CN1931718A - Prepn process of hollow silica ball - Google Patents
Prepn process of hollow silica ball Download PDFInfo
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- CN1931718A CN1931718A CN 200610096601 CN200610096601A CN1931718A CN 1931718 A CN1931718 A CN 1931718A CN 200610096601 CN200610096601 CN 200610096601 CN 200610096601 A CN200610096601 A CN 200610096601A CN 1931718 A CN1931718 A CN 1931718A
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Abstract
The preparation process of hollow silica ball includes the following steps: adding alcohol solvent into ammonia water solution of polymer electrolyte in 3-500 g/L concentration, dropping silicon source precursor solution of 1.1-4.4 mol/L concentration in the speed of 0.05-0.2 ml and silicon source precursor/ammonia water volume ratio of 1/15 to 2, reaction in a sealed container at 10-40 deg.c for 2-24 hr, and washing and drying the product, with the ammonia water having concentration of 10-25 wt% and the volume ratio between alcohol solvent and ammonia water being 3 to 25. The preparation process of the present invention is simple and suitable for industrial production, and has mild reaction condition, no environmental pollution and high yield, and the obtained hollow silica ball is loose, has inner diameter of 10-250 nm and water thickness of 10-40 nm, and may be used as medicine carrier and catalyst carrier.
Description
Technical field:
The invention belongs to the nano material preparation technical field, be specifically related to adopt sol-gel method to prepare the method for hollow silica ball.
Background technology:
The common method of existing preparation hollow silica ball has organic formwork method, tensio-active agent vesicle mold method, layer-layer self-assembly method etc.As: U.S.'s " Langmuir " (Langmuir,, 21 volumes, 6572-6575 page or leaf in 2005) has reported with organic sacrifice template and has prepared hollow silica ball, for template is removed, need carry out calcination processing to product at 660 ℃.The hollow ball that adopts this traditional template to obtain is reunited more serious, is not suitable for further use.
U.S.'s " Langmuir " (Langmuir, 2003,19 volumes, the 1069-1074 page or leaf), Britain's " materials chemistry magazine " (Journal of Materials Chemistry, calendar year 2001,11 volumes, the 1968-1971 page or leaf) and Germany " advanced material " (Advanced Materials, 2000,12 volumes, the 1286-1290 page or leaf) vesica that the employing tensio-active agent of mentioning forms in water solvent is as the template for preparing hollow silica ball, and this method often needs the long time (14 days) reaching liquid equilibrium, and the pH value of reaction system is had higher requirement; The shortcoming that the hollow ball that obtains also exists particle diameter to differ, be easy to reunite is not suitable for large-scale commercial production.U.S.'s " colloidal interface science magazine " (Journal of ColloidInterface Science,, 297 volumes, 157-160 page or leaf in 2006) mentions and adopts ultrasonic technique to improve preparation process, yet need react 10 hours under 180 ℃ temperature.
U.S.'s " materials chemistry " (Chemistry of Materials, 1999,11 volumes, the 3309-3314 page or leaf) reported that employing layer-layer self-assembly method prepares hollow silica ball, but need adsorb the repeatedly ionogen of multilayer opposite charges, be a kind of more time-consuming, the effort technology, be not suitable for modern large-scale commercial production.
Germany " advanced material " (Advanced Materials, 2006,18 volumes, the 801-806 page or leaf) proposes, prepare positively charged polystyrene (PS) bead in surface earlier, use it again, under 50 ℃ and certain ammonia concn as template, tetraethoxy becomes silicon-dioxide at PS bead surface hydrolysis, and meanwhile PS is by ammonia solvent; Although this method has been save follow-up thermal treatment, yet the preparation of PS bead and functionalization process thereof and remarkable are unsuitable for large-scale commercial production equally.
Summary of the invention:
The objective of the invention is to propose a kind of preparation method of hollow silica ball, need not to use organic sacrifice template and tensio-active agent, and the hollow silica ball monodispersity that makes is better, is suitable for suitability for industrialized production; Need prepare template in advance or use tensio-active agent, preparation process complexity, consuming time, and the shortcoming that the hollow silica ball that obtains can be reunited and size differs to overcome prior art.
