CN103570026A - Silicon dioxide material with super-hydrophobic-hydrophilic reversible switch function - Google Patents
Silicon dioxide material with super-hydrophobic-hydrophilic reversible switch function Download PDFInfo
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- CN103570026A CN103570026A CN201310548265.0A CN201310548265A CN103570026A CN 103570026 A CN103570026 A CN 103570026A CN 201310548265 A CN201310548265 A CN 201310548265A CN 103570026 A CN103570026 A CN 103570026A
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Abstract
The invention provides a silicon dioxide material with a super-hydrophobic-hydrophilic reversible switch function and a preparation method thereof. The preparation method is characterized in that the one-step silane mixing and agitating method is carried out. The method comprises the following steps of: feeding silicon dioxide and a certain amount of silane X-Si(OR) 3 and Y-Si(OR)3 into an organic solvent; reflowing for 4 to 8 hours along with agitating; washing; carrying out vacuum filtering to obtain the silicon dioxide material with the super-hydrophobic-hydrophilic reversible switch function, wherein the silicon dioxide material has pH response capacity and can directly pass through an oil-water two-phase interface by changing the pH. The silicon dioxide material can be applied to the catalysis, coating, separation technology, sensing and other fields.
Description
Technical field
The present invention relates to earth silicon material, particularly a kind of earth silicon material with super-hydrophobic-hydrophilic invertible switch function and preparation method thereof, this material can be applicable to the fields such as catalyzed reaction, modified paint, sensor, useful for drug delivery.
Background technology
Surface wettability is one of key character of solid, and mainly microtexture and the chemical constitution by material surface determined.In recent years, there is specific function material super-hydrophobic, Superhydrophilic matter, in daily life and industrial and agricultural production, obtain applying more and more widely.People are by adjusting the surface microstructure of material and hydrophobicity and the hydrophilic mutual conversion that chemical constitution reaches solid surface.Particularly utilize multiple extraneous factor to stimulate, such as light, heat, electricity, pH value and solvent etc. realized the adjusting of Wettability of Solid Surface, prepared the intelligent response functional material of hydrophobic-hydrophilic reversible transformation.The material with this property has potential application foreground at aspects such as drug delivery, microfluid switch and isolation technique.The employings such as Jiang Lei two step solution reactions have been prepared orderly zinc oxide nano-rod film, this film can by UV-irradiation and dark store alternately change reach super-hydrophobic-super hydrophilic reversible transformation (J.Am.Chem.Soc.2004,126,62-63).They also by Transfer Radical Polymerization by the copolymer grafted with thermal response component and pH value response component in coarse silicon base, successfully prepared the controlled super-hydrophobic and super hydrophilic reversible transformation film that temperature, pH value double-bang firecracker are answered, under temperature, pH value or both control simultaneously, the wetting property of film can super-hydrophobic and super hydrophilic between reversible transition (Advanced Materials, 2006,18,432-436).Chinese patent (200810182214.X) discloses a kind of preparation method of super hydrophobic-super hydrophilic converting paining.Researchist has prepared polytetrafluoro wax/carbon fluoride nano-tube compound coating, regulates surface chemical composition and the microstructure of coating by different Heating temperatures, thereby realizes super-hydrophobic-super hydrophilic transformation of coatingsurface.
Nano silicon, as a kind of structured material and functional materials of excellent performance, has the characteristics such as specific surface area is high, high temperature resistant, corrosion-resistant, nontoxic, in pottery, biological medicine, catalysis, prepare composite, is widely used.To the finishing of silicon-dioxide existing more research both at home and abroad, the nanometer titanium dioxide silicon materials at present with hydrophobic-hydrophilic switching function, its finishing is mainly limited to the high molecular polymerization of silica sphere, the Silica Surface polymerization that Wu etc. modify at chloromethyl by the method for atom transferred free radical graft copolymerization generates spiropyran polymers and brushes, because polymer brush can be realized hydrophobic-hydrophilic reversible transformation under the optical radiation (UV-light and visible ray) of different wave length, therefore resulting silica gel compound illumination can be between profit two-phase under causing reversible transfer (Langmuir, 2010, 26 (12), 9442 – 9448).Yet the surperficial high molecular polymerization of silicon-dioxide has process complexity, is difficult to the shortcomings such as control.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method simple, and there is the earth silicon material of super-hydrophobic-hydrophilic invertible switch function.
