CN103585938B - Monodisperse silicozirconium hollow microsphere - Google Patents
Monodisperse silicozirconium hollow microsphere Download PDFInfo
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- CN103585938B CN103585938B CN201310548425.1A CN201310548425A CN103585938B CN 103585938 B CN103585938 B CN 103585938B CN 201310548425 A CN201310548425 A CN 201310548425A CN 103585938 B CN103585938 B CN 103585938B
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Abstract
The present invention discloses a kind of Monodisperse silicozirconium hollow microsphere, and material quality ratio is: the presoma 5 ~ 25% of silicon, the presoma 1 ~ 20% of aluminium, calcium carbonate 1% ~ 5%, dispersant 0.01 ~ 0.25%, structure directing agent 0.1 ~ 2.5%, and surplus is reaction medium; (1) dispersant is joined in reaction medium; (2), after being stirred to homogeneous phase, calcium carbonate and structure directing agent is added respectively; (3), after stirring, the presoma of silicon and the presoma of aluminium is alternately added; (4) continue to stir, system is warming up to 70 ~ 90 DEG C of reactions simultaneously; (5) room temperature is cooled to, washing, dry powder; (6) powder is joined in dilute hydrochloric acid solution; (7) wash, after drying and get final product.The present invention, in conjunction with template and sol-gel process, take inorganic microsphere as template, prepares nano-scale hollow silicon-aluminum microsphere powder through sol-gel, alternating deposit; Without the need to high temperature sintering, technique is simple to operation, is easy to form large-scale production.
Description
Technical field
The present invention relates to a kind of functional nanocomposite, particularly a kind of nano-silicon zirconium microballoon of hollow-core construction.
Background technology
Hollow microspheres has the characteristic of low-density, high-specific surface area, and hollow space can hold a large amount of guest molecule or large scale object, produces microcosmic parcel effect character, hollow microspheres is had broad application prospects as a kind of new function material.In recent years, hollow microspheres has been widely used in controlled transport and the delivery systmes such as dyestuff, cosmetics, medicine, sensitiveness reagent, protein, also can be used as light filler, high-selectivity catalyst or catalyst carrier.
Compare with the hollow microspheres of traditional one-component, compounding ingredients hollow microspheres owing to introducing metal, metal oxide, semiconductor, inorganic or organic material etc. on shell, can significantly improve and improve the performance such as compression strength, optics, magnetics, catalysis of hollow microspheres, interparticle caking and reunion can also be prevented simultaneously.Britain's " materials chemistry " (Journal of Materials Chemistry, 2005,15th volume, 2041-2046 page) Jiang Yan autumn group adopt sol-gel process in the emulsion of oil-water-oil phase, synthesize micron silicon zirconium tiny balloon, but the method can only synthesizing micron-grade tiny balloon, preparation process is complicated, and balling-up productive rate is lower, is not suitable for large-scale production.
Summary of the invention
The object of the invention is to provide the Monodisperse silicozirconium hollow microsphere that performance is all significantly increased such as a kind of compression strength, optics, magnetics, catalysis, this product is not only applied to the fields such as dyestuff, cosmetics, medicine, sensitiveness reagent, protein, also can be used as light filler, high-selectivity catalyst or catalyst carrier.