The preparation method of hollow silica ball of the present invention, comprise: the ammonia soln at polyelectrolyte mixes with alcoholic solvent in the colloidal solution that forms, drip the silicon source precursor of 1.1～4.4 mol with 0.05～0.2 milliliter/hour speed, the volume ratio of described silicon source precursor and ammoniacal liquor is 1: 15～2: 1, place in the airtight container, 10～40 ℃ the reaction 2～24 hours, then to product wash, drying treatment; It is characterized in that: described colloidal solution adopts following method to make: the volume ratio by alcoholic solvent and ammoniacal liquor is 3: 1～25: 1, alcoholic solvent is joined in the ammonia soln that contains 3～500 grams per liter polyelectrolytes; The concentration of described ammoniacal liquor counts 10～25% with ammonia quality percentage composition.
Described polyelectrolyte is polyacrylic acid, sodium polyacrylate or sodium polymethacrylate.
Described alcoholic solvent is the ethanolic soln of concentration expressed in percentage by volume 〉=99.7% and/or the aqueous isopropanol of concentration expressed in percentage by volume 〉=99.5%.
Described silicon source precursor is tetraethoxy, methyl silicate or water glass.
The invention provides under a kind of polyelectrolyte effect, the method of the one-step synthesis hollow silica ball that the preparation particle diameter is controlled, because the present invention adopts colloid that polyelectrolyte the forms matrix as silicon source precursor hydrolytic polymerization in alcoholic solution, not only need not to prepare template in advance and use any tensio-active agent, and to not strict demand of temperature, the process gentleness is easy to control, therefore simplify preparation process greatly, shortened generated time; Because formed colloidal particle size is normal distribution, the hollow silica ball uniform particle diameter that obtains, better dispersed; What the inventive method adopted is common nontoxic industrial chemicals, environmentally friendly, pollution-free and energy expenditure is low, is suitable for industrialization and amplifies.
Ammonia soln owing to polyelectrolyte among the present invention forms colloidal solution in alcoholic solvent, the concentration that needs polyelectrolyte is greater than threshold concentration, and concentration is excessive, and the hollow silica ball that then obtains is reunited serious, so the concentration of polyelectrolyte is elected 3～500 grams per liters as.
Adopt resulting hollow silica ball internal diameter 10～250 nanometers of preparation method of the present invention, wall thickness 10～40 nanometers, the volume ratio of concentration that its size can be by changing polyelectrolyte solution and/or silicon source precursor and ammoniacal liquor is regulated.The preparation-obtained hollow silica ball quality of the inventive method is loose, and silica species inherent lightweight, favorable mechanical performance and thermostability can be used for pharmaceutical carrier or support of the catalyst in addition.
Description of drawings:
Fig. 1 is transmission electron microscope (TEM) photo of the hollow silica ball of internal diameter 40 nanometers that prepare among the embodiment 1, wall thickness 10～20 nanometers;
Fig. 2 is transmission electron microscope (TEM) photo of the hollow silica ball of internal diameter 50～60 nanometers that prepare among the embodiment 2, wall thickness 40 nanometers;
Fig. 3 is transmission electron microscope (TEM) photo of the hollow silica ball of internal diameter 20 nanometers that prepare among the embodiment 3, wall thickness 42 nanometers.
Embodiment:
Below in conjunction with embodiment the present invention is done specific description.
Embodiment 1: preparing internal diameter with polyacrylic acid is that 40 nanometers, wall thickness are the hollow silica ball of 10～20 nanometers
In the present embodiment, polyelectrolyte is example with the polyacrylic acid, and alcoholic solvent is example with ethanol, and silicon source precursor is example with the tetraethoxy; Get 0.08 gram polyacrylic acid and place 50 milliliters of tool plug Erlenmeyer flasks, the ammoniacal liquor gentle agitation that adds 1.50 milliliter 25% is to dissolving fully, add 30 milliliters of ethanol rapidly, vigorous stirring 30 minutes, the tetraethoxy of the 0.50 milliliter of 4.4 mol speed with 0.05 milliliter/hour is dripped, and reinforced finishing continues to stir 4 hours.The product usefulness distilled water that the reaction end obtains and each centrifuge washing of dehydrated alcohol at least three times are to remove impurity.With product in 60 ℃ of vacuum drying ovens dry 6 hours, obtain the white powder solid at last.