The present invention realizes by the following method:
An earth silicon material with super-hydrophobic-hydrophilic invertible switch function, makes by the following method:
Particle diameter is less than to 100nm silicon-dioxide and silane coupling agent X～～Si (OR)
3and Y～～Si (OR)
3be placed in organic solvent, stir lower backflow 4～8 hours, wash, drain, obtain the earth silicon material of surface modification, the visible schematic diagram of its finishing process (Fig. 1).
The umber that the total amount of wherein said silane coupling agent X～～Si (OR) 3 and Y～～Si (OR) 3 accounts for the amount of substance of silicon-dioxide is 6%～30%; Two kinds of silane coupling agent X～～Si (OR) 3 with the molar ratio of Y～～Si (OR) 3 are: 0.02～1.
R in described X～～Si (OR) 3 and Y～～Si (OR) 3 is methyl or ethyl;
Described X～～Si (OR)
3in X be-(CH
2cH
2z) nCH
3, wherein Z is oxygen or nitrogen, n=1～6;
Described Y～～Si (OR)
3in Y be that carbonatoms is 3,8,12,18 alkyl.
Described organic solvent is toluene, methyl alcohol, ethanol, Virahol, normal hexane or methylene dichloride.
The SiO 2 powder taking a morsel after surface modification is put into test tube, and Xian Jiashui adds oil phase substance again, then under slowly stirring, adds the pH value that acid or alkali are adjusted water, SiO 2 powder can oily, water two-phase interface is reversible walks.This earth silicon material can be in field application such as catalyzed reaction, modified paint, sensor, useful for drug delivery.Oil phase in described profit two-phase is ether, ethyl acetate, fatty hydrocarbons and their derivates, or fragrant hydrocarbons and their derivates.
Tool of the present invention has the following advantages:
1, the prepared earth silicon material of the present invention has the wetting property of pH response, and when pH=2～5 of solution, material has wetting ability, and when pH=8～12 of solution, material has hydrophobicity.The contact angle scope of water is 30 °～160 °.
2, realize earth silicon material and walked oil, the reversible of water two-phase interface, reached super-hydrophobic-hydrophilic reversible transformation.
3, earth silicon material of the present invention adopts a simple step silane mixture paddling process preparation, mild condition, and controllability is good.
In sum, the inventive method is simple, mild condition, and resulting earth silicon material can be in field application such as catalyzed reaction, modified paint, sensor, useful for drug delivery.
Figure of description
The earth silicon material finishing process schematic diagram of super-hydrophobic-hydrophilic invertible switch function that Fig. 1 has
Specific implementation method:
Embodiment 1:
Get the silicon-dioxide of 1g particle diameter 80nm and put into the test tube that fills 5ml toluene, add 0.0089g aminoethyl aminopropyl trimethoxysilane and 0.7498g octadecyl Trimethoxy silane, stir after lower backflow 4 hours washing, drain, obtain the silicon-dioxide of surface modification.
The SiO 2 powder taking a morsel after surface modification is put into test tube, Xian Jiashui, then add ether, powder suspension is in ether; Under slowly stirring, acid adding regulates pH=2, and SiO 2 powder slowly enters water layer through oil, water two-phase interface from ether; Add alkali again and regulate pH=9, powder is got back in ether through oil, water two-phase interface again.
Embodiment 2:
Get the silicon-dioxide of 1g particle diameter 50nm and put into the test tube that fills 5ml methyl alcohol, add 0.0556g aminopropyl trimethoxysilane and 0.6411g propyl-triethoxysilicane, stir after lower backflow 6 hours, washing, drains, and obtains the silicon-dioxide of surface modification.
The SiO 2 powder taking a morsel after surface modification is put into test tube, Xian Jiashui, then add ethyl acetate, powder suspension is in ethyl acetate; Under slowly stirring, acid adding regulates pH=3, and SiO 2 powder slowly enters water layer through oil, water two-phase interface from ethyl acetate; Add alkali again and regulate pH=8, powder is got back in ethyl acetate layer through oil, water two-phase interface again.