Monodisperse silicozirconium hollow microsphere, is characterized in that, shell is made up of silica and zirconia, and sphere diameter size is 300-900nm, and shell thickness is 100 ~ 200nm; Described Monodisperse silicozirconium hollow microsphere is prepared from by following steps, (1) neopelex being dissolved into ethylene glycol and water is in the solution of 1:4 mixing with volume ratio, after stirring, styrene monomer is added under 75 DEG C of conditions, ultrasonic disperse 30min, adds potassium persulfate solution, reacts 6h under nitrogen protection condition, 50 DEG C of dry process, namely obtain white polystyrene powder; (2) Polystyrene powder ultrasonic disperse step (1) obtained is in distilled water, add zirconium oxychloride, urea, ethyl orthosilicate and polyvinylpyrrolidone respectively, ageing 8 ~ 10 hours in 60 ~ 90 DEG C of water-baths after mixing, the distilled water washing 3 ~ 5 times of solid particle after filtration, obtains hydration silicon zirconium/polystyrene core-shell microsphere after 60 DEG C of dry process; (3) by being placed in tube furnace with the programming rate of 2 DEG C/min after hydration silicon zirconium/polystyrene core-shell microsphere and carbon black mixing, being heated to 650 DEG C and being incubated 3 hours, monodisperse hollow silicon zirconium microballoon can be obtained.
Further, described in step (1), the ratio of the amount of substance of neopelex, monomer styrene, potassium peroxydisulfate is 1:(200 ~ 500): (1 ~ 2); Described in step (2), the mass ratio of polystyrene, zirconium oxychloride, urea, ethyl orthosilicate and polyvinylpyrrolidone is 1:(1 ~ 5): (0.5 ~ 2): (10 ~ 20): (0.1 ~ 1); Described in step (3), the mass ratio of hydration silicon zirconium/polystyrene core-shell microsphere and carbon black is 1:(1 ~ 10).
Beneficial effect: Monodisperse silicozirconium hollow microsphere of the present invention is compared with the hollow microspheres of traditional one-component, in compression strength, optics, magnetics, catalysis etc., performance is significantly increased and improves, and prevents interparticle caking and reunion simultaneously.The present invention is in conjunction with emulsion polymerisation and template, by selecting and control surface activating agent, reaction dissolvent, reaction condition, prepare the Monodisperse silicozirconium hollow microsphere that particle diameter is 300 ~ 900nm, shell thickness is the size tunable of 100 ~ 200nm, introduce carbon black in sintering process, the dispersiveness of tiny balloon can be improved.
Detailed description of the invention
Embodiment 1
Taking 0.2g neopelex is dissolved in the mixed solution of 50ml ethylene glycol and 200ml water; after stirring; styrene monomer 11.97g is added under 75 DEG C of conditions; ultrasonic disperse 30min; add potassium peroxydisulfate 0.16g; under nitrogen protection condition, react 6h, 50 DEG C of dry process, obtain white polystyrene powder.Take 1g Polystyrene powder ultrasonic disperse in 150ml distilled water, add zirconium oxychloride 1g respectively, urea 0.5g, ethyl orthosilicate 10g and polyvinylpyrrolidone 0.1g, ageing 8 hours in 60 DEG C of water-baths after mixing, solid particle distilled water after filtration washs 3 times, obtains hydration silicon zirconium/polystyrene core-shell microsphere after 60 DEG C of dry process.Hydration silicon zirconium/polystyrene core-shell microsphere and carbon black are put into tube furnace with the programming rate of 2 DEG C/min with mass ratio 1:1 mixing, and be heated to 650 DEG C and be incubated 3 hours, can obtain particle diameter 300nm, shell thickness is the monodisperse hollow silicon zirconium microballoon of 100nm.
Embodiment 2
Taking 0.2g neopelex is dissolved in the mixed solution of 50ml ethylene glycol and 200ml water; after stirring; styrene monomer 19.57g is added under 75 DEG C of conditions; ultrasonic disperse 30min; add potassium peroxydisulfate 0.16g; under nitrogen protection condition, react 6h, 50 DEG C of dry process, obtain white polystyrene powder.Take 1g Polystyrene powder ultrasonic disperse in 150ml distilled water, add zirconium oxychloride 3g urea 1.5g respectively, ethyl orthosilicate 15g and polyvinylpyrrolidone 0.6g, ageing 8 hours in 60 DEG C of water-baths after mixing, solid particle distilled water after filtration washs 3 times, obtains hydration silicon zirconium/polystyrene core-shell microsphere after 60 DEG C of dry process.Hydration silicon zirconium/polystyrene core-shell microsphere and carbon black are put into tube furnace with the programming rate of 2 DEG C/min with mass ratio 5:1 mixing, and be heated to 650 DEG C and be incubated 3 hours, can obtain particle diameter 450nm, shell thickness is the monodisperse hollow silicon zirconium microballoon of 150nm.
