃ deionized water is removed polystyrene uncrosslinked in the complex shell and 1-chlorinated dodecane with carrene and temperature respectively, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
Embodiment 2:
At first, with the 0.3g particle diameter is in the ordered porous aza titania microsphere adding 110g deionized water of 50 μ m, after stirring treats that it fully is uniformly dispersed, add the 15g mass fraction again and be 13% contain carboxyl monodisperse polystyrene microsphere emulsion, and the pH value of regulating mixed solution is 2, stir 6h in 30 ℃, since aza-titanium oxide with contain carboxyl monodisperse polystyrene microsphere surface band xenogenesis electric charge, thereby contain carboxyl monodisperse polystyrene microsphere out-phase and condense in the porous aza titania surface, then stir 6h in 90 ℃, make between the monodisperse polystyrene microsphere inter-adhesive, thing A.Secondly adding 8g acrylic acid hexafluoro isopropyl ester, 1.0g divinylbenzene, 0.24g 1-chlorinated dodecane, 0.12g potassium peroxydisulfate carry out swelling to containing the carboxyl monodisperse polystyrene microsphere in thing A, in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex behind the swelling 12h.At last, be that 60 ℃ deionized water is removed polystyrene uncrosslinked in the complex shell and 1-chlorinated dodecane with carrene and temperature respectively, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
Embodiment 3:
At first, with the 0.25g particle diameter is in the ordered porous aza titania microsphere adding 100g deionized water of 80 μ m, after stirring treats that it fully is uniformly dispersed, add the 10g mass fraction again and be 13% contain carboxyl monodisperse polystyrene microsphere emulsion, and the pH value of regulating mixed solution is 3, stir 8h in 25 ℃, since aza-titanium oxide with contain carboxyl monodisperse polystyrene microsphere surface band xenogenesis electric charge, thereby contain carboxyl monodisperse polystyrene microsphere out-phase and condense in the porous aza titania surface, then stir 6h in 90 ℃, make between the monodisperse polystyrene microsphere inter-adhesive, thing A.Secondly adding 6g acrylic acid seven fluorine normal butane base esters, 0.8g ethylene glycol diacrylate, 0.12g 1-chlorinated dodecane, 0.10g potassium peroxydisulfate carry out swelling to containing the carboxyl monodisperse polystyrene microsphere in thing A, in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex behind the swelling 12h.At last, be that 60 ℃ deionized water is removed polystyrene uncrosslinked in the complex shell and 1-chlorinated dodecane with carrene and temperature respectively, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
Embodiment 4:
At first, with the 0.4g particle diameter is in the ordered porous aza titania microsphere adding 120g deionized water of 100 μ m, after stirring treats that it fully is uniformly dispersed, add the 20g mass fraction again and be 12% the carboxyl list that contains and disperse the poly (methyl methacrylate) micro-sphere emulsion, and the pH value of regulating mixed solution is 3, stir 6h in 25 ℃, since aza-titanium oxide with contain the carboxyl list and disperse poly (methyl methacrylate) micro-sphere surface band xenogenesis electric charge, thereby contain the carboxyl list and disperse poly (methyl methacrylate) micro-sphere out-phase to condense in the porous aza titania surface, then stir 7h in 90 ℃, make contain the carboxyl list disperse between the poly (methyl methacrylate) micro-sphere inter-adhesive, thing A.Secondly adding 10g acrylic acid trifluoro ethyl ester, 1.4g divinylbenzene, 0.3g dimethylbenzene, 0.20g potassium peroxydisulfate disperse poly (methyl methacrylate) micro-sphere to carry out swelling to containing the carboxyl list in thing A, in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex behind the swelling 12h.At last, be that 60 ℃ deionized water is removed polymethyl methacrylate uncrosslinked in the complex shell and dimethylbenzene with carrene and temperature respectively, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
Embodiment 5:
At first, with the 0.3g particle diameter is in the ordered porous aza titania microsphere adding 120g deionized water of 200 μ m, after stirring treats that it fully is uniformly dispersed, add the 15g mass fraction again and be 12% the carboxyl list that contains and disperse the poly (methyl methacrylate) micro-sphere emulsion, and the pH value of regulating mixed solution is 3, stir 6h in 25 ℃, since aza-titanium oxide with contain the carboxyl list and disperse poly (methyl methacrylate) micro-sphere surface band xenogenesis electric charge, thereby contain the carboxyl list and disperse poly (methyl methacrylate) micro-sphere out-phase to condense in the porous aza titania surface, then stir 6h in 90 ℃, make contain the carboxyl list disperse between the poly (methyl methacrylate) micro-sphere inter-adhesive, thing A.Secondly adding 6g trifluoroethyl methacrylate, 0.8g pentaerythritol acrylate, 0.15g dimethylbenzene, 0.15g ammonium persulfate disperse poly (methyl methacrylate) micro-sphere to carry out swelling to containing the carboxyl list in thing A, in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex behind the swelling 12h.At last, be that 60 ℃ deionized water is removed polymethyl methacrylate uncrosslinked in the complex shell and dimethylbenzene with carrene and temperature respectively, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
Embodiment 6:
At first, with the 0.3g particle diameter is in the ordered porous aza titania microsphere adding 110g deionized water of 150 μ m, after stirring treats that it fully is uniformly dispersed, add the 15g mass fraction again and be 12% the carboxyl list that contains and disperse the poly (methyl methacrylate) micro-sphere emulsion, and the pH value of regulating mixed solution is 3, stir 6h in 25 ℃, since aza-titanium oxide with contain the carboxyl list and disperse poly (methyl methacrylate) micro-sphere surface band xenogenesis electric charge, thereby contain the carboxyl list and disperse poly (methyl methacrylate) micro-sphere out-phase to condense in the porous aza titania surface, then stir 6h in 90 ℃, make contain the carboxyl list disperse between the poly (methyl methacrylate) micro-sphere inter-adhesive, thing A.Secondly adding 8g methacrylic acid hexafluoro isopropyl ester, 2g divinylbenzene, 0.2g dimethylbenzene, 0.12g potassium peroxydisulfate disperse poly (methyl methacrylate) micro-sphere to carry out swelling to containing the carboxyl list in thing A, in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex behind the swelling 12h.At last, be that 60 ℃ deionized water is removed polymethyl methacrylate uncrosslinked in the complex shell and dimethylbenzene with carrene and temperature respectively, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
The bound value and the interval value of ordered porous aza titania microsphere of the present invention, deionized water, surperficial carboxylic monodisperse polymer micro-sphere emulsion, fluorochemical monomer, crosslinking agent, pore-foaming agent, initator raw material can both be realized the present invention, just do not enumerate embodiment one by one at this; Technological parameter of the present invention can both be realized the present invention as bound value and the interval value of temperature, time, does not just enumerate embodiment one by one at this.
