CN103272543B - Method for preparing hollow silicon ball by self-templating method - Google Patents
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- CN103272543B CN103272543B CN201310240231.5A CN201310240231A CN103272543B CN 103272543 B CN103272543 B CN 103272543B CN 201310240231 A CN201310240231 A CN 201310240231A CN 103272543 B CN103272543 B CN 103272543B
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Abstract
The invention belongs to a method for preparing a hollow silicon ball by a self-templating method. The method comprises the steps as follows: taking a dimethylaminoethyl polymethacrylate or polydimethylaminopropyl methacrylamide linear polymer with positive charges as a silicon ball surface stabilizer and a silicon dioxide microsphere with negative charges on the surface as a template; adsorbing the surface stabilizer onto the surface of a silicon ball through electrostatic compounding; reacting for etching off the internal components of the silicon ball in the presence of an alkaline etching agent; and centrifuging, washing by water, washing by alcohol and drying to obtain the hollow silicon ball. According to the method, the silicon dioxide microsphere is taken as the template, any other templates are not needed, high-temperature high-pressure and inert gas does not need to be used for protection, a reaction system is simple and practicable, the conditions are moderate, and the hollow silicon ball is easy to produce on a large scale. The diameter of the hollow silicon ball prepared with the method is one hundred nanometers to hundreds of nanometers, and the wall thickness is a few nanometers to dozens of nanometers. The hollow silicon ball prepared with the method can be used in the fields of chemical engineering, environmental pollution, separation adsorption, biomedicine, drug delivery and the like.
Description
Technical field
The invention belongs to inorganic porous field of functional materials; Relate to a kind of by the method for self-template legal system for hollow silicon ball.
Background technology
In recent years, have hollow-core construction, the silicon dioxide microsphere of nanoscale receives and pays close attention to widely, becomes the study hotspot of domestic and international researcher.Hollow silicon ball has density low, specific area is large, toxicity is low, biocompatibility is high, at high temperature still have very high toughness and mechanical stability, and its boring structure can be used for drug loading and Small molecular, therefore have broad application prospects in the controlled release, stored energy, sensing, the depollution of environment etc. of medicine and biomolecule.Therefore, the new technology of the preparation hollow silicon ball that development technology is simple, with low cost or method significant.
The method preparing hollow silicon ball of current report mainly comprises spray drying process, emulsion method and template etc.Spray drying process can not prepare the hollow microsphere of nanoscale.Emulsion method and template can prepare the hollow microsphere of nanoscale.But the wayward and poor reproducibility of the synthesis condition of emulsion method; Template can obtain the hollow microsphere of nanoscale, and uniform particle diameter, Stability Analysis of Structures, be therefore widely applied.Template is first using predetermined substance as pattern adminicle, namely template is served as, then material is coated on template surface by physics and chemistry methods such as assembling, absorption, deposition and sol-gels, finally by the method such as organic solvent dissolution, high-temperature calcination, template is removed, obtain required hollow-core construction.Template mainly comprises hard template method and soft template method.Hard template method refers to use the material with rigid structure, and as polystyrene spheres, calcium carbonate, the solid materials such as material with carbon element synthesize the method for desired structure material as template.Soft template method refers to the molecule or the aggregation that use and have flexible structure, and as emulsion, surfactant micella, vesica etc. synthesize the method for hollow silicon ball.Hard template method needs the spherical template first preparing rigidity, and process is complicated, is not suitable for modern large-scale production, when template is removed in calcining, silicon ball is easily reunited, in addition, easily cause shell defect in hard template removal process, therefore hard template method prepares silicon dioxide hollow microsphere is not desirable especially.Soft template method overcomes some defects of hard template method to a certain extent, but soft template needs long time to reach liquid equilibrium, and system is more complicated, and operating condition is harsher, and being difficult to regulate and control the microstructure of hollow silicon ball, the hollow ball particle diameter obtained is uneven.Recently, with
the standby silicon dioxide microsphere of legal system is from obtaining great concern as Template preparation hollow silicon ball.
method prepares the most frequently used method of silicon dioxide microsphere, and this method is
to invent in nineteen sixty-eight Deng people.Utilize self-template legal system for hollow silicon ball, without the need to preparing template in advance, course of reaction is gentle, with low cost.This technique mainly utilize can with the polymer of silicon ball surface hydroxyl generation hydrogen bond action, if PVP (PVP) etc. is as silicon ball surface stabilizing agent.But because hydrogen bond action is more weak, surface-stable effect is poor, the hollow silicon ball of preparation has more breakage and blemish, have impact on its widespread adoption.