Embodiment 3:
Get the silicon-dioxide of 1g particle diameter 100nm and put into the test tube that fills 5ml Virahol, add 0.4719g diethylenetriamine base propyl trimethoxy silicane and 0.9376g dodecyl triethoxyl silane, stir after lower backflow 7 hours.Washing, drains, and obtains the silicon-dioxide of surface modification.
The SiO 2 powder taking a morsel after surface modification is put into container, Xian Jiashui, then add normal hexane, powder suspension is in normal hexane; Under slowly stirring, acid adding regulates pH=4, and SiO 2 powder slowly enters water layer through oil, water two-phase interface from normal hexane; Add alkali again and regulate pH=10, powder is got back in normal hexane through oil, water two-phase interface again.
Embodiment 4:
Get the silicon-dioxide of 1g particle diameter 30nm and put into the test tube that fills 5ml methylene dichloride, add 0.2199g aminopropyl triethoxysilane and 0.5345g octyl group Trimethoxy silane, stir after lower backflow 8 hours.Washing, drains, and obtains the silicon-dioxide of surface modification.
The SiO 2 powder taking a morsel after surface modification is put into test tube, Xian Jiashui, then add methylene dichloride, powder suspension is in methylene dichloride; Under slowly stirring, acid adding regulates pH=2, and SiO 2 powder slowly enters water layer through oil, water two-phase interface from methylene dichloride; Add alkali again and regulate pH=11, powder is got back in methylene dichloride through oil, water two-phase interface again.
Embodiment 5:
Get the silicon-dioxide of 1g particle diameter 100nm and put into the test tube that fills 5ml ethanol, add 0.2685g aminopropyl trimethoxysilane and 0.3516g octyl group Trimethoxy silane, stir after lower backflow 5 hours, washing, drains, and obtains the silicon-dioxide of surface modification.
The SiO 2 powder taking a morsel after surface modification is put into test tube, Xian Jiashui, then add hexanaphthene, powder suspension is in hexanaphthene; Under slowly stirring, acid adding regulates pH=5, and SiO 2 powder slowly enters water layer through oil, water two-phase interface from hexanaphthene; Add alkali again and regulate pH=10, powder is got back in hexanaphthene through oil, water two-phase interface again.
Embodiment 6:
The earth silicon material of the resulting surface modification of the present invention is applied to the experiment of aqueous catalysis reaction
After the earth silicon material loaded metal palladium of the surface modification that embodiment 1 is obtained, be applied in styrene hydrogenation reaction.Using water as reaction solvent, reaction conditions: 0.1mol%Pd(accounts for the amount of carrier); H
2pressure: normal atmosphere; Temperature of reaction: room temperature.Catalyzer is put into the vinylbenzene aqueous solution, can see that catalyzer is in oil phase, after catalyzed reaction finishes, solid catalyst is still at oil phase, under slowly stirring, the pH value of water is adjusted to 3～4, and catalyzer enters water from oil phase, and in oil phase, product utilization is simply toppled over mode and catalyst separating.Add new reactant, then adjusting pH value is 8～9, and catalyzer enters oil phase through water-oil interface from water again and again carries out catalyzed reaction, thereby completes once circulation.Utilize this method, catalyzer recirculation is used after 20 times, and the selectivity of product and productive rate still can reach more than 90%.
Claims (3)
1. an earth silicon material with super-hydrophobic-hydrophilic invertible switch function, is characterized in that, makes by the following method:
Particle diameter is less than to 100nm silicon-dioxide and silane coupling agent X～～Si (OR) 3 and Y～～Si (OR) 3 and is placed in organic solvent, stir lower backflow 4～8 hours, wash, drain, obtain having the earth silicon material of super-hydrophobic-hydrophilic invertible switch function; The umber that the total amount of described silane coupling agent X～～Si (OR) 3 and Y～～Si (OR) 3 accounts for the amount of substance of silicon-dioxide is 6%～30%; Two kinds of silane coupling agent X～～Si (OR) 3 with the molar ratio of Y～～Si (OR) 3 are: 0.02～1;
R in described X～～Si (OR) 3 and Y～～Si (OR) 3 is methyl or ethyl;
Described X～～Si (OR)
3in X be-(CH
2cH
2z) nCH
3, wherein Z is oxygen or nitrogen, n=1～6;
Described Y～～Si (OR)
3in Y be that carbonatoms is 3,8,12,18 alkyl.