Employed silicon source precursor tetraethoxy in the foregoing description also can select for use methyl silicate or water glass to replace.
Adopt Diamond TG/DTA thermal analyzer (TG), the ALV-5000F laser light scattering instrument (LLS) of H-800 of Hitachi and JEOL-2010 transmission electron microscope (TEM), JEOL-JSM-6700F field emission scanning electron microscope (SEM), Philips X ' Pert PRO SUPER x-ray diffractometer (XRD), Perkin Elmer company, the Fluorolog 3-TAU-P fluorescence spectrophotometer (PL) of Jobin Yvon company that sample is characterized respectively.
Fig. 1 has provided transmission electron microscope (TEM) photo of the hollow silica ball for preparing in the present embodiment 1.TEM observation shows that the product that obtains is a hollow structure, and size is more even, internal diameter about 40 nanometers, wall thickness 10～20 nanometers, monodispersity is better.
SEM observation shows that the ball surface ratio is more coarse, this be since tetraethoxy due to polymer surfaces hydrolysis rate difference.
XRD figure is composed the diffraction peak that a broadening is arranged 20～30 ° of scopes, shows that the product that obtains is a soft silica.
TG analyzes demonstration, and hollow ball contains a certain amount of physics and crystalline hydrate water, and some unreacteds organic composition completely.
LLS analysis revealed, polyelectrolyte form sphere aggregates in poor solvent, particle diameter is normal distribution.
PL spectrum shows have luminously in 412 nanometers, and excitation wavelength is 355 nanometers.
When the ammonia consumption is respectively 0.25 milliliter, 1.00 milliliters, 1.50 milliliters, 2.00 milliliters, 3.00 milliliters, 30 milliliters of ethanol consumptions, polyacrylic acid consumption 0.08 gram, 0.50 milliliter of tetraethoxy consumption, the product that obtains is gradually varied to hollow ball from solid sphere, the final reunion.
When the polyacrylic acid consumption is respectively 0.015 gram, 0.065 gram, 0.14 gram, 30 milliliters of ethanol consumptions, 0.50 milliliter of tetraethoxy consumption, 1.50 milliliters of ammonia consumptions, the product that obtains is gradually varied to hollow ball from solid sphere, the final reunion.
When the tetraethoxy consumption is respectively 0.50 milliliter, 1.00 milliliters, 1.50 milliliters, 30 milliliters of ethanol consumptions, polyacrylic acid consumption 0.09 gram, 1.50 milliliters of ammonia consumptions, the wall thickness of the product that obtains increases gradually.
Embodiment 2: preparing internal diameter with sodium polyacrylate is that 50～60 nanometers, wall thickness are the hollow silica ball of 40 nanometers
In the present embodiment, polyelectrolyte is example with the sodium polyacrylate, and alcoholic solvent is example with ethanol, and silicon source precursor is example with the tetraethoxy; Get 0.1 gram sodium polyacrylate and place 50 milliliters of tool plug Erlenmeyer flasks, the ammoniacal liquor gentle agitation that adds 2.50 milliliter 20% is to dissolving fully, add 30 milliliters of ethanol rapidly, vigorous stirring 30 minutes, the tetraethoxy of the 2.00 milliliter of 2.2 mol speed with 0.2 milliliter/hour is dripped, and reinforced finishing continues to stir 10 hours.The product usefulness distilled water that the reaction end obtains and each centrifuge washing of dehydrated alcohol at least three times are to remove impurity.With product in 60 ℃ of vacuum drying ovens dry 6 hours, obtain the white powder solid at last.
Employed silicon source precursor tetraethoxy in the foregoing description also can select for use methyl silicate or water glass to replace.
Characterizing method is the same.
Fig. 2 has provided transmission electron microscope (TEM) photo of the hollow silica ball for preparing among the embodiment 2.TEM observation shows that the product that obtains is a hollow structure, and size is more even, internal diameter about 50～60 nanometers, wall thickness 40 nanometers, monodispersity is better.