In a word, the preparation method of current Nano/micron yardstick hollow silicon ball still has some shortcomings part, the object of the present invention is to provide the hollow silicon ball self-template method preparation technology that a kind of process is more controlled, preparation is more simple, be easy to large-scale industrial production.The nucleocapsid structure of hollow silicon ball prepared by the method stablize controlled, pattern is complete, size uniform.
Summary of the invention
The object of the present invention is to provide that a kind of process is simply controlled, reaction condition is gentle, raw material is cheap and easy to get, reproducible, be easy to the self-template method preparation method of large-scale industrial production Nano/micron yardstick hollow silicon ball.Hollow silicon ball uniform particle sizes, the pattern of preparation are complete, nucleocapsid structure is stablized controlled, and the present invention mainly proposes a kind of new technology preparing hollow silicon ball, new method.Utilize the electrostatic interaction between polymer and electronegative silicon ball such as positively charged polymethylacrylic acid dimethylaminoethyl, make Polymer adsorption to silicon ball surface, play a stronger surface-stable effect, can structure be prepared thus more complete, the hollow silicon ball that blemish is less.
Technical scheme of the present invention is as follows:
A kind of by the method for self-template legal system for hollow silicon ball, with the linear polymer of polymethylacrylic acid dimethylaminoethyl or poly-dimethylamino-propyl Methacrylamide for silicon ball surface stabilizing agent, the silicon dioxide microsphere of surface band negative electrical charge is template, by electrostatic compound, positively charged surface stabilizer is adsorbed on silicon ball surface, subsequently under the existence of alkaline etchant, reactive ion etching falls the inside component of silicon ball, then after centrifugal, washing, alcohol wash, drying, obtains hollow silicon ball.
Concrete steps are as follows:
(1) preparation of the silicon ball surface stabilizing agent aqueous solution: by dimethylaminoethyl methacrylate or poly-dimethylamino-propyl Methacrylamide, be dissolved in water the aqueous solution being configured to 2 ~ 10 ‰;
(2) preparation of silicon dioxide microsphere dispersion liquid: utilize
legal system is the silicon dioxide microsphere of 100 ~ 800nm for diameter; By obtained silicon dioxide microsphere ultrasonic disperse in water or ethanol, preparation concentration is 5 ~ 100mg/mL silicon dioxide microsphere dispersion liquid;
(3) in the silicon ball surface stabilizing agent aqueous solution of step (1), drip the silicon dioxide microsphere dispersion liquid of step (2), in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 1 ~ 5; Add alkaline etchant subsequently, the pH value of adjustment system is between 7.5 ~ 9.5; After stirring balance 4 ~ 8h, system temperature is elevated between 60 ~ 80 ° of C, reaction 12 ~ 48h; Through centrifugal, washing, alcohol wash, drying, obtain hollow silicon ball.
Described alkaline etchant is NaOH, ammoniacal liquor, sodium carbonate or sodium borohydride etc.
Technical scheme of the present invention be with
the silicon dioxide microsphere of the surface band negative electrical charge that legal system is standby is certainly as template, with linear polymers such as appropriate polymethylacrylic acid dimethylaminoethyl or poly-dimethylamino-propyl Methacrylamides for silicon ball surface stabilizing agent, by electrostatic compound, surface stabilizer is adsorbed on silicon ball surface, subsequently under the existence of appropriate alkaline etchant, reactive ion etching falls the inside component of silicon ball, again after centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention.