Embodiment 3
Taking 0.2g neopelex is dissolved in the mixed solution of 50ml ethylene glycol and 200ml water; after stirring; styrene monomer 29.88g is added under 75 DEG C of conditions; ultrasonic disperse 30min; add potassium peroxydisulfate 0.31g; under nitrogen protection condition, react 6h, 50 DEG C of dry process, obtain white polystyrene powder.Take 1g Polystyrene powder ultrasonic disperse in 150ml distilled water, add zirconium oxychloride 5g respectively, urea 2g, ethyl orthosilicate 20g and polyvinylpyrrolidone 1g, ageing 10 hours in 90 DEG C of water-baths after mixing, solid particle distilled water after filtration washs 3 times, obtains hydration silicon zirconium/polystyrene core-shell microsphere after 60 DEG C of dry process.Hydration silicon zirconium/polystyrene core-shell microsphere and carbon black are put into tube furnace with the programming rate of 2 DEG C/min with mass ratio 10:1 mixing, and be heated to 650 DEG C and be incubated 3 hours, can obtain particle diameter 900nm, shell thickness is the monodisperse hollow silicon zirconium microballoon of 200nm.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention; Any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (1)
1. Monodisperse silicozirconium hollow microsphere, is characterized in that, described Monodisperse silicozirconium hollow microsphere shell is made up of silica and zirconia, and sphere diameter size is 300-900nm, and shell thickness is 100-200nm; Be prepared from by following steps, (1) neopelex being dissolved into ethylene glycol and water is in the solution of 1:4 mixing with volume ratio, after stirring, styrene monomer is added under 75 DEG C of conditions, ultrasonic disperse 30min, adds potassium persulfate solution, reacts 6h under nitrogen protection condition, 50 DEG C of dry process, namely obtain white polystyrene powder; (2) Polystyrene powder ultrasonic disperse step (1) obtained is in distilled water, add zirconium oxychloride, urea, ethyl orthosilicate and polyvinylpyrrolidone respectively, after mixing in 60-90 DEG C of water-bath ageing 8-10 hour, distilled water washing 3-5 time of solid particle after filtration, obtains hydration silicon zirconium/polystyrene core-shell microsphere after 60 DEG C of dry process; (3) by being placed in tube furnace with the programming rate of 2 DEG C/min after hydration silicon zirconium/polystyrene core-shell microsphere and carbon black mixing, being heated to 650 DEG C and being incubated 3 hours, monodisperse hollow silicon zirconium microballoon can be obtained;
Described in step (1), the ratio of the amount of substance of neopelex, styrene monomer, potassium peroxydisulfate is 1:(200-500): (1-2); Described in step (2), the mass ratio of polystyrene, zirconium oxychloride, urea, ethyl orthosilicate and polyvinylpyrrolidone is 1:(1-5): (0.5-2): (10-20): (0.1-1); Described in step (3), the mass ratio of hydration silicon zirconium/polystyrene core-shell microsphere and carbon black is 1:(1-10).
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| US5352481A (en) * | 1992-05-29 | 1994-10-04 | Hughes Aircraft Company | Process for forming particles having a uniform size distribution |
| CN101259402B (en) * | 2004-11-11 | 2011-11-30 | 中国科学院化学研究所 | Method for preparing hollow ball with double-layer structure and hollow ball with multi-layer complex structure by template method |
| CN102133513A (en) * | 2010-01-22 | 2011-07-27 | 北京大学深圳研究生院 | Preparation method of monodisperse porous inorganic microsphere |
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