2. a kind of earth silicon material with super-hydrophobic-hydrophilic invertible switch function as claimed in claim 1, is characterized in that, described organic solvent is toluene, methyl alcohol, ethanol, Virahol, normal hexane or methylene dichloride.
3. the application of the earth silicon material with super-hydrophobic-hydrophilic invertible switch function as claimed in claim 1 in catalyzed reaction, modified paint, sensor, useful for drug delivery.
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Cited By (7)
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| CN104785291A (en) * | 2015-04-09 | 2015-07-22 | 山西大学 | PH-responsive dry water and preparation method thereof |
| CN104945569A (en) * | 2014-03-31 | 2015-09-30 | 中国科学院化学研究所 | Amphiphilic particle for super-hydrophobic coating, super-hydrophobic coating and preparation method of amphiphilic particles |
| CN109046480A (en) * | 2018-08-09 | 2018-12-21 | 广西大学 | Controllable micro-fluidic paper chip of fluid transport and preparation method thereof and application method |
| CN111330581A (en) * | 2020-03-10 | 2020-06-26 | 中国科学院山西煤炭化学研究所 | Acid-resistant hydrogenation catalyst, and preparation method and application thereof |
| CN113717709A (en) * | 2021-08-27 | 2021-11-30 | 西安长庆化工集团有限公司 | Nano fluid imbibition agent and preparation method and application thereof |
| WO2022120900A1 (en) * | 2020-12-09 | 2022-06-16 | 深圳先进技术研究院 | Silica filler and preparation method therefor, and epoxy resin composite material |
| CN115960538A (en) * | 2022-11-21 | 2023-04-14 | 陕西科技大学 | Fluorocarbon resin-based protective coating for protecting bronze ware and preparation method thereof |
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| CN104945569A (en) * | 2014-03-31 | 2015-09-30 | 中国科学院化学研究所 | Amphiphilic particle for super-hydrophobic coating, super-hydrophobic coating and preparation method of amphiphilic particles |
| CN104945569B (en) * | 2014-03-31 | 2018-09-25 | 中国科学院化学研究所 | Super-hydrophobic coat amphipathic particle and preparation method thereof and super-hydrophobic coat |
| CN104785291A (en) * | 2015-04-09 | 2015-07-22 | 山西大学 | PH-responsive dry water and preparation method thereof |
| CN109046480A (en) * | 2018-08-09 | 2018-12-21 | 广西大学 | Controllable micro-fluidic paper chip of fluid transport and preparation method thereof and application method |
| CN109046480B (en) * | 2018-08-09 | 2021-10-08 | 广西大学 | Microfluidic paper chip with controllable fluid transportation and preparation method and use method thereof |
| CN111330581A (en) * | 2020-03-10 | 2020-06-26 | 中国科学院山西煤炭化学研究所 | Acid-resistant hydrogenation catalyst, and preparation method and application thereof |
| WO2022120900A1 (en) * | 2020-12-09 | 2022-06-16 | 深圳先进技术研究院 | Silica filler and preparation method therefor, and epoxy resin composite material |
| CN113717709A (en) * | 2021-08-27 | 2021-11-30 | 西安长庆化工集团有限公司 | Nano fluid imbibition agent and preparation method and application thereof |
| CN113717709B (en) * | 2021-08-27 | 2023-02-17 | 西安长庆化工集团有限公司 | Nano fluid imbibition agent and preparation method and application thereof |
| CN115960538A (en) * | 2022-11-21 | 2023-04-14 | 陕西科技大学 | Fluorocarbon resin-based protective coating for protecting bronze ware and preparation method thereof |
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Application publication date: 20140212 |