The linear polymer such as polymethylacrylic acid dimethylaminoethyl or poly-dimethylamino-propyl Methacrylamide of molecular weight >=2000 is prepared preferably by active free radical polymerization method;
In the present invention, the polymer such as the polymethylacrylic acid dimethylaminoethyl related to or poly-dimethylamino-propyl Methacrylamide are prepared by active free radical polymerization.Active free radical polymerization had both had the advantage of general radical polymerization, suitable monomers scope is wide, polymerizing condition is gentle, and can implement in several ways, active free radical polymerization also has the advantage of living anion polymerization simultaneously, can synthesize the polymer of appointment molecular weight and Narrow Molecular Weight Distribution, be with special end functional group or side functional polymer.Recent two decades comes, and particularly RAFT polymerization and ATRP polymerization isoreactivity polymerization technique achieve huge progress, has been widely used in preparing molecular weight, molecular weight distribution, structure, chain length and chain length and has distributed controlled regular polymer.Utilize Active radical polymerization, by simply changing polymerization technique, as formula and polymerization time etc., the polymer such as people are easy to prepare that molecular weight is controlled, the polymethylacrylic acid dimethylaminoethyl of narrow molecular weight distribution or poly-dimethylamino-propyl Methacrylamide.
In the present invention, the silicon dioxide microsphere of size uniform, constitutionally stable, nanoscale be pass through
legal system is standby, or according to such as Publication about Document: J.Colloid Interface Sci., 1968,26,62-69.
method take ethyl orthosilicate as raw material, with ethanol or ethanol/water mixture for medium, to be hydrolyzed and monodisperse silica particle is prepared in cohesion by ammonia-catalyzed.
method is the method preparing silica spheres the most classical, and the multiple dimensioned adjustable regular silicon ball of synthesis is widely used.
After adding alkaline etchant; the pH value of reaction system regulates 7.5 ~ 9.5; now; polymethylacrylic acid dimethylaminoethyl or poly-dimethylamino-propyl Methacrylamide positively charged; silica is electronegative; produce electrostatic interaction between surface stabilizer polymer and silicon dioxide microsphere, can form stable sealer, the hollow silica microsphere surface texture of etching preparation is stable, pattern is complete.
Preparation technology of the present invention has the following advantages:
1, preparation process with silicon dioxide microsphere from as template, do not need make template in advance and use any surfactant, do not need to use hypertoxic hydrofluoric acid as etching agent yet, mild condition, simple to operate, raw material is easy to get, process safety environmental protection, is easy to control, and is suitable for large-scale industrial production.
2, the size of gained hollow silicon ball and structure depend on leading use
the silicon dioxide microsphere that legal system is standby, particle diameter and the structure of hollow silicon ball easily control, uniformly dispersed good.
3, in system, surface stabilizer is positively charged,
the silicon dioxide microsphere surface band negative electrical charge that legal system is standby, surface stabilizer, by electrostatic interaction, is adsorbed in silicon ball surface, and the hollow silica microsphere surface texture of preparation is stable, pattern intact unbroken, as shown in Figure 1.
4, the present invention is without the need to any template, without HTHP and inert gas shielding, and reaction system is simple, mild condition; The diameter of the hollow silicon ball utilizing this technique to prepare for tens nanometer to several micron and wall thickness be several nanometer to tens nanometers, can change along with the change of preparation technology.The hollow silicon ball prepared thus can be used for the numerous areas such as Chemical Engineering, environmental protection, separation absorption, biomedicine and drug delivery.
Accompanying drawing explanation
Fig. 1: hollow silicon ball transmission electron microscope picture prepared by implementation column 1.
Fig. 2: hollow silicon ball transmission electron microscope picture prepared by implementation column 3.
Fig. 3: hollow silicon ball transmission electron microscope picture prepared by implementation column 4.
Detailed description of the invention
Contribute to understanding the present invention by following embodiment, but do not limit the summary of the invention of this patent.
Embodiment 1: with polymethylacrylic acid dimethylaminoethyl for surface stabilizer prepares the hollow silicon ball of 100nm
The polymethylacrylic acid dimethylaminoethyl that molecular weight is 2,000 is prepared: with N-carbazole dithiocarbonic acid isobutyronitrile ester for RAFT reagent by RAFT activity polymerizating technology, azo-bis-isobutyl cyanide is initator, being monomer with PDMAEMA, take oxolane as solvent.Wherein, the mol ratio of monomer, RAFT reagent and initator is chosen for 200:5:1, is placed in 60 DEG C of water-baths and prepares by RAFT living polymerization the polymethylacrylic acid dimethylaminoethyl that molecular weight is 2,000.Obtained polymethylacrylic acid dimethylaminoethyl is dissolved in water the aqueous solution being configured to 10 ‰.