SEM observation shows that the ball surface ratio is more coarse, this be since tetraethoxy due to polymer surfaces hydrolysis rate difference.
XRD figure is composed the diffraction peak that a broadening is arranged 20～30 ° of scopes, shows that the product that obtains is a soft silica.
TG analyzes demonstration, and hollow ball contains a certain amount of physics and crystalline hydrate water, and some unreacteds organic composition completely.
LLS analysis revealed, polyelectrolyte form sphere aggregates in poor solvent, particle diameter is normal distribution.
Embodiment 3: preparing internal diameter with sodium polymethacrylate is that 20 nanometers, wall thickness are the hollow silica ball of 42 nanometers
In the present embodiment, polyelectrolyte is example with the sodium polymethacrylate, and alcoholic solvent is an example with ethanol and Virahol, and silicon source precursor is example with the tetraethoxy; Get 0.03 gram sodium polymethacrylate and place 50 milliliters of tool plug Erlenmeyer flasks, the ammoniacal liquor gentle agitation that adds 2.00 milliliter 25% is to dissolving fully, 30 milliliters of ethanol of adding and Virahol volume ratio are 1: 1 alcohol mixture solution rapidly, vigorous stirring 30 minutes, the tetraethoxy of the 1.80 milliliter of 4.4 mol speed with 0.15 milliliter/hour is dripped, and reinforced finishing continues to stir 8 hours.The product usefulness distilled water that the reaction end obtains and each centrifuge washing of dehydrated alcohol at least three times are to remove impurity.With product in 60 ℃ of vacuum drying ovens dry 6 hours, obtain the white powder solid at last.
Employed silicon source precursor tetraethoxy in the foregoing description also can select for use methyl silicate or water glass to replace.
Characterizing method is the same.
Fig. 3 has provided transmission electron microscope (TEM) photo of the hollow silica ball for preparing among the embodiment 3.TEM observation shows that the product that obtains is a hollow structure, and size is more even, internal diameter about 20 nanometers, wall thickness 42 nanometers, monodispersity is better.
SEM observation shows that the ball surface ratio is more coarse, this be since tetraethoxy due to polymer surfaces hydrolysis rate difference.
XRD figure is composed the diffraction peak that a broadening is arranged 20～30 ° of scopes, shows that the product that obtains is a soft silica.
TG analyzes demonstration, and hollow ball contains a certain amount of physics and crystalline hydrate water, and some unreacteds organic composition completely.
LLS analysis revealed, polyelectrolyte form sphere aggregates in poor solvent, particle diameter is normal distribution.
Claims (4)
1, a kind of preparation method of hollow silica ball, comprise: the ammonia soln at polyelectrolyte mixes with alcoholic solvent in the colloidal solution that forms, drip the silicon source precursor of 1.1～4.4 mol with 0.05～0.2 milliliter/hour speed, the volume ratio of described silicon source precursor and ammoniacal liquor is 1: 15～2: 1, place in the airtight container, 10～40 ℃ the reaction 2～24 hours, then to product wash, drying treatment; It is characterized in that: described colloidal solution adopts following method to make: the volume ratio by alcoholic solvent and ammoniacal liquor is 3: 1～25: 1, alcoholic solvent is joined in the ammonia soln that contains 3～500 grams per liter polyelectrolytes; The concentration of described ammoniacal liquor counts 10～25% with ammonia quality percentage composition.
2, the preparation method of hollow silica ball according to claim 1 is characterised in that described polyelectrolyte is polyacrylic acid, sodium polyacrylate or sodium polymethacrylate.
3, the preparation method of hollow silica ball according to claim 1 is characterised in that described alcoholic solvent is the ethanolic soln of concentration expressed in percentage by volume 〉=99.7% and/or the aqueous isopropanol of concentration expressed in percentage by volume 〉=99.5%.
4, the preparation method of hollow silica ball according to claim 1 is characterised in that described silicon source precursor is tetraethoxy, methyl silicate or water glass.
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| JP2013127065A (en) * | 2011-12-16 | 2013-06-27 | Eternal Chemical Co Ltd | Anti-reflection coating composition and method for preparing the same |
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