Claims (6)
1. the preparation of aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres, it comprises the steps:
1) at first, with particle diameter is in the ordered porous aza titania microsphere adding deionized water of 20 μ m-200 μ m, wherein the mass ratio of ordered porous aza titania microsphere and deionized water is 0.2-0.4: 100-120, after stirring treats that it fully is uniformly dispersed, adding mass fraction again is the surperficial carboxylic monodisperse polymer micro-sphere emulsion of 10%-13%, the mass ratio of monodisperse polymer micro-sphere emulsion and ordered porous aza titania microsphere is 10-20: 0.2-0.4, and the pH value of regulating mixed solution is 2-3, in 25-30 ℃, stir 6-8h, then, get thing A in 90 ℃ of stirring 6-8h;
2) adding mass ratio in thing A is 1: the fluorochemical monomer of 0.1-0.3: 0.01-0.03: 0.01-0.03, crosslinking agent, pore-foaming agent, initator, wherein fluorochemical monomer and ordered porous aza titania microsphere mass ratio are 5-10: 0.2-0.4, swelling time be behind the 12h in 85 ℃ of initiated polymerizations, form the shell of aza-titanium oxide/fluoropolymer nuclear-shell complex;
3) successively be the shell of deionized water washing aza-titanium oxide/fluoropolymer nuclear-shell complex of 60 ℃ with carrene and temperature, remove polymer uncrosslinked in the complex shell and pore-foaming agent, promptly get aza-titanium oxide/fluoropolymer nuclear-hull composite ordered porous microspheres.
2. the preparation of aza-titanium oxide according to claim 1/fluoropolymer nuclear-hull composite ordered porous microspheres is characterized in that: the carboxylic monodisperse polymer micro-sphere in described surface disperses poly (methyl methacrylate) micro-sphere for containing the carboxyl monodisperse polystyrene microsphere or containing the carboxyl list.
3. the preparation of aza-titanium oxide according to claim 1/fluoropolymer nuclear-hull composite ordered porous microspheres is characterized in that: described fluorochemical monomer is acrylic acid trifluoro ethyl ester, acrylic acid hexafluoro isopropyl ester, acrylic acid seven fluorine normal butane base esters, trifluoroethyl methacrylate or methacrylic acid hexafluoro isopropyl ester.
4. the preparation of aza-titanium oxide according to claim 1/fluoropolymer nuclear-hull composite ordered porous microspheres is characterized in that: described crosslinking agent is divinylbenzene, ethylene glycol diacrylate or pentaerythritol acrylate.
5. the preparation of aza-titanium oxide according to claim 1/fluoropolymer nuclear-hull composite ordered porous microspheres is characterized in that: described initator is ammonium persulfate or potassium peroxydisulfate.
6. the preparation of aza-titanium oxide according to claim 1/fluoropolymer nuclear-hull composite ordered porous microspheres is characterized in that: described pore-foaming agent is 1-chlorinated dodecane or dimethylbenzene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103396520A (en) * | 2013-08-05 | 2013-11-20 | 陕西科技大学 | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof |
| CN114786805A (en) * | 2019-10-31 | 2022-07-22 | 卡罗比亚咨询有限责任公司 | Polymer support nano-functionalized with photocatalytic nanoparticles based on titanium dioxide and use thereof as a photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1176743C (en) * | 2002-03-29 | 2004-11-24 | 徐瑞芬 | Nano titanium dioxide photocatalyst,prep. and use thereof |
| JP2004130429A (en) * | 2002-10-10 | 2004-04-30 | National Institute For Materials Science | Core shell structure, hollow oxide shell structure derived from the same, and method of manufacturing structures |
| CN1217734C (en) * | 2003-05-13 | 2005-09-07 | 武汉化工学院 | Method for preparing nano titanium oxynitrides by plasma process |
| MXPA06014734A (en) * | 2004-06-15 | 2007-02-12 | Ciba Sc Holding Ag | Polymeric particles. |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102989515A (en) * | 2012-12-17 | 2013-03-27 | 江南大学 | Preparation method of titanium dioxide/heteropolyacid compound photo-catalyst |
| CN103396520A (en) * | 2013-08-05 | 2013-11-20 | 陕西科技大学 | Core-shell structure nanometer titanium dioxide/ fluorine-containing polyacrylate soap-free composite emulsion and preparation method thereof |
| CN114786805A (en) * | 2019-10-31 | 2022-07-22 | 卡罗比亚咨询有限责任公司 | Polymer support nano-functionalized with photocatalytic nanoparticles based on titanium dioxide and use thereof as a photocatalyst |
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