Utilize
legal system is the silicon dioxide microsphere of 100nm for monodispersed particle diameter: mixed by the absolute ethyl alcohol of 4.16g ethyl orthosilicate and 50mL in 100mL beaker, stir, again in another 200mL beaker by the concentrated ammonia liquor (mass fraction is 28%) of 25g deionized water and 5mL, the absolute ethyl alcohol of 50mL mixes, under magnetic agitation, the weak solution of ethyl orthosilicate is dropwise added drop-wise in ammonia spirit, dropwise rear continuation stirring at room temperature 2h, centrifugal, upper solution is outwelled, with deionized water and ethanol washing, vacuum drying, obtain the silicon ball that particle diameter is about 100nm.By the silicon ball ultrasonic disperse of above-mentioned preparation in water, be made into 10mg/mL silicon dioxide microsphere dispersion liquid.
Self-template legal system is for hollow silicon ball: joined by silicon dioxide microsphere dispersion liquid in the polymethylacrylic acid dimethylaminoethyl aqueous solution of 10 ‰, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 5:1.Subsequently to the 0.01mol/L NaOH dripping trace in system, the pH value of adjustment system is 7.5.After stirring balance 4h, system temperature is elevated to 60 ° of C subsequently, reaction 48h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention, as shown in Figure 1, surface is very complete, does not have defect for the hollow silicon ball transmission electron microscope picture of preparation.
Embodiment 2: with polymethylacrylic acid dimethylaminoethyl for surface stabilizer prepares the hollow silicon ball of 100nm
The polymethylacrylic acid dimethylaminoethyl that molecular weight is 20,000 is prepared: with N-carbazole dithiocarbonic acid isobutyronitrile ester for RAFT reagent by RAFT activity polymerizating technology, azo-bis-isobutyl cyanide is initator, being monomer with PDMAEMA, take oxolane as solvent.Wherein, the mol ratio of monomer, RAFT reagent and initator is chosen for 500:5:1, is placed in 60 DEG C of water-baths and prepares by RAFT living polymerization the polymethylacrylic acid dimethylaminoethyl that molecular weight is 20,000.Obtained polymethylacrylic acid dimethylaminoethyl is dissolved in water the aqueous solution being configured to 2 ‰.
Utilize
legal system is the silicon dioxide microsphere of 100nm for monodispersed particle diameter: mixed by the absolute ethyl alcohol of 4.16g ethyl orthosilicate and 50mL in 100mL beaker, stir, again in another 200mL beaker by the concentrated ammonia liquor (mass fraction is 28%) of 25g deionized water and 5mL, the absolute ethyl alcohol of 50mL mixes, under magnetic agitation, the weak solution of ethyl orthosilicate is dropwise added drop-wise in ammonia spirit, dropwise rear continuation stirring at room temperature 2h, centrifugal, upper solution is outwelled, with deionized water and ethanol washing, vacuum drying, obtain the silicon ball that particle diameter is about 100nm.By the silicon ball ultrasonic disperse of above-mentioned preparation in water, be made into 20mg/mL silicon dioxide microsphere dispersion liquid.
Self-template legal system is for hollow silicon ball: joined by silicon dioxide microsphere dispersion liquid in the polymethylacrylic acid dimethylaminoethyl aqueous solution of 2 ‰, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 2:1.Subsequently to the 0.01mol/L NaOH dripping trace in system, the pH value of adjustment system is 7.5.After stirring balance 4h, system temperature is elevated to 60 ° of C subsequently, reaction 48h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention.
Embodiment 3: with polymethylacrylic acid dimethylaminoethyl for surface stabilizer prepares the hollow silicon ball of 400nm
The polymethylacrylic acid dimethylaminoethyl that molecular weight is 10,000 is prepared: with phenyl dithiocarbonic acid isobutyronitrile ester for RAFT reagent by RAFT activity polymerizating technology, benzoyl peroxide is initator, being monomer with PDMAEMA, take oxolane as solvent.Wherein, the mol ratio of monomer, RAFT reagent and initator is chosen for 500:5:1, is placed in 60 DEG C of water-baths and prepares by RAFT living polymerization the polymethylacrylic acid dimethylaminoethyl that molecular weight is 10,000.Obtained polymethylacrylic acid dimethylaminoethyl is dissolved in water the aqueous solution being configured to 5 ‰.
Utilize
legal system is the silicon dioxide microsphere of 400nm for monodispersed particle diameter: mixed by the absolute ethyl alcohol of 4.16g ethyl orthosilicate and 45mL in 100mL beaker, stir, again in another 100mL beaker by the concentrated ammonia liquor (mass fraction is 28%) of 25g deionized water and 9mL, the absolute ethyl alcohol rapid mixing of 20mL is even, under quick magnetic agitation, the weak solution of ethyl orthosilicate is joined in ammonia spirit fast, dropwise rear continuation room temperature low rate mixing 3h, centrifugal, upper solution is outwelled, with appropriate amount of deionized water and ethanol washing, vacuum drying, obtain the silicon ball that particle diameter is about 400nm.By the silicon ball ultrasonic disperse of above-mentioned preparation in water, be made into 50mg/mL silicon dioxide microsphere dispersion liquid.
Self-template legal system is for hollow silicon ball: joined by silicon dioxide microsphere dispersion liquid in the polymethylacrylic acid dimethylaminoethyl aqueous solution of 5 ‰, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 3:1.Subsequently to the concentrated ammonia liquor dripping trace in system, the pH value of adjustment system is 8.0.After stirring balance 4h, system temperature is elevated to 70 ° of C subsequently, reaction 36h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention, the hollow silicon ball transmission electron microscope picture of preparation as shown in Figure 2.
Embodiment 4: with polymethylacrylic acid dimethylaminoethyl for surface stabilizer prepares the hollow silicon ball of 800nm
The polymethylacrylic acid dimethylaminoethyl that molecular weight is 5,000 is prepared: take cuprous bromide as catalyst by ATRP activity polymerizating technology, 2-isobutyl bromide propyl ester is initator, with N, N, N ', N ' ', N ' ' '-five methyl diethylentriamine is part, being monomer with PDMAEMA, take oxolane as solvent.Wherein, the mol ratio of monomer, initator, part and catalyst is chosen for 50:1:1.5:1.5, fills nitrogen deoxygenation and is placed in 60 DEG C of water-baths and prepares by ATRP living polymerization the polymethylacrylic acid dimethylaminoethyl that molecular weight is 5,000.Obtained polymethylacrylic acid dimethylaminoethyl is dissolved in water the aqueous solution being configured to 10 ‰.
Utilize
legal system is the silicon dioxide microsphere of 800nm for monodispersed particle diameter: mixed by the absolute ethyl alcohol of 8.2g ethyl orthosilicate and 30mL in 100mL beaker, stir, again in another 100mL beaker by the concentrated ammonia liquor (mass fraction is 28%) of 25g deionized water and 12mL, the mixed solution rapid mixing of the ethanol of 20mL and propyl alcohol (1:1) is even, under quick magnetic agitation, the weak solution of ethyl orthosilicate is joined in ammonia spirit fast, dropwise rear continuation room temperature low rate mixing 4h, centrifugal, upper solution is outwelled, with appropriate amount of deionized water and ethanol washing, vacuum drying, obtain the silicon ball that particle diameter is about 800nm.By the silicon ball ultrasonic disperse of above-mentioned preparation in ethanol, be made into 100mg/mL silicon dioxide microsphere dispersion liquid.
Self-template legal system is for hollow silicon ball: joined by silicon dioxide microsphere dispersion liquid in the polymethylacrylic acid dimethylaminoethyl aqueous solution of 10 ‰, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 5:1.Subsequently to the aqueous sodium carbonate dripping trace in system, the pH value of adjustment system is 9.5.After stirring balance 4h, system temperature is elevated to 80 ° of C subsequently, reaction 12h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention, the hollow silicon ball transmission electron microscope picture of preparation as shown in Figure 3.
Embodiment 5: with poly-dimethylamino-propyl Methacrylamide for surface stabilizer prepares the hollow silicon ball of 100nm
The poly-dimethylamino-propyl Methacrylamide that molecular weight is 2,000 is prepared: with N-carbazole dithiocarbonic acid isobutyronitrile ester for RAFT reagent by RAFT activity polymerizating technology, azo-bis-isobutyl cyanide is initator, with dimethylamino-propyl Methacrylamide for monomer, take oxolane as solvent.Wherein, the mol ratio of monomer, RAFT reagent and initator is chosen for 200:5:1, is placed in 80 DEG C of water-baths and prepares by RAFT living polymerization the poly-dimethylamino-propyl Methacrylamide that molecular weight is 2,000.Obtained poly-dimethylamino-propyl Methacrylamide is dissolved in water the aqueous solution being configured to 5 ‰.
Self-template legal system is for 100nm hollow silicon ball: utilize according to the step of embodiment 1
legal system is 100nm silicon dioxide microsphere for monodispersed particle diameter.Finally, in the silicon ball surface stabilizing agent aqueous solution, drip silicon dioxide microsphere dispersion liquid, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 4:1.Subsequently to the 0.01mol/L sodium borohydride dripping trace in system, the pH value of adjustment system is 9.0.After stirring balance 5h, system temperature is elevated to 60 ° of C subsequently, reaction 24h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention.
Embodiment 6: with poly-dimethylamino-propyl Methacrylamide for surface stabilizer prepares the hollow silicon ball of 100nm
The poly-dimethylamino-propyl Methacrylamide that molecular weight is 10,000 is prepared: with N-carbazole dithiocarbonic acid isobutyronitrile ester for RAFT reagent by RAFT activity polymerizating technology, azo-bis-isobutyl cyanide is initator, with dimethylamino-propyl Methacrylamide for monomer, take oxolane as solvent.Wherein, the mol ratio of monomer, RAFT reagent and initator is chosen for 200:5:1, is placed in 80 DEG C of water-baths and prepares by RAFT living polymerization the poly-dimethylamino-propyl Methacrylamide that molecular weight is 10,000.Obtained poly-dimethylamino-propyl Methacrylamide is dissolved in water the aqueous solution being configured to 5 ‰.
Self-template legal system is for 100nm hollow silicon ball: utilize according to the step of embodiment 1
legal system is 100nm silicon dioxide microsphere for monodispersed particle diameter.Finally, in the silicon ball surface stabilizing agent aqueous solution, drip silicon dioxide microsphere dispersion liquid, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 3:1.Subsequently to the 0.01mol/L sodium borohydride dripping trace in system, the pH value of adjustment system is 9.0.After stirring balance 5h, system temperature is elevated to 60 ° of C subsequently, reaction 24h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention.
Embodiment 7: with poly-dimethylamino-propyl Methacrylamide for surface stabilizer prepares the hollow silicon ball of 400nm
The poly-dimethylamino-propyl Methacrylamide that molecular weight is 20,000 is prepared: with phenyl dithiocarbonic acid isobutyronitrile ester for RAFT reagent by RAFT activity polymerizating technology, benzoyl peroxide is initator, with dimethylamino-propyl Methacrylamide for monomer, take oxolane as solvent.Wherein, the mol ratio of monomer, RAFT reagent and initator is chosen for 500:5:1, is placed in 60 DEG C of water-baths and prepares by RAFT living polymerization the poly-dimethylamino-propyl Methacrylamide that molecular weight is 20,000.Obtained poly-dimethylamino-propyl Methacrylamide is dissolved in water the aqueous solution being configured to 8 ‰.
Utilize
legal system is the silicon dioxide microsphere of 400nm for monodispersed particle diameter: mixed by the absolute ethyl alcohol of 4.16g ethyl orthosilicate and 45mL in 100mL beaker, stir, again in another 100mL beaker by the concentrated ammonia liquor (mass fraction is 28%) of 25g deionized water and 9mL, the absolute ethyl alcohol rapid mixing of 20mL is even, under quick magnetic agitation, the weak solution of ethyl orthosilicate is joined in ammonia spirit fast, dropwise rear continuation room temperature low rate mixing 3h, centrifugal, upper solution is outwelled, with appropriate amount of deionized water and ethanol washing, vacuum drying, obtain the silicon ball that particle diameter is 400nm.By the silicon ball ultrasonic disperse of above-mentioned preparation in water, be made into 50mg/mL silicon dioxide microsphere dispersion liquid.
Self-template legal system is for 100nm hollow silicon ball: in the silicon ball surface stabilizing agent aqueous solution, drip silicon dioxide microsphere dispersion liquid, and in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 1:1.Subsequently to the concentrated ammonia liquor dripping trace in system, the pH value of adjustment system is 8.5.After stirring balance 4h, system temperature is elevated to 70 ° of C subsequently, reaction 32h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention.
Embodiment 8: with poly-dimethylamino-propyl Methacrylamide for surface stabilizer prepares the hollow silicon ball of 800nm
The poly-dimethylamino-propyl Methacrylamide that molecular weight is 5,000 is prepared: take cuprous bromide as catalyst by ATRP activity polymerizating technology, 2-isobutyl bromide propyl ester is initator, with N, N, N ', N ' ', N ' ' '-five methyl diethylentriamine is part, with dimethylamino-propyl Methacrylamide for monomer, take oxolane as solvent.Wherein, the mol ratio of monomer, initator, part and catalyst is chosen for 50:1:1.5:1.5, fills nitrogen deoxygenation and is placed in 60 DEG C of water-baths and prepares by ATRP living polymerization the poly-dimethylamino-propyl Methacrylamide that molecular weight is 5,000.Obtained poly-dimethylamino-propyl Methacrylamide is dissolved in water the aqueous solution being configured to 10 ‰.
Utilize
legal system is the silicon dioxide microsphere of 800nm for monodispersed particle diameter: mixed by the absolute ethyl alcohol of 8.2g ethyl orthosilicate and 30mL in 100mL beaker, stir, again in another 100mL beaker by the concentrated ammonia liquor (mass fraction is 28%) of 25g deionized water and 12mL, the mixed solution rapid mixing of the ethanol of 20mL and propyl alcohol (1:1) is even, under quick magnetic agitation, the weak solution of ethyl orthosilicate is joined in ammonia spirit fast, dropwise rear continuation room temperature low rate mixing 4h, centrifugal, upper solution is outwelled, with appropriate amount of deionized water and ethanol washing, vacuum drying, obtain the silicon ball that particle diameter is about 800nm.By the silicon ball ultrasonic disperse of above-mentioned preparation in ethanol, be made into 100mg/mL silicon dioxide microsphere dispersion liquid.
In the silicon ball surface stabilizing agent aqueous solution, drip silicon dioxide microsphere dispersion liquid, in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 5:1.Subsequently to the aqueous sodium carbonate dripping trace in system, the pH value of adjustment system is 9.5.After stirring balance 4h, system temperature is elevated to 80 ° of C subsequently, reaction 16h.Through centrifugal, washing, alcohol wash, drying, both obtained hollow silicon ball of the present invention.
Open and the self-template legal system that proposes of the present invention is for the method for hollow silicon ball, all material, method and technology of preparing, those skilled in the art are by using for reference present disclosure, the links such as suitable feed change and process route realize, although method of the present invention and technology of preparing are described by preferred embodiment, person skilled obviously can change Method and Technology route as herein described or reconfigure not departing from content of the present invention, spirit and scope, realizes final technology of preparing.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (2)
1. pass through self-template legal system for a preparation method for hollow silicon ball, it is characterized in that: it is characterized in that concrete steps are as follows:
(1) preparation of the silicon ball surface stabilizing agent aqueous solution: by dimethylaminoethyl methacrylate or poly-dimethylamino-propyl Methacrylamide, be dissolved in water the aqueous solution being configured to 2 ~ 10 ‰;
(2) preparation of silicon dioxide microsphere dispersion liquid: utilize
legal system is the silicon dioxide microsphere of 100 ~ 800nm for diameter; By obtained silicon dioxide microsphere ultrasonic disperse in water or ethanol, preparation concentration is 5 ~ 100mg/mL silicon dioxide microsphere dispersion liquid;
(3) in the silicon ball surface stabilizing agent aqueous solution of step (1), drip the silicon dioxide microsphere dispersion liquid of step (2), in system, the mass ratio of silicon ball surface stabilizing agent and silicon ball is 1 ~ 5; Add alkaline etchant subsequently, the pH value of adjustment system is between 7.5 ~ 9.5; After stirring balance 4 ~ 8h, system temperature is elevated between 60 ~ 80 DEG C, reaction 12 ~ 48h; Through centrifugal, washing, alcohol wash, drying, obtain hollow silicon ball.
2. preparation method according to claim 1, is characterized in that described alkaline etchant is NaOH, ammoniacal liquor, sodium carbonate or sodium borohydride.
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| 单分散介孔纳米载体合成及表征;王淑梅等;《化学工业与工程》;20120930;第29卷(第5期);18-22 * |
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